Detailed description of the invention
Within the scope of the invention, term " polyurethane prepolymer of water-insoluble, non-aqueous dispersion " refers to, this prepolymer dissolubility in water at 23 DEG C is lower than 10g/ liter, preferably lower than 5g/ liter, and prepolymer cannot produce the dispersion of settlement stability at 23 DEG C in water (especially deionized water).In other words,, in the experiment that it is dispersed in water, prepolymer is precipitated out.
Preferably, polyurethane prepolymer A1 used according to the invention) there is terminal isocyanate group, this NCO is at the chain end of prepolymer.Whole chain ends of prepolymer particularly preferably have NCO.
In addition, polyurethane prepolymer A1 used according to the invention) preferably substantially neither there is ionic group and also do not there is ion source group, be that the content of ionic group and ion source group is suitably lower than the polyurethane prepolymer A1 of 15 milliequivalents (Milliequivalent)/100g), preferably lower than 5 milliequivalents, particularly preferably lower than 1 milliequivalent with very particularly preferably lower than the polyurethane prepolymer A1 of 0.1 milliequivalent/100g).
Amino-functional compounds A2) be preferably selected from uncle and/or secondary amine and/or diamidogen.Especially, amino-functional compounds A2) comprise at least one diamidogen.Amino-functional compounds A2) preferably there is the amino-functional compounds A2-II of ionic group or ion source group), and do not there is the amino-functional compounds A2-I of ionic group or ion source group).
In particularly preferred embodiment of the present invention, amino-functional compounds A2) comprise at least one amino-functional compounds A2-II with ion and/or ion source (ion formation) group).The ionic group using and/or ion source group are particularly preferably sulfonate group or sulfonic acid group, more more preferably sodium group.
In the embodiment of present invention further optimization, amino-functional compounds A2) comprise the amino-functional compounds A2-II with ionic group and/or ion source group) and do not there is the amino-functional compounds A2-I of ionic group or ion source group) both.
According to hair setting composition of the present invention, especially moisture (being aqueous) compositions, wherein polyurethane exist with the form of non-dissolving substantially with discrete form.Except other liquid medium that may exist is for example solvent, water has formed the main component (> 50wt%) of dispersion medium conventionally, and this is the total amount meter based on liquid dispersion medium in cosmetic composition.
Preferably have lower than 80wt% according to cosmetic composition of the present invention, more preferably less than 55wt%, even more preferably less than VOC (VOC) content of 40wt%, taking cosmetic composition as basis.
For preferably having lower than 10wt% according to the aqueous pu dispersions of the preparation of cosmetic composition of the present invention, more preferably less than 3wt%, even more preferably less than VOC (VOC) content of 1wt%, taking this aqueous pu dispersions as basis.
This VOC (VOC) content is measured by gas chromatographic analysis in scope of the present invention.
The isocyanate-functional polyurethane prepolymer A1 of water-insoluble and non-aqueous dispersion used according to the invention) substantially neither there is ionic group and also do not there is ion source group.Water herein refers to not add the deionized water of surfactant.In scope of the present invention, this refers to ion and/or ion source (ion formation) group, if the ratio of anionic group (as carboxylate radical or sulfonate radical) or cation group is the polyurethane prepolymer A1 lower than 15 milliequivalents/100g), preferably lower than 5 milliequivalents, particularly preferably lower than 1 milliequivalent with very particularly preferably lower than the polyurethane prepolymer A1 of 0.1 milliequivalent/100g).
With regard to acid ion group and/or ion source group, the acid number of prepolymer is suitably lower than 30mg KOH/g prepolymer, preferably lower than 10mg KOH/g prepolymer.This acid number represent in and the needed potassium hydroxide quality of study sample (mg) of 1g (measuring according to DIN EN ISO211).The acid (being corresponding salt) of neutralization does not naturally have acid number or has the acid number of attenuating.According to the present invention, the acid number of corresponding free acid is here conclusive.
Be used for the prepolymer A1 of the preparation of polyurethane) preferably can react to obtain with polyisocyanates by one or more polyhydric alcohol that are selected from polyether polyol, polycarbonate polyol, polyether polycarbonate polyhydric alcohol and/or PEPA, this also will explain below in detail.
Particularly preferred polyurethane is by using polyether polyol and/or polymer poly carbonate polyol and/or polyethers-polycarbonate polyol or PEPA to obtain, each in these polymer has the number-average molecular weight (here and for molecular weight data below, this molecular weight is to be measured with respect to polystyrene standards at 23 DEG C in oxolane by gel permeation chromatography) of the about 6000g/mol of preferred about 400-.In the preparation process of polyurethane or polyurethane prepolymer, their use will cause the formation of in polyurethane corresponding polyethers and/or Merlon and/or polyethers-Merlon segment or polyester segment due to the result of reacting with polyisocyanates, and this polyurethane has the corresponding molecular weight of these segments.According to the present invention, particularly preferably be the polyurethane that polyether glycol from having linear structure and/or polymer poly carbonic ether glycol and/or polyethers-polycarbonate polyol or PEPA obtain.
According to preferably linear molecule of polyurethane of the present invention, but also branching.
The number-average molecular weight of polyurethane preferably used according to the invention is, for example, and about 1000-200000, preferably 5000 to 150000.
The polyurethane containing in cosmetic composition according to the present invention especially adds in described compositions with aqueous dispersion form.
Optimization polyurethane or the dispersions of polyurethanes used according to the present invention can be by methods well known in the prior art, use known component to obtain, and the open US2011/0027211 of for example United States Patent (USP), is incorporated in full by reference at this.Corresponding step is summarized as follows:
A) the isocyanate-functional polyurethane prepolymer A1 that preparation is formed by following component)
Organic multiple isocyanate,
Polymer polyatomic alcohol, preferably there is the number-average molecular weight of 400-8000g/mol (here with for molecular weight data below, at 23 DEG C, measured with respect to polystyrene standards in oxolane by gel permeation chromatography), more preferably 400-6000g/mol and particularly preferably 600-3000g/mol, with there is preferred 1.5-6, more preferably 1.8-3, particularly preferably the OH degree of functionality of 1.9-2.1
The hydroxy functional compound of the optional molecular weight with preferred 62-399g/mol, and
Optional non-ionic hydrophilized reagent,
With
B) then allow their some or all dissociateive NCOs group and one or more amino-functional compounds A2), as uncle and/or secondary amine and/or diamidogen react.Polyurethane used according to the invention preferably step b) before, in process or be dispersed in afterwards in water.
Carry out with chain extension with reacting particularly preferably of diamidogen or two or more diamidogen in b) in step.In this respect, the amine of simple function can add to control molecular weight as chain terminating agent in addition.
As component A2), especially can use the amine (component A2-I below) without ionic group or ion source group (as anionic hydrophilic group)), and likely use the amine (component A2-II below) for example, with ionic group or ion source group (anionic hydrophilic group)).
Polyurethane used according to the invention preferably has anionic group, preferably sulfonate radical.These anionic groups via step b) in the amine component A2-II of reaction) be introduced in polyurethane A) in.Polyurethane in the present invention optionally has the nonionic components for hydrophiling in addition.In particularly preferred polyurethane, only have sulfonate group to realize hydrophiling; These are via as component A2-II) corresponding diamidogen be introduced in polyurethane.
In order to obtain good sedimentation stability, the number average particle size of the dispersions of polyurethanes in the present invention is preferably lower than 750nm, particularly preferably lower than 500nm, this measures (instrument: Malvern Zetasizer1000, Malver Inst.Limited) by laser correlation spectrometry after with deionized water dilution.
Suitable organic multiple isocyanate is aliphatic, aromatics or the alicyclic polyisocyanates that known the having of person of ordinary skill in the field is more than or equal to 2 NCO degree of functionality.
The example of nonrestrictive this type of polyisocyanates is 1, 4-butylidene vulcabond, 1, 6-hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate (IPDI), 2, 2, 4-and/or 2, 4, 4-trimethyl hexamethylene diisocyanate, two (4, 4 ' isocyano cyclohexyl) mixture of methane isomer or these isomers, 1, 4-cyclohexylidene vulcabond, 4-isocyano methyl isophthalic acid, 8-octane vulcabond (nonane triisocyanate), 1, 4-phenylene diisocyanate, 2, 4-and/or 2, 6-toluene di-isocyanate(TDI), 1, 5-naphthalene diisocyanate, 2, 2 '-and/or 2, 4 '-and/or 4, 4 '-'-diphenylmethane diisocyanate, 1, 3-and/or 1, two (the 2-isocyano third-2-yl) benzene (TMXDI) of 4-, 1, two (isocyano methyl) benzene (XDI) of 3-, with there is 2 of C1-C8-alkyl, 6-bis-isocyano caproic acid Arrcostabs (lysinediisocyanate).
Except above-mentioned polyisocyanates, also likely use and there is urea diketone, isocyanuric acid ester, urea alkane, allophanate, biuret, imino group
diazine diketone or
the modifying diisocyanates of degree of functionality>=2 of diazine triketone structure, and the mixture of these components in certain proportion.
Hexamethylene diisocyanate, the mixture of isoflurane chalcone diisocyanate and aforementioned vulcabond is particularly preferred.
Polymer polyatomic alcohol has preferred 400-8000g/mol scope, more preferably 400-6000g/mol and particularly preferably the number-average molecular weight Mn of 600-3000g/mol, and preferably there is 1.5-6, particularly preferably 1.8-3 and very particularly preferably the OH degree of functionality of 1.9-2.1.
Term " polymer " " polyhydric alcohol especially refers to that described polyhydric alcohol has at least two, the more preferably repetitive connecting together of at least three here.
This type of polymer polyatomic alcohol is PEPA known in polyurethane coating technology, polyacrylate polyol, polyurethane polyol, polycarbonate polyol, polyether polyol, polyester polyacrylate polyol, polyurethane polyacrylate polyol, polyurethane polyureas ester polyol, polyurethane polyureas ethoxylated polyhydric alcohol, polyurethane polyureas carbonate polyol and polyester-polycarbonate polyhydric alcohol.They can be separately or with the form of mixing for the preparation of in polyurethane of the present invention.
Polymer polyatomic alcohol in the present invention is polytetramethylene glycol polyethers, polycarbonate polyol and their mixture preferably, particularly preferably polytetramethylene glycol polyethers.
The hydroxy functional compound with the molecular weight of 62-399mol/g has the non-polymer polyhydric alcohol of 20 carbon atoms at the most, as ethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., 1, 2-propylene glycol, 1, ammediol, 1, 4-butanediol, 1, 3-butanediol, cyclohexane diol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol, neopentyl glycol, hydroquinone dihydroxy ethyl ether, bisphenol-A (2, two (4-hydroxyphenyl) propane of 2-), hydrogenated bisphenol A (2, two (4-hydroxy-cyclohexyl) propane of 2-), trimethylolpropane, trimethylolethane, glycerol, tetramethylolmethane, with their any mixture.
What be also applicable to is the esterdiol with described molecular weight ranges, as ε-hydroxycaproic acid Alpha-hydroxy butyl ester, and γ-hydroxybutyric acid ω-hydroxyl hexyl ester, two (beta-hydroxyethyl) esters of adipic acid (beta-hydroxyethyl) ester or p-phthalic acid.
In addition, also can use the compound that contains isocyanate-reactive hydroxyl of the simple function with described molecular weight ranges.The example of this type of monofunctional compound is ethanol, n-butyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol list propyl ether, propylene glycol single-butyl ether, dipropylene glycol single-butyl ether, tripropylene glycol single-butyl ether, 2-Ethylhexyl Alcohol, 1-capryl alcohol, DODECANOL, 1-, Cetyl OH.
Suitable non-ionic hydrophilized reagent is for example to have isocyanate-reactive groups as the polyoxyalkylene ether of hydroxyl, amino or mercapto.Preferably there is (according to median average) 5-70, the preferably monohydroxy functionalized poly oxyalkylene Aethoxy Sklerol of 7-55 ethylene oxide unit/molecule, this polyoxyalkylene Aethoxy Sklerol can obtain (for example, at Ullmanns in accordance with known methods by the alkoxylate of suitable starter molecule
der technischen Chemie, 4th edition, Volume19, Verlag Chemie, in Weinheim pp.31-38).Above-mentioned non-ionic hydrophilized reagent is pure polyethylene glycol oxide ether or mixing polyoxyalkylene ether, and wherein they contain at least 30mol%, and the preferred at least ethylene oxide unit of 40mol%, taking existing whole oxyalkylene units as basis.
Component A2) be preferably selected from uncle or secondary amine and/or diamidogen.It especially comprises diamidogen.
Component A2), can use the amine (component A2-I below) without ionic group or ion source group (as anionic hydrophilic group)), and can use and there is ionic group or ion source group the amine (component A2-II below) of (for example especially anionic hydrophilic group)).Preferred ingredient A2-I) and component A2-II) mixture react.
For example, organic diamine or polyamines, as 1,2-diaminoethane, 1,2-and 1,3-diaminopropanes, 1,4-diaminobutane, 1,6-diaminohexane, isophorone diamine, 2,2,4-and 2,4, the isomer mixture of 4-trimethylhexamethylenediamine, 2-methyl pentamethylene diamine, diethylenetriamines, 4,4-diamino-dicyclohexyl methane, hydrazine hydrate, and/or dimethyl-ethylenediamine can be used as component A2-I).
In addition the compound that, also has secondary amino group or also have an OH group except primary amino radical except amino (uncle or secondary) also can be used as component A2-I).Its example is primary/secondary amine, as diethanolamine, and 3-amino-1-methylamino propane, 3-amino-1-ethylamino propane, 3-amino-1-cyclohexyl aminopropane, 3-amino-1-methylamino butane, alkanolamine, as N-amino ethyl ethanolamine, ethanolamine, 3-aminopropanol, neopentyl alcohol amine.
In addition, the amines of the isocyanate reaction activity of simple function also can be used as component A2-I), for example methyl amine, ethylamine, propyl group amine, butylamine, octyl amine, lauryl amine, stearic amine, different nonyl oxygen base propyl group amine, dimethyl amine, diethylamide, dipropylamine, dibutylamine, N-methylamino propyl group amine, diethyl (methyl) aminopropyl amine, morpholine, piperidines, with their suitable substitutive derivative, amide-the amine being formed by di-primary amine and monocarboxylic acid, the single ketones imines (Monoketim) of di-primary amine, primary/tertiary amine, as N, N-dimethylaminopropyl amine.
As component A2-I), preferably use 1,2-diaminoethane, two (4-aminocyclohexyl) methane, 1,4-Diaminobutane, isophorone diamine, ethanolamine, diethanolamine and diethylenetriamines.
Component A2) particularly preferably comprise at least one component A2-II).As component A2-II) suitable anion hydrophiling compound preferably contain sulfonic acid or sulfonate groups, particularly preferably sodium group.The example of this type of anionic hydrophilic reagent is 2-(2-aminoethylamino) ethane sulfonic acid, ethylenediamine-propyl group-or-butyl-sulfonic acid, the salt of 1,2-or 1,3-propane diamine-β-ethylsulfonic acid or taurine.In addition, the salt of the cyclohexyl aminopropanesulfonic acid (CAPS) of WO-A01/88006 can be used as anionic hydrophilic reagent.
Particularly preferred anionic hydrophilic reagent A 2-II) be contain sulfonate groups as ionic group and contain two amino those, as the salt of 2-(2-aminoethylamino) ethylsulfonic acid and 1,3-propane diamine-β-ethylsulfonic acid.
Polyurethane in the present invention particularly preferably comprises at least one sulfonate groups.
Optionally, at component A2-II) in anionic group can be also carboxylate or hydroxy-acid group.
The preparation of dispersions of polyurethanes can be carried out in one or more stages in homogeneous phase or for multistage reaction, part is carried out in decentralized photo.In this respect, can use all method well known in the prior art, for example, prepolymer mixed method, acetone method or melt dispersion method.Preferably use acetone method.
In the process of production polyurethane prepolymer, the amount of substance ratio (nco index) of isocyanate groups and isocyanate-reactive groups is generally in 1.05-3.5 scope, preferably in 1.1-3.0 scope with particularly preferably in 1.1-2.5 scope.
Be preferred for the normally 10-70wt% of solids content of the dispersions of polyurethanes of preparing cosmetic composition of the present invention, preferably 30-65wt%, particularly preferably 40-60wt%.Solids content is determined by weighing sample is heated to constant weight at 125 DEG C.Under constant weight, calculate solids content by weighing again sample.
Preferably, these dispersions of polyurethanes have lower than 5wt%, particularly preferably lower than the organic amine of the not keyed jointing of 0.2wt%, and the quality meter based on dispersion.Content in cosmetic composition is correspondingly also lower.
For the preparation of the dispersions of polyurethanes of cosmetic composition of the present invention preferably BayerMaterialsScience company produce
c1000,
c1001,
c1003,
c1004 and
c1008.Particularly preferably be
c1004 and
c1008.
Copolymer B in the present invention) polymer unit that comprises is mainly by monomers B mentioned above 1) and ampholytic monomer B2) introduce, and the polymer unit of being introduced by other monomer is no more than at most this copolymer B) 5wt%, be preferably no more than 1wt%.More preferably copolymer B) monomers B 1 by mentioned earlier only) and ampholytic monomer B2) be prepared from.
Copolymer B in the present invention) polymer unit that comprises can also introduce by ketopyrrolidine monomer.
Preferred monomers B 1) be acrylic acid, methacrylic acid, acrylic acid C
1-20arrcostab and methacrylic acid C
1-20arrcostab.
Particularly preferably be monomers B 1) be selected from acrylic acid, methacrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, lauryl acrylate, lauryl methacrylate, acrylic acid hexadecane ester, methacrylic acid hexadecane ester, acrylic acid octadecane ester, methacrylic acid octadecane ester.Especially particularly preferably be acrylic acid, methacrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, lauryl acrylate, lauryl methacrylate, acrylic acid octadecane ester and methacrylic acid octadecane ester.
Preferred monomers B 2 comprises suc as formula (methyl) acryloyl alkyl betaine shown in B2-I with suc as formula (methyl) acryloyl alkyl amine oxide shown in B2-II, wherein, and R
2and R
3in each situation, be all selected from independently of one another methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or the tert-butyl group, particularly preferably methyl.
Preferred monomers B 2 more comprises suc as formula (methyl) acryloyl alkyl betaine shown in B2-I with suc as formula (methyl) acryloyl alkyl amine oxide shown in B2-II, wherein, n is selected from respectively 1~5 integer, and preferably 1~3 integer is particularly preferably 2.
Preferred monomers B 2 also comprises suc as formula (methyl) acryloyl alkyl betaine shown in B2-I with suc as formula (methyl) acryloyl alkyl amine oxide shown in B2-II, wherein, and R
1represent CH
3.
In a preferred example, at least one ampholyte copolymer B) synthesized by following component:
At least three kinds of monomers B 1), the first monomer is selected from acrylic acid, methacrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate; The second monomer is selected from lauryl acrylate, lauryl methacrylate; And the third monomer is selected from acrylic acid octadecane ester, methacrylic acid octadecane ester.Meanwhile, B2) be (methyl) acryloyl alkyl amine oxide.
Meet the ampholyte copolymer B of above-mentioned condition) be known, comprise that business's label of being produced by Mitsubishi company is
z-611,
z-612,
z-631,
z-632,
z-651,
z-711N and
the products such as Z-731N, and the production of Lubrizol company
g-100,
plus,
superhold and
rSP etc.Wherein,
z-631 is preferred.
Cosmetic composition according to the present invention is except comprising polyurethane mentioned above or dispersions of polyurethanes A) and at least one ampholyte copolymer B), also comprise that the acceptable medium of cosmetics especially comprises water and optional cosmetics suitable solvent.Wherein, polyurethane A) in solid constituent or the active component percentage by weight that accounts for cosmetic composition be 0.1% to 10%, be preferably 0.1% to 5%.Ampholyte copolymer B) in solid constituent or the active component percentage by weight that accounts for cosmetic composition be 0.1% to 20%.The weight of solid constituent is determined by weighing sample is heated to constant weight at 125 DEG C.Under constant weight, calculate the weight of solid constituent by weighing again sample.
According to cosmetic composition of the present invention, wherein polyurethane A) solid constituent and ampholyte copolymer B) the weight ratio of solid constituent be 1: 30 to 30: 1, preferred weight ratio is 1: 10 to 10: 1, preferred weight ratio is 1: 3 to 3: 1.
Cosmetic composition according to the present invention preferably includes the polyurethane A as above of 0.1-30wt%) and ampholyte copolymer B) the weight sum of solid constituent, taking the gross weight of compositions as basis.
As mentioned above, the acceptable medium of cosmetics especially comprises water and optional cosmetics suitable solvent.Preferred solvent is the aliphatic alcohol with C2-4 carbon atom, as ethanol, and isopropyl alcohol, the tert-butyl alcohol, n-butyl alcohol; Polyhydric alcohol, as propylene glycol, glycerol, ethylene glycol and polyol ethers; Acetone; The hydrocarbon of nonbranched or branching, as pentane, hexane, isopentane and cyclic hydrocarbon, as Pentamethylene. and cyclohexane extraction; With their mixture.
Solvent is very particularly preferably ethanol.
For low VOC type hair setting composition, the content of this kind solvent is preferably lower than 80wt%, and more preferably less than 55wt%, then more preferably less than 40wt%, remainder is water, all taking the gross weight of compositions as basis.
Except polyurethane as above, can comprise according to compositions of the present invention the film former that other is suitable, this film former also can contribute to sizing and the pattern design of hair.
The concentration of one or more other film former can be 0-20wt%, particularly 0-10wt%, taking the gross weight of compositions as basis.
Film former can be selected from the water solublity different from the polyurethane using in the present invention or water-dispersible polyurethane, polyureas, polyorganosiloxane resin and/or polyester, and nonionic, anion, both sexes and/or cationic polymer and their mixture.
Can advantageously comprise in addition thickening agent according to cosmetic composition of the present invention.Favourable thickening agent is: crosslinked or uncrosslinked acrylic or methacrylic acid homopolymer or copolymer; Natural thickening polymer; Nonionic, anion, the association polymer of cation or both sexes, for example, taking the derivant of Polyethylene Glycol and they or polyurethane as basis; And crosslinked or uncrosslinked homopolymer or copolymer taking acrylamide or Methacrylamide as basis.
If use thickening agent, they are generally with the 0-2wt% of the gross weight based on compositions, and preferably the concentration of 0-1wt% exists.
Can comprise in addition gaseous propellant according to cosmetics compound of the present invention.Here, advantageously with the amount of 0-40wt% with particularly preferably use gaseous propellant with the concentration of 0-20wt%, taking the gross weight of preparaton as basis.
According to the present invention preferred propellant gas be hydro carbons as propane, iso-butane and normal butane, and their mixture.But, according to the present invention, compressed air, carbon dioxide, nitrogen, nitrogen dioxide and dimethyl ether, and all the mixture of these gases also can advantageously use.
In addition, hair nursing active component and common additive can both be used for cosmetic composition of the present invention.Above-mentioned additive comprises silicone or silicone derivative, wetting agent, wetting agent, softening agent is as glycerol, glycol and phthalic acid ester and ether, spice and aromatic, UV absorbent, dyestuff, pigment, with other coloring agent, anticorrosive, nertralizer, antioxidant, antitack agent, bonding agent and conditioner, antistatic additive, polishing material, antiseptic, protein and their derivant, aminoacid, vitamins, emulsifying agent, surfactant, viscosity modifier, thickening agent and rheology modifier, gel, opacifying agent, stabilizing agent, surfactant, sequestering agent, complexant, pearling agent, aesthetic feeling reinforcing agent, fatty acid, fatty alcohol, triglyceride, plant extract, clarification aid and film former.
These additives are generally the approximately 0.001wt%-15wt% with the gross weight based on cosmetic composition, and preferably the concentration of 0.01wt%-10wt% exists.
Can be with gel according to cosmetic composition of the present invention, particularly hair setting composition, emulsion, the form of solution or cream exists, as with hair styling mousse, sizing fluid, hair spray, pattern design gel, pattern design cream, the forms such as aerosol mouse.The mode such as cosmetic composition of the present invention is adopted to spraying or smear is applied to can play on the cutin protein fibers such as hair and is shaped and/or the effect of sizing.
Be the form of spray according to the preferred embodiment of hair setting composition of the present invention, it comprises one or more following ingredients in addition: the solvent that cosmetics are suitable, has the aliphatic alcohol of 2-4 carbon atom, preferred alcohol, polyhydric alcohol, acetone, the not hydrocarbon of branching or branching, cyclic hydrocarbon and their mixture, and propellant gas, as hydro carbons, compressed air, carbon dioxide, nitrogen, nitrogen dioxide, dimethyl ether, fluorohydrocarbon and Chlorofluorocarbons (CFCs), preferably dimethyl ether and/or propane/butane mix.
The present invention illustrates by following embodiment, and these embodiment should not be regarded as conditional.Except as otherwise noted, otherwise whole quantitative datas, mark and percent are based on weight or the gross weight based on compositions.
Embodiment
raw material and reagent
Embodiment in the present invention and comparative example can be prepared in the following manner: under the mixing speed of 500-600rpm, by EDTA Na
2, propylene glycol and rheological agent be added to the water, until be uniformly dispersed; Continue to add respectively as polyurethane A of the present invention) (
c1004 or
c1008) and ampholyte copolymer B) (
z-631), lasting stirring is uniformly dispersed it; Then add AMP PC2000 until pH is adjusted to 6.5 left and right; Finally add antiseptic Liquid Germall Plus, under the speed of 200-300rmp, stir until be uniformly dispersed.The gel sample of gained has > 10000, preferably the viscosity of 12000-15000mPa (use and measure rotor No. 63, at 25 DEG C, with the tachometric survey of 10rpm)
Embodiment in the present invention and comparative example all have component as shown in the following chart:
By regulating polyurethane A) with ampholyte copolymer B) composition and proportioning, obtain comparative example as shown in the table and embodiment:
Wt% wherein refers to that the solid constituent in this composition accounts for the percetage by weight of gel sample gross weight.And polyurethane A) with ampholyte copolymer B) in the percentage by weight sum of solid constituent remain 2wt%.
The cradle of hair below using in experiment is western part of China, the Asia hair being provided by Chinese Rebecca hair manufacturing company.All hairs are all healthy, without bleaching, dyeing or other chemical treatment.
evaluation experimental:
Each product of preparation is spread upon respectively on hair, wait for that after bone dry, the evaluation group being made up of trained five people gives a mark to each project, 1 point minimum the poorest, and 10 points preferably the strongest.Because marking is relative, thus between the mark of each group without comparability.
Before the evaluation of washing away property of shampoo, every bundle Hair grooming 1mL standard washing liquid (12% sodium dodecyl sulfate solution) is cleaned 60 seconds, and then with the tap water rinsing of 25 DEG C 30 seconds.Wait for that after topknot bone dry, estimating it has the film of non-polymer residual.
The evaluation result of table 1. to C1004 and Z-631 component
The evaluation result of table 2. to C1008 and Z-631 component
Can find out from above two groups of evaluation experimentals, with respect to only using polyurethane A) formula, use polyurethane A simultaneously) and ampholyte copolymer B) formula there is the washing away property of shampoo significantly improving, residual white scales on hair and comb still less, higher film forming consistency and elasticity.
curling reservation experiment under high humility:
For " curling reservation " experiment, first hair is carried out to standardization washing procedure.In water, the hair of softening 15 minutes, by using the sodium dodecyl sulfate solution hair washing 2 minutes of 12wt%, with warm water rinsing up hill and dale, dries up on cold wind shelves, then under 22 DEG C and 55% relative humidity, nurses one's health.The pigtail of 0.5cm width is taken advantage of wet being wound on propellers, dries up 35 minutes on hot blast shelves, then on hair, evenly smears polymer gel, spends the night and makes its finish-drying.
Should " curling reservation " experiment be what in the climatic chamber of relative humidity with > 90%, to carry out.The temperature of this case maintains 25 DEG C.Prepared pigtail is suspended in this chamber simultaneously, has the panel of altitude scale behind for mark.On graduated tile, read curling length in some time, and relatively draw a percent with initial length.Each data are the meansigma methods of four pigtails.
The curling reservation experimental result of table 3. to C1004 and Z-631 component
The curling reservation experimental result of table 4. to C1008 and Z-631 component
Can find out from above two groups of experiments, with respect to only using ampholyte copolymer B) formula, use polyurethane A simultaneously) and ampholyte copolymer B) formula have under high humility, the curling reservation significantly improving after long-time.
mechanical meaurement experiment:
The experiment of the mechanical property of the measurement film being designed by Stable Micro System Corporation (France) is widely known by the people in this area.This experiment contacts and has smeared polymer gel and be dried topknot surface afterwards with probe, measures the stress of film forming in making topknot distortion.From the curve of stress and deformation, can calculate the hardness of membrane, elasticity etc.
The instrument model of this experiment use is TA-XT Plus.Each software parameter is as shown in the following chart:
Before survey-speed |
2mm/sec |
Test-speed |
0.5mm/sec |
After surveying-speed |
1mm/sec |
Triggering power |
2gram |
Distortion |
4mm |
Periodicity |
10 |
Gel sample is uniformly applied on hair.At 25 DEG C, under 50% relative humidity condition, stretching hair is spent the night and dried.Every kind of sample is applied on 5 bundle hairs, after measurement, averages.
The mechanical meaurement result of table 5. to C1008 and Z-631 component
More than tested proving again with respect to only using polyurethane A) formula, use polyurethane A simultaneously) with ampholyte copolymer B) formula there is the film hardness that becomes significantly improving.
Those skilled in the art easily knows, the present invention is not limited only to aforesaid detail, and is not departing under the prerequisite of spirit of the present invention or key property, and the present invention can be embodied as other particular forms.Therefore all should be by described embodiment regarded as illustrative from any angle and nonrestrictive, thereby by claims but not above stated specification is pointed out scope of the present invention; And therefore any change, as long as it belongs in the implication and scope of claim equivalent, all should regard as and belong to the present invention.