CN104546549A - Facial mask composition containing sunscreen filter agent - Google Patents
Facial mask composition containing sunscreen filter agent Download PDFInfo
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- CN104546549A CN104546549A CN201310546209.3A CN201310546209A CN104546549A CN 104546549 A CN104546549 A CN 104546549A CN 201310546209 A CN201310546209 A CN 201310546209A CN 104546549 A CN104546549 A CN 104546549A
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Abstract
The invention relates to a facial mask composition containing a sunscreen filter agent, as well as composition, application and a use method thereof. The facial mask composition is characterized by containing a special polyurethane, at least one thickener, at least one non water-soluble sunscreen and water. According to the facial mask composition, the sunscreen filter agent is fixed in the facial mask composition, so that the facial mask composition has the functions of reducing skin allergy and prolonging the sunscreen duration. Meanwhile, after being moisturized by water, the facial mask composition provided by the invention can be stripped off from the skin in a whole piece, so that cleaning is easier.
Description
Technical field
The present invention relates to and be a kind ofly applied to the mask composition comprising sun-proof lightscreening agent and special polyurethane on skin and application thereof and using method.
Background technology
As everyone knows, solar rays has harmful effect to skin, this is because they penetrate to skin different depth according to its wavelength.In UVB scope (wavelength: 280-320nm), shorter wavelength radiation reaches uppermost skin layer.Ray in UVB scope causes the sun to burn and causes the risk of skin carcinoma to increase.Longer wavelength UVA ray (wavelength: 320-400nm) penetrates to darker skin layer.They cause the damage of extremely important collagen and elastin fiber for the structure of skin and intensity.In addition, this also causes too early skin aging (formed the wrinkle of skin and microgroove, irregular lax etc.).In order to protect skin from solar irradiation, oneself develops photoprotection lightscreening agent material (UVA and UVB lightscreening agent, it is included in Positivlist form as in the annex 7 of Cosmetic Act), and they are in cosmetics or skin care compositions and methods.So far, the sunscreen composition comprising UVA and UVB lightscreening agent generally exists with form below: frost, emulsion, gel, oil, cream, aqueous solution.
US Patent No. 7,097,828 disclose a kind of formula be applied on skin, and this formula comprises the polyether polyols with reduced unsaturation of aqueous, thickening agent, wetting agent, at least one sunscreen actives and emulsifying agent.The Avalure UR that the polyether polyols with reduced unsaturation of aqueous is preferably produced by BF Goodrich is serial, sunscreen actives can be any material being accepted the tool sun-proof result used on skin, and disclosed formula generally exists with the form of oil-in-water or water in oil cream and emulsion.
U.S. Patent Publication US2011/0064681 discloses a kind of cosmetics preparation component containing special polyurethane.This special polyurethane is that water is dispersible, and to comprise containing the basic of hydrophilic and hydrophobic section be alternately linear skeleton.This cosmetics preparation component is generally oil-in-water or water in oil emulsion, and wherein also can comprise the sunscreen of optionally water solublity, oil-soluble and/or pigment class.
The open KR20120028143 of Korean Patent disclose a kind of can on skin the compositions of film forming, comprise water-insoluble polymer and extender.Water-insoluble polymer can select the Ultrasol1000C of Baycusan100 or the Chemiland company of Bayer company.Said composition also can comprise thickening agent, rheological agent, emulsifying agent, wetting agent, the compositions such as desolventizing composition and oils and fats, pigment, UV blocking agent.
The open CN101980689A of Chinese patent discloses a kind of sunscreen composition comprising special polyurethane be applied on skin.This special polyurethane by one or more are water-fast, water, the polyurethane prepolymer of isocyanate-functional and one or more amino-functional compounds can not be scattered in carry out reacting and obtain.Have the multiple oil-in-water containing this special polyurethane simultaneously, the formula of Water-In-Oil and the water in oil emulsion of silicon, what have in these formula also contains oil-soluble and/or water miscible UV lightscreening agent.
The open CN102811703A of Chinese patent, on the basis of the above-mentioned CN101980689A mentioned, discloses the formula including a certain amount of octocrylene.This formula has sun protection factor accelerating effect.
All open specific descriptions all not providing the mask composition containing UV lightscreening agent above.
Summary of the invention
Containing that market exists at present is sun-proof, and the particularly cosmetic composition of UV lightscreening agent is generally the form of emulsion, cream or ointment.The common drawback that they have goes during sun-proof lightscreening agent may penetrate to the skin, thus cause the anaphylaxis of some crowd on the one hand, and order causes sun protection factor to reduce in time on the one hand; Therefore the sun-proof result in order to ensure, needs constantly again to apply, convenient not.In order to can use in the place that humidity is high, some cosmetic composition containing sun-proof lightscreening agent is very water-fast, thus not easily from washing away completely on the face, if things go on like this may cause the infringement to skin.
The object of the invention is to adopt the form of film forming to be applied on skin by sun-proof lightscreening agent, to overcome shortcoming above-mentioned.Advantage of the present invention comprises and sun-proof lightscreening agent can be fixed on skin surface preferably, thus reduce sun-proof lightscreening agent penetrate to the skin in and the number of times that again applies of the anaphylaxis that may cause and needing; Another advantage obtains not only resistance to high humility but also the easy cosmetic combinations composition formula containing sun-proof lightscreening agent peeled off from skin.
On the one hand, the invention discloses a kind of mask composition containing sun-proof lightscreening agent can peeled off from skin, comprise:
A) at least one aqueous polyurethane A),
B) at least one thickening agent,
C) the water-insoluble sun-proof lightscreening agent of at least one,
D) water; With
E) optionally emulsifying agent;
Further, in the solid constituent of aqueous polyurethane and mask composition, the weight ratio of oil phase component is not less than 2:3.
Wherein, aqueous polyurethane A) by the isocyanate-functional polyurethane prepolymer A1 of one or more water-insolubles, nonaqueous dispersion) with one or more amino-functional compounds A2) react to obtain.
Wherein, thickening agent comprises the thickening agent of polymer and/or the thickening agent of natural origin.And polymer viscosifier comprises anionic thickening polymer agent, amphoteric ion polymer thickening agent and/or Nonionic polymeric thickeners.
Wherein, water-insoluble sun-proof lightscreening agent comprises fat-soluble organic sunscreen lightscreening agent and/or inorganic sunscreens lightscreening agent.
Mask composition of the present invention also optionally comprises emulsifying agent; Oil phase component of the present invention comprises optional fat-soluble organic sunscreen lightscreening agent, optional oils and fats and/or optional emulsifying agent.When only using inorganic sunscreens lightscreening agent, in mask composition, also oil phase component can not be comprised.
Mask composition of the present invention also optionally comprises wetting agent.
On the other hand, the percentage by weight that the solid constituent of aqueous polyurethane accounts for mask composition of the present invention is about 3% to 59%, the percentage by weight that thickening agent accounts for mask composition is about 0.01% to 20%, the percentage by weight that water-insoluble sun-proof lightscreening agent accounts for mask composition is about 0.1% to 50%, the percentage by weight that wetting agent accounts for mask composition is about 0% to 40%, the percentage by weight that emulsifying agent accounts for mask composition is about 0% to 10%, all in the gross weight of mask composition for 100%.
In another, in mask composition of the present invention, the percentage by weight that electrolyte accounts for mask composition is not more than 2%, and more favourable is not more than 0.5%; The percentage by weight that chelating agen accounts for mask composition is not more than 2%, and more favourable is not more than 0.5%; All in the gross weight of mask composition for 100%.
The present invention discloses and use mask composition of the present invention to reach the sun-proof method of face, comprise and mask composition is applied to skin surface, after waiting its natural drying, form a film, when needing, with film described in water infiltration to peel off.
Containing the mask composition of sun-proof lightscreening agent disclosed in the present invention, when being applied on skin, can being formed and there is seriality and elastic facial film, and also can keep complete for a long time under the condition of Exposure to Sunlight or high humility; When needs remove, available water is by whole facial film moistening, due to the high resiliency of facial film, high tensile stress and water-fast character, facial film of the present invention intactly can be stripped skin surface, thus reaches convenient, the thorough object removing the sun-proof lightscreening agent of skin surface.
Detailed description of the invention
Within the scope of the invention, term " polyurethane prepolymer of water-insoluble, nonaqueous dispersion " refers to, the dissolubility of this prepolymer at 23 DEG C in water 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 it be dispersed in water, prepolymer is precipitated out.
Preferably, polyurethane prepolymer A1 used according to the invention) there is terminal isocyanate group, namely 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 having ionic group does not also have ionogenic group, namely the content of ionic group and ionogenic 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 ionogenic group), and not there is the amino-functional compounds A2-I of ionic group or ionogenic 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 used and/or ionogenic 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 ionogenic group) and not there is the amino-functional compounds A2-I of ionic group or ionogenic group) both.
According to mask composition of the present invention, wherein namely polyurethane exist with the form of non-dissolving in a dispersed form substantially.Except other liquid medium such as solvent that may exist, water usually constitutes the main component (>50wt%) of dispersion medium, and this is the total amount based on liquid dispersion medium in mask composition.
With regard to acid ion group and/or ionogenic group, polyurethane prepolymer A1) acid number suitably lower than 30mg KOH/g prepolymer, preferably lower than 10mg KOH/g prepolymer.With the potassium hydroxide quality (mg) (measuring according to DIN EN ISO211) required for study sample of 1g during this acid number represents.The acid (i.e. 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.
Prepolymer A1 in the preparation of polyurethane) preferably by being selected from one or more polyhydric alcohol in polyether polyol, polycarbonate polyol, polyether polycarbonate polyhydric alcohol and/or PEPA and polyisocyanates carries out reacting obtaining, this also will explain below in detail.
Particularly preferred polyurethane obtained by using polyether polyol and/or polymer poly carbonate polyol and/or polyether-polycarbonate polyhydric alcohol or PEPA, each in these polymer has the number-average molecular weight (here and for molecular weight data below, this molecular weight is measured relative to polystyrene standards at 23 DEG C in oxolane by gel permeation chromatography) that preferably about 400-is about 6000g/mol.In the preparation process of polyurethane or polyurethane prepolymer, the result owing to reacting to polyisocyanates is caused the formation of corresponding polyethers and/or Merlon and/or polyether-polycarbonate segment or polyester segment in polyurethane by their use, and this polyurethane has the corresponding molecular weight of these segments.According to the present invention, particularly preferably be the polyurethane from there is the polyether glycol of linear structure and/or polymer poly carbonate diol and/or polyether-polycarbonate polyhydric alcohol or PEPA obtaining.
According to aqueous polyurethane A of the present invention) preferably linear molecule, but may also be branching.
Aqueous polyurethane A preferably used according to the invention) number-average molecular weight be, such as, about 1000-200000, preferably about 5000 to about 150000.
The aqueous polyurethane contained in mask composition according to the present invention especially adds in described compositions with aqueous dispersion.
The optimization polyurethane used according to the present invention or dispersions of polyurethanes, by method well known in the prior art, use known component to obtain, and the open CN101980689A of such as Chinese patent, is incorporated in full by reference at this.Corresponding step is summarized as follows:
A) the isocyanate-functional polyurethane prepolymer A1 formed by following component is prepared)
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, measured relative to polystyrene standards at 23 DEG C 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 optional hydroxy functional compound with the molecular weight of preferred 62-399g/mol, and
Optional non-ionic hydrophilized reagent,
With
B) their some or all dissociateive NCOs group and one or more amino-functional compounds A2 are then allowed), as uncle and/or secondary amine and/or diamidogen react.Polyurethane used according to the invention is preferably in step b) before, in process or be dispersed in afterwards in water.
In step b) in particularly preferably carry out with chain extension with the reaction of diamidogen or two or more diamidogen.In this respect, the amine of simple function can add to control molecular weight as chain terminating agent in addition.
As component A2), especially the amine (component A2-I below) without ionic group or ionogenic group (as anionic hydrophilic group) can be used), and likely use the amine (component A2-II below) with ionic group or ionogenic group (such as anionic hydrophilic group)).
Polyurethane used according to the invention preferably has anionic group, preferred sulfonate radical.These anionic groups are via in 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.Only have sulfonate group to realize hydrophiling in particularly preferred polyurethane; 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 is measured (instrument: Malvern Zetasizer1000, Malver Inst.Limited) by laser correlation spectrometry after with deionized water dilution.
Suitable organic multiple isocyanate is that known the having of person of ordinary skill in the field is more than or equal to the aliphatic of the NCO degree of functionality of 2, aromatics or alicyclic polyisocyanates.
The example of this type of polyisocyanates nonrestrictive is 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate (IPDI), 2, 2, 4-and/or 2, 4, 4-trimethyl hexamethylene diisocyanate, two (4, 4 '-isocyanatocyclohexyl) mixture of methane isomer or these isomers, 1, 4-cyclohexylene diisocyanate, 4-iso-cyanatomethyl-1, 8-octane diisocyanate (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-base) benzene (TMXDI) of 4-, 1, two (iso-cyanatomethyl) benzene (XDI) of 3-, with there is 2 of C1-C8-alkyl, 6-bis-isocyano caproic acid Arrcostab (lysinediisocyanate).
Except above-mentioned polyisocyanates, also likely use and there is urea diketone, isocyanuric acid ester, urea alkane, allophanate, biuret, imino group
oxadiazinediones 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 diisocyanates is particularly preferred.
Polymer polyatomic alcohol has preferred 400-8000g/mol scope, more preferably the number-average molecular weight Mn of 400-6000g/mol and particularly preferably 600-3000g/mol, and preferably there is 1.5-6, the particularly preferably OH degree of functionality of 1.8-3 and very particularly preferably 1.9-2.1.
Term " polymer " " the especially described here polyhydric alcohol of polyhydric alcohol has at least two, the more preferably repetitive connected together of at least three.
This type of polymer polyatomic alcohol is PEPA known in polyurethane coating technology, polyacrylate polyol, polyurethane polyol, polycarbonate polyol, polyether polyol, polyester polyacrylate polyhydric alcohol, polyurethane polyacrylate polyhydric alcohol, polyurethane polyureas ester polyol, polyurethane polyureas ethoxylated polyhydric alcohol, polyurethane polycarbonate polyhydric alcohol and polyester polycarbonate polyols.They can 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 preferably polytetramethylene glycol polyethers, polycarbonate polyol and their mixture, particularly preferably polytetramethylene glycol polyethers.
The hydroxy functional compound with the molecular weight of 62-399mol/g can be the non-polymer polyhydric alcohol with 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-Hydroxyhexyl, adipic acid (beta-hydroxyethyl) ester or two (beta-hydroxyethyl) ester of p-phthalic acid.
In addition, the compound containing isocyanate-reactive hydroxyl of the simple function with described molecular weight ranges can also be used.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, glycol monobutyl ether, dipropylene glycol mono butyl base ether, tripropylene glycol monobutyl base ether, 2-Ethylhexyl Alcohol, 1-capryl alcohol, DODECANOL, 1-, Cetyl OH.
Suitable non-ionic hydrophilized reagent such as has the polyoxyalkylene ether of isocyanate-reactive groups as hydroxyl, amino or mercapto.Preferably there is (according to median average) 5-70, mono hydroxy functional's polyoxyalkylene polyethers alcohol of preferred 7-55 ethylene oxide unit/molecule, this polyoxyalkylene polyethers alcohol obtains (such as at Ullmanns in accordance with known methods by the alkoxylate of suitable starter molecule
der technischen Chemie, 4th edition, in Volume19, Verlag Chemie, 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 preferably the ethylene oxide unit of at least 40mol%, counts based on existing whole oxyalkylene units.
Component A2) be preferably selected from uncle or secondary amine and/or diamidogen.It especially comprises diamidogen.
Component A2), the amine (component A2-I below) without ionic group or ionogenic group (as anionic hydrophilic group) can be used), and the amine (component A2-II below) with ionic group or ionogenic group (such as especially anionic hydrophilic group) can be used).Preferred ingredient A2-I) and component A2-II) mixture react.
Such as, 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 also having 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-Cyclohexylamino propane, 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), such as 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-dimethylaminopropyl amine, diethyl (, methyl) aminopropyl amine, morpholine, piperidines, with their suitable substitutive derivative, the amide-amine 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 containing 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 Cyclohexylamino propane sulfonic acid (CAPS) of WO-A01/88006 can be used as anionic hydrophilic reagent.
Particularly preferred anionic hydrophilic reagent A 2-II) be containing sulfonate groups as ionic group with containing 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 also can be carboxylate or hydroxy-acid group.
The preparation of dispersions of polyurethanes can be carried out in one or more stage in homogeneous phase or for multistage reaction, part is carried out in decentralized photo.In this respect, all method well known in the prior art can be used, such as, prepolymer mixed method, acetone method or melt dispersion method.Preferably use acetone method.
In the process of producing 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 solids content normally 10-70wt% of the dispersions of polyurethanes preparing cosmetic composition of the present invention, preferred 30-65wt%, particularly preferably 40-60wt%.Solids content is by being heated to constant weight determine at 125 DEG C by weighing sample.Under constant weight, calculate solids content by weighing sample again.
Dispersions of polyurethanes for the preparation of mask composition of the present invention is preferably the production of Bayer Material Science company
c1000,
c1001,
c1003,
c1004 and
c1008.
Mask composition according to the present invention is except comprising polyurethane mentioned above or dispersions of polyurethanes A) except, also comprise the acceptable medium of facial film and especially comprise water and optional cosmetics suitable solvent.Wherein, polyurethane A) in solid constituent or the active component percentage by weight that accounts for mask composition be about 3% to 59%, be preferably about 3-30%, be more preferably about 3-20%.
As mentioned above, the acceptable medium of facial film especially comprises water and optional cosmetics suitable solvent.Wherein water can be pure demineralized water or fossil water.Preferred solvent is the aliphatic alcohol with C2-4 carbon atom, as ethanol, and isopropyl alcohol, polyhydric alcohol, as propylene glycol, glycerol, ethylene glycol and polyol ethers; 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.
In the present invention, in mask composition, the weight sum of water and/or solvent can be the about 1-95 % by weight of mask composition gross weight.
Can such as exist with form below before should forming facial film containing the mask composition of sun-proof lightscreening agent on skin: gel (semisolid), oil-in-water, the emulsion of water bag silicone or W/O/W form.
Mask composition of the present invention advantageously can comprise the thickening agent of aqueous phase, and favourable thickening agent is:
The polymer that nonionic, anion and/or amphion are relevant, such as, based on Polyethylene Glycol and their derivant, or polyurethane.
Crosslinked or uncrosslinked acrylic acid or methacrylic acid homo thing or copolymer.They comprise methacrylic acid or acrylic acid cross-linked homopolymer, the copolymer of acrylic acid and/or methacrylic acid and monomer, this monomer derived is from other acrylic compounds or vinyl monomer, such as acrylic acid C10-30 Arrcostab, methacrylic acid C10-30-Arrcostab and vinyl acetate and vinyl pyrrolidone.Suitable homopolymer or copolymer also should be nonionic, anion and/or zwitterionic.
Based on the crosslinked of acrylamide or Methacrylamide or uncrosslinked homopolymer or copolymer, the such as homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, the copolymer of the copolymer of acrylamide or Methacrylamide and methacryl-amidoethyl trimethyl ammonium chloride or acrylamide and 2-acrylamido-2-methyl propane sulfonic acid.Suitable homopolymer or copolymer also should be nonionic, anion and/or zwitterionic.
The thickening property polymer of natural origin, such as, based on cellulose, guar gum, xanthan gum, scleroglucan, gellan gum, rhamsan gum and karaya, alginate, maltodextrin, starch and its derivant, carob seed starches, hyaluronic acid, carrageenin.
Particularly advantageous thickening agent is the thickening property polymer of natural origin, the cross-linked copolymer of crosslinked acrylic acid or methacrylic acid homo thing or copolymer and 2-acrylamido-2-methyl propane sulfonic acid.
Other particularly advantageous thickening agent comprises methacrylic acid or acrylic acid cross-linked homopolymer, and it is in title
940,
941,
980,
981,
eTD2001,
eDT2050,
2984,
5984 Hes
under Ultrez10, city is sold by Lubrizol, in title
with
lower city is sold by 3V.
The anionic thickening polymer agent used in mask composition of the present invention needs in alkaline matter and to make the pH value of mask composition drop in the scope of 5-9 sometimes.NaOH is comprised, KOH, triethanolamine, 2-amido-2 methyl isophthalic acids-propanol etc. with material in suitable alkalescence.
These thickening agents account for the about 0.01-20 % by weight of mask composition gross weight usually, preferred 0.01-5 % by weight, more preferably 0.2-5 % by weight.
Mask composition of the present invention optionally can comprise emulsifying agent, and this emulsifying agent is non-ionic or anion.
Nonionic emulsifier comprises such as:
A) fatty acid partial ester of polyhydric alcohol and ethoxylated derivative thereof and fatty acid ester
B) ethoxylized fatty alcohol and fatty acid
C) ethoxylated fatty amine, fatty acid amide, Marlamid
D) alkyl phenol polyglycol ether (such as
)
E) ethoxylized fatty alcohol ether.
Particularly advantageous nonionic emulsifier is ethoxylized fatty alcohol or fatty acid, preferred PEG-100 stearate, PEG-40 stearate, PEG-50 stearate, cetearyl alcohol polyoxyethylene (20) ether, cetyl polyoxyethylene (20) ether, steareth (20) ether, cetearyl alcohol polyoxyethylene (12) ether, cetyl polyoxyethylene (12) ether, stearyl alcohol polyoxyethylene (12) ether, single-, the ester of widow-or polysaccharide and fatty acid, Isosorbide Dinitrate such as such as stearic acid Isosorbide Dinitrate (from Uniqema's
20 Hes
60), sorbitan palmitate (
40, Uniqema), glyceryl stearyl citrate, sucrose ester is such as sucrose stearate such as, PEG-20 Glucate SS), the dicarboxylic ester (tartaric acid two nutmeg base ester) of fatty alcohol.
Favourable anion emulsifier is soap class (sodium salt of such as stearic acid or Palmic acid or triethanolamine salt), the ester of citric acid, such as stearate citric acid base ester, aliphatic alcohol sulfate, and single-, two-and trialkyl phosphates and ethyl oxide thereof.
Have naturally occurring emulsifying agent in addition, it comprises Cera Flava, lanocerin, lecithin and sterin.
Based on facial film group and thing gross weight, the percentage by weight of emulsifying agent is about 0-10 % by weight.
Mask composition of the present invention also optionally comprises oils and fats.This oils and fats comprises nonvolatile oil and/or ethereal oil and wax.
Nonvolatile oil is advantageously selected from mineral oil, animal oil, and vegetable oil or synthesis are originated, polarity or nonpolar oil and composition thereof.
Ethereal oil of the present invention, it is selected from volatility hydrocarbon ils, silication oil or fluorinated oil.
Wax of the present invention is defined as lipotropy fatty material, and it is solid when room temperature (25 DEG C), and shows reversible solid-liquid state change when the melt temperature of 30 DEG C-200 DEG C.During higher than this fusing point, described wax becomes low viscous, and can be miscible with oil.
This wax is advantageously selected from native paraffin, synthetic wax and composition thereof.This wax can exist with the form of the stable dispersion of colloid Wax particles, it can be prepared by known method, such as, according to " Microemulsions Theory and Practicc ", and L.M.Princc Ed., Academic Press (1977), the method for 21-32 page.
About specific definition and the concrete kind of oil, see the open CN101980689A of Chinese invention patent application, paragraph [0191]-[0226], it is incorporated in full by reference.
In mask composition of the present invention, the content of oils and fats is about 0-30 % by weight, preferably about 0-10 % by weight, in the gross weight of mask composition for 100%.
In addition one or more wetting agents (humidizer) can be comprised according to mask composition of the present invention.Particularly advantageous wetting agent is non-ionic, such as glycerol, polyglycereol, dipropylene glycol, Sorbitol, Isosorbide dimethyl ether and/or lactic acid.In addition, the polymer humidizer be selected from below can also be used: water miscible and/or water-swellable and/or can by aqueous gelled polysaccharide.Particularly advantageously such as hyaluronic acid, chitosan and/or be rich in the polysaccharide of trehalose.Use wetting agent that facial film can be made more easily to be spontaneously wet out by water when needs peel off from skin, thus more easily keep the integrity being stripped facial film.
Based on facial film group and thing gross weight, the percentage by weight of wetting agent is about 0-40 % by weight, preferred 0-20 % by weight, more preferably 0-10 % by weight.
Mask composition according to the present invention comprises one or more sun-proof lightscreening agents.Described sun-proof lightscreening agent is UV lightscreening agent especially, and it filters in UV wave-length coverage, is particularly less than the light of 400nm.UV wave-length coverage is following division generally:
| UV light | In the wave-length coverage of nm |
| Nearly UV | 400-200nm |
| UV-A | 380-315nm |
| UV-B | 315-280nm |
| UV-C | 280-100nm |
| UV far away, vacuum irradiation | 200-10nm |
| Extreme UV | 31-1nm |
Sun-proof lightscreening agent of the present invention (or UV lightscreening agent) should be water-insoluble sun-proof lightscreening agent, comprises fat-soluble organic sunscreen lightscreening agent, inorganic sunscreens lightscreening agent and composition thereof.Sun-proof lightscreening agent of the present invention does not comprise water solublity organic sunscreen lightscreening agent.
Destination is conformed with for about 0.1-50 % by weight according to the amount of UV lightscreening agent of the present invention, be advantageously about 1-30 % by weight, be particularly advantageously about 1-20 % by weight, that wherein the content of fat-soluble organic sunscreen lightscreening agent is favourable is about 0-30 % by weight, being preferably about 1-25 % by weight, is particularly advantageously about 1-20 % by weight; That the content of inorganic sunscreens lightscreening agent is favourable is about 0-50 % by weight, and being preferably about 1-30 % by weight, is particularly advantageously about 1-20 % by weight; All according to the total weight of sunscreen composition of the present invention.The mixture of one or more lightscreening agents can be comprised, such as the mixture of UV-B lightscreening agent, UV-A lightscreening agent and broadband lightscreening agent according to sunscreen composition of the present invention, or the mixture of fat-soluble organic sunscreen lightscreening agent and inorganic sunscreens lightscreening agent.
UV-A lightscreening agent can be comprised especially, UV-B lightscreening agent or broadband lightscreening agent according to mask composition of the present invention.Including but not limited to the following UV lightscreening agent list mentioned.
The example of UV-B lightscreening agent is:
(1) salicyclic acid derivatives, particularly Neo Heliopan OS, the commodity provided by Symrise company are called
ethylhexyl salicylate and salicylic acid (4-isopropyl benzyl) ester; And commodity are called
the homosalate provided by Merck (Merck chemical industry) of HMS;
(2) cinnamic acid derivative, special 2-Parsol MCX, it is in title
under available from Givaudan and 1-methoxy-cinnamic acid isopentyl ester;
(3) liquid β, β '-diphenylacrylate, particularly 2-ethylhexyl α, β '-diphenylacrylate ester or octocrylene, it is in trade name
available from Merck (Merck chemical industry) under OCR (octocrilene);
(4) para-amino benzoic acid derivant, particularly 4-(dimethylamino) benzoic acid (2-ethylhexyl) ester, 4-(dimethylamino) benzoic acid amyl group ester;
(5) ester of benzal malonic acid, particularly 4-benzylidene malonic acid two (2-ethylhexyl) ester and 3-(4-(2, the two ethoxycarbonylethenyl of 2-)-phenoxy group) acrylic) methoxyl group siloxanes/dimethylsiloxane copolymer, it is in title
available from Roche Vitamines under SLX.
The example of UV-A lightscreening agent is:
(1) dibenzoylmethane derivative, special 4-(tert-butyl group)-4 '-methoxy dibenzoyl methane, it is in title
the commodity being provided by Givaudan and provided by Symrise company for 1789 times are called
the PAROSOL 1789 of 357;
(2) benzene-Isosorbide-5-Nitrae-[two (3-methylidenecamphor-10-sulfonic acid)], optional is neutralize completely or partly, in title
under SX, city is sold by Chimex;
(3) 2-(4 '-diethylamino-2 '-(2-hydroxybenzoyl)) benzoic acid hexyl ester (and aminobenzophenone);
(4) silane derivative or polysiloxane, have benzophenone group;
(5) pyrrolotriazine derivatives, particularly 2,4-pairs [5-1 (dimethyl propyl) benzoxazole-2-base-(4-phenyl) imino group]-6-(2-ethylhexyl) imino group-1,3,5-triazines, it is in title
thered is provided by 3V under K2A.
The example of broadband lightscreening agent is:
(1) benzophenone derivates, such as
-2,4-DihydroxyBenzophenone (BP-1);
-2,2 ', 4,4 '-tetrahydroxy hexichol first heir (BP-2);
-ESCALOL 567 (BP-3), with title
bB derives from Symrise company;
-2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone (benzophenone-6-);
-5-chlorine-2-hydroxyl benzophenone (benzophenone-7-);
-2,2 '-dihydroxy-4-methoxy benzophenone (benzophenone-8);
-2-hydroxyl-4-methoxyl group-4 '-methyl benzophenone (BP-1 0);
-hexichol first heir-11;
-2-hydroxyl-4-(octyl group oxygen) benzophenone (BP-1 2).
In inorganic sunscreens lightscreening agent, the sulfate of barium such as can be provided, titanyl compound (titanium dioxide, the rutile of amorphous or crystal form and/or anatase), the oxide of zinc, the oxide of ferrum, the oxide of zirconium, the oxide of cerium, the oxide of silicon, the oxide of manganese or its mixture.Described metal-oxide can exist with the particle form of micron order or nanoscale (nano dye) size.The particle mean size of described nano dye is such as 5 to 100nm.Preferred inorganic sunscreens lightscreening agent comprises the UV-titan provided by Sachtleben company
its composition is titanium dioxide, Alumina and glycerol.Inorganic sunscreens lightscreening agent can become hydrophilic or oil loving by surface modification.
One or more other additives conventional in cosmetics can also be comprised according to mask composition of the present invention, as antioxidant and/or other adjuvant and additive, as defoamer, surfactant, active component, packing agent, film former, solvent, coalescent, aromatic substance, odour absorbents, flavouring agent, gel former and/or other polymeric dispersant, filler, softening agent, pigment, dyestuff, flowable, thixotropic agent, softener, softening agent, antiseptic etc.The amount of various additive by use field technical staff institute oneself know, be such as about 0-25 % by weight, based on the total weight of mask composition.
Generally do not comprise according to mask composition of the present invention the material that a large amount of meetings destroys film forming, such as, exceed the electrolyte of 2 % by weight of composition total weight, such as NaCl and MgSO
4; And exceed composition total weight 2 % by weight can with the chelating agen of metal complex, such as EDTA-2Na.
Mask composition of the present invention is generally prepared by following method:
By water-soluble and/or be scattered in the composition of water, comprise thickening agent, optional wetting agent, optional hydrophilic inorganic sunscreens lightscreening agent and/or other optional composition, such as chelating agen, antiseptic, solvent etc. are mixed to form water phase components;
By oil and/or the composition being scattered in oil, comprise fat-soluble organic sunscreen lightscreening agent, oil loving inorganic sunscreens lightscreening agent, emulsifying agent, oils and fats, antiseptic etc. are mixed to form oil phase component.
By water phase components and oil phase component mixing, then by aqueous polyurethane A) add, mixing and stirring forming surface film composition.
In mask composition of the present invention, aqueous polyurethane A) solid constituent and mask composition in the weight ratio of oil phase component be not less than 2:3, be preferably not less than 1:1.
The present invention is illustrated by following embodiment, and these embodiments should not be regarded as conditional.Unless otherwise stated, whole quantitative datas, mark and percent are based on weight or the gross weight based on compositions.
Embodiment
raw material and reagent
formula preparation method
Following embodiment and comparative example can be prepared by method below:
Preparation comprises thickening agent, optional wetting agent, optional nertralizer, hydrophilic inorganic sunscreens lightscreening agent and the water phase components A of water;
Preparation comprises the oil phase component B of fat-soluble sun-proof lightscreening agent and optional emulsifying agent;
Aqueous polyurethane A) be component C;
In a reservoir component A is stirred while be heated to 80 DEG C, in another container, B component is stirred and be heated to 80 DEG C, when component A and B component are uniformly dispersed respectively, B component are added component A and be constantly stirred to homogenizing.Be cooled to room temperature, component C added and mix homogeneously, form the mask composition for experiment.
stripping means and criterion
1. by ready facial film uniform application on skin, generally reach the thickness of 0.2 millimeter;
2. wait for and make facial film bone dry in 10-15 minute;
3. use water-wet facial film, from edge, facial film is peeled off skin gently, evaluate stripping performance;
4. can be complete, the facial film peeled off from skin has good stripping performance not crackedly; Otherwise then not there is good stripping performance.
Embodiment in the present invention and comparative example have component as shown in the following chart:
The component of table 1. embodiments of the invention and peeling effect
Can see from upper table, when comprising the aqueous polyurethane as application claims in mask composition, as long as the ratio of the solids content of aqueous polyurethane and oil phase component content falls within a certain range, wherein oil phase component comprises optional emulsifying agent and/or fat-soluble sun-proof lightscreening agent, can from the facial film of the complete stripping of skin surface after using various different fat-soluble organic sunscreen lightscreening agent and/or inorganic sunscreens lightscreening agent can obtain being flooded profit.Except sun-proof lightscreening agent listed in table, suitable fat-soluble organic sunscreen lightscreening agent also comprises trade name and is
the ethylhexyl salicylate of OS (Symrise company); Suitable inorganic sunscreens lightscreening agent also comprises trade name
the titanium dioxide of M212 (Sha Haliben chemical company), the mixture of Alumina and glycerol.
The kind of table 2. aqueous polyurethane is on the impact of peeling effect
Table 2 compares the impact of kind on peeling effect of aqueous polyurethane.Wherein provided by BASF (BASF) company in comparative example 1
p.U.R. be not inconsistent and aqueous polyurethane of the presently claimed invention.Identical at sun-proof lightscreening agent, when the solids content of aqueous polyurethane and the ratio of oil phase component content are also identical, the component of comparative example 1 can from the facial film of the complete stripping of skin surface after can not obtaining being flooded profit.
The kind of table 3. sunscreen is on the impact of peeling effect
Table 3 compares the impact of kind on peeling effect of sun-proof lightscreening agent.Wherein comparative example 2 and 3 employs water solublity organic sunscreen lightscreening agent.When other composition is roughly the same, the component of comparative example 2 and 3 can from the facial film of the complete stripping of skin surface after can not obtaining being flooded profit.
The solids content of table 4. aqueous polyurethane and the ratio of oil phase component content are on the impact of peeling effect
The ratio of solids content and oil phase component content that table 4 compares aqueous polyurethane is on the impact of peeling effect.Wherein in comparative example 4, the solids content of aqueous polyurethane and the ratio of oil phase component content equal 2:3, and the solids content of aqueous polyurethane and the ratio of oil phase component content are greater than 2:3 in embodiment 2 and 5, when employing aqueous polyurethane according to the invention and fat-soluble organic sunscreen lightscreening agent equally, the component of comparative example 4 from the facial film of the complete stripping of skin surface, can describe the importance of the solids content of aqueous polyurethane and the ratio of oil phase component content after can not obtaining being flooded profit.
Those skilled in the art easily knows, the present invention is not limited only to aforesaid detail, and under the prerequisite not departing from spirit of the present invention or key property, the present invention can be embodied as other particular forms.Therefore from all should be nonrestrictive by described embodiment regarded as illustrative any angle, thus by claims but not scope of the present invention is pointed out in aforementioned explanation; And therefore any change, as long as in its implication belonging to claim equivalent and scope, all should regard as and belong to the present invention.
Claims (22)
1. the mask composition containing sun-proof lightscreening agent can peeled off from skin, comprises:
A) at least one aqueous polyurethane A),
B) at least one thickening agent,
C) the water-insoluble sun-proof lightscreening agent of at least one,
D) water;
Wherein, aqueous polyurethane A) solid constituent and mask composition in the weight ratio of oil phase component be not less than 2:3.
2. mask composition as claimed in claim 1, wherein, aqueous polyurethane A) by the isocyanate-functional polyurethane prepolymer A1 of one or more water-insolubles, nonaqueous dispersion) with one or more amino-functional compounds A2) react to obtain.
3. mask composition as claimed in claim 1, wherein, thickening agent comprises thickening agent and/or the polymer viscosifier of natural origin.
4. mask composition as claimed in claim 3, wherein, polymer viscosifier comprises anionic thickening polymer agent, amphoteric ion polymer thickening agent and/or Nonionic polymeric thickeners.
5. mask composition as claimed in claim 3, wherein, the content of thickening agent is the about 0.01-20 % by weight of mask composition gross weight.
6. mask composition as claimed in claim 5, wherein, the content of thickening agent is the about 0.01-5 % by weight of mask composition gross weight.
7. mask composition as claimed in claim 1, wherein, water-insoluble sun-proof lightscreening agent comprises fat-soluble organic sunscreen lightscreening agent and/or inorganic sunscreens lightscreening agent.
8. mask composition as claimed in claim 7, wherein, fat-soluble organic sunscreen lightscreening agent content is the about 0-30 % by weight of mask composition gross weight.
9. mask composition as claimed in claim 7, wherein, inorganic sunscreens lightscreening agent content is the about 0-50 % by weight of mask composition gross weight.
10. mask composition as claimed in claim 7, wherein, the content of water-insoluble sun-proof lightscreening agent is the about 0.1-50 % by weight of mask composition gross weight.
11. mask compositions as claimed in claim 1, also optionally comprise emulsifying agent.
12. mask compositions as claimed in claim 11, wherein, the content of emulsifying agent is the about 0-10 % by weight of mask composition gross weight.
13. mask compositions as claimed in claim 1, wherein, oil phase component comprises fat-soluble organic sunscreen lightscreening agent, emulsifying agent and/or oils and fats.
14. mask compositions as claimed in claim 13, wherein, the content of oil phase component is the about 0-30 % by weight of composition total weight.
15. mask compositions as claimed in claim 1, also optionally comprise wetting agent.
16. mask compositions as claimed in claim 15, wherein, wetting agent comprises dipropylene glycol.
17. mask compositions as claimed in claim 15, wherein, the content of wetting agent is the about 0-40 % by weight of composition total weight.
18. mask compositions as claimed in claim 1, wherein, aqueous polyurethane A) the solid constituent percentage by weight that accounts for mask composition be about 3-59 % by weight.
19. mask compositions as claimed in claim 1, wherein, the percentage by weight that electrolyte accounts for mask composition is not more than about 2 % by weight.
20. mask compositions as claimed in claim 1, wherein, the percentage by weight that chelating agen accounts for mask composition is not more than about 2 % by weight.
Mask composition as claimed in claim 1 containing sun-proof lightscreening agent is applied on skin with sun-proof application by 21..
The method that 22. faces are sun-proof, comprises:
A) mask composition as claimed in claim 1 containing sun-proof lightscreening agent is applied to skin surface, after natural drying, forms a film,
When this film b) need be removed, with film described in water infiltration to peel off from skin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310546209.3A CN104546549A (en) | 2013-10-28 | 2013-10-28 | Facial mask composition containing sunscreen filter agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310546209.3A CN104546549A (en) | 2013-10-28 | 2013-10-28 | Facial mask composition containing sunscreen filter agent |
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| Publication Number | Publication Date |
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Family
ID=53064338
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| CN201310546209.3A Withdrawn CN104546549A (en) | 2013-10-28 | 2013-10-28 | Facial mask composition containing sunscreen filter agent |
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| CN107126379A (en) * | 2017-05-16 | 2017-09-05 | 湖南御家化妆品制造有限公司 | Oil control and acne removal composition and its application |
| CN107582479A (en) * | 2017-09-13 | 2018-01-16 | 拉芳家化股份有限公司 | A kind of sun-proof mask composition and preparation method thereof |
| CN110169930A (en) * | 2019-06-26 | 2019-08-27 | 万华化学（宁波）有限公司 | A kind of aqueous dispersion of sun-screening agent and its preparation method and application of aqueous polyurethane cladding |
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| CN113350223A (en) * | 2020-03-02 | 2021-09-07 | 科思创德国股份有限公司 | Tearable mask composition |
| EP3900695A1 (en) * | 2020-04-20 | 2021-10-27 | Covestro Deutschland AG | Peel-off mask composition |
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| EP3878882A4 (en) * | 2018-11-06 | 2022-08-31 | Wanhua Chemical Group Co., Ltd. | Aqueous polyurethane functional mask substrate and application thereof |
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| CN107126379A (en) * | 2017-05-16 | 2017-09-05 | 湖南御家化妆品制造有限公司 | Oil control and acne removal composition and its application |
| CN107582479A (en) * | 2017-09-13 | 2018-01-16 | 拉芳家化股份有限公司 | A kind of sun-proof mask composition and preparation method thereof |
| US11964032B2 (en) | 2018-11-06 | 2024-04-23 | Wanhua Chemical Group Co., Ltd. | Aqueous polyurethane functional mask substrate and application thereof |
| EP3878882A4 (en) * | 2018-11-06 | 2022-08-31 | Wanhua Chemical Group Co., Ltd. | Aqueous polyurethane functional mask substrate and application thereof |
| CN110169930B (en) * | 2019-06-26 | 2022-07-12 | 万华化学（宁波）有限公司 | Aqueous polyurethane-coated sunscreen aqueous dispersion and preparation method and application thereof |
| CN110169930A (en) * | 2019-06-26 | 2019-08-27 | 万华化学（宁波）有限公司 | A kind of aqueous dispersion of sun-screening agent and its preparation method and application of aqueous polyurethane cladding |
| CN112676193A (en) * | 2019-10-18 | 2021-04-20 | 李和伟 | Application of spectrum detection in detecting quality of modified membrane cloth, detection method and detection equipment |
| CN112676193B (en) * | 2019-10-18 | 2022-08-09 | 李和伟 | Application of spectrum detection in detecting quality of modified membrane cloth, detection method and detection equipment |
| CN111643407A (en) * | 2019-12-30 | 2020-09-11 | 沈定 | Facial mask composition containing Chinese herbal medicines, preparation method thereof and method for removing freckles and yellow spots on face |
| CN113332177A (en) * | 2020-03-02 | 2021-09-03 | 科思创德国股份有限公司 | Tearable mask composition |
| CN113350223A (en) * | 2020-03-02 | 2021-09-07 | 科思创德国股份有限公司 | Tearable mask composition |
| EP3900793A1 (en) | 2020-04-20 | 2021-10-27 | Covestro Deutschland AG | Peel-off mask composition |
| EP3900695A1 (en) * | 2020-04-20 | 2021-10-27 | Covestro Deutschland AG | Peel-off mask composition |
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Application publication date: 20150429 |