WO2020093393A1 - 一种水性聚氨酯功能型面膜基质及其应用 - Google Patents

一种水性聚氨酯功能型面膜基质及其应用 Download PDF

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Publication number
WO2020093393A1
WO2020093393A1 PCT/CN2018/114894 CN2018114894W WO2020093393A1 WO 2020093393 A1 WO2020093393 A1 WO 2020093393A1 CN 2018114894 W CN2018114894 W CN 2018114894W WO 2020093393 A1 WO2020093393 A1 WO 2020093393A1
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WIPO (PCT)
Prior art keywords
oil
chain extender
aqueous polyurethane
polyurethane dispersion
mask
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Application number
PCT/CN2018/114894
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English (en)
French (fr)
Inventor
纪晓晓
贾海东
许诺
刘姗
刘云玲
张洁
纪学顺
孙家宽
Original Assignee
万华化学集团股份有限公司
万华化学（宁波）有限公司
上海万华科聚化工科技发展有限公司
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Application filed by 万华化学集团股份有限公司, 万华化学（宁波）有限公司, 上海万华科聚化工科技发展有限公司 filed Critical 万华化学集团股份有限公司
Priority to US17/278,533 priority Critical patent/US11964032B2/en
Priority to EP18939481.0A priority patent/EP3878882A4/en
Publication of WO2020093393A1 publication Critical patent/WO2020093393A1/zh

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • 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
    • A61K8/87—Polyurethanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/594—Mixtures of polymers

Definitions

  • the invention belongs to the field of chemical industry, and relates to a mask base, in particular to an aqueous polyurethane functional mask base and its application.
  • facial mask products have the characteristics of easy to use, obvious effect and immediate hydration, etc., and have gradually been widely recognized by consumers.
  • the commercially available facial masks are mainly classified into non-woven fabric, silk, bio-fiber, kaolin and powder blending by material.
  • Traditional masks mainly include carriers and skin care ingredients.
  • the carriers mainly include non-woven fabric and silk.
  • the traditional masks mainly have the following disadvantages when they are used: (1) they cannot fully fit on the face, (2) the mask of the human body, especially the role of the stratum corneum, makes the mask Only a very small part of the active substances in can be absorbed deeply through the epidermis.
  • the invention provides an aqueous polyurethane functional facial mask matrix composition and an aqueous polyurethane functional facial mask matrix based on the facial mask matrix composition.
  • Using the facial mask matrix composition or facial mask matrix can promote the penetration and absorption of active substances, and the facial mask matrix can be convenient , Evenly apply on the face, so it can perfectly fit the face.
  • Based on the mask matrix composition or mask matrix of the present invention a mask or body mask product is obtained.
  • the mask matrix can effectively promote the deep absorption of active ingredients in the skin during the drying process, and at the same time, the mask or body mask can be completely removed And there will be no pain.
  • the present invention provides a mask matrix composition, based on the total mass of the mask matrix composition, including the following components:
  • aqueous polyurethane dispersion b 10 to 95 wt% aqueous polyurethane dispersion b, preferably 10 to 70 wt%, more preferably 10 to 50 wt%;
  • the (a) aqueous polyurethane dispersion a adopts (a2) polyester polyol, (a3) low molecular weight glycol chain extender, (a1) polyisocyanate, (a4) polyamine chain extender a, (a5) The reaction raw materials of polyamine chain extender b and (a6) small molecule single amino end-capping agent are prepared;
  • the (a3) low molecular weight glycol chain extender is a glycol chain extender with a molecular weight of 80-120;
  • the (a4) polyamine chain extender a is a polyamine chain extender that is not substituted by ionic groups or latent ionic groups;
  • the (a5) polyamine chain extender b is a polyamine chain extender substituted with an ionic group or a latent ionic group
  • the (a6) small-molecule mono-amino blocking agent is a mono-amino blocking agent with a molecular weight of 300 or less;
  • aqueous polyurethane dispersion b is composed of (b1) polyisocyanate, (b2) polyester polyol, (b3) polyethylene glycol monomethyl ether, (b6) polyhydroxy chain extender, (b4) polyhydric
  • the reaction raw materials of amine chain extender a 'and (b5) polyamine chain extender b' are prepared by reaction;
  • the (b4) polyamine chain extender a ' is a polyamine chain extender that is not substituted by ionic groups or latent ionic groups;
  • the (b5) polyamine chain extender b ' is a polyamine chain extender substituted with an ionic group or a latent ionic group;
  • the (b6) polyhydroxy chain extender is a low molecular weight polyhydroxy chain extender and a polyhydroxy chain extender with a molecular weight of 300 or less.
  • the (a) aqueous polyurethane dispersion a adopts each reaction including the following mass percentages Raw material reaction:
  • polyester polyol 65 to 80 wt% of polyester polyol, preferably 71 to 75 wt%;
  • Polyamine chain extender a 0.01 to 3wt%, preferably 0.05 to 2wt%;
  • the (a) aqueous polyurethane dispersion a is prepared according to a method including the steps of: adding the (a2) polyester polyol and the (a3) low molecular weight glycol chain extender to 70-80 Mix at °C, lower the temperature to 45 ⁇ 60 °C, add the (a1) polyisocyanate to carry out prepolymerization reaction, when the theoretical NCO content is reached, the resulting prepolymer is cooled to 30 ⁇ 45 °C, dissolved in acetone solvent, The amount of acetone is (a) 100-150 wt% of the mass of the polyurethane of the aqueous polyurethane dispersion a; after mixing, the (a4) polyamine chain extender a and the (a5) polyamine chain extender b, 35 are added After the reaction is continued at ⁇ 45 °C for 15-30min, water is added under shear dispersion conditions, the amount of water is (a) 130 ⁇ 200wt% of the mass of the
  • the total solid content of the (a) aqueous polyurethane dispersion a is 20-50 wt%, preferably 35-45 wt%; the particle size is 100 nm-300 nm, preferably 150 nm-250 nm, such as 170 nm, 190 nm, 210 nm and 230 nm.
  • the (b) aqueous polyurethane dispersion b is reacted using each reaction raw material including the following mass percentages be made of:
  • polyester polyol 60-83.8% by weight of polyester polyol, preferably 70-80% by weight;
  • the (b) aqueous polyurethane dispersion b is prepared according to the following steps:
  • the (b1) polyisocyanate, the (b2) polyester polyol, the (b3) polyethylene glycol monomethyl ether, the (b6) polyhydroxy chain extender and acetone at 50-100 ° C Mix and carry out the prepolymerization reaction. When the theoretical NCO content is reached or approached, dissolve the prepolymer in the acetone solvent.
  • the total amount of acetone in the preparation process is (b) 100% of the mass of the polyurethane of the aqueous polyurethane dispersion b.
  • the total solid content of the (b) aqueous polyurethane dispersion b is 30-50 wt%, and the particle size is 120-190 nm, preferably 140-160 nm.
  • the (a1) polyisocyanate has 2 isocyanate groups, one or more selected from aliphatic isocyanate and alicyclic aliphatic isocyanate, preferably iso One or more of phorone diisocyanate, 1,6-hexyl diisocyanate, dicyclohexylmethane diisocyanate and tetramethyl xylylene diisocyanate, more preferably dicyclohexylmethane diisocyanate;
  • the (a2) polyester polyol has a number average molecular weight of 800 to 3000, preferably 1000 to 2000, and a functionality of 2 to 3;
  • the (a2) polyester polyol is composed of an organic polycarboxyl
  • the acid and / or its anhydride and polyhydric alcohol are prepared by polymerization reaction, wherein: the organic polycarboxylic acid and / or its anhydride is selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, One or more of azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and their anhydrides, preferably adipic acid;
  • the polyol includes ethylene glycol, 1, One or more of 2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, trimethylolpropane and neopentyl glyco
  • the (a3) low molecular weight glycol chain extender is selected from ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol , 1,3-butanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol and neopentyl glycol one or more, preferably 1,4-butanediol Alcohol and / or neopentyl glycol;
  • the (a4) polyamine chain extender a has 2 to 20 carbon atoms and a functionality of 2 to 3, preferably ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine , One or more of isophorone diamine, 1,4-cyclohexane diamine, 4,4'-dicyclohexylmethane diamine and diethylene triamine, more preferably ethylene diamine, hexane di One or more of amines, isophorone diamine, 1,4-cyclohexanediamine and 4,4'-dicyclohexylmethanediamine, most preferably ethylenediamine and / or isophorone Diamine
  • the (a5) polyamine chain extender b is a diamine substituted with an ionic group or a latent ionic group, preferably N- (2-aminoethyl) -2-aminoethanesulfonate
  • an ionic group or a latent ionic group preferably N- (2-aminoethyl) -2-aminoethanesulfonate
  • the (a6) small molecule monoamino end-capping agent has 2 to 10 carbon atoms and a functionality of 1, preferably diethanolamine, trihydroxyamine and / or 2-amino-2-methyl -1-propanol, more preferably 2-amino-2-methyl-1-propanol.
  • the (b1) polyisocyanate has 2 to 4 isocyanate groups, and is selected from one or more of aliphatic polyisocyanate and alicyclic polyisocyanate, It is preferably one or more selected from hexamethylene diisocyanate, dodecamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, more preferably 4,4 ' -Dicyclohexylmethane diisocyanate;
  • the (b2) polyester polyol has a number average molecular weight of 20 to 14,000, preferably 500 to 3000, and a functionality of 2 to 3;
  • the (b2) polyester polyol is composed of organic polycarboxyl
  • the acid and / or its anhydride and polyhydric alcohol are prepared by polymerization reaction, wherein the organic polycarboxylic acid and / or its anhydride is selected from succinic acid, adipic acid, suberic acid, isophthalic acid and their anhydrides
  • the polyol includes one or more of ethylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, preferably butylene Glycol and / or neopentyl glycol;
  • the (b3) polyethylene glycol monomethyl ether number average molecular weight is 700-2000, preferably 1000-1500;
  • the (b4) polyamine chain extender a has 2 to 13 carbon atoms and a functionality of 2 to 3, preferably 1,2-ethylenediamine, 1,6-hexamethylene Diamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophorone diamine), piperazine, 1,4-diaminocyclohexane, bis- One or more of (4-aminocyclohexyl) methane, N- (2-hydroxyethyl) ethylenediamine and diethylenetriamine, more preferably 1,6-hexamethylenediamine , 1-Amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophorone diamine) and N- (2-hydroxyethyl) ethylenediamine Or more, most preferably 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophorone diamine) and / or 1,6-hex
  • the (b5) polyamine chain extender b ' is a diamine substituted with an ionic group or a latent ionic group, preferably N- (2-aminoethyl) -2-aminoethyl
  • an ionic group or a latent ionic group preferably N- (2-aminoethyl) -2-aminoethyl
  • the (b6) polyhydroxy chain extender is trimethylolpropane.
  • the present invention also provides a mask matrix, including the mask matrix composition described in any one of the above, based on the total mass of the mask matrix, the (a) water-based in the mask matrix composition
  • the mass percentages of polyurethane dispersion a and (b) aqueous polyurethane dispersion b in the mask matrix are as follows:
  • aqueous polyurethane dispersion b 10 to 95 wt% aqueous polyurethane dispersion b, preferably 10 to 70 wt%, more preferably 10 to 50 wt%;
  • the mask matrix further includes the following components in mass percentage:
  • oils and fats preferably 2-18 wt%, more preferably 3-15 wt%;
  • the (d) emulsifier can increase the stability of oils and fats, oil-soluble active ingredients, oil-soluble flavors and preservatives in the mask;
  • the (e) grease can improve the skin feel of the functional mask matrix and increase the dissolution of oil-soluble active substances.
  • the mask matrix is in the form of an emulsion, and based on the total mass of the mask matrix, it includes the following components:
  • emulsifier 0 to 6 wt% emulsifier, preferably 0.5 to 5 wt%, more preferably 1 to 4 wt%;
  • oils and fats preferably 2 to 8 wt%, more preferably 3 to 6 wt%;
  • the mask matrix is cream-shaped, and based on the total mass of the mask matrix, it includes the following components:
  • emulsifier 0 to 7 wt% emulsifier, preferably 0.5 to 6 wt%, more preferably 1 to 5 wt%;
  • oils and fats preferably 2 to 13 wt%, more preferably 4 to 10 wt%;
  • the mask matrix is in a gel form, and based on the total mass of the mask matrix, it includes the following components:
  • oils and fats preferably 3-18 wt%, more preferably 5-15 wt%;
  • the (c) thickener is an acrylic thickener, a polyurethane thickener (HEUR), a cellulose thickener, a binder
  • HEUR polyurethane thickener
  • a cellulose thickener a binder
  • HEUR polyurethane thickener
  • a binder One or more of cold gum, xanthan gum, carbomer, guar gum, diatomaceous earth, starch, gum arabic, soy protein gum, gelatin, sodium alginate, casein, chitosan, natural lanolin and agar Species
  • the (d) emulsifier is selected from stearyl esters, polyether silicone oils, alkyl ethers, carboxylates, sulfates, sulfonates, amine derivatives, polyoxygen One or more of vinyl ethers and polyoxypropylene ethers;
  • the (e) oil is selected from one or more of natural oils, synthetic oils, mineral oils, fatty acids, fatty alcohols and fatty esters, preferably calendula oil, olive oil, lanolin oil , Castor oil, cottonseed oil, soybean oil, sesame oil, almond oil, peanut oil, corn oil, rice bran oil, tea seed oil, sea buckthorn oil, avocado oil, stone chestnut oil, European nut oil, walnut oil, cocoa oil, mink oil , Egg butter, coconut oil, lecithin, squalane, lanolin derivatives, polysiloxane, fatty acids, fatty alcohols, fatty acid lipids, glycerin and petroleum jelly;
  • the (f) preservative is a mild preservative, preferably one or more of phenoxyethanol, ethylhexylglycerol, octylglycol, and 1,2-hexanediol.
  • the (c) thickener is: 0-3.0 wt% of hydroxyethyl cellulose, 0-3.0 The wt% xanthan gum and 0 ⁇ 2.0wt% carbohydrate, in order to achieve a better appearance and skin experience, preferably 0.05 ⁇ 1wt% hydroxyethyl cellulose, 0.05 ⁇ 1.0wt% xanthan gum and 0.05 ⁇ 0.5wt% Carbo;
  • the (d) emulsifier is 0-4.0wt% cetearyl ether-20 and 0-4.0wt% PEG-10 polydimethylsiloxane, in order to achieve a better appearance and skin feel experience , Preferably 2 to 3.0% by weight of cetearyl ether-20 and 2 to 3.0% by weight of PEG-10 polydimethylsiloxane;
  • the (e) oil and fat are 0-10 wt% coconut oil, 0-10 wt% castor oil and 0-10 wt% polydimethylsiloxane, in order to achieve a better appearance and skin-feeling experience, preferably 2.0-10 wt % Coconut oil, 2.0-10 wt% castor oil and 2.0-10 wt% polydimethylsiloxane.
  • the (c) thickener in the cream-like mask base, based on the total mass of the mask base, is 0.1-5.0% by weight of hydroxyethyl cellulose, 0.1-5.0
  • the wt% xanthan gum and 0 ⁇ 5.0wt% carbohydrate, in order to achieve a better appearance and skin feel experience preferably 0.5 ⁇ 3.0wt% hydroxyethyl cellulose, 0.5 ⁇ 3wt% xanthan gum and 0.8 ⁇ 3.0wt% Carbo.
  • the (d) emulsifier is 0-4.0wt% cetearyl ether-20 and 0-5.0wt% PEG-10 polydimethylsiloxane, in order to achieve a better appearance and skin feel experience , Preferably 1.0 to 4.0 wt% of cetearyl ether-20 and 1.0 to 5.0 wt% of PEG-10 polydimethylsiloxane;
  • the (e) oil and fat is 2.0 to 10% by weight of coconut oil, 2.0 to 10% by weight of castor oil and 2.0 to 10% by weight of dimethicone.
  • 5.0 to 10% is preferred %
  • the (c) thickener is 0.1-2.0 wt% gellan gum, 0.1-6.0 wt% Xanthan gum and 0.1 to 5.0 wt% carbohydrate, in order to achieve a better appearance and skin feel experience, preferably 0.1 to 1.5 wt% gellan gum, 1.0 to 1.5 wt% xanthan gum and 1.0 to 4.0 wt% Cabo
  • the (d) emulsifier is 0-4.0wt% cetearyl ether-20 and 0-4.5wt% PEG-10 polydimethylsiloxane, in order to achieve a better appearance and skin feel experience , Preferably 1.0 to 3.0 wt% of cetearyl ether-20 and 1.0 to 4.5 wt% of PEG-10 polydimethylsiloxane;
  • the (e) oil and fat is 0-10 wt% coconut oil, 0-12 wt% castor oil and 0-12 wt% polydimethylsiloxane.
  • 4-10 wt% is preferred %
  • the present invention also provides a method for preparing a mask matrix according to any one of the above, including the following steps:
  • phase A Mix the (a) aqueous polyurethane dispersion a and the (b) aqueous polyurethane dispersion b to obtain phase A; mix the (h) deionized water and the (c) thickener to obtain B Phase; mix the (d) emulsifier and the (e) grease to obtain phase C;
  • phase C In the presence of phase C, heat phase B and phase C to 70-85 °C and mix well to obtain phase B + C. After the temperature drops to the range of 50 °C to room temperature, add phase A and other components , Mix well;
  • phase C mix phase A and phase B at room temperature to obtain phase A + B, then add other components and mix well;
  • the other components include the (f) preservative and / or the (g) flavor.
  • the present invention also provides a facial mask or body mask, which comprises the facial mask matrix composition according to any one of the above or the facial mask matrix according to any one of the above and an active substance;
  • the body membrane is preferably a neck membrane, a back membrane or a leg membrane;
  • the active substances include but are not limited to active ingredients such as whitening, freckle removal, antioxidant, moisturizing, and / or anti-wrinkle.
  • the present invention also provides a method for preparing the facial mask or body mask, which includes the step of mixing the facial mask matrix composition described in any one of the above or the facial mask matrix described in any one of the above with an active substance.
  • the present invention also provides the application of the mask base composition described in any one of the above or the mask base described in any one of the above or the mask or body film in promoting the penetration and absorption of active substances, preferably in promoting The application of active substances in osmotic absorption in the skin.
  • the functional ingredients in cosmetics pass through the skin barrier to be better absorbed by the skin.
  • the waterborne polyurethane mask matrix of the present invention has at least the following two beneficial effects:
  • the waterborne polyurethane mask base of the present invention can be partially or completely applied to the face, and after the mask is dried, it can be completely attached to the face. There is no pain in the process, it will not stick to the skin and tear the pores, so it will not cause the problem of sagging skin and enlarged pores. On the contrary, during the drying process, the mask also has the effect of shrinking pores and tightening the skin, so that the skin has a more perfect state.
  • the water-based polyurethane mask matrix of the present invention has good compatibility with various cosmetic active ingredients such as whitening, moisturizing and anti-wrinkle ingredients.
  • various cosmetic active ingredients such as whitening, moisturizing and anti-wrinkle ingredients.
  • two kinds of water-based polyurethanes with special cross-linked structures interact during the film formation process to achieve In order to transfer the active ingredients deep into the skin, the active substances are better absorbed by the body, so that the functional mask products can achieve better results.
  • the use of one of the water-based polyurethanes alone does not significantly promote the absorption of active ingredients.
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • A95 N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium is Evonik's product.
  • AMP-95 (2-amino-2-methyl-1-propanol, molecular weight 89.14) is a product of Dow Chemical Company.
  • Isophorone diamine is a Bayer product.
  • PN110 poly neopentyl terephthalate glycol, number average molecular weight 1000, functionality 2
  • Stepan Najing Chemical Co., Ltd.
  • MPEG1200 polyethylene glycol monomethyl ether, number average molecular weight 1200 is a product of Korea Lotte Chemical Co., Ltd.
  • TMP trimethylolpropane
  • Anionic water-based polyurethane dispersion-1a synthesized according to the following method: adding 250g CMA-654 (71.18wt%, four weight percent to the mass percentage of the solid (ie polyurethane) in the anionic waterborne polyurethane dispersion-1a in a four-necked flask , The same below), 1.8g neopentyl glycol (0.51wt%), mixed and stirred at 70 °C for 10min, 78g was added after cooling to 50 °C HMDI (22.21wt%) was prepolymerized.
  • Anionic waterborne polyurethane dispersion-2a synthesized according to the following method: add 250g CMA-654 (75.02wt%, four weight percent to the mass percentage of solid (ie polyurethane) in anionic waterborne polyurethane dispersion-2a in a four-necked flask , The same below), 2.5g 1,4-butanediol (0.75wt%), mixed and stirred at 70 °C for 10min, lowered the temperature to 50 °C and added 65g HMDI (19.50wt%) was used for prepolymerization.
  • the obtained prepolymer was cooled to 40 ° C and dissolved in 330g of acetone solvent (99.0wt%). After mixing for 15min, Add 0.2g ethylenediamine (0.06wt%) and 14g A95 (4.20wt%) solution formed in 56.8g deionized water.
  • Anionic waterborne polyurethane dispersion-3a synthesized according to the following method: add 250g CMA-654 (71.2wt% in a four-necked flask, wt% represents the mass percentage of the solid (ie polyurethane) in the anionic waterborne polyurethane dispersion-3a , The same below), 3g neopentyl glycol (0.86wt%), mixed and stirred at 70 °C for 10min, cooled to 50 °C and added 75g HMDI (21.38wt%) was used for prepolymerization reaction.
  • the obtained prepolymer was cooled to 40 ° C and dissolved in 350g of acetone solvent (100wt%). After mixing for 15min, add 5g isophorone diamine (1.42wt%) and 15.5g A95 (4.42wt%) solution formed in 82g deionized water.
  • Anionic waterborne polyurethane dispersion -1b synthesized according to the following method: add 65g in a four-necked flask HMDI (18.40wt%, wt% represents the mass percentage of the solid (ie polyurethane) in the anionic waterborne polyurethane dispersion -1b, the same below), 225g PBA2000 (63.39wt%), 50g PN110 (14.15wt%), 5g MPEG1200 (1.42wt%), 1g of TMP (0.28wt%) and 30g of acetone are stirred evenly at 70 ° C and the prepolymerization reaction is carried out for 2 to 3 hours.
  • the prepolymer is dissolved in 500g of acetone (The total amount of acetone in the preparation process is 140wt%), after mixing for 15min, add 3.8g of hexamethylenediamine (1.08wt%) and 4.5g A95 (1.27wt%) solution formed in 20g deionized water. After continuing the reaction at 45 ° C for 30min, add 421g (117.88wt%) water under shearing conditions, then remove acetone under reduced pressure to obtain a solid content of about 47wt % Polyurethane dispersion with a particle size of 150 nm, ie anionic waterborne polyurethane dispersion-1b.
  • Anionic waterborne polyurethane dispersion-2b synthesized according to the following method: add 75g in a four-necked flask HMDI (30.36wt%, wt% represents the mass percentage of the solid (ie polyurethane) in the anionic waterborne polyurethane dispersion-2b, the same below), 150g PN110 (60.73wt%), 6.5g MPEG1200 (2.63wt%), 2gTMP (0.81wt%) and 30g of acetone were stirred evenly at 70 °C and prepolymerization reaction was carried out for 2 ⁇ 3h.
  • the prepolymer was dissolved in 500g of acetone (the total amount of acetone during the preparation process) In an amount of 202.5wt%), after mixing for 15min, add 10g of hexamethylenediamine (4.05wt%) and 4.5g A95 (1.82wt%) solution formed in 20g deionized water. After continuing the reaction at 45 ° C for 30min, add 403g water (163.22wt%) under shearing conditions, and then remove the acetone by vacuum distillation to obtain a solid content of about 47wt % Polyurethane dispersion with a particle size of 140 nm, ie anionic waterborne polyurethane dispersion-2b.
  • Hydroxyethyl cellulose is a product of The Dow Chemical Company.
  • the product catalog number is CELLOSIZE TM HYDROXYETHYL CELLULOSE QP100MH. It is a thickener.
  • Xanthan gum is a product of Jungbunzlauer Company.
  • the product catalog number is E415food grade, which is a thickener.
  • Cabo is a Lubrizol product, the catalog number is Ultrez 21 is a thickener.
  • Gellan gum is a Spike product, the catalog number is Xanthan Gum is a thickener.
  • Ceteareth-20 is a Corning product with a catalog number of EUMULGIN B2, which is an emulsifier.
  • PEG-10 polydimethylsiloxane is a product of Guangdong Biaomei Silicon Fluorine New Material Co., Ltd.
  • the product catalog number is BioMaxSF-9336, which is an emulsifier.
  • Coconut oil is a product of Guangzhou Hanbaisi Daily Chemical Technology Development Co., Ltd. It is a kind of oil.
  • Castor oil is a product of Jinan Xinnuo Chemical Co., Ltd. and is a kind of oil.
  • Polydimethylsiloxane is a product of Dow Corning.
  • the catalog number is DC200-350, which is a kind of oil.
  • the essence is a product of Shanghai Fuxi Flavor and Fragrance Co., Ltd.
  • the product catalog number is OLY007BOOMBASTIC.
  • Phenoxyethanol is a product of The Dow Chemical Company.
  • the catalog number is NEOLONE TM PH100, which is a preservative.
  • Hydrolyzed glucosaminoglycan is a product of Guangzhou Fuwei Biotechnology Co., Ltd.
  • the product catalog number is PLUS is a moisturizer.
  • phase C Examples 3, 5, 6, 8, 9, 10, 11, 12, and 13
  • Comparative Example 1 According to the components and their mass percentages shown in Table 2, mix the components of phase B and phase C at room temperature, stir at 600r / min speed for 5 minutes and heat to 75 °C, mix phase B and phase C, maintain the temperature at 75 °C and homogenize at 8000r / min for 5 minutes to obtain phase B + C. After the temperature drops to 50 ° C, add other components, and homogenize at 5000r / min for 5 minutes to make a mask matrix.
  • Comparative Examples 2 and 3 Mix the components of Phase B and Phase C at room temperature according to the components and mass percentages shown in Table 2, stir at 600r / min for 5 minutes, and heat At 75 ° C, phase B and phase C were mixed, the temperature was maintained at 75 ° C and homogenized at 8000r / min for 5 minutes to obtain phase B + C. After the temperature drops to 50 °C, add phase A and other components, and make the mask matrix after homogenizing at 5000r / min for 5 minutes.
  • Detection method Use transdermal moisture loss tester (TEWL), epidermal moisture tester Corneometer and Visiacr to test wrinkles to detect skin epidermal water content and wrinkle reduction.
  • TEWL transdermal moisture loss tester
  • epidermal moisture tester Corneometer Corneometer
  • Visiacr to test wrinkles to detect skin epidermal water content and wrinkle reduction.
  • the average wrinkle reduction of the subject reached 18% and the skin epidermal water content increased by 61% compared to before the facial mask was not used.
  • the prepared facial mask can significantly reduce the transdermal moisture Loss, skin smoothness has been significantly improved;
  • the subject's wrinkle reduction was 16% and the skin epidermal water content was increased by 49% compared to before the facial mask was not used.
  • the average amount of wrinkle reduction was 16.1% and 16.7%, and the skin epidermal water content increased by 51% and 51%, respectively. 50.4%.
  • the comparison test results confirm that: compared with Comparative Example 1, the aqueous polyurethane functional mask base prepared in Example 10 can increase the amount of wrinkle reduction by up to 12.5% and the moisturizing effect by up to 24.5%. It shows that the mixed use of the anionic waterborne polyurethane dispersions a and b of the present invention has a significant effect of promoting the deep conduction of active substances in facial masks. At the same time, the results of Comparative Examples 2 and 3 show that the use of anionic waterborne polyurethane dispersions a or b alone in facial masks has no significant effect of promoting the deep conduction of the active substance.
  • the facial mask matrix prepared from Examples 11, 12, and 13 is a matrix-based facial mask, which is more effective in terms of appearance, skin feel, and consumer experience.
  • the mask matrix prepared in Examples 1-13 as a matrix.
  • the mask can be completely dried after about 15 minutes. After wetting the mask with water, the subjects can completely remove the mask from the face. Peeled off without pain.

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Abstract

本发明公开了一种水性聚氨酯功能型面膜基质及其应用，该面膜基质是以两种水性聚氨酯分散体作为主要成分。通过聚氨酯膜的特殊交联结构促进面膜类产品中的美白、保湿和抗衰老等功效成分的透皮渗透吸收。使用时将面膜均匀涂抹于面部，待面膜干燥后，可直接将面膜整片取下或用水湿润后整片取下。本发明的面膜基质同样适用于手膜、颈膜和背膜等体膜。

Description

一种水性聚氨酯功能型面膜基质及其应用 技术领域
本发明属于化工领域，涉及一种面膜基质，具体涉及一种水性聚氨酯功能型面膜基质及其应用。
背景技术
随着社会发展和人们生活品质的提高，消费者对化妆品有了更多的需求。其中，面膜类产品具有使用方便、效果明显和即刻补水等特点，逐渐得到消费者的广泛认可。
目前，市售面膜按材质分类主要有无纺布、蚕丝、生物纤维、高岭土和粉末调和等。传统的面膜主要包括载体和护肤成分，载体主要有无纺布和蚕丝等。但是，由于人脸存在个体差异，传统的面膜在使用时主要存在以下缺点：(1)不能完全贴合在脸部，(2)由于人体的皮肤屏障作用，特别是角质层的作用，使得面膜中的活性物质只有极少部分可以透过表皮深层吸收。
为了改善传统面膜的缺点，超导面膜和透皮促进剂等作为主要解决方案被提出。中国专利CN206404053 U公布了一种超导凝膜海藻纤维面膜布，CN206548844 U公开了一种银纤维超导面膜，这两种超导面膜均通过改变面膜布的形状和材质，使面膜布与人脸有了更好的贴合，从而有助于护肤成分导入肌肤深层。CN102793639 A、CN104042502 B、CN105012185 A和CN1943546 B等分别公开了几种透皮促进剂，可以促进皮肤更好地吸收化妆品中的功效成分，这类透皮促进剂均来自于天然的植物提取。
但是，目前尚无使用聚氨酯类高分子聚合物形成功能型的面膜基质来促进面膜中的功效成分吸收的报道。
发明内容
本发明提供一种水性聚氨酯功能型面膜基质组合物和基于该面膜基质组合物的水性聚氨酯功能型面膜基质，使用所述面膜基质组合物或面膜基质，可以促进活性物质渗透吸收，面膜基质可以方便、均匀地涂抹在面部，因而可与脸部完 美贴合。基于本发明的面膜基质组合物或面膜基质得到面膜或体膜制品，在使用时，面膜基质在干燥过程中可以有效地促进活性成分被皮肤深层吸收，同时，面膜或体膜可以被完整揭下且不会产生痛感。
为解决上述技术问题，本发明提供一种面膜基质组合物，以所述面膜基质组合物的总质量计，包括以下组分：
(a)5～90wt％的水性聚氨酯分散体a,优选10～70wt％，更优选10～50wt％；
(b)10～95wt％的水性聚氨酯分散体b,优选10～70wt％，更优选10～50wt％；
其中，所述(a)水性聚氨酯分散体a采用包括(a2)聚酯多元醇、(a3)低分子量二元醇扩链剂、(a1)多异氰酸酯、(a4)多元胺扩链剂a、(a5)多元胺扩链剂b和(a6)小分子单氨基封端剂的反应原料反应制得；
所述(a3)低分子量二元醇扩链剂是分子量为80-120的二元醇扩链剂；
所述(a4)多元胺扩链剂a为没有被离子基团或潜离子基团取代的多元胺扩链剂；
所述(a5)多元胺扩链剂b为被离子基团或潜离子基团取代的多元胺扩链剂；
所述(a6)小分子单氨基封端剂是分子量300以下的单氨基封端剂；
所述(b)水性聚氨酯分散体b采用包括(b1)多异氰酸酯、(b2)聚酯多元醇、(b3)聚乙二醇单甲醚、(b6)多羟基扩链剂、(b4)多元胺扩链剂a’和(b5)多元胺扩链剂b’的反应原料反应制得；
所述(b4)多元胺扩链剂a’为没有被离子基团或潜离子基团取代的多元胺扩链剂；
所述(b5)多元胺扩链剂b’为被离子基团或潜离子基团取代的多元胺扩链剂；
所述(b6)多羟基扩链剂为低分子量多羟基扩链剂，为分子量300以下的多羟基扩链剂。
在一些优选实施方式中，上述面膜基质组合物中，以所述(a)水性聚氨酯分散体a中的聚氨酯的质量计，所述(a)水性聚氨酯分散体a采用包括如下质量百分比的各反应原料反应制得：
(a2)聚酯多元醇65～80wt％，优选71～75wt％；
(a3)低分子量二元醇扩链剂0.1～3wt％，优选0.5～1wt％；
(a1)多异氰酸酯15～25wt％，优选19～23wt％；
(a4)多元胺扩链剂a 0.01～3wt％，优选0.05～2wt％；
(a5)多元胺扩链剂b 1～8wt％，优选2～5wt％；
(a6)小分子单氨基封端剂0.1～2wt％，优选0.4～1wt％；
优选地，所述(a)水性聚氨酯分散体a按照包括如下步骤的方法制备：将所述(a2)聚酯多元醇、所述(a3)低分子量二元醇扩链剂，在70～80℃条件下混合，降温至45～60℃加入所述(a1)多异氰酸酯进行预聚反应，当达到理论NCO含量时，使得到的预聚物冷却到30～45℃，溶解在丙酮溶剂中，丙酮用量为(a)水性聚氨酯分散体a的聚氨酯的质量的100～150wt％；混合后，加入所述(a4)多元胺扩链剂a和所述(a5)多元胺扩链剂b，35～45℃条件下继续反应15～30min后，在剪切分散条件下加入水，水的用量为(a)水性聚氨酯分散体a的聚氨酯的质量的130～200wt％，然后加入所述(a6)小分子单氨基封端剂的稀释水溶液封端，真空脱除丙酮，得到所述(a)水性聚氨酯分散体a；
所述(a)水性聚氨酯分散体a的总固含量为20～50wt％，优选35～45wt％；粒径为100nm～300nm，优选150nm～250nm，例如170nm、190nm、210nm和230nm。
上述任一所述的面膜基质组合物中，以所述(b)水性聚氨酯分散体b中的聚氨酯的质量计，所述(b)水性聚氨酯分散体b采用包括如下质量百分比的各反应原料反应制得：
(b1)多异氰酸酯14～35wt％，优选15～23wt％；
(b2)聚酯多元醇60～83.8wt％，优选70-80wt％；
(b3)聚乙二醇单甲醚1～3wt％，优选1.8～2.5wt％；
(b6)多羟基扩链剂0.1～1wt％，优选0.2～0.5wt％；
(b4)多元胺扩链剂a’0.1～5wt％，优选0.5～2wt％；
(b5)多元胺扩链剂b’1～2wt％，优选1.4～1.6wt％；
优选地，所述(b)水性聚氨酯分散体b按照包括如下步骤的方法制备：
将所述(b1)多异氰酸酯、所述(b2)聚酯多元醇、所述(b3)聚乙二醇单甲醚、所述(b6)多羟基扩链剂和丙酮在50～100℃下混匀并进行预聚反应，当 达到或接近理论NCO含量时，将预聚物溶解在丙酮溶剂中，制备过程中丙酮的总体用量为(b)水性聚氨酯分散体b的聚氨酯的质量的100～210wt％；混合后，加入所述(b4)多元胺扩链剂a’和所述(b5)多元胺扩链剂b’，35～45℃条件下继续反应15～30min后，在剪切分散条件下加入水，水的用量为(b)水性聚氨酯分散体b的聚氨酯的质量的100～170wt％，然后真空脱除丙酮，得到所述(b)水性聚氨酯分散体b；
所述(b)水性聚氨酯分散体b的总固含量为30～50wt％，粒径为120～190nm,优选140～160nm。
在一些优选实施方式中，上述面膜基质组合物中，所述(a1)多异氰酸酯具有2个异氰酸酯基团，选自脂肪族异氰酸酯和脂环脂族异氰酸酯中的一种或多种，优选为异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、二环己基甲烷二异氰酸酯和四甲基苯二甲基二异氰酸酯中的一种或多种，更优选二环己基甲烷二异氰酸酯；
在一些优选实施方式中，所述(a2)聚酯多元醇的数均分子量为800～3000，优选1000～2000，官能度为2～3；所述(a2)聚酯多元醇由有机多元羧酸和/或其酸酐与多元醇通过聚合反应制得，其中：所述有机多元羧酸和/或其酸酐选自丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸和它们的酸酐中的一种或多种，优选己二酸；所述多元醇包括乙二醇、1,2-丙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇、三羟甲基丙烷和新戊二醇的一种或多种，优选1,6-己二醇和/或新戊二醇；
在一些优选实施方式中，所述(a3)低分子量二元醇扩链剂选自乙二醇、二乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,3-丁二醇、环己二醇、1,4-环己烷二甲醇、1,6-己二醇和新戊二醇中的一种或多种，优选1,4-丁二醇和/或新戊二醇；
在一些优选实施方式中，所述(a4)多元胺扩链剂a的碳原子为2～20个，官能度为2～3，优选乙二胺、丙二胺、丁二胺、己二胺、异佛尔酮二胺、1,4-环己烷二胺、4,4’-二环己基甲烷二胺和二乙烯三胺中的一种或多种，更优选乙二胺、己二胺，异佛尔酮二胺、1,4-环己烷二胺和4,4’-二环己基甲烷二胺中的一种或多种，最优选乙二胺和/或异佛尔酮二胺；
在一些优选实施方式中，所述(a5)多元胺扩链剂b为被离子基团或潜离子基团取代的二元胺，优选N-(2-氨基乙基)-2-氨基乙磺酸的钠盐和/或N-(2-氨基乙基)-2-氨基丙磺酸的钠盐；
在一些优选实施方式中，所述(a6)小分子单氨基封端剂碳原子为2～10个，官能度为1，优选二乙醇胺、三羟基胺和/或2-氨基-2-甲基-1-丙醇，更优选2-氨基-2-甲基-1-丙醇。
在一些优选实施方式中，上述面膜基质组合物中，所述(b1)多异氰酸酯具有2～4个异氰酸酯基团，选自脂肪族多异氰酸酯和脂环族多异氰酸酯中的一种或多种，优选选自六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯中的一种或多种，更优选4,4’-二环己基甲烷二异氰酸酯；
在一些优选实施方式中，所述(b2)聚酯多元醇的数均分子量为20～14000，优选500～3000，官能度为2～3；所述(b2)聚酯多元醇由有机多元羧酸和/或其酸酐与多元醇通过聚合反应制得，其中，所述有机多元羧酸和/或其酸酐选自琥珀酸、己二酸、辛二酸、间苯二甲酸和它们的酸酐中的一种或多种，优选间苯二甲酸和/或己二酸；所述多元醇包括乙二醇、丁二醇、新戊二醇、己二醇中的一种或多种，优选丁二醇和/或新戊二醇；
在一些优选实施方式中，所述(b3)聚乙二醇单甲醚数均分子量为700～2000，优选1000～1500；
在一些优选实施方式中，所述(b4)多元胺扩链剂a’的碳原子为2～13，官能度为2～3，优选1,2-乙二胺、1,6-六亚甲基二胺、1-氨基-3,3,5-三甲基-5-氨甲基环己烷(异佛尔酮二胺)、哌嗪、1,4-二氨基环己烷、双-(4-氨基环己基)甲烷、N-(2-羟乙基)亚乙基二胺和二亚乙基三胺中的一种或多种，更优选1,6-六亚甲基二胺、1-氨基-3,3,5-三甲基-5-氨甲基环己烷(异佛尔酮二胺)和N-(2-羟乙基)亚乙基二胺中的一种或多种，最优选1-氨基-3,3,5-三甲基-5-氨甲基环己烷(异佛尔酮二胺)和/或1,6-六亚甲基二胺；
在一些优选实施方式中，所述(b5)多元胺扩链剂b’为被离子基团或潜离子基团取代的二元胺，优选N-(2-氨基乙基)-2-氨基乙磺酸的钠盐和/或N-(2-氨基乙基)-2-氨基丙磺酸的钠盐；
在一些优选实施方式中，所述(b6)多羟基扩链剂为三羟甲基丙烷。
为解决上述技术问题，本发明还提供一种面膜基质，包括上述任一项所述的面膜基质组合物，以所述面膜基质的总质量计，所述面膜基质组合物中的(a)水性聚氨酯分散体a和(b)水性聚氨酯分散体b在所述面膜基质中的质量百分比如下：
(a)5～90wt％的水性聚氨酯分散体a,优选10～70wt％，更优选10～50wt％；
(b)10～95wt％的水性聚氨酯分散体b,优选10～70wt％，更优选10～50wt％；
优选地，以所述面膜基质的总质量计，所述面膜基质中还包括如下质量百分比的各组分：
(c)0～10wt％的增稠剂，优选0.05～8wt％，更优选0.1～6wt％；
(d)0～10wt％的乳化剂，优选0.5～8wt％，更优选1～7wt％；
(e)0～20wt％的油脂，优选2～18wt％，更优选3～15wt％；
(f)0～1wt％的防腐剂；
(g)0～3wt％的香精；
(h)0～80wt％的去离子水；
其中，所述(d)乳化剂可以增加油脂、油溶性的活性成分、油溶性的香精和防腐剂等在面膜中的稳定性；
所述(e)油脂可以改善功能型面膜基质的肤感和增加油溶性活性物的溶解。
上述面膜基质中，所述面膜基质为乳液状，以所述面膜基质的总质量计，包括以下组分：
(a)20～70wt％的水性聚氨酯分散体a；
(b)20～70wt％的水性聚氨酯分散体b；
(c)0～5wt％增稠剂，优选0.05～3.5wt％，更优选0.15～2.5wt％；
(d)0～6wt％的乳化剂，优选0.5～5wt％，更优选1～4wt％；
(e)0～10wt％的油脂，优选2～8wt％，更优选3～6wt％；
(f)0～1wt％的防腐剂；
(g)0～3wt％的香精；
(h)0～60wt％去离子水。
上述面膜基质中，所述面膜基质为膏霜状，以所述面膜基质的总质量计，包括以下组分：
(a)10～50wt％的水性聚氨酯分散体a；
(b)10～50wt％的水性聚氨酯分散体b；
(c)0.2～10wt％的增稠剂，优选0.5～8wt％，更优选1～6wt％；
(d)0～7wt％的乳化剂，优选0.5～6wt％，更优选1～5wt％；
(e)0～15wt％的油脂，优选2～13wt％，更优选4～10wt％；
(f)0～1wt％的防腐剂；
(g)0～3wt％的香精；
(h)0～79.8wt％的去离子水。
上述面膜基质中，所述面膜基质为啫喱状，以所述面膜基质的总质量计，包括以下组分：
(a)10～60wt％的水性聚氨酯分散体a；
(b)10～60wt％的水性聚氨酯分散体b；
(c)0.5～10wt％增稠剂，优选1～8wt％，更优选1.5～5wt％；
(d)0～10wt％的乳化剂，优选1～8wt％，更优选3～7wt％；
(e)0～20wt％的油脂，优选3～18wt％，更优选5～15wt％；
(f)0～1wt％的防腐剂
(g)0～3wt％的香精；
(h)0～71.5wt％去离子水。
在一些优选实施方式中，上述任一项所述的面膜基质中，所述(c)增稠剂为丙烯酸型增稠剂、聚氨酯类增稠剂(HEUR)、纤维素类增稠剂、结冷胶、黄原胶、卡波、瓜尔胶、硅藻土、淀粉、阿拉伯树胶、大豆蛋白胶、明胶、海藻酸钠、干酪素、甲壳胺、天然羊毛脂和琼脂中的一种或多种；
在一些优选实施方式中，所述(d)乳化剂选自硬脂基酯类、聚醚硅油类、烷基醚类、羧酸盐、硫酸盐、磺酸盐、胺的衍生物、聚氧乙烯醚类和聚氧丙烯醚类中的一种或多种；
在一些优选实施方式中，所述(e)油脂选自天然油、合成油、矿物油、脂 肪酸、脂肪醇和脂肪酯类中的一种或多种，优选金盏花油、橄榄油、羊毛脂油、蓖麻油、棉籽油、大豆油、芝麻油、杏仁油、花生油、玉米油、米糠油、茶籽油、沙棘油、鳄梨油、石栗子油、欧洲坚果油、胡桃油、可可油、水貂油、蛋黄油、椰子油、卵磷脂、角鲨烷、羊毛脂衍生物、聚硅氧烷、脂肪酸、脂肪醇、脂肪酸脂、甘油和凡士林中的一种或多种；
在一些优选实施方式中，所述(f)防腐剂为对皮肤温和的防腐剂，优选苯氧乙醇、乙基己基甘油、辛甘醇和1,2-己二醇中的一种或多种。
在一些优选实施方式中，上述乳液状的面膜基质中，以所述面膜基质的总质量计，所述(c)增稠剂为：0～3.0wt％的羟乙基纤维素、0～3.0wt％的黄原胶和0～2.0wt％的卡波，为了达到更好的外观和肤感体验，优选0.05～1wt％的羟乙基纤维素、0.05～1.0wt％的黄原胶和0.05～0.5wt％的卡波；
所述(d)乳化剂为0～4.0wt％的鲸蜡硬脂基醚-20和0～4.0wt％的PEG-10聚二甲基硅氧烷，为了达到更好的外观和肤感体验，优选2～3.0wt％的鲸蜡硬脂基醚-20和2～3.0wt％的PEG-10聚二甲基硅氧烷；
所述(e)油脂为0～10wt％的椰子油、0～10wt％的蓖麻油和0～10wt％聚二甲基硅氧烷，为了达到更好的外观和肤感体验，优选2.0～10wt％的椰子油、2.0～10wt％的蓖麻油和2.0～10wt％聚二甲基硅氧烷。
在一些优选实施方式中，上述膏霜状的面膜基质中，以所述面膜基质的总质量计，所述(c)增稠剂为0.1～5.0wt％的羟乙基纤维素、0.1～5.0wt％的黄原胶和0～5.0wt％的卡波，为了达到更好的外观和肤感体验，优选0.5～3.0wt％的羟乙基纤维素、0.5～3wt％的黄原胶和0.8～3.0wt％的卡波。
所述(d)乳化剂为0～4.0wt％的鲸蜡硬脂基醚-20和0～5.0wt％的PEG-10聚二甲基硅氧烷，为了达到更好的外观和肤感体验，优选1.0～4.0wt％的鲸蜡硬脂基醚-20和1.0～5.0wt％的PEG-10聚二甲基硅氧烷；
所述(e)油脂为2.0～10wt％的椰子油、2.0～10wt％的蓖麻油和2.0～10wt％聚二甲基硅氧烷，为了达到更好的外观和肤感体验，优选5.0～10wt％的椰子油、4.0～10wt％的蓖麻油和5.0～10wt％聚二甲基硅氧烷。
在一些优选实施方式中，上述啫喱状的面膜基质中，以所述面膜基质的总质量计，所述(c)增稠剂为0.1～2.0wt％的结冷胶、0.1～6.0wt％的黄原胶和0.1～ 5.0wt％的卡波，为了达到更好的外观和肤感体验，优选0.1～1.5wt％的结冷胶、1.0～1.5wt％的黄原胶和1.0～4.0wt％的卡波；
所述(d)乳化剂为0～4.0wt％的鲸蜡硬脂基醚-20和0～4.5wt％的PEG-10聚二甲基硅氧烷，为了达到更好的外观和肤感体验，优选1.0～3.0wt％的鲸蜡硬脂基醚-20和1.0～4.5wt％的PEG-10聚二甲基硅氧烷；
所述(e)油脂为0～10wt％的椰子油、0～12wt％的蓖麻油和0～12wt％聚二甲基硅氧烷，为了达到更好的外观和肤感体验，优选4～10wt％的椰子油、3～10wt％的蓖麻油和4～12wt％聚二甲基硅氧烷。
为解决上述技术问题，本发明还提供上述任一项所述的面膜基质的制备方法，包括以下步骤：
将所述(a)水性聚氨酯分散体a和所述(b)水性聚氨酯分散体b混匀得到A相；将所述(h)去离子水和所述(c)增稠剂混匀得到B相；将所述(d)乳化剂和所述(e)油脂混匀得到C相；
在C相存在的情况下，分别将B相和C相加热至70-85℃后混匀，得到B+C相，待温度降至50℃至室温的范围后，加入A相和其他组分，混匀；
在C相不存在的情况下，室温下将A相和B相混匀，得到A+B相，再加入其他组分，混匀；
所述其他组分包括所述(f)防腐剂和/或所述(g)香精。
为解决上述技术问题，本发明还提供一种面膜或体膜，包含上述任一项所述的面膜基质组合物或上述任一项所述的面膜基质以及活性物质；
所述体膜优选为颈膜、背膜或腿膜；
所述活性物质包括但不限于美白、祛斑、抗氧化、保湿和/或抗皱等活性成分。
为解决上述技术问题，本发明还提供上述面膜或体膜的制备方法，包括上述任一项所述的面膜基质组合物或上述任一项所述的面膜基质与活性物质混合的步骤。
为解决上述技术问题，本发明还提供上述任一项所述的面膜基质组合物或上述任一项所述的面膜基质或上述面膜或体膜在促进活性物质渗透吸收中的应用，优选在促进活性物质在皮肤中的渗透吸收中的应用。
本发明首次通过使用具有促进活性物渗透吸收功能的水性聚氨酯面膜基质，使化妆品中的功效成分通过皮肤屏障从而更好的被皮肤吸收。本发明的水性聚氨酯面膜基质至少具有以下两方面的有益效果：
1、根据使用者的不同需求，本发明的水性聚氨酯面膜基质可以局部或完整涂抹于面部，待面膜干燥后与面部完整贴合，可直接被完整揭下也可以经水润湿后剥离，剥离过程无任何痛感，不会粘连皮肤和撕扯毛孔，因而不会引起皮肤松弛和毛孔变大的问题。相反，面膜在干燥过程中，还兼有收缩毛孔和紧致皮肤的效果，令肌肤拥有更完美的状态。
2、本发明的水性聚氨酯面膜基质与各种化妆品的活性成分如美白、保湿和抗皱成分等相容性好，其中两种具有特殊的交联结构的水性聚氨酯在成膜过程中相互作用，实现了向皮肤深层传导活性成分的功效，活性物质被人体更好的吸收，从而使功能型面膜产品达到更优的效果。但是，单独使用其中一种水性聚氨酯无法达到显著促进活性成分吸收的作用。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
以下结合具体实施例，对本发明作进一步说明。应理解，以下实施例仅用于说明本发明而非用于限定本发明的范围。
CMA-654(聚己二酸己二醇新戊二醇酯二元醇，数均分子量为1500左右，OH值＝74mgKOH/g)为烟台华大化学工业有限公司产品。
Figure PCTCN2018114894-appb-000001
HMDI(4,4’-二环己基甲烷二异氰酸酯)为万华化学集团股份有限公司产品。
Figure PCTCN2018114894-appb-000002
A95(N-(2-氨基乙基)-2-氨基乙磺酸钠)为赢创产品。
AMP-95(2-氨基-2-甲基-1-丙醇，分子量为89.14)为陶氏化学公司产品。
异佛尔酮二胺为拜耳产品。
PBA2000(聚己二酸-1,4-丁二醇酯二醇，数均分子量为2000，官能度为2，OH值＝56mg KOH/g)为烟台华大化学工业有限公司产品。
PN110(聚对苯二甲酸新戊二醇酯二元醇，数均分子量为1000，官能度为2) 为斯泰潘(南京)化学有限公司产品。
MPEG1200(聚乙二醇单甲醚，数均分子量为1200)为韩国乐天化学有限公司产品。
TMP(三羟甲基丙烷)为山东富丰柏斯托化工有限公司产品。
阴离子型水性聚氨酯分散体-1a：按照以下方法合成：在四口烧瓶内加入250g CMA-654(71.18wt％，wt％表示占阴离子型水性聚氨酯分散体-1a中固体(即聚氨酯)的质量百分比，下同)、1.8g新戊二醇(0.51wt％)，70℃条件下混合搅拌10min，降温至50℃加入78g
Figure PCTCN2018114894-appb-000003
HMDI(22.21wt％)进行预聚反应，测试该反应约NCO％＝2.66wt％时，使得到的预聚物冷却到40℃，溶解在360g丙酮溶剂(102.5wt％)中，混合15min后，加入3.2g乙二胺(0.91wt％)和15.7g
Figure PCTCN2018114894-appb-000004
A95(4.46wt％)在75.6g去离子水中形成的溶液，45℃条件下继续反应30min后，在剪切分散条件下加入575g水(163.2wt％)，然后加入2.5g AMP-95(0.71wt％)的稀释水溶液对所得乳液封端，然后减压蒸馏脱除丙酮得到固含量约40wt％的聚氨酯分散体，粒径为240nm，即阴离子型水性聚氨酯分散体-1a。
阴离子型水性聚氨酯分散体-2a：按照以下方法合成：在四口烧瓶内加入250g CMA-654(75.02wt％，wt％表示占阴离子型水性聚氨酯分散体-2a中固体(即聚氨酯)的质量百分比，下同)、2.5g 1,4-丁二醇(0.75wt％)，70℃条件下混合搅拌10min，降温至50℃加入65g
Figure PCTCN2018114894-appb-000005
HMDI(19.50wt％)进行预聚反应，测试该反应约NCO％＝1.30wt％时，使得到的预聚物冷却到40℃，溶解在330g丙酮溶剂(99.0wt％)中，混合15min后，加入0.2g乙二胺(0.06wt％)和14g
Figure PCTCN2018114894-appb-000006
A95(4.20wt％)在56.8g去离子水中形成的溶液，45℃条件下继续反应30min后，在剪切分散条件下加入498g水(149.54wt％)，然后加入1.5g AMP-95(0.45wt％)的稀释水溶液对所得乳液封端，然后减压蒸馏脱除丙酮得到固含量约40wt％聚氨酯分散体，粒径为230nm，即阴离子型水性聚氨酯分散体-2a。
阴离子型水性聚氨酯分散体-3a：按照以下方法合成：在四口烧瓶内加入250g CMA-654(71.2wt％，wt％表示占阴离子型水性聚氨酯分散体-3a中固体(即聚氨酯)的质量百分比，下同)、3g新戊二醇(0.86wt％)，70℃条件下混合搅拌10min，降温至50℃加入75g
Figure PCTCN2018114894-appb-000007
HMDI(21.38wt％)进行预聚反应，测试该反应约NCO％＝2.13wt％时，使得到的预聚物冷却到40℃，溶解在350g丙酮溶 剂(100wt％)中，混合15min后，加入5g异佛尔酮二胺(1.42wt％)和15.5g
Figure PCTCN2018114894-appb-000008
A95(4.42wt％)在82g去离子水中形成的溶液，45℃条件下继续反应30min后，在剪切分散条件下加入520g水(148.5wt％)，然后加入2.3g AMP-95(0.66wt％)的稀释水溶液对所得乳液封端，然后减压蒸馏脱除丙酮得到固含量约40wt％聚氨酯分散体，粒径为210nm，即阴离子型水性聚氨酯分散体-3a。
阴离子型水性聚氨酯分散体-1b：按照以下方法合成：在四口烧瓶内加入65g 
Figure PCTCN2018114894-appb-000009
HMDI(18.40wt％，wt％表示占阴离子型水性聚氨酯分散体-1b中固体(即聚氨酯)的质量百分比，下同)、225g PBA2000(63.39wt％)、50g PN110(14.15wt％)、5g MPEG1200(1.42wt％)、1gTMP(0.28wt％)和30g丙酮在70℃下搅拌均匀并进行预聚反应2～3h，测试该反应NCO约NCO＝1.55wt％时，将预聚物溶解在500g丙酮(制备过程中丙酮的总体用量为140wt％)中，混合15min后，加入3.8g六亚甲基二胺(1.08wt％)和4.5g
Figure PCTCN2018114894-appb-000010
A95(1.27wt％)在20g去离子水中形成的溶液，45℃条件下继续反应30min后，在剪切条件下加入421g(117.88wt％)水，然后减压蒸馏脱除丙酮得到固含量约47wt％聚氨酯分散体，粒径为150nm，即阴离子型水性聚氨酯分散体-1b。
阴离子型水性聚氨酯分散体-2b：按照以下方法合成：在四口烧瓶内加入75g
Figure PCTCN2018114894-appb-000011
HMDI(30.36wt％,wt％表示占阴离子型水性聚氨酯分散体-2b中固体(即聚氨酯)的质量百分比，下同)、150g PN110(60.73wt％)、6.5g MPEG1200(2.63wt％)、2gTMP(0.81wt％)和30g丙酮在70℃下搅拌均匀并进行预聚反应2～3h，测试该反应NCO约NCO＝3.1wt％时，将预聚物溶解在500g丙酮(制备过程中丙酮的总体用量为202.5wt％)中，混合15min后，加入10g六亚甲基二胺(4.05wt％)和4.5g
Figure PCTCN2018114894-appb-000012
A95(1.82wt％)在20g去离子水中形成的溶液，45℃条件下继续反应30min后，在剪切条件下加入403g水(163.22wt％)，然后减压蒸馏脱除丙酮得到固含量约47wt％聚氨酯分散体，粒径为140nm，即阴离子型水性聚氨酯分散体-2b。
阴离子型水性聚氨酯分散体-3b：按照以下方法合成：在四口烧瓶内加入40g
Figure PCTCN2018114894-appb-000013
HMDI(14.84wt％,wt％表示占阴离子型水性聚氨酯分散体-3b中固体(即聚氨酯)的质量百分比，下同)、220g PBA2000(81.48wt％)、5g MPEG1200(1.85wt％)、1gTMP(0.37wt％)和30g丙酮在70℃下搅拌均匀并进行预聚反应2～3h，测试该反应NCO约NCO＝1.15wt％时，将预聚物溶解在500g丙酮 (制备过程中丙酮的总体用量为185wt％)中，混合15min后，加入0.5g六亚甲基二胺(0.19wt％)和4.5g
Figure PCTCN2018114894-appb-000014
A95(1.66wt％)在20g去离子水中形成的溶液，45℃条件下继续反应30min后，在剪切条件下加入415g水(153.55wt％)，然后减压蒸馏脱除丙酮得到固含量约47wt％聚氨酯分散体，粒径为160nm，即阴离子型水性聚氨酯分散体-3b。
羟乙基纤维素为陶氏化学公司产品，产品目录号为CELLOSIZE TMHYDROXYETHYL CELLULOSE QP100MH，是一种增稠剂。
黄原胶为Jungbunzlauer公司产品，产品目录号为E415food grade，是一种增稠剂。
卡波为路博润产品，产品目录号为
Figure PCTCN2018114894-appb-000015
Ultrez 21，是一种增稠剂。
结冷胶为斯比凯可产品，产品目录号为
Figure PCTCN2018114894-appb-000016
Xanthan Gum，是一种增稠剂。
鲸蜡硬脂基醚-20为科宁产品，产品目录号为EUMULGIN B2，是一种乳化剂。
PEG-10聚二甲基硅氧烷为广东标美硅氟新材料有限公司产品，产品目录号为BioMaxSF-9336，是一种乳化剂。
椰子油为广州汉佰斯日化科技发展有限公司产品，是一种油脂。
蓖麻油为济南鑫诺化工有限公司产品，是一种油脂。
聚二甲基硅氧烷为道康宁产品，产品目录号为DC200-350，是一种油脂。
香精为上海伏羲香精香料有限公司产品，产品目录号为OLY007BOOMBASTIC。
苯氧乙醇为陶氏化学公司产品，产品目录号为NEOLONE TMPH100，是一种防腐剂。
水解葡糖氨基聚糖为广州孚维生物科技有限公司产品，产品目录号为
Figure PCTCN2018114894-appb-000017
PLUS，是一种保湿剂。
以下实施例和对比例的表中所示的数值为质量百分含量，具体表示各组分的质量占制备面膜基质的各个组分的质量之和的百分比。
实施例1-13
按照表1所示的各个组分及其质量百分含量，在C相存在的情况下(实施例3、5、6、8、9、10、11、12和13)，室温下分别将B相和C相的各组分混合，在600r/min转速下搅拌5分钟后加热到75℃，将B相和C相混合，温度维持75℃并在8000r/min的转速下均质5分钟后得到B+C相。待温度降至50℃后，再加入A相和其他组分，5000r/min均质5分钟后制成面膜基质。在C相不存在的情况下(实施例1、2、4和7)，室温下分别将A相和B相的各组分混合，再将A相和B相混合，得到A+B相，在A+B相中加入其他组分(如果存在的话)，5000r/min均质5分钟后制成面膜基质。
表1
Figure PCTCN2018114894-appb-000018
Figure PCTCN2018114894-appb-000019
对比例1-3
对比例1：按照表2所示的各个组分及其质量百分含量，在室温下，分别将B相和C相的各组分混合，在600r/min转速下搅拌5分钟后加热到75℃，将B相和C相混合，温度维持75℃并在8000r/min的转速下均质5分钟后得到B+C 相。待温度降至50℃后，再加入其他组分，5000r/min均质5分钟后制成面膜基质。
对比例2和3：按照表2所示的各个组分及其质量百分含量，在室温下，分别将B相和C相的各组分混合，在600r/min转速下搅拌5分钟后加热到75℃，将B相和C相混合，温度维持75℃并在8000r/min的转速下均质5分钟后得到B+C相。待温度降至50℃后，再加入A相和其他组分，5000r/min均质5分钟后制成面膜基质。
表2
Figure PCTCN2018114894-appb-000020
对比测试：
面膜制备：室温下，在实施例10和对比例1-3制备的面膜基质中分别加入占面膜基质1wt％的水解葡糖氨基聚糖(即，水解葡糖氨基聚糖：面膜基质＝1:100，质量比)，均质5分钟后制成面膜，分别得到以实施例10和对比例1-3制备的面膜基质为基质的面膜。
功能型面膜基质的功效评价：17名受试者分别使用上述得到的以实施例10和对比例1-3制备的面膜基质为基质的面膜，并在15分钟后将面膜从脸部揭下。
检测方法：使用经皮水分流失测试仪(TEWL)、表皮水分测试仪Corneometer和测试皱纹使用的Visiacr检测皮肤表皮含水量以及皱纹减少量。
测试结果：
使用以实施例10制备的面膜基质为基质的面膜，与未使用面膜之前相比，受试者平均皱纹减少量达到18％，皮肤表皮含水量增加61％，制备的面膜能明显减少经皮水分流失，皮肤平滑度得到明显改善；
使用以对比例1制备的面膜基质为基质的面膜，与未使用面膜之前相比，受试者皱纹减少量达16％，皮肤表皮含水量增加49％。使用以对比例2和对比例3制备的面膜基质为基质的面膜，与未使用面膜之前相比，受试者平均皱纹减少量分别为16.1％和16.7％，皮肤表皮含水量分别增加51％和50.4％。
对比测试结果证实：与对比例1相比，实施例10制备的水性聚氨酯功能型面膜基质可以使皱纹减少量提高高达12.5％，保湿效果提高高达24.5％。表明本发明的阴离子型水性聚氨酯分散体a和b混合使用在面膜中有明显的促进活性物质深层传导的功效。同时，对比例2和3的结果表明单独使用阴离子型水性聚氨酯分散体a或b用在面膜中没有明显的促进活性物质深层传导的功效。
将实施例1-9和11-13制备的面膜基质进行如上对比测试同样得到了与实施例10相似的结论。
同时，由实施例11、12和13制备的面膜基质为基质的面膜在外观、肤感和消费者体验方面效果更佳。
另外，10名受试者使用由实施例1-13制备的面膜基质为基质的面膜，约15分钟后面膜可完全干燥，用水将面膜润湿后，受试者均可以将面膜完整的从面部剥离，且没有痛感。

Claims (17)

  1. 一种面膜基质组合物，以所述面膜基质组合物的总质量计，包括以下组分：
    (a)5～90wt％的水性聚氨酯分散体a；
    (b)10～95wt％的水性聚氨酯分散体b；
    其中，所述(a)水性聚氨酯分散体a采用包括(a2)聚酯多元醇、(a3)低分子量二元醇扩链剂、(a1)多异氰酸酯、(a4)多元胺扩链剂a、(a5)多元胺扩链剂b和(a6)小分子单氨基封端剂的反应原料反应制得；
    所述(b)水性聚氨酯分散体b采用包括(b1)多异氰酸酯、(b2)聚酯多元醇、(b3)聚乙二醇单甲醚、(b6)多羟基扩链剂、(b4)多元胺扩链剂a’和(b5)多元胺扩链剂b’的反应原料反应制得；
    所述(a4)多元胺扩链剂a和(b4)多元胺扩链剂a’均为没有被离子基团或潜离子基团取代的多元胺扩链剂；
    所述(a5)多元胺扩链剂b和(b5)多元胺扩链剂b’均为被离子基团或潜离子基团取代的多元胺扩链剂；
    所述(b6)多羟基扩链剂为低分子量多羟基扩链剂。
  2. 根据权利要求1所述的面膜基质组合物，其中，以所述(a)水性聚氨酯分散体a中的聚氨酯的质量计，所述(a)水性聚氨酯分散体a采用包括如下质量百分比的各反应原料反应制得：
    (a2)聚酯多元醇65～80wt％，优选71～75wt％；
    (a3)低分子量二元醇扩链剂0.1～3wt％，优选0.5～1wt％；
    (a1)多异氰酸酯15～25wt％，优选19～23wt％；
    (a4)多元胺扩链剂a 0.01～3wt％，优选0.05～2wt％；
    (a5)多元胺扩链剂b 1～8wt％，优选2～5wt％；
    (a6)小分子单氨基封端剂0.1～2wt％，优选0.4～1wt％；
    优选地，所述(a)水性聚氨酯分散体a按照包括如下步骤的方法制备：将所述(a2)聚酯多元醇、所述(a3)低分子量二元醇扩链剂，在70～80℃条件下混合，降温至45～60℃加入所述(a1)多异氰酸酯进行预聚反应，当达到理论NCO含量时，使得到的预聚物冷却到30～45℃，溶解在丙酮溶剂中，丙酮用量为(a)水 性聚氨酯分散体a的聚氨酯的质量的100～150wt％；混合后，加入所述(a4)多元胺扩链剂a和所述(a5)多元胺扩链剂b，35～45℃条件下继续反应15～30min后，在剪切分散条件下加入水，水的用量为(a)水性聚氨酯分散体a的聚氨酯的质量的130～200wt％，然后加入所述(a6)小分子单氨基封端剂的水溶液封端，真空脱除丙酮，得到所述(a)水性聚氨酯分散体a；
    所述(a)水性聚氨酯分散体a的总固含量为20～50wt％，优选35～45wt％；粒径为100nm～300nm，优选150nm～250nm。
  3. 根据权利要求1或2所述的面膜基质组合物，其中，以所述(b)水性聚氨酯分散体b中的聚氨酯的质量计，所述(b)水性聚氨酯分散体b采用包括如下质量百分比的各反应原料反应制得：
    (b1)多异氰酸酯14～35wt％，优选15～23wt％；
    (b2)聚酯多元醇60～83.8wt％，优选70-80wt％；
    (b3)聚乙二醇单甲醚1～3wt％，优选1.8～2.5wt％；
    (b6)多羟基扩链剂0.1～1wt％，优选0.2～0.5wt％；
    (b4)多元胺扩链剂a’ 0.1～5wt％，优选0.5～2wt％；
    (b5)多元胺扩链剂b’ 1～2wt％，优选1.4～1.6wt％；
    优选地，所述(b)水性聚氨酯分散体b按照包括如下步骤的方法制备：
    将所述(b1)多异氰酸酯、所述(b2)聚酯多元醇、所述(b3)聚乙二醇单甲醚、所述(b6)多羟基扩链剂和丙酮在50～100℃下混匀并进行预聚反应，当达到或接近理论NCO含量时，将预聚物溶解在丙酮溶剂中，制备过程中丙酮的总体用量为(b)水性聚氨酯分散体b的聚氨酯的质量的100～210wt％；混合后，加入所述(b4)多元胺扩链剂a’和所述(b5)多元胺扩链剂b’，35～45℃条件下继续反应15～30min后，在剪切分散条件下加入水，水的用量为(b)水性聚氨酯分散体b的聚氨酯的质量的100～170wt％，然后真空脱除丙酮，得到所述(b)水性聚氨酯分散体b；
    所述(b)水性聚氨酯分散体b的总固含量为30～50wt％，粒径为120～190nm,优选140～160nm。
  4. 根据权利要求2所述的面膜基质组合物，其中，所述(a1)多异氰酸酯具有2个异氰酸酯基团，选自脂肪族异氰酸酯和脂环脂族异氰酸酯中的一种或多 种，优选为异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、二环己基甲烷二异氰酸酯和四甲基苯二甲基二异氰酸酯中的一种或多种，更优选二环己基甲烷二异氰酸酯；
    所述(a2)聚酯多元醇的数均分子量为800～3000，优选1000～2000，官能度为2～3；所述(a2)聚酯多元醇为有机多元羧酸和/或其酸酐与多元醇通过聚合反应制得，其中：所述有机多元羧酸和/或其酸酐优选选自丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸和它们的酸酐中的一种或多种，进一步优选己二酸；所述多元醇优选选自乙二醇、1,2-丙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇、三羟甲基丙烷和新戊二醇中的一种或多种，进一步优选1,6-己二醇和/或新戊二醇；
    所述(a3)低分子量二元醇扩链剂选自乙二醇、二乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,3-丁二醇、环己二醇、1,4-环己烷二甲醇、1,6-己二醇和新戊二醇中的一种或多种，优选1,4-丁二醇和/或新戊二醇；
    所述(a4)多元胺扩链剂a的碳原子为2～20个，官能度为2～3，优选乙二胺、丙二胺、丁二胺、己二胺、异佛尔酮二胺、1,4-环己烷二胺、4,4’-二环己基甲烷二胺和二乙烯三胺中的一种或多种，更优选乙二胺、己二胺、异佛尔酮二胺、1,4-环己烷二胺和4,4’-二环己基甲烷二胺中的一种或多种，最优选乙二胺和/或异佛尔酮二胺；
    所述(a5)多元胺扩链剂b为被离子基团或潜离子基团取代的二元胺，优选N-(2-氨基乙基)-2-氨基乙磺酸的钠盐和/或N-(2-氨基乙基)-2-氨基丙磺酸的钠盐；
    所述(a6)小分子单氨基封端剂碳原子为2～10个，官能度为1，优选二乙醇胺、三羟基胺和/或2-氨基-2-甲基-1-丙醇，更优选2-氨基-2-甲基-1-丙醇。
  5. 根据权利要求3所述的面膜基质组合物，其中，所述(b1)多异氰酸酯具有2～4个异氰酸酯基团，选自脂肪族多异氰酸酯和脂环族多异氰酸酯中的一种或多种，优选选自六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯中的一种或多种，更优选4,4’-二环己基甲烷二异氰酸酯；
    所述(b2)聚酯多元醇的数均分子量为20～14000，优选500～3000，官能度为2～3；所述(b2)聚酯多元醇由有机多元羧酸和/或其酸酐与多元醇通过聚合反 应制得，其中，所述有机多元羧酸和/或其酸酐优选选自琥珀酸、己二酸、辛二酸、间苯二甲酸和它们的酸酐中的一种或多种，进一步优选间苯二甲酸和/或己二酸；所述多元醇优选包括乙二醇、丁二醇、新戊二醇、己二醇中的一种或多种，进一步优选丁二醇和/或新戊二醇；
    所述(b3)聚乙二醇单甲醚数均分子量为700～2000，优选1000～1500；
    所述(b4)多元胺扩链剂a’的碳原子为2～13，官能度为2～3，优选1,2-乙二胺、1,6-六亚甲基二胺、异佛尔酮二胺、哌嗪、1,4-二氨基环己烷、双-(4-氨基环己基)甲烷、N-(2-羟乙基)亚乙基二胺和二亚乙基三胺中的一种或多种，更优选1,6-六亚甲基二胺、异佛尔酮二胺和N-(2-羟乙基)亚乙基二胺中的一种或多种，最优选异佛尔酮二胺和/或1,6-六亚甲基二胺；
    所述(b5)多元胺扩链剂b’为被离子基团或潜离子基团取代的二元胺，优选N-(2-氨基乙基)-2-氨基乙磺酸的钠盐和/或N-(2-氨基乙基)-2-氨基丙磺酸的钠盐；
    所述(b6)多羟基扩链剂为三羟甲基丙烷。
  6. 一种面膜基质，包括权利要求1-5任一项所述的面膜基质组合物，以所述面膜基质的总质量计，所述面膜基质组合物中的(a)水性聚氨酯分散体a和(b)水性聚氨酯分散体b在所述面膜基质中的质量百分比如下：
    (a)5～90wt％的水性聚氨酯分散体a；
    (b)10～95wt％的水性聚氨酯分散体b；
    优选地，以所述面膜基质的总质量计，所述面膜基质中还包括如下质量百分比的各组分：
    (c)0～10wt％的增稠剂；
    (d)0～10wt％的乳化剂；
    (e)0～20wt％的油脂；
    (f)0～1wt％的防腐剂；
    (g)0～3wt％的香精；
    (h)0～80wt％的去离子水。
  7. 根据权利要求6所述的面膜基质，其中，所述面膜基质为乳液状，以所述面膜基质的总质量计，包括以下组分：
    (a)20～70wt％的水性聚氨酯分散体a；
    (b)20～70wt％的水性聚氨酯分散体b；
    (c)0～5wt％增稠剂；
    (d)0～6wt％的乳化剂；
    (e)0～10wt％的油脂；
    (f)0～1wt％的防腐剂；
    (g)0～3wt％的香精；
    (h)0～60wt％去离子水。
  8. 根据权利要求6所述的面膜基质，其中，所述面膜基质为膏霜状，以所述面膜基质的总质量计，包括以下组分：
    (a)10～50wt％的水性聚氨酯分散体a；
    (b)10～50wt％的水性聚氨酯分散体b；
    (c)0.2～10wt％的增稠剂；
    (d)0～7wt％的乳化剂；
    (e)0～15wt％的油脂；
    (f)0～1wt％的防腐剂；
    (g)0～3wt％的香精；
    (h)0～79.8wt％的去离子水。
  9. 根据权利要求6所述的面膜基质，其中，所述面膜基质为啫喱状，以所述面膜基质的总质量计，包括以下组分：
    (a)10～60wt％的水性聚氨酯分散体a；
    (b)10～60wt％的水性聚氨酯分散体b；
    (c)0.5～10wt％增稠剂；
    (d)0～10wt％的乳化剂；
    (e)0～20wt％的油脂；
    (f)0～1wt％的防腐剂
    (g)0～3wt％的香精；
    (h)0～71.5wt％去离子水。
  10. 根据权利要求6-9任一项所述的面膜基质，其中，所述(c)增稠剂为 丙烯酸型增稠剂、聚氨酯类增稠剂、纤维素类增稠剂、结冷胶、黄原胶、卡波、瓜尔胶、硅藻土、淀粉、阿拉伯树胶、大豆蛋白胶、明胶、海藻酸钠、干酪素、甲壳胺、天然羊毛脂和琼脂中的一种或多种；
    所述(d)乳化剂选自硬脂基酯类、聚醚硅油类、烷基醚类、羧酸盐、硫酸盐、磺酸盐、胺的衍生物、聚氧乙烯醚类和聚氧丙烯醚类中的一种或多种；
    所述(e)油脂选自天然油、合成油、矿物油、脂肪酸、脂肪醇和脂肪酯类中的一种或多种，优选金盏花油、橄榄油、羊毛脂油、蓖麻油、棉籽油、大豆油、芝麻油、杏仁油、花生油、玉米油、米糠油、茶籽油、沙棘油、鳄梨油、石栗子油、欧洲坚果油、胡桃油、可可油、水貂油、蛋黄油、椰子油、卵磷脂、角鲨烷、羊毛脂衍生物、聚硅氧烷、脂肪酸、脂肪醇、脂肪酸脂、甘油和凡士林中的一种或多种；
    所述(f)防腐剂选自苯氧乙醇、乙基己基甘油、辛甘醇和1,2-己二醇中的一种或多种。
  11. 根据权利要求7所述的面膜基质，其中，以所述面膜基质的总质量计，所述(c)增稠剂为：0～3.0wt％的羟乙基纤维素、0～3.0wt％的黄原胶和0～2.0wt％的卡波，优选0.05～1wt％的羟乙基纤维素、0.05～1.0wt％的黄原胶和0.05～0.5wt％的卡波；
    所述(d)乳化剂为0～4.0wt％的鲸蜡硬脂基醚-20和0～4.0wt％的PEG-10聚二甲基硅氧烷，优选2～3.0wt％的鲸蜡硬脂基醚-20和2～3.0wt％的PEG-10聚二甲基硅氧烷；
    所述(e)油脂为0～10wt％的椰子油、0～10wt％的蓖麻油和0～10wt％聚二甲基硅氧烷，优选2.0～10wt％的椰子油、2.0～10wt％的蓖麻油和2.0～10wt％聚二甲基硅氧烷。
  12. 根据权利要求8所述的面膜基质，其中，以所述面膜基质的总质量计，所述(c)增稠剂为0.1～5.0wt％的羟乙基纤维素、0.1～5.0wt％的黄原胶和0～5.0wt％的卡波，优选0.5～3.0wt％的羟乙基纤维素、0.5～3wt％的黄原胶和0.8～3.0wt％的卡波。
    所述(d)乳化剂为0～4.0wt％的鲸蜡硬脂基醚-20和0～5.0wt％的PEG-10聚二甲基硅氧烷，优选1.0～4.0wt％的鲸蜡硬脂基醚-20和1.0～5.0wt％的 PEG-10聚二甲基硅氧烷；
    所述(e)油脂为2.0～10wt％的椰子油、2.0～10wt％的蓖麻油和2.0～10wt％聚二甲基硅氧烷，优选5.0～10wt％的椰子油、4.0～10wt％的蓖麻油和5.0～10wt％聚二甲基硅氧烷。
  13. 根据权利要求9所述的面膜基质，其中，以所述面膜基质的总质量计，所述(c)增稠剂为0.1～2.0wt％的结冷胶、0.1～6.0wt％的黄原胶和0.1～5.0wt％的卡波，优选0.1～1.5wt％的结冷胶、1.0～1.5wt％的黄原胶和1.0～4.0wt％的卡波；
    所述(d)乳化剂为0～4.0wt％的鲸蜡硬脂基醚-20和0～4.5wt％的PEG-10聚二甲基硅氧烷，优选1.0～3.0wt％的鲸蜡硬脂基醚-20和1.0～4.5wt％的PEG-10聚二甲基硅氧烷；
    所述(e)油脂为0～10wt％的椰子油、0～12wt％的蓖麻油和0～12wt％聚二甲基硅氧烷，优选4～10wt％的椰子油、3～10wt％的蓖麻油和4～12wt％聚二甲基硅氧烷。
  14. 权利要求6-13任一项所述的面膜基质的制备方法，包括以下步骤：
    将所述(a)水性聚氨酯分散体a和所述(b)水性聚氨酯分散体b混匀得到A相；将所述(h)去离子水和所述(c)增稠剂混匀得到B相；将所述(d)乳化剂和所述(e)油脂混匀得到C相；
    在C相存在的情况下，分别将B相和C相加热至70-85℃后混匀，得到B+C相，待温度降至50℃至室温的范围后，加入A相和其他组分，混匀；
    在C相不存在的情况下，室温下将A相和B相混匀，得到A+B相，再加入其他组分，混匀。
  15. 一种面膜或体膜，包含权利要求1-5任一项所述的面膜基质组合物或权利要求6-13任一项所述的面膜基质以及活性物质。
  16. 权利要求15所述的面膜或体膜的制备方法，包括将权利要求1-5任一项所述的面膜基质组合物或权利要求6-13任一项所述的面膜基质与活性物质混合的步骤。
  17. 权利要求1-5任一项所述的面膜基质组合物或权利要求6-13任一项所述的面膜基质或权利要求15所述的面膜或体膜在促进活性物质渗透吸收中的应 用，优选在促进活性物质在皮肤中的渗透吸收中的应用。
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