CN108699385A - surface protection composition - Google Patents

surface protection composition Download PDF

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Publication number
CN108699385A
CN108699385A CN201680082839.1A CN201680082839A CN108699385A CN 108699385 A CN108699385 A CN 108699385A CN 201680082839 A CN201680082839 A CN 201680082839A CN 108699385 A CN108699385 A CN 108699385A
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CN
China
Prior art keywords
composition
polyurethane
acid
group
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201680082839.1A
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Chinese (zh)
Inventor
熊晓辉
A.刘
S.德尔
S.维亚拉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
A Polymer (china) Cosmos Co Ltd
Covestro Polymers China Co Ltd
Original Assignee
A Polymer (china) Cosmos Co Ltd
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Publication date
Application filed by A Polymer (china) Cosmos Co Ltd filed Critical A Polymer (china) Cosmos Co Ltd
Publication of CN108699385A publication Critical patent/CN108699385A/en
Pending legal-status Critical Current

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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
    • A61K8/18—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
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G18/0833—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups together with anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/08—Processes
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08G18/4804—Two or more polyethers of different physical or chemical nature
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Abstract

Pharmaceutical composition is provided, wherein the composition includes polyurethane.Further it is provided that the composition for including polyurethane as drug.It provides for protecting surface to prevent the composition for including polyurethane of potential pollutant.Further it is provided that purposes of the composition comprising polyurethane as surface proofing dust and protecting.It provides for protecting the surface of mankind or animal to prevent the urethane composition of pollutant.There is provided multilayered structure comprising at least two layers of A) and B), middle level A) include polyurethane, middle level B) be different from layer A).The film for including polyurethane of method and offer with various special characteristics for improving the ability that potential pollutant is removed from surface is also provided.

Description

Surface protection composition
The present invention relates to the pharmaceutical compositions comprising polyurethane.The composition comprising polyurethane as drug is also this hair Bright theme.Moreover, it relates to the composition comprising polyurethane as anti-potential pollutant or dust surface protection with The purposes for making them be influenced from potential pollutant, and include the multilayered structure of two layers, wherein at least one layer includes poly- Urethane.The invention further relates to the methods improved from the ability of removal of contaminants.
Particulate matter or PM are the terms for particle present in air, preferably include dust, dirt, cigarette ash, smog and Drop.Particle can for a long time suspend in air.Some particles are sufficiently large or dark to be counted as cigarette ash or smog.Other are such as This is small so that they are each can only to use electron microscope or the detection of PM instrument.
The other pollutants for forming PM are reacted in many artificial and natural origin direct emission PM or discharge in an atmosphere.These Solid and liquid particle are in wide particle size range.
Diameter is less than 10 microns of particle(PM10)Healthy worry is caused, because they may be inhaled and accumulate in respiratory system In and some of which also skin-permeable.The measurement of the particle of these diameters can be provided by optical measurement.Optics Corpuscular counter is mainly used for this purposes, such as laser optical particle counter, is such as spread out according to the laser of ISO 13320-1 It penetrates.Most harmful particle is that diameter is less than those of 2.5 microns, also referred to as PM2.5。PM2.5Particle includes that at least 150 kinds pollutions are empty The mixture of the different chemical product of gas.Harmful gaseous chemicals is normally incorporated in small particles and is converted to harmless particle harmful Particle.Many small molecules(Haptens)The known agglomerate being attached on these PM and form initiation allergy, it is also referred to as potential Pollutant.
These potential pollutants, especially PM10And PM2.5Source be mainly traffic, factory, forest fire and power station. Diameter is less than 2.5 microns of particle(PM2.5)Referred to as " thin " particle and it is believed that causing maximum health risk.It is small due to them Size(About the 1/30 of the mean breadth of human hair), particulate can go deep into skin and lung.But diameter is less than 10 microns of particle (PM10)It is also believed that the health to animals and humans has adverse effect.PM10And PM2.5Mixture often be referred to as " fine dust ".
Especially in a large amount of populations and the cities and towns of a large amount of traffic and factory, fine dust problem becomes to be more and more obvious. Therefore, in many countries, there is PM2.5And PM10The regulations of rate.The World Health Organization(WHO)Air matter has also been issued in 2006 Measure global more new editions in 2005 of guide(WHO/SDE/PHE/OEH/06.02), show PM2.5 10 µg/m3Annual mean, 25 µg/m324 hourly average values, and PM10 20 g/m3Annual mean and 50 μ g/m324 hourly average values.Due to especially most Number industrial area PM amounts increase, and skin irritatin and/or the generation of allergy increase.Therefore, it is necessary to protect the mankind to contact these grains Son.
Purposes of the polyurethane in cosmetic composition has been described.EP 1352642 describes the anionic of dissolving Purposes of the polyurethane in skin care compositions.Polyurethane used preferably comprises the carboxylic acid of 2,2- methylols substitution.It is preferable to use the moon The mixture of ionic polyurethanes and polyacrylate.The property of polyurethane used in embodiment is unknown.Similarly, JP 2005200320 and JP 2006062995 describes the combination of polyacrylate and polyurethane as the receipts for showing at least 20% The purposes of the film forming agent of contracting.WO 2002010243 discloses purposes of the polyurethane in cosmetic applications.Use sulfonic polyester two Alcohol prepares prepolymer.WO 02070577 discloses the purposes that anionic polyurethane is used to prepare skin care and make-up composition.Not yet There are open cosmetics or the specific example of pharmaceutical composition.Polyurethane typically without description as drug.
It is an object of the present invention to provide especially anti-potential pollutants when on the surface for being applied to mankind or animal Composition.
It is a further object of the present invention to provide especially when on the surface for being applied to mankind or animal dust protection composition.
It is a further object of the invention to provide the composition for preventing surface dirty.
It is a further object of the present invention to provide the drugs for preventing the surface of mankind or animal from locally being stimulated by potential pollutant Composition.
It is a further object of the invention to provide the multilayered structure of anti-potential pollutant.
It is a further object of the present invention to provide the sides for improving the ability that potential pollutant is removed from the surface of mankind or animal Method.
It is a further object of the invention to provide preventing the method that fabric surface is polluted by potential pollutant.
Surprisingly, realizing the purpose by using polyurethane or the composition for preferably comprising polyurethane.
Propose the present invention or its(It is one or more)When the element of preferred embodiment, article " one ", "the" and " institute State " it is intended to mean that in the presence of one or more elements.It is that term "comprising", " comprising " and " having " mean inclusiveness and mean That there may be the additional elements in addition to listed elements.
According to the first aspect of the invention, pharmaceutical composition is provided, wherein the composition includes polyurethane.The composition is excellent Choosing is the pharmaceutical composition for being alternatively makeup reason and having applied, and wherein the composition includes polyurethane.Drug and/or cosmetics Composition should also cover the dermatological compositions comprising polyurethane.
Include the body surface that the composition of polyurethane has protection mankind or animal as drug, as skin, scalp, Hair or other surfaces to prevent potential pollutant ability.Potential pollutant according to the present invention is possible be to touching these grains Any material that the body of the mankind or animal of son causes damages.The most air-borne transmission of these materials.The reality of potential pollutant Example is toxic gas, particulate matter and indoor pollutant.The example of toxic gas is sulfur dioxide, nitrogen oxide, photochemical derivatization Ozone and volatile organic compounds.Particulate matter(PM)Preferred embodiment be inhalable particle PM10, inhalable particle PM2.5, example Such as generate active oxygen(ROS)Organic compound and/or metal(Iron, copper, zinc and heavy metal)Particle carrier.Except they make At certain toxic effects outside, heavy metal, which has to reduce, resists the cell of free radical the active Xing Zhi &#91 of means;See, for example, R. S. Dwivedi, J. Toxicol. Cut. & Ocular Toxical. 6(3), 183-191 (1987)].Therefore, Heavy metal aggravates the toxic effect of gaseous pollutant by reducing the effect of nature mean of defense, and causes cell senescence phenomenon Acceleration.This is especially suitable for direct and Long Term Contact external environment keratin material, especially skin, scalp and hair. The example of indoor pollutant is smoke from cigarette, the smog from Indoor Combustion and the carbon dust from printing machine.As already mentioned above, gas State pollutant can be incorporated on particle, and particulate matter is become pollutant.PM is also been described as and the present invention Just because of this Relevant potential pollutant.
Preferably, composition of the invention has substantially reduces PM on the surface of composition for having applied the present invention2.5With PM10Ability.It still preferably, can be by PM by applying the pharmaceutical composition of the present invention2.5And/or PM10Value, is preferably touched The PM of human or animal subject10And/or PM2.5Population, which is reduced, is based on original PM10And/or PM2.5Gauge is more than 50%, or preferably More than 70%, or it is more than 80%, or is more than 90%.This preferably means that PM present in the air for preventing mankind or animal from exposing2.5 And/or PM10Concentration is more than 50%, more preferably greater than 70%, and most preferably greater than 80% contacts with mankind or animal.Herein, art Language " contact " preferably refers to adhering to and/or being absorbed on the skin, scalp and/or hair of mankind or animal and/or enter the mankind Or in the respiratory system of animal.
Including the composition as cosmetics of polyurethane has the body surface for preventing mankind or animal, such as skin, head Skin, the dirty ability of hair or other surfaces.According to the present invention, it means that simple cosmetic composition is preferably prevented from the mankind Or PM present in the air of animal exposure2.5And/or PM10Concentration is more than 50%, more preferably greater than 70%, most preferably greater than 80% It is contacted with mankind or animal.But pharmaceutical composition prevents mankind or animal by the harm as caused by the particle, and make up Product composition is only used for preventing surface dirty from cosmetics angle.
The drug and/or cosmetic composition are preferably dermatological compositions.
Drug, cosmetics or dermatological compositions are not differentiated between below.If not making differentiation, term between them " composition " should cover pharmaceutical composition and cosmetic composition and dermatological compositions.
When being applied in at least part on the surface of mankind or animal, composition of the invention provides anti-tablet Son, in particular, for example PM10And PM2.5The pollutant as mentioned above of particulate forms at least partly with the surface of body The ability of contact.In addition, there is the composition the when of being incorporated in the composition without using the present invention can contact the composition user Particle ability.After in the case where surface is exposed to particle, it is easy to wash off the particle of combination together with the composition.This effect is aobvious Show in Fig. 5 a As described in detail below, 5b and 6.
The optional self energy of polyurethane present in composition according to the present invention provides barrier function to potential pollutant and appoints What polyurethane.
The polyurethane preferably has the structure that can especially form a film when being applied on surface.It is formed by polyurethane thin Film preferably has barrier function to particle.The film be preferably prevented from 50 to 100% or preferably 70 to 100% or preferably 90 to 100% or It is preferred that 100% diameter is contacted less than 10 μm of particle with the surface of mankind or animal, wherein these percentage be based on the mankind or The population of animal exposure.The film is preferably prevented from 50 to 100% or preferably 70 to 100% or preferably 90 to 100% or preferably 100% Diameter contacted with the surface of mankind or animal higher than 5 μm of particle, wherein these percentage are based on existing population.It should Film be preferably prevented from 50 to 100% or preferably 70 to 100% or preferably 90 to 100% or preferably 100% diameter higher than 2.5 μm Particle is contacted with the surface of mankind or animal, and wherein these percentage are based on existing population.The diagram of this effect is visible In Fig. 8, wherein the film formed by polyurethane in side carbon pollution.It shows in fig. 8, none infiltration of carbon black particle penetrates The film made of polyurethane.The details of this film is provided in attached drawing description section below.
According to a preferred embodiment of the invention, the composition includes the gross mass meter 1 to 20 based on the composition The polyurethane of the amount of weight %.
Preferably, the composition includes the amount of 2 to the 15 weight % of gross mass meter based on the composition, or preferably 3 to 10 weights The polyurethane of the amount of amount % or the preferably amount of 4 to 7 weight %.
Preferably, the drug and/or cosmetic composition include at least one can by make one or more water-insolubles, The polyurethane prepolymer A of nonaqueous dispersion, isocyanate-functional) at least one amino-functional compounds B) react obtain it is poly- Urethane.
In addition, the present invention provides drug and/or cosmetic composition, it includes at least one can be one or more by making Substantially without the ionic group and not polyurethane prepolymer A of the isocyanate-functional of ionogenic group) and one or more ammonia Base functional compound B) react the polyurethane obtained.
In the present invention, term " water-insoluble, nonaqueous dispersion polyurethane prepolymer " particularly relates to be made according to the present invention Solubility of the prepolymer at 23 DEG C in water is less than 10 grams per liters, more preferably less than 5 grams per liters, and the prepolymer is at 23 DEG C Under in water, do not generate the dispersion of settlement stability in deionized water especially.In other words, it is attempting to be dispersed in water When, which settles.
Polyurethane prepolymer A used) preferably there is terminal isocyanate group group, i.e., isocyanate groups are in the prepolymer The end of the chain.All end of the chains of polymer particularly preferably have isocyanate groups.
In addition, polyurethane prepolymer A used) preferably there is no ionic group and no ionogenic group substantially(It can be formed Ionic group), i.e. the content of ionic group and ionogenic group is suitably below 15 milliequivalent/100 gram polyurethane prepolymer A), Preferably shorter than 5 milliequivalents, especially preferably less than 1 milliequivalent are very particularly preferably less than 0.1 milliequivalent/100 gram polyurethane prepolymer Object A).
In a preferred embodiment of the composition, amino-functional compounds B) it is selected from primary and/or secondary amine and/or two Amine.Particularly, amino-functional compounds B) include at least one diamines.
In a preferred embodiment, amino-functional compounds B) at least one is selected from ionic group or ion source The amino-functional compounds B2 of group) and it is at least one without ionic group or the amino-functional compounds B1 of ionogenic group).
In a particularly preferred embodiment of the present invention, at least one amino-functional compounds B) include extremely It is few a kind of with ionic group and/or ion source(Form ion)The amino-functional compounds B2 of group).Ionic group used And/or ionogenic group is particularly preferably sulfonate or sulfonic acid group, more preferably sodium group.
In the embodiment of present invention further optimization, amino-functional compounds B) both included it is at least one have from The amino-functional compounds B2 of subbase group and/or ionogenic group), and include at least one there is no ionic group or ion source base The amino-functional compounds B1 of group).
In addition, polyurethane is to have at least two in the present invention, preferably at least three following acid esters containing urethane groups Repetitive unit polymerizable compound:
Preferably include that also there is those of repetitive unit containing urea groups polyurethane as follows due to preparing:
It is as especially in isocyanate-terminated prepolymer A) at least one amino-functional compounds B) react in shape At.
The composition is preferably aqueous, i.e., polyurethane is in a dispersed form(It is generally not dissolved form)Existing aqueous combination Object.In general, any other liquid medium that may be present is removed, such as outside solvent, based in composition according to the present invention Liquid dispersion medium total amount meter, water forms the main component of the decentralized medium(>50 weight %), and in some cases Constitute unique liquid dispersion medium.
Preferably there is the composition the total weight based on the composition to be less than 80 weight %, more preferably less than 55 weight %, Even more preferably it is less than the volatile organic compounds of 40 weight %(VOC)Content.
The aqueous polyurethane dispersion for being used to prepare composition according to the present invention preferably has based on the aqueous polyurethane The total weight of dispersion is less than 10 weight %, more preferably less than 3 weight %, is even more preferably less than the volatile organic of 1 weight % Close object(VOC)Content.
In the present invention volatile organic compounds is measured especially through gas chromatographic analysis(VOC)Content.
The polyurethane prepolymer of the isocyanate-functional of water-insoluble and nonaqueous dispersion used according to the invention is preferred Substantially there is no ionic group and no ionogenic group.
In water insoluble and/or to lack dispersibility in water refer to the deionized water for being not added with surfactant. In the present invention, this refers to ionic group and/or ion source(Form ion)Group, especially such as anionic group, such as carboxylate radical Or the ratio of sulfonate radical or cation group is less than 15 milliequivalent/100 gram polyurethane prepolymer A), preferably smaller than 5 milliequivalents are special Not You Xuan little Yu 1 milliequivalent, very particularly preferably be less than 0.1 milliequivalent/100 gram polyurethane prepolymer A).
In the case of acid ion group and/or ionogenic group, the acid value of the prepolymer is suitably below 30 mg KOH/g prepolymers, preferably shorter than 10 mg KOH/g prepolymers.Acid value refers to needed for 1 gram of sample studied of neutralization with milligram The potassium hydroxide quality of meter(It is measured according to DIN EN ISO 211).The acid of neutralization, i.e., corresponding salt is naturally without acid value or tool There is the acid value of reduction.According to the present invention, the acid value of corresponding free acid is conclusive herein.
As explained below, be used to prepare the prepolymer A of polyurethane) preferably can by make selected from polyether polyol, The one or more polyalcohols and polyisocyanic acid of polycarbonate polyol, polyether polycarbonate polyalcohol and/or polyester polyol Ester reaction obtains.
Polyurethane present in the composition includes correspondingly --- via prepolymer A) --- preferably at least one kind is selected from The sequence of polyethers, makrolon, polyether-polycarbonate and polyester sequences.According to the present invention, this especially means that the polyurethane contains There is the repetitive unit of ether-containing group and/or carbonate group or ester group.The polyurethane can for example contain only polyether sequence or only Sequence containing makrolon contains only polyester sequences.But they can also have both polyethers and makrolon sequence, following article is more Detailed description is for example formed during preparing polycarbonate polyol using polyetherdiol.In addition, they can have it is as follows The polyether-polycarbonate sequence by using polyether-polycarbonate polyalcohol to generate is described in more detail in text.
Particularly preferred polyurethane is by using polyhydroxyl polyether polyalcohol and/or polymerization polycarbonate polyol and/or gathers Ether-polycarbonate polyol or polyester polyol obtain, these polyalcohols respectively have preferably approximately 400 to about 6000 g/ The number-average molecular weight of mol(In the case of molecular weight data herein and below, by tetrahydrofuran at 23 DEG C it is opposite It is measured in the gel permeation chromatography of polystyrene standards).At least one of these polyalcohols is in polyurethane or polyurethane prepolymer Use in the preparation process of object is caused due to the reaction to polyisocyanates in the corresponding molecular weight with these sequences Corresponding polyethers and/or makrolon and/or polyether-polycarbonate sequence or polyester sequences are formed in polyurethane.Particularly preferably Be by polyhydroxyl polyether glycol and/or polymerization polycarbonate glycol and/or polyether-polycarbonate polyalcohol with linear structure Or the polyurethane that polyester polyol obtains.
Polyurethane according to the present invention is preferably substantially linear molecule, but can also be branched, this is less preferably.
It is preferred that the number-average molecular weight of polyurethane used according to the invention is such as about 1000 to 200000, preferably 5000 To 150000.
Polyurethane present in the composition is preferably especially added in the composition with aqueous dispersion.
As the composition a part or want preferred polyurethane or dispersions of polyurethanes used according to the invention can be such as Lower acquisition
A isocyanate functional prepolymer's object of following ingredients) is prepared
A1) organic multiple isocyanate,
A2) polymerized polyalcohol preferably has 400 to 8000 g/mol(Herein and for molecular weight data hereafter, pass through It is measured relative to the gel permeation chromatography of polystyrene standards at 23 DEG C in tetrahydrofuran), more preferable 400 to 6000 G/mol, the number-average molecular weight of particularly preferred 600 to 3000 g/mol and preferably 1.5 to 6, more preferable 1.8 to 3, particularly preferably 1.9 to 2.1 OH degrees of functionality,
A3) optionally, there is the hydroxy functional compound of the preferably molecular weight of 62 to 399 g/mol, and
A4) optionally, non-ionic hydrophilized dose
With
B) and then their some or all of dissociateive NCOs is made to roll into a ball and at least one amino-functional compounds B), such as primary and/or Secondary amine and/or diamine reactant.
Polyurethane used according to the invention is preferably in step B) before, among or be dispersed in water later.
In step B) in particularly preferably carried out under chain extension with a kind of diamines or reacting for two or more diamines.At this Aspect can additionally incorporate monofunctional amines as chain terminating agent to control molecular weight.
As component B), no ionic group or ionogenic group can be especially used, such as anionic hydrophiling group Amine(Following component B1), and can use with ionic group or ionogenic group, especially such as anionic hydrophiling The amine of group(Following component B2).
Preferably, the prepolymer reaction step B) in, make component B1) and component B2) mixture react.By making With component B1), high molecular weight can be established, and the viscosity of the isocyanate functional prepolymer's object prepared before is not increased to resistance Hinder the degree of processing.By using component B1) and combination B2), optimum balance between hydrophily and chain length may be implemented simultaneously Thus pleasant dermal sensation is established.
The polyurethane preferably has anionic group, preferably sulfonate group.Via in step B) in react amine component B2) these anionic groups are introduced into polyurethane.In addition polyurethane used according to the invention optionally has is used for hydrophiling Nonionic components.Particularly preferably there is only sulfonate groups to be used for hydrophiling in polyurethane used according to the invention;It Via as component B2) corresponding diamines be introduced into polyurethane.
In order to realize good sedimentation stability, measured by laser correlation spectroscopy after being diluted with deionized water(Instrument Device:Malvern Zetasizer 1000, Malvern Inst. Limited)The special dispersions of polyurethanes the equal grain of number Degree is preferably smaller than 750 nm, particularly preferably less than 500 nm.
It is preferred for preparing the solid content of the dispersions of polyurethanes of the composition being usually the total of the dispersions of polyurethanes 10 to 70 weight % of weight, preferably 30 to 65 weight %, particularly preferred 40 to 60 weight %.By by the sample weighed at 125 DEG C Under be heated to constant weight, determine solid content.Under constant weight, by the way that sample is re-weighed calculating solid content.
These dispersions of polyurethanes preferably there is the total weight based on the dispersions of polyurethanes to be less than 5 weight %, especially Preferably smaller than 0.2 weight %'s is not bonded organic amine.Content in the composition is correspondingly also lower.
Component A1) Suitable polyisocyanates especially this as it is well known by persons skilled in the art have be greater than or equal to Aliphatic series, aromatics or the alicyclic polyisocyanates of 2 NCO degrees of functionality.
The example of such suitable polyisocyanates is 1,4- fourths diisocyanate, 1,6- hexamethylene diisocyanates (HDI), isophorone diisocyanate(IPDI), 2,2,4- and/or 2,4,4- trimethyl hexamethylene diisocyanates, isomery Double-(4,4'Isocyanatocyclohexyl) methane or its mixture, 1,4- hexamethylenes two with any required content of isomer it is different Cyanate, 4- isocyanatomethyl -1,8- octane diisocyanates(Nonane triisocyanate), 1,4- phenylene diisocyanates, 2,4- and/or 2,6- toluene di-isocyanate(TDI)s, 1,5- naphthalene diisocyanates, 2,2 '-and/or 2,4 '-and/or 4,4 '-diphenyl Methane diisocyanate, 1,3- and/or bis- (the 2- isocyanato- propyl- 2- yls) benzene of 1,4-(TMXDI), bis- (the isocyanos of 1,3- Close methyl) benzene(XDI)Caproic acid Arrcostab is closed with the 2,6- diisocyanate roots with C1-C8- alkyl(Lysine diisocyanate).
In addition to above-mentioned polyisocyanates, can also proportionally it use with urea diketone, isocyanuric acid ester, carbamic acid The modification with >=2 degree of functionality of ester, allophanate, biuret, formimidoyl oxadiazine diketone Huo oxadiazine triketone structures Diisocyanate and their mixture.
Preferably only isocyanate groups of aliphatic series or alicyclic bonding or with their mixture and 2 to 4, It is preferred that 2 to 2.6, particularly preferred 2 to 2.4, the very particularly preferably class described above of the average NCO functionality of 2 mixture The polyisocyanates or polyisocyanate mixtures of type.
In A1) in particularly preferably use hexamethylene diisocyanate, isophorone diisocyanate or isomery bis- (4,4 '-isocyanatocyclohexyl) methane and above-mentioned diisocyanate mixture.
In A2) in, using with preferably 400 to 8000 g/mol, more preferable 400 to 6000 g/mol, particularly preferred 600 To the number-average molecular weight M of 3000 g/molnPolymerized polyalcohol.They are non-preferably with 1.5 to 6, particularly preferred 1.8 to 3 Often particularly preferred 1.9 to 2.1 OH degrees of functionality.
Term " polymerization " polyalcohol particularly relates to the polyalcohol according to the present invention has at least two, more preferably at least three A repetitive unit to link together.
Such polymerized polyalcohol is that itself known polyester polyol, polyacrylate in polyurethane coating technology are more First alcohol, polyurethane polyol, polycarbonate polyol, polyether polyol, polyester polyacrylate polyalcohol, polyurethane polyureas propylene Acid esters polyalcohol, polyurethane polyureas ester polyol, polyurethane polyureas ethoxylated polyhydric alcohol, polyurethane polycarbonate polyalcohol and the poly- carbonic acid of polyester Ester polyol.They can be used for A2 independently or in the form of with mutual any required mixture).
It is preferable to use polyester polyol be two-and optional three-and tetrahydroxylic alcohol and two-and optional three-and tetrabasic carboxylic acid or hydroxyl The condensation polymer known per se of yl carboxylic acid or lactone.Instead of the polycarboxylic acid that dissociates, corresponding multi-carboxy anhydride or low-carbon can also be used The corresponding polycarboxylate of alcohol prepares the polyester.
The example of suitable glycol is ethylene glycol, butanediol, diethylene glycol, triethylene glycol, ployalkylene glycol, such as poly- second two Alcohol and 1,2-PD, 1,3-PD, butanediol (1,3), butanediol (Isosorbide-5-Nitrae), hexylene glycol (1,6) and isomers, new penta Glycol or 3-hydroxypivalic acid neopentyl glycol ester, wherein hexylene glycol (1,6) and isomers, butanediol (Isosorbide-5-Nitrae), neopentyl glycol or hydroxyl Pivalic acid neopentyl glycol ester is preferred.In addition, polyalcohol, such as trimethylolpropane, glycerine, antierythrite, pentaerythrite, three Methylol benzene or three hydroxyl ethyl ester of isocyanuric acid are also preferred polyalcohol.
Preferred dicarboxylic acids is selected from phthalic acid, M-phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, hexahydro Phthalic acid, cyclohexane cyclohexanedimethanodibasic, adipic acid, azelaic acid, decanedioic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, richness Horse acid, itaconic acid, malonic acid, suberic acid, 2- methylsuccinic acids, 3,3- diethyl glutarates and/or 2,2- dimethyl succinates Or in which at least two mixture.Corresponding acid anhydrides can also be used as acid source.
If the average functionality for the polyalcohol to be esterified is more than 2, monocarboxylic acid, such as benzoic acid in addition can also be used in conjunction with With hexane formic acid.
Preferred acid is the aliphatic series or aromatic acid of the above-mentioned type.What it is particularly preferable as acid is adipic acid, M-phthalic acid And phthalic acid.
The hydroxycarboxylic acid that the reactant in the preparation of the polyester polyol with terminal hydroxy group can be collectively served as is such as hydroxyl Caproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxy stearic acid etc..Suitable lactone is caprolactone, butyrolactone and homologue.Preferably It is caprolactone.
It is used to prepare the preferred ingredient A2 of polyurethane) it is the polyester polyol that number-average molecular weight is 600 to 3000 g/mol, It is based particularly on aliphatic carboxylic acid and aliphatic polyol, is based particularly on adipic acid and aliphatic alcohol, such as hexylene glycol and/or neopentyl glycol Aliphatic polyester polylol.
It can also use number-average molecular weight MnFor preferably 400 to 8000 g/mol, the preferably tool of 600 to 3000 g/mol There is the makrolon of hydroxyl, preferably polycarbonate glycol is as component A2).These can be by making carbonic acid derivative, such as carbonic acid two Phenyl ester, dimethyl carbonate or phosgene and polyalcohol, preferred diol reaction obtain.
The example of such glycol be ethylene glycol, 1,2- and 1,3- propylene glycol, 1,3- and 1,4- butanediols, 1,6- oneself two The bis- methylol hexamethylenes of alcohol, 1,8- ethohexadiols, neopentyl glycol, 1,4-, 2- methyl-1,3-propanediols, 2,2,4- trimethyls penta 2 Alcohol -1,3, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, bisphenol-A and lactone-modified the above-mentioned type glycol or Wherein at least two kinds of any mixture.
The diol component preferably comprises the hexylene glycol of 40 to the 100 weight % of total weight based on diol component, preferably 1,6-HD and/or hexane diol derivatives.Such hexane diol derivatives are preferably based on hexylene glycol and are gone back in addition to OH end groups With ester or ether group.Such derivative can be by making hexylene glycol be reacted with excessive caprolactone or being etherified production certainly by hexylene glycol Raw two-or three hexylene glycols obtain.
Instead of or in addition to other than pure polycarbonate glycol, in A2) in can also use polyether-polycarbonate glycol.
Makrolon with hydroxyl is preferably with linear structure.
Polyether polyol can also be used as component A2).
For example, can such as pass through the polymerization of tetrahydrofuran(By cationic open loop)Obtain itself in polyurethane chemistry The polytetramethylene glycol polyethers known is especially suitable.
Equally suitable polyether polyol is styrene oxide, ethylene oxide, propylene oxide, epoxy butane and/or table chlorine Alcohol adds to the addition compound product known per se in two functions or multifunctional starter molecules.Therefore, poly- alkane can especially be used Glycol is supportted, such as polyethylene glycol, polypropylene glycol and/or polytetramethylene glycol, especially there is those of preferred molecular weight described above.
The available starter molecules for being suitable for polymerization are according to all compounds known in the art, such as water, fourth Base diethylene glycol (DEG), glycerine, diethylene glycol, trimethylolpropane, propylene glycol, D-sorbite, ethylenediamine, triethanolamine, 1,4- fourths two Alcohol.
A2 the particularly preferred component in) is polytetramethylene glycol polyethers and polycarbonate polyol and its mixture, especially excellent Select polytetramethylene glycol polyethers.
In a preferred embodiment of the invention, component A2) be correspondingly:
Include the mixture of at least one polyether polyol and at least one polycarbonate polyol,
Including the mixture of more than one polyether polyol or two or more polyether polyol with different molecular weight Mixture, especially poly- (butanediol) polyether polyol(Such as HO- (CH2-CH2-CH2-CH2-O)x-H),
Include the mixture of more than one polyether polyol and at least one polycarbonate polyol, and
It is particularly preferred that number-average molecular weight be 600 to 3000 g/mol polyester polyol, be based particularly on aliphatic carboxylic acid and Aliphatic polyol is based particularly on adipic acid and aliphatic alcohol, such as hexylene glycol and/or the aliphatic polyester polylol of neopentyl glycol,
Wherein component A) it is basic without ionic group and no ionogenic group according to definition.
As component A3), it can be on demand using the described preferred of 66 to 399 mol/g with most 20 carbon atoms The polyalcohol of molecular weight ranges, especially non-polymeric polyalcohol, as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-PD, 1,3- propylene glycol, 1,4- butanediols, 1,3 butylene glycol, cyclohexanediol, 1,4 cyclohexane dimethanol, 1,6-HD, new penta 2 Alcohol, hydroquinore dihydroxyethylether, bisphenol-A(Bis- (4- hydroxyphenyls) propane of 2,2-), hydrogenated bisphenol A(2,2- bis- (4- hydroxy-cyclohexyls) Propane), trimethylolpropane, trimethylolethane, glycerine, mixture needed for pentaerythrite and they any.
The esterdiol of shown molecular weight ranges is also suitable, such as ε-hydroxycaproic acid α-hydroxyl butyl ester, gamma-hydroxybutyric acid ω-hydroxyl Hexyl ester, adipic acid (beta-hydroxyethyl) ester or bis- (beta-hydroxyethyl) esters of terephthalic acid (TPA).
In addition, as component A3), monofunctional isocyanates reactivity hydroxy-containing compounds can also be used.Such list The example of functional compound is ethyl alcohol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono butyl base Ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol list propyl ether, propylene glycol list Butyl ether, dipropylene glycol mono butyl base ether, tripropylene glycol monobutyl base ether, 2-Ethylhexyl Alcohol, 1- octanols, DODECANOL, 1-, 1- 16 Alkanol.
In a preferred embodiment of the invention, polyurethane used includes the component A3 less than about 10 weight %), The preferably smaller than component A3 of 5 weight %), the gross mass meter based on polyurethane, does not use component A3 more preferably in each case) Prepare polyurethane.
In order to prepare polyurethane, the non-ionic hydrophilized of one or more special isocyanate-reactives is preferably optionally employed Agent is as component A4).As component A4) hydrophilic agent be especially different from component A2) and A3).
As component A4) suitable non-ionic hydrophilized compound be for example with isocyanate-reactive group, such as The polyoxyalkylene ether of hydroxyl, amino or thiol group.It preferably such as can be by the alkoxylate of suitable starter molecule with this What mode known to body obtained has per molecule statistical average 5 to 70, the monohydroxy function of preferably 7 to 55 ethylene oxide units Polyoxyalkylene polyethers alcohol(Such as in Ullmanns Encyclop die der technischen Chemie, the 4th edition, Volume 19, in the 31-38 pages of Verlag Chemie, Weinheim).These are pure polyethylene oxide ether or mixing polyoxyalkylene Ether, wherein they contain the molar amount based on existing all epoxy alkane units at least 30 moles of %, preferably at least 40 moles of % Ethylene oxide unit.
Particularly preferred non-ionic compound is that have 40 to 100 moles of % ethylene oxide units and 0 to 60 mole of % epoxy The simple function mixing polyoxyalkylene polyethers of oxide unit.
Suitable starter molecule for such non-ionic hydrophilized dose is especially saturated single methanol, such as methanol, ethyl alcohol, just Propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, isomery amylalcohol, hexanol, octanol and nonyl alcohol, Decanol, n-dodecane alcohol, N-tetradecanol, cetyl alcohol, n-octadecane alcohol, cyclohexanol, isomery methyl cyclohexanol or methylol hexamethylene, 3- ethyls- 3- hydroxymethyl-oxetanes or tetrahydrofurfuryl alcohol, diethylene glycol monoalky lether, such as diethylene glycol monobutyl ether, unsaturated alcohol, It is fragrant and mellow such as allyl alcohol, 1,1- dimethallyls alcohol or oleyl alcohol, such as phenol, isomery cresols or methoxyl group phenol, aromatic grease group alcohol, as benzylalcohol, Anise alcohol or cinnamyl alcohol, secondary monoamine, such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutyl amine, bis- (2- ethylhexyls) Amine, N- methyl-and N- Ethylcyclohexylamines or dicyclohexylamine and heterocyclic secondary, such as morpholine, pyrrolidines, piperidines or 1H- pyrroles Azoles.Preferred starter molecules are the saturation single methanols of type illustrated above.Particularly preferably using diethylene glycol monobutyl ether or N-butanol is as starter molecules.
Oxyalkylene especially ethylene oxide and propylene oxide suitable for alkoxylation, they can be with any required Sequence is used for alkoxylation as a mixture.
Component B) it is preferably selected from primary or secondary amine and/or diamines.Itself particularly including diamines.
As component B), no ionic group or ionogenic group can be especially used, such as anionic hydrophiling group Amine(Following component B1)), and can use with ionic group or ionogenic group, especially such as anionic hydrophiling The amine of group(Following component B2)).Preferably, in the step B of the reaction of the prepolymer) in, make component B1) and component B2) Mixture reacts.
It is, for example, possible to use organic diamine or polyamines, such as 1,2- ethylenediamines, 1,2- and 1,3- diaminopropanes, Isosorbide-5-Nitrae- The isomery of diaminobutane, 1,6- diamino hexanes, isophorone diamine, 2,2,4- and 2,4,4- trimethylhexamethylenediamines Body mixture, 2- methyl pentamethylene diamines, diethylenetriamines, 4,4- diamino-dicyclohexyl methanes, hydrazine hydrate and/or two Methyl ethylenediamine is as component B1).
In addition it is also possible to using also there is secondary amino group in addition to primary amino group or remove amino(Primary or secondary)Also there is OH groups outside Compound is as component B1).The example is primary/secondary amine, such as diethanol amine, 3- amino -1- methylamino-propanes, 3- amino -1- Ethylamino propane, 3- amino -1- Cyclohexylaminos propane, 3- amino -1- methylaminos butane, alkanolamine, such as N- amino second Ethylethanolamine, ethanol amine, 3- aminopropanols, neopentyl alcohol amine.
In addition it is also possible to using monofunctional isocyanates reactive amine compound as component B1), such as methyl amine, second Base amine, propyl amine, butylamine, octyl amine, lauryl amine, stearylamine, different nonyl epoxide propyl amine, dimethyl amine, diethylamide, dipropyl Base amine, dibutylamine, N- dimethylaminopropyls amine, diethyl (methyl) aminopropyl amine, morpholine, piperidines and theirs is suitable The single ketones imines of substitutive derivative, the amidoamines of di-primary amine and monocarboxylic acid, di-primary amine(monoketime), primary/tertiary amine, such as N, N- dimethylaminopropyl amine.
As component B1), it is preferable to use 1,2- ethylenediamine, bis- (4- aminocyclohexyls) methane, 1,4-Diaminobutane, different Isophoronediamine, ethanol amine, diethanol amine and diethylenetriamines or in which at least two mixture.
Component B) preferably include at least one component B2).As component B2) suitable anionic hydrophiling compound Preferably comprise sulfonic acid or sulfonate groups, particularly preferred sodium group.As component B2) suitable anionic hydrophiling Compound is especially mono- and diamino sulfonic acid alkali metal salt.The example of such anionic hydrophilic agent is 2- (2- amino Ethylamino) ethanesulfonic acid, ethylenediamine propyl sulfonic acid or butyl sulfonic acid, 1,2- or 1,3- propane diamine-β-ethanesulfonic acid or taurine Salt or in which at least two mixture.In addition it is possible to use the Cyclohexylamino propane sulfonic acid from WO-A 01/88006 (CAPA)Salt as anionic hydrophilic agent.
Particularly preferred anionic hydrophilic agent B2) it is to contain sulfonate group as ionic group and two amino Those, such as 2- (2- aminoethylaminos) ethanesulfonic acid and 1, the salt of 3- propane diamine-β-ethanesulfonic acid.
According to a preferred embodiment of the invention, at least one amino-functional compounds B) include at least one Amino-functional compounds B2 with ionic group and/or ionogenic group), preferably 2- (2- aminoethylaminos) ethanesulfonic acid And/or its salt.
Further preferred embodiment according to the present invention, at least one amino-functional compounds B) include at least It is a kind of without ionic group and/or the amino-functional compounds B1 of ionogenic group), preferably without ionic group and/or ion The diamines of source group.
The polyurethane preferably comprises at least a sulfonate group.
Optionally, component B2) in anionic group can also be carboxylate radical or carboxylic acid group.Component B2) it is then preferred Selected from diamino monocarboxylic acid.But this embodiment is less preferable, and because of the component B2 based on carboxylic acid) it must be with higher concentration It uses.
Further preferred embodiment according to the present invention, prepolymer A) it can be by making selected from polyether polyol, poly- carbon Acid esters polyalcohol, one or more polyalcohols of polyether-polycarbonate polyalcohol and/or polyester polyol and one or more more Isocyanates reaction obtains.
For hydrophiling, anionic hydrophilic agent B2 can also be used) and non-ionic hydrophilic agent A4) mixing Object.
In a preferred embodiment for being used to prepare the special dispersions of polyurethanes, component A1) to A4) and B1) extremely B2 it) is used with following amounts, 100 weight % is added up to always wherein respectively estimating one's own ability:
The component A1 of 5 to 40 weight %),
The A2 of 55 to 90 weight %),
The sum of the component A3 of 0.5 to 20 weight %) and/or B1),
The component A4 of 0.1 to 25 weight %) and/or the sum of B2), wherein be based on component A1) to A4) and B1) to B2) total amount Meter, particularly preferably using the anionic of 0.1 to 5 weight % or potential anionic hydrophilic agent B2).
In a particularly preferred embodiment for being used to prepare the special dispersions of polyurethanes, component A1) to A4) and B1) to B2) it is used with following amounts, 100 weight % are added up to always wherein respectively estimating one's own ability:
The component A1 of 5 to 35 weight %),
The A2 of 60 to 90 weight %),
The sum of the component A3 of 0.5 to 15 weight %) and/or B1),
The component A4 of 0.1 to 15 weight %) and/or the sum of B2), wherein be based on component A1) to A4) and B1) to B2) total amount Meter, particularly preferably using the anionic of 0.2 to 4 weight % or potential anionic hydrophilic agent B2).
In an embodiment very particularly preferably for being used to prepare the special dispersions of polyurethanes, component A1) extremely A4) and B1) to B2) it is used with following amounts, 100 weight % are added up to always wherein respectively estimating one's own ability:
The component A1 of 10 to 30 weight %),
The A2 of 65 to 85 weight %),
The sum of the component A3 and/or B1 of 0.5 to 14 weight %),
The component A4 of 0.1 to 13.5 weight %) and/or the sum of B2), wherein it is based on component A1) to A4) and B1) to the total amount of B2 Meter, particularly preferably using 0.5 to 3.0 weight % come from B2) anionic or potential anionic hydrophilic agent.
The preparation of dispersions of polyurethanes can carry out in one or more stages in homogeneous, or in the feelings of reaction of high order Under condition, carried out in dispersed phase sometimes.In A1) to A4) complete or partial addition polymerization after, preferably disperseed, emulsified or dissolved Step.Hereafter, further addition polymerization or modification optionally occur in dispersed phase.
Herein, all methods well known in the prior art, such as prepolymer mixing method, acetone method or molten can be used Body dispersion method prepares dispersions of polyurethanes.It is preferable to use acetone methods.
In order to be prepared according to acetone method, the polyurethane for being used to prepare isocyanate-functional is usually initially introduced completely or partially The component A2 of prepolymer) to A4) and polyisocyanate component A1), and optionally with it is miscible with water but to isocyanate groups in lazy Property solvent dilution, and be heated to 50 to 120 DEG C of temperature.In order to improve the rate of isocyanates addition reaction, can use Known catalyst in polyurethane chemistry.
Suitably solvent is conventional aliphatic ketone function solvent, and such as acetone, 2- butanone, they can not only start in preparation When be added, also can optionally portioning be added later.Preferably acetone and 2- butanone, particularly preferably acetone.It can also add Enter other solvents of isocyanate-free reactive group, but not preferably.
Then the metered A1 not being added when the reaction starts) to A4) any ingredient.
By A1) to A4) during prepare polyurethane prepolymer, isocyanate groups and isocyanate-reactive group Quantity than be usually 1.05 to 3.5, preferably 1.1 to 3.0, particularly preferred 1.1 to 2.5.
Component A1) to A4) reactive moieties or carry out completely to generate prepolymer, but preferably completely carry out.Thus to obtain Diluent free or in the solution containing free isocyanate groups group polyurethane prepolymer.
For potential anionic group to be partially or completely converted in the neutralization procedure of anionic group, using alkali, Such as tertiary amine, such as have 1 to 12 in each alkyl, preferably 1 to 6 carbon atom, the trialkyl of particularly preferred 2 to 3 carbon atoms Amine, or very particularly preferably alkali metal base, such as corresponding hydroxide.
It is preferable to use organic amines.
Available neutralizer is preferably inorganic base, such as ammonia spirit or sodium hydroxide or potassium hydroxide.
Preferably sodium hydroxide and potassium hydroxide.
The amount of the alkali(quantitative amount)For 50 to 125 moles of % of the amount for the acidic group to be neutralized, preferably 70 To 100 moles of %.Neutralization can also be carried out at the same time with the dispersion by the disperse water containing neutralizer.
Hereafter, in further processing step, if this not yet occurs or only part occurs, by aliphatic ketone, such as acetone Or 2- butanone dissolving gained prepolymer.
Component A1) to A4) reactive moieties or carry out completely to generate prepolymer, but preferably completely carry out.Thus to obtain Diluent free or in the solution containing free isocyanate groups group polyurethane prepolymer.
In stage B) in chain extension process in, make NH2And/or the residual isocyanate of NH- functional components and the prepolymer Group reacts.It is preferred that chain extension/chain termination is carried out before dispersion in water.
Component B suitable for chain extension) it is especially organic diamine or polyamines B1), it is preferably selected from ethylenediamine, 1,2- and 1,3- bis- Aminopropane, 1,4- diaminobutanes, 1,6- diamino hexanes, isophorone diamine, 2,2,4- and 2,4,4- trimethyls six are sub- Isomer mixture, 2- methyl pentamethylene diamines, diethylenetriamines, the diamino-dicyclohexyl methane and two of first man diamines Methyl ethylenediamine or in which at least two mixture.
In addition it is also possible to using also there is secondary amino group in addition to primary amino group or remove amino(Primary or secondary)Also there is OH groups outside Compound B-11).Compound B-11) it is preferably selected from diethanol amine, 3- amino -1- methylamino-propanes, 3- amino -1- ethylaminos Propane, 3- amino -1- Cyclohexylaminos propane, 3- amino -1- methylaminos butane, alkanolamine, as N- amino ethyl ethanolamines, Ethanol amine, 3- aminopropanols, neopentyl alcohol amine(For chain extension and chain termination)Or in which at least two mixture primary/secondary amine.
For chain termination, usually using the amine B1 with isocyanate-reactive group), such as methyl amine, ethylamine, propyl Amine, butylamine, octyl amine, lauryl amine, stearylamine, different nonyl epoxide propyl amine, dimethyl amine, diethylamide, dipropylamine, two fourths Base amine, N- dimethylaminopropyls amine, diethyl (methyl) aminopropyl amine, morpholine, piperidines and their suitable substitution derive Single ketones imines, the primary/tertiary amine of object, the amidoamines of di-primary amine and monocarboxylic acid, di-primary amine, such as N, N- dimethylaminopropyls amine or Wherein at least two kinds of mixture.
If containing NH2Or NH groups with B2) the corresponding anionic hydrophilic agent of definition be used for chain extension, preferably point The chain extension of the prepolymer is carried out before dissipating.
Chain extension degree is used for the free NCO of the NCO reactive groups and the prepolymer of the compound of chain extension and chain termination The equivalent proportion of group is usually 40 to 150%, and preferably 50 to 110%, particularly preferred 60 to 100%.
It is amine-containing(aminic)Component B1) and B2) optionally alone or can mix with water or solvent dilute form and be used for the party To prepare polyurethane, any of which order of addition is possible to method in principle.
If water or organic solvent collectively serve as diluent, in B) in for chain extension component in amount of diluent it is excellent It is selected as 40 to 95 weight %.
It is preferred that being disperseed after chain extension.For this purpose, optionally by Strong shear, such as will dissolving and chain extension by being vigorously stirred Polyether polyols be introduced into disperse water, or on the contrary, disperse water is stirred in the polyurethane polymer solution of chain extension.It is preferred that It adds water in the polyether polyols of the chain extension of dissolving.
Then the solvent being still in after dispersion steps in dispersion is usually removed by distillation.Can equally it disperse It removes in the process.
Thus the residual content of the organic solvent in the dispersions of polyurethanes prepared is usually total score granular media less than 10 weights Measure %, preferably smaller than 3 weight %.
The pH of aqueous polyurethane dispersion used according to the invention is usually less than 8.0, preferably smaller than 7.5, particularly preferably It is 5.5 to 7.5.
In the present invention, the composition can advantageously exist with following form:Frost, lotion(lotion), emulsion, gel, Oil, face cream, aqueous solution.
Composition according to the present invention includes the preferably above-mentioned polyurethane of 0.1 to 20 weight %, especially 0.5 to 10 weight % is measured, in each case the total weight based on the composition.
Including the composition according to the present invention of above-mentioned polyurethane or its water-borne dispersions should meet drug and/or makeup The above-mentioned property of product and/or dermatological product.After the application, composition according to the present invention is at least partly retained in skin, Especially on skin of face, therefore the product different from for example removing after use on the skin, such as cosmetic facial mask and cleaning Product, such as soap.The Haircare composition that composition according to the present invention is also typically not included in forming hair or is molded in meaning. Composition according to the present invention is also not usually color make-up composition, such as color cosmetic, is not color make-up lipstick, and not nail polish Deng.In addition, the composition is preferably free of UV- filtering agents.
In the present invention, the composition is especially distinguished according to their consistency:Solid or foam(Solid), frost(Viscosity), Lotion or emulsion(It is flowable), cream or gel(Semisolid), oil and face cream, essence, ointment or aqueous solution(Liquid).According to Their formula, composition according to the present invention can be used as such as face cream, day cream or late frost, body lotion, it is also possible to make for baby Frost, lotion or the other products that youngster uses on the skin.Alternatively or additionally, the composition can be applied to user Scalp or hair on.
The composition is preferably for example to be selected from aqueous solution, water-alcohol solution, oily solution, oil-in-water, Water-In-Oil, water packet silicon Ketone(silicone-in-water), silicone Bao Shui(water-in-silicone), Water-In-Oil packet oil, W/O/W emulsus Liquid, aqueous gel, oil-base gel, paste anhydrous product, solid water-free product, in spherula(spherules)In the presence of fat Mutually the form of the dispersion in water phase provides.
The composition can also be used propellant gas to foam.Above-mentioned emulsion can use O/W, W/O or W/Si emulsifier, thickening Agent(Such as aqueous dispersion(hydrodispersion))Or solid(Such as pickering emulsion)It stabilizes.
The composition may include one or more emulsifying agents or surfactant.
Therefore, particularly, oil-in-water emulsion according to the present invention(O/W)It preferably comprises at least a kind of with >7 HLB (Hydrophile-lipophile balance)The emulsifier of value and if appropriate, assistant for emulsifying agent.
The O/W emulsifiers of the composition can be advantageously selected from nonionic, anionic, cationic or both sexes emulsification Agent.
Nonionic emulsifier includes:
A) fatty acid partial ester of polyalcohol and aliphatic ester and its ethoxylated derivative
B) ethoxylized fatty alcohol and aliphatic acid
C) ethoxylated fatty amine, fatty acid amide, fatty acid alkanol amides
D) alkyl phenol polyglycol ether(Such as Triton®X)
E) ethoxylized fatty alcohol ether.
Particularly advantageous nonionic O/W emulsifiers are ethoxylized fatty alcohol or aliphatic acid, preferably PEG-100 stearic acid Ester, PEG-40 stearates, PEG-50 stearates, ceteareth -20, ceteth -20, stereth - 20, the ester of ceteareth -12, ceteth -12, stereth -12, monosaccharide, oligosaccharides or polysaccharide and aliphatic acid, It is preferred that cetearyl glucoside, methyl glucoside distearate, glycerin monostearate(Self-emulsifying), sorbitan Ester, such as sorbitan stearate(Tween from Uniqema®20 and Tween®60), sorbitan palm fibre Glycerin monostearate(Span®40, Uniqema), glyceryl stearate alcohol citrate, sucrose ester, such as sucrose stearate, PEG-20 first Base glucose scsquistcaratc), the dicarboxylic ester of fatty alcohol(Two myristyl alcohol tartrates).
Advantageous anionic emulsifier is soap(Such as the sodium or triethanolamine salt of stearic acid or palmitic acid), citric acid Ester, such as Glyceryl stearate citrate, fatty alcohol sulfate and mono-, two- and trialkyl phosphates and its ethoxylation Object.
Cationic emulsifier includes the quaternary ammonium compound for having long-chain aliphatic group, such as distearyl dimethylammonium chloride Ammonium.
Amphoteric emulsifier includes:
A) alkyl amino alkane carboxylic acid
B) glycine betaine, sulfobetaines
C) imidazolidine derivatives.
Also naturally occurring emulsifier comprising beeswax, lanocerin, lecithin and sterol.
The suitable assistant for emulsifying agent of O/W emulsion to can be used for preparing the composition is the fat with 8 to 30 carbon atoms Fat alcohol has 8 to 24 carbon atoms, the saturation or unsaturation of the chain length of especially 12 to 18 carbon atoms, branched or non-branching The monoglyceride of alkanoic acid has 8 to 24 carbon atoms, the saturation of the chain length of especially 12 to 18 carbon atoms or insatiable hunger With branched or non-branching alkane carboxylic acid propylene glycol ester, and there are 8 to 24 carbon atoms, especially 12 to 18 carbon atoms The saturation or unsaturation of chain length, branched or non-branching alkane carboxylic acid sorbitan ester.
Particularly advantageous assistant for emulsifying agent is glycerin monostearate, glyceryl monooleate, two glyceride of monostearate, dehydration D-sorbite list isostearate, sucrose distearate, cetanol, stearyl alcohol, docosyl alcohol, different docosyl alcohol and polyethylene glycol (2) stearyl ether(Stereth -2).
In the present invention, it can be advantageous to prepare composition according to the present invention using additional emulsifiers.Thus, for example, The water resistance of preparation according to the present invention can be improved.Suitable emulsifier is such as alkyl methicone copolyol and alkane Base dimethicone copolyol, especially Abil EM 90, laurylmethicone are total Polyalcohols, W/O emulsifiers, such as sorbitan stearate, tristerin(glyceryl stearate), glycerine it is hard Resin acid ester(glycerol stearate), sorbitanoleate, lecithin, glyceryl isostearate, the oil of polyglycereol -3 Acid esters, polyglyceryl-3 diisostearate, PEG-7- rilanit specials, -4 isostearate of polyglycereol, acrylate/acrylic acid C10-30Alkyl ester cross-linked polymer, sorbitan isostearate, poloxamer 101, -2 dimerization hydroxyl of polyglycereol are hard Resin acid ester, polyglyceryl-3 diisostearate, -4 dimerization hydroxy stearic acid ester of polyglycereol, PEG-30 dimerization hydroxy stearic acid ester, - 3 dimerization hydroxy stearic acid ester of two isostearoyl base polyglyceryl-3 diisostearates, glycol distearate and polyglycereol.
Composition according to the present invention, especially for example O/W compositions can advantageously comprise the thickener of water phase.It is advantageous Thickener is:
Crosslinking or uncrosslinked acrylic or methacrylic acid homopolymer or copolymer.These include methacrylic acid or propylene Cross-linked homopolymer, acrylic acid and/or the methacrylic acid of acid and the monomer derived from other acrylic acid series or vinyl monomer, such as The copolymerization of acrylic acid C10-30 Arrcostab, methacrylic acid C10-30- Arrcostabs and vinyl acetate and vinyl pyrrolidone Object.
Natural thickening polymer, for example, based on cellulose, guar gum, xanthans, scleroglucan, gellan gum, Sandlwood glue(rhamsan)With karaya gum, alginates, maltodextrin, starch and its derivative, carob flour(carob seed flour), hyaluronic acid, carrageenan.
Nonionic, anion, cation or both sexes association polymer, such as based on polyethylene glycol and its derivative, or Polyurethane.
Crosslinking based on acrylamide or Methacrylamide or uncrosslinked homopolymer or copolymer, such as 2- acryloyls Homopolymer, acrylamide or the Methacrylamide and methacryloxyethyl trimethyl chlorine of amino-2-methyl propane sulfonic acid Change the copolymer of ammonium or the copolymer of acrylamide and 2- acrylamido -2- methyl propane sulfonic acids.
Particularly advantageous thickener be natural thickening polymer, cross-linked acrylic acid or methacrylic acid homo object or The cross-linked copolymer of copolymer and 2- acrylamido -2- methyl propane sulfonic acids.
Very particularly advantageous thickener is xanthans, if CP Kelco are with Keltrol®And Kelza®It runs after fame supply Product is run after fame product and guar gum from RHODIA with Rhodopol, such as can be with Jaguar®HP105, which runs after fame, to be obtained from The product of RHODIA.
Further very particularly advantageous thickener be can be with Carbopol® 940,Carbopol® 941,Carbopol® 980,Carbopol® 981,Carbopol® ETD 2001,Carbopol® EDT 2050,Carbopol® 2984, Carbopol®5984 and Carbopol®Ultrez 10 runs after fame purchased from Noveon, with Synthalen® K,Synthalen® L And Synthalen®MS runs after fame the cross-linked homopolymer of methacrylic acid or acrylic acid purchased from 3V.
Further very particularly advantageous thickener is acrylic or methacrylic acid and acrylic acid C10-30Arrcostab or first Base acrylic acid C10-30The cross-linked polymer and acrylic or methacrylic acid of Arrcostab and the copolymer of vinyl pyrrolidone. This analog copolymer can be for example with Carbopol® 1342,Carbopol® 1382,Pemulen®TR1 or Pemulen® TR2 It runs after fame purchased from Noveon and with Ultrathix P-100(INCI:Acrylic acid/VP cross-linked polymers)It runs after fame and is purchased from Ashland.
Very particularly advantageous thickener is the cross-linked copolymer of 2- acrylamido -2- methyl propane sulfonic acids.Such copolymerization Object can be for example with Aristoflex®AVC runs after fame obtained from Clariant(INCI:Ammonium acryloyldime-thyltaurate/VP copolymerization Object).
These thickeners are preferably with about 0 weight % of the total weight of the composition to 2 weight %, preferably 0 weight % to 1 weight The concentration of amount % is present in the composition.
Preferably, the composition is Water-In-Oil or silicone packet aqueous emulsion.Preferably include it is one or more have≤ The silicone emulsifier of 8 HLB value(W/S)Or it is one or more with <It the W/O emulsifiers of 7 HLB value and chooses any one kind of them or more Kind has >The Water-In-Oil of the O/W emulsifiers of 10 HLB value(W/O)Or silicone packet aqueous emulsion(W/Si).
The silicone emulsifier can be advantageously selected from alkyl dimethicone copolyol, such as cetyl PEG/PPG 10/1 dimethicone copolyol(ABIL from Evonik®EM 90)Or the poly- diformazans of lauryl PEG/PPG-18/18 Radical siloxane(Dow Corning from Dow Corning Ltd.®5200)And dimethicone copolyol, such as PEG-10 Polydimethylsiloxane(KF-6017 from Shin Etsu), PEG/PPG-18/18 dimethyl silicone polymers(It comes from The Dow Corning 5225C of Dow Corning Ltd.), PEG/PPG-19/19 dimethyl silicone polymers(From Dow The Dow Corning BY-11 030 of Corning Ltd.), trimethyl silyl ammonia end dimethyl silicone polymer or in which extremely Few two kinds of mixture.
Ju You <The W/O emulsifiers of 7 HLB value can be advantageously selected from following group:Fat with 8 to 30 carbon atoms Alcohol has 8 to 24, the saturation and/or unsaturation of the chain length of especially 12 to 18 carbon atoms, branched and/or non-branching alkane carboxylic Acid monoglyceride, have 8 to 24, the saturation and/or unsaturation of the chain length of especially 12 to 18 carbon atoms, it is branched and/or Two glyceride of non-branching alkane carboxylic acid, have 8 to 24, the saturation and/or unsaturation of the chain length of especially 12 to 18 carbon atoms, Branched and/or non-branching alcohol single glycerin ether has 8 to 24, the saturation of the chain length of especially 12 to 18 carbon atoms and/or not Saturation, branched and/or non-branching alcohol two glycerin ethers have 8 to 24, the saturation of the chain length of especially 12 to 18 carbon atoms And/or unsaturated, branched and/or non-branching alkane carboxylic acid propylene glycol ester, and there are 8 to 24, especially 12 to 18 carbon originals The saturation and/or unsaturation, branched and/or non-branching alkane carboxylic acid sorbitan ester of the chain length of son, or in which at least two The mixture of kind.
Particularly advantageous W/O emulsifiers are:Glycerin monostearate, single glyceryl isostearate, single myristic acid glycerine Ester, glyceryl monooleate, two glyceride of monostearate, two glyceride of single isostearic acid, propylene glycol monostearate, propylene glycol list Isostearate, Sefsol 218, propylene glycol monolaurate, sorbitan list isostearate, anhydrosorbitol Sugar alcohol monolaurate, sorbitan list caprylate, sorbitan list vaccenic acid ester, sucrose distearate, whale Ceryl alcohol, stearyl alcohol, arachidic alcohol, docosyl alcohol, different docosyl alcohol, selachyl alcohol(selachyl alcohol), chimyl alcohol, polyethylene glycol (2) stearyl ether(Stereth -2), glyceryl monolaurate, Capmul MCM C10 and Capmul MCM C8 or in which at least two The mixture of kind.
In addition possible W/O emulsifiers are selected from -2 dimerization hydroxy stearic acid ester of polyglycereol, PEG-30 dimerization hydroxy stearic acids Ester, Abil EM 90 and polyglyceryl-3 diisostearate or in which at least two mixture.
C_SUB_SEM[ABCJ >The O/W emulsifiers of 10 HLB value can be advantageously selected from lecithin, -4 phosphate of Trilaureth, Polysorbate -20, polysorbate -60, PEG-22 dodecanediols copolymer, sucrose stearate and sucrose lauric acid Ester or in which at least two mixture.
Oily thickener is advantageously used for making W/O emulsion stabilizations according to the present invention to prevent drops of water fall down or flocculation.
Particularly advantageous oily thickener is organo-clay, such as organic modified bentonite(Bentone from Rheox® 34), organically-modified hectorite(Bentone from Rheox®27 and Bentone®38)Or it is organically modified montmorillonite clay, hydrophobic Pyrolytic silicon dioxide, wherein silanol are replaced by trimethylsiloxy(AEROSIL from Evonik®R812) Or replaced by dimethyl silane oxygroup or dimethyl silicone polymer(AEROSIL from Evonik® R972,AEROSIL® R974, the CAB-O-SIL from Cabot® TS-610,"CAB-O-SIL®TS-720), magnesium stearate or aluminum stearate or benzene Ethylene copolymer, such as the different propylene-styrene of s-B-S, styrene-, styrene-ethylene/butylene-benzene Ethylene or styrene-ethylene/propylene-styrene.
Thickener for fatty phase can be with 0.1 to 5 weight % of the total weight of the emulsion, preferably 0.4 to 3 weight The amount for measuring % exists.
Water phase also may include stabilizer.The stabilizer can be such as sodium chloride, magnesium chloride or magnesium sulfate and its mixture.
Oil can be used in W/O, W/Si and O/W emulsion.
If it does, the fat of composition according to the present invention mutually may include a kind of fixed oil and/or volatile oil and wax. The O/W compositions advantageously comprise the oil of 0.01 to the 45 weight % of total weight based on the composition, particularly advantageously 0.01 to The oil of 20 weight %.W/O the or W/Si compositions advantageously comprise at least oil of 20 weight % of the total weight based on the composition.
Fixed oil is advantageously selected from or mixtures thereof mineral, animal, plant or synthesis source, polarity or non-polar oil.
According to the present invention cosmetic or dermatology emulsion lipid mutually can be advantageously selected from following substance group:
Mineral oil, mineral wax, polar oil, such as capric acid or the triglycerides and natural oil of octanoic acid, such as castor oil, fat, wax With other natural and synthctic fat bodies(fatty bodies), preferred fatty acid and low carbon number alcohol, for example, with isopropanol, propylene glycol The ester or fatty alcohol of glycerine and low carbon number alkanoic acid or with the ester of aliphatic acid or in which at least two mixture;
Benzoic acid alkyl base ester;Silicone oil, such as dimethyl polysiloxane, diethyl based polysiloxane, diphenylpolysiloxane, and wherein At least two mixture.
The polar oil is advantageously selected from:
A) saturation and/or unsaturation of 3 to 30 carbon atoms of chain length, branched and/or unbranched alkyl radical carboxylic acid and chain length 3 to 30 The saturation and/or unsaturation of a carbon atom, branched and/or non-branching alcohol ester or in which at least two mixture;
B) saturation and/or unsaturation of 3 to 30 carbon atoms of aromatic carboxylic acid and chain length, branched and/or non-branching alcohol ester, or Wherein at least two kinds of mixture.
Such ester oil then can be advantageously selected from:
Isopropyl myristate, isopropyl palmitate, isopropyl stearate, acid isopropyl, n-butyl stearate, lauric acid are just The positive last of the ten Heavenly stems ester of own ester, oleic acid, Ethylhexyl stearate, the different nonyl ester of stearic acid, isononyl isononanoate, isononanoic acid isotridecyl ester, palm fibre Palmitic acid acid 2- ethylhexyls, lauric acid 2- ethylhexyls, isostearic acid 2- ethylhexyls, stearic acid 2- hexyls last of the ten Heavenly stems ester, palmitic acid 2- Octyldodecyl, coconut oil 2- ethylhexyls, oleic acid oleic alcohol ester, oleyl erucate, erucyl alcohol oleate(erucyl oleate), erucyl alcohol eruciate, carbonic acid dioctyl ester(Cetiol®CC)With cocounut oil acid glyceride(Myritol®331)And The synthesizing of such ester, semi-synthetic and natural mixture, such as SIMMONDSIA CHINENSIS SEED OIL or in which at least two mixture.
C) benzoic acid alkyl base ester, benzoic acid C12-15- Arrcostabs(Finsolv from Finetex®TN)Or benzoic acid 2- phenyl chlorocarbonates(X-Tend from Ashland®226)
D) lecithin and fatty acid triglycercide, i.e. chain length 8 to 24, the saturation of especially 12 to 18 carbon atoms and/or insatiable hunger With branched and/or non-branching alkane carboxylic acid glyceryl ester.For example, the fatty acid triglycercide can be selected from cocounut oil acid glyceride, olive Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat-germ oil, Portugal Grape seed oil, safflower oil, evening primrose oil, macadimia nut oil, apricot kernel oil, avocado oil etc. or in which at least two mixture.
E) dialkyl ether and dialkyl carbonate, such as dicaprylyl ether(Cetiol from BASF®OE)And/or carbonic acid Dioctyl ester(Such as the Cetiol from BASF®CC)It is advantageous
F) saturation or unsaturated, branched or non-branching alcohol, such as octyldodecanol.
The fixed oil can also equally be advantageously selected from branched and non-branching hydrocarbon, especially mineral oil, vaseline oil, Paraffin oil, saualane and squalene, polyolefin, such as poly decene, Parleam, C13-16 isoparaffins and isohexadecane Or in which at least two mixture non-polar oil.
The nonpolarity fixed oil can be selected from non-volatile silicone oil.
The non-volatile silicone oil may include the dimethyl silicone polymer of optional phenylating(PDMS), such as the poly- trimethyl silicane of phenyl Oxygen alkane, or optionally by aliphatic series and/or aromatic group or by functional group, such as hydroxyl, thiol group and/or amino substitution;Quilt Aliphatic acid, fatty alcohol or polyoxyalkylene-modified polysiloxanes and its mixture.
Particularly advantageous oil is isostearic acid 2- ethylhexyls, octyldodecanol, isononanoic acid isotridecyl ester, different two Ten alkane, coconut oil 2- ethylhexyls, benzoic acid C12-15 Arrcostabs, caprylic/capric triglyceride, dicaprylyl ether, mineral oil, carbon Dioctyl phthalate, cocounut oil acid glyceride, butanediol dicaprylate/dicaprate, Parleam, cetostearyl alcohol isononanoic acid Ester, Dermol 105, saualane, C13-16 isoparaffins or in which at least two mixture.
Composition according to the present invention preferably comprises wax.
Herein, wax is defined as in room temperature(25℃)Under be solid and in 30 DEG C to 200 DEG C of melting temperature following table Reveal the lipophilic fatty substance of reversible solid-liquid state change.When higher than fusing point, which becomes low viscosity and miscible with oil.
The wax is advantageously selected from native paraffin, such as cotton wax, Brazil wax, candelila wax, esparto wax(esparto wax), Japan tallow, montanin wax, sugarcane wax, beeswax, lanocerin, shellac, microwax, ceresine(ceresine), paraffin (ozokerite), ouricury wax, cork fibrous wax, lignite wax, fruit wax(berry wax), sher butter or synthetic wax, such as Solid paraffin(paraffin waxes), polyethylene wax, the wax made of F- T synthesis, hydrogenated oil and fat, aliphatic ester and 25 It is glyceride, silicone wax and the derivative of solid at DEG C(Alkyl derivative, alkoxyl derivatives and/or polymethyl siloxane Ester)Or in which at least two mixture.The wax can be with can be by known method, such as such as "Microemulsions Theory and Practice", L.M. Prince Ed., Academic Press (1977) are made in the 21-32 pages Colloid wax particle stabilising dispersions form exist.
Wax can exist with 0 to 10 weight % of the total weight of the composition, the amount of preferably 0 to 5 weight %.
The composition preferably comprises the volatile oil selected from volatility hydrocarbon ils, silicone oil or fluorinated oil.
The volatile oil can with 0 to 25 weight % of the total weight of the emulsion, preferably 0 to 20 weight %, even more preferably 0 to The amount of 15 weight % exists.
In this specification, volatile oil is to be evaporated in less than 1 hour when with skin contact at room temperature and atmospheric pressure Oil.The volatile oil is liquid at room temperature, and has 0.13 to 40 000 Pa at room temperature and atmospheric pressure(10-3To 300 mmHg), preferably 1.3 to 13 000 Pa(0.01 to 100 mmHg), particularly preferred 1.3 to 1300 Pa(0.01 to 10 mmHg) Vapour pressure and 150 to 260 DEG C, preferably 170 to 250 DEG C of boiling point.
Hydrocarbon ils is understood to be the oil formed substantially by carbon atom and hydrogen atom and optional oxygen atom or nitrogen-atoms, and not Silicon atoms or fluorine atom, wherein its can be also made of carbon atom and hydrogen atom;But can also contain ester group, ether group, Amino or amide group.
Silicone oil is understood to be containing at least one silicon atom, the especially oil of Si-O groups.
Fluorinated oil is understood to be the oil containing at least one fluorine atom.
Volatility hydrocarbon ils according to the present invention can be selected from having 40 to 102 DEG C, preferably 40 to 55 DEG C, more preferable 40 to 50 DEG C Flash-point hydrocarbon ils.
For example, the volatility hydrocarbon ils is that have those of 8 to 16 carbon atoms and its mixture, especially branched C8-16- Alkane, such as different alkane with 8 to 16 carbon atoms(It is also referred to as isoparaffin), Permethyl 99A, isodecane, isohexadecane and example Such as with trade name Isopars®Or Permetyls®The oil of supply;With branched C8-16Ester, such as isohexyl neopentanoate ester, or in which at least Two kinds of mixture.
Volatility hydrocarbon ils, as Permethyl 99A, isodecane and isohexadecane are particularly advantageous.
Volatility silicone oil is preferably selected from 40 to 102 DEG C of flash-point, preferably higher than 55 DEG C and most 95 DEG C, especially excellent Select the silicone oil of 65 to 95 DEG C of flash-point.
For example, the volatility silicone oil is straight chain or ring shape silicone oil with 2 to 7 silicon atoms, wherein these silicone Optionally containing alkyl or alkoxy with 1 to 10 carbon atom.
Volatility silicone oil is preferably selected from octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six silicon Oxygen alkane, seven methylhexyl trisiloxanes, seven Methyl Octyl trisiloxanes, hexamethyldisiloxane, octamethyltrisiloxane, ten first Base tetrasiloxane, ten dimethyl, five siloxanes or in which at least two mixture.
The volatile fluorinated oil usually not flash-point.
For example, the volatile fluorinated oil be nine fluorine ethoxy butanes, Nonafluoromethoxybutcompositions, Decafluoropentane, ten tetrafluoros oneself Alkane, R-4112 or in which at least two mixture.
The composition preferably comprises water and optional miscible organic solvents.
Water used in the composition is preferably selected from Hua Shui, pure softened water, mineral water, thermal water(thermal water) With seawater or in which at least two mixture.
In the case of O/W compositions, the score of water can be 40 to 95 weight % of the total weight of the composition, preferably 50 to 90 weight %, very special 60 to 80 weight %.In the case of W/O compositions, the score of water is the gross weight of the composition 0 to the 60 weight %, preferably 10 to 50 weight %, highly preferred 30 to 50 weight % of amount.
Preferred solvent is the aliphatic alcohol for example with C1-4 carbon atom, such as ethyl alcohol and isopropanol;Polyalcohol and its spread out Biology, such as propylene glycol, dipropylene glycol, 1,3 glycol of butyl-, polypropylene glycol, glycol ethers are for example mono-, two- or tripropylene glycol or mono-, two- Or alkyl (C1-4) ether and its mixture of triethylene glycol.
The score of a kind of solvent or multi-solvents in the composition(quantitative fraction)The preferably group Close 0 to the 25 weight % or preferably 0 to 15 weight % of the total weight of object.
The composition can additionally comprise additive conventional in cosmetics, such as antioxidant, light protective agent and/or other auxiliary Auxiliary agent and additive, such as emulsifier, interface active agent, antifoaming agent, thickener, as standard aqueous or lipophilic gelling agent and/ Or thickener, surfactant, active constituent be for example hydrophilic or lipophilic active agents, moisturizer, filler, UV filtering agents, film forming agent, molten Agent, coalescent, aromatic substance, odor absorber, essence, fragrance, emulsifier, wetting agent, colorant, decolorising agent, keratolytic, Vitamin, emollient, chelating agent, surfactant, polymer, acidification or basifier, ceramide, are prevented free radical scavenger Shine agent, especially ultraviolet light screener, pest repellant, slim dose(slimming agents), dyestuff, fungicide and dandruff removing agent, Gel former and/or other polymeric dispersions, such as the dispersion based on polyacrylate, pigment, dyestuff, levelling agent And/or thixotropic agent, softener, softening agent, preservative.The use scope of the amount of various additives is known to those skilled in the art 's.Additive total amount is preferably 0 to 25 weight % of the total weight of the composition.Each for the additive mentioned preferably should A part for composition and for the composition total weight 0 to 5 weight % or preferably 0 to 3 weight % or preferably 0.1 to 2 weight Measure %.
The composition preferably also includes sense organ additive.Sense organ additive should be understood for example to be further improved preparation It organoleptic properties and for example leaves velvet or silk and slides the colourless or white of dermal sensation, mineral or synthesis, stratiform, spherical shape or elongated Inert particle or non-particulate sense organ additive.
Sense organ additive can be for example with 0 to 10 weight % of the total weight of the composition, and the amount of preferably 0 to 7 weight % is deposited It is in composition according to the present invention.
Advantageous particle sense organ additive is talcum, mica, silica, kaolin, starch and its spreads out in the present invention Biology(Such as tapioca, distarch phosphate, starch ocentyl succinic aluminium and sodium etc.), pyrolytic silicon dioxide, do not have substantially Ultraviolet filtering agent acts on also the not pigment of pigmentation(Such as boron nitride etc.), boron nitride, calcium carbonate, calcium monohydrogen phosphate, carbon The powder such as polyamide of sour magnesium, magnesium bicarbonate, hydroxyapatite, microcrystalline cellulose, synthetic polymer(Such as it can be with trade name; Nylon®"The polymer of acquisition), polyethylene, poly- Beta-alanine, poly- tetrahydrochysene ethylene("Teflon®"), polyacrylate, poly- ammonia Ester, lauroyl lysine, silicone resin(Such as it can be with trade name;Tospearl®"Obtained from the poly- of Kobo Products Inc. Close object), Polyvinylidene(polyvinylidene)The hollow-particle of/acrylonitrile(Expancel from Akzo Nobel®)Or The hollow-particle of silica(Silica Beads from MAPRECOS®).
Advantageous non-particulate sense organ additive is preferably selected from dimethiconol(Such as from Dow Corning Ltd. 1503 Fluid of Dow Corning), silicone copolymer(Such as divinyl polydimethylsiloxane/poly dimethyl Silicone copolymers, the Dow Corning HMW 2220 from Dow Corning Ltd.)Or silicone elastomer (elasters)(Such as Dimethicone Crosspolymer, the Dow Corning from Dow Corning Ltd. 9040 Silicone Elastomer Blend)Or in which at least two mixture.
The composition preferably comprises sunscreen filters, and the wherein total amount of sunscreen filters is the composition according to the present invention 0 weight % of total weight is to 30 weight %, or preferably 0 weight % to 20 weight %, particularly preferred 0 weight % to 10 weight %.This is sun-proof Filtering agent(Or ultraviolet filtering agent)Especially can be selected from organic filters, physical filtering agent or in which at least two mixture. In a preferred embodiment of the invention, the composition is free of sunscreen filters.
Composition according to the present invention may include UV-A filtering agents, UV-B filtering agents or wideband-filtered agent.Ultraviolet light used Filtering agent can be oil-soluble or water-soluble.The list of ultraviolet filtering agent shown in following is of course not restrictive.
The example of UV-B filtering agents includes:
(1) salicyclic acid derivatives, especially Neo-Heliopan HMS(homomenthyl salicylate), octyl salicylate With salicylic acid 4- isopropyl benzyl esters;
(2) cinnamic acid derivative, especially can be with Parsol MCX®The p-methoxycinnamic acid 2- ethyls run after fame obtained from DSM Own ester and 4- methoxycinnamate isoamyl valerates;
(3) liquid beta, β 'Diphenylacrylate, especially can be with UVINUL N539®It runs after fame obtained from BASF's α,β'Diphenylacrylate 2- ethylhexyls or Octocrilene;
(4) p-aminobenzoic acid derivative, especially 4- (dimethylamino) benzoic acid 2- ethylhexyls, 4- (dimethylaminos Base) amyl benzoate;
(5) Unisol S-22 derivative, especially can be with EUSOLEX 6300®3- (the 4- methyl run after fame purchased from Merck Benzal) camphor, Unisol S-22, benzylidene camphor sulfonic acid and polyacrylamide amino methyl benzylidene camphor;
It (6) can be with EUSOLEX 232®The 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID run after fame obtained from Merck;
(7) 1,3,5-triazines derivative, especially:By BASF with UVINUL T150®Run after fame the 2,4,6- tri-s &#91 of supply;p- (2'Ethylhexyl -1'Epoxide carbonyl) Ben Anji &#93;1,3,5-triazines, and-by Sigma 3V with UVASORB HEB®It runs after fame The Uvasorb HEB of supply;
(8) ester of benzylidene malonic acid, especially 4- methoxybenzylidenes malonic acid two (2- ethylhexyls) ester and can With Parsol®3- (4- (the bis- ethoxycarbonylethenyls of 2,2-)-phenoxy group) acrylic that SLX runs after fame obtained from DSM) methoxyl group Siloxanes/dimethyl-siloxane copolymer;With
(9) in these filtering agents (1) to (8) at least two mixture.
The example of UV-A filtering agents is:
(1) dibenzoylmethane derivative, especially by DSM with PARSOL 1789®Run after fame the 4- (tertiary butyl)-of supply 4'Methoxy dibenzoylmethane and 1- phenyl -3- (4'Isopropyl phenyl) propane-1,3-dione;
(2) benzene -1,4-&#91;Two (3- methylidenecamphor -10- sulfonic acid)s &#93;, optionally neutralize completely or partially, it can be with MEXORYL SX®It runs after fame and is purchased from Chimex;
• (3) 2-(4'Diethylamino -2'Hydroxy benzoyl) hexyl-benzoate(Also referred to as aminobenzophenone);
(4) silane derivative or polysiloxane with benzophenone group;
(5) Anthranilate, especially by Symrise with NEO HELIOPAN MA®It runs after fame the adjacent aminobenzene of supply Formic acid menthyl ester;
(6) per molecule contains at least two benzoxazolyl groups(benzoazolyl)Or the chemical combination of at least one benzodiazole base Object, the Isosorbide-5-Nitrae-that is especially purchased from Symrise is bis--benzimidazolyl phenylene -3,3',5,5'Tetrasulfonic acid and its salt;
(7) silicon derivative of the silicon derivative of the benzimidazolyl indoles of N- substitutions or benzofuranyl indoles, especially It is:– 2-&#91;1-&#91;3-&#91;1,3,3,3- tetramethyls -1-&#91;(trimethyl silyl) Yang Ji &#93;Disiloxane Ji &#93;Bing Ji &#93;- 1H- benzos Imidazoles -2- Jis &#93;Benzoxazole;– 2-&#91;1-&#91;3-&#91;1,3,3,3- tetramethyls -1-&#91;(trimethyl silyl) Yang Ji &#93;Disiloxane Ji &#93;Bing Ji &#93;- 1H- benzimidazolyl-2 radicals-Ji &#93;Benzothiazole;– 2-&#91;1- (3- trimethylsilyls propyl) -1H- benzimidazoles - 2- Jis &#93;Benzoxazole;- 6- methoxyl groups -1,1'Bis- (3- trimethylsilyls propyl) 1H, 1'H-&#91;2,2'&#93;Bisbenzimidazole base Benzoxazole;– 2-&#91;1- (3- trimethylsilyls propyl) -1H- benzimidazolyl-2 radicals-Ji &#93;Benzothiazole;They are described in patent Apply in EP-A-1 028 120;
(8) pyrrolotriazine derivatives, especially by 3V with Uvasorb®K2A runs after fame the bis- &#91 of 2,4- of supply;5-1 (dimethyl propyl) Benzoxazole -2- bases-(4- phenyl) Ya Anji &#93;- 6- (2- ethylhexyls) imino group -1,3,5- triazines;With
(9) in these filtering agents (1) to (8) at least two mixture.
The example of wideband-filtered agent is:
(1) benzophenone derivates, such as -2,4-DihydroxyBenzophenone(Benzophenone-1);– 2,2',4,4'- four hydroxyls Base benzophenone(Benzophenone-2);It can be with UNIVNUL M40®2- hydroxyl -4- methoxyl group hexichol the first run after fame obtained from BASF Ketone(Benzophenone-3);It can be with UVINUL MS40®The 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid run after fame purchased from BASF (UVINUL MS 40)And its sulfonate form(Benzophenone -5);– 2,2'Dihydroxy -4,4'Dimethoxy-benzophenone(Two Benzophenone -6-);- 5- chlorine-2-hydroxyl benzophenone(Benzophenone -7-);– 2,2'Dihydroxy -4- methoxy benzophenones (Benzophenone -8);– 2,2'Dihydroxy -4,4'Dimethoxy-benzophenone -5,5'The disodium salt of disulfonic acid(Hexichol first Ketone -9-);- 2- hydroxyl -4- methoxyl groups -4'Methyl benzophenone(Benzophenone-1 0);Benzophenone-1 1;- 2- hydroxyls- 4- (octyloxy) benzophenone(Benzophenone-1 2)
(2) pyrrolotriazine derivatives, especially by BASF with TINOSORB S®Run after fame the bis- { &#91 of 2,4- of supply;4-2- ethyl hexyl oxygen Ji &#93;- 2- hydroxyls } phenyl } -6- (4- methoxyphenyls) -1,3,5-triazines, and can be with TINOSORB M®It runs after fame obtained from BASF's 2,2'Ya Jiajishuan &#91;6- (2H- benzotriazole -2- bases) -4- (1,1,3,3- tetramethyl butyls) Ben Fen &#93;;With
(3) 2- (1H- benzotriazole -2- bases) -4- methyl -6-&#91 of the entitled Ethylhexysalicylates of INCI;2- methyl -3- &#91;1,3,3,3- tetramethyls -1-&#91;(trimethyl silyl) Yang Ji &#93;Disiloxane Ji &#93;Bing Ji &#93;Phenol.
Mixture and UV-B filtering agents, the UV-A filtering agents and broadband mistake of two or more filtering agents can also be used The mixture of filtering agent, and the mixture with physical filtering agent.
Physical filtering agent may include the sulfate of barium, titanyl compound(Titanium dioxide, amorphous or with rutile and/or sharp Titanium ore form crystallizes), the oxide of zinc, the oxide of iron, the oxide of zirconium, the oxide of cerium, silicon oxide, manganese oxidation Or mixtures thereof object.The metal oxide can be to have in micron range or nanometer range(Nano dye)The grain of interior size Sub- form exists.The average particle size of nano dye is such as 5 to 100 nanometers.
Composition according to the present invention can further include moisturizer.Preferably, composition of the invention includes 1 to 15 weight Measure %, or preferably 5 to 10, or the moisturizer of preferably 6 to 9 weight %.
Particularly advantageous moisturizer or wetting agent are such as glycerine, polyglycereol, D-sorbite, isobide two in the present invention Methyl ether, lactic acid and/or lactate, especially sodium lactate, butanediol, propylene glycol, biological carbohydrate gum 1, soybean glycin, ethoxy Urea, ethyl hexyl oxy glycerine, pyrrolidones formic acid and urea.In addition, especially advantageously using selected from water-soluble and/or water-swellable And/or the polymerization " wetting agent " of water gelling polysaccharide.For example, hyaluronic acid, chitosan and/or can be with Fucogel 1000 Name is especially advantageous obtained from the polysaccharide rich in fucose of SOLABIA S.A.
In the present invention, can particularly advantageously use water soluble antioxidant, such as vitamin, for example, ascorbic acid and Its derivative.Vitamin E and its derivative and vitamin A and its derivative are very particularly advantageous.
Other advantageous active constituents in the composition are 'alpha '-hydroxy acids, as glycolic, lactic acid, malic acid, tartaric acid, Citric acid and mandelic acid, beta-hydroxy acid, such as salicylic acid and its acylated derivatives, 2- hydroxy alkanoic acids and its derivative;Natural activity Ingredient and/or its derivative, such as alpha-lipoic acid, folic acid, phytoene, D-Biotin, Co-Q10, alpha-glucosyl rue Fragrant glycosides(glucosylrutin), carnitine, carnosine, natural and/or synthesis isoflavones, creatine, kreatinin, taurine and/or &#91;β&#93;Alanine and 8- hexadecene-1s, 16- dioctyl phthalate(Dioic acid, CAS 20701-68-2;Interim INCI names 18 Carbene diacid)With Licochalcon A and plant extracts or in which at least two mixture.
Another aspect of the present invention is used as the composition for including polyurethane of drug.The drug preferably applies in vitro.It should Drug is preferably applied at least part surface of mankind or animal.It is exposed to or will be exposed to it is preferred that the drug is applied to On the body region for polluting the mankind or animal under environment.The surface is preferably selected from skin, scalp and hair or in which at least two The mixture of kind.The composition includes preferably 1 to the 30 weight % of the total weight based on the composition, or preferably 2 to 20 weight %, Or preferably 3 to 15 weight %, or preferably 4 to 10 weight % polyurethane.Pair with drug and/or cosmetic and/or dermatology group Component, material, component and the material ranges, their property and size for closing the relevant polyurethane description of object are also applied for being used as medicine The polyurethane of product.
Another aspect of the present invention is the composition for including polyurethane for protecting surface to prevent potential pollutant.The table Face can be that those skilled in the art select any surface protected with polyurethane.The surface is preferably selected from skin, scalp, hair Or in which at least two combination.The surface is preferably the surface of mankind or animal.In addition, the surface is preferably mankind or animal Skin, scalp or hair.Especially preferred surface is skin, especially human face.Potential pollutant can be this field Any pollutant known to technical staff.The example of pollutant has been mentioned in the context of pharmaceutical composition.These potential dirts Contaminating object may be identical for protecting surface to prevent the composition comprising polyurethane of the potential pollutant.It is preferred that Ground, the potential pollutant are noxious pollutants.Harmful contaminants or pollutant in the present invention be it is known to organism at least A part and to dead object(death materials), such as particulate matter that causes damages such as at least part of textile (PM)The contaminants or pollutant of form.The harm can be that the health status, face or any of appearance of live body or dead object change Become.The change of health status can be allergic reaction or the inflammation of live body and the contact portion of pollutant or harmful contaminants.Have One example of evil pollutant or dangerous contaminants is smoke from cigarette.Smoke from cigarette preferably comprises PM10And/or PM2.5Particle.
In another aspect of the invention, purposes of the composition comprising polyurethane as surface proofing dust and protecting is provided.Root It is fixed in any embodiment of polyurethane pharmaceutical composition as mentioned above according to the respective embodiment of the purposes of the present invention Justice.The surface can be that those skilled in the art select any surface protected with polyurethane.The surface is preferably selected from skin, head Skin, hair, textile, floor, automobile, plant, screen or in which at least two combination.The surface is preferably mankind or animal Surface.In addition, the surface is preferably skin, scalp or the hair or spray mask of mankind or animal.The surface is preferably people The skin or scalp of class or animal.The surface is particularly preferably the skin of the mankind, especially facial.Dust can be this field skill It can be used as any particulate matter of an air part known to art personnel.Dust may include potential pollutant, but be not required.It is excellent Selection of land, the amount that the polyurethane on surface is applied to via the composition of the present invention are 0.01 mg/cm2To 1 mg/cm2, or preferably 0.05 mg/cm2To 0.5 mg/cm2, or preferably 0.08 mg/cm2To 0.7 mg/cm2。
Another aspect of the present invention is for protecting the surface of mankind or animal to prevent the polyurethane composition of potential pollutant Object.The surface can be that those skilled in the art select any surface in the mankind or animal protected with polyurethane.The surface Be preferably selected from skin, scalp, hair or in which at least two combination.The surface is preferably the surface of mankind or animal.In addition, The surface is preferably the skin, scalp or hair of the mankind.The surface is particularly preferably the skin of the mankind, especially facial.Pollution Object can be known to the skilled in the art any pollutant.In pharmaceutical composition and for protecting surface to prevent pollutant Including having mentioned the example of pollutant in the context of the composition of polyurethane.These pollutants are for protecting surface to prevent this It may be identical in the case of the composition comprising polyurethane of pollutant.Preferably, which is noxious pollutant.The present invention In noxious pollutant be known at least part to organism and dead object, such as at least part of textile caused to endanger Harmful pollutant.The harm can be any change of the health status, face or appearance of live body or dead object.Noxious pollutant or One example of dangerous contaminants is smoke from cigarette.The preferably available water of the pollutant almost removes.It " can almost remove Go " refer to by being rinsed with water the dirt for removing and being attached on the urethane composition being applied on skin in the sense of the present invention Contaminate object is more than 70 weight %, preferably more than 80 weight % or preferably more than 90 weight %.From the skin protected by the urethane composition The pollutant removed on skin of the degree of pollutant preferably never by urethane composition protection is removed on skin at least Twice or preferably at least three times or preferably at least 10 times.With the pollution removed on the skin never by urethane composition protection Object is compared, by the skin especially can be by PM using the urethane composition2.5And PM10The infiltration of pollutant reduces preferred At least twice or preferably at least three times or preferably at least 10 times.
Another aspect of the present invention is multilayered structure, and it includes at least two layers of A) and B), middle level A) include polyurethane And its middle level B) be different from layer A).Layer A) preferably comprise polyurethane as described above.It is highly preferred that layer A) include 10 to 100 weights The polyurethane for measuring % or preferably 50 to 100 weight % or preferably 80 to the 100 weight weight weight of % or 80 to 95 of % or 80 to 98 %, In each case be based on layer A) total weight.Polyurethane is preferably in a manner of described in the context such as aforementioned pharmaceutical compositions It obtains.
Layer B) it may include that technical staff is any material of multilayered structure selection.Be preferably based on a layer B) total weight Meter, layer B) in at least degree of 10 weight %, or preferably in at least degree of 30 weight %, or preferably at least 70 weight % Degree on include and layer A) the different material of material.Preferably, layer B) material be selected from textile, non-woven fabric, fiber, Composite material or in which at least two combination.Layer B) material be preferably selected from cotton, wool, viscose glue, polymer or in which at least Two kinds of mixture or combination.The polymer is preferably selected from polyacrylate, polyamide, polyester, makrolon, polyurethane, gathers Acid imide or in which at least two combination.Preferably, layer B) it is spray mask, protection cap, at least part of protective cloth.
Another aspect of the present invention relates to the methods for improving the ability that potential pollutant is removed from surface, include at least down Row step:
I. the composition comprising at least one polyurethane is applied in at least part on surface, thus to obtain the place on surface Manage part;
Ii. optionally, the process part on the surface of step i. is made to be exposed under potential pollutant at least 1 minute;
Iii. optionally, potential pollutant is removed from the process part on the surface of step i. or ii..
Can be any surface of those skilled in the art's selection from the surface of removing pollutant thereon in this approach. The surface is preferably selected from the surface of the purposes description relative to pharmaceutical composition or polyurethane in drug.It preferably selects on the surface From skin, scalp, hair, spray mask or in which at least two combination.The pollutant can be that those skilled in the art are Any pollutant of this method selection.Preferably, which is the pollutant having been described above.The polyurethane is preferably above The polyurethane described relative to drug and/or cosmetic composition.Preferably, if the surface is the table of mankind or animal Face, in terms of method of the invention only relates to protect the cosmetics aspect on the surface and do not include any drug.
The composition comprising at least one polyurethane is applied at least part surface and can be led in step i. Any applying method for crossing those skilled in the art's selection is realized.Preferably, the composition in step i. applies to be selected from and be applied with hand Add, apply with brush application, with scraper, applied, by the combination of printing application or in which at least two by spraying.It is preferred that using Hand provides application with scraper or with brush.
Optionally, in addition to step i., further step, such as step ii. and/or step iii. can be this method A part.Step ii. preferably makes processing surface be exposed under potential pollutant.Step ii. is preferably by making surface, especially The skin of user is exposed to pollution environment, especially pollutes and is realized under air.But since pollution level is sometimes unknown, step Rapid ii. is not the pressure part of the method for the present invention.It pollutes this means that contemplating that and therefore carries out step i. but do not have actually There is the case where pollution within the scope of the present invention.Potential pollutant can be times that possible cause damages to mankind or animal What material.The example of pollutant has been described above.Preferably, handle surface exposure answer it is for 1 seconds to 48 hours, or preferably 30 Second to 36 hours, or preferably 1 minute to 24 hours time.
In further optional step iii., realizes from the process part on the surface and remove potential pollutant.According to appoint The step ii. of choosing, step iii. are also optional, because under some cases according to the present invention, it is latent to be practically without removing In pollutant.By being rinsed with water the process part of skin, realizes the process part from surface, preferably removed from the skin of user Depollute object.The flushing is preferred to be carried out 1 second to 15 minutes, or preferably 30 seconds to 10 minutes, or preferably 1 minute to 5 minutes when Between.It is preferred that being removed by the pollutant applied to surface in pressure support ventilation step iii..Applying for pressure can be realized by scrub Add.
Another aspect of the present invention relates to the films comprising polyurethane, wherein the film has at least the one of following features It is a:
A. it is based on PM2.5The total amount meter 0 to 20% of particle, or preferably 0 to 10%, preferably 0 to 5% PM2.5Impregnation rate;
B. it is based on PM10The total amount meter 0 to 20% of particle, or preferably 0 to 10%, preferably 0 to 5% PM10Impregnation rate;
C. the tensile strength under 100% elongation of 1 to 10 N/mm2 or preferably 1 to 7 N/mm2 or preferably 1 to 5 N/mm2;
D. the fracture tensile strength of 5 to 40 N/mm2 or preferably 10 to 35 N/mm2 or preferably 10 to 30 N/mm2;
E. 300 to 2500% or preferably 400 to 2300% or preferably 500 to 2000% elongation at break;
F. 5 to the 100 weight % of gross mass meter based on the film or preferably 10 to 95 weight % or preferably 50 to 95 weight % or It is preferred that the polyurethane content of 80 to 95 weight %;
G. 1 to 500 μm or preferably 10 to 450 μm or preferably 50 to 400 μm or preferably 90 to 300 μm of thickness.
According to the present invention, term " permeability " is preferably defined as respective particle and is transmitted via the permeable membrane of diffusion.In this side Face does not preferably apply external pressure, i.e., particle is according to general physical law free diffusing.But due to polyurethane and respective particle Interaction, it is also possible to there are the active transfer mechanisms of permeable membrane.Finally, it is also possible to screening situation in addition occur, such as pass through Size exclusion particle.Correspondingly, permeability preferably refers to passing through the particle of the time in the case of no any external pressure Flux.It also includes that mankind or animal is exhaled by the spray mask of the composition protection by the present invention not have any external pressure preferably It inhales.The measurement of the feature of composition or film according to the present invention is always in room temperature(23℃ ± 1℃)And normal pressure(1013 mbar ± 10 mbar)Lower progress.
According to DIN 53504 in standard conditions(20 DEG C and 65% atmospheric humidity)Lower storage measures after 24 hours according to this hair The engineering properties of bright film sample.Drying measures film engineering properties after 30 minutes at 150 DEG C.
Pass through PM-Meter(Company:NuoFangWei China, Type: SDL301)Measure permeability.Permeability is real The result tested describes to show together in figure 3 with it.
Tensile strength is used as σ as known in the artmax=with N/mm2The stretching strength measurement of meter.
Elongation at break is used as ε as known in the artb=the elongation at break in terms of % measures.
SEM described in description of the thickness by following article connection with figures chapters and sections is measured.
With reference to embodiment illustrate the present invention, although these be understood not to it is restrictive.Unless otherwise specified, all numbers Data, score and percentage are measured based on weight and total amount meter or based on the total weight of the composition.
Embodiment:
Unless otherwise specified, all analysis measurements are related to measuring at a temperature of 23 DEG C.
By the way that the sample weighed is heated to constant weight at 125 DEG C, solid content or solid content are measured.Under constant weight, lead to It crosses and sample is re-weighed calculating solid content.
Unless separately clearly referring to, stereometry NCO content is pressed according to DIN-EN ISO 11909.
By IR spectroscopic methodologies(In 2260 cm-1Under bands of a spectrum)Carry out the control of dissociateive NCO group.
These described viscosity are used at 23 DEG C from Anton Paar by according to the rotational viscometry of DIN 53019 Germany GmbH, Ostfildern, German rotary viscosity design determining.
By laser correlation spectrometry after being diluted with deionized water(Instrument:Malvern Zetasizer 1000, Malver Inst. Limited)Measure the average particle size of dispersions of polyurethanes(It is equal to provide number).
Substance used and abbreviation:
Diamino sulfonic acid salt:NH2-CH2CH2-NH-CH2CH2-SO3Na(45% concentration in water)
Desmophen®2020/C2200:Polycarbonate polyol, OH values 56 mg KOH/g, 2000 g/mol of number-average molecular weight (Covestro Deutschland AG, Leverkusen, Germany)
PolyTHF®2000:Polytetramethylene glycol polyalcohol, OH values 56 mg KOH/g, 2000 g/mol of number-average molecular weight(BASF AG, Ludwigshafen, Germany)
PolyTHF®1000:Polytetramethylene glycol polyalcohol, OH values 112 mg KOH/g, 1000 g/mol of number-average molecular weight(BASF AG, Ludwigshafen, Germany)
Polyethers LB 25:Monofunctional polyethers based on ethylene oxide/propylene oxide, 2250 g/mol of number-average molecular weight, OH values 25 mg KOH/g(Covestro Deutschland AG, Leverkusen, Germany).
Embodiment 1:Dispersions of polyurethanes 1
987.0 grams of PolyTHF®2000(Component A2)), 375.4 grams of PolyTHF®1000(Component A2)), 761.3 grams Desmophen®C2200(Component A2))With 44.3 grams of polyethers LB 25(Component A4))It is heated to 70 in standard agitating device ℃.Then 237.0 grams of hexamethylene diisocyanates are added(Component A1))With 313.2 grams of isophorone diisocyanate(Component A1))Mixture and the mixture is stirred at 120 DEG C until reach theoretical NCO value.It is pre- made of 4830 grams of acetone solutions Thus polymers is simultaneously cooled to 50 DEG C, then metered 25.1 grams of ethylenediamines(Component B1)), 116.5 grams of isophorone diamine(Group Divide B1)), 61.7 grams of diamino sulfonic acid salt(Component B2))With the solution of 1030 grams of water.Mixing time is 10 minutes afterwards.Then lead to Cross 1250 grams of mixtures water-dispersed of addition.Solvent is removed by vacuum distillation.
Gained white dispersion has the following property:
Solid content: 61%
Granularity (LCS): 312 nm
Viscosity(Viscosimeter, 23 DEG C): 241 mPas
pH (23℃): 6.02。
Embodiment 2:Dispersions of polyurethanes 2
By 450 grams of PolyTHF®1000(Component A2))With 2100 grams of PolyTHF®2000(Component A2))It is heated to 70 DEG C.So Afterwards, 225.8 grams of hexamethylene diisocyanates are added(Component A1))With 298.4 grams of isophorone diisocyanate(Component A1)) Mixture and stirred at 100-115 DEG C the mixture until practical nco value fall below theoretical NCO value.It is used at 50 DEG C Prepolymer made of 5460 grams of acetone solutions, then metered 29.5 grams of ethylenediamines(Component B1)), 143.2 grams of diamino sulphurs Hydrochlorate(Component B2))With the solution of 610 grams of water.Mixing time is 15 minutes afterwards.Then it is mixed by adding 1880 grams of water-dispersed these Close object.Solvent is removed by vacuum distillation and obtains the dispersion of stable storing.
Solid content: 56%
Granularity (LCS): 276 nm
Viscosity: 1000 mPas.
Embodiment 3:Dispersions of polyurethanes 3
By the adipic acid of 1649.0 grams of number-average molecular weights with 1700 g/mol, the polyester of hexylene glycol and neopentyl glycol(Component A2))It is heated to 65 DEG C.Then 291.7 grams of hexamethylene diisocyanates are added(Component A1))And it is stirred at 100-115 DEG C The mixture is until practical nco value falls below theoretical NCO value.The prepolymer made of 3450 grams of acetone solutions at 50 DEG C, Then metered 16.8 grams of ethylenediamines(Component B1)), 109.7 grams of diamino sulfonic acid salt(Component B2))It is molten with 425 grams of water Liquid.Mixing time is 15 minutes afterwards.Then by adding 1880 grams of mixtures water-dispersed.Solvent is removed by vacuum distillation simultaneously Obtain the dispersion of stable storing.
Solid content: 42%
Granularity (LCS): 168 nm
Viscosity: 425 mPas
pH: 7.07。
Embodiment 4:Dispersions of polyurethanes 4
By the adipic acid of 340 grams of number-average molecular weights with 1700 g/mol, the polyester of hexylene glycol and neopentyl glycol(Component A2)) It is heated to 65 DEG C.Then 60.1 grams of hexamethylene diisocyanates are added(Component A1))And it is straight that the mixture is stirred at 105 DEG C Theoretical NCO value is fallen below to practical nco value.The prepolymer made of 711 grams of acetone solutions, then metered at 50 DEG C 2.1 grams of ethylenediamines(Component B1)), 32.4 grams of diamino sulfonic acid salt(Component B2))With the solution of 104.3 grams of water.Mixing time afterwards It is 15 minutes.Then by adding 1880 grams of mixtures water-dispersed.Solvent is removed by vacuum distillation and obtains stable storing Dispersion.
Solid content: 40%
Granularity (LCS): 198 nm
Viscosity: 700 mPas
pH: 6.31。
Embodiment 5:Dispersions of polyurethanes 5
By 450 grams of PolyTHF®1000(Component A2))With 2100 grams of PolyTHF®2000(Component A2))It is heated to 70 DEG C.So 225.8 grams of hexamethylene diisocyanates are added afterwards(Component A1))With 298.4 grams of isophorone diisocyanate(Component A1)) Mixture and stirred at 100-115 DEG C the mixture until practical nco value fall below theoretical NCO value.It is used at 50 DEG C Prepolymer made of 5460 grams of acetone solutions, then metered 351 grams of diamino sulfonic acid salt(Component B2))With 610 grams of water Solution.Mixing time is 15 minutes afterwards.Then by adding 1880 grams of mixtures water-dispersed.Solvent is removed by vacuum distillation And obtain the dispersion of stable storing.
Solid content: 40%
Viscosity: 1370 mPas.
Application Example:
Embodiment 6:Composition 6
Preparation method:
1. in room temperature(23℃)Under be sufficiently stirred phase A;
2. phase B is added in phase A, it is sufficiently stirred;
3. phase C is added in phase A/B, it is sufficiently stirred.
Polyurethane total amount in the composition
Embodiment 7:Composition 7
Incremental data in following table is the weight % of the total amount meter based on the composition.
Preparation method:
4. while stirring half an hour at 60 ~ 70 DEG C pre-dispersed phase A.
5. phase B is added in phase A at 60 ~ 70 DEG C while stirring 1 hour.
6. stir 1 hour while at 60 ~ 70 DEG C pre-dispersed phase C, be then added in phase A+B.
7. then mixture phase A/B/C is homogenized 20 minutes.
8. phase D and phase E is added when temperature is less than 45 DEG C, while stirring until mutually uniformly.
Embodiment 8:Composition 8
Incremental data in following table is the weight % of the total amount meter based on the composition.
Preparation method:Phase A and B scraper mixes 5 minutes to realize homogeneous compositions.The polyurethane of the composition always contains Amount is 4 weight %, because polyurethane -35 is provided as the dispersion with 40% solid content.
Embodiment 9:Film 9
In order to form film by polyurethane, by the polyurethane -35 with the 40 weight % solid contents of total weight based on the dispersion Dispersion be mounted in film-making machine(Company: Shanghai Moderner;ProductName: Film maker Equipment (90 µ m))In.The film-making machine is placed on glass plate and the path along at least 10 centimetres is moved on a glass.Gained film is in room temperature Lower drying at least 10 hours.Hereafter, which is easy to remove from glass.
The present invention is illustrated by Fig. 1 to 9.Attached drawing only provides example and is not construed as the feature of the limitation present invention.It is attached Figure is shown:
Fig. 1:By the schematic diagram of the skin of the composition protection of the present invention;
Fig. 2:The schematic diagram of the room of the protective effect of composition for measuring the present invention;
Fig. 3:Compared with mask and unshielded state, the chart of the protection result of the composition of the present invention of form of film;
Fig. 4:Compared with the cloth of no the composition and without the state of cloth, the polyurethane composition of the present invention used on a piece of cloth The chart of the protection result of object;
Fig. 5 a:After being exposed to charcoal night and being rinsed with water compared with the unprotected section of skin, by the composition of the present invention The black-and-white photograph of the parts of skin of protection;
Fig. 5 b:The photochrome of identical parts of skin with shown in Fig. 5 a;
Fig. 6:Compared with applying carbon black in the unprotected section in skin, by applying this hair before being exposed to charcoal night The diagram of the method for the present invention of bright composition;
Fig. 7 a:Cloth by the composition protection of the present invention comprising different amounts of polyurethane is exposed to PM2.5Result under atmosphere Chart;
Fig. 7 b:Cloth by the composition protection of the present invention comprising different amounts of polyurethane is exposed to PM10Result under atmosphere Chart;
Fig. 8:The photo for the bottle equipped with carbon black that film covers made of the polyurethane the present invention
Fig. 9:Before and after being exposed under carbon black bottle, the diagram of the SEM records on foil two sides.
Fig. 1 is covered by form of film after applying comprising the composition according to the polyurethane 120 of any one of embodiment 1 to 5 Schematic diagram on 100 part of skin with epidermal cell 140 of lid.Skin 100 is overlooked, polyurethane film 120 has as small Structure shown in photo 130 is applied to the SEM records of the composition according to embodiment 6 on glass surface.SEM is aobvious Micro mirror comes from Olympus and the entitled CX21 of product.Polyurethane film 120 is shown as the layered structure with small―gap suture.In photo These gaps also shown as black line in 130 have the size of most 20 to 30 nm.Particle with about 10 μ m diameters And pollutant 110(PM10)And belong to PM with about 2.5 μ m diameters2.5Particle or pollutant 150 have than these The much bigger size in gap, therefore polyurethane film 120 can not be permeated.Polyurethane film 120 is to belonging to PM2.5Or PM10Particle Constitute certain barrier.The not contaminated object 110 and 150 of the protected portion of skin 100 pollutes, because of 110 He of particle or pollutant 150 will not even reach the top layer 160 of skin 100.Top layer 160 be made of the dead cell of skin 100 and may have than The big gap of the diameter of particle 110 or 150.If without polyurethane protective film 120, pollutant 110 and 150 may touch table The very sensitive living cells of skin 140.Pollutant 110 or 150 can cause to endanger when contacting with them to these epidermal cells 140 Evil.This may cause allergic reaction or stimulation in epidermis.Therefore, polyurethane film 120 prevents skin to be contaminated 110 He of object 150 pollutions.
Fig. 2 shows room 200 in a schematic way, is boundary with plastic foil 230.It builds room 200 and has to provide artificial establish There is the possibility of the granularity of clear stipulaties and the pollution air of amount.Therefore, room 200 is completely enclosed system and no grain Son such as leaves the room for 110 and 150 grams.In order to ensure the particle of the amount of clear stipulaties, there will be a certain amount of particle(All have Similar granularity)Plate 240 be placed in room 200.By ventilation blower 210 be placed in room 200 with will from plate 240 particle rule It is distributed in room 200.In this example, particle is the silicon dioxide granule 150 with 2.5 μm ± 10% of grain size to survey Measure PM2.5Value or particle 110 with 10 μm ± 10% of grain size are to measure PM10Value.By PM-Meter 220(Company: NuoFangWei, Type: SDL301)Measure particle weight.PM-Meter 220(Or also referred to as PM-Tester)With entrance, This particle can enter PM-Meter during the test.This entrance can be covered by different materials, such as cloth or film to measure this The infiltration of a little materials hinders effect.The volume of room 200 is 37.5cm*24cm*29cm.Following all realities are carried out using this device It tests.The PM-Meter measures particle weight per cubic centimeter.
Fig. 3 shows the breathing for the entitled Jiweida of product that measurement Maidong Company are arranged shown in Fig. 3 Mask(It is designated as PM2.5Mask)The chart of the ability of the infiltration of particle 150 is prevented with polyurethane film 120.Therefore, PM- The entrance of Meter 220 is not covered by any material in the first experiment, and A is referred to as in the x-axis 310 of the chart.Such as this Shown in column 320 in chart, the PM that is shown in for this arrangement in Y-axis 3002.5Value is 329.In the chart, it is close to Column 320 is shown the PM of mask by column 3302.5.Mask can be by the PM in room 2002.5Particle value 300 is down to 5.3 value. This result is shown based on 329 PM without being measured when any material2.5About 98% is reduced for value 300.By in such as Fig. 1 The polyurethane film 120 of the identical material can more effectively reduce PM2.5Value.Here, can be by PM2.5Value 340 is down to 2.4 Value, this is greater than 99% barrier effectiveness compared with original value 300.Film 120 is by this field used in this experiment Known film-making machine(Company: Shanghai Moderner;ProductName: Film maker Equipment)Manufacture is to form Film with about 120 μm of thickness.The thickness of the film is measured by SEM.
Fig. 4 shows the chart of similar experiment as shown in Figure 3, and difference lies in for preventing particle contact PM-Meter's The material of sensor is different.First column 420 of position A in X-axis 410 shows PM2.5Particle value still has 329 Value.The particle weight that the detector of PM-Meter 220 is reached in testing B can be being down to 36.5 as shown in column 430 Value.By with the nylon by 0.3 mm of thickness(nylond)Manufactured cloth covers the PM-Meter 220 of device shown in Fig. 2 Entrance realize the reduction.This value is further decreased when applying polyurethane film 120 on the cloth.By by 0.2 gram of root Acquisition polyurethane film 120 on the area of the 2*2 cm of the cloth is applied to according to the composition of embodiment 7.By scraper by basis After the composition 7 of embodiment 7 is applied on cloth, it is dried at room temperature for 2 hours.PM is shown by column 4402.5Particle value has 4.5 value.
Fig. 5 a, which are shown, uses hydrocarbon black powder(Unipure from Sensient Cosmetic Technologies China Black LC902, d=20 30 μm)The black and white copy of the photo of the parts of skin of processing.In advance 500 Hes are handled with polyurethane 510 are not handled with polyurethane in advance.The original photo of this two parts skin is shown in figure 5b.Herein in region(field) The protected or process part of skin is shown in 520, and unprotected or unprocessed portion is shown in region 530.With following side Formula is tested.Cover corresponding with part 500 or 520 part with according to the composition of embodiment 7 first, and with region 510 Or 530 corresponding parts of skin do not handled with any material.After such treatment, two parts of skin 500 and 510(Or 520 With 530)In each region 500 and 510(Or 520 and 530)On by the carbon black of similar quantity(About 0.2 gram)Covering.Hereafter with 200 Milliliter water rinses skin, this spends about 10 seconds and slowly rinses.The result is that having used the skin of the urethane composition processing of the present invention Skin part 500 is 520 completely clean, and the parts of skin 510 or 530 of unused urethane composition processing shows to cover it The black thin film of the preceding entire skin area by carbon black covering.This result shows process part of the urethane composition to skin 500 or 520 good protection property.
Fig. 6 shows similar experiment as illustrated in figures 5 a and 5b.Here, parts of skin 600 or 610 is with 2 grams according to reality The urethane composition for applying example 8 is handled by scraper, and parts of skin 620 or 630 before being covered by carbon black not by polyurethane Composition is protected.After urethane composition on being applied to parts of skin 600 or 620 dries 2 hours processes, parts of skin 600 and 620 each personal 2 grams of carbon blacks coverings.Parts of skin 600 is rinsed with 200 milliliters of water and the result after 620 half a minute is shown in In part 610 and 630.As a result with it is equally apparent in the experiment of Fig. 5 a and 5b.
Fig. 7 a and 7b show the result of the urethane composition of various concentration.The basis of the composition is always by embodiment 6 Component A and C provide.The different amounts of polyurethane according to embodiment 6 is added.The display of curve 720 has different polyurethane amounts The trend of the protective capability of these different components.The amount for the dispersions of polyurethanes being added in the composition is to be based on used group The %710 for closing the total weight of object is shown in X-axis 730.It is as follows to measure arrangement:It is applied on the entrance of PM-Meter in room 200 In addition the cloth of system of Federation of Literary and Art Circles Fig. 2 descriptions.By silica containing plate(Evonic Germany;ACEMATT TS 100)It is placed in room In 200.329 PM are established by ventilation blower 210 in room 2002.5Concentration.When PM-Meter entrance apply have without appoint The composition of what polyurethane(It is equivalent to the embodiment 6 without phase B)Cloth when, PM2.5It is down to 71.4.This value passes through in chart Point 721 display in figure 7 a, wherein PM2.5Value is pointed out by Y-axis 740.When with the combination for including 1.3 weight % dispersions of polyurethanes When object covers the cloth, the PM of 722 instruction 37.7 of point2.5Value.Since the dispersion has the solid content of 40 weight %, polyurethane total amount For 0.55 weight %.When with including 3 weight % dispersions of polyurethanes(Correspondingly 1.2 weight % polyurethane)Composition cover the cloth When, the PM of 723 instruction 27.8 of point2.5Value.When with including 5 weight % dispersions of polyurethanes(Correspondingly 2 weight % polyurethane)Combination When object covers the cloth, the PM of 724 instruction 13.8 of point2.5Value.When with including 10 weight % dispersions of polyurethanes(Correspondingly 1 weight % is poly- Urethane)Composition when covering the cloth, the PM of 725 instruction 10.2 of point2.5Value.The weight % values of the composition are pointed out by X-axis 730.
Fig. 7 b display using with Fig. 7 a are described similar arrangement as a result, difference lies in measure PM10Value.When in PM- When the entrance of Meter applies the cloth with the composition without any polyurethane, by PM2.5It is down to 677.3.This value passes through figure In table point 761 display in fig.7b, wherein PM10Value is pointed out by Y-axis 770.When with including 1.3 weight % dispersions of polyurethanes When composition covers the cloth, the PM of 762 instruction 301.3 of point10Value.Since the dispersion has the solid content of 40 weight %, polyurethane Total amount is 0.55 weight %.When with including 3 weight % dispersions of polyurethanes(Correspondingly 1.2 weight % polyurethane)Composition covering When the cloth, the PM of 763 instruction 277.7 of point10Value.When with including 5 weight % dispersions of polyurethanes(Correspondingly 2 weight % polyurethane)'s When composition covers the cloth, the PM of 764 instruction 97.3 of point10Value.When with including 10 weight % dispersions of polyurethanes(Correspondingly 1.2 weight Measure % polyurethane)Composition when covering the cloth, the PM of 765 instruction 77.5 of point2.5Value.The weight % values of the composition are by X-axis 780 It points out.
Fig. 8, which is shown, is equipped with carbon black(INCI:Carbon Black come from YEXI, trade name:YH-3600)And it opens at it The photo of the bottle 830 covered with the film 840 formed by the polyurethane according to the present invention described in embodiment 9 on mouth.Foil 840 by not from bottle 830 leak out carbon black in a manner of closed bottle 830.This can be confirmed by contacting film 840 with calico 820. The outer surface 800 of film 840 is not by carbon pollution.Carbon black only contacts the inside 810 of film 840.
Fig. 9 shows four SEM records of the film 840 used in experiment shown in fig. 8.Figure 90 0 and 920 is shown 100.000 surface amplification, and recording 910 and recording 930 has by 50.000 amplifications on the surface after carbon pollution.It has been used for From company JEOL Ltd. China, type:The SEM microscopies of JSM-6510 establish record 900 to 930.For record 900 It is 1 μm by the distance that column 960 is shown with 920, and column 950 shows the distance of 500 nm, this is suitable for 910 Hes of record 930.The SEM photograph of outer surface 800 before 900 display experiment as shown in fig. 8 of record, and record 910 displays institute in fig. 8 The SEM photograph of outer surface 800 after the experiment shown.In addition to film 840 is flattened due to the stretching when being applied on bottleneck, do not have Have and finds out architectural difference.When observing SEM photograph 920 and 930, this is different, shows the SEM notes of the inner surface 810 of film 840 It records 920 and handles the SEM records 930 of the inner surface 810 of rear film 840 as described in contact Fig. 8.Visible carbon black particle herein Huge particle agglomeration.But these particles can be seen that by the smooth structure of Figure 92 0 none can be with 840 He of osmotic membrane Reach the outer surface 800 of film 840.

Claims (17)

1. pharmaceutical composition, wherein the composition includes polyurethane.
2. composition according to claim 1, wherein the composition includes 1 to 20 weight of gross mass meter based on the composition Measure the polyurethane of the amount of %.
3. according to the composition of claims 1 or 2, wherein the polyurethane can be by making one or more water-insolubles, non-aqueous Dispersibility, isocyanate-functional polyurethane prepolymer A) at least one amino-functional compounds B) react acquisition.
4. according to the composition of claims 1 or 2, wherein the amino-functional compounds B) it is selected from primary and/or secondary amine and/or two Amine.
5. according to the composition of claims 1 or 2, wherein the amino-functional compounds B) include at least one diamines.
6. according to the composition of claims 1 or 2, wherein the amino-functional compounds B) at least one is selected from ion radical The amino-functional compounds B2 of group and/or ionogenic group) and it is at least one without ionic group and/or the ammonia of ionogenic group Base functional compound B1).
7. according to the composition of claims 1 or 2, wherein the amino-functional compounds B) include at least one there is ion radical The amino-functional compounds B2 of group and/or ionogenic group), preferably 2- (2- aminoethylaminos) ethanesulfonic acids and/or its salt.
8. according to the composition of claims 1 or 2, wherein the amino-functional compounds B) include at least one there is no ion radical The amino-functional compounds B1 of group and/or ionogenic group), preferably without ionic group and/or the diamines of ionogenic group.
9. according to the composition of claims 1 or 2, wherein the amino-functional compounds B) both included at least one with ion The amino-functional compounds B2 of group and/or ionogenic group), and include at least one there is no ionic group or ionogenic group Amino-functional compounds B1).
10. according to the composition of claims 1 or 2, wherein the prepolymer A) it can be by making selected from polyether polyol, poly- carbonic acid Ester polyol, one or more polyalcohols of polyether polycarbonate polyalcohol and/or polyester polyol and one or more polyisocyanates Polyisocyanate reactant obtains.
11. the composition for including polyurethane as drug.
12. for protecting surface to prevent the composition for including polyurethane of potential pollutant.
13. purposes of the composition comprising polyurethane as surface proofing dust and protecting.
14. for protecting the surface of mankind or animal to prevent the composition for including polyurethane of pollutant.
15. multilayered structure comprising at least two layers of A) and B), middle level A) include polyurethane and its middle level B) it is different from layer A)。
16. the method for improving the ability for removing potential pollutant from surface includes at least the following steps:
I. the composition comprising at least one polyurethane is applied in at least part on surface;
Ii. optionally, the process part of the process part on the surface of step i. is made to be exposed under potential pollutant at least 1 minute;
Iii. optionally, potential pollutant is removed from the process part on the surface of step i. or step ii..
17. including the film of polyurethane, wherein the film has at least one of following features:
A) it is based on PM2.5The PM of the total amount meter 0 to 10% of particle2.5Impregnation rate;
B) it is based on PM10The PM of the total amount meter 0 to 10% of particle10Impregnation rate;
C) tensile strength under 100% elongation of 1 to 10 N/mm2;
D) fracture tensile strength of 5 to 40 N/mm2;
E) elongation at break of 300-2500%;
F) polyurethane content of 5 to the 100 weight % of gross mass meter based on the film;
G) 1 to 500 μm of thickness.
CN201680082839.1A 2016-02-29 2016-02-29 surface protection composition Pending CN108699385A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105814A (en) * 2020-01-13 2021-07-13 万华化学集团股份有限公司 Single-component waterborne polyurethane waterproof coating and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101980689A (en) * 2008-03-26 2011-02-23 拜尔材料科学股份公司 sunscreen composition
CN101980692A (en) * 2008-03-26 2011-02-23 拜尔材料科学股份公司 Skin care compositions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19807908A1 (en) * 1998-02-25 1999-08-26 Basf Ag Cosmetic agent
US20050228491A1 (en) * 2004-04-12 2005-10-13 Snyder Alan J Anti-adhesive surface treatments
DE102004036146A1 (en) * 2004-07-26 2006-03-23 Basf Ag Crosslinked polytetrahydrofuran-containing polyurethanes
FR2898603B1 (en) * 2006-03-20 2010-06-11 Oreal NOVEL POLYURETHANES, COMPOSITIONS COMPRISING THEM AND COSMETIC TREATMENT METHOD
US7854210B2 (en) * 2007-06-04 2010-12-21 Loy A. Moore Clean room utility pouch
EP2103638A1 (en) * 2008-03-20 2009-09-23 Bayer MaterialScience AG Hydrophilic polyurethane solutions
CN102811703B (en) * 2010-03-05 2016-07-06 拜耳知识产权有限责任公司 Sunscreen composition
DE102010063927A1 (en) * 2010-12-22 2012-06-21 Henkel Ag & Co. Kgaa Hair treatment agents
CN104042453B (en) * 2013-03-13 2018-07-06 科思创聚合物（中国）有限公司 Cosmetic composition
CN104892882B (en) * 2014-03-03 2018-02-27 长春工业大学 A kind of transparent polyurethane material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101980689A (en) * 2008-03-26 2011-02-23 拜尔材料科学股份公司 sunscreen composition
CN101980692A (en) * 2008-03-26 2011-02-23 拜尔材料科学股份公司 Skin care compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105814A (en) * 2020-01-13 2021-07-13 万华化学集团股份有限公司 Single-component waterborne polyurethane waterproof coating and preparation method thereof

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