EP3423536A1

EP3423536A1 - Surface protection composition

Info

Publication number: EP3423536A1
Application number: EP16891932.2A
Authority: EP
Inventors: Xiaohui Xiong; Alice Liu; Sebastian Doerr; Sophie Viala
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2016-02-29
Filing date: 2016-02-29
Publication date: 2019-01-09
Also published as: WO2017147739A1; EP3423536A4; CN108699385A

Abstract

A pharmaceutical composition is provided, whereby the composition comprises a polyurethane. Furthermore, a composition comprising a polyurethane for use as a pharmaceutical product is provided. A composition comprising a polyurethane for use in the protection of a surface against pollutants is provided. Further, a use of a composition comprising a polyurethane as protection of a surface against dust. A polyurethane composition for protecting a surface of a human or an animal against pollutants is provided. A multi-layer structure comprising at least two layers A) and B), wherein layer A) comprises a polyurethane, wherein layer B) is different from layer A) is provided. Also, a method for increasing the removability of a potential pollutant from a surface is provided as well as a film comprising polyurethane with varies specifiv features is provided.

Description

Surface protection composition

The present invention relates to pharmaceutical compositions comprising a polyurethane. Also, a composition comprising a polyurethane for use as a pharmaceutical product is subject of the inven-tion. Additionally, the use of a composition comprising a polyurethane as protection of a surface against potential pollutants or dust for protecting them from potential pollutants is related to the invention as well as a mulit-layer structure comprising two layers, whereby at least one layer com-prises a polyurethane. Also, a method of increasing the removability of a pollutant from a surface is related to the invention.
Particulate matter, or PM, is the term for particles found in the air, preferably including dust, dirt, soot, smoke, and liquid droplets. Particles can be suspended in the air for long periods of time. Some particles are large or dark enough to be seen as soot or smoke. Others are so small that individually they can only be detected with an electron microscope or a PM-Meter.
Many manmade and natural sources emit PM directly or emit other pollutants that react in the atmosphere to form PM. These solid and liquid particles come in a wide range of sizes.
Particles less than 10 micrometers in diameter (PM₁₀) pose a health concern because they can be inhaled into and accumulate in the respiratory system and also some of them can penetrate the skin. The determination of particles of these diameters can be provided by optical measurements. Optical particle counters are mainly used for this purpose, e.g. a laser optical particle counter like laser diffraction following ISO 13320-1. The most harmful particles are those with a diameter of less than 2.5 micrometers, also called PM_2.5. The PM_2.5 particles comprise a mixture of at least 150 different chemicals that are polluting the air. Often harmful gaseous chemicals are bound to small particles and convert non-harmful particles into harmful ones. It is known that many small molecules (haptenes) are bound to these PMs and build allergy provoking agglomerations, also called potential pollutants.
The origin of these potential pollutants, especially PM₁₀ and PM_2.5, is mainly traffic, factories, forest fires and power stations. Particles less than 2.5 micrometers in diameter (PM_2.5) are referred to as "fine" particles and are believed to pose the greatest health risks. Because of their small size (approximately 1/30^th the average width of a human hair) , fine particles can lodge deeply into the skin and lungs. However, also particles less than 10 micrometer in diameter (PM₁₀) , are believed to have a negative impact on the health of animals and humans. A mixture of both PM₁₀ and PM_2.5 is often referred to as “fine dust” .
Especially, in towns with a huge amount of population and a lot of traffic and factories the problem with fine dust becomes more and more apparent. Therefore, in many countries a regulation of the PM_2.5 and PM₁₀ rates are manifested. Also, the World Health Organization (WHO) has published a global update 2005 of the Air quality guideline (WHO/SDE/PHE/OEH/06.02) in the year 2006 for the exposition of PM_2.5 of 10 μg/m³ annual mean, 25 μg/m³ 24-hour mean, and for PM₁₀ 20 g/m³ annual mean and 50 μg/m³ 24-hour mean. Because of the rising amount of PMs especially in most industrial areas, the development of skin irritations and/or allergies has increased. Thus, there is a need to protect people to come into contact with these particles.
The use of polyurethanes in cosmetic compositions has already been described. EP 1352642 de-scribes the use of a solubilized, anionic polyurethane in a skincare composition. The polyurethanes used preferably comprise 2, 2-hydroxymethyl-substituted carboxylic acids. Preference is given to using mixtures of anionic polyurethanes with polyacrylates. The nature of the polyurethanes used in the examples is unclear. Similarly, JP 2005200320 and JP 2006062995 describe the use of a combination of polyacrylates and polyurethanes as film formers which exhibit shrinkage of at least 20％. WO 2002010243 discloses the use of polyurethanes in cosmetic applications. The prepoly-mers are prepared using sulphopolyester diols. WO 02070577 discloses the use of anionic polyure-thanes for the preparation of skincare and make-up compositions. Specific examples of cosmetic or pharmaceutical compositions are not disclosed. Especially, a polyurethane as pharmaceutical is not described.
One object of the present invention is to provide a composition which is protective against potential pollutants, especially when applied on a surface of a human or animal.
It is a further object of the present invention to provide a composition which is protective against dust, especially when applied to a surface of a human or animal.
Furthermore, it is an object to provide a composition preventing a surface from getting dirty.
A further object of the present invention is to provide a pharmaceutical composition which prevents the surface of a human or an animal from being irritated in areas with potential pollutants.
Further, it is an object of the present invention to provide a multi-layer structure providing protec-tion against potential pollutants.
A further object of the present invention is to provide a method to improve the removability of a potential pollutant from the surface of a human or an animal.
Furthermore, it is an object of the present invention to provide a method to prevent the surface of a textile from being contaminated by a potential pollutant.
Surprisingly, the object was achieved through the use of a polyurethane or preferably a composi-tion comprising a polyurethane.
When introducing elements of the present invention or the preferred embodiments (s) thereof, the articles "a" , "an" , "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising" , "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.
According to a first aspect of the present invention, a pharmaceutical composition is provided, whereby the composition comprises a polyurethane. Preferably, the composition is a pharmaceuti-cal composition which can also be applied for cosmetic reasons, whereby the composition com-prises the polyurethane. Pharmaceutical and/or cosmetic composition should also cover a derma-tological composition comprising polyurethane.
As pharmaceutical, the composition comprising the polyurethane has the ability to protect a surface of a body, like skin, scalp, hair or other surfaces of a human or animal against potential pollutants. Potential pollutants according to the invention are any material that may cause harm to the body of human or animal when coming into contact with these particles. Most of these materials are dis-tributed via air. Examples of potential pollutants are toxic gases, particular matter and indoor pol-lutants. Examples for toxic gases are sulfur dioxides, nitrogen oxides, photochemically derived ozone and volatile organic compounds. Preferred examples for particular matter (PM) are respir-able particles PM₁₀, respirable particles PM_2.5, particle carriers of e.g. reactive oxygen species (ROS) generating organic compounds and/or metal (iron, copper, zinc and heavy metals) . In addition to certain toxic effects which they cause, heavy metals have the property of reducing the activity of the cellular defense means against free radicals [see for example R.S. Dwivedi, J. Toxicol. Cut. &Ocular Toxical. 6 (3) , 183-191 (1987) ) . Thus, heavy metals aggravate the toxic effects of gaseaus pollutants by reducing the efficacy of the natural defense means, and bring about an acceleration of the phenomenon of cell ageing. This is particularly true for keratin materials and especially the skin, the scalp and the hair, which are in direct and permanent contact with the external environment. Examples for indoor pollutants are cigarette smoke, smoke from indoor combustion and carbon dust from printers. As already mentioned gaseous pollutants may bind to particles, turning particle matter into pollutants. That is why PM is described also as potential pol-lutant in connection with the present invention.
Preferably, the composition of the present invention has the ability to reduce the PM_2.5 and PM₁₀ significantly on the surfaces where the composition of the present invention has been applied to. Still preferably, the PM_2.5 and/or PM₁₀ values, preferably the number of PM₁₀ and/or PM_2.5 particles reaching the human or animal subject, can be reduced by applying the pharmaceutical composition of the present invention in a range of from more than 50 ％, or preferably in a range of more than 70 ％, or in a range of more than 80 ％, or in a range of more than 90 ％based on the amount of the original PM₁₀ and/or PM_2.5. That preferably means that more than 50 ％, more preferably more than 70 ％and most preferably more than 80 ％of the PM_2.5 and/or PM₁₀ concentration being present in the air a human or animal is exposed to is prevented from getting into contact with the human or animal. In this context the expression “to get into contact” preferably means adhering and/or ab-sorbing to the human’s or animal’s skin, scalp and/or hair and/or getting into the respiratory system of the human or animal.
The composition as cosmetic comprising the polyurethane has the ability to protect a surface of a body, like skin, scalp, hair or other surfaces of a human or animal from getting dirty. According to the present invention, this means that a solely cosmetical composition preferably prevents that more than 50 ％, more preferably more than 70 ％and most preferably more than 80 ％of the PM_2.5 and/or PM₁₀ concentration being present in the air a human or animal is exposed to get into contact with this human or animal. However, while a pharmaceutical composition prevents the human or animal from harm caused by the mentioned particles, the cosmetic composition solely serves to prevent the surface from getting dirty from a cosmetical point of view.
The pharmaceutical and/or cosmetic composition preferably is a dermatological composition.
Following, no distinction between pharmaceutical, cosmetic or dermatologic composition is made. The expression “composition” should cover pharmaceutical compositions as well as cosmetic com-positions and dermatological compositions if no differentiation is made between them.
When applied to at least a part of the mentioned surface of a human or animal, the composition of the present invention provides the ability to prevent particles, especially pollutants as mentioned above for example in form of PM₁₀ and PM_2.5 partivles, at least partly from coming into contact with said surface of the body. Furthermore, the composition has the ability to bind particles which without the use of the composition of the present invention would come into contact with the user of the composition. Together with the composition, the bound particles can easily be washed apart after exposition of the surface to the particles. This effect is illustrated in Figures 5a, 5b and 6 as described in detail below.
The polyurethane present in the composition according to the present invention can be selected from any polyurethane that is able to provide a barrier function against potential pollutants.
Preferably, the polyurethane has a structure that it is able to form films, especially when applied to a surface. Preferably, the film formed by the polyurethane has a barrier function against particles. Preferably, the film prevents particles with a diameter lower than 10 μm in a range of from 50 to 100 ％, or preferably in a range of from 70 to 100 ％, or preferably in a range of from 90 to 100 ％, or preferably 100 ％, from getting into contact with the surface of a human or animal, wherein the percentages are based on the number of particles the human or animal is exposed to. Preferably, the film prevents particles with a diameter higher than 5 μm in a range of from 50 to 100 ％, or pref- erably in a range of from 70 to 100 ％, or preferably in a range of from 90 to 100 ％, or preferably 100 ％, from getting into contact with the surface of a human or animal, wherein the precentages are based on the number of particles present. Preferably, the film prevents particles with a diameter higher than 2.5 μm in a range of from 50 to 100 ％, or preferably in a range of from 70 to 100 ％, or preferably in a range of from 90 to 100 ％, or preferably 100 ％, from getting into contact with the surface of a human or animal, wherein the precentages are based on the number of particles present. Illustration of this effect can be found in Figure 8, where a film from the polyurethane is contami-nated on one side with carbon black. In figure 8 it is shown that none of the carbon black particles penetrate through the film made of polyurethane. Details of this film are given in the descriptive part of the figures below.
According to a preferred embodiment of the invention the composition comprises the polyurethane in an amount in the range of from 1 to 20 wt. -％, based on the total mass of the composition.
Preferably, the composition comprises the polyurethane in an amount in the range of from 2 to 15 wt. -％, or preferably in an amount in the range of from 3 to 10 wt. -％, or preferably in an amount in the range of from 4 to 7 wt. -％, based on the total mass of the composition.
Preferably, the pharmaceutical and/or a cosmetic composition comprises at least one polyurethane obtainable by reacting one or more water-insoluble, non-water-dispersible, isocyanate-functional polyurethane prepolymers A) with at least one amino-functional compound B) .
Furthermore, the present invention provides a pharmaceutical and/or cosmetic composition com-prising at least one polyurethane obtainable by reacting one or more isocyanate-functional polyure-thane prepolymers A) which have essentially neither ionic nor ionogenic groups, with one or more amino-functional compounds B) .
Within the context of the invention, the term "water-insoluble, non-water-dispersible polyurethane prepolymer" means in particular that the solubility in water of the prepolymer used according to the invention at 23℃ is less than 10 g/litre, more preferably less than 5 g/litre, and the prepolymer does not produce a sedimentation-stable dispersion in water, in particular deionized water, at 23℃. In other words, the prepolymer settles out upon attempting to disperse it in water.
Preferably, the polyurethane prepolymer A) used has terminal isocyanate groups, i.e. the isocyanate groups are at the chain ends of the prepolymer. All of the chain ends of a polymer particularly pref-erably have isocyanate groups.
Furthermore, the polyurethane prepolymer A) used preferably has essentially neither ionic nor io-nogenic groups (capable of forming ionic groups) , i.e. the content of ionic and ionogenic groups is expediently below 15 milliequivalents per 100 g of polyurethane prepolymer A) , preferably below 5 milliequivalents, particularly preferably below 1 milliequivalent and very particularly preferably below 0.1 milliequivalent per 100 g of polyurethane prepolymer A) .
In a preferred embodiment of the composition the amino-functional compound B) is selected from primary and/or secondary amines and/or diamines. In particular, the amino-functional compound B) includes at least one diamine.
In a preferred embodiment the amino-functional compound B) is selected from at least one amino-functional compound B2) , which has ionic or ionogenic group, and at least one amino-functional compound B1) , which has no ionic or ionogenic group.
In a particularly preferred embodiment of the invention, the at least one amino-functional com-pound B) includes at least one amino-functional compound B2) which has ionic and/or ionogenic (ion-forming) groups. The ionic and/or ionogenic group used is particularly preferably a sulphonate or a sulphonic acid group, yet more preferably a sodium sulphonate group.
In a further preferred embodiment of the invention, the amino-functional compound B) includes both, at least one amino-functional compound B2) which has ionic and/or ionogenic group, and also at least one amino-functional compound B1) which has no ionic or ionogenic group.
Accordingly, polyurethanes within the context of the invention are polymeric compounds which have at least two, preferably at least three, repeat units containing urethane groups:
Preferably included are those polyurethanes which, as a result of the preparation, also have repeat units containing urea groups:
as are formed in particular in the reaction of the isocyanate-terminated prepolymers A) with the at least one amino-functional compound B) .
The composition is preferably water-containing, i.e. aqueous compositions in which the polyure-thane is present in dispersed form, i.e. essentially not in dissolved form. In general, besides any other liquid media which may be present, such as, for example, solvents, water forms the main con-stituent (> 50％by weight) of the dispersion media, based on the total amount of the liquid disper- sion media in the composition according to the invention, and in some cases also forms the sole liquid dispersion medium.
The composition preferably has a content of volatile organic compounds (VOCs) of less than 80％by weight, more preferably of less than 55％by weight, even more preferably of less than 40％by weight, based on the total weight of the composition.
The aqueous polyurethane dispersions used for the preparation of the composition according to the invention preferably have a content of volatile organic compounds (VOCs) of less than 10％by weight, more preferably of less than 3％by weight, even more preferably of less than 1％by weight, based on the total weight of the aqueous polyurethane dispersion.
The content of volatile organic compounds (VOCs) is determined within the context of the present invention in particular by gas chromatographic analysis.
The non-water-soluble and non-water-dispersible, isocyanate-functional polyurethane prepolymers used according to the invention have preferably essentially neither ionic nor ionogenic groups. The insolubility in water and/or lack of dispersibility in water refers to deionized water without the ad-dition of surfactants. Within the context of the present invention this means that the proportion of ionic and/or ionogenic (ion-forming) groups, such as, in particular, anionic groups, such as car-boxylate or sulphonate, or of cationic groups is less than 15 milliequivalents per 100 g of polyure-thane prepolymer A) , preferably less than 5 milliequivalents, particularly preferably less than 1 milliequivalent and very particularly preferably less than 0.1 milliequivalent per 100 g of poly-urethane prepolymer A) .
In the case of acidic ionic and/or ionogenic groups, the acid number of the prepolymer is expedi-ently below 30 mg of KOH/g of prepolymer, preferably below 10 mg of KOH/g of prepolymer. The acid number indicates the mass of potassium hydroxide in mg which is required to neutralize 1 g of the sample under investigation (measurement in accordance with DIN EN ISO 211) . The neutralized acids, i.e. the corresponding salts, naturally have no acid number or a reduced acid number. According to the invention, the acid number of the corresponding free acid is decisive here. The prepolymer A) used for the preparation of the polyurethanes is preferably obtainable by react-ing one or more polyols selected from the group which consists of polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols, and polyisocyanates, as is ex-plained in more detail below.
The polyurethanes present in the composition accordingly comprise, via the prepolymer A) , pref-erably at least one sequence selected from the group which consists of: polyether, polycarbonate, polyether-polycarbonate and polyester sequences. According to the invention, this means in par-ticular that the polyurethanes contain repeat units containing ether groups and/or carbonate groups or ester groups. The polyurethanes can contain, for example, exclusively polyether sequences or exclusively polycarbonate sequences or exclusively polyester sequences. However, they can also have both polyether and polycarbonate sequences, as are formed, for example, during the prepara-tion of polycarbonate polyols using polyetherdiols, as is described in more detail below. In addition, they can have polyether-polycarbonate sequences which arise from the use of polyether-polycarbonate polyols, as described in more detail below.
Particularly preferred polyurethanes are obtained using polymeric polyether polyols and/or poly-meric polycarbonate polyols and/or polyether-polycarbonate polyols or polyester polyols, each of which have number-average molecular weights of preferably about 400 to about 6000 g/mol (here and in the case of the molecular weight data below, determined by gel permeation chromatography relative to polystyrene standard in tetrahydrofuran at 23℃) . The use of at least one of these polyols during the preparation of the polyurethanes or polyurethane prepolymers leads, as a result of the reaction with polyisocyanates, to the formation of corresponding polyether and/or polycarbonate and/or polyether-polycarbonate sequences or polyester sequences in the polyurethane with a corre-sponding molecular weight of these sequences. Particular preference is given to polyurethanes which are obtained from polymeric polyetherdiols and/or polymeric polycarbonatediols and/or polyether-polycarbonate polyols or polyester polyols with a linear structure.
The polyurethanes according to the invention are preferably essentially linear molecules, but may also be branched, which is less preferred.
The number-average molecular weight of the polyurethanes preferably used according to the inven-tion is, for example, about 1000 to 200 000, preferably from 5000 to 150 000.
The polyurethanes present in the composition is preferably added to the specified composition in particular in the form of aqueous dispersions.
Preferred polyurethanes or polyurethane dispersions as part of the composition or to be used ac-cording to the invention are obtainable by
A) preparing isocyanate-functional prepolymers of
A1) organic polyisocyanates,
A2) polymeric polyols, preferably with number-average molecular weights of from 400 to 8000 g/mol (here and for the molecular weight data below, determined by gel permeation chromatography relative to polystyrene standard in tetrahydrofuran at 23℃) , more preferably 400 to 6000 g/mol and particularly preferably from 600 to 3000 g/mol, and OH functionalities of preferably 1.5 to 6, more preferably 1.8 to 3, particularly preferably from 1.9 to 2.1,
A3) optionally hydroxy-functional compounds with molecular weights of preferably 62 to 399 g/mol, and
A4) optionally nonionic hydrophilizing agents,
and
B) then reacting some or all of their free NCO groups
with at least one amino-functional compound B) , such as primary and/or secondary amines and/or diamines.
The polyurethanes used according to the invention are preferably dispersed in water before, during or after step B) .
The reaction with a diamine or two or more diamines in step B) particularly preferably takes place with chain extension. In this connection, monofunctional amines can additionally be added as chain terminators to control the molecular weight.
As component B) , in particular amines can be used which have no ionic or ionogenic, such as anionically hydrophilizing groups (component B1 below) ) and it is possible to use amines which have ionic or ionogenic, such as, in particular, anionically hydrophilizing groups (component B2 below) ) .
Preferably, in step B) of the reaction of the prepolymer, a mixture of component B1) and compo-nent B2) is reacted. By using component B1) it is possible to build up a high molar mass without the viscosity of the previously prepared isocyanate-functional prepolymer increasing to a degree which would be an obstacle to processing. By using the combination of components B1) and B2) it is possible to achieve an optimum balance between hydrophilicity and chain length and thus estab-lish a pleasant skin feel.
The polyurethanes preferably have anionic groups, preferably sulphonate groups. These anionic groups are introduced into the polyurethanes via the amine component B2) reacted in step B) . The polyurethanes used according to the invention optionally additionally have nonionic components for hydrophilization. Exclusively, sulphonate groups are particularly preferably present in the poly-urethanes used according to the invention for the hydrophilization； these are introduced into the polyurethane via corresponding diamines as component B2) .
In order to achieve a good sedimentation stability, the number-average particle size of the special polyurethane dispersions is preferably less than 750 nm, particularly preferably less than 500 nm, determined by means of laser correlation spectroscopy following dilution with deionized water (in-strument: Malvern Zetasizer 1000, Malvern Inst. Limited) .
The solids content of the polyurethane dispersions which is preferably used for preparing the com-position is generally 10 to 70％by weight, preferably 30 to 65％by weight, particularly preferably 40 to 60％by weight, based on the total weight of the polyurethane dispersion. The solids contents are ascertained by heating a weighed sample at 125℃ to constant weight. At constant weight, the solid-body content is calculated by reweighing the sample.
Preferably, these polyurethane dispersions have less than 5％by weight, particularly preferably less than 0.2％by weight, of unbonded organic amines, based on the total weight of the polyurethane dispersions. The content in the composition is correspondingly yet lower.
Suitable polyisocyanates of component A1) are in particular the aliphatic, aromatic or cycloaliphatic polyisocyanates with an NCO functionality of greater than or equal to 2 known per se to the person skilled in the art.
Examples of such suitable polyisocyanates are 1, 4-butylene diisocyanate, 1, 6-hexamethylene diiso-cyanate (HDI) , isophorone diisocyanate (IPDI) , 2, 2, 4-and/or 2, 4, 4-trimethylhexamethylene diiso-cyanate, the isomeric bis (4, 4‘-isocyanatocyclohexyl) methanes or mixtures thereof of any desired isomer content, 1, 4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1, 8-octane diisocyanate (nonane triisocyanate) , 1, 4-phenylene diisocyanate, 2, 4-and/or 2, 6-tolylene diisocyanate, 1, 5-naphthylene diisocyanate, 2, 2‘-and/or 2, 4‘-and/or 4, 4‘-diphenylmethane diisocyanate, 1, 3-and/or 1, 4-bis (2-isocyanatoprop-2-yl) benzene (TMXDI) , 1, 3-bis (isocyanatomethyl) benzene (XDI) , and alkyl 2, 6-diisocyanatohexanoates (lysine diisocyanates) with C1-C8-alkyl groups.
Besides the aforementioned polyisocyanates, it is also possible to use modified diisocyanates which have a functionality of ≥ 2 with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadi-azinedione or oxadiazinetrione structure, and also mixtures of these proportionately.
Prefered are polyisocyanates or polyisocyanate mixtures of the type specified above with exclu-sively aliphatically or cycloaliphatically bonded isocyanate groups or mixtures of these and an av-erage NCO functionality of the mixture of from 2 to 4, preferably 2 to 2.6 and particularly prefera-bly 2 to 2.4, very particularly preferably 2.
Hexamethylene diisocyanate, isophorone diisocyanate or the isomeric bis (4, 4‘-isocyanato- cyclohexyl) methanes, and mixtures of the aforementioned diisocyanates are particularly preferably used in A1) .
In A2) , polymeric polyols with a number-average molecular weight M_n of preferably 400 to 8000 g/mol, more preferably from 400 to 6000 g/mol and particularly preferably from 600 to 3000 g/mol are used. These preferably have an OH functionality of from 1.5 to 6, particularly pref-erably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.
The expression "polymeric" polyols means according to the invention in particular that the speci-fied polyols have at least two, more preferably at least three, repeat units joined together.
Such polymeric polyols are the polyester polyols, polyacrylate polyols, polyurethane polyols, poly-carbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbon-ate polyols and polyester polycarbonate polyols known per se in polyurethane coating technology. These can be used in A2) individually or in any desired mixtures with one another.
The preferably used polyester polyols are the polycondensates known per se of di-and optionally tri-and tetraols and di-and optionally tri-and tetracarboxylic acids or hydroxycarboxylic acids or lactones. Instead of the free polycarboxylic acids, it is also possible to use the corresponding poly-carboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
Examples of suitable diols are ethylene glycol, butylene glycol, diethylene glycol, triethylene gly-col, polyalkylene glycols, such as polyethylene glycol, also 1, 2-propanediol, 1, 3-propanediol, bu-tanediol (1, 3) , butanediol (1, 4) , hexanediol (1, 6) and isomers, neopentyl glycol or hydroxypivalic neopentyl glycol ester, where hexanediol (1, 6) and isomers, butanediol (1, 4) , neopentyl glycol and hydroxypivalic neopentyl glycol ester are preferred. In addition, polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate are also preferred polyols.
Preferred dicarboxylic acids are selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fu-maric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3, 3-diethylglutaric acid and/or 2, 2-dimethylsuccinic acid or a mixture of at least two thereof. The corresponding anhydrides may also be used as acid source.
If the average functionality of the polyol to be esterified is > than 2, monocarboxylic acids, such as benzoic acid and hexanecarboxylic acid, can additionally also be co-used.
Preferred acids are aliphatic or aromatic acids of the type specified above. Particular preference as acid is given to adipic acid, isophthalic acid and phthalic acid.
Hydroxycarboxylic acids which can be co-used as reactants in the preparation of a polyester polyol with terminal hydroxyl groups are, for example, hydroxycaproic acid, hydroxybutyric acid, hy-droxydecanoic acid, hydroxystearic acid and the like. Suitable lactones are caprolactone, butyrolac-tone and homologues. Preference is given to caprolactone.
Preferred components A2) for the preparation of the polyurethanes are polyester polyols with a number-average molecular weight of from 600 to 3000 g/mol, in particular aliphatic polyester polyols based on aliphatic carboxylic acids and aliphatic polyols, in particular based on adipic acid and aliphatic alcohols, such as hexanediol and/or neopentyl glycol.
Polycarbonates having hydroxyl groups, preferably polycarbonatediols, with number-average mo-lecular weights M_n of from preferably 400 to 8000 g/mol, preferably 600 to 3000 g/mol can like-wise be used as component A2) . These are obtainable by reacting carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
Examples of such diols are ethylene glycol, 1, 2-and 1, 3-propanediol, 1, 3-and 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 1, 4-bishydroxymethylcyclohexane, 2-methyl-1, 3-propanediol, 2, 2, 4-trimethylpentanediol-1, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the type specified above or any mixtures of at least two thereof.
Preferably, the diol component comprises 40 to 100％by weight, based on the total weight of the diol component, of hexanediol, preference being given to 1, 6-hexanediol and/or hexanediol deriva-tives. Such hexanediol derivatives are preferably based on hexanediol and, besides terminal OH groups, have ester or ether groups. Such derivatives are obtainable by reacting hexanediol with ex-cess caprolactone or by etherifying hexanediol with itself to give the di-or trihexylene glycol.
Instead of or in addition to the pure polycarbonatediols, it is also possible to use polyether-polycarbonatediols in A2) .
Polycarbonates having hydroxyl groups preferably have a linear structure.
Polyether polyols can likewise be used as component A2) .
For example, the polytetramethylene glycol polyethers known per se in polyurethane chemistry, as are obtainable through polymerization of tetrahydrofuran by means of cationic ring opening, are particularly suitable.
Likewise suitable polyether polyols are the addition products, known per se, of styrene oxide, eth-ylene oxide, propylene oxide, butylene oxide and/or epichlorohydrin onto di-or polyfunctional starter molecules. Thus, in particular polyalkylene glycols, such as polyethylene glycols, polypro-pylene glycols and/or polybutylene glycols, can be used, in particular those with the preferred mo-lecular weights specified above.
Suitable starter molecules for the polymerisation which can be used are all compounds known ac-cording to the prior art, such as, for example, water, butyl diglycol, glycerol, diethylene glycol, trimethyolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine 1, 4-butanediol.
Particularly preferred components in A2) are polytetramethylene glycol polyethers and polycar-bonate polyols and mixtures thereof and particularly preferably polytetramethylene glycol polyeth-ers.
In preferred embodiments of the invention, component A2) is accordingly:
-mixtures comprising at least one polyether polyol and at least one polycarbonate polyol,
-mixtures comprising more than one polyether polyol, or a mixture of two or more poly-ether polyols with different molecular weights, which are in particular poly (tetramethylene glycol) polyether polyols (such as HO- (CH₂-CH₂-CH₂-CH₂-O) _x-H) ,
-mixtures comprising more than one polyether polyol and at least one polycarbonate polyol, and also
-particularly preferably polyester polyols with a number-average molecular weight of from 600 to 3000 g/mol, in particular aliphatic polyester polyols based on aliphatic carboxylic acids and aliphatic polyols, in particular based on adipic acid and aliphatic alcohols, such as hexanediol and/or neopentyl glycol,
where component A) , according to the definition, has essentially neither ionic nor ionogenic groups.
As component A3) , polyols, in particular nonpolymeric polyols, of the specified preferred molecu-lar weight range from 66 to 399 mol/g with up to 20 carbon atoms, such as ethylene glycol, di-ethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butylene -glycol, cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol, neopentyl glycol, hydro-quinone dihydroxyethyl ether, bisphenol A (2, 2-bis (4-hydroxyphenyl) propane) , hydrogenated bisphenol A (2, 2-bis (4-hydroxycyclohexyl) propane) , trimethylolpropane, trimethylolethane, glyc-erol, pentaerythritol and any desired mixtures thereof, can be used as desired.
Also suitable are ester diols of the specified molecular weight range, such as α-hydroxybutyl ε-hydroxycaproic acid ester, ω-hydroxyhexyl γ-hydroxybutyric acid ester, adipic acid (β-hydroxy-ethyl) ester or terephthalic acid bis (β-hydroxyethyl) ester.
In addition, as component A3) , it is also possible to use monofunctional isocyanate-reactive hy-droxyl-group-containing compounds. Examples of such monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol.
In one preferred embodiment of the invention, the polyurethane used comprises less than about 10％by weight of component A3) , preferably less than 5％by weight of component A3) , in each case based on the total mass of the polyurethane, yet more preferably component A3) is not used for the preparation of the polyurethane.
To prepare the polyurethanes, preferably one or more in particular isocyanate-reactive nonionic hydrophilizing agents are optionally used as component A4) . The hydrophilizing agents used as component A4) are in particular different from components A2) and A3) .
Suitable nonionically hydrophilizing compounds as component A4) are, for example, polyoxyal-kylene ethers which have isocyanate-reactive groups, such as hydroxy, amino or thiol groups. Pref-erence is given to monohydroxy-functional polyalkylene oxide polyether alcohols having, on statis-tical average, 5 to 70, preferably 7 to 55, ethylene oxide units per molecule, as are accessible in a manner known per se by alkoxylation of suitable starter molecules (e.g. in Ullmanns der technischen Chemie [Ullmanns encyclopaedia of industrial chemistry] , 4th edition, Volume 19, Verlag Chemie, Weinheim pp. 31-38) . These are either pure polyethylene oxide ethers or mixed polyalkylene oxide ethers, where they contain at least 30 mol％, preferably at least 40 mol％, ethyl-ene oxide units, based on the molar amount of all of the alkylene oxide units present.
Particularly preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyeth-ers which have 40 to 100 mol％ethylene oxide units and 0 to 60 mol％propylene oxide units.
Suitable starter molecules for such nonionic hydrophilizing agents are in particular saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec- butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, di-ethylene glycol monoalkyl ethers, such as, for example, diethylene glycol monobutyl ether, unsatu-rated alcohols, such as allyl alcohol, 1, 1-dimethylallyl alcohol or oleyl alcohol, aromatic alcohols, such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols, such as benzyl alco-hol, anisyl alcohol or cinnamyl alcohol, secondary monoamines, such as dimethylamine, diethyl-amine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl-and N-ethylcyclohexylamine or dicyclohexylamine, and also heterocyclic secondary amines, such as mor-pholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoal-cohols of the type specified above. Particular preference is given to using diethylene glycol mono-butyl ether or n-butanol as starter molecules.
Alkylene oxides suitable for the alkoxylation reaction are in particular ethylene oxide and propyl-ene oxide, which can be used in the alkoxylation reaction in any desired order or else in a mixture.
Component B) is preferably selected from primary or secondary amine and/or diamines. It includes in particular diamines.
As component B) it is possible to use in particular amines which have no ionic or ionogenic, such as anionically hydrophilizing groups (component B1) below) , and it is possible to use amines which have ionic or ionogenic, such as, in particular, anionically hydrophilizing groups (compo-nent B2) below) . Preferably, in step B) of the reaction of the prepolymer, a mixture of component B1) and of component B2) is reacted.
For example, organic di-or polyamines, such as, for example, 1, 2-ethylenediamine, 1, 2-and 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixture of 2, 2, 4-and 2, 4, 4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethyl-enetriamine, 4, 4-diaminodicyclohexylmethane, hydrazine hydrate, and/or dimethylethylenediamine, can be used as component B1) .
Moreover, compounds which, besides a primary amino group, also have secondary amino groups or, besides an amino group (primary or secondary) , also have OH groups, can also be used as com-ponent B1) . Examples thereof are primary/secondary amines, such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines, such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine.
In addition, monofunctional isocyanate-reactive amine compounds can also be used as component B1) , such as, for example, methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, and suitable substituted derivatives thereof, amidoamines of diprimary amines and monocarboxylic acids, monoketime of diprimary amines, primary/tertiary amines, such as N, N-di-methylaminopropylamine.
As component B1) , preference is given to using 1, 2-ethylenediamine, bis (4-aminocyclohexyl) methane, 1, 4-diaminobutane, isophoronediamine, ethanolamine, diethanolamine and diethylenetriamine or a mixture of at least two thereof.
Component B) preferably includes at least one component B2) . Suitable anionically hydrophilizing compounds as component B2) preferably contain a sulphonic acid or sulphonate group, particularly preferably a sodium sulphonate group. Suitable anionically hydrophilizing compounds as compo-nent B2) are, in particular, the alkali metal salts of mono-and diaminosulphonic acids. Examples of such anionic hydrophilizing agents are salts of 2- (2-aminoethylamino) ethanesulphonic acid, ethyl-enediaminepropyl-or –butylsulphonic acid, 1, 2-or 1, 3-propylenediamine-β-ethylsulphonic acid or taurine or a mixture of at least two thereof. Furthermore, the salt of cyclohexylaminopropanesul-phonic acid (CAPS) from WO-A01/88006 can be used as anionic hydrophilizing agent.
Particularly preferred anionic hydrophilizing agents B2) are those which contain sulphonate groups as ionic groups and two amino groups, such as the salts of 2- (2-aminoethylamino) ethylsulphonic acid and 1, 3-propylenediamine-β-ethylsulphonic acid.
According to a preferred embodiment of the present invention, the at least one amino-functional compound B) includes at least one amino-functional compound B2) which has ionic and/or iono-genic groups, preferably 2- (2-aminoethylamino) ethanesulphonic acid and/or salts thereof.
According to a further preferred embodiment of the present invention, the at least one amino-functional compound B) includes at least one amino-functional compound B1) which has no ionic and/or ionogenic groups, preferably a diamine which has no ionic and/or ionogenic groups.
The polyurethanes preferably comprise at least one sulphonate group.
Optionally, the anionic group in component B2) may also be a carboxylate or a carboxylic acid group. Component B2) is then preferably selected from diaminocarboxylic acids. However, this embodiment is less preferred since carboxylic-acid-based components B2) have to be used in higher concentrations.
According to a further preferred embodiment of the present invention, the prepolymers A) are ob- tainable by reacting one or more polyols selected from the group which consists of polyether poly-ols, polycarbonate polyols, polyether-polycarbonate polyols and/or polyester polyols, and one or more polyisocyanates.
For the hydrophilization, it is also possible to use mixtures of anionic hydrophilizing agents B2) and nonionic hydrophilizing agents A4) .
In a preferred embodiment for the preparation of the special polyurethane dispersions, components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always add-ing up to 100％by weight:
5 to 40％by weight of component A1) ,
55 to 90％by weight of A2) ,
0.5 to 20％by weight sum of components A3) and/or B1) ,
0.1 to 25％by weight sum of components A4) and/or B2) , where, based on the total amounts of components A1) to A4) and B1) to B2) , particularly preferably 0.1 to 5％by weight of anionic or potentially anionic hydrophilizing agents B2) are used.
In a particularly preferred embodiment for the preparation of the special polyurethane dispersions, components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100％by weight:
5 to 35％by weight of component A1) ,
60 to 90％by weight of A2) ,
0.5 to 15％by weight sum of components A3) and/or B1) ,
0.1 to 15％by weight sum of components A4) and/or B2) , where, based on the total amounts of components A1) to A4) and B1) to B2) , particularly preferably 0.2 to 4％by weight of anionic or potentially anionic hydrophilizing agents B2) are used.
In a very particularly preferred embodiment for the preparation of the special polyurethane disper-sions, components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100％by weight:
10 to 30％by weight of component A1) ,
65 to 85％by weight of A2) ,
0.5 to 14％by weight sum of components A3 and/or B1) ,
0.1 to 13.5％by weight sum of components A4) and/or B2) , where, based on the total amounts of components A1) to A4) and B1) to B2, particularly preferably 0.5 to 3.0％by weight of anionic or potentially anionic hydrophilizing agents from B2) are used.
The preparation of the polyurethane dispersions can be carried out in one or more stage (s) in ho-mogeneous phase or, in the case of multistage reaction, sometimes in disperse phase. Following complete or partial polyaddition from A1) to A4) , a dispersion, emulsification or dissolution step preferably takes place. Afterwards, a further polyaddition or modification optionally takes place in the disperse phase.
In this context, all of the methods known from the prior art, such as, for example, prepolymer mix-ing process, acetone process or melt dispersion process, can be used for the preparation of a poly-urethane dispersion. Preference is given to using the acetone process.
For the preparation in accordance with the acetone process, constituents A2) to A4) and the poly-isocyanate component A1) for the preparation of an isocyanate-functional polyurethane prepolymer are usually initially introduced in their entirety or in part and optionally diluted with a solvent which is miscible with water but inert towards isocyanate groups, and heated to temperatures in the range from 50 to 120℃. To increase the rate of the isocyanate addition reaction, the catalysts known in polyurethane chemistry can be used.
Suitable solvents are the customary aliphatic, keto-functional solvents such as acetone, 2-butanone, which can be added not only at the start of the preparation, but optionally in parts also later on. Preference is given to acetone and 2-butanone, and particular preference is given to acetone. The addition of other solvents without isocyanate-reactive groups is also possible, but not preferred.
Any constituents of A1) to A4) not added at the start of the reaction are then metered in.
During the preparation of the polyurethane prepolymer from A1) to A4) , the quantitative ratio of isocyanate groups to isocyanate-reactive groups is generally 1.05 to 3.5, preferably 1.1 to 3.0, par-ticularly preferably 1.1 to 2.5.
The reaction of components A1) to A4) to give the prepolymer takes place partially or completely, but preferably completely. Polyurethane prepolymers which contain free isocyanate groups are thus obtained without a diluent or in solution.
In the neutralization step for the partial or complete conversion of potentially anionic groups to anionic groups, bases such as tertiary amines, e.g. trialkylamines having 1 to 12, preferably 1 to 6, carbon atoms, particularly preferably 2 to 3 carbon atoms in each alkyl radical or very particularly preferably alkali metal bases such as the corresponding hydroxides are used.
The use of organic amines is not preferred.
Neutralizing agents which can be used are preferably inorganic bases, such as aqueous ammonia solution or sodium hydroxide or potassium hydroxide.
Preference is given to sodium hydroxide and potassium hydroxide.
The quantitative amount of the bases is 50 and 125 mol％, preferably between 70 and 100 mol％of the quantitative amount of the acid groups to be neutralized. The neutralization can also take place at the same time as the dispersion by the dispersion water already comprising the neutralizing agent.
Afterwards, in a further process step, in cases where it has still not happened or has only happened partially, the resulting prepolymer is dissolved with the help of aliphatic ketones such as acetone or 2-butanone.
The reaction of components A1) to A4) to give the prepolymer takes place partially or completely, but preferably completely. In this way, polyurethane prepolymers which contain free isocyanate groups are obtained without a diluent or in solution.
During the chain extension in stage B) , NH₂-and/or NH-functional components are reacted with the remaining isocyanate groups of the prepolymer. Preferably, the chain extension/termination is carried out prior to the dispersion in water.
Suitable components B) for the chain extension are, in particular, organic di-or polyamines B1) , preferably selected from the group consisting of ethylenediamine, 1, 2-and 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixture of 2, 2, 4-and 2, 4, 4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, diaminodi-cyclohexylmethane and dimethylethylenediamine or mixtures of at least two thereof.
Moreover, it is also possible to use compound B1) which, besides a primary amino group, also has secondary amino groups or, besides an amino group (primary or secondary) , also has OH groups. Preferably compound B1) is a primary/secondary amine selected from the group consisting of di-ethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclo-hexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines, such as N-aminoethylethanol-amine, ethanolamine, 3-aminopropanol, neopentanolamine for the chain extension and termination or mixtures of at least two thereof.
For the chain termination, use is usually made of amines B1) having a group which is reactive to-wards isocyanates, such as methylamine, ethylamine, propylamine, butylamine, octylamine, lauryl-amine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibu-tylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, and suitable substituted derivatives thereof, amidoamines of diprimary amines and monocarboxylic acids, monoketime of diprimary amines, primary/tertiary amines, such as N, N-dimethyl-aminopropylamine or mixtures of at least two thereof.
If anionic hydrophilizing agents corresponding to the definition of B2) with NH₂ or NH groups are used for the chain extension, the chain extension of the prepolymers preferably takes place before the dispersion.
The degree of chain extension, i.e. the equivalent ratio of NCO-reactive groups of the compounds used for the chain extension and chain termination to free NCO groups of the prepolymer is gener-ally between 40 and 150％, preferably between 50 and 110％, particularly preferably between 60 and 100％.
The aminic components B1) and B2) can optionally be used in water-or solvent-diluted form in the process to prepare the polyurethane, individually or in mixtures, with any order of the addition be-ing possible in principle.
If water or organic solvents are co-used as diluents, then the diluent content in the component used in B) for chain extension is preferably 40 to 95％by weight.
The dispersion preferably takes place after the chain extension. For this, the dissolved and chain-extended polyurethane polymer is optionally either introduced into the dispersion water with strong shear, such as, for example, with vigorous stirring, or, conversely, the dispersion water is stirred into the chain-extended polyurethane polymer solutions. Preferably, the water is added to the dis-solved chain-extended polyurethane polymer.
The solvent still present in the dispersions after the dispersion step is then usually removed by dis-tillation. Removal during dispersion is likewise possible.
The residual content of organic solvents in the polyurethane dispersions prepared in this way is typically less than 10％by weight, preferably less than 3％by weight, based on the total dispersion.
The pH of the aqueous polyurethane dispersions used according to the invention is typically less than 8.0, preferably less than 7.5 and is particularly preferably between 5.5 and 7.5.
Within the context of the present invention, the composition can advantageously be present in the following forms: cream, lotion, milk, gel, oil, balm, aqueous solution.
The composition according to the invention comprises preferably 0.1 to 20％by weight of the polyurethane described above and in particular 0.5 to 10％by weight, in each case based on the total weight of the composition.
The composition according to the invention which comprises the polyurethane described above or its aqueous dispersion should satisfy the aforementioned properties of a pharmaceutical and/or cosmetic and/or dermatological product. Following application, the composition according to the invention remains at least partially on the skin, in particular facial skin, and thus differs, for exam-ple, from products which are removed following use on the skin, such as, for example, cosmetic face masks and cleansing products, such as soaps etc. The composition according to the invention, furthermore, generally also does not include a haircare composition in the sense that hair is styled or formed. The compositions according to the invention are also generally not make-up composi-tions, such as make-up etc., are not make-up lipsticks and are not nail varnishes or the like. Fur-thermore, the composition preferably does not comprise a UV-filter.
Within the context of the present invention, the composition is differentiated in particular according to their consistency: solid or foam (solid) , cream (viscous) , lotion or milk (flowable) , paste or gels (semisolid) , oils, and also balm, serum, ointment or aqueous solutions (liquid) . Depending on their formulation, the composition according to the invention can be used, for example, as face cream, day or night cream, body lotion and also as creams, lotions or other products for babies to be used on the skin. Alternatively or additionally, the composition can be applied to the scalp or hair of the user.
The composition is preferably provided, for example, in the form selected from the group consist-ing of an aqueuous solution, an aqueous-alcoholic solution, an oily solution, oil-in-water, water-in-oil, silicone-in-water, water-in-silicone, oil-in-water-in-oil, water-in-oil-in-water emulsion, an aqueous gel, an oily gel, a pasty anhydrous product, a solid anhydrous product, a dispersion of a fatty phase in an aqueous phase in the presence of spherules.
The composition can also be foamed using a propellant gas. The emulsions described above can be stabilized by an O/W, W/O or W/Si emulsifier, thickener (such as, for example, hydrodispersion) or solids (such as, for example, Pickering emulsion) .
The composition can comprise one or more emulsifiers or surface-active agents.
Thus, in particular oil-in-water emulsions (O/W) according to the invention comprise preferably at least one emulsifier with an HLB (hydrophilic-lipophilic balance) value of > 7 and, if appropriate, a coemulsifier.
O/W emulsifiers can advantageously be selected from the group of nonionic, anionic, cationic or amphoteric emulsifiers to the composition.
The nonionic emulsifiers include:
a) partial fatty acid esters and fatty acid esters of polyhydric alcohols and ethoxylated derivatives thereof
b) ethoxylated fatty alcohols and fatty acids
c) ethoxylated fatty amines, fatty acid amides, fatty acid alkanolamides
d) alkylphenol polyglycol ethers (e.g. X)
e) ethoxylated fatty alcohol ethers.
Particularly advantageous nonionic O/W emulsifiers are ethoxylated fatty alcohols or fatty acids, preferably PEG-100 stearate, PEG-40 stearate, PEG-50 stearate, ceteareth-20, ceteth-20, steareth-20, ceteareth-12, ceteth-12, steareth-12, esters of mono-, oligo-or polysaccharides with fatty acids, preferably cetearyl glucoside, methylglucose distearate, glyceryl monostearates (self-emulsifying) , sorbitan esters, such as, for example, sorbitan stearates ( 20 and 60 from Uniqema) , sorbitan palmitates ( 40, Uniqema) , glyceryl stearyl citrates, sucrose esters, such as, for ex-ample, sucrose stearates, PEG-20 methyl glucose sesquistearate) , dicarboxylic acid esters of fatty alcohol (dimyristyl tartrate) .
Advantageous anionic emulsifiers are soaps (e.g. sodium or triethanolamine salts of stearic acid or palmitic acid) , esters of citric acid, such as glyceryl stearate citrate, fatty alcohol sulphates, and also mono-, di-and trialkyl phosphoric acid esters and ethoxylates thereof.
The cationic emulsifiers include quaternary ammonium compounds with a long-chain aliphatic radical, e.g. distearyl dimonium chloride.
The amphoteric emulsifiers include:
a) alkylaminoalkane carboxylic acids
b) betaines, sulphobetaines
c) imidazoline derivatives.
Furthermore, there are naturally occurring emulsifiers, which include beeswax, wool wax, lecithin and sterols.
Suitable coemulsifiers for the O/W emulsions which can be used for the preparation of the compo-sition are fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated or unsatu-rated, branched or unbranched alkanecarboxylic acids with a chain length of from 8 to 24 carbon atoms, in particular 12 to 18 carbon atoms, propylene glycol esters of saturated or unsaturated, branched or unbranched alkanecarboxylic acids with a chain length of from 8 to 24 carbon atoms, in particular 12 to 18 carbon atoms, and also sorbitan esters of saturated or unsaturated, branched or unbranched alkanecarboxylic acids with a chain length of from 8 to 24 carbon atoms, in particular 12 to 18 carbon atoms.
Particularly advantageous coemulsifiers are glyceryl monostearate, glyceryl monooleate, diglyceryl monostearate, sorbitan monoisostearate, sucrose distearate, cetyl alcohol, stearyl alcohol, behenyl alcohol, isobehenyl alcohol and polyethylene glycol (2) stearyl ether (steareth-2) .
Within the context of the present invention, it may be advantageous to use further emulsifiers for the preparation of the composition according to the invention. Thus, for example, the water resis-tance of the preparations according to the invention can be increased. Suitable emulsifiers are, for example, alkylmethicone copolyols and alkyldimethicone copolyols, in particular cetyldimethicone copolyol, laurylmethicone copolyol, W/O emulsifiers, such as sorbitan stearate, glyceryl stearate, glycerol stearate, sorbitan oleate, lecithin, glyceryl isostearate, polyglyceryl-3 oleate, polyglyceryl-3 diisostearate, PEG-7-hydrogenated castor oil, polyglyceryl-4 isostearate, acrylate/C_10-30-alkyl acrylate crosspolymer, sorbitan isostearate, poloxamer 101, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-3 diisostearate, polyglyceryl-4 dipolyhydroxystearate, PEG-30 dipolyhydroxystearate, diisostearoyl polyglyceryl-3 diisostearate, glycol distearate and polyglyceryl-3 dipolyhydroxys-tearate.
The composition according to the invention, such as, in particular, the O/W composition, can ad-vantageously comprise thickeners of the water phase. Advantageous thickeners are:
-Crosslinked or uncrosslinked acrylic acid or methacrylic acid homopolymers or copoly-mers. These include crosslinked homopolymers of methacrylic acid or acrylic acid, co-polymers of acrylic acid and/or methacrylic acid and monomers which are derived from other acrylic or vinyl monomers, such as C10-30 alkyl acrylates, C10-30-alkyl methacry-lates and vinyl acetate and vinylpyrrolidones.
-Thickening polymers of natural origin, for example based on cellulose, guar gum, xanthan, scleroglucan, gellan gum, rhamsan and karaya gum, alginates, maltodextrin, starch and its derivatives, carob seed flour, hyaluronic acid, carrageenan.
-Nonionic, anionic, cationic or amphoteric associative polymers, e.g. based on polyethylene glycols and their derivatives, or polyurethanes.
-Crosslinked or uncrosslinked homopolymers or copolymers based on acrylamide or methacrylamide, such as homopolymers of 2-acrylamido-2-methylpropanesulphonic acid, copolymers of acrylamide or methacrylamide and methacryloyloxyethyltrimethylammo-nium chloride or copolymers of acrylamide and 2-acrylamido-2-methylpropanesulphonic acid.
Particularly advantageous thickeners are thickening polymers of natural origin, crosslinked acrylic acid or methacrylic acid homopolymers or copolymers and crosslinked copolymers of 2-acrylamido-2-methylpropanesulphonic acid.
Very particularly advantageous thickeners are xanthan gum, such as the products supplied under the names and by CP Kelco or the products from RHODIA with the name Rhodo-pol, and guar gum, such as the products available under the name HP 105 from RHODIA.
Further very particularly advantageous thickeners are crosslinked homopolymers of methacrylic acid or acrylic acid which are commercially available from Noveon under the names 940, 941, 980, 981, ETD 2001, EDT 2050, 2984, 5984 and Ultrez 10, from 3V under the names K, L and MS.
Further very particularly advantageous thickeners are crosslinked polymers of acrylic acid or methacrylic acid and a C_10-30-alkyl acrylate or C_10-30-alkyl methacrylate and copolymers of acrylic acid or methacrylic acid and vinylpyrrolidone. Such copolymers are commercially available, for example, from Noveon under the names 1342, 1382, TR1 or Pe- TR2 and from Ashland under the names Ultrathix P-100 (INCI: Acrylic Acid/VP Cross-polymer) .
Very particular advantageous thickeners are crosslinked copolymers of 2-acrylamido-2-methylpropanesulphonic acid. Such copolymers are available, for example, from Clariant under the names AVC (INCI: Ammonium Acryloyldimethyltaurate/VP Copolymer) .
These thickeners are preferably present in the composition in a concentration in the range of from about 0％to 2％by weight, preferably 0％to 1％by weight, based on the total weight of the com-position.
Preferably, the composition is a water-in-oil or water-in-silicone emulsion. Preference is given to water-in-oil (W/O) or water-in-silicone emulsions (W/Si) which comprise one or more silicone emulsifiers (W/S) with an HLB value of ≤ 8 or one or more W/O emulsifiers with an HLB value of < 7 and optionally one or more O/W emulsifiers with an HLB value of > 10.
The silicone emulsifiers can advantageously be selected from the group selected from alkyldime-thicone copolyols, such as, for example, cetyl PEG/PPG 10/1 dimethicone copolyol ( EM 90 from Evonik) or lauryl PEG/PPG-18/18 dimethicones (Dow 5200 from Dow Corning Ltd. ) and dimethicone copolyols, such as, for example, PEG-10 dimethicones (KF-6017 from Shin Etsu) , PEG/PPG-18/18 dimethicones (Dow Corning 5225C from Dow Corning Ltd. ) , PEG/PPG-19/19 dimethicones (Dow Corning BY-11 030 from Dow Corning Ltd. ) , trimethylsilylamodimethi-cones or mixtures of at least two thereof.
The W/O emulsifiers with an HLB value of < 7 can advantageously be selected from the following group: fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and/or unsatu-rated, branched and/or unbranched alkanecarboxylic acids of chain length of from 8 to 24, in par-ticular 12-18 carbon atoms, diglycerol esters of saturated and/or unsaturated, branched and/or un-branched alkanecarboxylic acids of chain length from 8 to 24, in particular 12-18, carbon atoms, monoglycerol ethers of saturated and/or unsaturated, branched and/or unbranched alcohols of chain length of from 8 to 24, in particular 12-18, carbon atoms, diglycerol ethers of saturated and/or un-saturated, branched and/or unbranched alcohols of chain length from 8 to 24, in particular 12-18, carbon atoms, propylene glycol esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids of chain length from 8 to 24, in particular 12-18, carbon atoms, and also sorbitan esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids of chain length from 8 to 24, in particular 12-18, carbon atoms or a mixture of at least two thereof.
Particularly advantageous W/O emulsifiers are: glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate, diglyceryl monostearate, diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan mono-caprylate, sorbitan monoisooleate, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alco-hol, behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2) , glyceryl monolaurate, glyceryl monocaprate and glyceryl monocaprylate or mixtures of at least two thereof.
Further possible W/O emulsifiers are selected from the group consisting of polyglyceryl-2 dipoly-hydroxystearate, PEG-30 dipolyhydroxystearate, cetyldimethicone copolyol and polyglyceryl-3 diisostearate or mixtures of at least two thereof.
The O/W emulsifiers with an HLB value of > 10 can advantageously be selected from the group consisting of lecithin, trilaureth-4 phosphate, polysorbate-20, polysorbate-60, PEG-22 dodecyl gly-col copolymer, sucrose stearate and sucrose laurate or mixtures of at least two thereof.
An oil thickener can advantageously be used for stabilizing the W/O emulsion according to the in-vention against sedimentation or flocculation of the water droplets.
Particularly advantageous oil thickeners are organomodified clays, such as organomodified ben-tonites ( 34 from Rheox) , organomodified hectorites ( 27 and 38 from Rheox) or organomodified montmorillonite, hydrophobic pyrogenic silica, where the silanol groups are substituted by trimethylsiloxy groups ( R812 from Evonik) or with dimethylsiloxy groups or polydimethylsiloxane ( R972, R974 from Evonik, CAB-O-TS-610, "CAB-O- TS-720 from Cabot) , magnesium or aluminium stearate, or styrene co-polymers, such as, for example, styrene-butadiene-styrene, styrene-isopropene-styrene, styrene-ethylene/butene-styrene or styrene-ethylene/propene-styrene.
The thickener for the fatty phase can be present in an amount of from 0.1 to 5％by weight, based on the total weight of the emulsion, and better 0.4 to 3％by weight.
The aqueous phase can also comprise stabilizers. The stabilizer can be, for example, sodium chlo-ride, magnesium chloride or magnesium sulphate and mixtures thereof.
Oils can be used in W/O, W/Si and O/W emulsions.
If present, the fatty phase of the composition according to the invention can comprise one non-volatile oil and/or volatile oils and waxes. The O/W composition comprises advantageously 0.01 to 45％by weight of oils, based on the total weight of the composition, and particularly advanta-geously 0.01 to 20％by weight of oils. The W/O or W/Si composition advantageously comprises at least 20％by weight of oils, based on the total weight of the composition.
The non-volatile oil is advantageously selected from the group of mineral, animal, vegetable or synthetic origin, polar or nonpolar oils and mixtures thereof.
The lipid phase of the cosmetic or dermatological emulsions according to the invention can advan-tageously be selected from the following group of substances:
mineral oils, mineral waxes, polar oils, such as triglycerides of capric acid or of caprylic acid, also natural oils, such as, for example, castor oil, fats, waxes and other natural and synthetic fatty bodies, preferably esters of fatty acids with alcohols of low carbon number, e.g. with isopropanol, propyl-ene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low carbon number or with fatty acids, or mixtures of at least two thereof；
alkyl benzoates； silicone oils, such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysi-loxanes, and mixtures of at least two thereof.
The polar oils are advantageously selected from the group:
a) esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids of chain length from 3 to 30 carbon atoms and saturated and/or unsaturated, branched and/or un-branched alcohols of chain length from 3 to 30 carbon atoms, or mixtures of at least two thereof；
b) esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or un-branched alcohols of chain length from 3 to 30 carbon atoms, or mixtures of at least two thereof.
Such ester oils can then advantageously be selected from the group:
isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, isotridecyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-ethylhexyl isostearate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, 2-ethylhexyl cocoate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, dicaprylyl carbonate ( CC) and cocoglycerides ( 331) , and also syn-thetic, semisynthetic and natural mixtures of such esters, e.g. jojoba oil, or mixtures of at least two thereof.
c) alkyl benzoates C12-15-alkyl benzoate ( TN from Finetex) or 2-phenylethyl benzoate (X- 226 from Ashland)
d) lecithins and the fatty acid triglycerides, namely the triglycerol esters of saturated and/or unsatu-rated, branched and/or unbranched alkanecarboxylic acids of chain length from 8 to 24, in particu-lar 12 to 18 carbon atoms. For example, the fatty acid triglycerides can be selected from the group of cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, safflower oil, evening primrose oil, macada-mia nut oil, apricot kernel oil, avocado oil and the like, or mixtures of at least two thereof.
e) of dialkyl ethers and dialkyl carbonates, e.g. dicaprylyl ether ( OE from BASF) and/or dicaprylyl carbonate (for example CC from BASF) are advantageous
f) of saturated or unsaturated, branched or unbranched alcohols, such as, for example, octyldodeca-nol.
The non-volatile oil can likewise advantageously also be a nonpolar oil which is selected from the group of branched and unbranched hydrocarbons, in particular mineral oil, vaseline oil, paraffin oil, squalane and squalene, polyolefins, for example polydecenes, hydrogenated polyisobutenes, C13-16 isoparaffin and isohexadecane or mixtures of at least two thereof.
The nonpolar non-volatile oil can be selected among the non-volatile silicone oils.
Of the non-volatile silicone oils, the polydimethylsiloxanes (PDMS) , which are optionally phenylated, such as phenyltrimethicone, or are optionally substituted with aliphatic and/or aromatic groups or with functional groups, for example hydroxyl groups, thiol groups and/or amino groups； polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes and mixtures thereof can be given.
Particularly advantageous oils are 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isonona-noate, isoeicosane, 2-ethylhexyl cocoate, C12-15 alkyl benzoate, caprylic/capric triglyceride, di-caprylyl ether, mineral oil, dicaprylyl carbonate, cocoglycerides, butylene glycol dicapry-late/dicaprate, hydrogenated polyisobutenes, cetaryl isononanoates, isodecyl neopentanoates, squalane, C13-16 isoparaffin or mixtures of at least two thereof.
The composition according to the invention preferably comprises a wax.
Within the context of the present specification, a wax is defined as a lipophilic fatty substance which is solid at room temperature (25℃) and exhibits a reversible solid/liquid change in state at a melting temperature between 30℃ and 200℃. Above the melting point, the wax becomes low vis-cosity and is miscible with oils.
The wax is advantageously selected from the group consisting of natural waxes, such as, for exam-ple, cotton wax, carnauba wax, candelilla wax, esparto wax, Japan wax, Montan wax, sugarcane wax, beeswax, wool wax, shellac, microwaxes, ceresine, ozokerite, ouricury wax, cork fibre wax, lignite waxes, berry wax, shea butter or synthetic waxes, such as paraffin waxes, polyethylene waxes, waxes produced by Fischer-Tropsch synthesis, hydrogenated oils, fatty acid esters and glycerides which are solid at 25℃, silicone waxes and derivatives (alkyl derivatives, alkoxy de-rivatives, and/or esters of polymethylsiloxane) or mixtures of at least two thereof. The waxes can be present in the form of stable dispersions of colloidal wax particles which can be prepared by known processes, for example as in "Microemulsions Theory and Practice" , L.M. Prince Ed., Aca-demic Press (1977) , pages 21-32.
Waxes may be present in amounts of from 0 to 10％by weight, based on the total weight of the composition, and preferably 0 to 5％by weight.
The composition preferably comprises a volatile oil which is selected from the group of volatile hydrocarbon oils, siliconized oils or fluorinated oils.
The volatile oil can be present in an amount of from 0 to 25％by weight, based on the total weight of the emulsion, preferably 0 to 20％by weight and even more preferably 0 to 15％by weight.
Within the context of the present specification, a volatile oil is oil which, upon contact with the skin at room temperature and atmospheric pressure, evaporates in less than one hour. The volatile oil is liquid at room temperature and, at room temperature and atmospheric pressure, has a vapour pressure of from 0.13 to 40 000 Pa (10^–3 to 300 mm Hg) , preferably 1.3 to 13 000 Pa (0.01 to 100 mmHg) and particularly preferably 1.3 to 1300 Pa (0.01 to 10 mmHg) and a boiling point of from 150 to 260℃ and preferably 170 to 250℃.
Hydrocarbon oil is understood as an oil which is formed essentially from carbon atoms and hydro-gen atoms and optionally oxygen atoms or nitrogen atoms and contains no silicon atoms or fluorine atoms, where it may also consist of carbon atoms and hydrogen atoms； however, it can also contain ester groups, ether groups, amino groups or amide groups.
Siliconized oil is understood as oil which contains at least one silicon atom and in particular Si-O groups.
Fluorinated oil is to be understood as oil which contains at least one fluorine atom.
The volatile hydrocarbon oil according to the invention can be selected from the hydrocarbon oils with a flash point of from 40 to 102℃, preferably 40 to 55℃ and even more preferably 40 to 50℃.
For example, the volatile hydrocarbon oils are those with 8 to 16 carbon atoms and mixtures thereof, in particular branched C_8-16-alkanes, such as the isoalkanes (which are also referred to as isoparaffins) with 8 to 16 carbon atoms, isododecane, isodecane, isohexadecane and, for example, the oils which are supplied under the tradenames or ； and the branched C_8-16-esters, such as isohexyl neopentanoate or mixtures of at least two thereof.
The volatile hydrocarbon oils such as isododecane, isodecane and isohexadecane are particularly advantageous.
The volatile siliconized oil is preferably selected from the siliconized oils with a flash point of from 40 to 102℃, preferably a flash point above 55℃ and at most 95℃ and particularly preferably in the range from 65 to 95℃.
For example, the volatile siliconized oils are straight-chain or cyclic silicone oils having 2 to 7 sili-con atoms, where these silicones optionally contain alkyl or alkoxy groups having 1 to 10 carbon atoms.
The volatile siliconized oils are preferably selected from the group consisting of octamethylcy-clotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyl-hexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, de-camethyltetrasiloxane, dodecamethylpentasiloxane or mixtures of at least two thereof.
The volatile fluorinated oil generally has no flash point.
For example, the volatile fluorinated oils are nonafluoroethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane or mixtures of at least two thereof. Preferably, the composition comprises water and optionally a water-miscible organic solvent.
The water used in the composition preferably is selected from the group consisting of a blossom water, pure demineralized water, mineral water, thermal water and seawater or mixtures of at least two thereof.
In the case of an O/W composition, the water fraction can be in the range from 40 to 95％by weight, preferably in the range from 50 to 90％by weight, very particularly in the range from 60 to 80％by weight, based on the total weight of the composition. In the case of a W/O composition, the water fraction is in the range from 0 to 60％by weight, preferably in the range from 10 to 50％by weight, very preferably in the range from 30 to 50％by weight, based on the total weight of the composition.
Preferred solvents are, for example, the aliphatic alcohols with C1-4 carbon atoms, such as ethanol and isopropanol； polyol and derivatives thereof, such as propylene glycol, dipropylene glycol, bu-tylene-1, 3 glycol, polypropylene glycol, glycol ethers such as alkyl (C1-4) ethers of mono-, di-or tripropylene glycol or mono-, di-or triethylene glycol, and mixtures thereof.
The quantitative fraction of the solvent or solvents in the composition are preferably in the range of from 0 to 25％by weight, or preferably 0 to 15％by weight, based on the total weight of the com-position.
The composition can additionally comprise additives which are customary in cosmetics, such as antioxidants, photoprotective agents and/or other auxiliaries and additives, such as, for example, emulsifiers, interface-active substances, antifoams, thickeners, like standard aqueous or lipophilic gelling agents and/or thickeners, surfactants, active ingredients like hydrophilic or lipophilic active agents, humectants, filler, UV filters, film formers, solvents, coalescing agents, aroma substances, odour absorbers, perfumes, fragrances, emulsifiers, moisturizers, pigmenting agents, depigmenting agents, keratolytic agents, vitamins, emollients, sequestering agents, surfactants, polymers, acidify-ing or basifying agents, free-radical scavengers, ceramides, sunscreens, especially ultraviolet screening agents, insect repellents, slimming agents, dyestuffs, bactericides and anti-dandruff agents, gel formers and/or other polymer dispersions, such as, for example, dispersions based on polyacrylates, pigments, dyes, flow agents and/or thixotropic agents, suppleness agents, softeners, preservatiing agents. The amounts of the various additives are known to the person skilled in the art for the range to be used. The total amount of additives is preferably in the range of from 0 to 25 wt. -％, based on the total weight of the composition. Each of the mentioned additives is prefera-bly part of the composition in a range of from 0 to 5 wt. -％, or preferably in a range of from 0 to 3 wt. -％, or preferably in a range of from 0.1 to 2 wt. -％, based on the total weight of the composi-tion.
The composition preferably also comprises sensory additives. Sensory additives are to be under-stood as colourless or white, mineral or synthetic, lamellar, spherical or elongated inert particles or a nonparticulate sensory additive which, for example, further improve the sensory properties of the formulations and, for example, leave behind a velvety or silky skin feel.
The sensory additives can be present in the composition according to the invention, for example, in an amount of from 0 to 10％by weight, based on the total weight of the composition, and prefera-bly from 0 to 7％by weight.
Advantageous particulate sensory additives within the context of the present invention are talc, mica, silicon dioxide, kaolin, starch and derivatives thereof (for example tapioca starch, distarch phosphate, aluminium and sodium starch octenyl succinate and the like) , pyrogenic silica, pigments which have neither primarily a UV-filter effect nor colouring effect (such as e.g. boron nitride etc. ) , boron nitride, calcium carbonate, dicalcium phosphate, magnesium carbonate, magnesium hydro-gencarbonate, hydroxyapatites, microcrystalline cellulose, powders of synthetic polymers, such as polyamides (for example the polymers available under the trade name ) , polyethylene, poly-β-alanine, polytetrafluoroethylene polyacrylate, polyurethane, lauroyl-lysine, silicone resin (for example the polymers available under the trade name from Kobo Products Inc. ) , hollow particles of polyvinylidene/acrylonitriles ( from Akzo Nobel) or hollow particles of silicon oxide (Silica from MAPRECOS) .
Advantageous nonparticulate sensory additives are preferably selected from the group consisting of dimethiconols (e.g. Dow Corning 1503 Fluid from Dow Corning Ltd. ) , silicone copolymers (e.g. divinyldimethicone/dimethicone copolymer, Dow Corning HMW 2220 from Dow Corning Ltd. ) or silicone elasters (e.g. dimethicone crosspolymer, Dow Corning 9040 Silicone Elastomer Blend from Dow Corning Ltd. ) or mixtures of at least two thereof.
The composition preferably comprises sunscreen filters, where the total amount of the sunscreen filter is 0％by weight to 30％by weight, or preferably 0％by weight to 20％by weight, particularly prferably 0％by weight to 10％by weight, based on the total weight of the composition according to the invention. The sunscreen filters (or UV filters) can in particular be selected from the organic filters, the physical filters or mixtures of at least two thereof. In a preferred embodiment of the in- vention the composition does not comprise a sunscreen filter.
The composition according to the invention can comprise UV-A filters, UV-B filters or broadband filters. The UV filters used can be oil-soluble or water-soluble. The list of specified UV filters be-low is of course not limiting.
Examples of the UV-B filters are:
· (1) salicylic acid derivatives, particularly homomenthyl salicylate, octyl salicylate and 4-isopropylbenzyl salicylate；
· (2) cinnamic acid derivatives, in particular 2-ethylhexyl p-methoxycinnamate, which is available from DSM under the name Parsol and isopentyl 4-methoxycinnamate；
· (3) liquid β, β' -diphenylacrylate derivatives, in particular 2-ethylhexyl α, β' -diphenylacrylate or octocrylene, which is available from BASF under the name UVINUL
· (4) p-aminobenzoic acid derivatives, in particular 2-ethylhexyl 4- (dimethylamino) benzoate, amyl 4- (dimethylamino) benzoate；
· (5) 3-benzylidenecamphor derivatives, in particular 3- (4-methylbenzylidene) camphor which is commercially available from Merck under the name EUSOLEX 3-benzylidenecamphor, benzylidenecamphor sulphonic acid and polyacrylamidomethyl-benzylidenecamphor；
· (6) 2-phenylbenzimidazole-5-sulphonic acid, which is available under the name EUSOLEX from Merck；
· (7) 1, 3, 5-triazine derivatives, in particular: –2, 4, 6-tris [p- (2' -ethylhexyl-1' -oxycarbonyl) anilino] -1, 3, 5-triazine, which is supplied by BASF under the name UVINUL and –dioctylbutamidotriazone, which is supplied by Sigma 3V under the name UVASORB
· (8) esters of benzalmalonic acid, in particular di (2-ethylhexyl) 4-methoxybenzalmalonate and 3- (4- (2, 2-bisethoxycarbonylvinyl) -phenoxy) propenyl) methoxysiloxane/dimethyl-siloxane copolymer, which is available from DSM under the name SLX； and
· (9) a mixture of at least two of these filters (1) to (8) .
Examples of UV-A filters are:
· (1) dibenzoylmethane derivatives, particularly 4- (t-butyl) -4' -methoxydibenzoylmethane, which is supplied by DSM under the name PARSOL and 1-phenyl-3- (4’ -isopropylphenyl) propane-1, 3-dione；
· (2) benzene-1, 4- [di (3-methylidenecamphor-10-sulphonic acid) ] , optionally completely or partially neutralized, commercially available under the name MEXORYL from Chimex.
· (3) hexyl 2- (4’ -diethylamino-2’ -hydroxybenzoyl) benzoate (also aminobenzophenone) ；
· (4) silane derivatives or polyorganosiloxanes with benzophenone groups；
· (5) anthranilates, particularly menthyl anthranilate, which is supplied by Symrise under the name NEO HELIOPAN
· (6) compounds which contain at least two benzoazolyl groups or at least one benzodiazolyl group per molecule, in particular 1, 4-bis-benzimidazolylphenylene-3, 3' , 5, 5' -tetrasulphonic acid and its salts, which are commercially available from Symrise；
· (7) silicon derivatives of benzimidazolylbenzazoles, which are N-substituted, or of benzo-furanylbenzazoles, in particular: –2- [1- [3- [1, 3, 3, 3-tetramethyl-l-[ (trimethylsilyl) oxy] disiloxanyl] propyl] -1H-benzimidazol-2-yl] benzoxazole； –2- [1- [3- [1, 3, 3, 3-tetramethyl-l- [ (trimethylsilyl) oxy] disiloxanyl] propyl] -1H-benzimidazol-2-yl] benzothiazole； –2- [1- (3-trimethylsilanylpropyl) -1H-benzimidazol-2-yl] benzoxazole； –6-methoxy-1, 1' -bis (3-trimethylsilanylpropyl) 1H, 1' H- [2, 2' ] dibenzimidazolyl-benzoxazole； –2- [1- (3-trimethylsilanylpropyl) -1H-benzimidazol-2-yl] benzothiazole； which are described in the patent application EP-A-1 028 120；
· (8) triazine derivatives, in particular 2, 4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, which is supplied by 3V under the name K2A； and
· (9) a mixture of at least two of these filters (1) to (8) .
Examples of broadband filters are:
· (1) benzophenone derivatives, for example –2, 4-dihydroxybenzophenone (benzophenone-1) ； –2, 2' , 4, 4' -tetrahydroxybenzophenone (benzophenone-2) ； –2-hydroxy-4-methoxybenzophenone (benzophenone-3) , available from BASF under the name UNIVNUL –2-hydroxy-4-methoxybenzophenone-5-sulphonic acid (benzophe-none-4) , and its sulphonate form (benzophenone-5) , commercially available from BASF under the name UVINUL –2, 2' -dihydroxy-4, 4' -dimethoxybenzophenone (benzo-phenone-6-) ； –5-chloro-2-hydroxybenzophenone (benzophenone-7-) ； –2, 2' -dihydroxy-4-methoxybenzophenone (benzophenone-8) ； –the disodium salt of 2, 2' -dihydroxy-4, 4' -dimethoxybenzophenone-5, 5' -disulphonic acid (benzophenone-9-) ； –2-hydroxy-4-methoxy-4' -methylbenzophenone (benzophenone-10) ； –benzophenone-11； –2-hydroxy-4- (octyloxy) benzophenone (benzophenone-12) .
· (2) triazine derivatives, in particular 2, 4-bis { [4-2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3, 5-triazine, which is supplied by BASF under the name TINOSORB and 2, 2' -methylenebis [6- (2H-benzotriazol-2-yl) 4- (1, 1, 3, 3-tetramethylbutyl) phenol] , which is available from BASF under the name TINOSORBand
· (3) 2- (1H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1, 3, 3, 3-tetramethyl-1- [ (trimethylsilyl) oxy] disiloxanyl] propyl] phenol with the INCI name Drometrizole Trisilox-ane.
It is also possible to use a mixture of two or more filters and a mixture of UV-B filters, UV-A fil-ters and broadband filters, and also mixtures with physical filters.
Of the physical filters, the sulphates of barium, oxides of titanium (titanium dioxide, amorphous or crystalline in the form of rutile and/or anatase) , of zinc, of iron, of zirconium, of cerium, silicon, manganese or mixtures thereof may be given. The metal oxides can be present in particle form with a size in the micrometre range or nanometre range (nanopigments) . The average particle sizes for the nanopigments are, for example, 5 to 100 nm.
The compositions according to the invention can furthermore comprise humectants. Preferably, the composition of the invention comprises a humectrant in a range of from 1 to 15 wt. -％, or prefera-bly in a range of from 5 to 10, or preferably in a range of from 6 to 9 wt. -％.
Particularly advantageous humectants or moisturizers within the context of the present invention are, for example, glycerol, polyglycerol, sorbitol, dimethyl isosorbide, lactic acid and/or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, hy-droxyethylurea, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. In addition, it is es-pecially advantageous to use polymeric “moisturizers” from the group of water-soluble and/or wa-ter-swellable and/or water-gellable polysaccharides. For example, hyaluronic acid, chitosan and/or a fucose-rich polysaccharide, which is available under the name Fucogel^TM 1000 from SOLABIA S.A., are especially advantageous.
Within the context of the present invention, water-soluble antioxidants can be used particularly ad-vantageously, such as, for example, vitamins, e.g. ascorbic acid and derivatives thereof. Vitamin E and derivatives thereof, and also vitamin A and derivatives thereof are very particularly advanta-geous.
Further advantageous active ingredients in the composition are α-hydroxy acid, such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and mandelic acid, β-hydroxy acid, such as salicylic acid, and acylated derivatives thereof, 2-hydroxyalkanoic acid and its derivatives； natural active ingredients and/or derivatives thereof, such as, for example, alpha-lipoic acid, folic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and/or syn-thetic isoflavonoids, creatin, creatinine, taurine and/or [beta] -alanine and also 8-hexadecene-1, 16-dicarboxylic acid (dioic acid, CAS number 20701-68-2； provisional INCI name Octadecenedioic acid) and Licochalcon A and the plant extracts or mixtures of at least two thereof.
A further aspect of the invention is a composition comprising a polyurethane for use as a pharma-ceutical product. Preferably, the pharmaceutical product is applied extracorporally. The pharma-ceutical is preferably applied to at least a part of a surface of a human or an animal. Preferably, the pharmaceutical product is applied to the areas of a body of a human or animal that is or will be ex-posed to a polluted surrounding. The surface is preferably selected from the group consisting of skin, scalp and hair or mixtures of at least two thereof. The composition comprises the polyure-thane preferably in the range of from 1 to 30 wt. -％, or preferably in the range of from 2 to 20 wt. -％, or preferably in the range of from 3 to 15 wt. -％, or preferably in the range of from 4 to 10 wt. -％, based on the total weight of the composition. The components, materials, ranges of components and materials, their properties and dimensions described for the polyurethane in relation to the pharmaceutical and/or cosmetic and/or dermatologic composition also apply to the polyurethane for use as a pharmaceutical product.
A further aspect of the invention is a composition comprising a polyurethane for use in the protec-tion of a surface against potential pollutants. The surface could be any surface the person skilled in the art would select to protect with the polyurethane. The surface is preferably selected from the group consisting of a skin, a scalp, hair or a combination of at least two thereof. Preferably, the sur-face is a surface of a human or an animal. Furthermore, preferably the surface is a skin, a scalp or hair of a human or an animal. Especially preferred the surface is the skin, especially the face of a human. The potential pollutant could be any pollutant that is known to the person skilled in the art. Examples of pollutants have already been mentioned in the context of the pharmaceutical composi-tion. These potential pollutants might be the same in the context of the composition comprising a polyurethane for use in the protection of a surface against it. Preferably, the potential pollutant is a hazardous contaminant. A hazardous contaminant or pollutant in the context of the invention is a contaminant or pollutant, for example in form of a particular matter (PM) which is known to cause harm to at least a part of living beings but also to a least a part of death materials, like textiles. The harm could be any change of state of the health, look or appearance of the living body or death ma-terial. A change of a state of health could be an allergic reaction or an inflammation of the con-tacted part of the living body with the pollutant or hazardous contaminant. An example of a harm-ful pollutant or hazardous contaminant is the smoke of a cigarette. Preferably, the smoke of a ciga-rette comprises PM₁₀ and/or PM_2.5 particles.
In a further aspect of the present invention, the use of a composition comprising a polyurethane as protection of a surface against dust is provided. According to a respective embodiment of the uses of the present invention, the polyurethane is as defined in any one of the embodiments of the phar-maceutical composition mentioned before. The surface could be any surface the person skilled in the art would select to protect with the polyurethane. The surface is preferably selected from the group consisting of a skin, a scalp, hair, a textile, a floor, a car, a plant, a screen or a combination of at least two thereof. Preferably, the surface is a surface of a human or an animal. Furthermore, preferably the surface is a skin, a scalp or hair of a human or an animal or a breathing mask. Pref-erably, the surface is a skin or a scalp of a human or an animal. Especially preferred the surface is the skin, especially the face of a human. The dust could be any particle matter known by the person skilled in the art that can be part of the atmosphere. The dust could incorporate potential pollutants, however does not have to. Preferably, the amount of polyurethane applied to the surface via the composition of the invention is in a range of from 0.01 mg/cm² to 1 mg/cm², or preferably in a range of from 0.05 mg/cm² to 0.5 mg/cm², or preferably in a range of from 0.08 mg/cm² to 0.7 mg/cm².
A further aspect of the invention is a polyurethane composition for protecting a surface of a human or an animal against potential pollutants. The surface could be any surface the person skilled in the art would select to protect on a human or animal with the polyurethane. The surface is preferably selected from the group consisting of a skin, a scalp, hair or a combination of at least two thereof. Preferably, the surface is a surface of a human or an animal. Furthermore, preferably the surface is a skin, a scalp or hair of a human. Especially preferred the surface is the skin, especially the face of a human. The pollutant could be any pollutant that is known to the person skilled in the art. Exam-ples of pollutants have already been mentioned in the context of the pharmaceutical composition and the composition comprising a polyurethane for use in the protection of a surface against pollut-ants. These pollutants might be the same in the context of the composition comprising a polyure-thane for use in the protection of a surface against it. Preferably, the pollutant is a hazardous con-taminant. A hazardous contaminant in the context of the invention is a contaminant which is known to cause harm to at least a part of living beings but also to a least a part of death materials, like tex-tiles. The harm could be any change of state of the health, look or appearance of the living body or death material. An example of a harmful pollutant or hazardous contaminant is the smoke of a ciga-rette. Preferably, the pollutants are removable nearly completely by the use of water. Nearly com-pletely removable in the sense of the invention means, that more than 70 wt. -％, preferably more than 80 wt. -％, or preferably more than 90 wt. -％of the pollutants bound to the polyurethane com-position applied to the skin are removed by rinsing with water. The extend of removed pollutants from the skin protected by the polyurethane composition is preferably at least twice, or preferably at least three times, or preferably at least 10 times higer than the removed pollutants from the skin that has not been protected by the polyurethane composition. Especially, the penetration of PM_2.5 and PM₁₀ pollutants can be reduced by the use of the polyurethane composition on skin in the ranges of preferably at least twice, or preferably at least three times, or preferably at least 10 times compared to the removed pollutants from the skin that has not been protected by the polyurethane composition.
A further aspect of the invention is a multi-layer structure comprising at least two layers A) and B) , wherein layer A) comprises a polyurethane and wherein layer B) is different from layer A) . The layer A) preferably comprises the polyurethane as described above. More preferably, layer A) comprises the polyurethane in a range of 10 to 100 wt. -％, or preferably in a range of from 50 to 100 wt. -％, or preferably in a range of from 80 to 100 wt. -％, or in a range of from 80 to 98 wt. -％, or in a range of from 80 to 95 wt. -％, in each case based on the total weight of the layer A) . The polyurethane is preferably obtained in a way as described in the context of the pharmaceutical composition above.
Layer B) can comprise any material the person skilled would select for the multi-layer structure. Preferably, the layer B) comprises a material that is different from the material of layer A) to ex-tend of at least 10 wt. -％, or preferably to an extend of at least 30 wt. -％, or preferably to an extend of at least 70 wt. -％, based on the total weight of layer B) . Preferably, the material of layer B) is selected from a textile, a non-woven, a fibre, a composite or a combination of at least two thereof. The material of layer B) is preferably selected from the group consisting of a cotton, a wool, a vis-cose, a polymer or a mixture or combination of at least two thereof. The polymer is preferably se-lected from the group consisting of a polyacrylate, a polyamide, a polyester, a polycarbonate, a polyurethane, a polyimide or a combination of at least two thereof. Preferably, the layer B) is at least a part of a breathing mask, a protection cap, protection cloth.
A further aspect of the invention is related to a method for increasing the removability of a poten-tial pollutant from a surface comprising at least the following steps:
i. Applying a composition comprising at least one polyurethane to at least a part of the surface, whereby a treated part of surface is achieved；
ii. Optionally, exposing the treated part of surface of step i. for at least 1 minute to the potential pollutant；
iii. Optionally, removing the potential pollutant from the treated part of the surface of step i. or ii.
The surface from which the pollutant is removed in this method can be any surface the person skilled in the art would choose. Preferably, the surface is selected from the surfaces already de-scribed with respect to the pharmaceutical composition or the use of a polyurethane in a pharma-ceutical. Preferably, the surface is selected from the group consisting of skin, scalp, hair, a breath-ing mask or a combination of at least two thereof. The pollutant can be any pollutant the person skilled in the art would select for the method. Preferably, the pollutant is one that has already been described above. The polyurethane is preferably one that has been described before with respect to the pharmaceutical and /or cosmetical composition. Preferably, if the surface is a surface of a hu-man or animal the method of the present invention solely relates to the cosmetical aspects of pro-tecting the surface and does not include any pharmaceutical aspects.
Applying a composition comprising the at least one polyurethane to at least a part of the surface in step i. can be achieved by any application method the person skilled in the art would choose. Pref-erably, applying the composition in step i. is selected from the group consisting of applying by hand, applying by brush, applying by spatula, applying by spraying, applying by printing or a com-bination of at least two thereof. Preferably, the applying is provided by hand, by spatula or by brush.
Optionally, in addition to step i. a further step, e.g. step ii. and/or step iii. can be part of the method. Step ii. is preferably an exposing of the treated surface to a potential pollutant. Step ii. preferably is achieved by exposing the surface, preferably the skin of the user, to a polluted surrounding, espe-cially to a polluted air. However, because the degree of pollution sometimes is unkown, step ii. is no mandatory part of the method of the present invention. This means that cases where a pollution is expected and therefore step i. is conducted, but in fact there is no pollution, are encompassed by the scope of the present invention. Potential pollutants could be any material that might cause harm to a human or animal. Examples of pollutants have already been described above. Preferably, ex-posing of the treated surface should last for a period in a range of from 1 second to 48 hours or pre-ferably in a range of from 30 seconds to 36 hours, or preferably in a range from 1 minute to 24 hours.
In a further optional step iii. a removing of the potential pollutant from the treated part of the sur-face is achieved. In accordance with step ii. being optional, step iii. is optional, too, because in some cases according to the present invention, in fact there is no potential pollutant to be removed. Removing the pollutant from the treated part of surface, preferably from the skin of a user is estab-lished by rinsing the treated part of skin with water. The rinsing is preferably established for a pe-riod of time in a range of from 1 second to 15 minutes or preferably in a range of from 30 seconds to 10 minutes, or preferably in a range from 1 minute to 5 minutes. The removing of the pollutant in step iii. preferably is supported by applying a pressure to the surface. The applying of a pressure could be established by brushing.
A further aspect of the invention is related to a film comprising a polyurethane, whereby the film has at least one of the following features:
a. a permeability for particles with a PM_2.5 in the range of from 0 to 20 ％, or preferably in the range of from 0 to 10 ％, preferably in the range of from 0 to 5 ％, based on the total amount of particles with PM_2.5；
b. a permeability for particles with a PM₁₀ in the range of from 0 to 20 ％, or preferably in the range of from 0 to 10 ％, preferably in the range of from 0 to 5 ％, based on the total amount of particles with PM₁₀；
c. a tensile strength at 100％elongation in the range of from 1 to 10 N/mm², or preferably in the range of 1 to 7 N/mm², or preferably in the range of 1 to 5 N/mm²；
d. a tensile strength at break in a range of from 5 to 40 N/mm², or preferably in a range of from 10 to 35 N/mm², or preferably in a range of from 10 to 30 N/mm²,
e. a break at an elongation in the range of from 300 to 2500％, or preferably in a range of from 400 to 2300 ％, or preferably in a range of from 500 to 2000 ％；
f. a content of polyurethane in a range of from 5 to 100 wt. -％, or preferably in a range of from 10 to 95 wt. -％, or preferably in a range of from 50 to 95 wt. -％, or preferably in a range of from 80 to 95 wt. -％, based on the total mass of the film；
g. a thickness in a range of from 1 to 500 μm, or preferably in a range of from 10 to 450 μm, or preferably in a range of from 50 to 400 μm, or preferably in a range of from 90 to 300 μm.
According to the present invention the term “permeability” is preferably defined as the transport of the respective particles through the film via diffusion. In this context it is preferred that no external pressure is applied, i.e. that the particles freely diffuse according to general physical laws. Howev-er, due to interactions of the polyurethane and the respective particles an active transport mechan-ism through the film might be also present. Finally, also sieving aspects, e.g. the exclusion of par-ticles by their size, might also additional occur. Accordingly, permeability preferably means the flux of the particles through the time without any external pressure. Without any external pressure preferably also includes the breathing of a human or animal through a breathing mask protected by the composition according to the invention. The determination of the features of the composition or the film according to the invention are always established at room temperature (23 ℃ ± 1℃) and normal pressure (1013 mbar ± 10 mbar) .
The mechanical properties of the film samples according to the invention are determined after 24 h of storage under standard conditions (20℃ and 65％atmospheric humidity) in accordance with DIN 53504. Mechanical film properties are determined after 30 minutes of drying at 150℃.
The permeability is determined by a PM-Meter (Company: NuoFangWei China, Type: SDL301) . Results of permeability experiments are shown in figure 3 together with its description.
The tensile strength has been measured as σ_max ＝ tensile strength in N/mm² as knownto the person skilled in the art.
The elongation at breack is measured in ε_b ＝ elongation at break in ％as well known to the persion skilled in the art.
The thickness is determined by SEM as described in connection with the description of the figures section below.
The present invention is illustrated by reference to examples, although these are not to be under-stood as being limiting. Unless stated otherwise, all of the quantitative data, fractions and percent-ages are based on the weight and the total amount or on the total weight of the compositions.
Examples:
Unless noted otherwise, all of the analytical measurements refer to measurements at temperatures of 23℃.
The solid or solid-body contents are determined by heating a weighed sample at 125℃ to constant weight. At constant weight, the solid-body content is calculated by reweighing the sample.
Unless expressly mentioned otherwise, NCO contents were determined volumetrically in accor-dance with DIN-EN ISO 11909.
The control on free NCO groups was carried out by means of IR spectroscopy (band at 2260 cm^-1) .
These stated viscosities were determined by means of rotary viscometry in accordance with DIN 53019 at 23℃ using a rotary viscometer from Anton Paar Germany GmbH, Ostfildern, Germany.
The average particle sizes (the number-average is given) of the polyurethane dispersions were de-termined following dilution with deionized water by means of laser correlation spectroscopy (in-strument: Malvern Zetasizer 1000, Malver Inst. Limited) .
Substances used and abbreviations:
Diaminosulphonate: NH₂-CH₂CH₂-NH-CH₂CH₂-SO₃Na (45％strength in water)
2020/C2200: Polycarbonate polyol, OH number 56 mg of KOH/g, number-average molecular weight 2000 g/mol (Covestro Deutschland AG, Leverkusen, Germany)
2000: Polytetramethylene glycol polyol, OH number 56 mg of KOH/g, number-average molecular weight 2000 g/mol (BASF AG, Ludwigshafen, Germany)
1000: Polytetramethylene glycol polyol, OH number 112 mg of KOH/g, number-average molecular weight 1000 g/mol (BASF AG, Ludwigshafen, Germany)
Polyether LB 25: monofunctional polyether based on ethylene oxide/propylene oxide of number-average molecular weight 2250 g/mol, OH number 25 mg of KOH/g (Covestro Deutschland AG, Leverkusen, Germany)
Example 1: Polyurethane dispersion 1
987.0 g of 2000 (component A2) ) , 375.4 g of 1000 (component A2) ) , 761.3 g of C2200 (component A2) ) and 44.3 g of polyether LB 25 (component A4)) were heated to 70℃ in a standard stirring apparatus. Then, a mixture of 237.0 g of hexamethylene diiso-cyanate (component A1) ) and 313.2 g of isophorone diisocyanate (component A1) ) was added and the mixture was stirred at 120℃ until the theoretical NCO value was reached. The finished pre-polymer was dissolved with 4830 g of acetone and in so doing cooled to 50℃, and then a solution of 25.1 g of ethylenediamine (component B1) ) , 116.5 g of isophoronediamine (component B1)) , 61.7 g of diaminosulphonate (component B2) ) and 1030 g of water was metered in. The afterstir-ring time was 10 min. The mixture was then dispersed by adding 1250 g of water. The solvent was removed by distillation in vacuo.
The resulting white dispersion had the following properties:
Example 2: Polyurethane dispersion 2
450 g of 1000 (component A2) ) and 2100 g of 2000 (component A2)) were heated to 70℃. Then, a mixture of 225.8 g of hexamethylene diisocyanate (component A1)) and 298.4 g of isophorone diisocyanate (component A1) ) was added and the mixture was stirred at 100-115℃ until the actual NCO value had dropped below the theoretical NCO value. The finished pre-polymer was dissolved with 5460 g of acetone at 50℃ and then a solution of 29.5 g of ethyl-enediamine (component B1) ) , 143.2 g of diaminosulphonate (component B2) ) and 610 g of water was metered in. The afterstirring time was 15 min. The mixture was then dispersed by adding 1880 g of water. The solvent was removed by distillation in vacuo and a storage-stable dispersion was obtained.
Solids content: 56％
Particle size (LCS) : 276 nm
Viscosity: 1000 mPas
Example 3: Polyurethane dispersion 3
1649.0 g of a polyester of adipic acid, hexanediol and neopentyl glycol with an average molecular weight of 1700 g/mol (component A2) ) were heated to 65℃. Then, 291.7 g of hexamethylene diisocyanate (component A1) ) were added and the mixture was stirred at 100-115℃ until the ac-tual NCO value had dropped below the theoretical NCO value. The finished prepolymer was dis-solved with 3450 g of acetone at 50℃ and then a solution of 16.8 g of ethylenediamine (compo-nent B1) ) , 109.7 g of diaminosulphonate (component B2) ) and 425 g of water was metered in. The afterstirring time was 15 min. The mixture was then dispersed by adding 1880 g of water. The sol-vent was removed by distillation in vacuo and a storage-stable dispersion was obtained.
Example 4: Polyurethane dispersion 4
340 g of a polyester of adipic acid, hexanediol and neopentyl glycol with an average molecular weight of 1700 g/mol (component A2) ) were heated to 65℃. Then, 60.1 g of hexamethylene diiso-cyanate (component A1) ) were added and the mixture was stirred at 105℃ until the actual NCO value had dropped below the theoretical NCO value. The finished prepolymer was dissolved with 711 g of acetone at 50℃ and then a solution of 2.1 g of ethylenediamine (component B1) ) , 32.4 g of diaminosulphonate (component B2) ) and 104.3 g of water was metered in. The afterstirring time was 15 min. The mixture was then dispersed by adding 1880 g of water. The solvent was removed by distillation in vacuo and a storage-stable dispersion was obtained.
Example 5: Polyurethane dispersion 5
450 g of 1000 (component A2) ) and 2100 g of 2000 (component A2)) were heated to 70℃. Then, a mixture of 225.8 g of hexamethylene diisocyanate (component A1) ) and 298.4 g of isophorone diisocyanate (component A1) ) was added and the mixture was stirred at 100-115℃ until the actual NCO value had dropped below the theoretical NCO value. The finished pre-polymer was dissolved with 5460 g of acetone at 50℃ and then a solution of 351 g of diaminosul-phonate (component B2) ) and 610 g of water was metered in. The afterstirring time was 15 min. The mixture was then dispersed by adding 1880 g of water. The solvent was removed by distilla-tion in vacuo and a storage-stable dispersion was obtained.
Solids content: 40％
Viscosity: 1370 mPas
APPLICATION EXAMPLES:
Example 6: Composition 6
Process of preparation:
1. Stir phase A well at room temperature (23 ℃) ；
2. Add phase B to phase A, stir well；
3. Add phase C to phase A/B, stir well.
The total amount of polyurethane in the composition
Example 7: Composition 7
The quantitative data in the tables below are ％by weight based on the total amount of the compo-sitions.
Process of preparation:
4. Phase A was pre-dispersed at 60～70℃ while stirring for half an hour.
5. Phase B was added to Phase A at 60～70℃ while strring for an hour.
6. Phase C was pre-dispersed at 60～70℃ while strring for an hour, and then added to Phase A+B.
7. Then the mixture Phase A/B/C was homogenized for 20 minutes.
8. Phase D and Phase E were added when the temperature was below 45℃, while stirring un-til phases were homogeneous.
Example 8: Composition 8
The quantitative data in the tables below are ％by weight based on the total amount of the compo-sition.
Process of Preparatrion: Phases A and B had been mixed with a spatula for 5 minutes to achieve a homogenous composition. The total content of polyurethane of the composition had been 4 wt. -％as the polyurethane-35 was provided as a dispersion with a solid content of 40 ％.
Example 9: Film 9
For froming a film from polyurethane, a dispersion of polyurethane-35, with a solid content of 40 wt. -％, based on the total weight of the dispersion, is filled in a film maker (Company: Shang-hai Moderner； Product Name: Film maker Equipment (90 μm) ) . The film maker is positioned on a glas plate and moved along a path of at least 10 cm over the glas plate. The resulted film was dried at room temperature for at least 10 hours. Afterwards, the film can be easily subtracted from the glas.
The invention is illustrated by figures 1 to 9. The figures only provide examples and should not be seen as restrictive to the features of the invention. The figures show:
Figure 1: a schematic view of a skin protected by a composition according to the invention；
Figure 2: a schematic view of a room for measuring the effect of protection by the composition according to the invention；
Figure 3: a diagram of results of the protection of a polyurethane composition according to the invention in form of a film compared to a mask and the status without protection；
Figure 4: a diagram of results of the protection of a polyurethane composition according to the invention used on a piece of cloth compared to the cloth without the composition and the status without cloth；
Figure 5a: a black and white photo of a skin part protected by the composition according to the invention compared to an unprotected part of skin after exposing to carbon black and rinsing with water；
Figure 5b: a colored photo of the same skin parts as shown in Figure 5a；
Figure 6: an illustration of a method according to the invention by applying the composition ac-cording to the invention prior to the exposing to carbon black compared to an applica-tion of carbon black on an unprotected part of skin；
Figure 7a: a diagram of results of the exposure of a cloth protected by a composition according to the invention comprising different amounts of polyurethane to a PM_2.5 atmosphere；
Figure 7b: a diagram of results of the exposure of a cloth protected by a composition according to the invention comprising different amounts of polyurethane to a PM₁₀ atmosphere；
Figure 8: a photo of a bottle filled with carbon black covered by a film made of a polyurethane according to the invention；
Figure 9: a diagram of a SEM recordings of both sides of a foil before and after exposition to car-bon black bottle.
Figure 1 is a schematic view onto a part of a skin 100 with cells of the epidermis 140 which is cov-ered by a film form after the application of a composition comprising polyurethane 120 according to any of examples 1 to 5. From a top view onto the skin 100, the film of polyurethane 120 has a structure as shown in the small picture 130 which is an SEM record of a composition according to example 6 applied to glass surface. The SEM microscope was from Olympus and the product name was CX21. The film of polyurethane 120 is illustrated as a layered structure with small gaps. These gaps which could also be seein in the picture 130 as black lines, have a dimension in the range of maximal 20 to 30 nm. Particles and also pollutants 110 with a diameter of around 10 μm (PM₁₀) , and also particles or pollutants 150 belonging to PM_2.5 with a diameter of around 2.5 μm have a dimension which is much bigger than these gaps and therefore can not penetrate the film of poly-urethane 120. The film of polyurethane 120 forms a kind of barrier against the particles blonging to PM_2.5 or PM₁₀. The protected part of skin 100 is not contaminated by the pollutants 110 and 150 because the particles or pollutants 110 and 150 don’ t even reach the uppest layer 160 of the skin 100. The uppest layer 160 is built by death cells of the skin 100 and may have gaps which are big-ger than the diameter of particles 110 or 150. Without the protecting film of polyurethane 120 the pollutants 110 and 150 may reach the very sensitive living cells of the epidermis 140. The pollut-ants 110 or 150 could cause harm to these epidermis cells 140 when coming into contact with them. This may cause allergic reactions or inflammations in the epidermis. Thus, the film of polyurethane 120 prevents the skin from getting polluted by the pollutants 110 and 150.
Figure 2 shows a room 200 in a schematical way which is bordered by a plastic floil 230. The room 200 is build to provide the possibility to artificially build a polluted volume of air with a well de-fined particle size and amount. Therefore, the room 200 is a totally closed system and no particles, like 110 and 150 can leave the room. To guarantee a well defined amount of particles a plate 240 with a certain amount of particles which all have a similar particle size is deposited in the room 200. A ventilator 210 is positioned in the room 200 to distribute the particles from plate 240 regularely in the room 200. In this example the particles are silica particles 150 with a particle diameter of 2.5 μm ± 10 ％to measure PM_2.5 values or particles 110 with a particle diameter of 10 μm ± 10 ％to measure PM₁₀ values. The amount of particles is measured via a PM-Meter 220 (Company: Nu-oFangWei, Type: SDL301) . The PM-Meter 220 (or also called PM-Tester) has an inlet where the particles can enter the PM-Meter during the tests. This inlet could be covered by different materials, like cloths or flims to measure the penetration hindering effect of these materials. The volume of room 200 is 37.5cm*24cm*29cm. This setup is used to establish all experiments that will follow. The PM-Meter measures the amount of particles per cm³.
Figure 3 shows a diagram for the measurement of the ability to prevent particles 150 from penetrat-ing a breathing mask of Maidong Company with the product name Jiweida (which is specified as PM_2.5 Mask) and a film of polyurethane 120 with the set-up shown in figure 3. Therefore, the inlet of the PM-Meter 220 has not been covered by any material for the first experiment, which is named A on the x-achses 310 of the diagram. The value of PM_2.5, which is illustrated on the Y-achses 300 for this set-up, was 329, as shown by bar 320 in the diagram. In the diagram, next to the bar 320, the PM_2.5, of the mask is illustrated by the bar 330. The value of the PM_2.5 particles 300 in the room 200 could be decreased by the mask to a value of 5.3. This results show a decrease of about 98 ％, based on the PM_2.5 value 300 of 329 which had been measured without any material. The PM_2.5 value could even be decreased more efficiently by a film of polyurethane 120 of the same material as described in figure 1. Here, the PM_2.5 value 340 could be lowered to a value of 2.4, which is a preventing efficiency of more than 99 ％compared to the original value 300. The film 120 used in this test has been produced via a film forming tool (Company: Shanghai Moderner； Product Name: Film maker Equipment) known in the art to from films with a thickness of around 120 μm. The thickness of the film has been measured by SEM.
Figure 4 shows a diagram with a similar test as shown in figure 3, with the difference that the mate-rials used to prevent particles from getting into contact with with the sensor of the PM-Meter dif-fered. The first bar 420 in position A on the X-achses 410 shows the particle value of PM_2.5, again with a value of 329. The amount of particles reaching the detector of the PM-Meter 220 for test B could be decreased to a value of 36.5 as illustrated in bar 430. The decrease was reached by cover-ing the inlet of the PM-Meter 220 of the set-up shown in figure 2 with a cloth made from nylond with a thickness of 0.3 mm. This value had been decreased further when applying a polyurethane film 120 to the cloth. The polyurethane film 120 was reached by applying 0.2 gramms of a compo-sition according to example 7 to an area of 2*2 cm of the cloth. After applying the composition 7 according to example 7 by a spatula to the cloth has been dried for 2 h at room temperature. The particle value of PM_2.5 is illustrated by bar 440 with a value of 4.5.
Figure 5a shows a black and white copy of a photograph of a part of a skin treated with carbon black powder (unipure black LC902, d＝20 30 μm from Sensient Cosmetic Technologies China) . With prior treatment with polyurethane 500 and without prior treatment with polyurethane 510. The original photograph of the two parts of skin are shown in figure 5b. Here the protected or treated part of skin is shown in field 520, whereas the unprotected or untreated part is shown in field 530. The test has been established in the following manner. First the part corresponding to part 500 respectively 520 was covered by a composition according to example 7 whereas the part of skin corresponding to filed 510 respectively 530 were not treated by any material. After this treatment, both parts of the skin 500 and 510 (respectively 520 and 530) had been covered by a similar amount of carbon black (around 0.2 g of carbon black) on each field 500 and 510 (respec-tively 520 and 530) . After that the skin had been rinsed with 200 ml of water which took about 10 seconds of slowly rinsing. The result was a totally clean part of skin 500 respectively 520 which had been treated with the inventive polyurethane composition, whereas the part of skin 510 respec-tively 530 which had not been treated with the polyurethane composition shows a black film cover-ing the whole skin area which had been covered by the carbon black before. This result shows the good protecting property of the polyurethane composition of the treated part of skin 500, respec-tively 520.
Figure 6 shows a similar experiment as shown in figure 5a and 5b. Here, the skin parts 600 or 610 had been treated with 2 g of a polyurethane composition according to example 8 via a spatula, whereas the skin parts 620 or 630 had not been protected by the polyurethane composition before covered by carbon black. After a drying process of the polyurethane composition applied to skin part 600 or 620 for 2 h, the skin parts 600 and 620 were each covered with 2 g carbon black. The result after rinsing the skin parts 600 and 620 with 200 ml of water in half a minute are shown in parts 610 and 630. The results are as obvious as in the testing of figure 5a nd 5b.
Figures 7a and 7b show results of differently concentrated polyurethane compositions. The basis of the composition is always given by the components A and C of the example 6. Different amounts of polyurethane according to example 6 were added. The curve 720 shows a trend of the protection capability of these different compositions with differing polyurethane amount. The amount of the polyurethane dispersion added to the composition is illustrated on the X-achses 730 in ％710, based on the total weight of the composition used. The measurement set-up was as follows: A cloth as described above in connection with figure 2 was applied over the inlet of the PM-Meter in the room 200. A plate with silica (Evonic Germany； ACEMATT TS 100) was put in the room 200. In the room 200 a concentration of 329 PM_2.5 was established by the ventilator 210. When applying the cloth with a composition not comprising any polyurethane (corresponding to example 6 without Phase B) to the inlet of the PM-Meter, the PM_2.5 was decreased to 71.4. This value is illustrated in figure 7a by point 721 in the diagram, where the PM_2.5 value is indicated by the Y-achses 740. Point 722 is illustrative for the PM_2.5 value of 37.7, when the cloth is covered with a composition comprising 1.3 wt. -％of polyurethane dispersion. As the dispersion has a solid content of 40 wt. -％, the total amount of polyurethane is 0.55 wt. -％. Point 723 is illustrative for the PM_2.5 value of 27.8, when the cloth is covered with a composition comprising 3 wt. -％of polyurethane dispersion (cor-respondingly 1.2 wt. -％polyurethane) . Point 724 is illustrative for the PM_2.5 value of 13.8, when the cloth is covered with a composition comprising 5 wt. -％of polyurethane dispersion (corre-spondingly 2 wt. -％polyurethane) . Point 725 is illustrative for the PM_2.5 value of 10.2, when the cloth is covered with a composition comprising 10 wt. -％of polyurethane dispersion (correspond-ingly 1 wt. -％polyurethane) . The wt. -％values of the compositions are illustrated by the X-achses 730.
Figure 7b shows the results with a similar set-up as described for figure 7a with the difference that PM₁₀ values were measured. When applying the cloth with a composition not comprising any poly-urethane to the inlet of the PM-Meter, the PM_2.5 was decreased to 677.3. This value is illustrated in figure 7b by point 761 in the diagram, where the PM₁₀ value is indicated by the Y-achses 770. Point 762 is illustrative for the PM₁₀ value of 301.3, when the cloth is covered with a composition comprising 1.3 wt. -％of polyurethane dispersion. As the dispersion has a solid content of 40 wt. -％, the total amount of polyurethane is 0.55 wt. -％. Point 763 is illustrative for the PM₁₀ value of 277.7, when the cloth is covered with a composition comprising 3 wt. -％of polyurethane dispersion (cor-respondingly 1.2 wt. -％polyurethane) . Point 764 is illustrative for the PM₁₀ value of 97.3, when the cloth is covered with a composition comprising 5 wt. -％of polyurethane dispersion (correspond-ingly 2 wt. -％polyurethane) . Point 765 is illustrative for the PM_2.5 value of 77.5, when the cloth is covered with a composition comprising 10 wt. -％of polyurethane dispersion (correspondingly 1.2 wt. -％polyurethane) . The wt. -％values of the compositions are illustrated by the X-achses 780.
Figure 8 shows a photograph of a bottle 830 which is filled with carbon black (INCI name: Carbon Black from YEXI, Commercial name: YH-3600) and covered on its opening with a film 840 formed from a polyurethane according to the invention described in Example 9 . The foil 840 locks the bottle 830 in a way that no carbon black could leak from the bottle 830. This had been proven by touching the film 840 by a white cloth 820. The outer surface 800 of the film 840 has not been contaminated by the carbon black. The carbon black only comes into contact with the inner side 810 of the film 840.
Figure 9 shows four SEM recordings of the film 840 used in the experiment shown in figure 8. Figures 900 and 920 show a magnification of the surfaces of 100.000, whereas record 910 and re-cord 930 have a magnification of 50.000 of the surfaces after the contamination with carbon black. The records 900 to 930 have been established with an SEM microscopy from the company JEOL Ltd. China, Type: JSM-6510. For records 900 and 920 the distance illustrated by bar 960 is 1 μm, whereas the bay 950 shows a distance of 500 nm, which apply for the recordings 910 and 930. Re-cording 900 shows an SEM picture of the outer surface 800 before the experiment illustrated in figure 8 and recording 910 shows an SEM picture of the outer surface 800 after the experiment il-lustrated in figure 8. No structural differences can be seen besides a flattening of the film 840 due to the stretching when applied to the opening of the bottle. This is different when looking at the SEM pictures 920 and 930 which show the SEM record 920 of the inner surface 810 of the film 840 and the SEM record 930 of the inner surface 810 of the film 840 after it had been handles as described in connection with Figure 8. Here huge particle agglomerations of the carbon black parti-cles can bee seen. However, none of these particles could penetrate the film 840 and reach the outer surface 800 of the film 840 as can be seen via the smooth structure of figure 920.

Claims

A pharmaceutical composition, whereby the composition comprises a polyurethane.
The composition according to claim 1, whereby the composition comprises the polyure-thane in an amount in the range of from 1 to 20 wt. -％, based on the total mass of the com-position.
The composition according to claim 1 or 2, whereby the polyurethane is obtainable by reacting one or more water-insoluble, non-water-dispersible, isocyanate-functional polyu-rethane prepolymers A) with at least one amino-functional compound B) .
The composition according to claim 1 or 2, whereby the amino-functional compound B) is selected from primary and/or secondary amines and/or diamines.
The composition according to claim 1 or 2, whereby the amino-functional compound B) includes at least one diamine.
The composition according to claim 1 or 2, whereby the amino-functional compound B) is selected from at least one amino-functional compound B2) which has ionic and/or ionogen-ic groups, and at least one amino-functional compound B1) which has no ionic and/or io-nogenic groups.
The composition according to claim 1 or 2, whereby the amino-functional compound B) include at least one amino-functional compound B2) which has ionic and/or ionogenic groups, preferably 2- (2-aminoethylamino) ethanesulphonic acid and/or salts thereof.
The composition according to claim 1 or 2, whereby the amino-functional compound B) includes at least one amino-functional compound B1) which has no ionic and/or ionogenic groups, preferably a diamine which has no ionic and/or ionogenic groups.
The composition according to claim 1 or 2, whereby the amino-functional compound B) includes both, at least one amino-functional compound B2) which has ionic and ionogenic groups, and also at least one amino-functional compound B1) which has no ionic and/or ionogenic group.
The composition according to claim 1 or 2, whereby the prepolymers A) are obtainable by reacting one or more polyols selected from the group which consists of polyether polyols, polycarbonate polyols, polyether-polycarbonate polyols and/or polyester polyols, and one or more polyisocyanates.
A composition comprising a polyurethane for use as a pharmaceutical product.
A composition comprising a polyurethane for use in the protection of a surface against po-tential pollutants.
Use of a composition comprising a polyurethane as protection of a surface against dust.
A composition comprising a polyurethane for protecting a surface of a human or an animal against pollutants.
A multi-layer structure comprising at least two layers A) and B) , wherein layer A) com-prises a polyurethane and wherein layer B) is different from layer A) .
A method for increasing the removability of a potential pollutant from a surface compris-ing at least the following steps:

i. Applying a composition comprising at least one polyurethane to at least a part of the surface；

ii. Optionally, exposing the treated part of the treated part of the surface of step i. for at least 1 minute to a potential pollutant；

iii. Optionally, removing the potential pollutant from the treated part of the surface of step i. or step ii..
A film comprising a polyurethane, whereby the film has at least one of the following fea-tures:

a) a permeability for particles with a PM_2.5 in the range of from 0 to 10 ％, based on the total amount of particles with PM_2.5；

b) a permeability for particles with a PM₁₀ in the range of from 0 to 10 ％, based on the total amount of particles with PM₁₀；

c) a tensile strength at 100％ elongation in the range of from 1 to 10 N/mm²；

d) a tensile strength at break in the range of from 5 to 40 N/mm²；

e) a break at an elongation in the range of from 300 -2500％；

f) a content of polyurethane in a range of from 5 to 100 wt. -％, based on the total mass of the film；

g) a thickness in a range of from 1 to 500 μm.