DE19726172A1 - Oil-in-water or multiple emulsion with high concentration of suspended UV B filter - Google Patents

Abstract

Oil-in-water (O/W) emulsions, especially O/W microemulsions, O/W/O or O/W/O' emulsions, contain (a) an aqueous phase, (b) optionally usual water-soluble or -dispersible substances, (c) an oil phase containing suspended cosmetic or dermatological ultra-violet (UV) filter(s), (d) emulsifier(s) (A) with pH-dependent lipophilic property and/or becoming more lipophilic with increasing temperature and more hydrophilic with decreasing temperature and (e) optionally other usual substances soluble or dispersible in the oil, preferably selected from other emulsifiers, especially W/O emulsifiers. The UV filter is selected from 2-(4-carbamoylphenylamino) -4,6-bis(4-carboxyphenylamino)- or 2,4-bis(4-carbamoylphenylamino) -6-(4-carboxyphenylamino)- 1,3,5-triazine derivatives of formula (I). In (I), R = 1-18 carbon (C) alkyl or 5-12 C cycloalkyl (optionally mono- or poly-substituted by 1-4 C alkyl); X = oxygen (O) or imino (NH); R1 = as R, hydrogen (H), an alkali metal atom, an ammonium group or a group of formula AOCH2C(R3)n- (II); A = 1-8 C alkyl, 5-12 C cycloalkyl or aryl, optionally mono- or poly-substituted by 1-4 C alkyl; R3 = H or methyl; n = 1-10; R2 = as R if X = NH and as R1 if X = O. Also claimed is a method of incorporating (I) in these emulsions.

Description

The present invention relates to cosmetic and dermatological light protection tions, in particular skincare cosmetic and dermatological sunscreen preparations.

The damaging effect of the ultraviolet part of solar radiation on the skin is well known. While rays with a wavelength smaller than 290 nm (the so-called UVC range), absorbed by the ozone layer in the earth's atmosphere be, cause rays in the range between 290 nm and 320 nm, the soge called UVB, erythema, simple sunburn or even more or less severe burns.

As a maximum of the erythema efficiency of sunlight becomes the narrower area indicated at 308 nm.

To protect against UVB radiation, numerous compounds are known in which It is mostly derivatives of 3-Benzylidencamphers, the 4-aminobenzoic acid, the Cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole is.

Also for the range between about 320 nm and about 400 nm, the so-called UVA Area, it is important to have filter substances available as well Radiation can cause damage. So it is proven that UVA radiation to a Damage to the elastic and collagen fibers of the connective tissue leads to what the Skin ages prematurely, and that they are the cause of numerous phototoxic and pho  allergic reactions can be seen. The damaging influence of UVB radiation can be amplified by UVA radiation.

The UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products interfere with the skin metabolism.

Predominantly, such photochemical reaction products are radi kalische connections, z. B. hydroxyl radicals. Also undefined radical Photopro Due to their high reactivity, unreacted substances which are formed in the skin itself controlled controlled reactions to the day. But also singlet oxygen, a Non-radical excited state of the oxygen molecule can under UV irradiation occur, as are short-lived epoxides and many others. Singlet oxygen, for example is distinguished from the normally existing triplet oxygen (radical ground state) by increased reactivity. However exist also excited, reactive (radical) triplet states of the oxygen molecule.

Furthermore, UV radiation counts as ionizing radiation. So there is a risk that also arise ionic species on UV exposure, which in turn oxidative in to be able to intervene in the biochemical processes.

An advantageous UVB filter is the 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester), synonymous: 2, 4,6-Tris [anilino (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine, octyltriazone.

This UVB filter substance is, for example, from BASF Aktiengesellschaft under the product name UVINUL® T 150 and is characterized by good UV Absorption properties. The main drawback of this UVB filter is the bad one Solubility in lipids. Known solvents for this UVB filter can maximum about 15 wt .-% of this filter, corresponding to about 1-1.5 wt .-% dissolved, and thus according to conventional evaluation standards: active UV filter substance.

Other than solid-state UV filter substances whose incorporation in cosmetic or dermatological sunscreen formulations at least certain problems Pro have known. Thus, in EP-A-570 838 s-triazine derivatives be described whose chemical structure by the generic formula

is reproduced, wherein
R is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
X represents an oxygen atom or an NH group,
R _{1 is} a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group the formula

means in which
A is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and
a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which
A is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
when X represents an oxygen atom.

Even if, in principle, some UV protection for a given limited solubility (and thus by conventional standards: poor incorporation into one) cosmetic or dermatological preparation) can be achieved, a res problem, the recrystallization. This occurs just in poorly soluble sub punch in comparatively quickly, either by temperature fluctuations or at caused by these influences. Uncontrolled recrystallization of a substantial acc However, preparation component such as a UV filter has extremely adverse effects on the properties of the given preparation and, not least, on the targeted sunscreen.  

Common cosmetic and dermatological formulations are emulsions NEN. In simple emulsions are in one phase finely dispersed, by an Emulga Torhülle enclosed droplets of the second phase (water droplets in W / O or Li pidvesicles in O / W emulsions). In a multiple emulsion (second degree) conditions are emulsified in such droplets of fine disperse droplets of the first phase. In turn, even finer disperse droplets may be present in these droplets (third-degree multiple emulsion) and so on.

It is known that multiple emulsions - among others - by a particular fine emulsion texture can distinguish. This property makes it perfect as a base for both cosmetic and medical topical preparations.

Just as one speaks for the simple emulsions of W / O or O / W emulsions (Water-in-oil or oil-in-water), there are multiple emulsions W / O / W-, O / W / O-, O / W / O / W, W / O / W / O emulsions and so on.

Multiple emulsions in which the respective inner and outer water phases or inner and outer oil phases are (essentially) different in nature (eg W / O / W 'and O / W / O'emulsions) are ready for preparation by two-pot procedures consistently. Such emulsions in which the inner and outer water or Ölpha are not different, are both by one and by two-pot available.

The multiple second degree emulsions are sometimes called "bimultiple systems", such third degree as "trimultiple systems", etc. (W.Seifriz, Studies in Emulsions, J. Phys. Chem., 29 (1925) 738-749).

Processes for the preparation of multiple emulsions are familiar to the person skilled in the art. Thus, there are two-pot processes in which a simple emulsion (eg, a W / O emuls sion) and by adding a further phase (eg., A water phase) with a corresponding emulsifier (eg an O / W emulsifier) into a multiple emulsion (eg, a W / O / W emulsion).

A second known method is to emulsifier mixtures with an oil phase and a water phase in a one-pot process into a multiple W / O / W emulsion  convict. The emulsifiers are dissolved in the oil phase and with the water phase united. A prerequisite for such a method is that the HLB values (HLB = Hy drophil-lipophile balance) of the individual emulsifiers used clearly from a different.

The definition for the HLB value for polyol fatty acid esters is given by the formula I.

HLB = 20. (1-S / A).

For a group of emulsifiers whose hydrophilic portion consists only of Ethylenoxideinhei th, the formula II applies

HLB = E / 5

in which
S = saponification value of the ester,
A = Acid value of the recovered acid
E = mass fraction of ethylene oxide (in%) of the total molecule
mean.

Emulsifiers with HLB values of 6-8 are generally W / O emulsifiers, those with HLB values of 8-18 are generally O / W emulsifiers.

Literature: "Cosmetic development, production and application of cosmetic products"; W. Umbach (ed.), Georg Thieme Verlag 1988.

Hydrophilic emulsifiers (with high HLB values) are usually O / W emulsifiers. Accordingly, hydrophobic or lipophilic emulsifiers (with low HLB values) are in usually W / O emulsifiers.

US Pat. No. 4,931,210 describes a process for producing W / O / W Emulsion, being used as emulsifiers Polyglycerinpolyricinoleate.

The droplet diameter of the ordinary "simple", ie non-multiple Emulsio nen are in the range of about 1 micron to about 50 microns. Such "macroemulsions" are, without further coloring additives, milky white colored and opaque. Finer macroemulsions, whose droplet diameters range from about 10 ^-1 μm to about 1 μm, are bluish white in color and opaque, as is the case with no coloring additives. Such macroemulsions usually have high viscosity.

Micellar and molecular solutions with particle diameters less than about 10 ^-2 microns, which are no longer considered as true emulsions, however, are reserved to appear clear and transparent.

By contrast, the droplet diameter of microemulsions ranges from about 10 ^-2 μm to about 10 ^-1 μm. Microemulsions are translucent and usually low viscosity. The viscosity of many O / W type microemulsions is comparable to that of water.

Advantage of microemulsions is that in the disperse phase drugs much finer may be present disperse than in the disperse phase of "macroemulsions". A white terer advantage is that they can be sprayed due to their low viscosity. Be Mi used as cosmetics, are characterized by corresponding products high cosmetic elegance.

It is known that hydrophilic emulsifiers with increasing temperature their solubility Change from water-soluble to fat-soluble. The temperature range in which the Emulsifiers have changed their solubility becomes phase inversion temperature range Called (PIT).

S. Matatsumoto (Journal of Colloid and Interface Science, Vol. 94, No. 2, 1983) describes that the development of a W / O / W emulsion of a phase inversion concentrated W / O Emulsions stabilized by Span 80, a pronounced W / O emulsifier are, precedes. Matsumoto goes from an extremely non-polar oil, namely liquid paraffin wax out. In addition, a certain amount of hydrophilic emulsifiers for Development of a W / O / W emulsion from a W / O emulsion necessary.

T.J. Lin, H. Kurihara and H. Ohta (Journal of the Society of Cosmetic Chemists 26, p. 139, March 1975 show that non-polar oils are extremely unstable in the PIT range multiple emulsions may be present.

Object of the present invention was therefore to remedy these evils fen.  

It has surprisingly been found, and therein is the solution of the tasks be based, that O / W emulsions, in particular O / W microemulsions, or O / W / O emulsions or O / W / O'-emulsions containing

• (a) a water phase,
• (b) optionally conventional, water-soluble or dispersible substances,
• (c) an oil phase, in which at least one cosmetic or dermatological UV filter substance selected from the group of s-triazine derivatives of the general structural formula
  is reproduced, wherein

R is a branched or unbranched C ₁

-C ₁₈

-Alkyl, a C ₅

-C ₁₂

-Cyclo alkyl, optionally substituted with one or more C ₁

-C ₄

Alkyl groups, represents
X represents an oxygen atom or an NH group,
R ₁

a branched or unbranched C ₁

-C ₁₈

-Alkyl, a C ₅

-C ₁₂

-Cyclo alkyl, optionally substituted with one or more C ₁

-C ₄

Alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which
A is a branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₅ alkyl groups, when X represents the NH group, and a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group the formula

means in which
A is a branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
when X represents an oxygen atom,
is present in suspended form,

• (D) at least one emulsifier (emulsifier A) selected from the group of Emulga doors with the following features
• - Their lipophilicity is either pH-dependent, such that it is due to Er increasing or decreasing the pH, the lipophilicity increases or decreases, it is irrelevant which of the two possibilities of changing the Li pophilie is caused by increasing or decreasing the pH, and or
• - Their lipophilicity is dependent on the temperature, such that the Lipophi increases with increasing temperature and their hydrophilicity decreases with decreasing Temperature increases,  
• (e) furthermore, if appropriate, further substances which are soluble or dispersible in the oil phase, including preferably those selected from the group of emulsifiers not covered by the definition of emulsifier A, in particular those which predominantly act as W / O emulsifiers,
  to remedy the disadvantages of the prior art.

According to the invention, it is possible to use high levels of use according to the invention put s-triazine derivatives, d. h., Typically about 5 wt .-%, based on the Ge total weight of an O / W microemulsion or an O / W / O emulsion with an oil phase senanteil of about 50 wt .-%, again based on the total weight of Zuberei tion, and thus the advantageous properties of this sunscreen filter fully exploit.

Advantageously in accordance with the invention, the s-triazines are selected from the group of substances which are described in EP-A-570 838. All mentioned in this document s-triazines, be they disclosed by generic formulas, are by concrete form Meln disclosed are to be used advantageously in the context of the present invention.

Advantageously in accordance with the invention, the s-triazines are selected from the group of substances in which X represents an oxygen atom, R ₁ and R _{2 are} identical and a branched or unbranched C ₁₈ -C ₁ -alkyl radical, a C ₅ -C ₁₂ - Cycloalkyl radical, if appropriate substituted with one or more C ₁ -C ₄ alkyl groups represent. It is also advantageous if R ₁ and R _{2 are} identical and one is a group of the formula

in which R _{3 represents} a hydrogen atom, A represents a branched or unbranched C ₁ -C ₁₈ -alkyl radical and n = 2.

Also advantageous in the context of the invention, the s-triazines are selected from the group of substances in which X represents an NH group, R ₁ and R _{2 are} identical or different and a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ - C ₁₂ cycloalkyl, optionally substituted with one or more C ₁ -C ₄ -Alkylgrup groups represent.

A particularly advantageous representative of the s-triazines used according to the invention is the following substance:

As an advantageous embodiment of the present invention is also considered a method for incorporation of the above-described s-triazine derivatives in O / W Emulsio NEN, O / W microemulsions or O / W / O emulsions, characterized in that

• (a) the components of a water phase,
• (b) optionally conventional, water-soluble or dispersible substances,
• (c) the components of an oil phase
• (c1) the previously described s-triazine derivatives
• (d) at least one emulsifier (emulsifier A) selected from the group of emulsifiers having the following properties
  • their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
  • their lipophilicity is dependent on the temperature, such that the lipophil increases with increasing temperature and the hydrophilicity increases with decreasing temperature,
• (e) further optionally further oil phase soluble or dispersible sub punching, including preferably those selected from the group of non-die Definition of the emulsifier A falling emulsifiers, in particular those before predominantly acting as W / O emulsifiers,

be combined and formed under agitation a mixture such that

• (f) this mixture by appropriate choice of the parameters selected from the group pH, temperature and concentration or concentrations at least ei of the emulsifiers selected, is placed in the phase inversion region, in which W / O emulsions convert to O / W emulsions,
• (g) by varying at least one parameter chosen from the group pH value, Temperature and the concentration or concentrations of at least one of selected emulsifiers, the formed W / O emulsion from the phase inversion is brought out in which a formed W / O emulsion in egg ne O / W emulsion, whereby an O / W emulsion or O / W microemuls produced
• (h) if appropriate, by an appropriate choice of framework conditions, another Pha seninversion is initiated to O / W / O emulsion,
• (i) the mixture optionally further processing steps, in particular ei one or more Homogenisierungsschritten.

Equally advantageous according to the invention are methods in which the variation of the parameter or of the parameters consists in that

• (1) at a given pH and concentration of the emulsifier A or the plurality of emulsifiers A, the temperature of the mixture and Gege if appropriate, in addition, the concentration of at least one further emulsifier A. is varied, that
• (2) at a given temperature and given concentration of the emulsifier A. or the plurality of emulsifiers A, the pH of the mixture and give If appropriate, in addition, the concentration of at least one further emulsifier A va is riiert that
• (3) at a given temperature and pH, the concentration min at least one emulsifier A and optionally in addition the concentration at least one further emulsifier A is varied, that
• (4) at a given pH, the temperature of the mixture and additionally the Concentration of at least one emulsifier A and optionally in addition the concentration of at least one further emulsifier A can be varied, that
• (5) at a given temperature of the mixture it is the pH of the mixture as well in addition, the concentration of at least one emulsifier A and given  if, in addition, the concentration of at least one further emulsifier A varies be that
• (6) at a predetermined concentration of at least one emulsifier A, the pH value so as in addition the temperature of the mixture and possibly additionally the Concentration of at least one further emulsifier A can be varied.

In principle, it is possible and advantageous to use the one or more according to the invention s-triazines at any time the underlying the emulsions Add mixture. However, a method according to the invention is preferred. which is characterized in that the one or more used in the invention s-triazines before the emulsification process in the oil phase, optionally under heating men, are dispersed and the remaining steps of the process followed who the.

It is preferred that the s-triazine derivative (s) described above be heated with the oil phase, in particular advantageous in a non-polar oil component or a Ge mixed with non-polar oil components, to disperse.

It is preferred, first, the solubility of the or the s-triazine derivatives in the To determine totality of the oil components, it being advantageous to such Ölkom components in which the benzotriazole derivative or % By weight are soluble. To make this preselection does not exceed the general wis sen of the professional.

Insofar as the phase inversion is initiated essentially by varying the temperature are O / W emulsions, in particular O / W microemulsions available, the Size of the oil droplets essentially by the concentration of or used emulsifiers is determined, such that a higher emulsifier concentration smaller droplets causes lower emulsifier concentration and larger droplets leads. It is when the phase inversion is essentially due to variation of the tem It is quite advantageous, for others, not under the definition of Emulsifier A falling, further emulsifiers, namely W / O emulsifiers, verzich th.  

Provided that the phase inversion initiated essentially by varying the pH are O / W emulsions, in particular O / W microemulsions, but also O / W / O emulsions. Emulsions available. It is when the phase inversion is essentially due to variation the pH is initiated, quite beneficial, one or more others, not under the definition of emulsifier A, other emulsifiers, namely W / O Emulsifiers, use.

In the present invention, O / W / O emulsions can be obtained when the oil phase Part higher than about 15 wt .-%, in particular higher than about 20 wt .-%, based on the total weight of the composition is more than about 5% by weight, especially about 5-10 wt .-% of an additional, not falling under the definition of the emulsifier A. W / O emulsifier present and / or if the oil phase, a low proportion of pola ren oils has.

According to the invention, O / W microemulsions can be obtained when the oil phase proportion below about 20% by weight, in particular below about 15% by weight, based on the Total weight of the preparation, less than about 5% by weight of an additional, not covered by the definition of the emulsifier A W / O emulsifier and / or when the oil phase has a high proportion of polar oils.

According to the invention, O / W emulsions ("macroemulsions") can be obtained when less than about 5% by weight of an additional not under the definition of the emulsifier A falling W / O emulsifier and more than about 20 wt .-% of a polar oil phase before lie. Advantageously, additional gelling agents (eg, carbopols, xanthan gum, cel lulosederivatives).

It is possible in an individual case that the aforementioned concentration limits easily exceeded or fallen below and still the respective emulsion types erhal be. This comes in the face of the wide variety of suitable Emulga Doors and oil components for the expert not unexpected, so he knows that at such overrun or underruns the soil of the present invention is not ver will let.

It has surprisingly been found that the or the invention employed s-triazine derivatives as solids, in a sense "encapsulated",  namely separated from other constituents of the preparations in which they may sometimes even have limited solubility. It is believed that the solid particles of the poorly soluble UV filter substances by the erfindungsge suitable incorporation process obtain a cladding film, which probably as wesentli component contains emulsifier molecules.

According to the invention, the recrystallization of the invention or the used s-triazine derivatives are prevented. In addition, according to the invention light protection available formulations which have excellent application properties.

The phase inversion range can be represented mathematically as a point quantity within the rectilinear coordinate system Σ, which is formed by the variables temperature, pH and concentration of a suitable emulsifier or of an emulsifier mixture in the preparation, according to:

Σ = {O, θ, a, m},

With
O - coordinate origin
θ - temperature
a - pH
m - concentration.

To be precise, of course, in a multicomponent emulsifier system, the contribution m _{i of} each individual emulsifier to the overall function must be taken into account in terms of the overall function of what is the relationship with an i-component emulsifier system

Σ = {O, θ, a, m ₁ , m _2,. , ., m _i }

leads.

The phase inversion region Φ in the mathematical sense represents a coherent region or a plurality of contiguous regions within the coordinate system Σ. Φ represents the total quantity of the coordinate points K (θ, a, m ₁ , m ₂ , ..., m _i ), which inventive mixtures of water and oil phase, i inventions to the invention emulsifiers concentration m _i at the temperature θ and the pH determine a, and for which applies that the transition from a coordinate K ₁ ∉ Φ to a coordinate K ₂ ∈ Phase inversion occurs, as described in Fig. 1. As the variable coordinates in Fig. 1, the temperature and pH of a given mixture were specified while keeping the concentration of m ₁ - m _i constant. In the transition from K ₁ to K ₂ , only the temperature is increased.

Under the conditions according to the invention, this process is not necessarily reversible, ie if the system returns from the coordinate K ₂ ∈ Φ back to the coordinate K ₁ ∉ Φ, other types of emulsion can be obtained according to the invention than the prior art would have expected. For example, by increasing the temperature of a mixture according to the invention of water and oil phase, according to the invention emulsifiers of concentrations m _i , the pH a remains constant, starting from a temperature which is too low for phase inversion conditions a conventional O / W emulsion vorläge, which would remain on cooling to room temperature such), is heated, so that phase inversion occurs, after cooling, z. B. at room temperature, no conventional O / W emulsion he hold, but an inventive O / W microemulsion. Or, mutatis mutandis: an O / W / O emulsion according to the invention.

It is irrelevant whether the phase inversion range of a given system is a represents the single contiguous (i + 2) -dimensional domain or of several coherent, but separate, such areas multiple phase inversion regions of a given system accordingly. in the The scope of the disclosure presented here is therefore always generalized by ei spoken phase inversion, even in the presence of two or more separate such areas.

The practice of preparing an emulsion according to the invention is advantageously after selection of suitable raw materials, d. h., water and oil phase, one or more Emulsifiers front type A, the latter or latter present in concentrations, wel phase inversion for the given mixture is possible, and optionally white ture the individual components under agitation to a temperature in which phase inversion is possible for the given mixture, and by Er increase or decrease in the pH of the mixture causes phase inversion Afterwards, under constant agitation, the mixture is cooled down to room temperature to cool. One or more intermediary homogenization steps are advantageous, but not mandatory.  

A further advantageous embodiment of the method according to the invention exists therein, after the selection of suitable raw materials, d. h., water and oil phase, one or a plurality of emulsifiers of type A the latter or the latter present in concentrations, in which phase inversion is possible for the given mixture, and given if further substances, the individual components under agitation to a pH value in which phase inversion is possible for the given mixture, and by inducing phase inversion by raising the temperature of the mixture after continuing to cool the mixture to room temperature while continuing agitation sen. One or more intermediary homogenization steps are advantageous, but not mandatory.

A third advantageous embodiment of the method according to the invention exists therein, after the selection of suitable raw materials, d. h., water and oil phase, one or several emulsifiers front type A and possibly other substances, the individual to bring components under agitation to a pH and a temperature at which phase inversion is possible for the given mixture, and by addition of the emulsifier A or of the emulsifiers A to the mixture causes phase inversion Thereafter, under constant agitation, cool the mixture to room temperature allow. One or more intermediary homogenization steps are advantageous liable, but not mandatory.

In practice it is possible and possibly even advantageous in the production of a emulsion of the invention, the temperature range of the Phaseninversionsbe can also be assigned to rich, because when cooling on Raumtempe then this area will inevitably go through.

The emulsifiers A are preferably selected from the group of emulsifiers, which represent good proton donors or proton acceptors, being ensured must that their lipophilicity be either dependent on the pH, so that by Er increasing or decreasing the pH, the lipophilicity increases or decreases, where un It is significant which of the two possibilities of lipophilicity change Increasing or lowering the pH is caused, or their lipophilicity is dependent from the temperature, such that the lipophilicity increases with increasing temperature and whose hydrophilicity increases with decreasing temperature, or their lipophilicity dependent  is of pH and temperature, such that by increasing or decreasing the pH increases or decreases the lipophilicity, which is irrelevant which of the possibilities of changing the lipophilicity by increasing or decreasing the pH is effected, and that the lipophilicity increases with increasing temperature and whose hydrophilicity increases with decreasing temperature.

Advantageously, the emulsifiers of the type A are selected from the group of sorbitan ester and sucrose esters, in particular the branched and unbranched alkyl esters and alkenyl esters having carbon chains of 4-24 carbon atoms, preferably sorbi tanstearat, sorbitan oleate, glyceryl sorbitan stearate, sucrose monostearate, sucrose semolaurate, sucrose palmitate.

Advantageously, the emulsifiers of the type A can be selected from the group of mono-glycerol-monocarboxylic monoesters, in particular those which are characterized by the structures

wherein R 'is a branched or unbranched acyl radical having 6-14 Represents carbon atoms. Advantageously, R 'is selected from the group of unbranched th acyl radicals.

The acids underlying these esters are the

Particularly advantageous R 'is the octanoyl (CaprylsÄureurer) or the Decanoyl rest (CaprinsÄureest), that is so by the formulas

R '= -C ₇ H ₁₅ or R' = -C ₉ H ₁₉

represents.

Advantageously, the emulsifiers of the type A also from the group of di- and tri glycerol monocarboxylic monoester can be selected. According to the invention are the Di- or triglycerol units of the inventive diglycerol monocarboxylic acid monoester or triglycerol monocarboxylic monoester as linear, unbranched Molecules, ie etherified via the respective OH groups in the 1- or 3-position "Mo noglycerin molecules ".

A small proportion of cyclic di- or triglycerol units and the OH group 2-etherified glycerol molecules can be tolerated. However, it is advantageous to keep such impurities as low as possible.

The monocarboxylic acid monoesters according to the invention are preferably characterized by the following structure:

where R "is a hydrocarbon radical, advantageously a branched or unbranched branched alkyl or alkenyl radical of 5 to 17 carbon atoms.

The monocarboxylic acid esters of triglycerin according to the invention are preferably characterized by the following structure:

where R '' 'is a hydrocarbon radical, preferably a branched or unbranched branched alkyl or alkenyl radical alkyl radical of 5 to 17 carbon atoms.

The acids underlying these esters are the

Particularly favorable R and R '' 'are selected from the group of unbranched Al kylreste with odd C numbers, in particular with 9, 11 and 13 C atoms.

In general, the monocarboxylic acid monoesters of diglycerol are those of tri glycerol is preferred.

According to the invention are very particularly favorable

As preferred monocarboxylic monoester of the invention diglycerol has the diglycerol monocaprinate (DMC) proved.

According to an advantageous embodiment of the present invention, an additional proportion of di- or triglycerin esterified in other places, as well as optionally a proportion of the different diesters of di- or triglycerol used.  

Also advantageous are triglyceryl diisostearate (nomenclature analog CTFA: polyglyceryl-3 diisostearate), isostearyl diglyceryl succinate, diglyceryl sesquiisostearate (nomenclature ana log CTFA: polyglyceryl-2-sesquiisostearate), triglyceryl polyhydroxystearate (nomenclature analogous to CTFA: polyglyceryl-2-polyhydroxystearate).

Also cetearyl isononanoate, dicocoyl-pentaerythrityl-distearyl citrate, furthermore the methicon copolyols, cyclomethicone copolyols, alkyl methicone copolyols, especially laurylmethane concopolyol, Cetyldimethiconcopolyol, have inventively advantageous he grasslands.

Particularly advantageous are the emulsifiers or the type A selected from the Group of branched or unbranched alkyl monocarboxylic acids, alkenyl monocar Bonsäuren and alkylenedicarboxylic acids having 4 to 30 carbon atoms, in particular Stearic acid, oleic acid, succinic acid, hexanoic acid (caproic acid), heptanoic acid (Enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (Capric acid), undecanoic acid, undecenoic acid (undecylenic acid), dodecanoic acid (laurin acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecane acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearin acid), isostearic acid, behenic acid. It is also advantageous to use the emulsifiers A from the Group of cosmetically or pharmaceutically acceptable salts of the above ge called carboxylic acids to choose, in particular the alkali, ammonium, monoalkylam monium, dialkylammonium, trialkylammonium and tetraalkylammonium salts.

Also particularly advantageous or the Emulagtoren A are selected from the Group of mono-, oligo- and polyethoxylated compounds, in particular poly ethoxylated monohydric or polybasic alcohols or fatty acids, for example cetea reth-20, PEG-20 glyceryl stearate, steareth-20, PEG-20 stearate, PEG-30 stearate, PEG- 40-castor oil, PEG-1-glycerol sorbitan oleostearate, PEG-7 hydrogenated castor oil, PEG- 40 sorbitan peroleate, PEG45 dodecyl glycol copolymer.

The emulsions according to the invention are advantageously characterized in that the Emulsifier A or the emulsifiers A in concentrations of 0.01-20 wt .-%, before zugt 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, each based on the Total weight of the composition, whether present or present.  

It is possible according to the invention, the amounts of in per se in oil components poorly soluble or insoluble UV filters, especially 4,4 ', 4' '- (1,3,5-triazine-2,4,6- triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), but also 2-phenylbenzimidazole-5 sulfonic acid or salts thereof in cosmetic or dermatological preparations to multiply over the prior art.

The total amount of UV filter substances sparingly soluble in oil components, in particular 4,4 ', 4 "- (1, -3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), but also 2-phenylbenzirnidazole-5-sulfonic acid or salts thereof in the finished Cosmetic or dermatological preparations will be advantageous in the field from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations.

It is advantageous according to the invention, in the preparations according to the invention addi oil-soluble UVA filters and / or UVB filters in the lipid phase and / or water-soluble Use UVA filter and / or UVB filter in the aqueous phase.

Advantageously, the sunscreen formulations according to the invention can be further substituents containing UV radiation in the UVB range, the total amount the filter substances z. 0.1% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6 wt .-%, based on the total weight of the preparation to provide cosmetic preparations that protect the skin from the skin protect entire area of ultraviolet radiation.

The additional UVB filters can be oil-soluble or water-soluble. Advantageous oil-soluble UVB filter substances are e.g. B .:

• 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3 benzylidenecamphor;
• 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2- ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4- Methoxyzirntsäureisopentylester;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;  
• - Benzalmalonic acid esters, preferably 4-Methoxybenzalmalonsäurndi (2-ethylhe xyl ester);
• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester).

Advantageous water-soluble UVB filter substances are z. B .:

• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or tri ethanolammonium salt, as well as the sulfonic acid itself, provided that the pH chosen is that these are present in water-soluble form,
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzene zophenone-5-sulfonic acid and its salts, provided that the pH is chosen such that these are present in water-soluble form,
• - Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bornylidenme thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and their Salts, provided that the pH is chosen so that they are present in water-soluble form gene.

The list of said UVB filters used in combination with the invention Drug combinations can be used, of course, not limitie be his.

It may also be advantageous to add additional UVA filters in the invention use preparations that have traditionally been ent in cosmetic preparations ent are holding. These substances are preferably derivatives of di benzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane 1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. Also this Kombina tions or preparations containing these combinations are the subject of Invention. The quantities used for the UVB combination can be used become.

Cosmetic and dermatological preparations according to the invention also advantageously contain inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O) ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding metals and Blends of such oxides. Particular preference is given to pigments based on TiO ₂ .

It is particularly advantageous in the context of the present invention, although not zwin when the inorganic pigments are in hydrophobic form, d. h. that she are superficially treated water-repellent. This surface treatment can consist in that the pigments according to known methods with a thin be provided hydrophobic layer.

One such method is, for example, that the hydrophobic surface layer after a reaction according to

nTiO ₂ + m (RO) ₃ Si-R '→ n TiO ₂ (surface)

is produced. n and m are random stoichiometric parameters meter, R and R 'are the desired organic radicals. For example, in analogy to DE OS 33 14 742 illustrated hydrophobized pigments are advantageous.

Advantageous TiO ₂ pigments are available, for example, under the trade names MT 100 T from TAYCA.

The cosmetic and / or dermatological sunscreen formulation according to the invention ments may be composed as usual and the cosmetic and / or the Photological light protection, furthermore for the treatment, care and cleaning of the Skin and / or hair and serve as a make-up product in decorative cosmetics.

For use, the cosmetic and dermatological according to the invention Preparations in the usual way for cosmetics on the skin and / or hair in applied sufficient amount.

Particularly preferred are such cosmetic and dermatological preparations, which are in the form of a sunscreen. Advantageously, these can additionally at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably an inorganic micro pigment, included.  

The cosmetic and dermatological preparations according to the invention can contain cosmetic excipients, as ver usually in such preparations ver be used, for. As preservatives, bactericides, perfumes, substances for Ver foaming, dyes, pigments having a coloring effect, Ver thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes or other common ingredients of a cosmetic or dermatological formulation Such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic Solvent or silicone derivatives.

An additional content of antioxidants is generally preferred. Erfindungsge As favorable antioxidants, they can all be used for cosmetic and / or dermatological purposes Applications of suitable or common antioxidants can be used.

Advantageously, the antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urotroic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, Butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesterol and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and Salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthione insulfone, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (eg. (Μmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives ( eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and also coniferyl benzoate of the benzine resin, rutinic acid and derivatives thereof , α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnS O ₄ ) selenium and its derivatives (e.g. B. selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.

The amount of the aforementioned antioxidants (one or more compounds) in the Preparations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 - 20 wt .-%, in particular 1-10 wt .-%, based on the total weight of Zuberei tung.

If vitamin E and / or its derivatives are the antioxidant (s) advantageous, their respective concentrations in the range of 0.001-10 wt .-%, based on the total weight of the formulation to choose.

If vitamin A, or vitamin A derivatives, or carotenes or their derivatives, the or which are antioxidants is advantageous, their respective concentrations from the Range of 0.001-10% by weight based on the total weight of the formulation choose.

The lipid phase can advantageously be selected from the following substance group:

• - Oils, such as triglycerides of capric or caprylic acid
• - Fats, waxes and other natural and synthetic fats, preferably Esters of fatty acids with lower C-number alcohols, e.g. B. with isopropanol, propy glycol or glycerol, or esters of fatty alcohols with lower alkanoic acids C number or with fatty acids;
• - alkyl benzoates.

Most preferably, the lipid phase can be selected from the group of Si silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and Mixed forms thereof.

The aqueous phase of the preparations according to the invention may contain some geous

• - Alcohols, diols or polyols low C number, and their ethers, preferably Ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol mo noethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl- or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous Products, also low C-number alcohols, e.g. For example, ethanol, isopropanol, 1,2-Pro pandiol, glycerol and in particular one or more thickening agents, wel Ches or which can be advantageously selected from the group silicon di oxide, aluminum silicates, polysaccharides or their derivatives, for. Hyaluronic acid, Xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the Group of polyacrylates, preferably a polyacrylate from the group of soge named carbopols, for example carbopols of types 980, 981, 1382, 2984, 5984, each individually or in combination.

The cosmetic or dermatological sunscreen preparations contain advantageous inorganic pigments, in particular micropigments, for. B. in amounts of 0.1 wt .-% to 30 wt .-%, preferably in amounts of 0.5 wt .-% to 10 wt .-%, in particular but 1 wt .-% to 6 wt .-%, based on the total weight of the preparations.

Below is briefly to some specifics and differences of the Vorausset for O / W emulsions, O / W microemulsions or O / W / O emulsions according to the invention. Emulsions are received.

Among other things, oils and fats differ in their polarity, which is difficult to achieve is defined. It has already been proposed to oppose the interfacial tension To assume water as a measure of the polarity index of an oil or an oil phase. because in that the polarity of the relevant oil phase is greater, the lower the Interfacial tension between this oil phase and water is. According to the invention the interfacial tension is given as a possible measure of the polarity of a given Oil component considered.

The interfacial tension is the force that is at an imaginary, in the Grenzflä between the two-phase line of one meter length. The phy The physical unit for this interfacial tension is calculated classically according to the Relationship force / length and is usually expressed in mN / m (millinewton divided by meters)  played. It has a positive sign, if it has the endeavor, the limit area to zoom out. In the opposite case, it has a negative sign.

As a limit, below which an oil phase as "polar" and above which an oil phase is considered to be "non-polar", 30 mN / m are considered according to the invention.

According to the invention, the oily phase is advantageously selected from O-W microemulsions Group of polar oil components, which have a polarity between 10 and 30 mN / m it must be ensured that at least one non-polar Ölkompo is present.

Advantageous O / W microemulsions are obtained when the oil phase is selected the group of polar oil components, more preferably from the group of na natural, synthetic or semi-synthetic oil components which have one polarity between 10 and 20 mN / m, it being necessary to ensure that at least a non-polar oil component is present.

It is also advantageous to use polar vegetable oils as polar oils of the O / W invention. To use emulsions. The vegetable oils can be chosen favorably from the group of oils of the plant families Euphorbiaceae, Poaceae, Fabaceae, Brassi caceae, Pedalaceae, Asteraceae, Linaceae, Flacourticaceae, Violales, preferably selected from the group of virgin castor oil, wheat germ oil, grapeseed oil, kukui nut oil, Safflower oil, safflower oil, evening primrose oil and other oils which at least 1.5 wt .-% of Linoleic acid glycerides included.

In contrast, according to the invention O / W / O emulsions of such oil components have only minor amounts and instead mainly those whose Polarity value is higher than 30 mN / m. As beneficial have alike naturli che, synthetic and semi-synthetic oils, fats and waxes.

The addition of electrolytes causes a change in the solubility behavior of a hydrophilic emulsifier. The hydrophilic emulsifiers with the previously described Structures or properties go through a partial phase inversion, in which it too a solubilization of water through the oil phase occurs, which in a stable Mi Kroemulsion or, if desired, also results in a stable O / W / O emulsion.  

The microemulsions according to the invention therefore advantageously contain electrolytes, esp in particular one or more salts having the following anions: chlorides, also inorganic of these oxo-element anions, in particular sulfates, carbonates, phosphates, Borates and aluminates. Also on organic anions based electrolytes can be used advantageously, for example, lactates, acetates, benzoates, propionates, Tartrates, citrates and more. Similar effects are also due to ethylene di Amintetraessigsäure and their salts to achieve.

Preferred cations of the salts are ammonium, alkylammonium, alkali metal, Alkaline earth metal, - used magnesium, iron or zinc ions. It does not take care of itself mentions that only physiologically harmless electrolytes are used in cosmetics should be. Special medical applications of the invention On the other hand, microemulsions can, at least in principle, the use of Electrolytes condition, which should not be used without medical supervision.

Particularly preferred are potassium chloride, common salt, magnesium sulfate, zinc sulfate and Mi. from it. Also advantageous are salt mixtures as in natural salt occur from the Dead Sea.

The concentration of the electrolyte or electrolytes should be about 0.01-10.0% by weight, particularly advantageously about 0.03-8.0 wt .-%, based on the total weight the preparation.

The emulsifiers of type A can universally considered as O / W emulsifiers who the. A content of about 5-10 wt .-% of conventional W / O emulsifiers promotes beneficial way, the formation of O / W / O emulsions, a content of well above 10 wt. % of such emulsifiers leads to the destabilization of the O / W / O emulsions.

Further, if desired, for the preparation of inventive O / W / O emulsions advantageous to use hydrophilic and / or lipophilic gelling agents. Although they carry in usually do not contribute to the formation of multiple droplets, but promote stability once formed multiple droplets.

When in a production method for O / W / O emulsions of the present invention pH should be varied to an otherwise predetermined system in the phases To bring version range, it is advantageous at the beginning of the process initially possible  Use as low as possible electrolyte concentration in the water phase, if possible to next to refrain entirely. It is also advantageous, the emulsifier A in the oil phase, for example for stearic acid in the concentration range of 0.5-5 Wt .-%, in particular 2 wt .-%. Advantageous is the presence of a not under the Definition of the Emulsifier A falling emulsifier in the concentration range of about 5 - 10 wt .-%, in particular about 7 wt .-%.

The variation of the pH value should advantageously be done only when the W / O emulsion is has formed, for example by adding NaOH.

This is generally the expertise of the skilled person and requires no erfinderi for a given emulsifier or emulsifier system in a given water / oil phase system the temperature or pH range determine in which phase inversion takes place. As a general guideline for the PIT at usual emulsifier concentrations, a temperature range of about 40-90 ° C. be specified. In general, the PIT decreases with increasing emulsifier concentration tion.

If desired, it is also possible, during this process, to use those in cosmetics or medical galenics usual basic, auxiliary, additional, and / or active ingredients added become. It will be clear to those skilled in the art at which time such substances will be in the process can be added without the properties of the emulsion to be achieved be significantly affected.

The following examples are intended to further delineate the nature of the present invention without limiting the invention. The abbreviation TST stands for the connection

example 1 O / W microemulsion

Wt .-% Ceteareth-12 8.00 cetearyl 20.00 cetearyl 4.00 TST 4.80 _MgSO4 3.00 pH = 5.0 @ Dyes, perfume, preservatives q.s. water ad 100.00

The components of the oil phase are combined and homogenized, then with the water phase and at a temperature of 80-85 ° C (i.e., in the phase inversions temperature range of the system), then cooled to room temperature (ie out of the phase inversion temperature range of the system introduced).

Example 2 O / W microemulsion

Wt .-% Ceteareth-12 12,00 cetearyl 20.00 cetearyl 6.00 TST 4.80 Parsol® 1789 2.00 _MgSO4 3.00 pH = 5.0 Dyes, perfume, preservatives q.s. water ad 100.00

The components of the oil phase are combined and homogenized, then with the water phase and at a temperature of 80-85 ° C (i.e., in the phase inversions temperature range of the system), then cooled to room temperature (ie out of the phase inversion temperature range of the system introduced).  

Example 3 O / W microemulsion

Wt .-% Ceteareth-12 8.00 cetearyl 10.00 mineral oil 10.00 cetearyl 4.00 TST 4.80 _MgSO4 3.00 Dyes, perfume, preservatives q.s. water ad 100.00

TST is pre-suspended in the mineral oil and combined with the remaining oil phase, whereupon this and homogenized and then combined with the water phase and on a tempe temperature of 80-85 ° C (i.e., in the phase inversion temperature range of the system) then cooled to room temperature (ie from the Phaseninversionstempe temperature range of the system).

Example 4 O / W microemulsion

Wt .-% Ceteareth-12 12,00 cetearyl 10.00 mineral oil 10.00 cetearyl 6.00 Eusolex® 6300 2.00 Parsol® 1789 0.50 TST 4.80 _MgSO4 3.00 Dyes, perfume, preservatives q.s. water ad 100.00

TST is pre-suspended in the mineral oil and combined with the remaining oil phase, whereupon this and homogenized and then combined with the water phase and on a tempe temperature of 80-85 ° C (i.e., in the phase inversion temperature range of the system) then cooled to room temperature (ie from the Phaseninversionstempe temperature range of the system).  

Example 5 O / W microemulsion

Wt .-% Ceteareth-12 8.00 cetearyl 10.00 cetearyl 4.00 TST 6.00 _MgSO4 3.00 pH = 5.0 @ Dyes, perfume, preservatives q.s. water ad 100.00

The components of the oil phase are combined and homogenized, then with the water phase and at a temperature of 80-85 ° C (i.e., in the phase inversions temperature range of the system), then cooled to room temperature (ie out of the phase inversion temperature range of the system introduced).  

Example 6 O / W microemulsion

Wt .-% Ceteareth-12 8.00 cetearyl 10.00 mineral oil 10.00 cetearyl 4.00 TST 5.00 _MgSO4 3.00 Dyes, perfume, preservatives q.s. water ad 100.00

TST is pre-suspended in the mineral oil and combined with the remaining oil phase, whereupon this and homogenized and then combined with the water phase and on a tempe temperature of 80-85 ° C (i.e., in the phase inversion temperature range of the system) then cooled to room temperature (ie from the Phaseninversionstempe temperature range of the system).

Example 7 O / W / O emulsion

Wt .-% glyceryl 5.00 mineral oil 25,00 stearic acid 2.00 TST 2.00 NaOH ad pH 7.0 Dyes, perfume, preservatives q.s. water ad 100.00

TST is dispersed in the oil phase. Water is added and the system is set to ca. Heated to 40 ° C. NaOH is added until a pH of 7 is reached, afterwards cooled to room temperature.  

Example 8 O / W / O emulsion

Wt .-% Polyglyceryl-2 polyhydroxystearate 7.00 Cetearylisononaoat 12.50 mineral oil 12.50 stearic acid 2.00 TST 4.00 Parsol® 1789 2.00 NaOH ad pH 7.0 Dyes, perfume, preservatives q.s. water ad 100.00

TST is pre-suspended in mineral oil and combined with the remaining oil phase. water is added and the system is heated to about 40 ° C. NaOH is added until one pH is 7, then cooled to room temperature.

Example 9 O / W / O emulsion

Wt .-% Polyglyceryl-2 polyhydroxystearate 5.00 Cetearylisononaoat 12.50 mineral oil 12.50 stearic acid 2.00 TST 4.00 Eusolex® 6300 2.00 Parsol® 1789 1.00 NaOH ad pH 7.0 Dyes, perfume, preservatives q.s. water ad 100.00

TST is dispersed in the oil phase. Water is added and the system is set to ca. Heated to 40 ° C. NaOH is added until a pH of 7 is reached, afterwards cooled to room temperature.  

Example 10 O / W macroemulsion

Wt .-% Polyglyceryl-2 polyhydroxystearate 2.00 Cetearylisononaoat 12.50 mineral oil 12.50 stearic acid 2.00 TST 2.00 NaOH ad pH 7.0 Dyes, perfume, preservatives q.s. water ad 100.00

TST is pre-suspended in mineral oil and combined with the remaining oil phase. water is added and the system is heated to about 40 ° C. NaOH is added until one pH is 7, then cooled to room temperature.

Claims (11)

1. O / W emulsions, in particular O / W microemulsions, or O / W / O emulsions or O / W / O'emulsions containing

• (a) a water phase,
• (b) optionally conventional, water-soluble or dispersible substances,
• (c) an oil phase,
  • in which at least one cosmetic or dermatological UV filter substance selected from the group of s-triazine derivatives of the general structural formula
    is reproduced, wherein
    R is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
    X represents an oxygen atom or an NH group,
    R _{1 is} a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula
    means in which
    A is a branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
    R _{3 represents} a hydrogen atom or a methyl group,
    n represents a number from 1 to 10,
    R _{2 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and
    a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group the formula
    means in which
    A is a branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
    R ^{3 represents} a hydrogen atom or a methyl group,
    n represents a number from 1 to 10,
    when X represents an oxygen atom,
    is present in suspended form,
• (D) at least one emulsifier (emulsifier A), selected from the group of Emulga factors having the following properties
  • their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
  • their lipophilicity is dependent on the temperature, such that the lipophilic substance increases with increasing temperature and its hydrophilicity increases with decreasing temperature,
• (E) further optionally further in the oil phase soluble or dispersible sub stances, including preferably those selected from the group of not falling under the definition of the emulsifier A emulsifiers, in particular those which act predominantly as W / O emulsifiers.

2. Method for incorporating s-triazine derivatives of the general structural formula
in which
R is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
X represents an oxygen atom or an NH group,
R _{1 is} a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group the formula
means in which
A is a branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R ^{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and
a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group the formula
means in which
A is a branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
when X represents an oxygen atom,
in O / W emulsions, O / W microemulsions or O / W / O emulsions, characterized in that

• (a) the components of a water phase,
• (b) optionally conventional, water-soluble or dispersible substances,
• (c) the components of an oil phase
• (c1) the previously described s-triazine derivatives
• (d) at least one emulsifier (emulsifier A) selected from the group of emulsifiers having the following properties
  • their lipophilicity is either dependent on the pH, such that increasing or decreasing the pH increases or decreases the lipophilicity, it being irrelevant which of the two possibilities of changing the Li pophilie by increasing or decreasing the pH Value is effected, and / or
  • their lipophilicity is dependent on the temperature, such that the lipophil increases with increasing temperature and the hydrophilicity increases with decreasing temperature,
• (e) furthermore, if appropriate, further substances which are soluble or dispersible in the oil phase, including preferably those selected from the group of emulsifiers not covered by the definition of emulsifier A, in particular those which predominantly act as W / O emulsifiers,
  be combined and formed under agitation a mixture such that
• (f) this mixture is brought into the phase inversion range by suitable choice of the parameters selected from the group of pH, temperature and concentration or concentrations of at least one of the emulsifiers chosen, in which W / O emulsions in O / Convert W emulsions,
• (G) by varying at least one parameter selected from the group pH, temperature and the concentration or concentrations of at least one of the selected emulsifiers, the formed W / O emulsion is brought out of the phase inversion area, in which a formed Converts W / O emulsion into an O / W emulsion to form an O / W emulsion or O / W microemulsion,
• (h) optionally initiating a further phase inversion to the O / W / O emulsion by suitable choice of the framework conditions,
• (i) the mixture is optionally subjected to further treatment steps, in particular egg nem or more Homogenisierungsschritten.

3. O / W emulsions, in particular O / W microemulsions, or O / W / O emulsions or O / W / O'-emulsions according to claim 1 or method according to claim 2, characterized in that the or the s Triazines are selected from the group of substances in which X represents an oxygen atom, R ₁ and R _{2 are} identical and a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups. 4. O / W emulsions, in particular O / W microemulsions, or O / W / O emulsions or O / W / O'-emulsions according to claim 1 or method according to claim 2, characterized in that the or the s Triazines are selected from the group of substances in which X represents an oxygen atom, R ₁ and R _{2 are} identical and one is a group of formula
in which R _{3 represents} a hydrogen atom, A represents a branched or unbranched C ₁ -C ₁₈ -alkyl radical and n = 2. 5. O / W emulsions, in particular O / W microemulsions, or O / W / O emulsions or O / W / O'-emulsions according to claim 1 or method according to claim 2, characterized in that the or the s Triazines are selected from the group of substances in which X represents an NH group, R ₁ and R _{2 are} identical or different and a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl groups. 6. The method according to claim 2 for the preparation of O / W / O emulsions, characterized ge indicates that the oil phase content is higher than about 15 wt .-%, in particular higher more than 20% by weight, based on the total weight of the preparation about 5 wt .-%, in particular about 5-10 wt .-% of a not below the definition of Emulsifier A falling W / O emulsifier and / or if the oil phase a low proportion of polar oils or is largely free of such oils. 7. The method according to claim 2 for the preparation of O / W microemulsions, characterized ge indicates that the oil phase content below about 20 wt .-%, in particular below about 15 wt .-%, based on the total weight of the preparation is less than about 5 Wt .-% of an additional, not falling under the definition of the emulsifier A W / O Emulsifier present and / or if the oil phase, a high proportion of polar oils having. 8. The method according to claim 2 for the preparation of O / W macroemulsions, characterized ge indicates that about 5% by weight of one not covered by the definition of the emulsifier A falling W / O emulsifier, and more than about 20 wt .-% of a polar oil phase here gene.   9. The method according to claim 2, characterized in that in the oil components poorly soluble UV filter substance or substances prior to the emulsification process in the oil phase in particular advantageous in a non-polar oil component or a Mixture of non-polar oil components, optionally with heating, dispersed be followed and the remaining steps of the process. 10. OW macroemulsions or O / W microemulsions or O / W / O emulsions or O / W / O'-emulsions according to claim 1, characterized in that the emulsifier A is selected from the group of polyethoxylated mono- or polybasic alcohols or Fatty acids, from the group of sorbitan esters and sucrose esters, in particular the branched and unbranched alkyl esters and alkenyl esters with carbon chains of 4- 24 carbon atoms, preferably sorbitan stearate, sorbitan oleate, glyceryl sorbitan stearate rat, sucrose monostearate, sucrose monolaurate, sucrose palmitate, monoglyme cerin monocarboxylic acid monoester, the di- and triglycerol monocarboxylic acid mono ester, further triglyceryl diisostearate, isostearyl diglyceryl succinate, diglycerylsesquiisostea rat, triglyceryl polyhydric stearate, cetearyl isononanoate, dicocoyl-pentaerythrityl-distea ryl citrate, furthermore the methicone copolyols, cyclomethicone copolyols, alkyl methicone copolyols, Laurylrnethiconcopolyol, Cetyldimethiconcopolyol, as well as the group of branched or unbranched alkyl monocarboxylic acids, alkenyl monocarboxylic acids and alkylenedi carboxylic acids having 4 to 30 carbon atoms, in particular stearic acid, oleic acid, Succinic acid, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (Caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, Undecenoic acid (undecylenic acid), dodecanoic acid (lauric acid), tridecanoic acid, tetra decanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), hepta decanoic acid (margaric acid), octadecanoic acid (stearic acid), isostearic acid, beehives acid or its cosmetically or pharmaceutically acceptable salts, in particular the alkali, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium salts. 11. OW macroemulsions or O / W microemulsions or O / W / O emulsions or O / W / O'-emulsions according to claim 1, characterized in that the emulsifier A or the emulsifiers A in concentrations of 0.01-20 wt .-%, preferably 0.05-10 Wt .-%, particularly preferably 0.1-5 wt .-%, each based on the total weight the composition is present or present.