EP0729343A1

EP0729343A1 - Cold-water emulsifiable agents

Info

Publication number: EP0729343A1
Application number: EP95900674A
Authority: EP
Inventors: Achim Ansmann; Rolf Kawa; Helga Gondek; Gabriele Strauss
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-11-15
Filing date: 1994-11-07
Publication date: 1996-09-04
Also published as: JPH09505235A; CN1135169A; WO1995013787A3; WO1995013787A2; DE4338999C1

Abstract

Proposed are agents containing: a) 10 to 40 wt. % addition product of 5 to 15 mol ethylene oxide to hydrogenated castor oil, b) 30 to 80 wt.% oil bases and c) 1-15 wt.% magnesium soap, provided that the components add up to 100 wt.%. The agents are characterized by a high stability in storage and can be emulsified with aqueous phases without heating.

Description

Cold water cleanable agents

Field of the Invention

The invention relates to cold water emulsifiable agents based on castor oil derivatives, oil bodies and magnesium soaps, emulsions containing these agents, a process for the preparation of these emulsions and the use of the agents for the preparation of emulsions.

State of the art

In recent years, the use of W / O emulsions for the development of modern cosmetic creams and lotions has become increasingly important. Cosmetic oil bodies of different polarities are used to build up the oil phase of the emulsions. To prepare an aqueous emulsion based on medium-polar oils, it is sufficient to mix the fat phase and the aqueous phase cold - ie without melting the fat phase - in the presence of a suitable emulsifier, for example a castor oil derivative (cf. A. Ansmann , R.Kawa in Soap-Oil-Fat-Waxes, 117, 518 (1991). Oil bodies with high or low polarity can only be satisfactorily emulsified with water and emulsifiers of the type mentioned if metal soaps are present. However, since these can only be worked into the fat phase when hot, the advantage in terms of energy and time savings in cold emulsification is lost. A manufacturer of cosmetic or pharmaceutical emulsions who intends to use very polar or very nonpolar oil bodies has therefore been forced to melt the fat phase (oil + emulsifier + optionally co-emulsifier) at temperatures around 100 ° C., the stabilizer enter and then add the aqueous phase.

The object of the invention was therefore to provide the manufacturer of emulsions with a means which can be emulsified in the cold with water, optionally with the addition of a further oil phase, the complex step of hot emulsification being thus reliably avoided can.

Description of the invention

The invention relates to cold water emulsifiable agents containing

a) 10 to 40 wt .-% of an adduct of 5 to 15

Moles of ethylene oxide to hydrogenated castor oil, b) 30 to 80% by weight of oil body and c) 1 to 15% by weight of magnesium soap, with the proviso that the components add up to 100% by weight.

Surprisingly, it has been found that mixtures which contain components a), b) and c) are stable even after prolonged storage and show no segregation. The agents can be emulsified in the cold with aqueous phases, which in turn results in stable emulsions. The invention includes the knowledge that only magnesium soaps are suitable as stabilizers for the production of the cold water emulsifiable agents; If aluminum and / or zinc soaps are used in the same recipes, agents are obtained which do not have sufficient storage stability, separate and cannot be marketed.

Emulsifiers

Suitable emulsifiers which form component a) are addition products of on average 5 to 15, preferably 6 to 9, mol of ethylene oxide onto hydrogenated (“hardened”) castor oil. A product with the CTFA name "PEG 7-Hydrogenated Castor Oil", which corresponds to the 7 EO adduct of hardened castor oil, is particularly preferred. The proportion of emulsifiers in the agents according to the invention can usually make up 10 to 40 and preferably 25 to 35% by weight. Oil body

Suitable oil bodies which represent component b) are all liquid, water-insoluble, branched or linear, physiologically compatible aliphatic hydrocarbons, linear and / or branched alcohols, ethers or esters at ambient temperature (20 ° C.). Solid or higher-melting paraffins, esters, waxes or fats can also be used.

Typical examples of suitable aliphatic hydrocarbons are squalane, squalenes, dioctylcyclohexane, di-n-octyl ether, di-2-ethylhexyl ether, paraffinum perliquidum, paraffinum subliquidum and isohexadecane (hydrogenated polybutylene).

Esters of trihydric and polyhydric alcohols, in particular vegetable triglycerides, such as, for example, olive oil, almond oil, peanut oil, sunflower oil, synthetic triglycerides, such as, for example, Cg-Ci _Q trifatty acid glycerol esters, or also the esters of pentaerythritol, are also particularly suitable as oil bodies eg pelargonic acid or oleic acid.

Finally, mono- and diesters of fatty acids of the formulas (Ia) to (Ic) are also suitable as oil bodies,

RicO-OR ² (Ia)

R ² OOC-R ³ -COOR ² (Ic) in which R ^ -CO stand for aliphatic acyl radicals with 8 to 22 carbon atoms, R ² for alkyl radicals with 3 to 22 carbon atoms and R3 for alkylene groups with 2 to 16 carbon atoms, with the proviso that the total of the esters is at least 12 and contain at most 40 carbon atoms.

Oil bodies of the formulas (Ia) to (Ic) are known as cosmetic and pharmaceutical oil components and as lubricant and lubricant components.

Among the mono- and diesters of the formula (Ia), the products which are liquid at ambient temperature (20 ° C.) are of the greatest importance. Typical examples are the esters of ^~ 2 ~ ^~ 1 ~ fatty acids with isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate. Other suitable monoesters are, for example, n-butyl stearate, n-hexyl laurate, n-octyl stearate, n-decyl oleate, isooctyl stearate, isononyl palmitate, isononyl isononanoate, 2-ethyl hexyl palmitate, 2-ethyl hexyl stearate, 2-octyldecyl aryl etherolate, ocyl paletate, erylatedylyl erylate, erylatedylyl erylate, cyl oleate, cyl oleate, cyl oleate, ethyl cylyl ether and also esters which are obtainable from technical aliphatic alcohol mixtures and technical aliphatic carboxylic acids, for example esters from saturated and unsaturated fatty alcohols with 12 to 22 carbon atoms and saturated and unsaturated fatty acids with 12 to 22 carbon atoms, as are obtainable from animal and vegetable fats and oils are. Naturally occurring monoester or wax ester mixtures, such as those present in jojoba oil or sperm oil, are also suitable.

Suitable dicarboxylic acid esters of the formula (Ib) are, for example, di-n-butyl adipate, di-n-butyl sebacate, di- (2-ethylhexyl) adipate, di- (2-hexyldecyl) succinate and diisotridecylacelaate. Suitable diol esters of the formula (Ic) are, for example, ethylene glycol dioleate, ethylene glycol diotridecanoate, propylene glycol di (2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanol diisostearate and neopentyl glycol dicaprylate.

Branched primary alcohols such as those known under the name "Guerbet alcohols" {cf. A.J. O'Lennick et al., Soap Cosm.Chem.Spec. 52 (1987)} are known. Typical examples are 2-butyl octanol, 2-hexyl decanol or 2-0 octyl decanol, and also esters of Guerbet alcohols with long-chain aliphatic carboxylic acids, in particular stearic acid. Finally, so-called Guerbet carbonates come into consideration, as are described in German patent application DE-Al 40 40 154 (Henkel).

The proportion of the oil bodies in the agents according to the invention can usually make up 30 to 80 and preferably 60 to 70% by weight.

Magnesium soaps

Magnesium soaps (component c) are substances which follow the formula (Ha) and / or (IIb)

(R COO) 2-Mg (Ha)

(R ⁴ COO) (OH) Mg (Hb) in which R ⁴ CO represents a fatty acyl radical having 12 to 22 carbon atoms. Typical examples are the magnesium salts of lauric acid, myristic acid, palmitic acid, oleic acid, behenic acid and erucic acid and technical Geraische such as Ci2 / 14 ^Ko l ^cos f ^ETTs äure or technical Fatty acid cuts. Neutral and / or basic magnesium stearate is preferably used.

Magnesium soaps, in particular magnesium stearates, are commercial products, for example from Barlocher, Munich / FRG. The qualities "PM", "AV", "SW / F" and "Pharma" are considered, which have a proportion of 7.5% by weight. %, have a free fatty acid content of at most 3% by weight and a water content of at most 6% by weight. The average grain size is preferably in the range from 7.5 to 12.5 μm, the surface in the range from 8 to 9 m / g and the vibrating weight in the range from 300 to 600 g / l.

The proportion of magnesium soaps in the agents according to the invention can usually make up 1 to 15 and preferably 5 to 10% by weight.

Co-emulsifiers

The agents according to the invention can contain co-emulsifiers as further ingredients, which are selected from the group of esters of fatty acids with glycerol, oligo- or polyglycerols and / or sorbitan. Typical examples are technical mono- and / or Diesterge- mix of C6-C22 ^fatty änren with glycerol, technical mono-, di-, tri- and / or Tetraester of CSS C22 ^_Fetts ä ren go- with olive or polyglycerols which in turn have a degree of self-condensation in the range from 1.5 to 10 and technical mono-, di- and / or triester ^mixtures of C5-C22 ^fatty acids with sorbitan.

For example, glycerol monolaurate, glycerol monopalmitate, glycerol monostearate, glycerol monooleate, glycerol mono / distearate, polyglycerol diisostearate, polyglycerol dioleate, sorbitan monolaurate, sorbitan monostearate, sorbitan sesquioleate, sorbitol and sorbitan danduranate, are particularly suitable.

The proportion of co-emulsifiers in the agents according to the invention can usually amount to 0.5 to 20 and preferably 5 to 15% by weight.

Production of funds

For the preparation of the agents, it is advisable to first dissolve the magnesium soap at a temperature below its softening point in component b) or a part thereof, to cool the solution to 50 to 85 ° C. and then to stir in the other constituents, their order is not critical. Industrial applicability

The agents according to the invention are low viscosity, stable in storage and can be cold emulsified with aqueous phases. The resulting emulsions are preferably W / O emulsions.

Another object of the invention therefore relates to emulsions containing 5 to 80, preferably 10 to 60% by weight of the agents according to the invention, 20 to 80, preferably 25 to 75% by weight of an aqueous phase and 0 to 50, preferably 0 up to 25% by weight of additives, with the proviso that the amounts given add up to 100% by weight.

The invention further relates to a process for the preparation of emulsions, in which 5 to 80, preferably 10 to 60% by weight of the agents according to the invention are mixed with 20 to 80, preferably 25 to 75% by weight of an aqueous phase and 0 to 50, preferably 0 to 25% by weight of additives, with the proviso that the amounts add up to 100% by weight, cold emulsified. If desired, further oil bodies, emulsifiers and auxiliaries can also be added and co-emulsified at this point.

The term "aqueous phase" means water and mixtures of water with lower alcohols, such as ethanol or isopropyl alcohol, or polyols, such as ethylene glycol, diethylene glycol, butylene glycol or glycerin. The aqueous phase can also contain electrolyte salts, such as sodium chloride, magnesium chloride or magnesium sulfate. The term "cold emulsified" means that the Formation of the emulsion at ambient temperature (20 ° C) can be carried out, so melting of the components is not necessary.

“Auxiliaries” are understood to mean, for example, perfume oils, antioxidants, oxides and pigments, pH regulators, dyes and UV filters.

Finally, the invention relates to the use of the compositions according to the invention for the production of cosmetic or pharmaceutical emulsions, in which they can be present in amounts of 5 to 80, preferably 10 to 60% by weight, based on the emulsions.

Examples

I. Recipe components

AI) adduct of an average of 7 moles of ethylene oxide onto hydrogenated castor oil (Dehymuls ( ^R ) HRE 7)

Bl) hexyl laurate (Cetiol ( ^R ) A)

B2) octyl stearate (Cetiol ( ^R ) 868)

B3) Ceterylisononanoate (Cetiol ( ^R ) SN)

^B4) C _{_8/10} triglyceride (Myritol ^(R) 318)

B5) mineral oil

CI) Magnesium stearate C2) Aluminum stearate C3) Zinc tearate

Dl) oleic acid monoglyceride (Monomuls ^(R ) 90-018) D2) Polyglycerol diisostearate (Lameform ( ^R ) TGI)

All substances marked with trademarks represent sales products of Henkel KGaA, Dusseldorf / FRG. The recipe components D1 and D2 are sales products of CF Grünau, Illertissen / FRG.

II. Recipes

To produce the cold water emulsifiable agents, the metal soaps were dissolved in mineral oil, the mixture was cooled to 85 ° C. and the other constituents were metered in, the sequence being uncritical. The dispersions were then cooled to room temperature. The storage took place at 45 ° C for a period of 4 weeks. The composition of the formulations according to the invention (Examples 1 to 5) and of the comparison formulations (Examples VI to V5) can be found in Table 1.

Tab. 1; Comparative formulations according to the invention, percentages as% by weight

Example AI Bl B2 B3 B5 CI C2 C3 Dl D2

%%%%%%%%%%

1 25 - - 28 29 8 - - 5 5

2 30 - 15 - 30 10 - - - 15

3 30 - 25 - 30 5 - - - 10

4 35 20 - - 25 10 - - 10 -

5 32 - 18 - 31 6 - - - 13

VI 25 - - 28 29 - 8 - 5 5

V2 30 - 15 - 30 - 10 - - 15

V3 30 - 25 - 30 - 5 - - 10

V4 35 20 - - 25 - - 10 10 -

V5 32 - 18 - 31 - - 6 - 13 The comparison formulations VI to V5 showed segregation after a storage time of just a few days. The same result was achieved at a storage temperature of 20 ° C. In contrast, the formulations 1 to 5 according to the invention showed a stable phase behavior at 45 ° C. over the entire storage period without any signs of segregation or sedimentation.

III. Emulsions

To prepare the emulsions, the fat phase I was stirred homogeneously at ambient temperature and the aqueous phase II was added cold while stirring. The emulsion was stirred for 5 to 10 minutes and then homogenized. Examples of emulsions are listed in Table 2:

Tab. 2: Emulsions

E.g. components phase I phase II Vis.

% By weight% of Paε

6 Recipe 5 10 10

B2 20

Glycerin (86% by weight) 5

MgS04 * ^{7 H} 2 ° 1

Water 64

7 Recipe 3 10 15

B4 20

Glycerin (86% by weight) 5

MgSO 4 * 7 H2O 1

Water 64

Legend; Viε = Brookfield viscosity, RVF, 23 ° C,

Spindle 5, 10 rpm

Claims

claims

1. Containing cold water emulsifiable agents

a) 10 to 40% by weight of an adduct of 5 to 15 mol of ethylene oxide with hydrogenated castor oil, b) 30 to 80% by weight of oil body and c) 1 to 15% by weight of magnesium soap,

with the proviso that the components add up to 100% by weight.

2. Composition according to claim 1, characterized in that they contain oil bodies which are selected from the group formed by aliphatic hydrocarbons, fatty acid esters of trihydric or polyhydric alcohols, mono- and diesters of fatty acids, Guerbet alcohols, Guerbet esters and Guerbet carbonates .

3. Composition according to claims 1 and 2, characterized gekennzeich¬ net that they contain magnesium soaps of the formula (Ila) and / or (Ilb),

(R ⁴ COO) 2Mg (Ha)

(R ⁴ COO) (OH) Mg (Ilb)

in which R ⁴ CO stands for a fatty acyl radical having 12 to 22 carbon atoms.

4. Composition according to claims 1 to 3, characterized gekennzeich¬ net that they contain co-emulsifiers as further ingredients, which are selected from the group of esters of fatty acids with glycerol, oligoglycerols and / or sorbitan.

5. Composition according to claim 4, characterized in that the co-emulsifiers are present in amounts of 0.5 to 20 wt .-% - based on the composition.

6. emulsions containing 5 to 80 wt .-% of the composition according to claim 1, 20 to 80 wt .-% of an aqueous phase and 0 to 50 wt .-% additives, with the proviso that the amount of 100 wt. - add%.

7. A process for the preparation of emulsions, in which 5 to 80% by weight of the composition according to claim 1 is combined with 75 to 95% by weight of an aqueous phase and 0 to 50% by weight of additives, with the proviso that that the amounts add up to 100 wt .-%, cold emulsified.

8. Use of the cold water emulsifiable agents according to claim 1 for the production of cosmetic or pharmaceutical emulsions.