CA2207113A1 - .alpha., -polyether polysiloxanes as w/o emulsifiers - Google Patents
.alpha., -polyether polysiloxanes as w/o emulsifiersInfo
- Publication number
- CA2207113A1 CA2207113A1 CA002207113A CA2207113A CA2207113A1 CA 2207113 A1 CA2207113 A1 CA 2207113A1 CA 002207113 A CA002207113 A CA 002207113A CA 2207113 A CA2207113 A CA 2207113A CA 2207113 A1 CA2207113 A1 CA 2207113A1
- Authority
- CA
- Canada
- Prior art keywords
- emulsifiers
- formulations
- emulsions
- oil
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/28—Zirconium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/54—Silicon compounds
Abstract
Use of copolymers of the general formula (see fig. I) R = -(CH2-)mO-(C2H4O-)x(C3H6O-)yR1 m = 2 to 4, x = 3 to 100, y = 0 to 50, R1 = H, CH3, CH2CH3, n = 50 to 200, as emulsifiers in W/O emulsions in amounts from 0.1 to 20% by weight, based on the total weight of the emulsion.
Description
CA 02207113 1997-06-0~
-Th. G o 1 d s c h m i d t AG, Essen a,~-Polyether polysilox~nec as W/O emulsifiers The invention relates to the use of a,~-polyether polysiloxanes as W/O emulsifiers, in particular in antiperspirant formulations.
As a rule, the antiperspirant gels which are known and available on the market consist of - active ingredients having antiperspirant activity, such as, for example, al-im;nllm chloride, alnm;nllm hydroxychloride, active alllm;nllm hydroxychlorides and zirconium salts, - water, - oils, in particular silicone oils, and - emulsifiers.
Customarily, these formulations are prepared by dissolving the active compound salts in water and intro~llc; ng this solution with stirring into the oil phase, which contains appropriate W/O emulsifiers, as a batchwise component.
Normally, these W/O formulations are cloudy. However, if the refractive index of the water phase is matched with the refractive index of the oil phase, clear W/O gels result. For this purpose, polyalcohols, such as sugar alcohols, or poly-ethylene glycols are customarily added to the water phase in amounts from 25 to 50~ by weight. The amount nep~e~ is ~pen~ent on the nature and amount of the constituents of the emulsion and can easily be determined by simple experiments.
- Further constituents of the emulsion, such as preservatives, perfume oils, colorants and stabilizers, as a rule are added to the phase in which they are soluble or easily dispersible. If required, the mixture can then be hollloy~llized~ e.g. with the aid of a colloid mill.
The use of emulsifier systems based on polys;lo~n~ is known and described in detail, for- example, in US-A-4 988 504.
Co~red with the polysiloxane ~1l1 s; fiers known until then, US-A-4 988 504 proposes those which consist of a) units of the formula R2SiO2/2 R = hydrogen or a substituted or unsubstituted hydrocarbon radical having 1 to 12 carbon atoms, b) units of the formula RR1SiO22 R1 = polyalkylene ether of the formula ~Ra3 ~ (oR2 ) n~OR4 R2 = -CH2CH2-, R3 = substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R4 = R, n has a value from 5 to 20 and a is 0 or 1, and c) final member~ of the siloxane chain, where the molecular weight of c~l-~onent a) should be a~lo~imately 25,000 to 35,000.
These emulsifiers having lateral polyoxyalkylene groups should achieve improved properties for antiperspirant sticks with respect to stability and low wax content.
EP-B-0 407 089 relates to a transparent water-in-silicone oil emulsion, suitable for external application to m~mm~ n skin or hair, c~ ising, in addition to water:
i. 1 to 50~ by weight of a volatile polydimethylsiloxane;
ii. 0.1 to 20~ by weight of a silicone surfactant con-stituent, colu~lising a polymer of dimethylpolysiloxane having poly-oxyethylene and/or polyoxypropylene side chA; n~ having a molecular CA 02207113 1997-06-0~
weight of 10,000 to 50,000 and the structural fonmula:
CH3~ O ~ i-O - i-O ~ i-CH3 CH3 CH3 - x - CH3 in which R is -H or [cH2CH20]a[cH2cHO ]bH
~H3 a has a value from 9 to 115, b has a value from 0 to 50, x has a value from 133 to 673, y has a value from 25 to 0.25 and iii. 1 to 50~ by weight of a transparency-imparting agent, which is at least a polyhydric alcohol.
The siloxane emulsifiers proposed here accordingly also have polyoxyethylene and polyoxypropylene groups in the side chain and are characterized by a high molecular weight. The emulsions described should have a good storage and temperature stability as well as skin-compatible properties. A disadvantage of these siloxane emulsifiers, however, is their extremely high visco-sity, so that they can only be handled in solvents. They are CA 02207113 1997-06-0~
therefore preferably employed as a dispersion in short-chain (D4, D5) silicone oils, wh-ich must have a viscosity of below 5 mm2.s~1. Preferably, a 10~ strength emulsifier formulation is employed here. The use of these emulsifiers is thus inevitably associated with the introduction of short-chain silicone oils and thus means a restriction in the selection of the components of the desired antiperspirant gels.
The object of the present invention is the provision of emulsifiers for antiperspirant formulations based on W/O emul-sions which have a low viscosity and thus can be- handled without the use of solvents or dispersions and display the desired emulsifying action at the lowest po~sible concen-tration. The emulsifiers should have high stability and also retain this under thermal stress. On account of the cosmetic application area, the emulsifiers must in this case be physio-logically acceptable.
According to the invention, this object is achieved by the use of copolymers of the general formula R-- i-O i-O ~ i-R
CH3 CH3 n CH3 R = - (CH2-)mO- (c2H4o-)x(c3H6o-)yR
m = 2 to 4, x = 3 to 100, y = 0 to 50, R1 = H, CH3, CH2CH3, n = 50 to 200, as emulsifiers in W/O emulsions in amounts from 0.1 to 20~ by weight, based on the total weight of the emulsion.
The weight ratio of oxyethylene to oxypropylene groups is preferably selected here such that the weight ratio of poly-ethylene oxide to polypropylene oxide is 100 : 10 to 20 : 80.
Copolymers in which R1 = H and n = 100 to 150 and the weight ratio of polyethylene oxide to polypropylene oxide is 80 : 20 to 40 : 60 are particularly preferred.
The oxyethylene and oxypropylene units can be r~n~o~ly distributed or arranged blockwise.
In contrast to the known emulsifiers, the emulsifier according to the invention is modified - at the termlnal siloxane groups - by polyether groups. In contrast to the customary types which are modified in a comb-like m~nner, this type of graft copolymer has a lower degree of modification of two polyether groups per polymer molecule. By modification of the hydrophobic radicals (index y and index n) and the hydrophilic radicals (index x) in the whole molecule, the polyethersilox~nes used CA 02207113 1997-06-0~
according to the invention can be adjusted to the desired HLB
values and necess~ry interfacial activities. Emul-sifiers having a relatively low molecular weight result here, using which it is surprisingly possible to prepare emulsions having outst~n~;ng stability with respect to elevated temperature, freeze/thaw cycles and long-term storage. Com~red with the prior art, the emulsifier employed according to the invention here has a mlmh~r of advantages. As a 100~ strength product, it is of low viscosity and readily handleable and can be prepared more easily than defined compounds. In comp~rison with solvent-cont~;n;ng products, lower use conce~trations are necessary, which leads to considerable savings in the logistics area. In the products of the prior art, silicone oil is used. In contrast, it turns out to be an advantage of the compounds according to the invention that, if required, silicone-oil-free formulations are also possible.
The emulsifiers according to the invention are suitable for the preparation of W/O emulsions using silicone oils which can be linear or cyclic. Silicone oils such as octamethylcyclotetra-siloxane are preferred. Further oils or waxes can be emulsified together with the silicone oils.
Examples of such oily substances are synthetic skin oils, such as isopropyl myristate, isopropyl stearate, hexyl laurate, oleyl oleate. Liquid waxes, such as jojoba oil, are furthermore suitable.
CA 02207113 1997-06-0~
Further constituents of the oily phase can be natural vegetable or ~n;m~l oils, such as, for example, mink oil, fish oil, neat's foot oil, bone oil, castor oil, sunflower oil, avocado oil, olive oil, groundnut oil, palm oil. Microwaxes or other thickeners by means of which the consistency of the emulsions obt~;ne~ can be adjusted from liquid to solid can furthermore be added to the ester and silicone oils to be emulsified.
To increase the stability to cold, polyalcohols, e.g. glycerol, 1,2-propylene glycol or sorbitol, can be added to the emulsion in amounts from 0.5 to 15% by weight. The heat stability can be ~ uv~d by addition of electrolytes, e.g. sodium chloride, calcium chioride and/or m~nesium sulfate. These additives are employed at 0.5 to 10.0% by weight. Moreover, the stability of the formulation can be inl~luved by addition of zinc stearate or al-lm;m~m stearate.
The use conc~ntration of the emulsifier should be at least 1%
by weight; the oil phase can make up 15 to 50% by weight of the total formulation.
At a water content of 70 to 85% by weight, the emulsion has a pasty consistency. Less water lowers the viscosity of the system to a lotion-like consistency, and even less water can be used in order to prepare an emulsion of very low viscosity.
The antiperspirant W/O emulsions are prepared in a customary mann~r by dissolving and dispersing silicone oils, preferably the polysiloxanes D4 and D5, on their own or in combination CA 02207113 1997-06-0~
with skin oils, in the emul~ifying agent, the polyether-siloxane. If the latter co~ta; ns relatively high-melting cu,.,~llents, e.g. silicone wax or beeswax, the oily phase is warmed above the melting range of these constituents.
The water phase is then slowly added to the oily phase with stirring. In the case of transparent W/O emulsions, the refractive indices of the water phase are matched with those of the oil phase. This can be carried out by ap~Lo~riate adjustment of the ratio of polyalcohols (glycerol, propylene glycol, sorbitol and the like) to water in the water phase.
Examples 1. Emulsifiers The table shows the chemical structure of some emulsifiers which are suitable for the use according to the invention:
Table 1: emulsifiers according to the invention (C2H4o-)x(c3H6o-)yR~ Weight ratio R' n average desired C2H4O : C3H6O
molecular weight [g/mol]
Emulsifier 1 H 50 1 600 58 : 42 Emulsifier 2 H 150 400 100 : 0 Emulsifier 3 H 100 1 400 42 : 58 Emulsifier 4 H 200 500 60 : 40 Emulsifier 5CH3 100 2 550 42 : 58 Emulsifier 6 H 100 1 400 12 : 88 CA 02207113 1997-06-0~
-Th. G o 1 d s c h m i d t AG, Essen a,~-Polyether polysilox~nec as W/O emulsifiers The invention relates to the use of a,~-polyether polysiloxanes as W/O emulsifiers, in particular in antiperspirant formulations.
As a rule, the antiperspirant gels which are known and available on the market consist of - active ingredients having antiperspirant activity, such as, for example, al-im;nllm chloride, alnm;nllm hydroxychloride, active alllm;nllm hydroxychlorides and zirconium salts, - water, - oils, in particular silicone oils, and - emulsifiers.
Customarily, these formulations are prepared by dissolving the active compound salts in water and intro~llc; ng this solution with stirring into the oil phase, which contains appropriate W/O emulsifiers, as a batchwise component.
Normally, these W/O formulations are cloudy. However, if the refractive index of the water phase is matched with the refractive index of the oil phase, clear W/O gels result. For this purpose, polyalcohols, such as sugar alcohols, or poly-ethylene glycols are customarily added to the water phase in amounts from 25 to 50~ by weight. The amount nep~e~ is ~pen~ent on the nature and amount of the constituents of the emulsion and can easily be determined by simple experiments.
- Further constituents of the emulsion, such as preservatives, perfume oils, colorants and stabilizers, as a rule are added to the phase in which they are soluble or easily dispersible. If required, the mixture can then be hollloy~llized~ e.g. with the aid of a colloid mill.
The use of emulsifier systems based on polys;lo~n~ is known and described in detail, for- example, in US-A-4 988 504.
Co~red with the polysiloxane ~1l1 s; fiers known until then, US-A-4 988 504 proposes those which consist of a) units of the formula R2SiO2/2 R = hydrogen or a substituted or unsubstituted hydrocarbon radical having 1 to 12 carbon atoms, b) units of the formula RR1SiO22 R1 = polyalkylene ether of the formula ~Ra3 ~ (oR2 ) n~OR4 R2 = -CH2CH2-, R3 = substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, R4 = R, n has a value from 5 to 20 and a is 0 or 1, and c) final member~ of the siloxane chain, where the molecular weight of c~l-~onent a) should be a~lo~imately 25,000 to 35,000.
These emulsifiers having lateral polyoxyalkylene groups should achieve improved properties for antiperspirant sticks with respect to stability and low wax content.
EP-B-0 407 089 relates to a transparent water-in-silicone oil emulsion, suitable for external application to m~mm~ n skin or hair, c~ ising, in addition to water:
i. 1 to 50~ by weight of a volatile polydimethylsiloxane;
ii. 0.1 to 20~ by weight of a silicone surfactant con-stituent, colu~lising a polymer of dimethylpolysiloxane having poly-oxyethylene and/or polyoxypropylene side chA; n~ having a molecular CA 02207113 1997-06-0~
weight of 10,000 to 50,000 and the structural fonmula:
CH3~ O ~ i-O - i-O ~ i-CH3 CH3 CH3 - x - CH3 in which R is -H or [cH2CH20]a[cH2cHO ]bH
~H3 a has a value from 9 to 115, b has a value from 0 to 50, x has a value from 133 to 673, y has a value from 25 to 0.25 and iii. 1 to 50~ by weight of a transparency-imparting agent, which is at least a polyhydric alcohol.
The siloxane emulsifiers proposed here accordingly also have polyoxyethylene and polyoxypropylene groups in the side chain and are characterized by a high molecular weight. The emulsions described should have a good storage and temperature stability as well as skin-compatible properties. A disadvantage of these siloxane emulsifiers, however, is their extremely high visco-sity, so that they can only be handled in solvents. They are CA 02207113 1997-06-0~
therefore preferably employed as a dispersion in short-chain (D4, D5) silicone oils, wh-ich must have a viscosity of below 5 mm2.s~1. Preferably, a 10~ strength emulsifier formulation is employed here. The use of these emulsifiers is thus inevitably associated with the introduction of short-chain silicone oils and thus means a restriction in the selection of the components of the desired antiperspirant gels.
The object of the present invention is the provision of emulsifiers for antiperspirant formulations based on W/O emul-sions which have a low viscosity and thus can be- handled without the use of solvents or dispersions and display the desired emulsifying action at the lowest po~sible concen-tration. The emulsifiers should have high stability and also retain this under thermal stress. On account of the cosmetic application area, the emulsifiers must in this case be physio-logically acceptable.
According to the invention, this object is achieved by the use of copolymers of the general formula R-- i-O i-O ~ i-R
CH3 CH3 n CH3 R = - (CH2-)mO- (c2H4o-)x(c3H6o-)yR
m = 2 to 4, x = 3 to 100, y = 0 to 50, R1 = H, CH3, CH2CH3, n = 50 to 200, as emulsifiers in W/O emulsions in amounts from 0.1 to 20~ by weight, based on the total weight of the emulsion.
The weight ratio of oxyethylene to oxypropylene groups is preferably selected here such that the weight ratio of poly-ethylene oxide to polypropylene oxide is 100 : 10 to 20 : 80.
Copolymers in which R1 = H and n = 100 to 150 and the weight ratio of polyethylene oxide to polypropylene oxide is 80 : 20 to 40 : 60 are particularly preferred.
The oxyethylene and oxypropylene units can be r~n~o~ly distributed or arranged blockwise.
In contrast to the known emulsifiers, the emulsifier according to the invention is modified - at the termlnal siloxane groups - by polyether groups. In contrast to the customary types which are modified in a comb-like m~nner, this type of graft copolymer has a lower degree of modification of two polyether groups per polymer molecule. By modification of the hydrophobic radicals (index y and index n) and the hydrophilic radicals (index x) in the whole molecule, the polyethersilox~nes used CA 02207113 1997-06-0~
according to the invention can be adjusted to the desired HLB
values and necess~ry interfacial activities. Emul-sifiers having a relatively low molecular weight result here, using which it is surprisingly possible to prepare emulsions having outst~n~;ng stability with respect to elevated temperature, freeze/thaw cycles and long-term storage. Com~red with the prior art, the emulsifier employed according to the invention here has a mlmh~r of advantages. As a 100~ strength product, it is of low viscosity and readily handleable and can be prepared more easily than defined compounds. In comp~rison with solvent-cont~;n;ng products, lower use conce~trations are necessary, which leads to considerable savings in the logistics area. In the products of the prior art, silicone oil is used. In contrast, it turns out to be an advantage of the compounds according to the invention that, if required, silicone-oil-free formulations are also possible.
The emulsifiers according to the invention are suitable for the preparation of W/O emulsions using silicone oils which can be linear or cyclic. Silicone oils such as octamethylcyclotetra-siloxane are preferred. Further oils or waxes can be emulsified together with the silicone oils.
Examples of such oily substances are synthetic skin oils, such as isopropyl myristate, isopropyl stearate, hexyl laurate, oleyl oleate. Liquid waxes, such as jojoba oil, are furthermore suitable.
CA 02207113 1997-06-0~
Further constituents of the oily phase can be natural vegetable or ~n;m~l oils, such as, for example, mink oil, fish oil, neat's foot oil, bone oil, castor oil, sunflower oil, avocado oil, olive oil, groundnut oil, palm oil. Microwaxes or other thickeners by means of which the consistency of the emulsions obt~;ne~ can be adjusted from liquid to solid can furthermore be added to the ester and silicone oils to be emulsified.
To increase the stability to cold, polyalcohols, e.g. glycerol, 1,2-propylene glycol or sorbitol, can be added to the emulsion in amounts from 0.5 to 15% by weight. The heat stability can be ~ uv~d by addition of electrolytes, e.g. sodium chloride, calcium chioride and/or m~nesium sulfate. These additives are employed at 0.5 to 10.0% by weight. Moreover, the stability of the formulation can be inl~luved by addition of zinc stearate or al-lm;m~m stearate.
The use conc~ntration of the emulsifier should be at least 1%
by weight; the oil phase can make up 15 to 50% by weight of the total formulation.
At a water content of 70 to 85% by weight, the emulsion has a pasty consistency. Less water lowers the viscosity of the system to a lotion-like consistency, and even less water can be used in order to prepare an emulsion of very low viscosity.
The antiperspirant W/O emulsions are prepared in a customary mann~r by dissolving and dispersing silicone oils, preferably the polysiloxanes D4 and D5, on their own or in combination CA 02207113 1997-06-0~
with skin oils, in the emul~ifying agent, the polyether-siloxane. If the latter co~ta; ns relatively high-melting cu,.,~llents, e.g. silicone wax or beeswax, the oily phase is warmed above the melting range of these constituents.
The water phase is then slowly added to the oily phase with stirring. In the case of transparent W/O emulsions, the refractive indices of the water phase are matched with those of the oil phase. This can be carried out by ap~Lo~riate adjustment of the ratio of polyalcohols (glycerol, propylene glycol, sorbitol and the like) to water in the water phase.
Examples 1. Emulsifiers The table shows the chemical structure of some emulsifiers which are suitable for the use according to the invention:
Table 1: emulsifiers according to the invention (C2H4o-)x(c3H6o-)yR~ Weight ratio R' n average desired C2H4O : C3H6O
molecular weight [g/mol]
Emulsifier 1 H 50 1 600 58 : 42 Emulsifier 2 H 150 400 100 : 0 Emulsifier 3 H 100 1 400 42 : 58 Emulsifier 4 H 200 500 60 : 40 Emulsifier 5CH3 100 2 550 42 : 58 Emulsifier 6 H 100 1 400 12 : 88 CA 02207113 1997-06-0~
2. For~lAtion examples 2.1. Preparation Table 2 shows the composition of emulsions and emulsion gels according to the invention.
The preparation of the emulsion is carried out in a cont~;n~r which is provided with a stirrer. The constituents A are added to the cont~;n~r and optionally fused. The water, in which, if appropriate, sodium chloride, propylene glycol and, depending on the recipe, all]m;nl~m salts (in solution) are dissolved, is added to the mixture of emulsifier and oil with stirring.
In the case of clear, gelatinous formulations, the refractive index of the aqueous phase is matched with the refractive index of the oil phase by addition of polyalcohols (e.g. propylene glycol, glycerol or sorbitol).
The W/O emulsions or emulsion gels obtained can, if required, be homogenized, for example using a colloid mill or a homogenizer which operates on the pressure principle.
The emulsions prepared have particle sizes of c 1 ~ particle diameter.
2.2. Emll~ nn Examples 1 to 7 The emulsions 1, 3, 4, 5, 6 and 7 have a creamy or gelatinous consistency; the emulsion 2 is liquid. The emulsions and the emulsion gels are stable for 3 months, stored at 20~C and 45~C.
CA 02207113 1997-06-0~
The emulsions show no ;mr~irment of the stability after cooling to -15~C and subsequently warming to 20~C five times. Even after storage of the emulsions at 20~C for six months, no reduction in viscosity is to be found.
The exemplary formulations 2 and 5 are skin-care emulsions. The emulsions have a smooth and brilliant appearance. They can be distributed very easily on the skin, are absorbed rapidly and impart a ple~nt, velvety, slightly cooling sensation to the skin.
The exemplary formulations 1, 3, 4, 6 and 7 are transparent emulsions for use as antiperspirant. The transparency of these formulations is achieved by adjustment of the refractive index of the aqueous phase to that of the oily phase. These formulations can be distributed easily on the skin and leave a velvety sleek sensation on the skin surface.
CA 02207113 1997-06-0~
Table 2: r ll~si~n fon~ll~t;~nc r- l~ion example No.1 2 3 4 5 6 7 Constituents~ by ~ by ~ by ~ by ~ by ~ by ~ by wt. wt. wt. wt. wt. wt. wt.
r llcifier 1 3.0 - - ~
;fier 2 ~ 4-0 r~llc;fier 3 - 1.5 Emulsifier 4 - - - 3.04.0 r ~1 Ri fi ~r 5 _ _ _ _ _ 1.0 ~llc;fi~ 6 1.5 Phase A) Octylm~ethylcyclo- 13.0 - 7.2 6.5 - 7.5 7.0 tetrAC; 1 C~Y~n~
De~: -hylcyclopenta- - - 7.3 6.5 - 7.5 7.5 s; 1 oX 3n~
Isopropyl myristate - - - - 8.0 Liquid paraffin GP 8 - 12.5 - - 13.0 Avocado oil - - - - 1.0 Cetyl ~; ~th;cone *1) - - - - 0.5 Caprylic/capric - 12.5 triglyceride Zink ri~;nnl~te + - - - 2.5 tetrahydroxypropyl-ethyl ~n~;: ' n~ +
laureth-3 + 1,2-pro-pylene glycol *2) Phase B) Water 19.0 70.3 5.0 16.5 67.0 20.0 20.0 NaCl - 0.7 - - 2.0 1,2-Propylene glycol25.0 - 22.0 25.04.5 24.0 24.0 hydroxy- 40.0 ~ ~ 40-0 chloride solution *3) Al~ 'm zirkonium- - - 57.0 tetrahydro-hydroxy-chloride-glycine complex *4) Total 100.0100.0 100.0 100.0 100.0 100.0 100.0 CA 02207113 1997-06-0~
, *1) A~3IL Wax 9801 (polysiloxane/polyalkylene copolymer), Th. Goldschmidt AG
*2) TEGO Deo CW 90 (deodorant active ingredient), Th.
Goldschmidt AG
*3) Reach 501 (antiperspirant active ingredient, 50~ in water), Reheis *4) Reach 36GLY (antiperspirant active ingredient, 36~ in water), Reheis 3. Formulation examples 3.1. E~ f~ers For csmp~rison, the product "Formulation aid DC 3225 C", Dow Corning, available on the market is employed. This is a cloudy dispersion of a polydimethylsiloxane which is modified in a comb-like m~nner with polyethylene glycol/polypropylene glycol groups as the modification (graft copolymer) in octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
A pale deposit precipitates from this dispersion after just a short time.
The emulsifiers according to the invention, on the other hand, are clear and homogeneous products. Separation phenomena as in the case of the market comparison product have not been observed with the emulsifiers according to the invention.
3.2. Formulations The recipes in Table 3 are prepared as described previously.
Table 3: Formulation examples Antiperspirant Skin-care emulsions gels Formulation example 3 89 10 11 Constituents % by % by% by % by % by wt. wt. wt. wt. wt.
Emulsifier 3 1.5 - - - -Emulsifier 4 - - 3.0 - 3.0 DC 3225 C - 15.0 - 30.0 Phase A) Octamethylcyclotetra- 7.2 1.0 - - 13.5 siloxane Decamethylcyclopenta- 7.3 - - - 13.5 siloxane Isopropyl myristate - - 8.0 8.0 8.0 Liquid paraffin GP 8 - - 13.0 Avocado oil - - 1.0 1.0 1.0 Phase B) Water 5.0 5.071.0 59.059.0 NaCl - - - 2.0 2.0 2.0 1,2-Propylene glycol 22.0 22.02.0 Alllm;nl~m-zirconium 57.0 57.0 tetrahydroglycine complex *4) Total 100.0 100.0100.0 100.0100.0 *4) Reach 36GLY (antiperspirant active ingredient, 36% in water), Reheis CA 02207113 1997-06-0~
3.3. Comparison: viscosity of gel formulations Formulation example 3 8 Viscosity 45,000 mPas 49,000 mPas The viscosities of the recipe examplés 3 and 8 are similar.
3.4. Comparison: silicone oil content in skin-care formulations Formulation example 9 10 11 Silicone oil content 0~ 27% 27 in ~
The silicone oil content in the recipe examples is fixed by the emulsifer. The market comparison product, DC 3225 C, contains 89~ silicone oils. As example 10 shows, it is not possible-to prepare DC 3225 C emulsions which do not contain any silicone oil. With the emulsifiers according to the invention, on the other hand, it is possible to prepare both silicone-free formulations (example 9) and those formulations which contain the same amount of silicone oils as the formulations which can be prepared with DC 3225 C (example 11).
CA 02207113 1997-06-0~
The preparation of the emulsion is carried out in a cont~;n~r which is provided with a stirrer. The constituents A are added to the cont~;n~r and optionally fused. The water, in which, if appropriate, sodium chloride, propylene glycol and, depending on the recipe, all]m;nl~m salts (in solution) are dissolved, is added to the mixture of emulsifier and oil with stirring.
In the case of clear, gelatinous formulations, the refractive index of the aqueous phase is matched with the refractive index of the oil phase by addition of polyalcohols (e.g. propylene glycol, glycerol or sorbitol).
The W/O emulsions or emulsion gels obtained can, if required, be homogenized, for example using a colloid mill or a homogenizer which operates on the pressure principle.
The emulsions prepared have particle sizes of c 1 ~ particle diameter.
2.2. Emll~ nn Examples 1 to 7 The emulsions 1, 3, 4, 5, 6 and 7 have a creamy or gelatinous consistency; the emulsion 2 is liquid. The emulsions and the emulsion gels are stable for 3 months, stored at 20~C and 45~C.
CA 02207113 1997-06-0~
The emulsions show no ;mr~irment of the stability after cooling to -15~C and subsequently warming to 20~C five times. Even after storage of the emulsions at 20~C for six months, no reduction in viscosity is to be found.
The exemplary formulations 2 and 5 are skin-care emulsions. The emulsions have a smooth and brilliant appearance. They can be distributed very easily on the skin, are absorbed rapidly and impart a ple~nt, velvety, slightly cooling sensation to the skin.
The exemplary formulations 1, 3, 4, 6 and 7 are transparent emulsions for use as antiperspirant. The transparency of these formulations is achieved by adjustment of the refractive index of the aqueous phase to that of the oily phase. These formulations can be distributed easily on the skin and leave a velvety sleek sensation on the skin surface.
CA 02207113 1997-06-0~
Table 2: r ll~si~n fon~ll~t;~nc r- l~ion example No.1 2 3 4 5 6 7 Constituents~ by ~ by ~ by ~ by ~ by ~ by ~ by wt. wt. wt. wt. wt. wt. wt.
r llcifier 1 3.0 - - ~
;fier 2 ~ 4-0 r~llc;fier 3 - 1.5 Emulsifier 4 - - - 3.04.0 r ~1 Ri fi ~r 5 _ _ _ _ _ 1.0 ~llc;fi~ 6 1.5 Phase A) Octylm~ethylcyclo- 13.0 - 7.2 6.5 - 7.5 7.0 tetrAC; 1 C~Y~n~
De~: -hylcyclopenta- - - 7.3 6.5 - 7.5 7.5 s; 1 oX 3n~
Isopropyl myristate - - - - 8.0 Liquid paraffin GP 8 - 12.5 - - 13.0 Avocado oil - - - - 1.0 Cetyl ~; ~th;cone *1) - - - - 0.5 Caprylic/capric - 12.5 triglyceride Zink ri~;nnl~te + - - - 2.5 tetrahydroxypropyl-ethyl ~n~;: ' n~ +
laureth-3 + 1,2-pro-pylene glycol *2) Phase B) Water 19.0 70.3 5.0 16.5 67.0 20.0 20.0 NaCl - 0.7 - - 2.0 1,2-Propylene glycol25.0 - 22.0 25.04.5 24.0 24.0 hydroxy- 40.0 ~ ~ 40-0 chloride solution *3) Al~ 'm zirkonium- - - 57.0 tetrahydro-hydroxy-chloride-glycine complex *4) Total 100.0100.0 100.0 100.0 100.0 100.0 100.0 CA 02207113 1997-06-0~
, *1) A~3IL Wax 9801 (polysiloxane/polyalkylene copolymer), Th. Goldschmidt AG
*2) TEGO Deo CW 90 (deodorant active ingredient), Th.
Goldschmidt AG
*3) Reach 501 (antiperspirant active ingredient, 50~ in water), Reheis *4) Reach 36GLY (antiperspirant active ingredient, 36~ in water), Reheis 3. Formulation examples 3.1. E~ f~ers For csmp~rison, the product "Formulation aid DC 3225 C", Dow Corning, available on the market is employed. This is a cloudy dispersion of a polydimethylsiloxane which is modified in a comb-like m~nner with polyethylene glycol/polypropylene glycol groups as the modification (graft copolymer) in octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
A pale deposit precipitates from this dispersion after just a short time.
The emulsifiers according to the invention, on the other hand, are clear and homogeneous products. Separation phenomena as in the case of the market comparison product have not been observed with the emulsifiers according to the invention.
3.2. Formulations The recipes in Table 3 are prepared as described previously.
Table 3: Formulation examples Antiperspirant Skin-care emulsions gels Formulation example 3 89 10 11 Constituents % by % by% by % by % by wt. wt. wt. wt. wt.
Emulsifier 3 1.5 - - - -Emulsifier 4 - - 3.0 - 3.0 DC 3225 C - 15.0 - 30.0 Phase A) Octamethylcyclotetra- 7.2 1.0 - - 13.5 siloxane Decamethylcyclopenta- 7.3 - - - 13.5 siloxane Isopropyl myristate - - 8.0 8.0 8.0 Liquid paraffin GP 8 - - 13.0 Avocado oil - - 1.0 1.0 1.0 Phase B) Water 5.0 5.071.0 59.059.0 NaCl - - - 2.0 2.0 2.0 1,2-Propylene glycol 22.0 22.02.0 Alllm;nl~m-zirconium 57.0 57.0 tetrahydroglycine complex *4) Total 100.0 100.0100.0 100.0100.0 *4) Reach 36GLY (antiperspirant active ingredient, 36% in water), Reheis CA 02207113 1997-06-0~
3.3. Comparison: viscosity of gel formulations Formulation example 3 8 Viscosity 45,000 mPas 49,000 mPas The viscosities of the recipe examplés 3 and 8 are similar.
3.4. Comparison: silicone oil content in skin-care formulations Formulation example 9 10 11 Silicone oil content 0~ 27% 27 in ~
The silicone oil content in the recipe examples is fixed by the emulsifer. The market comparison product, DC 3225 C, contains 89~ silicone oils. As example 10 shows, it is not possible-to prepare DC 3225 C emulsions which do not contain any silicone oil. With the emulsifiers according to the invention, on the other hand, it is possible to prepare both silicone-free formulations (example 9) and those formulations which contain the same amount of silicone oils as the formulations which can be prepared with DC 3225 C (example 11).
CA 02207113 1997-06-0~
4. InvestigationQ on the efficacy of antiperQpirant formulations 4.1. Test recipeQ
The formulations listed in Table 4 are employed in all investigations for determination of the efficacy. The content of all~m;nl~m in all these formulations is 6~.
Table 4: Test recipes for efficacy determinations Formulation examples 12 13 Emulsifier 3 1.1~ -DC 3225 C - 10.0 Octamethylcyclotetrasiloxane 15.9~ 7.0~
Alnm;nl]m hydroxychloride 50.0~ 50.0%
solution *3) Propylene glycol 16.0~ 16.0 Water, distilled 17.0~ 17.0 Total 100.0~ 100.0~
*3) Reach 501 (antiperspirant active compound, 50~ in water), Reheis 4.2. Release of aluminum In the formulations investigated, the active constituent (all~m;nl~m hydroxychloride solution) is present in the internal, aqueous phase as a solution. In order to be efficacious, the alnm; n~m hydroxychloride solution must pass through the CA 02207113 1997-06-0~
external, oily phase. The rate of release of the active constituent (alllm;nl~m hydroxychloride solution) is investigated in Formulation Examples 12 and 13.
For this, the formulations are diluted with 95~ of water. After shaking for 5 minutes, the alllm;nllm content in an aliquot amount of the aqueous solution is determined. This 5-minute value marks the starting point. The dilutions are shaken further and, after 1 and 24 hours in each case 1 aliquot amounts are again taken for analysis. The content of all~m;nllm in the aqueous solution is determined by atomic absorption spectroscopy.
The results are compiled in Table 5. It is clear that the formulations 12 and 13 have an equally high rate of release of al-lm; m~m .
Table 5: Release of all~m; n~m -Formulation Example 12 ¦ 13 ~ all~m;nllm recovered 5 minutes 15 16 1 hour ~ 90 > 90 24 hours ~ 90 ~ 90 CA 02207113 1997-06-0~
4.3. In-vivo test for antiperspirant effectiveness 4.3.1.Prel;~;nary investigations (selection of the subjects) Subjects with a similar perspiration intensity (sweat production) on the volar surface of the forearm are selected.
To do this, the appropriate skin areas are first swabbed with alcohol. This is carried out to ~e-,love residual moisture. A
mixture of 3~ iodine in 95~ strength alcohol is then applied to the entire area. After drying of the surface, a suspension of starch and castor oil (50 : 50 w/w) is applied to the skin. The subjects are exposed to a temperature of 37~C and a relative humidity of 35~ in a climatically controlled room. The duration of the test in this case depends on the production of sweat in the individual subjects. An alternative procedure can consist in stimulating the subjects to produce perspiration by rapid walking.
As a result of perspiration, water is released. In the presence of water, iodine and starch form an intensively blue-colored inclusion compound (iodine-starch complex). The treated areas are ~X~m; ned for their similarity by means of visual lnspection.
CA 02207113 1997-06-0~
4.3.2.Treatment with the antiperspirant formulation For the treatment of the skin surface with the test formulations 12 and 13, the occlusion by immersion technique is used (OBIT).
The skin areas to be treated are first rinsed with water. Small plastic beakers (2.5 cm diameter) having a hole (1 cm diameter) in the bottom are fixed to the skin surface using an adhesive tape. This is carried out on 12 subjects using 2 to 3 beakers in each case on each forearm. Through the opening- in the beakers, aliquot amounts of the sample solution from 1.0 to 1.4 ml are applied. After a contact time of 30 minutes, this treatment is terminated. The beakers are then removed and Pxce~s antiperspirant agent is rinsed off with water. For later identification, the treated areas are marked.
4.3.3.Determ;n~tion of the antiper~pirant efficacy 30 minutes after the treatment and 4 hours after the treatment, a determination of the efficacy of the antiperspirant formulation is carried out. To do this, the appropriate skin areas are first swabbed with alcohol. This is carried out to remove residual moisture. A mixture of 3~ iodine in 95~
strength alcohol is then applied to the entire area. After drying of the surface, a suspension of starch and castor oiI
(50 : 50 w/w) is applied to the skin. The subjects are made to sweat in a climatically controlled room at a temperature of CA 02207113 1997-06-0~
37~C and a relative humidity of 35~. The duration of this treatment in this case depends on the production of sweat in each individual subject. The treated areas are then e~m;neA
visually and the antiperspirant activity is assessed using a scale from 0 to 100~. The numbers stand for the proportion of sweat glands which do not secrete any sweat as a result of the treatment with the antiperspirant agent.
Based on the abovementioned test design, in each case on average a reduction of perspiration by 20 to 30~ is achieved by each of the formulations 12 and 13 after 30 minutes or 4 hours.
The example shows that highly efficacious antiperspirant formulations can be prepared using the emulsifiers according to the invention.
The W/O emulsions prepared with the emulsifiers to be used according to the invention are also suitable for industrial purposes, e.g. for use as care compositions and polishes for furniture, painted sheet metal and floors.
The formulations listed in Table 4 are employed in all investigations for determination of the efficacy. The content of all~m;nl~m in all these formulations is 6~.
Table 4: Test recipes for efficacy determinations Formulation examples 12 13 Emulsifier 3 1.1~ -DC 3225 C - 10.0 Octamethylcyclotetrasiloxane 15.9~ 7.0~
Alnm;nl]m hydroxychloride 50.0~ 50.0%
solution *3) Propylene glycol 16.0~ 16.0 Water, distilled 17.0~ 17.0 Total 100.0~ 100.0~
*3) Reach 501 (antiperspirant active compound, 50~ in water), Reheis 4.2. Release of aluminum In the formulations investigated, the active constituent (all~m;nl~m hydroxychloride solution) is present in the internal, aqueous phase as a solution. In order to be efficacious, the alnm; n~m hydroxychloride solution must pass through the CA 02207113 1997-06-0~
external, oily phase. The rate of release of the active constituent (alllm;nl~m hydroxychloride solution) is investigated in Formulation Examples 12 and 13.
For this, the formulations are diluted with 95~ of water. After shaking for 5 minutes, the alllm;nllm content in an aliquot amount of the aqueous solution is determined. This 5-minute value marks the starting point. The dilutions are shaken further and, after 1 and 24 hours in each case 1 aliquot amounts are again taken for analysis. The content of all~m;nllm in the aqueous solution is determined by atomic absorption spectroscopy.
The results are compiled in Table 5. It is clear that the formulations 12 and 13 have an equally high rate of release of al-lm; m~m .
Table 5: Release of all~m; n~m -Formulation Example 12 ¦ 13 ~ all~m;nllm recovered 5 minutes 15 16 1 hour ~ 90 > 90 24 hours ~ 90 ~ 90 CA 02207113 1997-06-0~
4.3. In-vivo test for antiperspirant effectiveness 4.3.1.Prel;~;nary investigations (selection of the subjects) Subjects with a similar perspiration intensity (sweat production) on the volar surface of the forearm are selected.
To do this, the appropriate skin areas are first swabbed with alcohol. This is carried out to ~e-,love residual moisture. A
mixture of 3~ iodine in 95~ strength alcohol is then applied to the entire area. After drying of the surface, a suspension of starch and castor oil (50 : 50 w/w) is applied to the skin. The subjects are exposed to a temperature of 37~C and a relative humidity of 35~ in a climatically controlled room. The duration of the test in this case depends on the production of sweat in the individual subjects. An alternative procedure can consist in stimulating the subjects to produce perspiration by rapid walking.
As a result of perspiration, water is released. In the presence of water, iodine and starch form an intensively blue-colored inclusion compound (iodine-starch complex). The treated areas are ~X~m; ned for their similarity by means of visual lnspection.
CA 02207113 1997-06-0~
4.3.2.Treatment with the antiperspirant formulation For the treatment of the skin surface with the test formulations 12 and 13, the occlusion by immersion technique is used (OBIT).
The skin areas to be treated are first rinsed with water. Small plastic beakers (2.5 cm diameter) having a hole (1 cm diameter) in the bottom are fixed to the skin surface using an adhesive tape. This is carried out on 12 subjects using 2 to 3 beakers in each case on each forearm. Through the opening- in the beakers, aliquot amounts of the sample solution from 1.0 to 1.4 ml are applied. After a contact time of 30 minutes, this treatment is terminated. The beakers are then removed and Pxce~s antiperspirant agent is rinsed off with water. For later identification, the treated areas are marked.
4.3.3.Determ;n~tion of the antiper~pirant efficacy 30 minutes after the treatment and 4 hours after the treatment, a determination of the efficacy of the antiperspirant formulation is carried out. To do this, the appropriate skin areas are first swabbed with alcohol. This is carried out to remove residual moisture. A mixture of 3~ iodine in 95~
strength alcohol is then applied to the entire area. After drying of the surface, a suspension of starch and castor oiI
(50 : 50 w/w) is applied to the skin. The subjects are made to sweat in a climatically controlled room at a temperature of CA 02207113 1997-06-0~
37~C and a relative humidity of 35~. The duration of this treatment in this case depends on the production of sweat in each individual subject. The treated areas are then e~m;neA
visually and the antiperspirant activity is assessed using a scale from 0 to 100~. The numbers stand for the proportion of sweat glands which do not secrete any sweat as a result of the treatment with the antiperspirant agent.
Based on the abovementioned test design, in each case on average a reduction of perspiration by 20 to 30~ is achieved by each of the formulations 12 and 13 after 30 minutes or 4 hours.
The example shows that highly efficacious antiperspirant formulations can be prepared using the emulsifiers according to the invention.
The W/O emulsions prepared with the emulsifiers to be used according to the invention are also suitable for industrial purposes, e.g. for use as care compositions and polishes for furniture, painted sheet metal and floors.
Claims
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
Use of copolymers of the general formula R = -(CH2-)mO-(C2H4O-)x(C3H6O-)yR1 m = 2 to 4, x = 3 to 100, y = 0 to 50, R1 = H, CH3, CH2CH3, n = 50 to 200, as emulsifiers in W/O emulsions in amounts from 0.1 to 20%
by weight, based on the total weight of the emulsion.
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
Use of copolymers of the general formula R = -(CH2-)mO-(C2H4O-)x(C3H6O-)yR1 m = 2 to 4, x = 3 to 100, y = 0 to 50, R1 = H, CH3, CH2CH3, n = 50 to 200, as emulsifiers in W/O emulsions in amounts from 0.1 to 20%
by weight, based on the total weight of the emulsion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19624550A DE19624550A1 (en) | 1996-06-20 | 1996-06-20 | alpha, omega-polyether polysiloxanes as W / O emulsifiers |
| DE19624550.8 | 1996-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2207113A1 true CA2207113A1 (en) | 1997-12-20 |
Family
ID=7797427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002207113A Abandoned CA2207113A1 (en) | 1996-06-20 | 1997-06-05 | .alpha., -polyether polysiloxanes as w/o emulsifiers |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0819426B1 (en) |
| JP (1) | JPH1066856A (en) |
| AT (1) | ATE272386T1 (en) |
| CA (1) | CA2207113A1 (en) |
| DE (2) | DE19624550A1 (en) |
| ES (1) | ES2222490T3 (en) |
| PL (1) | PL186052B1 (en) |
| PT (1) | PT819426E (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2776513B1 (en) * | 1998-03-26 | 2001-04-20 | Oreal | W / O EMULSION, COMPOSITION COMPRISING SUCH AN EMULSION AND USE IN COSMETICS, PHARMACY OR HYGIENE |
| FR2776515B1 (en) * | 1998-03-26 | 2001-02-09 | Oreal | W / O EMULSION, COMPOSITION COMPRISING SUCH AN EMULSION AND USE IN COSMETICS, PHARMACY OR HYGIENE |
| FR2776514B1 (en) | 1998-03-26 | 2001-03-09 | Oreal | W / O EMULSION, COMPOSITION COMPRISING SUCH AN EMULSION AND USE IN COSMETICS, PHARMACY OR HYGIENE |
| DE19824418A1 (en) * | 1998-05-30 | 1999-12-02 | Goldschmidt Ag Th | Transparent sunscreen gels with high solar protection factors |
| ATE298233T1 (en) * | 2000-02-19 | 2005-07-15 | Goldschmidt Gmbh | COSMETIC AND PHARMACEUTICAL OIL-IN-WATER EMULSIONS OF POLYETHER-MODIFIED POLYSILOXANES |
| JP2002145803A (en) * | 2000-11-10 | 2002-05-22 | Pigeon Corp | Massage oil |
| DE10234882B4 (en) * | 2002-07-31 | 2004-09-09 | Beiersdorf Ag | Cosmetic and / or dermatological preparation and their use |
| DE10243992A1 (en) | 2002-09-21 | 2004-04-01 | Goldschmidt Ag | Amphiphilic organopolysiloxanes containing polyester groups and their use as emulsifiers or dispersing agents |
| US20060067962A1 (en) * | 2004-09-30 | 2006-03-30 | Kimberly-Clark Worldwide, Inc. | Skin cooling compositions |
| US20060067961A1 (en) * | 2004-09-30 | 2006-03-30 | Kimberly-Clark Worldwide,Inc. | Skin cooling compositions |
| US20080014166A1 (en) * | 2006-07-14 | 2008-01-17 | Clariant International, Ltd. | Cosmetic or pharmaceutical compositions comprising modified polyorganosiloxanes |
| US8735524B2 (en) * | 2011-09-09 | 2014-05-27 | Air Products And Chemicals, Inc. | Silicone containing compositions and uses thereof |
| US10851210B2 (en) | 2015-11-05 | 2020-12-01 | Basf Se | Process for preparing polyalkylene ether-modified polysiloxanes and use thereof |
| WO2017076856A1 (en) * | 2015-11-05 | 2017-05-11 | Basf Se | Process for preparing polyalkylene ether-modified polysiloxanes and use thereof |
| JP6641227B2 (en) | 2016-04-28 | 2020-02-05 | 信越化学工業株式会社 | Emulsified cosmetic |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0266921A3 (en) * | 1986-11-06 | 1990-05-30 | Shiseido Company Limited | Skin irritation alleviation agent and composition thereof |
| US4988504A (en) * | 1987-08-19 | 1991-01-29 | General Electric Company | Silicone surfactants |
| US5132047A (en) * | 1988-02-09 | 1992-07-21 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane emulsion composition |
| JPH0768115B2 (en) * | 1989-05-17 | 1995-07-26 | 花王株式会社 | Cleaning composition |
| GB8914905D0 (en) * | 1989-06-29 | 1989-08-23 | Unilever Plc | Cosmetic composition |
-
1996
- 1996-06-20 DE DE19624550A patent/DE19624550A1/en not_active Withdrawn
-
1997
- 1997-06-05 CA CA002207113A patent/CA2207113A1/en not_active Abandoned
- 1997-06-10 ES ES97109342T patent/ES2222490T3/en not_active Expired - Lifetime
- 1997-06-10 EP EP97109342A patent/EP0819426B1/en not_active Expired - Lifetime
- 1997-06-10 PT PT97109342T patent/PT819426E/en unknown
- 1997-06-10 DE DE59711819T patent/DE59711819D1/en not_active Expired - Lifetime
- 1997-06-10 AT AT97109342T patent/ATE272386T1/en not_active IP Right Cessation
- 1997-06-18 JP JP9160849A patent/JPH1066856A/en active Pending
- 1997-06-19 PL PL97320655A patent/PL186052B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE272386T1 (en) | 2004-08-15 |
| DE59711819D1 (en) | 2004-09-09 |
| EP0819426A2 (en) | 1998-01-21 |
| PT819426E (en) | 2004-10-29 |
| PL186052B1 (en) | 2003-09-30 |
| JPH1066856A (en) | 1998-03-10 |
| EP0819426A3 (en) | 2001-05-09 |
| PL320655A1 (en) | 1997-12-22 |
| ES2222490T3 (en) | 2005-02-01 |
| EP0819426B1 (en) | 2004-08-04 |
| DE19624550A1 (en) | 1998-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60117602T2 (en) | TRANSPARENT EMULSION HIGH OIL CONTENT WITH DIEN ELASTOMERS | |
| EP0627215B1 (en) | Silicone containing personal care products | |
| KR100421759B1 (en) | Spontaneously formed transparent silicone micro-emulsion and method for forming the same | |
| KR101044196B1 (en) | Water-in-oil emulsion cosmetic composit ion | |
| CA2207113A1 (en) | .alpha., -polyether polysiloxanes as w/o emulsifiers | |
| KR101801410B1 (en) | Water-in-oil emulsion-type cosmetic preparation | |
| JPH05186327A (en) | Cosmetic composition | |
| KR100550967B1 (en) | Water in oil form cosmetic composition | |
| JPH0532363B2 (en) | ||
| US9809750B2 (en) | Liquid crystal composition | |
| JP3491933B2 (en) | Sunscreen cosmetics | |
| JPH10291914A (en) | Solid oil-in-water type emulsified cosmetic | |
| KR101047694B1 (en) | Solid oil-in-water type cosmetic composition having a volatilization stability and excellent moisture retention | |
| JP3312679B2 (en) | Water-in-oil emulsion composition | |
| JPS63107911A (en) | Cosmetic | |
| JP2005314258A (en) | Solid water-in-oil type cosmetic | |
| JP3633820B2 (en) | Water-in-oil emulsion composition | |
| JPH11263721A (en) | Oil-in-water type gommage (peeling) cosmetic | |
| JP4919543B2 (en) | Water-in-oil emulsified cosmetic | |
| CN111032000B (en) | Water-in-oil type emulsified cosmetic | |
| US20020037302A1 (en) | Composition in the form of a water-in-oil emulsion with a variable shear rate and methods of using the same | |
| JPS61218509A (en) | Cosmetic | |
| JP2020097532A (en) | Alcohol-in-oil type emulsion composition | |
| JPH06135818A (en) | Cosmetic | |
| JP3483980B2 (en) | Solid non-aqueous powder cosmetics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |