WO2004071474A1

WO2004071474A1 - Natural polymer in a prepared form

Info

Publication number: WO2004071474A1
Application number: PCT/EP2003/001467
Authority: WO
Inventors: Jürgen E. GRÄFE
Original assignee: Gräfe Chemie GmbH
Priority date: 2003-02-14
Filing date: 2003-02-14
Publication date: 2004-08-26

Abstract

The invention relates to the use of modified natural polymers in a novel form, i.e. in a pre-prepared or formulated molecular disperse solution for cosmetic and dermatological preparations.

Description

Natural polymer in processed form

description

The prior art is already recognized in OS 101 28 799 and EP 1 051 967 by the same applicant. The present invention is a further development and relates to the use of modified natural polymers of certain compositions for cosmetic and dermatological preparations, in particular for leave-on and ^“ riήse-off applications based on starch , since they are biodegradable in contrast to analog synthetic products, it is an essential prerequisite for further development to use the modified starch in a new form, namely in the completely prepared or prepared liquid state.

(0002) The new form of natural polymers in the liquid phase shows significant superiorities. This is explained and achieved by the completely molecularly disperse solution state. The increased cost of producing the ready-to-use liquid modified starch is compensated for in an uncomplicated application and by a constant quality setting. Furthermore, the ready-made or prepared starch solution is characterized by the fact that, in the practical test results, only 50 - 60% of the amount added is sufficient compared to the powder form to achieve the same effectiveness in the cosmetic end product.

(0003) The starch products for starch production are cereal and tuber starch, or all starch-containing products produced in nature, such as Potatoes, corn, rice, tapioca / cassava in question.

The completely prepared or prepared natural polymer is produced from the starting starch (s) with molar masses up to 1,000,000,000 with or without modification to the still non-gelatinized grain structure according to (A) to (C). The digestion takes place with or without molecular breakage of the polymer structure and / or by molecular restructuring or by means of oxidation and / or by means of the action of weak to strong acids or their salts or by means of enzymes with new molar masses of up to 500,000,000 and possibly additional modifications in the fully prepared or prepared aqueous phase.

(A) etherification with anionic and / or cationic and / or nonionic substances

(B) esterifications with anionic and / or cationic and / or nonionic substances

(C) Or by means of the combination of (A) and (B), i.e. multiple etherification, multiple esterification or multiple etherification and esterification, or in a mixture of (A) and (B) after the etherification or esterification step (s) ). This multiple or multimodification leads to a significantly improved compatibility in cosmetic formulations and leads to high kiarosolubility in surfactant mixtures. (D) If necessary, sugar alcohols, fruit acids, alpha-hydroxy acids or their salts, urea and other hair- and skin-friendly substances can be added, which have nourishing and / or moisture-regulating properties and interact with or stabilize the aqueous starch.

(E) If necessary modified by the addition of compounds or salts with more than divalent cations. Such compounds are those of aluminum or zirconium. They produce significant improvements in effectiveness and form higher viscosities and apparent or real increases in molecular weight by a factor of 3 to 4.

(F) If necessary by adding Teflon and / or silicone microemulsions.

There is a need to improve the properties and effectiveness of skin care products. These leave-on products (creams and lotions) usually contain vegetable, animal and / or mineral oils and fats, as well as an emulsifying substance that form an O / W or W / O emulsion with water. Other cosmetic additives of numerous provenances are in use.

It has been discovered that starch esters and starch ethers in the previously prepared form described in cosmetic preparations for skin care produce novel, remarkable properties. They reduce the usual feeling of oiliness on the skin in the shortest time after application and they improve skin smoothing.

By means of the digestion described, it is now also possible to create fatty acid esters and ethers which emulsify fats / oils and can be exchanged in whole or in part for conventional emulsifiers. At the same time, the properties described in (0005) are obtained. The superiority is particularly evident in the fact that the starch emulsifier gives both the moisture and the emulsified fats / oils in O / W and W / O emulsions to the skin more evenly and the starch content ultimately remains on the skin as a film-forming substance, the feeling of fatness is reduced or eliminated and even high doses of fat / oil no longer appear as an oily skin feeling. They visibly improve the smoothing of the epidermis.

Formulations for hair coloring, formulated with cationic liquid starch preparations, bring about an improvement in the hair-coloring properties through cationic conditioning of the hair, bring about a higher and more uniform color yield and relieve the waste water of residual dyes.

In addition to the properties described above, the liquid starch preparations can, in addition to their care properties, also be used as a thickening component in leave-on and rinse-off formulations.

Furthermore, it has surprisingly been found that it is also possible to use the liquid starch preparations mentioned for preservative-free formulations.

It has been found that rinse-off products for skin and hair can be obtained if the aqueous-based formulation is structured as follows:

1. 2 to 60% by weight of at least one anionic surfactant, alone or in combination with:

2. 0.5 to 30% by weight of at least one nonionic surfactant, 3. 0.25 to 20% by weight of at least one amphoteric surfactant,

4. 0.025 to 10% by weight of at least one hair conditioning polymer,

5. copolymers from 0.01 to 15% by weight,

6. liquid prepared or prepared modified starch, with 0.01 to 10% by weight, based on dry matter, calculated on the formulation composition,

7. 0.05 to 5% by weight of at least one thickener

8. 0.0 to 2.5% sodium chloride

9. contains additional formulation components, optionally preservatives. It has been found that the effect of the modified starch products can be increased by combining them with other polymers (0014) while simultaneously reducing the concentration by up to 50% in order to improve specific properties in different formulations and applications.

These include e.g. Improvement of combing power, reduction of knot formation, improvement of hair shine, reduction of polymer content through synergistic effect, improvement of hair treatment properties and improvement of hair styling properties

A particular advantage in the use of such modified starch derivatives obtained from starch, with cationic substitution (DS = <0.003) and the starch esters and starches described is the pronounced smoothing of the skin, the smooth and flexible film formation, the moisture-retaining effect, the Dandruff-free (starch dandruff) combability, the particularly easy wash and washability and the formulation of clear products and the toxicological harmlessness.

(0012) Overloading of skin and hair by regular or multiple use could not be achieved with slightly cationic products with a degree of substitution of D.S. = <0.003 can still be found with the starch esters or starch ether / starch ester combinations.

Even if the binding of the polysaccharide esters to the skin and hair is only

C: 0-H-0

Hydroyl group bond can be explained, the cosmetic effect described are sufficient and measurable.

Rinse-off products for cleaning skin and hair usually contain at least one surface-active substance, predominantly an anionic surfactant and additional higher molecular film-forming polymers for protection, regeneration and care.

Polymers with different charges of synthetic and natural origin and silicone-based products have proven particularly useful for film formation. They are known under the (INCI names): Polyquaternium-2 to Polyquatemium-56, Guarhydroxypropyl-trimonium chloride, Polysilicone 1 to 14, Dimethicone, Dimethicone Copolyol, Phenyl Dimethicone, Cycloheptasiloxane, Cyclohexasiloxane, Cyclopentasiloxane, Cyclotetra-siloxane, Cyclotetra-siloxane.

Nevertheless, there is still a need to optimize the properties and efficacies of hair and skin care products, in particular with regard to the combability of Velcro-type, splitting hair ends that tend to knot, without simultaneously overloading of the hair due to excessive film formation and with regard to grease-free and emulsifier-free, moisture-retaining and skin-smoothing polymers.

Combined properties such as volume, shine, easy to comb and a pleasant, soft and well-groomed feeling of the treated hair and body parts are basic requirements. Good foam behavior, high foam volume, mild reaction to the hair and skin, toxicological and environmental toxicological harmlessness are among the required basic requirements that are placed on a cosmetic.

Suitable anionic surfactants (0009/1) for cosmetic preparations, especially those used for hair and body cleansing, such as Shower and foam baths, hair shampoos and other hair care products mostly contain anionic surfactants such as (according to the INCl name): ammonium lauryl sulfate, ammonium laureth sulfate (mainly with 1 to 4 ethylene oxide groups in the molecule), TEA - lauryl sulfate, MEA - lauryl sulfate , Sodium Laureth Sulfate, Sodium Laureth Sulfate (mainly with 1 to 4 ethylene oxide groups in the molecule), Disodium Laureth Sulfosuccinate (predominantly with 1 to 4 ethylene oxide groups in the molecule), Disodium PEG-5 Laurylcitrate Sulfosuccinate, Disodium Ricinolamido MEA-Sulfosuccinate or Disodium Lauramido MEA- Sulfosuccinate, Laureth-6 Carboxylate or Sodium Laureth-11 Carboxylate, Sodium C-14 C 18 Olein Sulfonate, Sodium Dodecylbenzenesulfonate, Sodium Tridecet Sulfate, Sodium Cocoyl Sarcosinate, Sodium Lauroyl Sarcosinate, Sodium Cocoyl Isothionate.

Suitable nonionic surfactants (0009/2) are e.g. alkoxylated fatty alcohols with a high degree of alkoxylation, e.g. from 11 to 50 and alkoxylated fatty acid esters, alkoxylated partial glycerides of branched or unbranched, saturated or unsaturated C6 to C20 fatty acids and a degree of alkoxylation from 11 to 400, e.g. PEG-200 glyceryl stearates, alkoxylated polyol esters such as e.g. ethoxylated sugar esters, e.g. PEG-120 methyl glucose dioleates and alkyl polyglucosides such as e.g. Coco-Glucoside, Lauryl-Glucoside or Decyl-Glucoside. Examples of suitable fatty alcohol ethoxylates are ethoxylated lauryl, tetradecyl, cetyl, oleyl or stearyl alcohol, which can be used alone or in a mixture, and fatty alcohols of ethoxylated lanolin or ethoxylated lanolin. The ethoxylated fatty alcohols, which are sold under the type name Dehydol® by the company COGNIS or under the type name Brij® by the company ICI Surfactants, are also suitable for the hair treatment composition according to the invention, provided that they have a sufficiently high degree of ethoxylation.

Among the fatty acid ester ethoxylates, especially diglyceride ethoxylates are to be mentioned, such as castor oil with the (INCl designation): PEG-25 Hydrogenated Castor Oil, sold by BASF under the trade name Arlatone® G and sold with 25 ethylene oxide units by ICI Surfactants the trade name Cremophor® EL, castor oil which is ethoxylated with 35 ethylene oxide units and has the (INCl name): PEG-35 Castor Oil, which is sold by BASF under the trade name Cremophor® RH 410 and which is hydrogenated castor oil which is ethoxylated with 40 ethylene oxide units with the (INCl designation): PEG-40 Hydrogenated Castor Oil, and the raw materials sold by Witco Surfactants under the name Rewoderm® Ll Furthermore, the ethoxylated fatty acid sugar esters known as nonionic surfactants, in particular the ethoxylated sorbitan fatty acid esters, but also non-ethoxylated surfactants, such as the fatty acid sugar esters, which are sold by the company ICI Surfactants under the trade names Tween® and Arlacel®, and the alkylpolyglycosides which are sold by the The company COGNIS under the trade name Plantaren® or Plantacare® or from the company Seppic under the trade name Oramix® are marketed for the cosmetic preparation according to the invention.

Non-ionic surfactants of the compound polyglyceryl-10 laurate and sodium cocoyl glutamate, such as those used in particularly skin-friendly cosmetics, must also be mentioned.

Suitable amphoteric surfactants (0009/3) are, for example, betaines (according to the INCl name): cocamidopropyl betaines or lauryl betaines, glycinates such as e.g. Cocoamphoglycinate (INCl name: Sodium Cocoamphoacetate and diacetate as well as Propionate such as Cocoamphopropionate. Disodium Cocoamphodiacetate, Coco-Betaine

Hair-conditioning polymers (0006/4), the proportion of which in the formulations according to the invention is between 0.01 and 8%, preferably about 0.05 to 3.5% by weight, based on the overall formulation of the skin care product, can be:

Vinyl pyrrolidone polymers such as e.g. Luviskol® K30, K 60, K 90, copolymers of vinyl pyrrolidone and vinyl acetate, e.g. Luviskol® VA 55, VA 64 from BASF.

Also suitable are nonionic polymers, such as e.g. Vinyl pyrrolidone / vinyl acetate / vinyl propionate copolymers Luviskol® VAP 343, vinyl pyrrolidone / (meth) acrylic acid ester copolymers, and chitosan derivatives.

Instead of or in addition to the nonionic polymers, in particular cationic and / or also anionic and / or amphoteric polymers can be used in the amounts mentioned as hair-conditioning polymers.

Preferred hair-conditioning polymers are the proven quaternary cellulose derivatives of the type Polymer JR (INCl name): Polyquaternium-10), as well as quaternized homo- and copolymers of dimethyldiallylammonium chloride and Polyquaternium-47, a terpolymer consisting of acrylic acid, methacrylamidopropyl trimethyl ammonium chloride and methyl acrylate , also known under the trade name Merquat® and dialkylaminoalkyl (meth) acrylates, known under the name Gafquat® (INCl name): Polyquaternium-11 and Polyquaternium-28, copolymers of vinylpyrrolidone and vinylimidazolinium methochloride, known under the trade name Luviquat® are long-chain bis-quaternary ammonium compounds, which are known under the INCI name Polyquatemium-2.

[0023] Polysiloxanes are also widely used as conditioning polymer additives in personal care. Their proportion is preferably between 0.1 and 5% by weight, based on the overall formulation.

Silicone oils or microemulsions, which are known as both volatile and low-volatility cyclic or linear polysiloxanes which are known as "dimethicones", "phenyldimethicones, cyclomethicones", have proven successful. Mixtures of different polymers can also be used to increase efficacy and / or to achieve special properties, provided there are no incompatibilities.

Amphoteric polymers which are used alone or in a mixture with at least one further cationic, nonionic or anionic polymer are copolymers of the Amphomer® and Yukaformer® types.

Usable anionic polymers are offered under the trade names Gantrez® AN or Gantrez®ES, Gantrez® ES 225.

The following trade names are to be mentioned as further anionic polymers which can be used for this area of application: Resyn®, Hydagen® F, Flexan® 130 and Ultrahold®.

Suitable copolymers (0009/5) are, for example, acrylic or methacrylic acid / acrylic or methacrylic acid polythoxyalkyl ester copolymers (INCl name): Acrylates / Steareth 20 methacrylate copolymer), such as those from Rohm and Haas USA under the names Acrysol® -22, Acrysol® ICS or Aculyn®-22 are sold or acrylic or methacrylic acid / polyethoxyalkyl allyl ether copolymers (INCl name): Steareth-10 allyl ether / acrylate copolymer), as described by Ciba Geigy, CH under the name Salcare ® SC 90 or acrylic or methacrylic acid / itaconic acid polyethoxyalkyl ester copolymers (INCI names): Acrylates / Steareth-20 itaconate copolymer and Acrylates / Ceteth-20 itaconate copolymer), as described by National, Starch USA under the names Structure® 2001 and Structure® 3001 are sold.

Suitable thickeners (0009/7) are sodium chloride, Laureth-2, Cocamide DEA, Carbomer, PEG-120 methyl glucose dioleates, PEG-120 methyl glucose trioleates, guar, cellulose and xanthan derivatives.

The main requirement for surface-active agents is to remove sweat, grease and dirt particles on the skin and in the hair without causing skin irritation. However, it is known from preparations which contain the abovementioned anionic surfactants that, to a certain extent, due to their strongly cleaning or degreasing action and the associated drying out, they cause a negative care effect on skin and hair.

For this reason, more skin-friendly formulations for daily use have been developed in recent years, in which so-called secondary surfactants partially replace the above-mentioned anionic surfactants.

The care effects of the substances can be classified as much stronger, but still do not meet the desired requirements for a hair or skin care cosmetic. Examples include Alkyl polyglucosides, betaines, glycinates, protein derivatives, ether carboxylates and sulfosuccinates and sarcosinates.

Mixtures of anionic surfactants and alkyl polyglucosides and their use in liquid personal cleansing agents are already known per se, as are the known mixtures of sulfosuccinates and alkyl polyglucosides.

The compositions according to the invention can therefore, as a further surfactant component, also amphoteric or zwitterionic surfactants (0009/3) in amounts of approximately 0.25% to about 20%, preferably from about 1 to 8% by weight, based on the total formulation.

The various betaines such as fatty acid amidoalkyl betaines and sulfobetaines, e.g. To name Lauryhydroxysulfobetaine. Long-chain alkyl amino acids such as cocoaminoacetate and diacetate, cocoaminopropionate and acetate have also been found to be useful.

It was therefore the task of providing hair and body cleansing agents and personal care products which, in addition to the required cleaning action, leave the skin with a pronounced care effect by keeping the skin moist and reducing the roughness of the skin and hair (improving the smoothness of the skin) after use, slight skin irritation Have effects through secondary components and production-related accompanying substances and at the same time show no or as little loss as possible in their other, desired properties, cleaning ability, foaming power, viscosity behavior, toxicological harmlessness, etc.

In addition, other possible additives, as are common in cosmetic formulations, can be used. Care and additives such as quaternized alkylamines, cationic polymers of natural or synthetic origin, such as protein hydrolyzates, polypeptides, elastin hydrolyzates, as well as vegetable and possibly also cationic proteins and their derivatives, such as e.g. Collagen, keratin, silk protein and wheat protein hydrolyzates. The following can also be used: perfume oils, dyes, opacifiers such as glycol distearate; further thickeners such as guar gums, silicates, methyl cellulose, hydroxyethyl cellulose, carboxyvinyl polymers; other hair conditioning agents such as synthetic or natural phospholipids or quaternary derivatives of starch or cellulose; Solubilizers such as short chain alcohols, e.g. Ethanol, n- and iso-propanol or glycols such as butylene or propylene glycol; Amino acids such as Histidine, glycine, alanine, threonine, arginine, cysteine and their derivatives such as e.g. Fatty acid condensation products or quaternary products; other active ingredients such as plant extracts, vitamins, allantoin, chitosan, preservatives as listed in Appendix 6 of the current European Cosmetics Regulation, complexing agents, pH regulators, viscosity regulators, α-hydroxy acids (lactic acid, citric acid and fruit acids in general), inorganic salts, pearlescent agents, humectants (e.g. urea, lactates), vegetable and / or animal oils such as jojoba oil, fatty acid esters, e.g. B. isopropyl myristate, ethyl palmitate, lecithin and its derivatives and many others. m. These ingredients are also described in the relevant cosmetic literature.

The use of generally known plant extracts is particularly popular. Known aqueous, alcoholic or aqueous / alcoholic plant extracts are in particular extracts from leaves, fruits, flowers, roots, barks, stems, from aloe vera, pineapple, artichokes, arnica, valerian, henbane, nettles, echinacea, ivy, angelica, gentian ferns, spruce needles , Gorse, oats, Hagebudden, witch hazel, hay flowers, elder, hops, coltsfoot, currants, chamomiles, carrots, chestnuts, clover, burdock roots, linden flowers, lily of the valley, seaweed, lemon balm, mistletoe, passion flowers, ratanhia, marigold, rosemary, Horse chestnuts, hawthorn, sage, horsetail, yarrow, cowslips, dead nettle, thyme, vine leaves, hawthorn and much more, e.g. Dermosoft 710 from Dr. Streatmans GmbH

The compositions according to the invention may also contain visible particles, such as pigments, pearlescent pigments, colored gloss pigments, which have also been surface-treated to emphasize the gloss, e.g. can be metallized.

The water content of the hair and body cleansing agent and skin care products according to the invention is preferably between 10 and 90 percent by weight. The viscosity of these products is preferably in the range from 2000 to 20,000 mPas.sec at 20 ° C. according to Brookfield spindle 4 or 5 or according to Höppler at a shear stress of 10 sec, the pH value is between 5 and 8.5; however, it can also be set below pH 5.

Claims

Patent claims

1. Natural polymer in prepared or prepared form, characterized in that it is used in skin and hair, washing and care formulations to 0.01 to 10% (dry matter) as a cosmetically active ingredient.

2. Cosmetic cleaning agent and / or dermatological care product, characterized in that a finished or prepared natural polymer, described in (0004, 0005 and (0006), is contained as a value-determining component and 0.01 to 10% (dry matter) is used and a starch with a molecular weight of up to 1,000,000,000 is used as the basis.

3. Cosmetic cleaning agent according to claim 1 and 2, characterized in that one or more of the raw materials listed under (0009, 0017 to 0027 and 0029 to 0032) are contained and as a value-determining constituent 0.01 to 10%, based on dry matter, prepared or prepared liquid starch (0004) is contained, as well as cosmetic care products containing prepared or prepared starch according to 0004, 0005 and 0006.

4. Aqueous cosmetic composition according to Claims 1 to 3, containing at least 2 to 60% by weight of at least one anionic surfactant or co-surfactant, as described in (0017) additionally containing 0.5 to 30% by weight of a nonionic surfactant or co-surfactant, as described in (0018), additionally containing 0.25 to 20% by weight of an amphoteric surfactant, as described in (0019).

5. Aqueous cosmetic composition according to Claims 1 to 4, containing polymers as described under (0020) to (0025) and / or additional copolymers according to (0026) and, if appropriate, additional formulation constituents, as described in (0034), (0035) and ( 0036) are described.

6. Composition according to one or more of claims 1-5, containing at least one alkyl polyglucoside, as offered by the company COGNIS under the Plantaren® product name and / or containing about 0.1 to 20% by weight of an amphoteric and / or zwitterionic surfactant , such as cocamidopropyl betaine, lauryl betaine, sulfobetaines such as Cocamidopropyl hydroxysultaine, glycinates such as e.g. Cocoamphoglycinate (INCl name): Sodium cocoamphoacetate and diglycinate as well as propionates such as Cocoamphopropionate. Disodium Cocoamphodiacetate, Coco Betaine.

7. Composition according to one or more of claims 1 to 10, containing care and additives as described in (0034).

8. Composition according to one or more of claims 1 to 10, containing 0.025 to 10 weight

% of particles visible in the composition, such as pigments, pearlescent pigments,

Color luster pigments.

Cosmetic composition according to one of claims 1 to 10, characterized in that it is a rinse-off product, such as e.g. Shampoo, conditioner, shower bath, bath product, liquid soap or detergent or a leave-on product, such as Conditioner, cream or lotion, styling or hair coloring product.

10. Cosmetic composition according to any one of claims 1-10, characterized in that the cosmetically acceptable medium used with preservatives, but preferably without the use of a preservative that requires declaration, is biologically stable.