JP2005530718A - Effervescent cleaning emulsion containing starch - Google Patents

Abstract

The present invention relates to a) one or several surfactants having an HLB-value greater than or equal to 16, b) one or several pregelatinized diagonally cross-linked starches Derivatives, c) Cosmetic cleansing emulsions containing an oil phase and optionally further cosmetic active ingredients, auxiliaries and additives.

Description

The present invention
a) one or more surfactants having an HLB value greater than or equal to 16;
b) one or more pregelatinized cross-linked starch derivatives,
c) relates to a cosmetic cleansing emulsion comprising an oil phase, optionally in addition to other cosmetic active ingredients, auxiliaries and additives.

  The manufacture of cosmetic cleansing compositions has shown a prosperity trend for many years. This is particularly due to increased health awareness and hygiene conditions by consumers.

  Cleansing means the removal of (environmental) dirt and thereby brings about psychological and physical well-being. Cleansing the skin and hair surfaces is a very complex operation that depends on many parameters. On the one hand, substances originating from the outside, for example hydrocarbons or inorganic pigments from a wide variety of surroundings, as well as cosmetic residues and unwanted microorganisms must be removed as completely as possible. On the other hand, excreta from the body, such as sweat, sebum, skin and hair flakes, must be washed away without significantly affecting physiological balance.

  Cosmetic or skin cleansing preparations are so-called “rinse off” preparations that are rinsed from the skin after application. They are generally applied to areas of the body that are to be cleansed in the form of a foam containing water. The basis of all cosmetic or skin cleansing preparations is a cleansing active surfactant. Surfactants are amphoteric substances that can dissolve organic non-polar substances in water. They are characterized by a two-sided performance on water and lipids, the surfactant molecule in each case containing at least one hydrophilic group and one lipophilic group, which is the two substances of the substance Allows position adjustment at the interface between. In this way, the surfactant reduces the surface tension of the water, moistens the skin, promotes soil removal and dissolution, provides easy rinsing, and also provides foam control if desired. This is the basis for decontamination of lipid-containing contaminants.

The hydrophilic part of the surfactant molecule is mostly polar functional groups such as —COO ⁻ , —OSO ₃ ²⁻ , —SO ₃ ^— , but the hydrophobic part is usually a nonpolar hydrocarbon group. Surfactants are generally classified according to the type and charge of the hydrophilic molecular moiety. There are four groups in this regard:
Anionic surfactant,
・ Cationic surfactants,
There are amphoteric surfactants and nonionic surfactants.

Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In aqueous solutions in acidic or neutral media, they produce negatively charged organic ions. Cationic surfactants are mostly identified exclusively by the presence of quaternary ammonium groups. In aqueous solutions in acidic or neutral media, they produce positively charged organic ions. Amphoteric surfactants contain both anionic and cationic groups and thus act as anionic or cationic surfactants in aqueous solution depending on the pH. They are positively charged in highly acidic media and negatively charged in alkaline media. However, in the neutral pH range, they are zwitterionic as the following example shows:
RNH ₂ ⁺ CH ₂ CH ₂ COOHX ⁻ (pH = 2) X ⁻ = anion, for example Cl ⁻
RNH ₂ ⁺ CH ₂ CH ₂ COO ⁻ (pH = 7)
RNHCH ₂ CH ₂ COO ⁻ B ⁺ (pH = 12) B ⁺ = cation, such as Na ⁺
A polyether chain is a typical nonionic surfactant. Nonionic surfactants do not generate ions in aqueous media.

  It can be seen that cleansing active surfactants intended to cleanse skin and hair of oily and water-soluble soil components also have a defatting effect on normal skin lipids. Skin cleansing also removes intercorneocytic lipids and sebum components to varying degrees. This means that the skin's natural water / lipid film is somewhat destroyed during the cleaning operation. This can lead to short-term changes in the barrier function of the skin, especially in the case of extreme defatting, where, of course, the specific condition of the area of skin treated for the indicated changes is considerable. Have an impact. For example, the thickness of the skin, the number of sebaceous glands and sweat glands, and the sensitivity associated with them can vary considerably.

  As a general rule, therefore, it is considered that the condition of the cleaning active surfactant is that the surfactant is as biologically inert as possible to avoid unwanted side effects. They should exhibit their cleansing action with optimal mildness, best skin compatibility and low degreasing properties.

  There have been no previous attempts to find a suitable cleansing preparation that simultaneously regenerates or “re-fats” the skin in combination with good cleansing power. However, the performance obtained often remains lower than expected, and the user is applied to the skin after cleansing and there remains a separate care product (the so-called “leave-on” product) You must borrow the power of.

  Cosmetic cleansing compositions generally comprise a mixture of various types of surfactants. The selection is primarily directed to the skin compatibility of the surfactant and the desired cosmetic performance. In addition, foaming power, compounding capacity and favorable performance / price ratio play an important role.

  Lipid soaps or cleansing lotions are used to cleanse the entire body, not just the hands, but generally the face. They are therefore also suitable for use as shower preparations. In the development of these products, dermatological conditions are major because the skin is in strong contact with the concentrated surfactant solution. Therefore, the selection of a low concentration of mildly irritating surfactant is particularly important. Another criterion is also good foaming power and a comfortable refreshing fragrance and simultaneous skin care. Wash lotions and especially shower baths generally have a viscosity of about 3000 to 10000 mPa · s, which on the one hand allows good dispersibility of rapidly foaming products, while on the other hand perfect by hand or flannel Must be high enough to allow application.

  Lipid soaps or cleansing lotions are generally characterized by some water content, but generally they have only a low oil content and thus do not have a significant care benefit.

  A relatively new technological development relates to surfactant-containing shower preparations with high oil content. In this regard, U.S. Patent No. 6,057,056 describes cosmetic or skin shower preparations having a surfactant content of at most 55% by weight and an oil content of more than 45% by weight, which preparations are essential. Does not contain water. Due to the high oil content, these preparations have a regenerative effect with respect to the general condition of the skin. In this case, they simultaneously have good foam production and high cleansing power.

Further, Patent Document 2 describes the following substances: 5 to 30% by weight of a water-donating active ingredient having a Vauhan solubility parameter (VSP) of 5 to 10, and 0.3 to 5% by weight of a water-dispersible gel-forming weight. coalescence, 5-30 wt% of synthetic surfactant, describes a 0-15% by weight of C ₈ -C ₁₄ fatty acid soaps and foaming liquid skin cleansing composition comprising water, the preparation of these where The article has a liquid deposition value (LDV) of at least 5 to 1000 and wherein the synthetic surfactant and soap have a common CMC equilibrium interfacial tension value of 15 to 50. However, this specification could not point out progress to the present invention.

  For skin cleansing and simultaneous care, the prior art also recognizes emulsion-based cleansing products. These are formulated by stabilizing the emulsion with an emulsifier and subsequently adjusting the surfactant system.

  Emulsifiers also have an amphoteric structure and thus have similarities to surfactants as far as structure is concerned. Emulsifiers allow or promote the uniform distribution of two or more mutually immiscible phases and at the same time prevent their separation. Since emulsions are generally broken by the addition of surfactants, the choice of surfactant system is very limited and the resulting cleansing preparations are based on expensive and complex preparations.

So what distinguishes cleaning actives from emulsifiers?
In the late 1940s, systems were developed that were intended to facilitate the selection of emulsifiers. Each emulsifier is given a so-called HLB value (a dimensionless number from 0 to 20) that indicates whether the preferred water or oil solubility exists. Numbers lower than 9 indicate oil-soluble hydrophobic emulsifiers and numbers higher than 11 indicate water-soluble hydrophilic emulsifiers. The HLB value simply refers to the balance between the size and strength of the hydrophilic and lipophilic groups of the emulsifier. From these considerations it can also be inferred that the effectiveness of an emulsifier can be identified by its HLB value. The following list shows the relationship between HLB values and possible application fields:
HLB value Fields of application 0-3 Antifoaming agent 3-8 W / O emulsifier 7-9 Wetting agent 8-18 O / W emulsifier 12-18 Dissolution accelerator Shows from the table the HLB gains for the various hydrophilic and hydrophobic groups the molecules are composed of. In this way, the HLB value can in principle be measured for detergent active surfactants, but the HLB system was originally intended only for emulsifiers. It has been found that the cleaning active generally has an HLB value significantly greater than 20.

  One way to stabilize a surfactant-containing cleansing emulsion against oil droplet emulsification is to use a gel former that constitutes the aqueous phase. A major problem in formulating effervescent emulsions is the selection of gel forming agents that are hydrophilic, especially ionic, compatible with both surfactants and oils. Known gel formers generally do not form storage stable gel networks in the presence of surfactants and oils, meaning that instability of the preparation occurs. In particular, gel formation of anionic gel formers is generally hampered to a very significant extent by anionic surfactants, and extremely high gel former concentrations must be used.

According to the prior art, in order to form a gel network in cosmetic cleansing preparations, one must rely on polyacrylates as gel formers. U.S. Patent No. 6,057,031 describes the stabilization of cleansing emulsions with polyacrylates. However, regarding their biological compatibility and, in particular, modification, it is desirable to replace the polyacrylates with other (natural) substances or reduce their concentration in the preparation.
German Patent Application Publication No. 4424210 International Publication No. 96/17591 Pamphlet European Patent No. 00011547

  The object of the present invention is therefore to overcome the drawbacks of the prior art and consequently provide a cleansing preparation based on an emulsion based on a simple and cost-effective preparation. These preparations also had to have a high care effect without making the cleansing effect secondary.

The purpose is: a) one or more surfactants having an HLB value greater than or equal to 16.
b) one or more pregelatinized cross-linked starch derivatives;
c) The oily phase is achieved by a cosmetic cleansing emulsion comprising optionally, in addition to other cosmetic active ingredients, auxiliaries and additives.

  The product according to the invention is characterized by an extremely comfortable smooth and silky feel on the skin during and after application.

  In this regard, it is preferred that the cosmetic cleansing emulsion comprises a surfactant at a concentration of 1 to 20% by weight and very preferably a concentration of 5 to 15% by weight, based on the total weight of the preparation. Is advantageous.

  US Pat. No. 6,248,338 describes an aqueous surfactant system containing a pregelatinized cross-linked starch derivative, but this specification cannot point to progress to the present invention. It was.

  One or more pregelatinized cross-linked starch derivatives are present in the cleansing emulsion according to the invention in a concentration of 0.1 to 20% by weight, preferably 0. 0%, based on the total weight of the preparation. It is advantageous according to the invention to be present in a concentration of 3 to 15% by weight and very particularly preferably in a concentration of 0.5 to 10% by weight.

  It is also advantageous according to the invention that the oil phase is present in the cleansing emulsion in a concentration of 5 to 80% by weight, particularly preferably in a concentration of 30 to 75% by weight and very particularly preferably in a concentration of 40 to 50% by weight. It is.

It is advantageous according to the invention that the pregelatinized cross-linked starch derivative used is a hydroxypropylated phosphate ester. Particularly preferred starch derivatives are those described in US Pat. No. 6,248,338, particularly preferably hydroxypropyl distarch phosphate. The use of phosphoric acid hydroxypropyl distarch such as sold as a product structure ^{(Structure) (R)} XL from National Starch (National Starch) is very particularly preferred here.

Detergent active anionic surfactants advantageous for the purposes of the present invention are:
Acrylic amino acids and their salts, eg acyl glutamate, especially sodium acyl glutamate,
Sarcosine salts, such as myristoyl sarcosine, lauroyl sarcosine acid TEA, sodium lauroyl sarcosine acid and sodium cocoyl sarcosine acid,
Sulfonic acids and their salts, such as acyl isethionates, such as sodium / ammonium cocoyl isethionate,
Sulfosulphates, such as dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and undecylenamide MEA sulfosuccinate disodium,
And sulfate esters such as alkyl ether sulfates such as sodium laureth sulfate, ammonium, magnesium, MIPA, TIPA, sodium milles sulfate and sodium C _12-13 palace sulfate,
Alkyl sulfates such as sodium lauryl sulfate, ammonium and TEA
It is.

  A preferred detergent active cationic surfactant for the purposes of the present invention is a quaternary surfactant. Quaternary surfactants contain at least one N atom covalently bonded to four alkyl or aryl groups. Benzalkonium chloride, alkylbetaines, alkylamidopropylbetaines and alkylamidopropylhydroxysultains are preferred.

Advantageous cleaning active amphoteric surfactants for the purposes of the present invention are:
Acyl- / dialkylethylenediamines, such as sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkylamphodiacetate, sodium acylammonium fohydroxypropylsulfonate, disodium acylamphodiacetate and sodium acylamphopropionate.

Advantageous cleaning active nonionic surfactants for the purposes of the present invention are:
Alkanolamides such as cocaamide MEA / DEA / MIPA,
Esters produced by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,
Ethers such as ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glycosides, decyl glycosides and cocoglycosides.

Another advantageous anionic surfactant is
Taurates, such as sodium lauroyl taurate and sodium methyl cocoyl taurate,
Ether carboxylic acids such as sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7 olive oil carboxylate,
-Phosphate esters and salts, such as DEA-oles-10 phosphate and dilaureth-4 phosphate,
Alkyl sulfonates such as sodium cocos monoglyceride sulfate, sodium C _12-14 -olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate.

Another advantageous amphoteric surfactant is
N-alkyl amino acids such as aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.

  Another advantageous nonionic surfactant is an alcohol.

Another suitable anionic surfactant for the purposes of the present invention is:
Acyl glutamates such as di-TEA-palmitoyl aspartate and sodium caprylate / sodium glutamate
Acyl peptides such as palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolyzed collagen,
And carboxylic acids and derivatives such as, for example, lauric acid, aluminum stearate, magnesium alkanolate and zinc undecylenate,
Ester carboxylic acids such as calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate,
-Alkyl aryl sulfonate.

Another suitable cationic surfactant for the purposes of the present invention is:
・ Alkylamine,
It is also an alkylimidazole and an ethoxylated amine.

  Another suitable nonionic surfactant for the purposes of the present invention is also an amine oxide, such as cocoamidopropylamine oxide.

  It is particularly preferred according to the invention that the surfactant used is an anionic surfactant. Here, the use of alkyl ether sulfates, in particular sodium lauryl ether sulfate or myristyl ether sulfate, is very particularly preferred according to the invention.

  One embodiment of the present invention that is particularly advantageous according to the present invention is in particular the combination of sodium lauryl ether sulfate and sodium cocoyl glutamate and / or decyl glycoside.

  According to the invention, polysorbate can also be advantageously introduced into the emulsion as a cleaning activator.

  Besides water, according to the invention, the preparations according to the invention can be used as the aqueous phase of the emulsion as other components such as alcohols, diols or low carbon number polyols and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol. Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and homologous products, and low carbon number alcohols such as ethanol, isopropanol, 1,2-propanediol and Glycerol can also be included.

  The oily phase of cosmetic or dermatological cleansing emulsions for the purposes of the invention is preferably saturated and / or unsaturated branched and / or unbranched having a chain length of 3 to 30 carbon atoms. Aromatic carboxylic acids from the group of esters of linear alkanecarboxylic acids with saturated and / or unsaturated branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms And esters of saturated and / or unsaturated branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils are then preferably isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, Isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, As well as synthetic, semi-synthetic and natural mixtures of such esters, for example selected from the group consisting of jojoba oil.

  Furthermore, the oil phase is advantageously branched and unbranched hydrocarbons and hydrocarbon waxes, silicone oils, groups of dialkyl ethers, saturated or unsaturated branched or unbranched chains. Alcohols and fatty acid triglycerides, ie 8-24, in particular 12-18, saturated and / or unsaturated branched and / or unbranched alkanecarboxylic acids having a chain length of carbon atoms From the group of triglycerol esters. The fatty acid triglycerides are for example advantageously selected from the group of synthetic, semi-synthetic and natural oils such as olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, coconut oil, coconut oil, coconut kernel oil, etc. be able to.

  The desired mixture of such oil and wax components is also advantageously used for the purposes of the present invention. In some cases it may be advantageous to use a wax, such as cetyl palmitate, as the single lipid component of the oil phase.

The oil phase is advantageously from 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, benzoic acid C _12-15 -alkyl ester, caprylic / capric triglyceride, dicaprylyl ether Selected from the group consisting of

Benzoate _{C 12-15} - alkyl esters and mixtures 2-ethylhexyl isostearate, benzoate _{C 12-15} - a mixture of alkyl ester and isotridecyl isononanoate, as well as benzoic acid _{C 12-15} - alkyl esters, 2-ethylhexyl isostearate And a mixture of isotridecyl isononanoate is particularly advantageous.

  Among the hydrocarbons, paraffin oil, squalane and squalene are particularly advantageously used for the purposes of the present invention.

  Advantageously, the oil phase may have a content of cyclic or linear silicone oils or may consist solely of such oils, but here an additional separate from one or more silicone oils It is preferred to use other oil phases with a content.

  Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the silicone oil used according to the invention. However, other silicone oils such as hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane) are also advantageously used for the purposes of the present invention.

  Also particularly advantageous are mixtures of cyclomethicone and isotridecyl isononanoate and of cyclomethicone and 2-ethylhexyl isostearate.

  The oil phase is also advantageously selected from the group of phospholipids. Phospholipids are acylated glycerol phosphate esters. Very important phosphatidylcholines include, for example, the general structure

[Wherein R ′ and R ″ are typically unbranched aliphatic groups having 15 or 17 carbon atoms and up to 4 cis double bonds]
Lecithin identified by

  It is advantageous according to the invention that the cosmetic cleansing emulsion comprises one or more polyacrylates.

Preferred polyacrylates according to the invention are polymers of acrylic acid, in particular those selected from the group of so-called carbomers or carbopols (Carbopol® is actually BF Goodrich ^). Company (registered trademark of BF Goodrich company).

  Polyacrylate is a general structural formula

And its molecular weight can be between about 400,000 and over 4,000,000. The group of polyacrylates includes acrylate / alkyl acrylate copolymers, such as the following structure:

Those identified by are also encompassed.

  Where R 'is a long chain alkyl group and x and y are numbers that symbolize a particular stoichiometric proportion of each comonomer. These polyacrylates are also advantageous for the purposes of the present invention.

Advantageous Carbopol, for example, product name 907,910,934,940,941,951,954,980,981,1342,1382,2984 and 5984 or Product Name ETD (Easy - Two - Disperse (E asy- t o - d isperse)) 2001,2020,2050, an aqua (Aqua) -SF1, wherein these compounds can be present in combination separately or together.

Copolymers of C _10-30 -alkyl acrylates and one or more acrylic acid, methacrylic acid monomers or their esters comparable to acrylate / alyl acrylate copolymers are also for the purposes of the present invention. It is advantageous. The INCI name for such compounds is “Acrylates / C10-30 Alkyl Acrylate Polymers”. B. F. Particular preference is given to those which can be obtained from the Goodrich Company under the trade names Pemulen TR1 and Pemlen TR2.

According to the invention, it is particularly advantageous that the polyacrylate used is a C ₁₀ -C ₃₀ -alkyl acrylate copolymer.

  Very particularly preferably 0. The content of one or more polyacrylates in the cosmetic or skin cleansing emulsion is in each case from 0.5 to 2% by weight, based on the total weight of the preparation. It is advantageous for the purposes of the present invention to be selected from the range of 7 to 1.5% by weight.

  Apart from the substances mentioned above, the compositions according to the invention are optionally additives universal in cosmetics, such as fragrances, dyes, antimicrobial substances, refatting agents, complexing agents and sequestering agents, pearls. Brighteners, plant extracts, vitamins, active ingredients, preservatives, bactericides, pigments with coloring action, thickeners, softeners, hydrating and / or moisturizing substances, or cosmetic or dermatological preparations Universal components such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

  An additional content of antioxidant is generally preferred. According to the invention, preferred antioxidants that can be used are all antioxidants that are suitable or universal for cosmetic and / or dermal application.

  The active ingredients, auxiliaries and additives that can advantageously be used according to the invention are not limited in any way to the substances and compounds mentioned by name.

  It is also advantageous according to the invention to add effect substances (for example colored beads and / or active ingredient beads, glitter substances etc.) to the preparation according to the invention and / or to give the preparation stable bubbles and water bubbles in the emulsion. is there.

  The use of cosmetic cleansing emulsions according to the invention as foam baths, shower baths (shower gels), bath baths and / or hair-washing compositions (shampoos) is according to the invention.

  The use of cosmetic cleansing emulsions for the prevention and / or treatment of inflammatory skin conditions and / or for the protection of identified sensitive and dry skin (ie as a skin preparation) is also in accordance with the invention.

  The following examples describing hair and body care cleaning preparations are intended to illustrate the compositions according to the invention, but are intended to limit the invention to these examples is not. The numerical values in the examples are percentages by weight, based on the total weight of the specific preparation.

Claims (9)

a) one or more surfactants having an HLB value greater than or equal to 16;
b) one or more pregelatinized cross-linked starch derivatives;
c) A cosmetic cleansing emulsion comprising an oil phase, optionally in addition to other cosmetic active ingredients, auxiliaries and additives. In each case, based on the total weight of the emulsion,
a) a surfactant at a concentration of 1 to 20% by weight,
b) one or more pregelatinized cross-linked starch derivatives at a concentration of 0.1 to 20% by weight,
c) Cosmetic cleansing emulsion according to claim 1, characterized in that it comprises an oil phase in a concentration of 5 to 80% by weight.   Cosmetic cleansing emulsion according to claim 1 or 2, characterized in that the pregelatinized cross-linked starch derivative used is a hydroxypropylated phosphate ester.   Cosmetic product according to any of the preceding claims, characterized in that the pregelatinized cross-linked starch derivative used is hydroxypropyl distarch phosphate (CAS No. 113894-92-1). Cleansing emulsion.   The cosmetic cleansing emulsion according to any one of claims 1 to 4, wherein the surfactant used is an anionic surfactant.   6. The surfactant according to claim 1, wherein the surfactant comprises an anionic surfactant, preferably an alkyl ether sulfate, particularly preferably sodium lauryl ether sulfate or sodium myristyl ether sulfate. Cosmetic cleansing emulsion.   Cosmetic cleansing emulsion according to any of the preceding claims, characterized in that it comprises one or more polyacrylates. Polyacrylate used is C _{10 -C} 30 _-, wherein the alkyl acrylate copolymer, cosmetic cleansing emulsion according to claim 6.   Use of the cosmetic cleansing emulsion according to any one of claims 1 to 8 as a shower bath, bath tub, and / or hair washing composition (shampoo).