EP0912671B1 - Hand dishwashing agent acceptable to the skin - Google Patents

Abstract

The acceptability to the skin of an aqueous hand dishwashing agent is to be improved. This is achieved by a cleaning agent which, besides several anionic and non-ionic tensides, foaming agents and other conventional components, systematically contains polyol fatty acid esters as an agent to improve the acceptability to the skin.

Description

The invention relates to skin-friendly cleaning compositions from surfactant mixtures, foam boosters and skin-friendly additives Basis of certain polyol fatty acid esters.

Skin-friendly cleaning compositions are known.

WO 94/16042 (Henkel Corporation) describes a temporary combination of APG, betaine and alkyl sulfate as an anionic surfactant in aqueous Hand dishwashing detergents. Skin protection is considered to be considered Called factor, but the foam-enhancing effect of the betaine component is the central teaching of Scripture. Addition of polyol fatty acid esters Skin protection is not mentioned.

WO 94/24248 (Henkel Corporation) contains APG, betaines, Stearic acid adducts and glycols in aqueous shampoo formulations, the optionally also contain anionic surfactants. It won't be a lesson discloses how skin protection is ensured by these components can.

EP 485 212 (Unilever) describes a combination of anionic and amphoteric or non-ionic surfactants, which besides others Ingredients may also contain pearlescent agents.

EP 453 238 (Unilever) describes a shampoo with a Total surfactant content of more than 8%, the anionic surfactants (including Na lauryl ether contains sulfate 2 EO), APG and betaine, is mild to skin and hair and is provides adequate foaming performance for the applications ("adequate foaming power "). If fatty alcohol ether sulfates are used as anionic surfactants, then the weight ratio between anionic, amphoteric and non-ionic surfactants 1.3-2.2: 0.9-1.2: 0.9-1.2 amount to one balanced performance between skin mildness and foam stability guarantee. Other ingredients may also be included, including also foam boosters and pearlescent agents.

EP 341 071 (Unilever) describes a hand dishwashing detergent containing APG, anionic surfactants, betaines and / or amine oxide and optionally Ethanolamine. It has a less adverse effect on the skin condition of the user and is environmentally safer. The use of Polyol fatty acid esters to protect the skin are not described.

The document DE 42 34 487 discloses that a mixture of anionic Surfactants (FAS-FAES), APG, and betaine with other common ingredients, such as other cosurfactants, foam boosters, fragrances, etc. an excellent washing, Has rinsing and cleaning performance and is synergistic and skin-friendly is ecotoxicologically compatible. The addition of polyol fatty acid esters Skin protection is not described.

Certain polyol fatty acid esters have been described as pearlescent agents. So one learns in DE 41 03 551 (Henkel) how to make pearlescent concentrates Can produce polyol fatty acid esters.

The detergent compositions of EP 520 551 contain Ethylene glycol distearate as pearlescent agent, alkyl sulfate, non-ionic surfactant and "pearlescent crystallization enhancer" (acids, salts, Alcohols and fatty acid esters) can be included.

Ethylene glycol distearate is also used as a suspending agent for oil phases, e.g. B. described in WO 93/09761, a "two-in-one hand care" that is mild and is foam-rich and 1-10% anionic surfactant (including Na laureth-3 sulfate), 0.4-15 pref. 5-15% suspending agent, 1-10% additional surfactant (mixed. Non-ionic surfactant and betaine possible), but also contains 0.1-10% dispersed oil phase. Here too there is no indication that the skin is protected by polyol fatty acid esters.

Skin protection is an important point when formulating new ones Detergent compositions that are becoming increasingly important. You have to take care that the cleaning performance is not subsides or is even improved. You should also keep an eye on the im Keep related tasks, for example in the foam stability, the emulsifying power, the user-friendliness or show a favorable price-performance ratio of the cleaning agent. The central point is also the ecological compatibility of the Applied funds. Even the tasks arising from the current Discussion about cleaning agents and the use of cleaning agents result should be taken into account.

The document EP-A-0 510 870 sets milky, cloudy detergent compositions for hard Open surfaces. A possible component, in addition to alkyl polyglycoside, are Partial esters of polyols derived from aliphatic hydrocarbons, the 2 to Have 9 carbon atoms and a melting point of 30 ° C or higher, and Fatty acids with an average number of at least 13 carbon atoms.

A possible polyol is, inter alia, ethylene glycol and the fatty acids preferably have at least 16 carbon atoms.
An explicitly named partial ester is ethylene glycol monostearate.
According to this prior art, glycerides remain in the skin after use of the detergent composition and have a protective function for the skin and hands.
The object of the invention is therefore to create a new cleaning agent that meets the above points.

The objects of the invention are achieved by a cleaning agent that in addition to several anionic and nonionic surfactants and Foam boosters and other common ingredients, definitely Contains polyol fatty acid esters as an agent for improving skin protection.

Another object of the invention is the use of Polyol fatty acid ester ethylene glycol distearate as a hand care product in hand dishwashing liquids.

They belong to the group of anionic surfactants which are according to the invention can be used, aliphatic sulfates such as fatty alcohol sulfates, Fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic Sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, Ester sulfonates, and lingnine sulfonates. Also in the frame of the present invention are usable fatty acid cyanamides, Sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (Fatty acid aurides), fatty acid sarcosinates, ether carboxylic acids and Alkyl (ether) phosphates and other anionic known in the patent literature Surfactants. According to the invention, preference is given to using 1-30% by weight, particularly preferably 5-25% by weight.

The ethoxylated fatty alcohol sulfates are preferred. Especially the sodium, ammonium and magnesium salts thereof are preferred Compounds or their mixtures.

The person skilled in the art generally understands alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. These ethoxylated alcohols are used afterwards sulfates and neutralizes to give fatty alcohol ether sulfates.

To the nonionic surfactants used in the agents according to the invention can be used include alkoxylates such as polyglycol ethers, Fatty alcohol polyglycol ether, alkylphenol polyglycol ether, end group capped Polyglycol ether, mixed ether and hydroxy mixed ether and Fatty acid polyglycol. Ethylene oxide-propylene oxide block polymers can also be used and fatty acid alkanolamides and fatty acid polyglycol ethers. A important class of nonionic surfactants which are used according to the invention can, are the polyol surfactants and especially the glucose surfactants, such as Alkyl polyglucoside and fatty acid glucamides and their mixtures. One uses according to the invention preferably 1 to 20% by weight, preferably 1 to 10% by weight.

The alkyl polyglycosides, fatty alcohol polyglycol ethers and Fatty acid.

Alkyl polyglycosides are particularly preferably used.

The person skilled in the art understands alkyl polyglycosides as surfactants which are characterized by the Reaction of sugars and alcohols according to the relevant procedures of preparative organic chemistry can be obtained, depending on the type the production to a mixture of monoalkylated, oligomeric or polymeric Sugar is coming. Preferred alkyl polyglycosides can be alkyl polyglucosides wherein the alcohol is particularly preferably a long-chain fatty alcohol or a Mixture of long-chain fatty alcohols and the degree of oligomerization is the sugar is between 1 and 10.

The C ₆ -C ₂₂ -alkylglycosides preferred according to the invention are therefore known substances which can be obtained by the relevant methods of preparative organic chemistry. As a representative of the extensive literature, reference is made to the documents EP-A 1-0 301 298 and WO 90/3977. The C ₆ -C ₂₂ alkylgycosides follow the formula I, R ^1- O- (G) _p in which R ^{1 is} a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, [G] is a glycosidic sugar and p is a number from 1 to 10.

The index number p in the general formula I indicates the degree of oligomerization (DP degree) on, i.e. the distribution of mono- and oligoglycosides, and stands for one Number between 1 and 10. During p in a given connection always must be an integer and, above all, can assume the values p = 1 to 6 the value p was determined analytically for a certain alkyl glycoside arithmetical size, which usually represents a fractional number. Preferably Alylglycoside with an average degree of oligomerization p of 1.1 to 3.0 used. From an application point of view, such alkyl glycosides are preferred, the degree of oligomerization is less than 1.8 and in particular is between 1.2 and 1.7. As glycosidic sugar units preferably glucose and xylose used.

The alkyl or alkenyl radical R ¹ is preferably derived from primary alcohols having 6 to 18, in particular 8 to 14, carbon atoms. Typical examples are caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.

Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents. Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, e.g. B. SÖFW-Joumal, 119, (1993), 794-808. Carbon chain lengths of C ₆ to C ₁₂ in the fatty acid residue are preferably used.

The person skilled in the art generally understands alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or mixtures thereof end-capped fatty alcohol ethoxylates.

As a foam booster, the detergent can do the job represents betaines and other amphoteric surfactants, amine oxides, alkanolamides, Fatty acid sarcosinates, alkyl polyglycosides and mixtures thereof are used become

The amphoteric surfactants which can be used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the Aminopropionate, just like the sulfobetaines and biosurfactants. You bet according to the invention preferably 1 to 20% by weight, particularly preferably 1 to 10 % By weight.

eingesetzt werden, in der R² einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und R³ und R⁴ gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten. Bevorzugt sind C₁₀-C₁₈-Alkyldimethylcarboxymethylbetain und C₁₁-C₁₇-Alkylamidopropyldimethylcarboxymethylbetain. Betaine compounds of the formula II are preferred as amphoteric surfactants

are used in which R ^{2 is} an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups, and R ³ and R ^{4 are} identical or different alkyl radicals with 1 to 3 carbon atoms. C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -Alkylamidopropyldimethylcarboxymethylbetaine are preferred.

Particularly preferred betaine compounds are cocoamidopropyl betaine and alkyldimethylammonium betaine

As a polyol fatty acid ester, which according to the invention is used as an agent for protecting the skin Are used, apply according to the usual rules of organic Chemically producible reaction products from longer chain fatty acids and shorter alkyl chains with more than one hydroxy group.

The monoesters and diesters of stearic acid and of are particularly preferred Ethylene glycol. According to the invention, preference is given to using 0.1 to 10% by weight, particularly preferably 0.2 to 2% by weight.

Other ingredients common in hand dishwashing detergents, such as Foam inhibitors, stabilizers, solvents, perfumes, dyes as well biogenic active substances can be used, preferably in amounts between 1 and 10% by weight.

Substances such as gelatin or Casein can be used without impairing performance. are Desired products with improved cold behavior can agents according to the invention also hydrotropes, e.g. Cumene sulfonate, octysulfate, Butyglucoside, butylene glycol can be added.

The solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol. As another solution broker, for example for dyes and perfume oils, for example alkanolamines, Polyols such as ethylene glycol, propylene glycol, glycerin and alkylbenzenesulfonates serve with 1 to 3 carbon atoms in the alkyl radical.

Preferred thickeners include urea, sodium chloride and ammonium chloride, Polysaccharides and the like, which are also used in combination can be. Examples of preservatives are sodium benzoate, To name formaldehyde and glutaraldehyde.

The pH of the compositions according to the invention is preferably between 5.0 and 7.5. It can be adjusted using conventional pH regulators such as citric acid, triethanolamine or NaOH.
Biogenic active substances are understood to mean, for example, plant extracts, protein hydrolyzates and vitamin complexes.

Claims (13)

1. Aqueous surfactant preparation for washing dishes, comprising

   at least one anionic surfactant,

   at least one nonionic surfactant,

   at least one amphoteric surfactant and

   polyol fatty acid esters

   and optionally non-surface-active components,

   where the polyol fatty acid esters are not partial esters of aliphatic C_2-9-polyols with fatty acids having, on average, at least 13 carbon atoms which have a melting point of 30°C or above.
2. Aqueous surfactant preparation according to Claim 1, characterized in that

   1 to 30% by weight of an anionic surfactant,

   1 to 20% by weight of a nonionic surfactant,

   1 to 20% by weight of an amphoteric surfactant and

   0.1 to 10% by weight of a polyol fatty acid ester and optionally

   1 to 20% by weight of non-surface-active components
   are present.
3. Aqueous surfactant preparation according to Claim 1 or 2, characterized in that

   5 to 25% by weight of an anionic surfactant,

   1 to 10% by weight of a nonionic surfactant,

   1 to 10% by weight of an amphoteric surfactant and

   0.2 to 2% by weight of a polyol fatty acid ester and optionally

   1 to 15% by weight of non-surface-active components
   are present.
4. Aqueous surfactant preparation for washing dishes, characterized in that

   fatty alcohol ether sulphates are present as anionic surfactant

   alkyl polyglycosides are present as nonionic surfactant,

   betaines are present as amphoteric surfactant and

   ethylene glycol distearate is present as polyol fatty acid ester and optionally

   non-surface-active components
   are present.
5. Aqueous surfactant preparation according to one of the preceding claims, characterized in that fatty alcohol ether sulphates with C₁₂ and/or C₁₄ carbon chains and/or mixtures thereof are present as anionic surfactants.
6. Aqueous surfactant preparation according to one of the preceding claims, characterized in that alkyl polyglycosides of the formula (I), R1-O-(G)_p in which R1 is a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms, (G) is a glycose unit having 5 or 6 carbon atoms and p is a number between 1 and 10, are present as nonionic surfactant.
7. Aqueous surfactant preparation according to one of the preceding claims, characterized in that the betaine present is cocoamidopropylbetaine and/or alkyldimethyl-ammoniumbetaine.
8. Aqueous surfactant preparation according to one of the preceding claims, characterized in that

   1 to 10% by weight of alcohols and

   0.1 to 2% by weight of perfume substances
   are present as non-surface-active components.
9. Use of the polyol fatty acid ester ethylene glycol distearate as hand care agent in hand dishwashing detergents.
10. Use according to Claim 9, characterized in that, in the hand dishwashing detergent,

    at least one anionic surfactant,

    at least one nonionic surfactant,

    at least one amphoteric surfactant and

    ethylene glycol distearate and optionally

    non-surface-active components
    are present.
11. Use according to Claims 9 and 10, characterized in that, in the hand dishwashing detergent,

    5 to 25% by weight of an anionic surfactant,

    1 to 10% by weight of a nonionic surfactant,

    1 to 10% by weight of an amphoteric surfactant and

    0.2 to 2% by weight of ethylene glycol distearate and optionally

    1 to 15% by weight of non-surface-active components
    are present.
12. Use according to Claims 9 to 11, characterized in that, in the hand dishwashing detergent,

    fatty alcohol ether sulphates are present as anionic surfactant,

    alkyl polyglycosides are present as nonionic surfactant,

    betaines are present as amphoteric surfactant and

    ethylene glycol distearate is present as polyol fatty acid ester and optionally

    non-surface-active components
    are present.
13. Use according to Claims 9 to 12, characterized in that ethylene glycol distearate is used in amounts of from 0.1 to 10% by weight.