EP0912671A1

EP0912671A1 - Hand dishwashing agent acceptable to the skin

Info

Publication number: EP0912671A1
Application number: EP97923890A
Authority: EP
Inventors: Hans Andree; Dagmar Zaika; Brigitte Giesen
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1996-05-23
Filing date: 1997-05-14
Publication date: 1999-05-06
Anticipated expiration: 2017-05-14
Also published as: ATE247705T1; WO1997044423A1; DE19620703A1; DE59710627D1; EP0912671B1

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

Skin-friendly dishwashing detergent

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

Skin-friendly cleaning compositions are known.

WO 94/16042 (Henkel Corporation) describes a ternary combination of APG, betaine and alkyl sulfate as an anionic surfactant in water-based hand dishwashing detergents Skin protection is not mentioned.

WO 94/24248 (Henkel Corporation) contains APG, betaines, stearic acid adducts and glycols in aqueous shampoo formulations, which can optionally also contain anionic surfactants. No teaching is disclosed on how skin protection can be ensured by these components.

EP 485 212 (Unilever) describes a combination of anionic and amphoteric or nonionic surfactants, which can also contain pearlescent agents in addition to other ingredients.

EP 453 238 (Unilever) describes a shampoo with a total surfactant content of more than 8%, which contains anionic surfactants (including Na lauryl ether sulfate 2 EO), APG and betaine, is mild to the skin and hair and one for the applications provides the required foam performance ("adequate foammg power "). If fatty alcohol ether sulfates are used as anionic surfactants, the weight ratio between anionic, amphoteric and nonionic surfactants must be 1.3-2.2: 0.9-1.2: 0.9-1.2 in order to ensure a balanced performance between skin mildness and foam stability. Others can also Contain ingredients, including foam enhancer 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 user's skin condition and is more environmentally safe. The use of polyol fatty acid esters to protect the skin has not been described.

In the document DE 42 34 487 it is disclosed that a mixture of anionic surfactants (FAS-FAES), APG, and betaine with other conventional ingredients, such as other cosurfactants, foam boosters, fragrances, etc., is excellent for washing, rinsing, and Has cleaning performance and is synergistically skin-friendly and ecotoxicologically compatible. The addition of polyol fatty acid esters to protect the skin is not described.

Certain polyol fatty acid esters have been described as pearlescent agents. DE 41 03 551 (Henkel) shows how pearlescent concentrates can be produced from polyol fatty acid esters.

The detergent compositions of EP 520 551 contain ethylene glycol distearate as pearlescent agent, which may also contain alkyl sulfate, nonionic surfactant and "pearlescent crystallization enhancer" (acids, salts, alcohols and fatty acid esters).

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 foaming 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 in the formulation of new detergent compositions, which is becoming more and more important. Care must be taken to ensure that cleaning performance does not deteriorate or is even improved. You should also keep an eye on the related tasks, which are shown, for example, in foam stability, emulsification capacity, user-friendliness or a favorable price-performance ratio of the cleaning agent. The central point is also the ecological compatibility of the agents used. The tasks arising from the current discussion about cleaning agents and the use of cleaning agents should also be taken into account.

The object of the invention is therefore to create a new cleaning agent that meets the above points.

The objects according to the invention are achieved by a cleaning agent which, in addition to several anionic and nonionic surfactants and foam boosters and other customary 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 esters to protect the skin in hand dishwashing detergents.

The group of anionic surfactants which can be used according to the invention includes 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 lingine sulfonates. Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and can also be used in the context of the present invention

Alkyl (ether) phosphates and other anionic surfactants known in the patent literature. 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. The sodium, ammonium and magnesium salts of these compounds or mixtures thereof are particularly preferred.

The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols in the sense of the present invention. As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. Another embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. These ethoxylated alcohols are then sulfated and neutralized to give fatty alcohol ether sulfates.

The nonionic surfactants which can be used in the agents according to the invention include alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenoipolyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and

Fatty acid polyglycol ester. Ethylene oxide-propylene oxide block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. An important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glucosurfactants, such as Alkyl polyglucoside and fatty acid giucamides and their mixtures. According to the invention, preference is given to using from 1 to 20% by weight, preferably from 1 to 10% by weight.

The alkyipolyglycosides, fatty alcohol polyglycol ethers and fatty acid alkanolamides are preferred.

Alkyipolyglycosides are particularly preferably used.

The person skilled in the art understands alkyipolyglycosides as surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols and the degree of oligomerization of the sugars being 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), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound always must be an integer and here can assume the values p = 1 to 6, the value p for a certain alkylglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Alylglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.8 and is in particular between 1.2 and 1.7. Glucose and xylose are preferably used as glycosidic sugar units.

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 those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from the Roelen oxo synthesis.

Fatty acid polyhydroxylam.de (glucamides) are aeylated 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, such as. B. in SÖFW-Journal, 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 by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols in the sense of the present invention. As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of Ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Betaines and other amphoteric surfactants, amine oxides, alkanolamides, fatty acid sarcosinates, alkyipolyglycosides and mixtures thereof can be used as foam enhancers in the cleaning agent which represents the solution to the problems

The amphoteric surfactants which can be used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the aminopropionates, as well as the sulfobetaines and biosurfactants. According to the invention, preference is given to using 1 to 20% by weight, particularly preferably 1 to 10% by weight.

Betaine compounds of the formula II are preferred as amphoteric surfactants

.R ³

R ² - N ^* - CH2COO ^"

, 2 are used, in which R is an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms and R ³ and R ^{4 which are the} same or different alkyl radicals and have 1 to 3 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups. C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetaine and C 1 -C ₁₈ -alkylamidopropyldimethylcarboxymethylbetaine are preferred. Particularly preferred betaine compounds are cocoamidopropyl betaine and alkyldimethylammonium betaine

The polyol fatty acid esters which are used according to the invention as agents for protecting the skin are the reaction products which can be prepared according to the usual rules of organic chemistry and which consist of longer-chain fatty acids and shorter alkyl chains with more than one hydroxyl group.

The mono- and diesters of stearic acid and ethylene glycol are particularly preferred. 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 customary in hand dishwashing detergents, such as foam inhibitors, stabilizers, solvents, perfume, dyes and biogenic active substances, can also be used, preferably in amounts between 1 and 10% by weight.

Substances such as gelatin or casein can be used to adjust the viscosity of the agents without impairing their performance. If products with improved cold behavior are desired, 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. Optional further solubilizers, for example for dyes and perfume oils, can be alkanolamines, polyols such as ethylene glycol, propylene glycol, glycerol and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical. The preferred thickeners include urea, sodium chloride and ammonium chloride, polysaccharides and the like, which can also be used in combination. Examples of preservatives which can be mentioned are sodium benzoate, formaldehyde and glutaraldehyde

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

Examples:

The following cleaning agents were checked for their dermatological properties. All figures are in% by weight based on the total cleaning agent.

Test method

The Duhπng chamber test is an occlusive, epicutaneous test method that is suitable for obtaining experimental data on the skin compatibility of raw materials or finished products.

The test substances are applied to the skin under occlusive plasters for 24 hours. The resulting irritation effects are evaluated after 6, 24, 48 and 72 hours. The test patches are on the back of the Subjects applied. (Literature: Kligman, Frosch; Contact Dermitis 5, (1979), 73-81)

Compared to the standard surfactants Texapon N 25 1% AS and SDS 0.5% AS, the detergent formulations according to the invention show a significant reduction in the negative skin reactions and thus a significantly better skin tolerance. This becomes particularly clear in the area of reddening of the skin, where compared to standard surfactants (sodium dodecyl sulfate SDS) only 5% of the unwanted skin reactions are observed.

Absolute measurements show that the polyol fatty acid esters in the investigated agents clearly have a gentle effect on the skin.

Claims

1. Aqueous surfactant preparation for cleaning dishes containing at least one anionic surfactant, at least one nonionic surfactant, at least one amphoteric surfactant and polyol fatty acid ester and / or non-surfactant components.

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 / or 1 to 20 % By weight does not contain surfactant components.

Aqueous surfactant preparation according to claim 1 and 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 / or

1 to 15% by weight does not contain surfactant components.

4. Aqueous surfactant preparation for cleaning dishes, characterized in that • fatty alcohol ether sulfates as anionic surfactant, Alkyipolyglycosides as nonionic surfactant,

• Betaine as an amphoteric surfactant and

• Ethylene glycol distearate as polyol fatty acid ester and / or

• Does not contain surfactant components.

5. Aqueous surfactant preparation according to one of the preceding claims, characterized in that fatty alcohol ether sulfates with C ₁₂ and / or C ₁₄ carbon chains and / or mixtures thereof are contained as anionic surfactants.

6. Aqueous surfactant preparation according to one of the preceding claims, characterized in that the alkyipolyglycosides of the formula (I) are present,

R1-0- (G) _p in which R1 represents a linear or branched alkyl or alkenyl radical with 4 to 22 carbon atoms, (G) for a glycose unit with 5 or 6 carbon atoms and p stands for a number between 1 and 10.

7. Aqueous surfactant preparation according to one of the preceding claims, characterized in that cocoamidopropyl betaine and / or alkyldimetylammonium betaine is contained as betaine.

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 contained as non-surfactant components.

9. Use of polyol fatty acid esters as hand care products in hand dishwashing detergents. 0. Use according to claim 9, characterized in that at least one anionic surfactant, at least one nonionic surfactant, at least one amphoteric surfactant and polyol fatty acid ester and / or non-surfactant components are included.

1. Use according to claims 9 and 10, characterized in that 5 to 25 wt .-% 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 / or 1 to 15% by weight of non-surfactant components.

2. Use according to claims 9 to 11, characterized in that fatty alcohol ether sulfates as anionic surfactant, alkyipolyglycosides as nonionic surfactant,

Betaines as amphoteric surfactant and ethylene glycol distearate as polyol fatty acid esters and / or non-surfactant components are included.

13. Use according to claims 9 to 11, characterized in that ethylene glycol distearate is used as the polyol fatty acid ester.

14. Use according to claims 9 to 13, characterized in that ethylene glycol distearate is used in amounts of 0.1 to 10 wt .-%.