WO1998020853A1

WO1998020853A1 - Use of anionic gemini surfactants in formulations for washing, cleaning and body-care products

Info

Publication number: WO1998020853A1
Application number: PCT/EP1997/005892
Authority: WO
Inventors: Michael Brock; Klaus Kwetkat; Herbert Koch
Original assignee: RWE-DEA Aktiengesellschaft für Mineraloel und Chemie
Priority date: 1996-11-14
Filing date: 1997-10-24
Publication date: 1998-05-22
Also published as: DE19647060A1

Abstract

The invention relates to the use of salts of di-α sulphodicarboxylic acid di-ester according to the formula (I) in formulations for washing and cleaning textiles, cleaning hard surfaces and cleaning and washing hair and skin. R?1 and R3¿ both stand for a hydrocarbon radical with 1-22 carbon atoms. R2 means a spacer from a chain with 2-100 carbon atoms which contain oxygen, nitrogen and/or phosphorus atoms and can have functional side groups. A and B stand for oxygen, alkoxylene groups or derivatized nitrogen.

Description

Use of anionic gemini surfactants in washing formulations. Cleaning and personal care products

The invention relates to the use of salts of di-α-sulfodicarboxylic acid diesters in formulations for washing and cleaning textiles, cleaning hard surfaces and cleaning and washing skin and hair.

The compilation of formulations for detergents, cleaning agents and personal care products is a complex task, since the formulations must be able to remove soiling of the most varied types from very different surfaces. The quick and efficient removal of greasy or oily stains is particularly problematic. In addition to the purely technical requirements, the ecotoxicological requirements for formulations for detergents, cleaning agents and personal care products are becoming increasingly stringent.

To conserve natural resources, however, not only the use of surfactants based on renewable raw materials is part of the process, but also particularly the production of formulations that are more and more effective with the same use of raw materials, but which still meet the requirements for biodegradability and skin mildness. In addition, the ever more compact surfactant-containing formulations for detergents and cleaning agents must be quickly soluble in water, even if the amount of water in the wash liquor is also falling for ecological reasons.

All of these requirements can no longer be met physically, but require the use of more powerful surfactants. The gemini or twin surfactants referred to as "New Generation of Surfactants" (MJ Rosen, Chemtech, No. 3 (1995) 30) are, provided their structure is optimally selected, surfactants with a significantly higher performance than their conventional equivalents and offer more In addition, when choosing the right structural variant, a high degree of multifunctionality and thus help to increase the washing or cleaning performance per unit mass of the formulation. The gemini polyhydroxy fatty acid and ge inipolyether fatty acid amides described in the applications WO 95/19953 and WO 95/19955 are nonionic gemini surfactants. In comparison to the nonionic surfactants known today, however, these compounds do not offer any particular increase in efficiency per charge. The multifunctionality of these compounds can also only be achieved by a significant increase in the molecular mass, which must be regarded as rather counterproductive in terms of protecting the ecosystem.

However, if anionic gemini surfactants, as described in application P 19633 497 (formula I), are used, a significant increase in the efficiency of entire end formulations is achieved. This is possible because the di-α-sulfodicarboxylic acid diesters are significantly more efficient than conventional anionic surfactants with regard to, for example, the critical micelle formation concentration, interfacial tension, water solubility, hardness stability, solvent-imparting effect and detergency, and, due to their special structure, they are particularly mild on the skin and biodegradable.

Formula (I):

The present invention relates to the use of anionic gemini surfactants of the formula I in washing, cleaning and personal care products in which they contain at least 0.1

n% are included. The salts of the di-α-sulfodicarboxylic acid diesters are described in published patent application WO 96/25393 and in German patent application P 196 33497, which we hereby introduce as a reference.

1 2 3 Here, R, R and R in formula I have the meanings described below:

1 3 R and R independently of one another represent an unbranched or branched, saturated or unsaturated hydrocarbon radical with 1 to

22, preferably 8 to 18, carbon atoms. Let R be the substituent

3 and R in detail the residues methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , n-

Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadec cyl, n-nonadecyl, n-eicosyl, n-uneicosyl, n-docosyl and their branched-chain isomers and the corresponding mono-, di- or tri-unsaturated radicals.

R 2 represents a spacer consisting of an unbranched or branched, saturated or unsaturated chain with 2 to 100 carbon atoms, 0 to 20 oxygen and / or 0 to 20 nitrogen and / or 0 to 4 sulfur and / or 0 to 3 Phosphorus atoms. The chain also has 0 to 20 functional side groups such as. B. hydroxyl, carbonyl, carboxyl, amino and / or acylamino groups and / or 0 to 4 cycles which are isolated or fused.

2 The spacer R means in particular

♦ unbranched or branched alkylene chains of the formula II as basic body

-C _a H _2a - (II) with a = 2 to 18, preferably a = 2 to 6;

♦ unbranched or branched alkenylene chains of the formula Ha as the base body

-C _b H _2b -CH = CH-C _c H _2c - (Ha) with b + c = 2 to 16, where b and c are each greater than zero;

♦ unbranched or branched alkynylene chains of the formula III - _Cd H _2d -C _≡ CC _e H _2e - (III) with d + e = 2 to 16, where d and e are each greater than zero, and with the compounds according to the formulas II, Ha and III the spacer may additionally contain 1 to 4 hydroxyl, carbonyl, carboxyl, amino or acylamino groups at any point in the chain;

Al icyclen according to formula IV

-C _f H _2f -cyclo C ₆ H ₁₀ -C ₈ H _2g - (IV) with tf and the same, independently of each other, 1 to 6 each

or according to formula V

-3 (4), 8 (9) -di (methylene) tricyclo [5.2.1.0 ^{2, 6} ] decan (V);

optionally substituted aromatics according to formula VI ^{- C} h ^H 2h ^"C 6 ^R 4 - ( ^C i 2 i ^-C 6 ^R 4) jl ^C j 2 ^H 2 j 2 ^" ( ^{V ϊ} )

or according to formula VII

-C _h H2h-CioR6-CjH _2j - (VII) with h, J! and j ₂ are independently 0 to 8, i = 0 to

8 and R are each independently H or C, - to C _c -Al-

1 o kyl;

2 Furthermore, in the spacer R there are 0 to 20, preferably 1 to 12,

Contain oxygen and / or nitrogen and / or 0 to 4 sulfur and / or 0 to 3 phosphorus atoms.

2 R therefore continues to have particular meaning

♦ a compound of the formula VIII -C _k H ₂ -C _χ R _y -ZC _x R _y -C ₁ H ₂₁ - (VIII) with k and 1, independently of one another, 0 to 8, x = 6 and y = 4 or x = 10 and y = 6 or x = 14 and y = 8, and Z = 0, C0, NH, N-CH -CHfOXj-R ¹ , NR ¹ , NC (0) R ¹ , SO

or according to the formula IX -CH -CH (0CH ₂ CH (0X) -R ¹ ) -CH - or an isomer (IX) with X = SO M

or 2,2'-methylene-bis- (1,3-dioxolane-5-methylene) - or acetals, in particular diacetals from dialdehydes and di-, oligo- or polyols, where R is a hydrocarbon radical having 1 to 22 carbon atoms,

♦ a compound of the formula X -C _m H ₂ m- (CnH2nO) p (C ₃ H ₆ 0) _q -C _r H _2r - (X) with m = 1 to 4, n = 2 or 4, p = 1 to 20, preferably p = 1 to 4, q = 0 to 4 and r = 1 to 4, mixed alkoxide units also being able to occur and the sequence of the alkoxide units then being arbitrary,

♦ a compound of the formula XI -C _r H _2r (RNC _s H _2s ) _t -C _u H _2u - (XI)

or according to formula XII - [C _r H _{2 r} [RN-C (0) -NR] _t -C _u H _2u ] _w - (XI I)

or according to the formula XI I I

- [C _r H _{2 r} [RNC (0) C _v H _2v C (0) NR] _t -C _u H _{2 u} ] _w - (XI II)

or according to formula XIV

- [C _r H _2r [RNC (0) C _x R _y C (0) NR] _t -C _u H _2u ] _w - (XIV) with r = 2 to 4, s = 2 to 4, t = 1 to 20, preferably t = 1 to 4, u = 2 to 4, v = 0 to 12, w = 1 to 6, x = 6 and y = 4 or x = 10 and y = 6 or x = 14 and y = 8 with R the same independently of one another H or C.- to C _c -alkyl.

1 6

R ² can also be derived from a methyl or ethyl ester of a polycarboxylic acid (MW 500 to 100000), the α-carbon atoms of which are sulfonated between 0 and 100%. However, the α-carbon atoms are preferably only between 10 and 60% sulfonated.

M, M '= alkali, ammonium, alkanolam onium or alkaline earth.

A and B independently of one another denote -0-, -0 (C ₂ H ₄ 0) _α (C ₃ H ₆ 0) β- (with α = 0 to 20, preferably 0 to 10, and β = 0 to 20, preferably 0 to 10, α and ß cannot be 0 at the same time), -NH-, -NR - (with R = methyl, ethyl, propyl, butyl or methoxyethyl, methoxypropyl, ethoxypropyl), - N (R ⁵ ) -0 ( C ₂ H ₄ 0) _α (C ₃ H ₆ 0) _β - (with α = 0 to 20, preferably 0 to 10, and β = 0 to 20, preferably 0 to 10, α and β cannot be 0 at the same time ) and R equal to R or equal to -0 (CH ₄ 0) _α (C ₃ H ₆ 0) ß- H, with the aforementioned conditions), -C (0) N (R ⁵ ) -0 (C ₂ H ₄ 0 ) _α (C ₃ H ₆ 0) ß-, n is a number from 1 to 200, preferably from 1 to 10.

Due to the production process, the di-α-sulfodicarboxylic acid diesters can also contain di-α-sulfodicarboxylic acid monoesters, mono-α-sulfodicarboxylic acid diesters and mono-α-sulfodicarboxylic acid monoesters.

In addition to at least 0.1% anionic gemini surfactant according to formula (I) (see also WO 96/25393), which as a mixture of different homologues of the same basic structure (both with regard to the C chain length of the lipophilic chains and also of the spacer or the alkoxy ether chains) and Mixture of compounds with different degrees of functionalization, for example sulfonation degrees between 0.1 and 2, preferably between 1 and 2, for n = 1, the formulations for detergents, cleaning agents and personal care agents can each contain at least 0.001% of one or more detergent, cleaning agents or personal care agent components which are explained in more detail below. All percentages are to be understood as percentages by weight, unless the percentages are explicitly related to another size. The following may be mentioned as such components:

a) Enzymes: A whole series of enzymes can be contained in the formulations according to the invention, for example proteases, amylases, lipases, cellulases and peroxidases and mixtures of the respective enzymes. Other enzymes can also be incorporated into detergent formulations, where, like the aforementioned, they come from a wide variety of origins from bacteria, fungi, e.g. B. yeasts, and other plants, but can also be of animal origin.

Different factors determine the selection of individual enzymes, such as, for example, the pH activity and / or stability optimal, the thermostability, the stability to various surfactants, builders, etc. Enzymes are weighed up to 50 mg, preferably 0.01 mg up to 3 mg of active enzyme used per gram of detergent formulation, d. H. 0.001% to about 5% in the detergent formulations according to the invention. For proteases, an application concentration of an activity of 0.005 to 0.1 Anson units (Anson units = AU) per gram of formulation according to the invention applies.

b) Enzyme stabilizers: These include water-soluble sources of calcium and / or magnesium ions, which must be added frequently so that the builder system does not also remove these central atoms of the enzymes and thus deactivate them. Calcium ions are generally more effective than magnesium ions. Additional stabilization can be achieved by adding borates (US 4,537,706, Severson). Typically, the formulations according to the invention contain 1 to 30, preferably 2 to 20, particularly preferably 5 to 15 and very particularly preferably 8 to 12 millimoles of calcium ions per liter of final formulation. Although the concentration in different formulations may vary depending on the enzymes used, there should always be enough calcium ions available after complexing by the builder system and soaps to keep the enzymes activated. Any water soluble calcium or Magnesium salt can be used. The following examples may be mentioned here without restricting the formulations according to the invention: calcium chloride, formate, sulfate, hydroxide, malate, maleate, acetate and the corresponding magnesium salts. Depending on the amount and type of the enzymes used, the detergent formulations according to the invention contain 0.05% to 2% water-soluble calcium and / or magnesium salts. Borate stabilizers are contained in the formulations according to the invention to 0.25% to 10%, preferably 0.5% to 5% and particularly preferably 0.75% to 3% - calculated as boric acid. The added borate stabilizers must be able to form boric acid. The direct use of boric acid is preferred here, but boron oxide, borax, other alkali borates and substituted boric acids, such as, for example, As phenyl, butyl and p-bromophenyl boric acid can be used.

c) Bleaching Systems - Bleaching Agents and Bleach Activators: For the formulations according to the invention, the use of a bleaching system, be it bleaching agent and activator or just a bleaching agent, is optional. If used, the bleaching agents are used in amounts of 1 to 30%, preferably 5 to 20%. If used, bleach activators are used in amounts of 0.1 to 60% of the bleach. 0.5 to 40% bleaching system, based on the formulation according to the invention, is preferably used. All bleaches suitable for cleaning textiles, hard surfaces (industrial and household cleaners, dishwashing detergents) or other cleaning tasks can be used. These include bleaches that work on an oxygen basis as well as other systems. Perborates, e.g. B. sodium perborates, be it as mono- or tetrahydrate, can be used, as can percarboxylic acid bleaches and their salts. Suitable representatives of this class include magnesium peroxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutanoic acid, diperoxydodecanedioic acid and, particularly preferably, 6-nonylamino-6-oxoperoxycapric acid (US 4634551, Bums et al). Peroxygen bleaches can also be used. Suitable representatives of this class include sodium carbonate peroxohydrate and comparable percarbonates, sodium pyrophosphate peroxohydrate, urea peroxohydrate, sodium peroxide and persulfate bleach. Mixtures of bleaching agents can also be used in the detergent and cleaning agent formulations according to the invention. Peroxygen bleaches are preferably combined with bleach activators, which include, but are not limited to, the formulations according to the invention, nonanoyloxyphenylsulfonate, tetraacetylethylenediamine and mixtures thereof, and other combinations of bleaching agent and activators mentioned in US Pat. No. 4,634,551. Amide derivatives of the formulas R ¹ N (R ⁵ C (0) R ² C (0) L or are very particularly preferred as bleach activators

R ¹ C (0) N (R ⁵ ) R ² C (0) L, where R ^{1 is} an alkyl group with 6 to 12

2 5

Carbon atoms, R is an alkylene group having 1 to 6 carbon atoms, R is a hydrogen atom or alkyl, aryl or alkylaryl having 1 to 10 carbon atoms and L is any suitable for nucleophilic reactions

Leaving group (z. B. Phenylsulfonate) means. The following compounds are mentioned as examples: (6-0ctanamido-caproyl) oxyphenylsulfonate,

(6-nonanamido-caproyl) oxyphenyl sulfonate, (6-decanamido-caproyl) oxyphenyl sulfonate and mixtures thereof. Acyl lactam activators belong to another class of preferred bleach activators, here especially acyl caprolactam and acyl valerolactam with alkyl, aryl,

Alkoxyaryl and alkyl aryl acyl groups containing 1 to 16 carbon atoms. Among the non-oxygen-based bleaching agents, sulfonated zinc and / or aluminum phthalocyanines are among the preferred systems.

d) Builder systems: The washing and cleaning agents according to the invention can also optionally contain builder systems (overall builders) which consist of water-softening silicates and / or other inorganic and / or organic builders. They are used in detergent formulations to help remove dirt and to control water hardness. Liquid formulations contain from 0 to 50%, preferably 5 to 30% of total builders. Granulated formulations contain 0 to 80%, preferably 15 to 50% of total builders. However, higher concentrations should not be excluded here.

Inorganic builders include in particular silicates and aluminosilicates.

Examples of silicate builders are alkali silicates, especially those with Si0 ₂ : Na ₂ 0 in the ratio 1.6: 1 to 3.2: 1 and layered silicates such as sodium silicates of the type NaMSi _x 0 _{2x + 1} yH ₂ 0 (M stands for Na or H , x = 1.9 - 4, y = 0-20). The type designated SKS-6 is particularly preferred. Magnesium silicates can also be used here. Are aluminosilicates also useful in the formulations of the invention and particularly important in granular detergent formulations. The usable aluminosilicate builders can be described with the empirical formula [M _z (zA10 ₂ ) _y ] xH ₂ 0, z and y assume values of at least 6, the molar ratio of z to y is in the range from 1.0 to 0, 5, x takes values from approx. 0 to 30. It can be crystalline as well as amorphous, synthetic or naturally occurring aluminosilicates. The silicate builders can contain 0 to 60%.

The inorganic builders further include, without restricting the formulations according to the invention, alkali, ammonium and alkanolammonium salts of polyphosphates (e.g. tripolyphosphates, pyrophosphates and polymeric metaphosphates), phosphonates, carbonates (also bicarbonates and sesquicarbonates) and sulfates.

Organic builders also belong to the builders which can be used in the formulations according to the invention. These include polycarboxylates such as ether carboxylates (cyclic or acyclic), hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethoxysuccinic acid, all in the form of the acid or its alkali , Ammonium or organoammonium salts can be used. Alkyl, ammonium or organoammonium salts of polyacetic acid are just as suitable as salts of citric acid or combinations of different builders. AI kenylsuccinic acids and salts are particularly preferred organic builders. Monocarboxylic acid salts can also be incorporated into the formulations according to the invention either alone or in combination with one of the abovementioned builders.

The inorganic (without silicates) and / or organic builders are 0 to 40% contained in the formulation.

e) Dirt-Removal Polymers: All dirt-release polymers belonging to the prior art can be used as ingredients in the formulations according to the invention. As a component of formulations, soil release polymers contribute to easier removal of oil and grease dirt, especially during washing processes and in textile finishing. Dirt release polymers are characterized by the fact that they are both hydrophilic and Have hydrophobic components. The mode of action of soil release polymers is based on a modification of the fiber surface of polyester or cotton / polyester blended fabrics with the help of the hydrophilizing polymer. The hydrophilic segment of the soil release polymer makes the surface easier to wet, while the hydrophobic segment acts as an anchor group.

Moisture transport (water absorption and absorbency) is significantly improved in the hydrophobic fabrics treated with the soil release polymer, such as polyester or polyester / cotton blended fabrics. They also give the fabrics antistatic and gliding properties, which makes handling these fibers easier when cutting and sewing (textile processing). The treatment of the fabric with the soil release polymer is to be understood as a kind of impregnation, i.e. the soil release polymer remains on the fiber for several wash cycles.

The most important group of soil release polymers include polyesters or oligoesters based on terephthalic acid / polyoxyalkylene glycols / monomeric glycols. Dirt release polymers from this group have been marketed for several years. The most important sales products include ZELCON (Du Pont), MILEASE T (ICI), ALKARIL QCF / QCJ (Alkaril Inc.) and REPEL-0-TEX (Rhone-Poulenc). Preferred within the formulations claimed in this invention are soil release polymers which can be described by the following empirical empirical formula:

(CAP) _x (E6 / PG) _γ (T) _z (I) _ (DEG) _s (En) _t (CAR) _r

(CAP) represents so-called "capping groups" which close the polymer at the end. The end group closure contributes to the stabilization of the polymers. (CAP) stands for a large number of possible end groups. Preferred end groups include sulfoaroyl groups such as the sulfobenzoyl group, which can be introduced in the form of a transesterification with alkyl sulfobenzoate. The incorporation of end groups on the one hand has a regulating effect on the molecular weight, on the other hand it leads to the stabilization of the polymers obtained. In addition to sulfoaroyl groups, it is also possible to use ethoxylated or propoxylated hydroxyethane and hydroxypropanesulfonates, as described, for example, in WO 95/02029 and WO 95/02030. Preferred end groups are also poly (oxyethylene) monoalkyl ethers in which the alkyl group contains 1 to 30 carbon atoms and the polyoxyethylene group consists of 2-200 oxyethylene units. End groups of this type are described, for example, in WO 92/17523 and DE 4001 415. EP 0 253 567 and EP 0357 280 describe in particular those end-capped polyesters (capped polyesters) which are, on the one hand, by nonionic groups such as, for example, C 1 -C 4 -alkyl, C 1 -C 4 -hydroxyalkyl, C 1 -C 4 -acyl and also by ionic groups Succinate groups are closed. In principle, mixtures of different end groups are also possible, where x assumes values from 0-2.

The group (EG / PG) stands for an oxyethyleneoxy, oxypropyleneoxy group or mixtures thereof, where y assumes numerical values from 0 to 80. As a variation of the above Polyester is also described as introducing branched monomeric glycol building blocks, e.g. 1,2-butylene, 3-methoxy-1,2-propylene glycols (EP 0241 985).

The group (T) is among others for a terephthaloyl group, which acts as an anchor group in the polymer between the soil release polymer and the substrate (fiber). In all of the state-of-the-art dirt release polymers based on oligo- or polyester, the presence of terephthaloyl groups is essential for the performance of this additive. In addition to terephthaloyl groups, aliphatic analogues can also be represented, e.g. Adipates that can be incorporated using adipic acid or adipic acid diesters. DE 4403866 e.g. aphiphile polyester claimed, which contain aromatic as well as aliphatic dicarboxylic acids and are used as detergent additive or soil release polymer. Z assumes values from 1 to 50.

Each (I) represents an internal anionic group with q = 0-30. The incorporation of anionic groups, primarily sulfoisopthaloyl groups, into the polymer backbone turns out to be very advantageous for the performance of the soil release polymer. The sulfoisophthaloyl groups stabilize the polymer and inhibit the transition from the desired amorphous form to the poorly soluble crystalline form of the polymer. In US 4427557 and EP 0 066 944 such anionic modifications of the above polyesters are described which contain the sodium salt of sulfoisophthalic acid as a further polymerization component. The polymerized polyethylene glycols (PEG) have molar masses of 200-1000 and result after their polymerization with ethylene glycol and terephthalic acid polyester with molecular weights from 2000 to 10000.

DEG stands for a di (oxyethylene) oxy group with s = 0 - 80.

Each (en) represents a poly (oxyalkylene) oxy group which is composed of 2 to 100 oxyalkylene groups, where t = 0-25 and the alkyl groups contain 2-6 carbon atoms. In most cases, the poly (oxyalkylene) oxy groups are poly (oxyethylene) oxy groups, although the molecular weights can vary considerably. In addition to poly (oxyethylene) oxy groups, poly (oxypropylene) oxy groups and all conceivable mixtures can also be represented. DE 14 69 403 e.g. describes a method for the surface-changing treatment of articles derived from polyesters. The polyesters produced are made up of ET units with ET: P0ET = 2-6: 1, with polyethylene glycols with molecular weights of 1000-4000 being used. US 3959230 claims ET / POET polyester with ET: POET = 25: 75-35: 65, low molecular weight polyethylene glycols with molecular weights of 300-700 being used and the polyesters obtained having molecular weights of 25000-55000.

Each (CAR) stands for a carbonyl group (C = 0) of a carbonate unit, where r stands for a number from 0 to 80. It can be seen that the incorporation of carbonate groups in the form of carbonic acid esters into the polymer structure can further increase the performance of the soil release polymers. On the one hand, polymers of this type can be dispersed more easily, and on the other hand, it is possible to obtain flowable, pumpable polymers with the aid of carbonic acid esters, which has clear advantages with regard to the usually customary packaging. The soil release polymers based on poly or oligoester described by the empirical empirical formula above have molecular weights between 200 and 100,000. Mostly preferred are molecular weights in the range from 500 to 25,000.

In addition to this class of soil release polymers, cellulose derivatives can also be used in the formulations claimed. Such products are commercially available, for example, as hydroxyethers of cellulose under the product name METH0CEL (Dow). Cellulose derivatives with C 1 -C 4 -alkyl and C 4 -hydroxyalkyl celluloses (US Pat. No. 4,000,093) are preferred. Another group of soil release polymers can also Poly (vinyl ester) compounds are used. Graft polymers of polyvinyl acetate and polyoxyethylene glycol are particularly preferred. Products of this type are commercially available, such as SOKALAN HP 22 (BASF). If dirt release polymers are used in the formulations according to the invention, the content is 0.01 to 10.0% by weight.

A content of 0.1 to 5% by weight, based on the corresponding formulation, is preferred.

f) Chelating Agents: In the formulations according to the invention, iron and manganese ions are optionally also complexing with chelation

Contain agents that belong to the group of aminocarboxylates, aminophosphonates, polyfunctionalized aromatics (e.g. dihydroxybenzenesulfonic acid derivatives). Mixtures of the various chelating agents are also effective. A preferred biodegradable chelating agent is ethylenediamine disuccinate. The above-mentioned agents are used in proportions of 0.1 to 10%, particularly preferably 0.1 to 3.0%, of the detergent formulation.

g) Components for removing clay or loam dirt and preventing reuse: For this purpose, the formulations according to the invention can contain alkoxylated, preferably ethoxylated, amines, regardless of whether they are mono-, oligo- or polymeric amines. The amount used for solid formulations is 0.01 to 10%, for liquid formulations 0.01 to 5% of the total formulation. Other groups of compounds which have these properties are cationic compounds (EP 0 111 984), zwitterionic polymers (EP 0 112 592) or carboxymethyl cellulose, which are likewise capable of increasing the dirt-carrying capacity of a washing liquor.

h) Polymeric dispersion aids (cobuilders): These additives are used in amounts of 0.1 to 7.0% of the total formulation according to the invention, which are polycarboxylates or polyethylene glycols which both enhance the action of the builder used and also incrustations and resurfacing Prevent use and play a role in the detachment of particles of dirt. The compounds which can be used here are obtained by polymerization or copolymerization of suitable unsaturated carboxylic acid or carboxylic anhydride monomers. Polyacrylates, but also maleic anhydride / acrylic acid copolymers are preferred here. moves. The molecular weights of the former range from 2,000 to 10,000, preferably 4,000 to 7,000 and particularly preferably in the range from 4,000 to 5,000. Suitable copolymers have molecular weights of 2,000 to 100,000, preferably 5,000 to 75,000 and particularly preferably 7,000 to 65000 on. Polyethylene glycols which can be used have molecular weights in the range from 500 to 100,000, particularly preferably from 1,500 to 10,000. Polyasparagates and glutamates can also be used together with zeolite builders, the polyasparagates that can be used having average molecular weights of approximately 10,000.

i) Optical brighteners: All optical brighteners known from the prior art can be used in the formulations according to the invention. They are incorporated at 0.05 to 1.2%, based on the total formulation. Some non-limiting examples of suitable connecting groups are mentioned below: stilbene derivatives, pyrazolines, coumarin, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxide, azoles and 5- and 6-membered heterocycles.

j) Foam inhibitors: Depending on the precise composition (i.e. foaming power of the surfactants used) and the type of foam inhibitor, 0 to 5% (based on the total formulation) of these must be used. Monofatty acid salts are used in an amount of 0 to 5%, but preferably 0.5 to 3%, silicones are used in an amount of up to 2, preferably however 0.01 to 1% and particularly preferably from 0.25 to 0 , 5% used. The compounds which can be used as foam inhibitors in the formulations according to the invention include monofatty acids and their salts with carbon chain lengths of 10 to 24, preferably 12 to 18, carbon atoms. High molecular weight non-surface-active compounds such as paraffins, fatty acid esters (eg triglycerides), aliphatic ketones, N-alkylated amino triazines or di- to tetraalkyldiaminochlorotriazines, monostearyl phosphates and monostearyl alcohol phosphate esters can also be used. Silicones can also be used as foam inhibitors in the present formulation, as can mixtures of silicones and silane-modified silicates. I. a. polyalkylene glycols can be used as solvents here.

k) Fabric softener: Various fabric softeners that can be used in the washing process can be used here, but especially Smectit-Tone and other softening clays in amounts between 0.5 and 10% (based on the total formulation). The above plasticizers can be used in combination with other plasticizers such as amines and the popular cationic plasticizers.

1) Surfactants: In addition to the anionic gemini surfactants of the formula (I) (see also DE 19505367 and 19633497), combinations or individual surfactants mentioned below can be combined with the gemini surfactants in the formulations according to the invention. 0.1 to 70% of these surfactants are used: without restricting the formulations, examples of nonionic surfactants include fatty acid glycerides, fatty acid polyglycerides, fatty acid esters, alkoxylates of higher alcohols, alkoxylated fatty acid glycerides, polyoxyethyleneoxypropylene glycol fatty acid esters, polyoxyethylene sorboxy fatty acid fatty acid esters, polyoxyethylene sorboxy fatty acid fatty acid esters or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, derivatives of alkanolamines, alkylamine oxides, derivatives of protein hydrolyzates, hydroxy mixed ethers, alkylpolyglycosides and alkylgluca ide (e.g. N-methylalkylglucamides) and non-ionic, non-ionic mixture Surfactants (as described in WO 95/19951 (polyhydroxyamine compounds), WO 95/19953, WO 95/19954 and WO 95/19955 and WO 95/20026).

Examples of anionic surfactants that can be used for combinations include soaps, ether carboxylic acids and their salts, alkyl sulfonates, α-olefin sulfonates, sulfo fatty acid derivatives (including those described in WO 93/25646), sulfonates of higher fatty acid esters, higher alcohol sulfates (primary and secondary), alcohol ether sulfates, hydroxy mixed ether sulfates, sulfates of alkoxylated carboxylic acid alkanols, salts of phosphate esters, taurides, isethionates, linear alkylbenzenesulfonates, bridged alkylbenzenesulfonates (such as DOWFAX types from Dow), alkylarylsulfonate derivatives and sulfates of polyacids Acylamino acids, alkyl ether carboxylic acids, alkyl and dialkyl sulfosuccinates, alkenyl sulfosuccinates, alkyl or alkenyl sarcosinates and sulfated glyceryl alkyl ethers. Examples of common cationic surfactants that can be used for combinations include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, imidazolini derivatives, alkylpyridinium salts, quaternized fatty acid esters of alkanolamines, alkyl isoquinolinium salts, benzethonium chlorides and cationic acylamino acid derivatives. Examples of surface-active substances, A pholytes and betaines that can be used for combinations are carbobetaines, such as. B. cocoacylamido propyldimethylbetaine, acylamidopentanediethylbetaine, dimethylammoniohexanoate acylamidopropane (or -ethane) dimethyl (or - diethyl-) betaine - all with C chain lengths between 10 and 18, sulfobetaines, I idazoline derivatives, soybean lipids and lecithin. The amine-N-oxides mentioned above can also be in polymeric form, a ratio of amine to amine-N-oxide of 10: 1 to 1: 1,000,000 being required. The average molecular weight is 500 to 1 000 000, but particularly preferably 5 000 to 100 000.

m) Additional components can be incorporated into the washing, cleaning or personal care formulations. These are carriers, hydrotropes, processing aids, dyes or pigments, perfumes, solvents for liquid formulations (alcohols with 1 to 6 carbon atoms and 1 to 6 hydroxyl groups are particularly preferred), solid fillers for bar soap formulations, pearlescent agents, e.g. B. distearoylglycerides, preservatives, buffering systems and so on. Should a higher foaming power of the formulation such. B. may be required in some personal care products, this can e.g. B. by the addition of C ₁₀ -C ₁₆ alkanolamides (in concentrations of 1 to 10% of the total formulation). Other water-soluble magnesium salts can also be added in amounts of 0.1 to 2% to increase the foaming power and the fat-dissolving power.

If necessary, some of the above-mentioned surfactant components can also be stabilized by adsorption on porous hydrophobic substances and sealed into the formulation with a further hydrophobic layer.

The formulations of the invention can be used in a wide variety of ways, such as. B. as a skin cleaner, bath additive, shower bath, denture cleaner, shampoo and care product, shaving soap, pre-shaving, disinfectant, dispersant, universal detergent and mild detergent, both in liquid form and as a powder or granulate, for textiles, hand and Dishwasher detergents, household cleaners and industrial cleaners. Examples

The following examples, which are not intended to restrict the claims, show the positive application properties of the gemini surfactants of the formula (I), which they have for use in the abovementioned. Predestine uses.

I. Cleaning hard surfaces

To determine the cleaning effect on hard surfaces, 7

Carrier strips made of hard PVC (455 x 39 x 2.5 mm) placed close together. A white PVC film (400 x 400 mm) was applied without bubbles on one side of the carrier strips. Then templates made of PVC (300 x 350 x 3 mm) with 260 x 280 mm cut-out were placed on the film so that the cut-out was over the center of the film. 2 g of test dirt (7% by weight special black 4, Degussa, 17% by weight Myritol 318, Henkel, 40% by weight process oil 310, Esso, 36% by weight, Exxon DSP 80/100, Exxon) distributed on the film using a flat brush. The carrier strips were separated with a knife. One test strip each was then placed in the metal guide rail of a Dardner washability and abrasion tester (model M-105-A, Erichsen) and with a damp sponge, which was placed in a sled, with 16 ml of the surfactant-containing formulations to be examined (Surfactant content: 1 wt .-%) cleaned. This was done by moving the carriage back and forth ten times. After the test strips had dried, the PVC film was detached from the carrier strip and stuck on white cardboard with the cleaned side up. The cleaning performance of the respective surfactant-containing formulations was determined spectrophotometrically with the aid of a "datacolor 3890" spectrophotometer at a wavelength of 560 nm relative to a white standard (= 100%) and a soiled standard (= 0 H).

Example 1 (not according to the invention):

The cleaning performance of a standard all-purpose cleaner was determined to be 65% as the standard formulation.

Examples 2 to 4 (According to the Invention): The cleaning performance of the anionic gemini surfactants according to the invention was determined using the following recipe:

anionic gemini surfactant: 3.0% by weight C ₁₃ alcohol with 8 E0 *: 1.0% by weight

Coconut fatty acid sodium salt: 0.25% by weight

Balance to 100 wt .-% water

*) MARLIPAL 013/80 (Hüls AG)

The following anionic gemini surfactants were examined:

1: According to formula (I), with R ¹ = R ³ = C ₈ alkyl, R ² = - (CH ₂ ) ₂ -, A = B = -0-, M, M '= Na, n = 1

2: According to formula (I), with R ¹ = R ³ = iso-C ₈ alkyl, R ² = - (CH ₂ ) ₂ -, A = B = -0-, M, M '= Na, n = 1

3: According to formula (I), with R ¹ = R ³ = C ₁₀ alkyl, R ² = - (CH ₂ ) ₆ -, A = B = -0-, M, M '= Na, n = 1

Example 2:

The cleaning performance of the formulation containing compound 1 was determined to be 73% and is therefore higher than that mentioned in Example 1.

Example 3:

The cleaning performance of the formulation containing compound 2 was determined to be 80% and is therefore higher than that mentioned in Example 1.

Example 4:

The cleaning performance of compound 3 was determined to be 72% and is therefore higher than that mentioned in example 1.

B) Washability on textiles

To determine the washability of textiles, the washing drum of a standard household washing machine was loaded with 4 kg (for the 95 ° and 60 ° C wash) or with 1 kg (for the 30 ° C wash) of soiled cotton balast fabric. Furthermore, test lobes of the WFK test fabric (laundry research, now Research Institute for Cleaning Technology eV, Krefeld) treated with skin fat pigment soiling were applied to a white cotton towel with the test soiled side up. sews. The cotton towel thus prepared was added to the ballast fabric in the drum of the household washing machine.

The following WFK test fabrics were used:

Cotton (BW): 10 D

Cotton-polyester blend (MG): 20 D Polyester (PE): 30 D

The washability of the anionic gemini surfactants according to the invention was determined using the following formulation of a liquid heavy-duty detergent formulation:

Anionic gemini surfactant 13.0% by weight

C _12/14 alcohol with 7 E0 ^{* 1} 15.5% by weight

K0H, 50% 3.9% by weight

Coconut fatty acid 10.0% by weight

Triethanolamine 5.0% by weight 1,2-propylene glycol 3.0% by weight

Ethanol 8.0% by weight

Dequest 2060 S ^{* 2} 1.5% by weight

Balance to 100 wt .-% water

* 1 Marlipal 24/70 * ¹ (Hüls company)

* 2 Diethylenetriamine-penta- (meth.phosph.acid) (Monsanto)

The amount of liquid heavy-duty detergent used was 25 g per wash. After washing, the WFK test fabrics were dried.

The detergency was determined spectrophotometrically by determining the remission using the datacolor 3890 spectrophotometer (white standard: 100% remission, test soiled tissue: 0% remission).

The following anionic gemini surfactants were examined:

4: According to formula (I), with R ¹ = R ³ = C _12/14 alkyl, R ² = - (CH ₂ ) ₆ -, A = B = - (C ₂ H ₄ 0) ₃ -, M, M '= Na, n = 1 5: According to formula (I), with R ¹ = R ³ = C _8/10 alkyl, R ² = - (CH ₂ ) ₆ -, A = B = -0-, M, M '= Na, n = 1

In order to be able to better assess the washing ability, the commonly used Marlon PS (sec-alkanesulfonate sodium salt, Hüls AG) was used in the same concentration in the above concentration instead of the gemini surfactants. Recipe used.

Example 5:

Remission values found in%

PE MG MG BW BW used in the recipe

30 ° C 30 ° C 60 ° C 60 ° C 95 ° C surfactant

Marlon PS (not according to the invention) 49 44 30 24 25

4 60 46 32 31 33

5 55 49 32 31 42

It can be seen that 4 and 5 have the same or significantly better reflectance values than Marlon PS.

Claims

Claims:

1. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I as a constituent of detergents, cleaners and personal care products

(I)

Dei R ¹ and R ³ uunnaabbhhäännggiigg from each other is an unbranched or branched, saturated or unsaturated hydrocarbon radical having 1 to 22 carbon atoms, R represents a spacer which consists of an unbranched or branched, saturated or unsaturated chain having 2 to 100 carbon and 0 to There are 20 oxygen and / or 0 to 20 nitrogen and / or 0 to 4 sulfur and / or 0 to 3 phosphorus atoms which have 0 to 20 functional side groups and / or 0 to 4 cycles which are isolated or fused, wearing,

A and B independently of one another -0-, -0 (C ₂ H ₄ 0) _α (C ₃ H ₆ θ) ß - (with α and ß = 0 to 20), -NH-, -NR ⁴ - (with R ⁴ = methyl, ethyl, propyl, butyl or

Methoxyethyl, methoxypropyl, ethoxypropyl), -N (R ⁵ ) -0 (C ₂ H ₄ 0) _α (C ₃ H ₆ 0) ß-

(it α and ß = 0 to 20 and R equals R or equals - 0 (C ₂ H 0) _α (C ₃ H ₆ 0) ß- H with the aforementioned conditions) or -

C (0) N (R ⁵ ) -0 (C ₂ H ₄ 0) _α (C ₃ H ₆ 0) _ß - (with α, ß and R ⁵ as in the abovementioned compounds),

M and M 'is alkali, ammonium, alkanolammonium or alkaline earth and the degree of substitution n is 1 to 200, preferably 1 to 10.

2. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to claim 1, characterized in that the hydrocarbon radicals R 1 and R 3 independently of one another for an unbranched or branched, saturated or unsaturated

Hydrocarbon radical having 8 to 18 carbon atoms.

3. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to claim 1 or 2, characterized in that the gemini compounds with the same basic structure are mixtures of homologues with lipophilic hydrocarbon radicals of different lengths.

4. Use of at least 0.1 wt .-% amphiphilic compounds of general formula I according to any one of the preceding claims, characterized in that the Gemini compounds with the same basic structure mixtures of

2 are homologs with spacers R of different lengths.

5. Use of at least 0.1 wt .-% surfactant Geminiverbin- fertilizers of general formula I according to at least one of the preceding claims, characterized in that further anionic, nonionic, cationic, betaine and / or amphoteric surface-active compounds are contained.

6. Use of at least 0.1 wt .-% amphiphilic compounds of general formula I according to at least one of the preceding claims, characterized in that as nonionic surface-active compounds fatty acid glycerides, fatty acid polyglycerides, fatty acid esters, alkoxylates of C ₆ -C ₃₀ alcohols, alkoxylated Fatty acid glycerides, polyoxyethylene oxypropylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, derivatives of alkyl amines, alkyl amine and benzyl glucide ionides, alkyl amine glucides, benzyl glucides their mixtures are used.

Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to at least one of the preceding claims, characterized in that the anionic surface-active compounds are soaps, ether carboxylic acids and their salts, alkyl sulfonates, alpha-olefin sulfonates, alpha sulfofatty acid derivatives, sulfonates of higher fatty acid esters, higher primary and secondary alcohol sulfates, alcohol ether sulfates, hydroxymixed ether sulfates, sulfates of alkoxylated carboxylic acid alkanolamides of amides Phosphate esters, taurides, isethionates, linear alkylbenzenesulfonates, bridged alkylbenzenesulfonates, alkyl arylsulfonates, sulfates of polyoxyethylene fatty acid amides and derivatives of acylamino acids, alkyl ether carboxylic acids, alkyl and dialkyl sulfosuccinates, alkyl or alkenyl arkate etherates and / or mixtures thereof and / are used.

8. Use of at least 0.1 wt .-% amphiphilic compounds of general formula I according to at least one of the preceding claims, characterized in that as cationic surface-active compounds AI kyltrimethyl ammonium salts, dialkyldimethylammonium salts, AI yldimethylbenzylammoniumsalze, imidazolinium derivatives, alkylpyridinium salts, quaternized fatty acid of AI kanolamines, alkylisoquinoline salts, benzethonium chlorides and / or cationic acylamino acid derivatives are used.

9. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to at least one of the preceding claims, characterized in that cocosacylamidopropylbetaine, acylamidopentanediethylbetaine, dimethylammoniohexanoate-acylamidopropane (or -ethane) as surface-active betaines and ampholytes dimethyl (or diethyl) betaine with carbon chain lengths of 10 to 18 carbon atoms, sulfobetaines, imidazoline derivatives, soybean oil lipids and / or lecithin can be used.

10. Use of at least 0.1 wt .-% amphiphilic compounds of general formula I according to at least one of the preceding claims for cleaning textiles.

11. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to at least one of the preceding claims for cleaning hard surfaces, in particular as a manual detergent.

12. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to at least one of the preceding claims for cleaning skin and hair.

13. Use of at least 0.1% by weight of amphiphilic compounds of the general formula I according to at least one of the preceding claims as a constituent of personal care products.