WO1994012602A1

WO1994012602A1 - Viscous aqueous tenside preparations

Info

Publication number: WO1994012602A1
Application number: PCT/EP1993/002962
Authority: WO
Inventors: Dieter Nickel; Rainer Hofmann; Hermann Hensen; Claudia Panzer
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-11-26
Filing date: 1993-10-26
Publication date: 1994-06-09
Also published as: DE4239677A1; EP0670878A1; JPH08503719A

Abstract

For low-concentration aqueous preparations (containing) 2 to 20 wt. % of an alkyl glycoside of the formula R1-O(G)n, in which R1 is an alkyl radical with 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10, the handlability in the conditions of use is to be facilitated and the formulation is to contain the smallest possible quantities of a non-alkyl glycosidic active substance. This is essentially achieved by the viscosity increasing addition of 0.05 to 8 wt. % of a cationic tenside of the formula R2-N(R3)3X, in which R2 is an alkyl or alkenyl residue with 10 to 22 C atoms and up to 3 C-C double bonds, R3 is an alkyl radical with 1 to 3 C atoms and X is an anion, and/or an amphotenside of the formula R4(R5)2N-(CH2)n-Y in which R4 is hydrogen or an alkyl or hydroxyalkyl residue with 1 to 3 C atoms, R5 is an alkyl radical with 1 to 3 C atoms or part (R5)2N is a possibly C-alkylised imidazoline residue, n is a number from 1 to 22 and Y is a carboxylate or sulphonate group, whereby the ratio by weight of alkyl glycoside to thickener is 35:1 to 1:1.

Description

"Viscous aqueous surfactant preparations"

The invention relates to low-concentration and highly viscous aqueous surfactant preparations which contain alkyl glycosides and certain amphoteric surfactants and / or cationic surfactants, a process for their preparation and the use of such preparations as detergents or cleaning agents.

It has long been known that alkyl glycosides with long-chain alkyl groups belong to the nonionic surfactants. The person skilled in the art also knows, for example in A.M. Schwartz, J.W. Perry, Surface Active Agents, Vol. I, Interscience Publishers, 1949, page 372, describe that surfactant mixtures generally have synergistic effects and often have better cleaning properties than would result from the sum of the values of the individual components .

Aqueous liquid detergents which contain alkyl glycosides and 12 to 30% of a surface-active betaine in combination with a customary anionic surfactant are described in European patent application EP 341 071. Liquid detergents which contain water, 1 to 50% by weight of an organic solvent and 5 to 50% by weight of a mixture of alkyl glycoside and anionic surfactant or optionally zwitterionic surfactant in a weight ratio of 1:10 to 10: 1 known from European patent application EP 070 074. Furthermore, from European patent application EP 094 118 detergents are known which contain alkyl glycosides together with optionally further nonionic surfactants and cationic surfactants in a weight ratio of 2: 1 to 12: 1. From the international patent application WO 87/2050, builder-free mild detergents are known which contain 30-90% by weight of water and 10-70% by weight of a mixture of alkyl glycosides and antistatic quaternary ammonium compounds in a weight ratio of 1: 3 to 10: 1. There, the antistatic effectiveness of the ammonium compounds is enhanced by the presence of the alkyl glycosides. In international patent application WO 86/5509 there are liquid disinfectants which contain 10 to 99.98% by weight of water and also germicidal quaternary Containing ammonium halides and alkyl glycosides in weight ratios of at least 0.65: 1.

The detergent or cleaning agent precursors based on alkyl glycoside mentioned in these documents are relatively highly concentrated aqueous solutions or pastes, since the components intended for mixing into finished agents should have the highest possible active substance content. At the same time, they must be easy to handle, which means that they should have the lowest possible viscosity, flow and be easy to pump. In contrast, aqueous liquid products used by the consumer, which include in particular liquid detergents, dishwashing detergents and universal cleaners, but also cosmetic products, for example hair shampoos or body cleaning lotions, are subject to a certain minimum viscosity, although the active substance content of such products is generally relative is low. Such products therefore normally contain thickeners, which generally have the disadvantage of not contributing to the cleaning performance of the surfactant component contained in the agents themselves. Typical thickeners are inorganic water-soluble salts, in particular sodium chloride, and salts of non-surface-active aromatic sulfonic acids, for example sodium cumene sulfonate.

Organic thickeners are usually fatty acid alkanolamides, such as coconut fatty acid monoethanolamide, lauric acid monoethanol amide, oleic acid diethanolamide and coconut fatty acid diethanolamide, polyethylene glycol difatty acid esters and a number of water-soluble polymers.

In most cases it is not possible, or only with the use of a large concentration, to build up the desired viscosity in the surfactant solution solely by using inorganic salts. It is therefore generally necessary to use organic thickeners in addition to the inorganic salts, which have a number of disadvantages. For example, solutions thickened with polyethylene glycol fatty acid diesters often have inadequate viscosity stability during storage, while water-soluble polymers often dissolve only with difficulty and cause undesirable flow behavior. In European patent application EP 306843 it is proposed to use adducts of ethylene oxide and / or propylene oxide with unsaturated fatty alcohols to thicken surfactant solutions. These products no longer have the disadvantages mentioned above; However, there is still a need for thickeners with comparable properties with an increased thickening effect. For a given thickener content, this would enable the production of systems with higher viscosity as well as a reduction in the thickener content for a given viscosity.

It is known from international patent application WO 91/04313 that the viscosity of agents which contain anionic and / or amphoteric surfactants is reduced by adding a combination of alkyl glycoside and alkali chloride. The content of alkali metal chloride should be kept as low as possible so that the main viscosity reduction is due to the alkyl glycoside.

Surprisingly, it has now been found that, in deviation from this finding, in aqueous solutions with relatively low alkyl glycoside concentrations, the addition of certain a photic and / or cationic surfactants results in a strongly pronounced viscosity maximum and a storage-stable, liquid, flowable alkyl glycoside preparation on an aqueous basis can be obtained which, due to its relatively high viscosity at a relatively low concentration, is easy to handle under conditions of use and contains the smallest possible amounts of non-surfactant active substance if alkyl glycoside and certain amphoteric or cationic surfactant are mixed in certain proportions.

The surfactant preparations according to the invention are accordingly gel-like aqueous

Mixtures that consist essentially of

2% by weight to 20% by weight of an alkyl glycoside of the formula I,

^ OCGJn (I)

in which R * is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10, 0.05% by weight to 6% by weight of a thickener in the form of a cationic surfactant of the formula II,

R2-N (R3) ₃ X (II)

in which R2 is an alkyl or alkenyl radical with 10 to 22 carbon atoms and up to 3 CC double bonds, R ^ is an alkyl radical with 1 to 3 carbon atoms and X is an anion, preferably a halide anion, and / or an amphoteric surfactant of the formula III,

R4 (R5) ₂ N- (CH ₂ ) _n -Y (III)

in which R ^{4 is} hydrogen or an alkyl or hydroxyalkyl radical with 1 to

3 carbon atoms, R ^ is an alkyl radical having 1 to 3 carbon atoms or the part (R ^ N is an optionally C-alkylated imidazoline radical, n is a number from 1 to

22 and Y represent a carboxylate or sulfonate group, the weight ratio of alkyl glycoside according to formula I to thickener being 35: 1 to 1: 1, preferably 15: 1 to 8: 1, and to 100% by weight of water or a mixture consist of water with a water-miscible organic solvent.

In the context of the present invention, gel-like preparations are understood to mean structured, isotropic, viscoelastic solutions with a visco-elastic network structure which is composed of rod micelles. They preferably have a viscosity, measured at a temperature in the range from 20 ° C. to 25 ° C. at a shear rate of 30 s "*, from 400 mPa-s to 10000 mPa-s, in particular from 500 mPa-s to 8000 mPa-s, on.

The alkyl glycoside preparations according to the invention preferably contain 3% by weight to 11% by weight, in particular 4% by weight to 8% by weight, of alkyl glycoside according to formula I, 0.075% by weight to 2.5% by weight, in particular 0.1% to 2% by weight of thickener according to formula II and / or III and per 100% by weight of water. Some of the water, in particular not more than 5% by weight, based on the preparation according to the invention, can be mixed with a water-miscible organic solvent, preferably from the group comprising alcohols with 1 to 4 carbon atoms, glycols with 2 to 4 carbon atoms and the di- and triglycols derived therefrom and the corresponding glycol ethers and mixtures of these substances.

Another object of the invention is a process for the preparation of storage-stable, gel-like surfactant preparations on an aqueous basis which have a viscosity in the range of 400 mPa at a temperature in the range from 20 ° C. to 25 ° C. at a shear rate of 30 s ^-1 . s to 10,000 mPa.s by mixing an alkyl glycoside of the formula I which is optionally present in aqueous solution,

R ¹ -0 (G) _n (I)

in which R ^{1 is} an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10, with a thickener in the form of a cationic surfactant of the formula II,

R ² -N (R ³ ) 3X (II)

in which R ^{2 is} an alkyl or alkenyl radical with 10 to 22 C atoms and up to 3 CC double bonds, R ^{3 is} an alkyl radical with 1 to 3 C atoms and X is an anion, preferably a halide anion, and / or an amphoteric surfactant of formula III,

R4 (R5) ₂ N- (CH ₂ ) _n -Y (III)

in which R ^ is hydrogen or an alkyl or hydroxyalkyl radical having 1 to 3 C atoms, R ^ is an alkyl radical with 1 to 3 C atoms or the part (R5) N is an optionally C-alkylated imidazoline radical, n is a number of 1 to 22 and Y represent a carboxylate or sulfonate group, in the weight ratio of alkyl glycoside according to formula I to thickening agent from 35: 1 to 1: 1, and with so much water or a mixture of water with a water-miscible organic solvent that the Total surfactant content in the preparation is 2.2% to 22% by weight. The procedure is preferably such that an aqueous paste which contains alkyl glycoside according to formula I in a concentration of 30% by weight to 60% by weight in such an amount with the cationic and / or a photosidic thickener or whose aqueous solution mixes, that the sum of the surfactants in the resulting aqueous preparation is in the range mentioned and in particular is 2.5% by weight to 10% by weight and the resulting gel is 88% by weight to 97.8 % By weight, in particular 90% by weight to 97.5% by weight of water. In principle, the water can be admixed at any point in the preparation of the agents according to the invention if the starting materials used do not already contain sufficient such solvent. The components are preferably heated to temperatures of 60 ° C. to 80 ° C. and mixed with conventional mixers, which are preferably heatable and are kept during the entire mixing process, in particular at temperatures in the range mentioned.

The alkyl glycosides suitable for the surfactant preparations according to the invention and their preparation are described, for example, in European patent applications EP 92355, EP 301 298, EP 357 969 and EP 362 671 or the US Pat. No. 3547828. The glycoside components ((G) _n in formula I) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose , Allose, Idose, Ribose, Arabinose, Xylose and Lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization (n in formula I) can also take non-integer numerical values as the quantity to be determined analytically; it is generally between 1 and 10, for the alkyl glycosides which are preferably used below 3, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability.

The alkyl part (R * in formula I) of the alkyl glycosides contained in the surfactant preparations according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols. alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used for the preparation of alkyl glycosides which can be used. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octa-decyl radicals and mixtures thereof are particularly useful. Particularly suitable alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R1 = dodecyl and R1 ^ tetradecyl.

The alkyl glycosides can contain small amounts, for example 1 to 2%, of unreacted free fatty alcohol due to the production process, which generally ^" does not have a disadvantageous effect on the properties of the preparations produced therewith.

The cationic surfactants of the formula (II) which can be used in the context of the invention preferably have a long-chain alkyl radical R ² having 10 to 24 C atoms, in particular 12 to 18 C atoms. This can be branched or straight-chain, the linear primary alkyl radicals, in particular the primary decyl, dodecyl, tetradecyl, hexadecyl or _^ octadecyl radicals and mixtures thereof, being preferred. The short-chain radical R ³ is preferably a propyl, ethyl or methyl group, compounds with the latter being particularly preferred. The anion X can be a sulfate, methosulfate or ethosulfate or a halide. It is preferably a chloride or bro id.

The suitable amphoteric surfactants according to formula (III) are derivatives of tertiary or quaternary amines which have at least one straight-chain or branched aliphatic radical, one of which carries a carboxyl or sulfato group. Examples of such amphoteric surfactants are N, N-dimethyl-N-tetradecyl-glycine, N, N-dimethyl-N-hexadecyl-glycine, N, N-dimethyl-N-octadecyl-glycine, 3- (dimethyl-dodecylammonio) -l-propanesulfonate and the amphoteric surfactants sold under the names Dehyton (R) AB, CB and G (manufacturer Hen¬ kel). Preferred, in particular in the case of preparations with higher alkyl glycoside concentrations in the range from 12% by weight to 20% by weight, are the imidazoline derivatives derived formally from aminocarboxylic acids, for example 4-aminobutyric acid or glycine, for example the 2 -Alkyl-N-carboxymethyl-N-hydroxyalkyl-imidazoline betaines, in which the alkyl group has 7 to 18 carbon atoms and the hydroxyalkyl group is a hydroxyethyl or hydroxypropyl group. The betaines obtainable by formal hydrolysis with cleavage of the imidazoline ring, the production of which is described, for example, in European patent application EP 040346, are also amphoteric surfactants which can be used according to the invention. The amphoteric surfactants preferably contain as little as possible, in particular not more than 5% by weight, based on amphoteric surfactant, of inorganic salt. These include the alkali metal chlorides and in particular the alkali metal sulfates. If salt contents in such low amounts are not already obtained during the production of the amphoteric surfactants, the ether sulfate can be reduced to contents not exceeding 5% by weight, in particular from 0.1% by weight to 1, by known methods, for example by recrystallization. 5 parts by weight, based on amphoteric surfactant, of inorganic salt.

The surfactant preparations according to the invention have excellent cleaning properties and high solubility in cold water. They are therefore preferably used as washing, rinsing or cleaning agents and in particular in hair and body care or serve as storage-stable, easy-to-use premixes for the production of such agents. The addition of other constituents customary in such agents, to which in particular builder substances such as zeolites and layered silicates, corrosion inhibitors, bleaching agents, bleach activators, optical brighteners, enzymes, graying inhibitors, antimicrobial active substances, abrasive agents, foam stabilizers, Preservatives, pH regulators, opacifiers and pearlescent agents, colorants and fragrances and additional surfactants are possible among the preparations according to the invention.

Examples

Aqueous mixtures of the mixtures of Ci2 / i4- given in Table 1 (sum of surfactant components 5% by weight), Table 2 (sum of surfactant components 10% by weight) and Table 3 (sum of surfactant components 20% by weight). Alkyl glucoside (degree of oligomerization 1.4) with various thickeners A (N, N, N-trimethyl-N-hexadecylammonium chloride), B (N, N, N-trimethyl-N-hexadecylammonium bromide), C (N, N-dimethyl- N-C8-i8 ^{-am '} ' ^c ' ⁰ P ^ro Py1-ammonium acetobetaine) and D (2-C7_i7-alkyl-N-carboxymethyl-N-hydroxyethyl-imidazoline according to ^" EP 040346) in the specified mixing ratios (alkyl glycoside to thickener) had the following viscosities (25 ° C, measured with a shear stress controlled rotation rheometer Carri-Med ( ^R ) CS 100 at a shear rate of 30 s " ¹ ), whereby the values for equally concentrated thickener-free aqueous solutions are also given for comparison.

Table 1: Properties of 5% by weight preparations (25 ° C)

Thickener Mixing ratio Viscosity [% by weight] [mPa.s]

- 5: 0 320

A 4: 1,400

B 4: 1,800

C 4: 1,700

D 4: 1,500

Table 2: Properties of 10% by weight preparations (25 ° C)

Thickener Mixing ratio Viscosity [% by weight] [mPa.s]

- 10: 0 700

A 4: 1 3100

A 2.4: 1 1100

B 9: 1 1300

B 4: 1 3000

B 2.4: 1 3000

C 9: 1 1600

C 4: 1 3600

D 9: 1 1200

Table 3: Properties of 20% by weight preparations (25 ° C)

Thickener Mixing ratio Viscosity [% by weight] [mPa.s]

- 20: 0 3000

A 1.5: 1 5000

C 9: 1 4000

C 1.5: 1 6500

Da) 1.5: 1 7500

a): contained 4.5% by weight NaCl (based on amphoteric surfactant)

Claims

1. Low-concentration and viscous surfactant preparation in the form of a gel-like aqueous mixture consisting essentially of

2% by weight to 20% by weight of an alkyl glycoside of the formula I,

in which R ^{1 is} an alkyl radical with 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10,

0.05% to 6% by weight of a thickener in the form of a cationic surfactant of the formula II,

R -N (R ³ ) 3X (II)

in which R ^{2 is} an alkyl or alkenyl radical with 10 to 22 C atoms and up to 3 CC double bonds, R ^{3 is} an alkyl radical with 1 to 3 C atoms and X is an anion, and / or an amphoteric surfactant of the formula III,

R4 (R5) ₂ N- (CH ₂ ) _n -Y (III)

in which R ^ is hydrogen or an alkyl or hydroxyalkyl radical having 1 to 3 C atoms, R ^ is an alkyl radical with 1 to 3 C atoms or the part (R5) ₂ N is an optionally C-alkylated imidazoline radical, n is a number from 1 to 22 and Y are a carboxylate or sulfonate group, the weight ratio of alkyl glycoside according to formula I to thickener being 35: 1 to 1: 1, and to 100% by weight of water or a mixture of water with a water-miscible organic solvents.

2. Surfactant preparation according to claim 1, characterized in that the weight ratio of alkyl glycoside according to formula I to thickening agent is 15: 1 to 8: 1.

3. surfactant preparation according to claim 1 or 2, characterized in that it has a viscosity, measured at a temperature in the range of 20 ° C to 25 ° C at a shear rate of 30 s ^{* 1} , from 400 mPa ^* s to 10000 mPa-s, in particular from 500 mPa ^* s to 8000 mPa-s.

4. Surfactant preparation according to one of claims 1 to 3, characterized gekenn¬ characterized in that it 3 wt .-% to 11 wt .-%, in particular 4 wt .-% to 8 wt .-% alkyl glycoside according to formula I, 0.075 wt .-% % to 2.5% by weight, in particular 0.1% to 2% by weight of thickener according to formula II and / or formula III and to 100% by weight of water or a mixture of water with not more than 5% by weight, based on the preparation, of a water-miscible organic solvent.

5. Surfactant preparation according to one of claims 1 to 4, characterized gekenn¬ characterized in that a thickener is used in the form of a cationic surfactant of the formula II, in which R ^{2 is} an alkyl radical having 12 to 18 carbon atoms and R ^{3 is} a methyl radical.

6. Surfactant preparation according to one of claims 1 to 5, characterized gekenn¬ characterized in that a thickener in the form of an A photensids of formula III, in which R ^{4 is} a hydroxyethyl or hydroxypropyl radical, the part (R5) N in a 2-position C7_i8 alkylated imidazoline radical and n is a number from 1 to 3, and / or a betaine obtainable therefrom by formal hydrolysis with cleavage of the imidazoline ring is used.

7. Surfactant preparation according to one of claims 1 to 6, characterized gekenn¬ characterized in that the alkyl glycoside according to formula I has an oligomerization degree n below 3, in particular between 1.2 and 1.4.

8. A process for the preparation of storage-stable, sodium gelför surfactant prepara- directions on an aqueous basis, at a temperature ranging from 20 ° C to 25 ° C and a shear rate of 30 s ^-1, a viscosity in the range from 500 mPa Be¬. s have up to 10,000 mPa.s by mixing an alkyl glycoside of the formula I which is optionally present in aqueous solution, R ¹ -0 (G) _n (I)

in which R ^{1 is} an alkyl radical with 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10, with a thickener in the form of a cationic surfactant of the formula II,

R ² -N (R ³ ) 3X (II)

in which R4 is hydrogen or an alkyl or hydroxyalkyl radical with 1 to 3 C atoms, R ^ is an alkyl radical with 1 to 3 C atoms or part (R5) ₂ N is an optionally C-alkylated imidazoline radical, n is a number of 1 to 22 and Y represent a carboxylate or sulfonate group, in the weight ratio of alkyl glycoside according to formula I to thickener of 35: 1 to 1: 1, and with as much water or a mixture of water with a water-miscible organic solvent, that the total surfactant content in the preparation is 2.2% by weight to 22% by weight.

9. The method according to claim 8, characterized in that an aqueous paste containing alkyl glycoside according to formula I in a concentration of 30 wt .-% to 60 wt .-%, in such an amount with the thickener according to formula II and / or formula II or its aqueous solution mixes that the sum of the surfactants in the resulting aqueous preparation is 2.5% by weight to 10% by weight and the resulting gel is 90% by weight to 97 , 5 wt .-% water contains.

10. Use of a surfactant preparation according to one of claims 1 to 7 as a washing, rinsing, cleaning, hair or body care agent.

11. Use of a surfactant preparation according to one of claims 1 to 7 as a storage-stable, easy-to-handle premix for the production of washing, rinsing, cleaning, hair or body care products.