DE19715836C1 - Liquid detergent for fine laundry - Google Patents

Abstract

Liquid fine laundry agent in micro-emulsion form contains: (a) 5-7 wt.% ester-quaternary; (b) 7-10 wt.% alkyl-benzene-sulphonates; and (c) 4-8 wt.% alk(en)yl-oligo-glycosides, balance being water and optionally other usual additives.

Description

Field of the Invention

The invention relates to liquid mild detergents in the form of microemulsions with a defined Content of ester quats, alkylbenzenesulfonates and alk (en) yl oligoglycosides.

State of the art

When using detergents, it is usually between liquid and powder or granulated products as well as those for universal use or the treatment of sensitive different textiles ("mild detergents"). Therefore, for this purpose, as a rule "Mild" surfactants are used, ie surface-active substances that are also effective against human beings Skin are not very aggressive. For example, in the international patent application WO 87/02050 (Henkel Corp.) mild detergent containing alkyl polyglucosides proposed. Aqueous detergent mixtures with alkyl oligoglucosides and ester quats and their use for Production of detergents are known from international patent application WO 94/06899 (Henkel) known. Powdered washing powder containing alkyl polyglucosides and alkylbenzenesul The exhibits are the subject of the two publications EP 0070070 B1 (Procter & Gamble) and EP 0554943 A2 (Unilever). Furthermore, from GB-A 2292155 (Procter & Gamble) Powdered hand washing detergent containing anionic and cationic surfactants as well Fatty acid N-alkyl polyhydroxyalkylamides are known.

A problem with the formulation of liquid mild detergents is to remove preparations windings that can not only be satisfactorily assessed from an application technology perspective, al so remove the dirt without attacking sensitive tissue and at the same time the tissue to give a pleasant soft feel and the electrostatic charge between the fibers reduce, but also as microemulsions are sufficiently viscous and stable in storage, so that Even when exposed to temperature for several months, neither the viscosity collapses nor ent  mixture entry. The object of the present invention was to provide microemulsions to provide this complex requirement profile.

Description of the invention

The invention relates to liquid mild detergents in microemulsion form containing

• (a) 5 to 7, preferably 5 to 6% by weight of ester quats,
• (b) 7 to 10, preferably 7 to 8 wt .-% alkylbenzenesulfonates and
• (c) 4 to 8, preferably 5 to 6 wt .-% alkyl and / or alkenyl oligoglycosides

with the proviso that the quantities indicated with water and possibly other usual Add auxiliaries and additives to 100% by weight.

It has surprisingly been found that the mixtures according to the invention are microemulsions form, have excellent washing and cleaning properties and thus treated Fabrics, especially sensitive textiles such as wool sweaters and the like, not only give it a pleasant soft feel, but also the electrostatic charge lower between the fibers. Another particular advantage is that the microemulsions are sufficiently viscous and can be stored for months, even when exposed to high temperatures, without segregate or decrease in viscosity and it despite the combination of an ionic and cationic surfactants do not salt formation.

Esterquats

The term "esterquats" (component a) generally means quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this context, reference is made to the international patent application WO 91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. German patent DE 43 08 794 C1 (Henkel) also discloses a process for the preparation of solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic are, for example, by R. Puchta et al. in tens. Surf. Det., 30, 186 (1993), M.Brock in Tens. Surf. Det. 30, 394 (1993), R. Lagerman et al. in J. Am. Oil. Chem. Soc., 71, 97 (1994) and I. Shapiro in Cosm. Toil. 109, 77 (1994). The quaternized fatty acid triethanolamine ester salts follow the formula (I)

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the sense of the inven tion are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures how they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids and C _16/18 fatty acid cuts rich in elaidic acid are preferably used. To prepare the quaternized esters, the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40) from. From an application point of view, quaternized fatty acid triethanol amine ester salts of the formula (I) have proven to be particularly advantageous in which R ¹ CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p are 0 and X is methyl sulfate. In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples mentioned for (I) also apply to the esterquats of the formulas (II) and (III). The esterquats usually come on the market in the form of 50 to 90% strength by weight alcoholic solutions, which can be diluted with water if required.

Alkylbenzenesulfonates

Alkylbenzenesulfonates which form component (b) are known anionic surfactants which can be obtained on an industrial scale by Friedel-Crafts alkylation of benzene with suitable olefins, core sulfonation of the alkylaromatics formed with gaseous sulfur trioxide and neutralization of the resulting sulfonic acids. The alkylbenzenesulfonates of the formula (IV) usually follow,

R ⁸ -Ph-SO ₃ X (IV)

in which R ^{8 is} a linear or branched alkyl radical having 10 to 16 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are dodecylbenzene sulfonate and tetradecylbenzene sulfonate in the form of their sodium salts.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides which form component (c) are known nonionic surfactants which follow the formula (V)

R ⁹ O- [G] _p (V)

in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry, for example by acid-catalyzed acetalization of glucose with fatty alcohols. The alkyl and / or alkenyl oligo glycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (V) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, as described above, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Fatty alcohol polyglycol ether

In a particular embodiment of the present invention, the compositions furthermore contain nonionic surfactants of the fatty alcohol polyglycol ether type, which follow the formula (VI),

R ¹⁰ O (CH ₂ CH ₂ O) _q H (VI)

in which R ^{10 represents} an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and q represents numbers from 1 to 10. Typical examples are addition products of an average of 1 to 10 and preferably 2 to 7 mol of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethyl hexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, petal alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, Emcyl alcohol and brassidyl alcohol and their technical mixtures, the z. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roe len's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Addition products of 3 to 5 moles of ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms such as, for example, coconut, palm, palm kernel or tallow fatty alcohol are preferred.

Other auxiliaries and additives

In addition to the surfactants mentioned, the agents can include other typical ingredients, for example Builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, thickeners, soil repel lants, foam inhibitors, solubilizers, inorganic salts and fragrances and dyes.

Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids. Among the compounds used as peroxy bleaching agents, sodium perborate tetrahydrate and sodium per borate monohydrate are of particular importance. Other bleaching agents are, for example, peroxycarbonate, citrate perhydrates and H ₂ O ₂ -producing peracid salts of peracids such as perbenzoates, peroxy phthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. As a thickening agent, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum , Magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably between 50,000 and 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight. Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. In addition to mono- and polyfunctional alcohols and phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes.

Examples

The nature of various test products was determined immediately after manufacture as well as after Storage assessed. In the line "microemulsion" (+) means that the mixture as a micro emulsion was present, (-) that no microemulsion was formed. The following line is the stability specified after storage; (+) stands for stable, (-) for separated. The viscosity of the preparations was reduced immediately after production using the Brookfield method in an RVT viscometer (20 ° C, Spindle 1.10 rpm). Then cotton fabric (test stain: Sebum) was in a household washing machine with a capacity of 50 l with the preparations Washed 40 ° C (amount used 1 g / l) and the whiteness photometrically against a standard certainly. The soft grip was subjective by a panel of experienced people on a scale of (1) = soft to (4) = hard valued. The compositions and results are shown in Table 1 together quantified. Examples 1 to 5 are according to the invention, experiments V1 to V4 are used for comparison.

Composition and performance of liquid detergents

Composition and performance of liquid detergents

The examples and comparative examples show that only within the specified narrow concentration stable microemulsions of sufficiently high viscosity are obtained, the same have a high washability at an early stage and the fabrics have a pleasant soft feel to lend.

Claims (7)

1. Containing liquid mild detergent in microemulsion form

• (a) 5 to 7% by weight of ester quats,
• (b) 7 to 10% by weight alkylbenzenesulfonates and
• (c) 4 to 8% by weight of alkyl and / or alkenyl oligoglycosides

with the proviso that the amounts given with water and, if appropriate, other conventional auxiliaries and additives are 100% by weight. 2. Composition according to claim 1, characterized in that they contain esterquats of the formula (I),
in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. 3. Composition according to claims 1 and 2, characterized in that they contain ester quats of the formula (II),
in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. 4. Compositions according to claims 1 to 3, characterized in that they contain ester quats of the formula (III),
in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. 5. Compositions according to claims 1 to 4, characterized in that they contain alkylbenzenesulfonates of the formula (IV),
R ⁸ -Ph-SO ₃ X (IV)
in which R ^{8 is} a linear or branched alkyl radical having 10 to 16 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolamine or glucammonium. 6. Composition according to claims 1 to 5, characterized in that they contain alkyl and alkenyl oligogly side of the formula (V),
R ⁹ O- [G] _p (V)
in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. 7. Compositions according to claims 1 to 6, characterized in that they further contain 1 to 10, preferably 3 to 5% by weight of fatty alcohol polyglycol ether of the formula (VI),
R ¹⁰ O (CH ₂ CH ₂ O) _q H (VI)
in which R ^{10 represents} an alkyl and / or alkenyl radical having 6 to 22 carbon atoms and q represents numbers from 1 to 10.