EP0771346A1

EP0771346A1 - Detergent mixtures with improved washing power

Info

Publication number: EP0771346A1
Application number: EP95943495A
Authority: EP
Inventors: Bernd Fabry
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1994-07-19
Filing date: 1995-07-10
Publication date: 1997-05-07
Anticipated expiration: 2015-07-10
Also published as: DE59507095D1; ES2138762T3; DE4425449A1; WO1996002620A1; EP0771346B1

Abstract

Detergent mixtures that contain (a) fatty acid N-alkylpolyhydroxyalkylamides and (b) sulfosuccinates in a ratio by weight from 80: 20 to 20: 80 are characterised by a strong synergistic washing and foaming power and are suitable for preparing surfactants.

Description

Detergent mixtures with improved cleaning performance

Area «» τ- RT-f-indunσ

The invention relates to detergent mixtures with synergistic enhancement of the cleaning and foaming power, containing fatty acid N-alkylpolyhydroxyalkylamides and sulfosuccinates and their use for the preparation of surface-active agents.

Stand of T «» r; h-n-ilr

Fatty acid-N-alkylpolyhydroxyalkylamides and in particular fatty acid-N-methylglucamides are nonionic surfactants which are used, for example, for the production of hand dishwashing detergents because of their good application profile.

The use of these substances has been the subject of a large number of publications. Their use as a thickener is known, for example, from European patent application EP-AI 0 285 768 (Hüls). French published patent application FR-A 1 580 491 (Henkel) describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic the and optionally described soaps containing fatty acid N-alkyl glucamides as foam regulators.

Subject of the international patent applications WO 92/6153; 6156; 6157; 6158; 6159 and 6160 (Procter & Gamble) are mixtures of fatty acid N-alkylglucamides with anionic surfactants, surfactants with a sulfate and / or sulfonate structure, ether carboxylic acids, ether sulfates, methyl ester sulfonates and nonionic surfactants. The use of these substances in a wide variety of washing, rinsing and cleaning agents is described in international patent applications WO 92/6152; 6154; 6155; 6161; 6162; 6164; 6170; 6171 and 6172 (Procter & Gamble).

In practice, however, it has been shown that the fatty acid N-alkylpolyhydroxyalkylamides, even in combination with other preferably anionic surfactants, have a cleaning and foaming power which are not always satisfactory.

The object of the invention was therefore to provide detergent mixtures based on fatty acid-N-alkylpolyhydroxyalkyl aids, which have improved cleaning and foaming power, without this advantage due to performance losses in other applications-relevant Properties must be paid for. Description of the Erf.τ- "rf» "q

The invention relates to detergent mixtures with improved cleaning performance, containing

(a) Fatty acid N-alkyl polyhydroxyalkylamides and

(b) sulfosuccinates

in a weight ratio of 80:20 to 20:80, preferably 50:50 to 25:75 and in particular 40:60 to 30:70.

Although mixtures based on fatty acid-N-alkylpolyhydroxyalkylamides, in particular fatty acid-N-methylglucamides and anionic surfactants, have already been known, surprisingly a strong synergistic interaction with sulfosuccinates of the sulfosuccinic acid mono type has been found with regard to the cleaning and foaming power within certain mixing ratios - and diesters found. The invention includes the knowledge that an improvement is also achieved with regard to wetting power and washing performance and that the ecotoxicological properties are at least retained at the level of the individual substances.

Fatty acid N-alkyl polydroxyalkylamides

The fatty acid N-alkylpolyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or one Fatty acid chloride can be obtained. With regard to the processes for their production, reference is made to US Pat. Nos. US 1985424, US 2016962 and US 2703798 and international patent application WO 92/06984. An overview of this topic by H. Kelkenberg can be found in Tens. Surf.Det. 25, 8 (1988).

The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (II):

R ² OH OH OH

I I I I

R ¹ CO-N-CH ₂ -CH-CH-CH-CH-CH2θH (II)

I OH

Glucamides of the formula (II) are preferably used as the fatty acid N-alkylpolyhydroxyalkylamides in which R ^{2 is} hydrogen or an amine group and R 1 -C 4 is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid , Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroseline acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with are particularly preferred Lauric acid or Ci2 / i4 coconut fatty acid or a corresponding derivative can be obtained. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Sulfosuccinates

Sulfosuccinates, which are also referred to as sulfosuccinic acid esters, are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. They follow formula (III)

SO3X

I.

R ³ (OCH ₂ H2) nOOC-CB-CH2-COO (CH2CH2θ) _m R ⁴ (III)

in which R-3 stands for an alkyl and / or alkenyl radical with 6 to 22 carbon atoms, R * for R ³ or X, m and n independently of one another for 0 or numbers from 1 to 10 and X for an alkali or alkaline earth metal , Ammonium, alkylammonium, alkanolamonium or glucamonium.

For their preparation, one usually starts from maleic acid, but preferably maleic anhydride, which are esterified in the first step with optionally ethoxylated primary alcohols. At this point, the mono / diester ratio can be set by varying the amount of alcohol and the temperature. In the second step, bisulfite is added, which is usually carried out in the solvent methanol. Recent reviews of manufacturing and The use of sulfosuccinates is, for example, from T. Schoenberg in Cosm.Toil. 104, 105 (1989), JAMilne in R.Soc.Chem. (Ind.Appl.Surf.il) 22, ⁷⁷ (1990) and W.Hreczuch et al. in J.Am.Oil.Cheπt.Soc. 7J5 _# 707 (1993) appeared.

Typical examples are sulfosuccinic acid monoesters and / or diesters in the form of their sodium salts which are derived from fatty alcohols having 8 to 18, preferably 8 to 10 or 12 to 14, carbon atoms; the fatty alcohols can be etherified with an average of 1 to 10 and preferably 1 to 5 moles of ethylene oxide and can have both a conventional and preferably a narrow hologmological distribution. Examples include di-n-octyl sulfosuccinate and monolauryl 3EO sulfosuccinate in the form of their sodium salts.

Detergent mixtures

The mixtures, which are preferably aqueous and then have a solids content of 5 to 70, preferably 25 to 50% by weight, are generally prepared by stirring aqueous solutions, pastes or concentrates of the starting materials, if necessary at a slightly elevated temperature. However, it is also possible to mix spray-dried powders of the two components and then to paste them on or to subject solutions of both ingredients to spray drying and / or granulation together. All of these cases are purely mechanical processes and there is no chemical reaction. Industrial applicability

The detergent mixtures according to the invention have a synergistic enhancement of the cleaning and foaming power. Another object of the invention therefore relates to their use for the production of surface-active agents, as there are:

o Powder-form universal detergents containing 10 to 30% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

Liquid universal detergents containing 10 to 70% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Liquid mild detergent containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o finishing agents containing 10 to 50% by weight, based on the agent, of the detergent mixtures according to the invention, and also conventional auxiliaries and additives.

o Hand dishwashing detergent, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o rinse aid, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention, and also conventional auxiliaries and additives. Liquid detergents and disinfectants, containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention, as well as customary auxiliaries and additives.

o Bar soaps of the combihar type, containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Syndet soaps containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hair shampoos containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention, and also conventional auxiliaries and additives.

o Haa rinses, containing 10 to 30 wt .-% - based on the agent - of the detergent mixtures according to the invention and conventional auxiliaries and additives.

o Hair colorants containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Hair waving compositions containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Bubble baths containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention, and also conventional auxiliaries and additives.

o Textile and fiber auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Leather greasing agent, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Flotation auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

o Aids for dewatering of solids, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

In this context, the use of the detergent mixtures according to the invention for the production of manual dishwashing detergents and hair shampoos is particularly preferred.

Surfactants

The above-mentioned agents can contain, as auxiliaries and additives, primarily other anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants. Typical examples of anionic surfactants are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, o-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerin ether sulfates, hydroxy acid ether sulfate sulfates, mono-ether ether sulfate sulfates, mono-ether ether sulfate sulfates, mono-ether ether sulfate sulfates, mono-ether ether sulfate sulfates, mono-ether ether sulfate sulfates, mono-ether ether sulfate sulfates, mono-ether ether sulfate sulfates, , Mono- and di-alkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially herbal products based on soy ph) and ph (alkyl ether products). If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, protein hydrolysate products (insol. Protein hydrolysate products) - acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, amino glycinates, imidazolinium betaines and sulfobetaines.

The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, relevant review articles include J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.) , "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217.

Other auxiliaries and additives

Washing, rinsing, cleaning and conditioning agents based on the detergent mixtures according to the invention can contain, for example, builders, salts, bleaching agents, bleach activators, optical brighteners, graying inhibitors, solubilizers and enzymes as auxiliaries and additives.

Common builders are sodium aluminum silicates (zeolites), phosphates, phosphonates, ethylenediaminetetraacetic acid, nitrilotriacetate, citric acid and / or polycarboxylates. Suitable salts or adjusting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass). Typical individual examples of further additives are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, long-chain soaps, silicones, mixed ethers, lipases and proteases. Hair shampoos, hair lotions or foam baths can contain, as auxiliaries and additives, bmulsifiers such as alkoxylated fatty alcohols or sorbitan esters. Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone and also and ammonium chloride. Biogenic active substances are understood to mean, for example, plant extracts, protein hydrolyzates and vitamin complexes. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentadiol or sorbic acid. Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid mono-glycol esters. The dyes which can be used are those which are suitable and approved for cosmetic purposes, such as, for example, in the publication "Cosmetic Dyes" of the dye emission of the German Research Foundation, published by the Chemie publishing house, Weinheim, 1984, p. 81-106 are compiled. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole. The. The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. Surfactants used

^A ) ^c 12/14 coconut fatty acid N-methylglucamide

B1) sulfosuccinic acid mono-n-octyl ester di Na salt

B2) Sulphosuccinic acid di-n-octyl ester Na salt

B3) Sulfosuccinic acid monolauryl 3EO ester di Na salt

Cl) Dodecylbenzenesulfonate sodium salt

C2) Alpha tallow fatty acid methyl ester sulfonate sodium salt C3) Ether carboxylic acid sodium salt based on Ci2 / 14- ^Ko * ^ ^os f ^e ' ^tt - "alkoho1-7EO adduct

YY. Tel ler rinsing ability

The dishwashing capacity was determined with the aid of the dish test [fats, soaps, paints. , 74, 163 (1972)]. For this purpose, plates with a diameter of 14 cm were soiled with 2 ml of beef tallow ("RiTa", acid number 9-10) and stored for 24 hours at room temperature. The plates were then rinsed at 50 ° C. with 5 liters of tap water with a hardness of 16 ° d. The test mixture was used at a dosage of 0.15 g active substance / l. The rinsing attempt was terminated as soon as the foam on the surface had completely disappeared. A market product based on alkyl benzene sulfonate / fatty alcohol ether sulfate served as the standard (= 100%). The results are summarized in Table 1 (percentages as% by weight). Table 1 Dishwashing capacity

YYY. Foam assets

The foaming power was examined in accordance with the Ross Miles Test DIN 53901, part 2) in a 1% strength by weight aqueous solution (water hardness 16 ° d, temperature 20 ° C.). The results on base foam and foam disintegration are summarized in Table 2 (percentages as% by weight).

Table 2: Base foam and foam breakdown

Table 2: Base foam and foam disintegration (cont.)

YYY. RezevturbexBOiele

III.J. Handshake spu Imi ttel

Texapon ^(R) N70 15% by weight

Texapon ( ^R) DOS 3% by weight

Coconut monoglyceride sulfate 12 wt.

Dehyton ( ^R) K 3% by weight

Ethanol 1% by weight

Water ad 100% by weight

YYY.2. Hand dishwashing liquid

Texapon ( ^R) N70 15% by weight

Coconut fatty acid N-methylglucamide 1% by weight

Plantaren ^(R) 1200 2 wt .- *

Texapon ^(R) DOS 12% by weight

Dehyton ( ^R) K 3% by weight

Ethanol 1% by weight

Water ad 100% by weight

J J.3. Hair shampoo

Texapon ( ^R ) K14S 15% by weight

Coconut fatty acid N-methylglucamide 3% by weight

Texapon ^(R) SB3 12% by weight

Nutrilan ^(R) 3% by weight

Water ad 100% by weight Explanation of the commercial products:

Texapon ( ^R ) N70 coconut fatty alcohol 2EO sulfate Na salt

Texapon ^(R) K14S coconut fatty alcohol 3,6EO sulfate Na salt

Texapon ^(R) DOS di-n-octylsulfosuccinate Na salt

Texapon ^(R) SB3 Monolauryl-3E0-sulfosuccinate-di-Na salt Plantaren ^(R) 1200 coconut alkyl oligoglucoside

Dehyton ( ^R ) K betaine based on coconut fatty acid amide Nutrilan collagen hydrolyzate

All products are sales products from Henkel KGaA, Düsseldorf / FRG.

Claims

P ^ * t - * »τι * t- ιτmprüche

1. Containing detergent mixtures with improved cleaning performance

(a) Fatty acid N-alkyl polyhydroxyalkylamides and

(b) sulfosuccinates

in a weight ratio of 80:20 to 20:80.

2. Detergent mixtures according to claim 1, characterized gekennzeich¬ net that they contain fatty acid-N-alkylpolyhydroxyalkylamides of the formula (I),

R ²

I

in which R --- C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.

3. Detergent mixtures according to claim 2, characterized gekennzeich¬ net that they contain fatty acid-N-alkylglucamides.

4. Detergent mixtures according to claims 1 to 3, characterized in that they contain sulfosuccinates of the formula (III), SO3Σ

I.

R ³ (OCH2CH2) _n OOC-CH-CH2-COO (CH2CH2O), "R ⁴ (HI)

in which R ^{3 represents} an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R ^{4 represents} R ³ or X, m and n independently of one another for 0 or numbers from 1 to 10 and X for an alkali or alkaline earth metal, Ammonium, alkyl ammonium, alkanol ammonium or glucamonium.

5. Detergent mixtures according to claims 1 to 4, characterized in that they contain components (a) and (b) in a weight ratio of 50:50 to 25:75.

6. Use of detergent mixtures according to claims 1 to 5 for the preparation of surface-active agents.