DE4111335A1 - Washing compsn. with reduced excessive foaming in machines - contains alkyl glycoside, di:alkyl-ether sulphate and sulphate or sulphonate anionic surfactant - Google Patents

Abstract

Washing compsn. comprises (I) surfactants comprising a mixt. of 0.5-12 wt.% (all on total compsn.) of alkyl glycoside RO-(G)x (I), 1-10 wt.% sec. dialkylether sulphate R1-O-(CNH2nO)p-CH2-CH(OSO3M)-R2 (II) and a sulphate or sulphonate anionic surfactant (III) plus (2) other standard components of liq. or solid compsns. The wt. ratio (II):(III) is 2:1-1:5. In formulae R = prim. or sec. 8-22C aliphatic gp.; G = 5 or 6C glycose residue; x, the degree of oligomerisation, = 1-10; R1 = 1-18C alkyl; R2 = 6-16C linear alkyl, with 7-28C in R1+R2; p = 1-30; n = 2-4; M = alkali, alkaline earth or NH4 ions. (III) is pref. an alkylbenzene sulphonate and the (II):(III) ratio is 1:1-4, or it is an alkyl(ether)sulphate and the ratio is 1.5:1-1:2. USE/ADVANTAGE - These compsns. are useful in washing machines at 30-90 deg.C. Addn. of (III) prevents the excessive foam consumption usually associated with (I)-based formulatio

Description

The invention relates to foam-regulated detergents based on a ternary surfactant mixture of an alkyl glycoside, an anionic surfactant from Sulfate type and another anionic surfactant from the group of sulfonates or sulfates for use in automatic washing machines.

From the US Pat. No. 3,219,656 (Rohm & Haas) it is known that alkyl glycosides with C ₈ -C ₁₈ alkyl radicals not only develop stable foam themselves, but also act as foam stabilizers for other anionic and nonionic surfactants. The European patent application EP 70 074 (P & G) describes foaming surfactant mixtures of alkylglycosides and anionic surfactants of the sulfate, sulfonate and carboxylate type. Preferred are surfactant mixtures in which one component is alkylbenzenesulfonate, and the use of alkyl sulfates and / or soaps in conjunction with amides and / or amine oxides.

From European patent application EP 2 16 301 (Henkel) are manual liquid dishwashing liquid known, which is a combination of anionic Surfactants of the sulfate and / or sulfonate type and surfactant fatty acid Realkanolamide and alkyl glycosides contain. The funds are free from Ionic surfactants with a petrochemical base, in particular free from alkyl benzenesulfonate.

The German patent application DE 39 20 480 (Henkel) discloses liquid washing medium from fatty alkyl sulfates, a soap mixture saturated and unsaturated saturated fatty acid soaps and 1 to 10 wt .-% alkyl glycosides. The liquid detergents are particularly suitable for manual washing with high sensitivity Textiles.  

From the international patent application WO 90/5772 (Henkel) are washing and cleaning agents, u. a. as a manual dishwashing detergent, be knows that a surfactant mixture of alkyl glycoside (A) and an anionic Surfactant (B) and other components of solid or liquid washing and Contain cleaning agents, wherein (B) the sulfate of a dialkyl ether represents secondary hydroxyl group. Such dialkyl ether sulfates can according to that described in European patent application EP 2 99 370 (Henkel) be obtained. These sulfate surfactants show in conjunction with other surfactants such as fatty alkyl sulfates or fatty alkyl ether sulfates a particularly strong foam formation, the foam also against limescale load is much more stable than the foam of the individual components. Mixtures of this type can therefore be used anywhere and especially in the present of fatty acid soaps where foam is required.

Alkyl glycoside-containing surfactant mixtures that develop stable foams, are preferred for manual washing of textiles or for manual Used to clean dishes. These funds can, however, because of their high foaming properties are not used in automatic machines, because they foam too much despite the defoamer additive.

The object of the invention was to provide detergents containing acylglycoside, for use in automatic washing machines between 30 and 90 ° C are suitable to provide.

The invention accordingly relates to a detergent which contains a mixture of an alkyl glycoside (A) and an anionic surfactant (B) and further constituents of solid or liquid detergents, the alkyl glycoside (A) having the general formula (I) RO (G) _x , in which R is a primary or secondary aliphatic radical with 8 to 22 C atoms, G is the symbol of a glycose unit with 5 or 6 C atoms and x is a degree of oligomerization of 1 to 10, and (B a secondary dialkyl ether sulfate of the general formula (II),

in which R _{1 is} a linear or branched alkyl radical having 1 to 18 C atoms, R _{2 is} a linear alkyl radical having 6 to 16 C atoms and the sum of R ₁ and R _{2 is} 7 to 28 C atoms, p is a number of 1 to 30, n is a number from 2 to 4 and M is a cation from the group of alkali metal, alkaline earth metal and ammonium ions, and this detergent is characterized in that it is a ternary surfactant mixture of 0.5 to 12 wt .-% (A), 1 to 10 wt .-% (B) and another anionic surfactant (C) from the group of sulfates and sulfonates, the quantities for (A) and (B) referring to the entire agent and the weight ratio (B): (C) is between 2: 1 and 1: 5.

The ternary surfactant mixtures show when used in automatic washing machines have less foam formation than the individual components or bi nary mixtures of (A) and (B), (A) and (C) or (B) and (C).

Suitable alkyl glycosides (A) are in particular glucosides with an alkyl radical consisting essentially of C ₁₂ to C ₁₈ , which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions which preferably contain saturated alcohols. The use of C ₁₂ -C ₁₄ alkyl glucosides is particularly preferred, in particular those whose alkyl radical contains 50 to 70% by weight of C ₁₂ and C ₁₈ to 30% by weight of C ₁₄ . The index number x is any number between 1 and 10; it indicates the degree of oligo merization, that is to say the distribution of monoglucosides and oligo glucosides. While x must always be an integer in a given connection and can above all assume the values x = 1 to 6, the value x is an analytically determined mathematical quantity for a special product, which usually represents a fractional number. The average degree of oligomerization x preferably has a value of 1.1 to 3.0 and in particular of significantly less than 1.5. Products with a degree of oligomerization between 1.1 and 1.4 are particularly preferred.

The content of alkylglycosides in the agents is preferably 0.5 to 8 % By weight and in particular 1 to 6% by weight.

Secondary dialkyl ether sulfates of the formula (II) are compounds in which R _{1 is} a linear or branched alkyl radical having 1 to 18, preferably 1 to 8 and in particular 4 to 8 carbon atoms, while R _{2 is} a linear alkyl radical having 6 to 16, preferably 6 to 14 and in particular 10 to 12 carbon atoms, the sum of the alkyl radicals (R ₁ + R ₂ ) being at least 7 and at most 28 and preferably being between 14 and 18. p can be a number from 1 to 30, preferably from 1 to 10, and n can be an integer from 2 to 4. Preferably n stands for the numbers 2 and 3 and in particular for the number 2. M in the above general formula (II) has the meaning of sodium, potassium, magnesium, ammonium or alkylammonium or alkanolammonium cations , where the alkyl and alkanol radicals of the organic ammonium ions mentioned may have 1 to 4 carbon atoms. The sodium salts of the secondary dialkyl ether sulfates are preferred. However, the salts of triethanolamine are also particularly useful for liquid agents.

Suitable anionic surfactants (C) from the group of the sulfonates are preferably the customary commercially available C ₉ -C ₁₃ -alkylbenzenesulfonates and the sulfonates based on oleochemicals, such as the esters of α-sulfofatty acids, the sulfo group being in its salt form (Mono salt), e.g. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fat, into consideration. The alkylbenzenesulfonates are preferred. Suitable surfactants (C) of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, that is, from C ₁₂ to C ₁₈ fatty alcohols, such as lauryl, myristyl or cetyl alcohol, from those from coconut oil, palm and palm kernel oil and tallow-derived fatty alcohol mixtures, which may also contain fractions of unsaturated alcohols, for example oleyl alcohol, or from C ₁₀ -C ₂₀ oxoalcohols, and the sulfuric acid monoesters of secondary alcohols of this chain length, the sulfuric acid monoesters of the primary alcohols being based on oleochemicals are preferred. Also preferred are the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as linear C ₁₂ -C ₁₈ fatty alcohols or 2-methyl-branched C ₉ -C ₁₁ alcohols with on average 3 to 4 moles of ethylene oxide.

The total content of the anionic surfactants (B) is preferably and (C) between 5 and 25% by weight, in particular between 5 and 15% by weight. Particularly preferred agents contain secondary dialkyl ether sulfate (B)  and alkylbenzenesulfonate (C) in a ratio between 1: 1 and 1: 4 or (B) and alkyl sulfate or alkyl ether sulfate (C) in a ratio between 1.5: 1 and 1: 2. In particular, agents which contain (B) and (C) in the above ratios and 1 to 5 wt .-%, based on the ge all agents containing alkyl glucoside (A), the ratio (A): (B + C) is particularly advantageously between 1: 4 and 1: 2.

Suitable other components of liquid or solid detergents are especially other anionic and nonionic surfactants, builder substance zen, bleach, additional foam inhibitors, complexing agents, optical brighteners, thickeners, dirt suspending agents, graying inhibitors, dyes, perfume oils, enzymes, bactericides and fungicides.

As further anionic surfactants, the soaps of saturated and unsaturated fatty acids with C ₁₂ to C ₂₂ chain lengths are preferably used individually and in particular in the form of their mixtures, soap mixtures based on technical fatty acid cuts being particularly preferred. A soap mixture which is preferably used for use in liquid detergents is formed from sodium oleate and the sodium salts of the saturated C ₁₂ -C ₁₆ -fatty acid mixtures, the proportion of C ₁₂ -C ₁₄ -fatty acids expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the short-chain portions with 10 and fewer carbon atoms are largely separated. As is customary in technical fatty acid cuts, oleic acid and coconut fatty acid can still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should be at most 25% by weight, preferably less than 20% by weight. A soap mixture of sodium oleate and the sodium salt of lauric acid is likewise preferred, the weight ratio preferably being 2: 1 to 1: 2. The soap content of the agents is generally not more than 22% by weight and is preferably in a range from 1 to 20% by weight, in particular liquid agents contain with particular advantage between 10 and 18% by weight.

Suitable nonionic surfactants are, for example, customary ethoxylated fatty alcohols, in particular addition products of 2 to 7 moles of ethylene oxide (EO) with linear primary alcohols, such as, for. B. on coconut, tallow or oleyl alcohol, or on 2-position methyl-branched primary alcohols (oxo alcohols). In particular, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₁₃ -C ₁₅ alcohols with 3, 5 or 7 EO, C ₁₂ -C ₁₈ alcohols with 3, 5 or 7 EO and mixtures of these, as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO used. The content of nonionic surfactants in the agents is preferably 1 to 8% by weight in solid and granular detergents and cleaning agents and 6 to 15% by weight in liquid detergents and cleaning agents.

Weakly acidic are suitable as organic and inorganic builders he, neutral or alkaline compounds, especially alkali metal compounds that precipitate or bind complex calcium ions capital. Suitable and especially ecologically harmless builder sub punches, like finely crystalline, synthetic water-containing zeolites of the type NaA, which has a calcium binding capacity in the range of 100 to 200 mg CaO / g (ge according to the information in DE 24 12 837) have a preferred use dung. Their average particle size (volume distribution, Coulter measurement method Counter) is usually in the range of 1 to 10 µm. The zeolites can NEN in the agents in amounts up to 40 wt .-%, preferably in amounts of 10 to 30 wt .-%, based on the anhydrous zeolite.

As additional components, in particular together with the zeolite are set, come (co) polymeric polycarboxylates, e.g. B. polyacrylates, Polymethacrylates and especially copolymers of acrylic acid with maleic acid re, preferably those from 50% to 10% maleic acid, into consideration. 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 free acid. A special ders preferred acrylic acid-maleic acid copolymer has a relative Mo lecular mass from 50,000 to 100,000. Suitable, if less before Compounds of this class are copolymers of acrylic acid or meth acrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of Acidity is at least 50%.  

Useful organic builder substances are preferred, for example polycarboxylic acids, such as lemons, used in the form of their sodium salts acid, and nitrilotriacetate (NTA), if such an insert from eco logical reasons is not objectionable.

Suitable inorganic, non-complexing salts are, for example, bicarbonates, carbonates, borates or silicates of the alkali metal ions; Of the alkali silicates, the amorphous or layered crystalline sodium silicates with a Na ₂ O: SiO ₂ ratio such as 1: 1 to 1: 3.5 are particularly useful.

The agents can additionally contain non-surfactant-like foam inhibitors, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bisacylamides derived from C ₁₂ -C ₂₀ alkylamines and C ₂ -C ₆ dicarboxylic acids can also be used. Mixtures of various foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

In a particularly preferred embodiment, powdery or granular detergents and cleaning agents with a bulk density between 400 and 900 g / l contain 1 to 4% by weight of C ₁₂ -C ₁₄ -alkyl glucoside (A), 5 to 10% by weight ( B + C), where (B) is a secondary dialkyl ether sulfate of the formula (II), in which R _{1 is} 1 to 8 and preferably 4 to 8, R ₂ 6 to 14 and preferably 10 to 12 C atoms, the sum of R ₁ and R _{2 are} a number between 14 and 18 carbon atoms, p is a number from 1 to 10 and n is the number 2, (C) an alkylbenzenesulfonate or C ₁₂ -C ₁₄ -alkyl sulfate or a C ₁₂ -C ₁₄ - Alkyl ether sulfate, 1 to 2% by weight of C ₁₆ -C ₂₂ sodium fatty acid soap, 2 to 7% by weight of ethoxylated C ₁₂ -C ₁₈ fatty alcohols and 1 to 3% by weight of silicone defoamer.

In a further preferred embodiment, liquid detergents and cleaning agents (A), (B) and (C) as above and additionally contain 10 to 14% by weight of a soap mixture of sodium oleate and the sodium salt of lauric acid in a ratio of 2: 1 to 1: 2, and 8 to 14 wt .-% ethoxylated C ₁₂ -C ₁₈ fatty alcohols.

The preparation of the agents can be carried out in the usual way, that is Liquid funds are, for example, simply by mixing the components and powdery to granular agents, for example by spraying dry the constituents which are stable under these conditions and then admixing the heat-sensitive components, such as bleaching agent tel, enzyme, fragrance, foam inhibitor, available. Other suitable ver driving are the granulation of the components, whereby water, salt solutions, Polymer solutions and / or non-ionic surfactants as granulating liquid can be used.

Examples

The foaming behavior of agents M1 to M3 according to the invention, of which M1 solid and M2 and M3 were liquid, as well as the comparison means V1 to V3 was placed close to the consumer in a household washing machine with horizontal arranged laundry drum (type Miele W760) under the following conditions tests:

I. Water hardness 3 ° d
fixed medium: pre-wash / main wash (94 g / 117 g)
liquid agents: main wash (120 g)
3.5 kg clean filling laundry

II. Water hardness 16 ° d
liquid agents: main wash (180 g)
3.5 kg of normal soiled household laundry.

The foam behavior was assessed using the marks 0 to 5; mean:

Grade 0: no foam in the drum
Grade 4.5: the drum is filled with foam
Grade 5.0: the foam overflows.

The compositions of the compositions are shown in Tables 1 and 2. Tables 3 and 4 contain the ratings of the foam behavior. The Agents according to the invention have overall better grades than that Comparative agents that are not the ternary surfactant combination according to the invention exhibited.

The abbreviations used in the tables mean:

ABS = C₉-C₁₃-alkylbenzenesulfonate sodium salt
FAS = C₁₂ alkyl sulfate sodium salt (sulfopone K 35, commercial product of the applicant)
DES = secondary dialkyl ether sulfate with R ₁ = 8, R ₂ = 10, n = 2, p = 4
APG = C₁₂-C₁₄ alkyl glucoside, x = 1.4
Nio = 20% C₁₂-C₁₄ fatty alcohol with 3 EO and 80% C₁₂-C₁₈ fatty alcohol with 5 EO
TFA = tallow fatty alcohol with 5 EO
S1 = C₁₆-C₂₂ fatty acid soap (sodium salt)
S2 = sodium oleate
S3 = C₁₂-C₁₈ coconut fatty acid soap (sodium salt)
CP5 = copolymer of acrylic acid and maleic acid salts, Sokalan® CP5 (BASF / Germany)
Perborate = sodium perborate tetrahydrate
TAED = tetraacetylethylenediamine
SIK = silicone defoamer
Soda = sodium carbonate
Silicate = sodium silicate with Na₂O: SiO₂ = 1: 3.0
Rest = enzymes, optical brighteners, colors and fragrances, salts, water (in the solid medium).

Table 1

Table 2

Table 3

Condition I

Table 4

Condition II

Claims (5)

1. detergent containing a surfactant mixture of an alkyl glycoside (A) and an anionic surfactant (B) and further constituents of solid or liquid detergents, the alkyl glycoside (A) having the general formula (I) RO- (G) _x , in which R is a primary or secondary aliphatic radical with 8 to 22 C atoms, G is the symbol of a glycose unit with 5 or 6 C atoms and x is a degree of oligomerization of 1 to 10, and (B) is a secondary dialkyl ether sulfate of the gen my formula (II), in which R _{1 is} a linear or branched alkyl radical having 1 to 18 carbon atoms, R _{2 is} a linear alkyl radical having 6 to 16 carbon atoms and the sum of R ₁ and R _{2 is} 7 to 28 carbon atoms, p is a number of 1 to 30, n is a number from 2 to 4 and M is a cation from the group of the alkali metal, alkaline earth metal and ammonium ions, characterized in that the agent is a ternary surfactant mixture of 0.5 to 12% by weight ( A), 1 to 10 wt .-% (B) and another anionic surfactant (C) from the group of sulfates and sulfonates, the amounts given for (A) and (B) refer to the total agent and that Weight ratio (B) to (C) is between 2: 1 and 1: 5. 2. Composition according to claim 1, characterized in that (C) is an alkylbene benzenesulfonate and the ratio (B) to (C) is between 1: 1 and 1: 4 lies. 3. Composition according to claim 1, characterized in that (C) is an alkyl sul is fat or an alkyl ether sulfate and the ratio (B) to (C) is between 1.5: 1 and 1: 2. 4. Agent according to one of claims 1 to 3, characterized in that it ent 0.5 to 8 wt .-%, preferably 1 to 6 wt .-% alkyl glucoside (A) ent holds and the ratio (A) to (B + C) is 1: 4 to 1: 2.   5. Agent according to one of claims 1 to 4, characterized in that it contains soap and ethoxylated fatty alcohols as further surfactants.