DE19526033A1 - Foam stabiliser for aq. surfactant compsns. - Google Patents

Abstract

The use of short-chain polysaccharides (I) is claimed as foam stabilisers in aq. surfactant compsns. Also claimed are aq. surfactant compsns. (A) (specifically manual dishwashing compsns.) contg.(by wt. based on the total compsn.) 0.2-15 (pref. 1-10)% (I), 1-50 (pref. 5-45)% anionic surfactant (II) and 1-20 (pref. 2-10)% nonionic surfactant (III).

Description

The present invention relates to the use of short chain polysaccha riden in aqueous surfactant compositions, especially aqueous hand dishwashing detergents, with strong foaming and good cleaning power.

Liquid cleaning agents usually consist of aqueous solutions from syntheti anionic and / or nonionic surfactants and customary additives fen. They are particularly useful for cleaning hard surfaces, e.g. B. of glass, ke ramischen materials, plastics, lacquered and polished surfaces ver turns. This is an important area of application for liquid cleaning agents manual washing of dishes and cookware. Dish washing is common chich at strongly elevated temperatures of about 25 to 45 ° C in ver thin fleets. Because of the contact of the hands with the Reini wash liquor over a longer period of time is for manual rinsing of Ge The skin-friendliness of the product is also of particular importance. Out For these reasons, the expert in the selection of the components and the Composition of an agent for manual cleaning of dishes others Considerations than when using liquid cleaning agents for other hard surfaces chen.

The cleaning power of an agent is generally considered by the consumer the better evaluated, the stronger and the longer the cleaning liquor foams. It there is therefore a constant need for additives and / or active substances that foam stabilization in aqueous surfactant compositions, in particular hand dishwashing detergents, without the cleaning performance of the detergents to impair or improve the cleaning performance of the agents at the same time ser.  

The present invention therefore relates to the use of short ketti gene polysaccharides in aqueous surfactant compositions, in particular aqueous dishwashing liquid.

As short-chain polysaccharides, preference is given to those which are are soluble in water and in aqueous solutions in a concentration of up to 10% by weight have no visibly thickening effect on the surfactant composition. The short-chain polysaccharides can, for example, by degradation of poly saccharides to oligomeric products, such as. B. dextrins, or by condensates tion of the mono- or disaccharides and their derivatives can be obtained. Both reactions can be carried out both by enzymes and by inorganic and catalyzed organic acids. As polysaccharides, the as used for the production of short-chain polysaccharides can be, for example, pectins, algins, carrageenan, agar, targant, Gum arabic, karaya gum, ghatti gum, xanthans, galactomannans, Inulin, starch and mixtures of the above, are suitable. The short chain Water-soluble polysaccharides usually have a degree of polymerization from 3 to 300, especially from 3 to 50. The degradation products of polyglucose have proven to be particularly suitable, with particular preference being given to Pro Products with up to 20 sugar units, especially those with 3 to 10 sugar units are used.

The short chain polysaccharides can be used in aqueous surfactant compositions gene in amounts of 0.5 to 15 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the finished composition.

Another object of the present invention are aqueous surfactants together containing compositions, in particular hand dishwashing detergents

• a) 0.2% by weight to 15% by weight, preferably 1 to 10% by weight, based on the entire composition, short chain polysaccharide,
• b) 1 wt .-% to 50 wt .-%, preferably 5 wt .-% to 45 wt .-%, bezo on the entire composition, anionic surfactant and
• c) 1% by weight to 20% by weight, preferably 2% by weight to 10% by weight, in each case based on the entire composition, non-ionic surfactant.

Aqueous surfactant compositions in the sense of the invention are e.g. B. foam baths, hair shampoos and in particular hand dishwashing detergents.

The total surfactant content in these compositions is preferably above 20% by weight, in particular over 33% by weight, based on the total composition.

The anionic surfactants which are suitable together in the surfactant according to the invention Settlements in particular C₆-C₂₂-alkyl sulfates, C₆-C₂₂-alkyl ether sulfates, C₉-C₁₃-alkylbenzenesulfonates, C₆-C₂₂-alkylsulfonates and any mixtures of the surfactants mentioned above.

Preferred anionic surfactants are the C₆-C₂₂ alkyl sulfates with the general formula I,

R¹-O-SO₃X (I),

in the R¹ for a saturated or unsaturated, linear or branched C₆-C₂₂-Al kylgruppe and X for an alkali, alkaline earth metal or a quaternary ammonium ion stands.

These substances are known chemical compounds which can be obtained by sulfation of linear or branched alcohols. Typical examples are the sulfates of fatty alcohols, such as capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol and technical grade alcohol, behenyl alcohol. Sulfates of technical C _12/14 or C _12/18 coconut _fatty alcohol _{cuts are} preferably used in the form of their sodium or magnesium salts.

C₆-C₂₂ alkyl ether sulfates that can be used in the sense of this invention NEN, follow Formula II,

R²O- (CH₂CH₂O) _n -SO₃X (II)

in the R² for a saturated or unsaturated, linear or branched C₂-C₂₂-alkyl group, n for numbers from 1 to 10 and X for an alkali or alkaline earth metal a quaternary ammonium ion.

These substances are also known chemical compounds, which can be obtained by sulfating C₆-C₂₂ alcohol polyglycol ethers nen. Also C₆-C₂₂ alkyl ether sulfates with a narrow homolog distribution (NRE = narrow range ethoxylates), as described, for example, in the international patent application WO 91/05764 and in the overview by D.L. Smith in J. Am. Oil. Chem. Soc. 68, 629 (1991) can be used.

Typical examples are the sulfation products of adducts from 1 to 10 Moles of ethylene oxide (conventional or narrow homolog distribution) to each Weil 1 mole of fatty alcohol, such as capronic alcohol, caprylic alcohol, capric alcohol, lau ryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, Oleyl alcohol, elaidyl alcohol oil, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol hol, behenyl alcohol and erucyl alcohol and their technical mixtures. Be sulfates of adducts of 2 to 7 moles of ethylene oxide with saturated Ko are preferred Cos fatty alcohols with 12 to 18 carbon atoms in the form of their sodium, potassium and / or Magnesium salts. For example, fatty alcohol ether sulfates are used which derive from corresponding fatty alcohol polyglycol ethers, which in turn in Presence of calcined or, in particular, hydrophobicized hydrotalcite have been produced and therefore have a narrow homolog distribution point.

The above C₉-C₁₆-alkylbenzenesulfonates and C₆-C₂₂-alkylsulfonates are also known surfactants, preferably alkylbenzenesulfonates with 9 to 12 carbon atoms in the alkyl radical and alkanesulfonates with preferably 12 to 18 carbon atoms can be used in the alkyl radical. As C₉-C₁₃ alkyl benzenesulfonates that can be used in the context of the invention are e.g. B. under the trade names Marlon® (Hüls) and Witconate® (Fa. Witco) distributed products. Other anionic surfactants are those Olefin sulfonates with 12 to 16, preferably 12 to 14 carbon atoms, in Al kylrest into consideration. The α-sulfofatty acid alkyl esters are also particularly suitable especially the methyl esters.  

Soaps, d. H. Alkali or ammonium salts of saturated or unsaturated C₆-C₂₂ fat acids, are invented because of their foam-suppressing properties Agents according to the invention preferably not included.

The feature "not included" should not mean that very ge rings of soap may not be included; Quantities of up to 2% by weight, based on the total agent, are even more tolerant in the sense of the invention bar.

The liquid cleaners according to the invention can be used as further components contain nonionic surfactants and amphoteric surfactants.

Preferred nonionic surfactants in the agents according to the invention C₆-C₂₂ alkyl glycosides contain. Alkyl glycosides are known substances that according to the relevant procedures in preparative organic chemistry can be. Representative of the extensive literature is here the documents EP-A 1-0 301 298 and WO 90/3977 referenced. The alkyl glycosides follow Formula III

R³O [G] _x (III),

in the R³ for a linear or branched, saturated or unsaturated Al alkyl radical with 6 to 22 carbon atoms, [G] for a glycosidic radical and x represents a number from 1 to 10.

The index number x in the general formula III indicates the degree of oligomerization (DP grade), i.e. H. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x is always in a given connection must be full-line and, above all, can assume the values x = 1 to 6 the value x for a certain alkyl glycoside is an analytically determined calculation size, which is usually a fractional number. Preferably be Alkylglycosides with an average degree of oligomerization x of 1.1 to 3.0 set. From an application point of view, such alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2  and 1.6 is. Glucose and xylo are preferred as glycosidic sugars se used.

The alkyl or alkenyl radical R³ can differ from primary alcohols with 6 to 22, preferably derive from 12 to 18 carbon atoms. Typical examples are Capronic alcohol, caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol hol, Oleyalcohol. Elaidyl alcohol, petroselinyl alcohol, arachylal are also alcohol, gadoleyl alcohol, behenyl alcohol, and / or erucyl alcohol and their technical mixtures, such as those used in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehyde which arise from Roelen's oxosynthesis, or the so-called goat alcoholic beverages.

The alkyl or alkenyl radical R³ is preferably derived from alcohol mixtures from how they ent in the hydrogenation of fatty acid methyl esters or fatty acids stand.

As further nonionic surfactants, fatty acid alkanolamides can be used, for. B. C _12/18 fatty acid _{monoethanolamide} or addition products from 4 to 20, preferably from 4 to 10 moles of alkylene oxide, preferably ethylene oxide to C₁₀-C₂₀-, preferably C₁₂-C₁₈ alkanols, but also the addition products of ethylene oxide to propylene glycols, which under the Pluronics® names are known, and addition products of 1 to 7 moles of ethylene oxide with 1 to 5 moles of propylene oxide reacted with C₁₂-C₁₈ alkanols. Fatty alkyl amine oxides are also suitable.

Furthermore, as nonionic surfactants C₆-C₂₂ alcohol alkoxylates with the For mills IV and V are used,

R⁴O- (CH₂CH₂O) _m -H (IV),

wherein R⁴ for a saturated or unsaturated, linear or branched C₆-C₂₂-Al kylgruppe and m stands for numbers from 1 to 20,

wherein R⁵ and o can have the same meaning as R⁴ and m in formula IV and n stands for numbers from 0.5 to 2.

In addition to the non-ionic surfactants already mentioned, alkylphae can also be used nolpolyglycolether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, Fatty amine polyglycol ether, mixed ether, alkoxylated triglycerides, fatty acid N-alkyl glucamides, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates in the compositions of the invention may be included. If not ionic surfactants containing polyglycol ether chains, they can be a conventional nelle, but also have a narrow homolog distribution.

As amphoteric surfactants, betaine compounds of the formula VI

are used, in which R⁶einen optionally by heteroatoms or hetero alkyl group interrupted by atomic groups having 8 to 25, preferably 10 to 21 Carbon atoms and R⁷ and R⁸ identical or different alkyl radicals with 1 mean up to 3 carbon atoms. C₁₀-C₁₈-Alkyldimethylcarboxy are preferred methyl betaine and C₁₁-C₁₇-alkylamidoprnpyldimethylcarboxymethyl-betaine.

As further amphoteric surfactants used in the agents according to the invention can be set come aminopropionates, aminoglycinates, imidazolinium betaine and sulfobetaine.

The agents according to the invention can also contain solvents as further constituents Contain tel, perfume, dyes and opacifiers, as well as skin protection compo nents, such as z. B. are known from EP-A1 522 756. To set the  Substances such as gelatin or casein can be used for the viscosity of the agents are without affecting the performance of the agents according to the invention pregnant.

The solvents to be added if necessary are niedermo molecular alkanols with 1 to 4 carbon atoms in the molecule, preferably around Ethanol and isopropanol. As a further solubilizer, for example for dyes and Perfume oils can optionally, for example, alkanolamines, polyols such as ethyl lenglycol, propylene glycol, glycerin and alkylbenzenesulfonates with 1 to 3 Koh serve lenstoffatomen in the alkyl radical.

The preferred thickeners include urea and ammonium chloride, which can also be used in combination. As a preservative Examples include sodium benzoate, formaldehyde and sodium sulfite. The Agents according to the invention can also contain conventional disinfectants.

The pH of the agents according to the invention is preferably between 5.0 and 7.5.

The following are examples of surfactant compositions according to the invention given. In a comparative example, a commercial surfactant is used composition with a formulation containing a short chain polysaccharide tion in which polyglucose is balanced against an anionic surfactant had been exchanged.

Examples A. Examples of surfactant compositions example 1

20% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
10% C _12/14 fatty alcohol sulfate Na salt
4% polyglucose (degree of polymerization 6)
2% coconut fatty acid amidopropyl betaine
9% ethanol
Rest on 100% water.

Example 2

20% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
1% C _12/14 fatty alcohol sulfate Na salt
5% polyglucose (degree of polymerization 6)
2% lauryldimethylamine oxide
7% ethanol
Rest on 100% water.

Example 3

18% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
8% C _12/14 fatty acid methyl ester sulfonate Na salt
8% polyglucose (degree of polymerization 8)
2% lauryldimethylamine oxide
7% ethanol
Rest on 100% water.

Example 4

20% alkylbenzenesulfonate Mg salt
8% C _12/14 fatty alcohol sulfate Mg salt
6% polyglucose (degree of polymerization 10)
2% lauryldimethylamine oxide
5% ethanol
3% cumene sulfonate
Rest on 100% water.

Example 5

12% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
4% C _12/14 fatty alcohol sulfate Na salt
2% polyglucose (degree of polymerization 55)
2% C _12/14 alkyl polyglucoside with a DP of 1.4
3% ethanol
Rest on 100% water.

Example 6

12% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
3% polyglucose (degree of polymerization 40)
2% C _12/14 alkyl polyglucoside with a DP of 1.4
4% ethanol
Rest on 100% water.

Example 7

13% C _12/14 fatty alcohol sulfate Na salt
3% polyglucose (degree of polymerization 30)
3% C _12/14 alkyl polyglucoside with a DP of 1.4
3% ethanol
3% PEG 400
Rest on 100% water.

Example 8

12% C _{12/18 fatty} alcohol (3EO) ether sulfate Na salt
4% C _12/18 fatty _alcohol sulfate Na salt
2% polyglucose (degree of polymerization 65)
2% coconut fatty acid monoalkanolamide
2% 1,2-propylene glycol
Rest on 100% water.

Example 9

15% alkylbenzenesulfonate Mg salt
5% C _12/14 fatty alcohol sulfate Na salt
3% polyglucose (degree of polymerization 25)
5% diisooctyl Na sulfosuccinate
3% ethanol
2% PEG 600
Rest on 100% water.

Example 10

15% C _12/14 fatty alcohol ether (3EO) sulfate Mg salt
1.5% polyglucose (degree of polymerization 120)
2% coconut fatty acid amidopropyl betaine
Rest on 100% water.

Example 11

15% C _12/14 fatty alcohol ether (3EO) sulfate Mg salt
1.5% polyglucose (degree of polymerization 180)
1.5% lauryl fatty acid N-methylglucamide
2% ethanol
Rest on 100% water.

Example 12

15% C _12/14 fatty alcohol ether (3EO) sulfate Na salt (NRE ethoxylate)
4% C _12/14 fatty alcohol sulfate Na salt
3% polyglucose (degree of polymerization 45)
4% ethanol
Rest on 100% water.

Example 13

12% C _12/14 fatty alcohol ether (2.5EO) sulfate Na salt (NRE ethoxylate)
4% C _12/14 fatty alcohol sulfate Na salt
3% polyglucose (degree of polymerization 15)
3% C _12/14 alkyl polyxyloside with a DP of 1.4
4% ethanol
Rest on 100% water.

Example 14

10% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
4% C _12/14 fatty alcohol sulfate Na salt
2% polyglucose (degree of polymerization 20)
2% C _12/14 alkyl polyglucoside with a DP of 1.5
2% coconut fatty acid, sodium salt
4% ethanol
Rest on 100% water.

Example 15

12% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
4% C _12/14 fatty alcohol sulfate Na salt
2% polyglucose (degree of polymerization 9)
2% C _12/14 alkyl polyglucoside with a DP of 1.5
2% coconut fatty acid amidopropyl betaine
4% ethanol
Rest on 100% water.

Example 16

12% C _12/14 fatty alcohol ether (3EO) sulfate Na salt
6% coconut fatty acid monoglyceride + 10 EO
2% polyglucose (degree of polymerization 38)
2% C _12/14 alkyl polyglucoside with a DP of 1.5
4% ethanol
Rest on 100% water.

Example 17

12% C _12/14 oxo alcohol ether (2EO) sulfate Na salt
6% coconut fatty acid monoglyceride + 10 EO
2% polyglucose (degree of polymerization 15)
2% C _12/14 alkyl polyglucoside with a DP of 1.5
4% ethanol
Rest on 100% water.

Example 18

14% C _12/14 fatty alcohol ether (2.5EO) sulfate Na salt (NRE)
6% C _10/14 fatty alcohol + 8 EO
2% polyglucose (degree of polymerization 8)
3% C _12/14 alkyl polyglucoside with a DP of 1.5
1.5% amidoethyl-N-2-hydroxyethylglycinate
6% ethanol
Rest on 100% water.

Example 19

14% C _12/14 fatty alcohol ether (1,2EO) sulfate Na salt (NRE)
6% C _10/14 fatty alcohol + 1.2 PO + 8 EO
2% polyglucose (degree of polymerization 180)
3% C _12/14 alkyl polyglucoside with a DP of 1.5
1.5% amidoethyl-N-2-hydroxyethylglycinate
6% ethanol
Rest on 100% water.

Example 20

29% C _12/14 fatty alcohol ether (1,2EO) sulfate Mg salt (NRE)
10% C _12/14 fatty alcohol sulfate Mg salt
10% C _10/14 fatty alcohol + 1.2 PO + 8 EO
8% polyglucose (degree of polymerization 6)
3% C _12/14 alkyl polyglucoside with a DP of 1.5
12% C₄-alkyl polyglucoside with a DP of 1.5
8% PEG 200
10% ethanol
Rest on 100% water.

Example 20 stands for a hand dishwashing liquid high concentrate, which in ver thin form is applied. During the manufacturing process, water-free ones are used Raw materials used.  

Example 21

29% C _12/14 fatty alcohol (3EO) sulfate Na salt
4.9% coconut amidopropyl betaine
1% polyglucose (degree of polymerization 8)
3% MgSO₄
Rest on 100% water.

Example 21 produces a hand dishwashing detergent, the production of which is analogous to PCT application 94/14947 is proceeding.

B. Determination of foaming power and rinsing power

The foaming power was determined using the Wagner Foam tests carried out. This is, for example, in DE 44 39 221 wrote.

Another measurement followed after the addition of a further 0.5 ml of olives oil / mixing cylinder and repeated "shaking".

The rinsing capacity was determined using a standard method (plate test). This is e.g. B. described in DE 43 11 158.

The surfactant compositions listed in Table 1 were obtained poses.  

Table 1

Test results

The foam amounts of the surfactant compositions at different dosages stances and the rinsing capacity were compared. The results are in the Tables 2 and 3 are shown.

It is clear from the tables that the surfactants according to the invention together setting shows improved foaming power, the rinsing power ge compared to a mixed contamination compared to the comparison test worsened and even improved compared to beef tallow.

Table 2

Table 3

Claims (10)

1. Use of short-chain polysaccharides as foam stabilizers in aqueous surfactant compositions. 2. Use according to claim 1, characterized in that the water surfactant compositions are aqueous hand dishwashing detergents. 3. Use according to one of claims 1 or 2, characterized net that the short-chain polysaccharides have a degree of polymerization of 3 have up to 300, in particular from 3 to 50. 4. Use according to one of claims 1 to 3, characterized in that that the short-chain polysaccharides in an amount of 0.5 to 15 wt .-%, based on the finished composition. 5. Use according to one of claims 1 to 4, characterized in that as short-chain polysaccharides, degradation products of pectins, algins, Carrageenan, Agar, Targant, Gum arabic, Karaya gum, Ghatti Gum, xanthan, galactomannans, inulin, starch, condensation pro Products from mono- and disaccharides as well as their derivatives and mixtures of the foregoing. 6. Containing aqueous surfactant composition, in particular hand dishwashing detergent

• a) 0.2% by weight to 15% by weight, preferably 1 to 10% by weight, based on the overall composition, short-chain polysaccharide,
• b) 1% by weight to 50% by weight, preferably 5% by weight to 45% by weight, based on the total composition, anionic surfactant and
• c) 1% by weight to 20% by weight, preferably 2% by weight to 10% by weight, based in each case on the total composition, of nonionic surfactant.

7. Aqueous surfactant composition according to claim 5, characterized records that as an anionic surfactant C₆-C₂₂-alkyl sulfate, C₆-C₂₂-alkyl ether sulfate, C₉-C₁₃-alkylbenzenesulfonate, C₆-C₂₂-alkylsulfonates or be arbitrary mixtures of the above-mentioned surfactants is used. 8. Aqueous surfactant composition according to claim 6, characterized records that used as nonionic surfactant C₆-C₂₂-alkyl glycoside becomes. 9. Aqueous surfactant composition according to one of claims 6 to 8, characterized in that the total surfactant content is more than 20% by weight, preferably more than 33 wt .-%, based on the total composition, amounts. 10. Aqueous surfactant composition according to one of claims 6 to 9, characterized in that it is free of alkali or ammonium salts is saturated or unsaturated C₆-C₂₂ fatty acids.