WO1996037590A1

WO1996037590A1 - Aqueous cleaning agent composition

Info

Publication number: WO1996037590A1
Application number: PCT/EP1996/002106
Authority: WO
Inventors: Udo Hees
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-05-26
Filing date: 1996-05-17
Publication date: 1996-11-28
Also published as: DE19519405A1

Abstract

The invention concerns an aqueous cleaning agent composition containing: (A) between 2 and 25 wt.% 2,3-secondary C10-C22 alkylsulphates; and (B) between 1 and 15 wt.% C10-C22 alkylsulphates, provided that the concentration of component (B) is not more than 50 wt.% of component (A). The cleaning agent composition is suitable both as an all-purpose cleaner and as a washing-up liquid, has very good properties as concerns the cleaning of soiling by grease and behaves well at low temperatures.

Description

"Aqueous detergent composition '

The present invention relates to an aqueous detergent composition which contains primary and secondary fatty alkyl sulfates and has a good cleaning power, in particular with respect to greasy soils.

Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and conventional additives. They are especially used for cleaning hard surfaces, e.g. of glass, ceramic materials, plastics, lacquered and polished surfaces. An important area of application for liquid detergents is the manual washing of eating and cooking utensils and the use as a so-called "household cleaner", which is used for cleaning floors, work surfaces, cupboards, etc. Both the cleaning of dishes and the cleaning of other surfaces are usually carried out at slightly elevated temperatures of about 35 to 45 ° C. using very dilute liquors.

The usual hand dishwashing detergents and all-purpose cleaners on the market are mostly based on a high proportion of anionic surfactants, which are the main service providers in the cleaning process. Organic sulfates, such as e.g. Fatty alcohol sulfates or fatty alcohol ether sulfates are used. Sulfonates, such as e.g. Alkanesulfonates or alkylbenzenesulfonates used.

The use of 2,3-alkyl sulfates in detergents and cleaning agents is described in German patents DE 27 51 350 C2 and DE 26 31 900 P2. International patent application WO 94/24245 discloses e.g. a hand dishwashing detergent is known which contains fatty alcohol ether sulfate and 2,3-sec. alkyl sulfates as anionic surfactants.

In the recent past, efforts have increasingly been made to increase the surfactant content of aqueous cleaning agents, in particular hand dishwashing detergents and all-purpose cleaners, in order to obtain concentrates. When developing new cleaning agents, one of the main goals is to improve tion of the. Means, in particular the improved cleaning of greasy soils, without changing other important parameters, such as the cold behavior.

The object of the present invention is to provide detergent compositions with a high total surfactant content which have a very good cleaning action against greasy soils, other parameters, such as e.g. the cold behavior is not changed, in particular not deteriorated.

The invention relates to an aqueous detergent composition containing

A) 2 to 45 wt .-% 2.3-sec -CC ₀ -C ₁₈ alkyl sulfates, and

B) 1 to 15% by weight of 1-C ₁₀ -C ₂₂ -alkyl sulfates, with the proviso that the concentration of (B) is not more than 50% of the concentration of (A).

The secondary alkyl sulfates are known anionic surfactants which are obtained according to the prior art by adding sulfuric acid to olefins of suitable chain length. Another method is to epoxidize olefins and then open the oxirane rings with sulfur trioxide. In the subsequent neutralization, however, certain proportions of hydroxysulfates or alkenesulfates can also arise. Processes for the preparation of secondary alkyl sulfates are described, for example, in the documents DE-OS 1568 741 (Henkel), WO 93/24452 and EP-A 0466243 (Shell) and WO 94/24245 (Procter & Gamble). Typical examples of secondary 2,3-alkyl sulfates are addition products of sulfuric acid onto technical olefin cuts with 12 to 14 carbon atoms or 16 to 18 carbon atoms in the form of their sodium and / or magnesium salts.

Primary fatty alkyl sulfates are contained in the agent according to the invention as further anionic surfactants.

Primary fatty alkyl sulfates (FAS) which can be used in the sense of the invention are e.g. those with the general formula I,

R ¹ -0-Sθ ₃ X (I), in the R ¹ for a saturated or unsaturated

and X represents an alkali or alkaline earth metal.

These substances are known chemical compounds that can be obtained by sulfating fatty alcohols. Typical examples are the sulfates of capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myhstial alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, alaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and technical-grade alcohol and erucyl alcohol. Sulphates of technical grade C ₁₂₁ are preferred. or C _{12 / .8} ocos fatty alcohol cuts in the form of their sodium or magnesium salts.

Also suitable as further anionic surfactants in the aqueous surfactant compositions

and / or C ₉ -C ₃ alkyl benzene sulfonates and / or C ₆ -C ₂₂ alkyl sulfonates.

Fatty alkyl ether sulfates (FAES) which can be used in the sense of this invention follow the formula II,

R ² 0- (CH ₂ CH ₂ 0) _n -Sθ ₃ X (II)

in which R ^{2 is} a saturated or unsaturated C ₆ -C ₂₂ alkyl group, n is a number from 0.5 to 10 and X is an alkali or alkaline earth metal.

These substances are also known chemical compounds which can be obtained by sulfating fatty alcohol polyglycol ethers. Also FAES with a narrow homolog distribution (NRE = narrow ranks ethoxylates), as described, for example, in 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 of 0.5 to 10 moles of ethylene oxide (conventional or restricted homolog distribution) with 1 mole of capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petro-selinyl alcohol , Gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as their technical mixtures. Sulfates of adducts of 1 to 7 moles of ethylene oxide with saturated coconut oil alcohols having 12 to 16 carbon atoms in the form of their sodium, potassium and / or magnesium salts are preferred. For example, fatty alcohol ether sulfates are used which are derived from corresponding fatty alcohol polyglycol ethers, which in turn have been prepared in the presence of calcined or, in particular, hydrophobicized hydrotalcite and therefore have a particularly advantageous narrow homolog distribution.

Other anionic surfactants include, for example, n-alkylbenzenesulfonates with 9 to 16, preferably 12 carbon atoms in the alkyl radical, alkanesulfonates with 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical and olefin sulfonates with 12 to 16, preferably 12 to 14, carbon atoms in the alkyl radical to call. Examples of C ₉ -C ₁₃ alkylbenzenesulfonates which can be used in the context of the invention are the products marketed under the trade names Marlon ^(R) (from Hüls) and Witconate ^(R) (from Witco).

Soaps, ie alkali or ammonium salts of saturated or unsaturated C ₆ -C ₂₂ fatty acids, are preferably not contained in the agents according to the invention because of their foam-suppressing properties.

The feature "not included" is not intended to mean that very small amounts of soap cannot be included; Quantities of up to 2% by weight, based on the total composition, are still tolerable in the sense of the invention.

The liquid cleaning agents according to the invention can contain nonionic surfactants and amphoteric surfactants as further components.

The agents according to the invention preferably contain C ₆ -Czr alkyl glycosides as nonionic surfactants.

Alkyl glycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. As a representative of the extensive literature, reference is made to the documents EP-A 1-0 301 298 and WO 90/3977. The alkyl glycosides follow the formula III,

R ³ 0 [Eq (III), in which R ^{3 is} a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, [G] is a glycosidic radical and x is a number from 1 to 10.

The index number x in the general formula III indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be full-time in a given connection and here can assume the values x = 1 to 6, the value x is for certain alkyl glycoside is an analytically calculated quantity, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From the point of view of application technology, preference is given to those alkyl glycosides whose degree of oligomerization is less than 1.8 and in particular between 1.2 and 1.7. Glucose and xylose are preferably used as glycosidic sugar units.

The alkyl or alkenyl radical R ³ can be derived from primary alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.

The alkyl or alkenyl radical R ³ is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oley alcohol. Elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures are also to be mentioned.

As a further non-ionic surfactants fatty acid alkanolamides may wer¬ used to, for example C ₁₂ i ₈ fatty acid monoethanolamide, or adducts of from 4 to 20, preferably from 4 to 10 moles of alkylene oxide, preferably ethylene oxide and C ₁₀ - C _Σ o-, preferably C ₁ -Cι ₈ alkanols, but also the addition products of ethylene oxide and propylene glycols, which are known under the name Pluronics ^®, as well as addition products of 1 to 7 moles of ethylene oxide with 1 to 5 moles of propylene oxide converted Cι ₂ -Cιβ alkanols suitable. Fatty alkyl amine oxides are also suitable. The betaine compounds with formula V and the fatty acid alkanolamides can each be present in the detergent composition according to the invention in an amount of up to 10% by weight.

In addition, fatty alcohol alkoxylates of the formulas IV and V can be used as nonionic surfactants,

R ⁴ 0- (CH ₂ CH ₂ 0) _m -H (IV),

in which R ^{4 represents} a saturated or unsaturated C ₆ -C ₂₂ alkyl group and m represents numbers from 1 to 20,

CH ₃ IR ⁵ 0- (CHCH ₂ 0) _n - (CH ₂ CH ₂ 0) oH (V),

wherein R ⁵ and o can have the same meaning as R ⁴ and m in formula IV and n stands for numbers from 0.5 to 2.

The fatty alcohol alkoxylates are known compounds which can be obtained by alkoxylating the fatty alcohols. The fatty alcohol alkoxylates can be present in the agent according to the invention in an amount of up to 15% by weight.

As amphoteric surfactants, betaine compounds of the formula VI

R ⁷ IR ⁶ - N ⁺ - CH ₂ COO ^_ (VI)

IR ⁸

are used in which R ^{6 is} an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms and R ⁷ and R ^8, which are optionally interrupted by heteroatoms or heteroatom groups, and R ⁷ and R ^{8 are} identical or different alkyl radicals with 1 to 3 carbon atoms. C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetaine and Cn-Cir-alkylamidopropyldimethylcarboxymethylbetaine are preferred.

As further constituents, the agents according to the invention can also contain solvents, perfume, dyes and opacifiers, as well as skin protection components, as are known, for example, from EP-A1 522 756. To adjust the viscosity Substances such as gelatin or casein can be used without impairing the performance of the agents according to the invention.

The solvents to be added if necessary are low molecular weight alkanols having 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol. Optional solubilizers, for example for dyes and perfume oils, can optionally be, for example, alkanolamines, polyols such as ethylene glycol, propylene glycol, glycerol and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical.

The preferred thickeners include urea and ammonium chloride, which can also be used in combination. Sodium benzoate, formaldehyde and sodium sulfite may be mentioned as preservatives. 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 total surfactant content is preferably more than 25% by weight, particularly preferably more than 33% by weight, based on the total composition.

The agent according to the invention can be used as a hand dishwashing agent and also as an all-purpose cleaner. If the detergent is used as a hand dishwashing detergent, it preferably contains from 10 to 45% by weight of 2.3-sec-C ₀ -C ₂₂ -alkyl sulfates, 3 to 15% by weight of C ₀ -C ₂₂ Alkyl sulfates. In a particularly preferred embodiment, the composition additionally contains 3 to 15% by weight of fatty alcohol ether sulfates, 1 to 10% by weight of alkyl glycosides, 1 to 10% by weight of betaines and up to 10% by weight of fatty acid alkanolamides.

If the agent according to the invention is used as an all-purpose cleaner, it preferably contains 2 to 25% by weight of 2.3-sec. -C- ₀ -C ₂₂ alkyl sulfate, 1 to 15% by weight of C ^ -C _∑ alkyl sulfate. In a preferred embodiment, the agent further contains 1 to 10% by weight of alkyl glycosides and up to 20% by weight of nonionic surfactants. Examples

Example 1:

20% C ₁₂ sec. 2,3-alkyl sulfate Na salt 10% C _{12 / .4} fatty alcohol sulfate Na salt

8% APG 600® (commercial product from Henkel KGaA, Düsseldorf) 2% coconut fatty acid amidopropyl betaine

4% PEG 400

9% ethanol

Rest on 100% water

Example 2:

20% Ci ₄ sec. 2,3-alkyl sulfate Na salt

7% C ₁₂₁₄ fatty alcohol ether (2EO) sulfate Na salt

8% APG 600®

2% coconut dimethylaminopropyl betaine

7% ethanol

Rest on 100% water

Example 3:

18% C ₁₂ i ₄ fatty alcohol ether (2EO) sulfate Na salt

8% C ₁₂ sec. 2,3-alkyl sulfate Na salt 8% APG 600®

4% coconut fatty acid amidopropyl betaine 7% ethanol

Rest on 100% water

Example 4:

10% C ₁₂ sec. 2,3-alkyl sulfate Na salt

5%

Fatty alcohol sulfate sodium salt 4% C _12/14 N-methyl glucamide

4% APG 600®

5% ethanol

3% cumene sulfonate balance on 100% water

Example 5: 12% C ₁₂ yi ₄ sec. 2,3-alkyl sulfate Na salt

5% C ₁₂ i ₄ fatty alcohol ether (1 EO) sulfate Na salt

2% lauryl monoethanolamide

6% Ci _{2 / .4} alkyl polyglucoside with a DP of 1.4

5% ethanol

Rest on 100% water

Example 6:

12% C ₁₂ sec. 2,3-alkyl sulfate Na salt 4% C ₁ i ₄ fatty alcohol sulfate Na salt

4% Ci _2/14 fatty alcohol ether (1 EO) sulfate Na salt

6% C _{12 1} -alkyl polyglucoside with a DP of 1.4

5% ethanol

Rest on 100% water

Example 7:

12% C ₁₂ sec. 2,3-alkyl sulfate Na salt

8% C ₁₂ fatty alcohol ether (2EO) sulfate Na salt

10% decanol + 1 PO + 8 EO

6% C _12/14 alkyl polyxyloside with a DP of 1.4

7% ethanol

3% PEG 400

Rest on 100% water

Example 8:

25% Cβ _/ io alkyl polyglucoside

20% C ₁₂ sec. 2,3-alkyl sulfate Na salt

5% palm kernel fatty acid

3% oxidized starch

10% cumene sulfonate x% potassium hydroxide solution to adjust the pH of the finished product to pH 8

Rest on 100% water

Example 8 represents an AZR high concentrate which is used in 0.1% solution.

Example 9: 3% Cβ _/ io-alkyl polyglucoside 1% butyl polyglucoside

1% sec. 2,3-alkyl sulfate Na salt 0.5% palm kernel fatty acid

2% polymethacrylate Acrysol ICS-1 0.05% polyethylene oxide, MW 600000 2% butylglycol x% sodium hydroxide solution to adjust the pH of the finished product to pH

8th

Rest on 100% water

Example 10:

0.2% do-alkyl polyglucoside

0.05% C ₁₂ sec. 2,3-alkyl sulfate Na salt

7% ethanol

1% oxidized starch x% ammonia to adjust to pH 8

Rest on 100% water

It is an all-purpose spray cleaner that is applied undiluted using a hand spray pump.

Example 11:

0.2% C ₁₂ sec. 2,3-fatty alcohol sulfate Na salt 0.05% alkylbenzenesulfonate Na salt 7% ethanol

1% sodium gluconate x% ammonia to adjust to pH 7.8 rest on 100% water

Example 12:

6% Cι ₂ sec. 2.3 fatty alcohol sulfate Na salt 6% C ₈₁₀ alkyl polyxyloside

2% octyl sulfate 5% ethanol

2% oxidized starch

Rest on 100% water

Example 13:

14% C ₁₂ sec. 2,3-fatty alcohol sulfate Na salt

18% Syntran 1501 (Kahl + Co.)

2% sodium gluconate

0.05% Keltrol T

1.2% Sequion 40 Na 32 (Polygon Chem.) With ammonia, the pH is adjusted to 8.5

Rest on 100% water

Application example 13 represents a floor cleaner with a protective component for the surface after cleaning.

Comparison of the cleaning effect of sec. 2.3-alkyl sulfates against 1-alkyl sulfates:

The following compositions were compared:

A: 14% by weight of C ₁₂ alkyl sulfate Na salt

8% by weight of C ₁₂ i ₄ fatty alcohol ether (2EO) sulfate Na salt 3% by weight of C ₁₂ alkyl polyglucoside with a DP of 1.4 5% by weight of ethanol

B: 12% by weight of C ₁₂ alkyl sulfate Na salt

8% by weight of C ₁₂ i ₄ fatty alcohol ether (2E0) sulfate Na salt

3% by weight of C ₂ alkyl polyglucoside with a DP of 1.4

2 wt% coco amidopropylamine

5% by weight ethanol

Test results:

1. Cold cloud points

A B

prim. 1-alkyl sulfate - 2.0 ° C -2.3 ° C sec. 2,3-alkyl sulfate -2.7 ° C -3.0 ° C

Plate test

The rinsing capacity in the mechanized plate test (c = 0.5 g / l) on soiling based on beef tallow (rinsing capacity at A with 1-alkyl sulfate Na salt = 100%):

A B

prim. 1-alkyl sulfate 100% 112% sec. 2,3-alkyl sulfate 112% 124%

It is clear from the test results that the cold cloud points and the cleaning power of the composition according to the invention have significantly better values than the comparative compositions.

All-purpose cleaner:

5% by weight APG 220

4 wt .-% -C ₂ alkyl sulfate Na salt

0.05% by weight polyethylene oxide, MW 600000

1% by weight sodium gluconate

2% by weight ethanol pH = 8.3 (adjusted with KOH)

The cleaning power according to the modified IPP test is 100% when using the primary alkyl sulfate, with sec. 2,3-alkyl sulfate 118%.

Claims

claims

1. Containing aqueous detergent compositions

(A) 2 to 25% by weight of 2.3 sec. C ₁₀ -C ₂₂ alkyl sulfates and

with the proviso that the concentration of component (B) is not more than 50% by weight of component (A).

2. Composition according to claim 1, characterized in that it contains 3 to 15 wt .-%, based on the total composition, fatty alkyl ether sulfates.

3. Composition according to claim 1 or 2, characterized in that it contains from 1 to 10 wt .-%, based on the agent, alkyl glycosides.

4. Agent according to one of claims 1 to 3, characterized in that it contains from 1 to 10 wt .-%, based on the agent, betaines.

5. Composition according to one of claims 1 to 4, characterized in that it contains up to 10 wt .-% fatty acid alkanolamides.

6. An aqueous detergent composition according to any one of claims 1 to 5, characterized in that the total surfactant content is more than 25% by weight, preferably more than 33% by weight, based on the total composition.

7. Aqueous detergent composition according to one of claims 1 to 6, characterized in that it is free of alkali or ammonium salts saturated or unsaturated

is.

8. Aqueous dishwashing liquid containing

(A) 10 to 45 wt .-%, based on the agent, 2,3-sec.-Cι ₀ -C ₂₂ alkyl sulfates, and

(B) 3 to 15 wt .-%, based on the agent, do-C ^ alkyl sulfates, with the proviso that the concentration of component (B) is not more than 50% of component (A). _). Liquid all-purpose cleaner containing:

(A) 2 to 25 wt .-%, based on the agent, 2,3-sec.-C ₁₀ -C ₂₂ alkyl sulfates and

(B) 1 to 15 wt .-%, based on the agent, do-C ^ alkyl sulfates, with the proviso that the concentration of component (B) is not more than 50% of the concentration of component (A).