WO1995024462A1

WO1995024462A1 - Aqueous washing-up agent

Info

Publication number: WO1995024462A1
Application number: PCT/EP1995/000736
Authority: WO
Inventors: Udo Hees; Rainer Jeschke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-03-08
Filing date: 1995-03-01
Publication date: 1995-09-14
Also published as: DE4407687A1

Abstract

The present invention concerns aqueous washing-up agents containing a ternary surfactant combination of lactobionic acid amide, C6-C22 fatty alkylsulphate and/or C6-C22 fatty alkylethersulphate and C6-C22 alkylglycoside.

Description

"Aqueous hand dishwashing liquid"

The present invention relates to aqueous, manually applicable skin-friendly dishwashing detergents with a ternary surfactant combination.

Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and customary additives. They are used especially for cleaning hard surfaces, for example of glass, ceramic materials, PVC, linoleum, etc. varnished and polished surfaces. An important area of application for liquid detergents is the manual washing of dishes and cookware. The dishes are usually cleaned at temperatures of around 35 to 45 ° C in very dilute liquors. In general, the cleaning power of an agent is judged by the consumer as the better, the stronger and the longer the cleaning liquor foams. Because of the contact of the hands with the cleaning liquor over a longer period of time, the skin-friendliness of the agent is of particular importance when washing dishes manually. For these reasons, the expert makes different considerations when selecting the components and the composition of an agent for the manual cleaning of dishes than with liquid detergents for other hard surfaces.

It is generally known that fatty alkyl sulfates, ie sulfated fatty alcohols having 6 to 22 carbon atoms, preferably 12 to 16 carbon atoms, and so-called fatty alkyl ether sulfates, ie salts of sulfated adducts of about 1 to 10 mol of ethylene oxide with fatty alcohols having 6 to 22 , preferably 12 to 16 carbon atoms in the aliphatic radical have good foaming and cleaning power. The commercially available manual dishwashing detergents are therefore generally aqueous solutions of such alkyl sulfates and / or alkyl ether sulfates in conjunction with other surfactants, in particular alkylbenzenesulfonates and solubilizers, colorants and fragrances. However, these handwashing detergents customary on the market are not in terms of skin-friendliness always satisfactory. O 95/24462

US Pat. No. 2,752,334 and European laid-open patent EP-Al-550106 describe the synthesis of N-substituted lactobionic acid amides. The two European patent applications EP-A-550281 and EP-A-550278 describe the use of lactobionic acid amides in cosmetic preparations or in detergents and cleaning agents, including hand dishwashing detergents. DE-A-4215478 discloses lactobionic acid compositions which, owing to their favorable foaming behavior, can also be used in hand dishwashing detergents.

The object of the present invention is to provide an aqueous hand dishwashing detergent which, in addition to particularly skin-friendly properties, has a strong, stable foam, good emulsifying power and good cleaning power.

Surprisingly, it has now been found that lactobionic acid amides, as a constituent of specific surfactant combinations in aqueous hand dishwashing detergents, not only have particularly skin-friendly properties, but also have a particularly strong foam development, high foam stability, particularly good emulsifying power and good cleaning power .

The invention relates to aqueous hand dishwashing detergents containing 0.1 to 30% by weight, preferably 0.5 to 10% by weight, of a lactobionic acid amide of the formula I,

O

II « ²

R3O-CH ₂ -CH (0H) -CH-CH (0H) -CH (0H) -CN

I Rl

0

(I),

wherein R * for a branched or unbranched, saturated or unsaturated alkyl group having 6 to 22 carbon atoms, R ² for hydrogen, a methyl or ethyl group or a branched or unbranched, saturated or unsaturated alkyl group having 3 to 22 carbon atoms and R ^ and R ^ independently of one another are hydrogen, alkyl groups with 1 to 4 carbon atoms or acyl groups with 6 to 22 carbon atoms, 0.1 to 40% by weight, preferably 5 to 35% by weight. -%, an alkyl sulfate of the formula II, R5-O-SO3X, in which R5 is a saturated or unsaturated Cö-C22-al yl group and X is an alkali metal, alkaline earth metal or ammonium ion, alkyl ether sulfate of the formula

III, R ⁶ -0- (CH2CH2θ) _n -Sθ3X, in which R ⁶ for a saturated or unsaturated Cö-C22- ^a ^ yl group, n for numbers from 1 to 10 and X for an alkali, Erd¬ alkali or Ammonium ion, or a mixture of both and 0.1 to 30% by weight, preferably 0.5 to 10% by weight, of an alkyl glycoside of the formula

IV, R ^ 0 [G] _x , in which R? represents a branched or unbranched, saturated or unsaturated C6-C22-al yl radical, G represents a glycosidic radical, in particular a glucose or xylose radical, and x represents numbers from 1 to 10.

The lactobionic acid amide of the formula I need not be a uniform compound.

Lactobionic acid amides are preferably used in which R * is a branched or unbranched, saturated or unsaturated C 1 -C 8 -alkyl group and R ² , R ³ and R ^{4 are} hydrogen.

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

R ⁵ -0-S0 ₃ X, (II),

in which R5 stands for a saturated or unsaturated Cö-C22-alkyl group and X stands for an alkali, alkaline earth or ammonium ion.

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, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures. Sulphates of technical grade C12 / 18- ^Ko * ^<os * fatty alcohol or CiO / i-tallow fatty alcohol cuts are preferably used in the form of their sodium salts.

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

R ⁶ 0- (CH2CH ₂ 0) _n -Sθ3X (III),

in which R6 is a saturated or unsaturated C5-C22 alkyl group, n is a number from 1 to 10 and X is an alkali metal, alkaline earth metal or ammonium ion.

These substances are also known chemical compounds which can be obtained by sulfating fatty alcohol polyglycol ethers. Among other things, FAES with narrow homolog distribution (NRE = narrow range ethoxylates) can also be used, as described, for example, in international patent application WO 91/05764 and in the overview by DLSmith in J.Am.Oil.Che .Soc . 68, 629 (1991).

Typical examples are the sulfation products of adducts of 1 to 10 moles of ethylene oxide (conventional or restricted homolog distribution) to 1 mole of capron alcohol, capryl alcohol, caprine alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, gadroelyl alcohol, petoleol alcohol, petoleol alcohol ¬ hol, behenyl alcohol and erucyl alcohol and their technical mixtures. Sulfates of adducts of 2 to 7 moles of ethylene oxide with saturated coconut oil alcohols having 12 to 18 carbon atoms in the form of their sodium, potassium and / or magnesium salts are preferred. Among other things, fatty alcohol ether sulfates can also be used, which are derived from corresponding fatty alcohol polyglycol ethers, which in turn were produced in the presence of calcined or, in particular, hydrophobicized hydrotalcite are and therefore have a particularly advantageous narrow homolog distribution.

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 here to the documents EP-Al-O 301 298 and WO 90/3977. The alkyl glycosides follow the formula IV,

R ⁷ 0 [G] _x , (IV),

in the R? represents a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, [G] a glycosidic radical, in particular a glucose radical or xylose radical, and x stands for a number from 1 to 10.

The index number x in the general formula IV 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 an integer in a given connection and, above all, can assume the values x = 1 to 6, the value x is for a certain alkyl glycoside is an analytically determined arithmetic size, 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 an application point of view, preference is given to those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.

The alkyl or alkenyl radical R? 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 those obtained 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. It is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Farther Elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures are to be mentioned.

The weight ratios of the surfactant components mentioned under a), b) and c) preferably have the following values: a / b: 4: 1 to 1: 7, a / c: 4: 1 to 1: 4, b / c: 10: 1 to 1: 2.

As further, optionally contained in the hand dishwashing detergents according to the invention are z. B. 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 n-alkyl radical name, which can be contained in amounts of up to 50 wt .-%, based on the entire agent.

However, the hand dishwashing detergents according to the invention are preferably free from surfactants with a sulfonate function.

Soaps too, i.e. Alkali or ammonium salts of saturated or unsaturated C5-C22 fatty acids are preferably not contained in the hand dishwashing detergents according to the invention because of their foam-suppressing properties.

"Free of" or "not included" should not mean that very small amounts of the above Substances cannot be contained; Quantities of up to 1% by weight, based on the total agent, are still tolerable in the sense of the invention.

Other surfactants optionally contained in the hand dishwashing detergents according to the invention are amphoteric surfactants and nonionic surfactants.

Betaine compounds of the formula can be used as amphoteric surfactants

are used in which R ^ is an alkyl radical with 8 to 20, preferably 10 to 18, carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups, and R ^ and R * 0 are identical or different alkyl radicals with 1 to 3 carbon atoms. Cio-Ciss-alkyl-dimethylcarboxymethylbetaine and Cn-Ci7-alkylamidopropyl-dimethyl-carboxymethyl-betaine are preferred.

If - apart from alkylglycosides of the formula IV - further nonionic surfactants are used, fatty alkylamine oxides, fatty acid glucamides, cio-cis fatty acid alkanolamides, for example monoethanolamides, or addition products of 4 to 20, preferably 4 to 10, mol of alkylene oxide, preferably ethylene oxide on C 1 -C 4 -alkylbenzenes, Ci0 "C20" «preferably Ci2-Ci8 ~ alkanols, Cιo-Cl8 ^_ _< fatty acid alkanolamides, but also the addition products of ethylene oxide on polypropylene glycols, which are known under the name Pluronics ( ^R ) , and addition products of 1 to 7 moles of ethylene oxide with 1 to 5 moles of propylene oxide reacted with Cβ-Cis-alkanols.

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. Solubilizers, for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, propylene glycol, glycerol and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical, and short-chain Ci-Cs-alkyl glycosides.

The preferred thickeners include urea, sodium chloride and ammonium chloride or poly thickeners such as. B. polyacrylates or guar gum, which can also be used in combination. Corrosion inhibitors and preservatives include, for example, sodium benzoate, formaldehyde and sodium sulfite. The hand dishwashing liquid can also Contain common disinfectants. The pH of the agents according to the invention is preferably between 4.5 and 8.0.

The agents according to the invention of the following examples were obtained by stirring the individual constituents together in any order and leaving the mixture to stand until there were no bubbles.

B e i s p i e l e

I. Surfactants used

APG: Ci2 / i4 ~ cocoalkyl oligoglucoside

Plantaren ( ^R ) APG 600 (50% by weight aqueous paste), Henkel

FAES: lauryl ether sulfate, sodium salt Texapon ( ^R ) N, Henkel

FAS: Lauryl sulfate, Na salt, Texapon (R) LS, Henkel

LBA: Lactobionic acid cocosamide from Solvay

NRE: narrow-range ethoxylate

II. Assessment of the dividing pollen assets (TSV)

The determination of the TeilerspülVermögens was carried out with the aid of the plate-test [Fette, Seifen, Anstrichmittel, _21/163 (1972)]. For this purpose, the plate with a diameter of 14 cm, each with 2 cm ^ beef tallow (acid number 9-10) (Rita) or with a soiling. based on baby food from Milupa (Mino) soiled 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 / 1. The rinse attempt was stopped as soon as the foam had completely disappeared; the number of dishes washed is the criterion for the divisible washing ability. The results of the rinsing tests are summarized in Table 1; the dishwashing capacity (TSV) is given in relation to an efficient standard, the TSV of which was set to 100. I. Reiniqunqsvermöqen (plate test)

The following compositions 1-10 (table 1) are ternary mixtures of LBA / APG / FAS (compositions 1-5) and LBA / APG / FAES (compositions 6-10).

The compositions each contain 60% by weight of FAS (compositions 1-5) and 60% by weight of FAES (compositions 6-10). The remaining 40% by weight are LBA and / or APG.

Table 1

a) Ternary mixtures with 60% by weight FAS

1 2 3 4 5

APG [in% by weight] 40 30 20 10 0

LBA [in% by weight] 0 10 20 30 40

TSV versus Rita 76 80 65 45 15

TSV versus Mino 153 153 141 112 53

b) Ternary mixtures with 60% by weight FAES

6 7 8 9 10

APG [in% by weight] 40 30 20 10 0

LBA [in% by weight] 0 10 20 30 40

TSV to Rita 81 76 86 71 62

TSV versus Mino 147 153 147 124 118

As can be seen from Table 1 a), a mixing ratio FAS / APG / LBA which is particularly favorable in terms of cleaning ability is 60:30:10.

Table 1 b) shows that a mixture ratio which is favorable for the ternary mixture FAES / APG / LBA is from 60:30:10 to 60:20:20.

II. Foam capacity (Wagner foam test)

equipment

- Wagner shaker from Guwina-Hoffmann GmbH

- temperature-controlled water bath

Test conditions

Water hardness: 16 ° d

Starting temperature: 45 ° C

Concentration: 1 g product / 1 execution

From the formulations to be investigated, stock solutions with concentrations of 10 g of product / l each were prepared with demineralized water in 100 ml volumetric flasks.

10 ml of these solutions were then pipetted into the mixing cylinder and made up to 50 ml with deionized water. The mixture was then made up from 32 ° d to 100 ml with water and heated to 45 ° d in a water bath.

The mixing cylinders were then clamped into the Wagner device and "shaken" for 20 revolutions.

The volume of foam was read off after 1 minute. Then the mixing cylinders were removed from the Wagner device, mixed with 0.5 ml of olive oil and clamped again. It was "shaken" again 20 times.

Another measurement followed after adding a further 0.5 ml of olive oil / mixing cylinder and repeated "shaking".

Table 2

a) Ternary mixtures with 60% by weight FAS

1 2 3 4 5

APG [in% by weight] 40 30 20 10 0

LBA [in% by weight] 0 10 20 30 40

Foam height [in cm] 88 95 90 78 60 without oil contamination

Foam height [in cm] 60 85 45 40 23 with 5 ml oil load

Foam height [in cm] 40 45 28 20 10 with 10ml oil load

As can be seen from Table 2 a), a particularly favorable mixture ratio with regard to the foam capacity is FAS / APG / LBA 60:30:10.

Further examples according to the invention:

Example 11:

12% Ci2 / i4 fatty alcohol ether (3E0) sulfate Na salt 4% Ci2 / i4 fatty alcohol sulfate Na salt 2% lactobionic acid cocosamide

2% Ci2 / i4 alkyl polyglucoside with a DP of 1.4

3% ethanol

Rest on 100% water

Example 12:

12% Ci2 / i4 fatty alcohol ether (3E0) sulfate Na salt 8% lactobionic acid cocosamide

2% Ci2 / i4 alkyl polyglucoside with a DP of 1.4

4% ethanol

Rest on 100% water

Example 13:

13% Ci2 / i4 fatty alcohol ether (3E0) sulfate Na salt 8% lactobionic acid cocosamide

3% Ci2 / i4 ~ alkyl polyglucoside with a DP of 1.4 3% ethanol

3% polyethylene glycol (HG = 400)

Rest on 100% water

Example 14:

12% Ci2 / i4 fatty alcohol ether (2.5E0) sulfate Na salt (NRE ethoxylate)

4% Ci2 / i4 fatty alcohol sulfate sodium salt 3% lactobionic acid lauryl fatty acid amide

3% Ci2 / i4 ~ alkyl polyxyloside with a DP of 1.4

4% ethanol

Rest on 100% water Example 15:

10% Ci2 / H fatty alcohol ether (3E0) sulfate Na salt

4% Ci2 / i4 fatty alcohol sulfate Na salt

2% lactobionic acid myristyl fatty acid amide

2% Ci2 / i4 alkyl polyglucoside with a DP of 1.5

2% coconut fatty acid, sodium salt

4% ethanol

Rest on 100% water

Example 16:

12% Ci2 / i4 fatty alcohol ether (3E0) sulfate Na salt

4% Ci2 / i4 fatty alcohol sulfate Na salt

2% lactobionic acid myristyl fatty acid amide

2% Ci2 / i4 alkyl polyglucoside with a DP of 1.5

2% coconut fatty acid amidopropyl betaine

4% ethanol

Rest on 100% water

Example 17:

12% Ci2 / i4 fatty alcohol ether (3E0) sulfate Na salt

6% coconut fatty acid monoglyceride + 10 E0

2% lactobionic acid myristyl fatty acid amide

2% Cχ2 / i4 alkyl polyglucoside with a DP of 1.5

4% ethanol

Rest on 100% water

Example 18:

12% Ci2 / i4-0xoalcohol ether (2E0) sulfate Na salt

6% coconut fatty acid monoglyceride + 10 E0

2% lactobionic acid coconut fatty acid amide

2% Ci2 / i4 alkyl polyglucoside with a DP of 1.5

4% ethanol

Rest on 100% water Example 19:

14% Ci2 / i4 fatty alcohol ether (2.5E0) sulfate Na salt (NRE) 6% Cιo / 14-fatty alcohol + 8 EO

2% lactobionic acid myristyl fatty acid amide

3% Ci2 / i4-alkyl polyglucoside with a DP of 1.5 1.5% amidoethyl-N-2-hydroxyethylglycinate

6% ethanol

Rest on 100% water

Example 20:

14% Ci2 / i4 fatty alcohol ether (l, 2E0) sulfate Na salt (NRE) 6% Cιo / 14-fatty alcohol + 1.2 PO + 8 EO

2% lactobionic acid myristyl fatty acid amide

6% ethanol

Rest on 100% water

Example 21:

29% Ci2 / i4 fatty alcohol ether (1,2E0) sulfate Mg salt (NRE)

10% Ci2 / i4 fatty alcohol sulfate Mg salt

10% Cιo / 14-fatty alcohol + 1.2 PO + 8 E0

8% lactobionic acid myristyl fatty acid amide

3% Ci2 / i4-alkyl polyglucoside with a DP of 1.5 12% C4-alkyl polyglucoside with a DP of 1.5

8% polyethylene glycol (MW = 200)

10% ethanol

Rest on 100% water

Example 22:

26% Ci2 / i4 fatty alcohol ether (3E0) sulfate Na salt

11% Ci2 / i4 fatty alcohol sulfate Na salt 5% lactobionic acid cocosamide

3% Cχ2 / 14 alkyl polyglucoside with a DP of 1.4

7% ethanol

Rest on 100% water Example 21 stands for a hand dishwashing liquid high concentrate which is used in a diluted form. Raw materials that are as water-free as possible are used in the manufacture.

Claims

95 / 24462-18P claims

1. Containing aqueous dishwashing liquid

a) 0.1 to 30% by weight, preferably 0.5 to 10% by weight, of a lactobionic acid amide of the formula I.

R2

R3θ-CH ₂ -CH (OH) -CH-CH (OH) -CH (OH) -CN /

I ^ Rl

wherein R stands for a branched or unbranched, saturated or unsaturated alkyl group with 6 to 22 C atoms, R2 for hydrogen, a methyl or ethyl group or a branched or unbranched, saturated or unsaturated alkyl group with 3 to 22 C atoms and R3 and R ^ independently of one another are hydrogen, alkyl groups with 1 to 4 carbon atoms or acyl groups with 6 to 22 carbon atoms,

b) 0.1 to 40% by weight, preferably 5 to 35% by weight, of an alkyl sulfate of the formula II, R5-0-S03X, in which R5 is a saturated or unsaturated Cδ-C22-alkyl group and X. is an alkali, alkaline earth or a moniumion, alkyl ether sulfate of the formula III, R ⁶ -0- (CH2CH2θ) _n -Sθ3X, lkylgruppe in which R ⁶ is a saturated or ungesät¬ preferential C6-C22 ^-A, "" for Numbers from 1 to 10 and X represents an alkali, alkaline or ammonium ion, or a mixture of both and c) 0.1 to 30% by weight, preferably 0.5 to 10% by weight, of an alkyl glycoside of the formula IV, R ^ 0 [G] _x , in which R? represents a branched or unbranched, saturated or unsaturated C6-C22 "al yl radical, G represents a glycosyl radical, in particular a glucose or xylose radical, and x represents numbers from 1 to 10.

2. Composition according to claim 1, characterized in that the weight ratios of the surfactant components mentioned under a), b) and c) have the following values: a / b 4: 1 to 1: 7, a / c 4: 1 to 1 : 4, b / c 10: 1 to 1: 2.

3. Composition according to claim 1 and 2, characterized in that it is free from surfactants with sulfonate function.

4. Composition according to claim 1 to 3, characterized in that it is free of alkali or ammononium salts of saturated or unsaturated C6-C22 fatty acids.