CH641836A5 - Aqueous liquid cleaning composition - Google Patents

Abstract

of the Invention An aqueous liquid detergent composition especially adapted for dishwashing, comprising 5-60% by weight of an organic synthetic surfactant system of at least two surfactants, and 5-50% by weight of a citrus juice, said organic synthetic surfactant system consisting of1) from about 30-90 parts by weight of the surfactant system of a Ca-sensitive first surfactant selected from the group consisting Water-soluble C8-16 alkyl benzene sulphonates; alkane sulphonates having 8-20 car-bon atoms; olefin sulphonates having from 8-20 carbon atoms; di-C8-20-alkyl sulpho-succinates; di-C6-12-alkyl phenol sulphosuccinates; primary and secondary alkyl suphates having 8-20 carbon atoms; C8-20 alkyl polyethoxy sulphates having 1-25 ethoxy groups and mixtures thereof, and2) from about 70-10 parts by weight of said system of a less Ca-sensitive second surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condensing from 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide with one mole of an organic hydrophobic compound, aliphatic or alkyl aromatic in nature, having 8 to 24 carbon atoms and at least one reactive hydrogen atom, particularly a reactive hydroxyl, amino, amido or carboxyl group; C8-20-alkylsulphobetaines; amines oxides containing one long chain alkyl moiety of from 10-28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals having from 1-4 carbon atoms; C8-20 alkyl-polyethoxy sulphates having from 1-25 ethoxy groups, and mixtures thereof, said surfactants of group (1) and the ion-active surfactants of group (2) being present in the form of their alkalimetal salts, ammonium salts, or mixtures thereof. The composition is an effective liquid dishwashing composition with improved cleaning performance on difficult soils.

Description

The invention relates to an aqueous, liquid cleaning agent with improved cleaning performance, in particular to an improved liquid cleaning agent, which is particularly suitable for cleaning plates, glasses, kitchen utensils, cutlery and the like by hand. The liquid cleaning agent according to the invention contains citrus fruit juice, such as lemon juice.

Liquid detergents containing lemon juice

are known in the art. U.S. Patent 3,650,968 describes fish odor removers containing 30-80 weight percent water, 0.1-35 weight percent detergent and 0.1-15 weight percent citrus juice (lemon juice). However, these liquid detergents have only moderate dishwashing properties and can therefore not be used in a satisfactory manner for cleaning plates, glasses, kitchen utensils, cutlery and the like.

The object of the invention is to provide an effective liquid dishwashing detergent which is also particularly effective against more difficult dirt, e.g. on plates, pots, pans and other kitchen utensils.

“Difficult dirt” refers to the difficult end of the dishwashing spectrum, such as baked-on proteins and starch-based dirt.

These and other objects of the invention, which will become apparent hereinafter, can be achieved by combining an organic synthetic surfactant system composed of at least two surfactants or surfactants as defined below with a citrus juice in an amount of 5 to 50 percent by weight based on the total agent. be solved. Any juice of a citrus fruit that belongs to the general class of citrus fruits can be used, such as sweet oranges (Citrus sinensis), sour or bitter oranges (Citrus auranticum), mandarins (Citrus reticulata), grapefruits (Citrus paradisi and Citrus grandis), limes (Citrus limon ), sour lime (Citrus aurantifolia), lemons (Citrus medica), Papeda (Citrus hystrix) and three-leafed oranges (Citrus trifoliata), although lime or. Lemon juice is preferred according to the invention in view of the fact that it is well accepted by the consumer.

Unless otherwise stated, the percentages of fruit juices in the present description refer to single strength fruit juices. The expression “simple strength” is intended to indicate the average strength of the fruit juice squeezed out of the fruit. If concentrated juices are used, they are indicated with the starch factor, e.g. "Quadruple concentrate".

The agents according to the invention are therefore especially designed for general use in conventional dishwashing, which can be used in concentrated aqueous form or in the conventional, highly diluted washing process and lead to a good cleaning effect combined with a foam content and foam stability accepted by the consumer.

Thus, the aqueous liquid cleaning agent according to the invention has 5-60 percent by weight of an organic, synthetic surface-active system composed of at least two different surface-active agents or surfactants, as defined below, and 5 to 50 percent by weight of a citrus juice.

The organic synthetic surfactant system or surfactant system consists of

A. 30-90 parts by weight of the surfactant system of a first surfactant from the group of water-soluble C8-Ci6-alkylbenzenesulfonates, alkanesulfonates with 8-20 carbon atoms, olefinsulfonates with 8-20 carbon atoms, di-C8_20-alkylsulfosuccinates, di-C6_12 -AlkylphenoIsulfosuccinate, primary and secondary alkyl sulfates with 8-20 carbon atoms, Cgjo-Alkylpolyäthyltenoxysulfate with 1-25 ethylene oxide groups and their mixtures and

B. 70-10 parts by weight of the system of a second surfactant, which is less Ca-sensitive than the first surfactant, from the group of water-soluble, non-ionic condensation products, from 5-30 moles of ethylene or propylene oxide and one mole of an organic, Hydrophobic compound of aliphatic or alkyl aromatic nature with 8-24 carbon atoms and at least one reactive hydroxyl, amino, amido or carboxyl group, C8_20-alkylsulfobe-taine, amine oxides with a long-chain alkyl radical with 10-28 carbon atoms and two radicals, which are either alkyl radicals or Are hydroxyalkyl radicals with 1 to 4 carbon atoms,

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641836

C8.2o-alkylpolyethylenoxysulfate with 1-25 ethylene oxide groups and their mixtures,

wherein the surfactants of group (1) and the surfactants of group (2), which are ion-active, are in the form of their alkali metal, ammonium, lower alkanolamine, lower alkylamine salts or mixtures thereof and the surfactant system is the Cg-20-alkylpolyethylene oxysulfates with 1-25 ethylene oxide groups may only be contained in one of groups 1 and 2.

Examples of nonionic water-soluble condensation products obtained by condensing 5-30 moles of an alkylene oxide with one mole of an organic hydrophobic compound are as follows:

a) the condensates of ethylene oxide with aliphatic, straight or branched chain, primary or secondary alcohols with more than 8 carbon atoms, such as those derived from tallow or coconut fatty acids, with 5-20 ethylene oxide groups, and branched chain Cu-Ci5 alcohols, condensed with 5-20 ethylene oxide groups;

b) the condensates of ethylene oxide with alkylphenols, in which the phenols can be mono- or polyalkylated and the total number of carbon atoms in the side chain (s) is 5-18. Specific examples are condensates of one mole of nonylphenol with 8-15 moles of ethylene oxide;

c) the condensates of ethylene oxide with fatty acid esters, preferably mono fatty acid esters of the sugar alcohols sorbitol and mannitol;

d) polyethoxy esters obtained by reacting ethylene oxide with carboxylic acids, the latter being natural fatty acids or synthetic fatty acids from oxidized paraffin wax with 8-20 carbon atoms or alkylbenzoic or naphthenic acids with 5-18 carbon atoms in the alkyl chain;

e) the condensation products of fatty acylalkanolamides of the type C7_17-alkyl-C0-NHC2H40H, Q-iralkyl-CO-'N- (C2H40H) 2 with ethylene oxide;

f) the condensation products of C8_i8-alkyl-, C8-i8-alkenyl- and C8_i8-alkylarylamines with ethylene oxide.

A specific example is the condensation product of one mole of a dodecylamine with 9-12 moles of ethylene oxide.

Specific examples of amine oxides are dimethyldodecylamine oxide, diethyltetradecylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide and dimethyl-2-hydroxydodecylamine oxide.

It has been found that the surfactant system defined above can be used effectively in combination with citrus juice, in particular lime juice or lemon juice, in the proportions given above in order to achieve the desired combined effect of good washing or cleaning performance, good foaming behavior and increased performance on difficult Dirt, especially baked or dried proteins or starch contamination, over a wide pH range from practically acidic pH to alkaline pH, e.g. from 4-10. A preferred pH range of the agent according to the invention is between about 5.5 and 9, in particular 6 and 8.5, very particularly between 7 and 8.5.

Any combination of the first and second surfactants described above can be used to produce the organic, synthetic surfactant system in the agent according to the invention.

Typical examples of surfactant systems are alkylbenzene sulfonate / alkylpolyethoxysulfate mixtures, alkylbenzenesulfonate / alkylpolyäthoxysulfate / nonionic material mixtures, alkylsulfate / alkylbenzenesulfonate / alkylpolyethoxysulfate mixtures and alkylsulfate / alkyl sulfate / aminoxysulfate / aminoxysulfate / aminoxysulfate / aminoxysulfate / aminoxysulfate.

As explained above, any type of citrus juice can be used in an amount of 5% by weight according to the invention, juices of lemon or lime, sour lime or limonelle, orange and grapefruit or grapefruit being representative of the general class. A minimum amount of 5 percent by weight of citrus juice is used, since the effect is insignificant to practically zero with smaller amounts. Although any portion above 5% citrus juice can in principle be used as practically possible, it has been found that high levels are not necessary to achieve the desired benefit. In addition, since there is a clear decrease in the improvement in performance with increasing juice content of more than 10% and a rapid decrease, in particular in the range of higher percentages, the use of excessively large quantities of juice does not justify the particularly high expenditure which occurs. 50%, preferably 25%, are regarded as a suitable practical upper limit for a citrus juice of simple strength in the agent according to the invention, since at concentrations above these percentages citrus juice offers no further advantages which would compensate for the high costs of additional citrus juice.

An extremely advantageously used citrus juice content in the liquid cleaning agent according to the invention is between 5 and about 10 percent by weight.

The invention thus provides an aqueous, liquid cleaning agent which is specially adapted to dishwashing and has improved cleaning performance, in particular in relation to dirt which presents difficulties, and 5 to 60% by weight of an organic, synthetic surfactant system, consisting of at least two surfactants, as previously determined, and 5-50 percent by weight of a citrus juice.

Citrus juices are available on the market. They are either used as single strength juices or as concentrates of different strengths, e.g. offered as double concentrates up to tenfold concentrates. Lemon or lemon juice contains a number of different classes of chemical compounds, including acids, sugars, amino acids, oils and trace elements. Analytical information on citrus juices can be found in the following literature:

a) “Chemical Constituents of Citrus Fruits”, Supp. 2 (1970), Kefford and Chandler;

b) "Biochemistry of Fruits and their Products", Vol. 1 (1970), A.C. Hulme.

Within each class there are several different components, each of which can be separately determined analytically. The main acid in citrus juice is citric acid, which is present in an amount of about 5-6 percent by weight.

It is not exactly known which of the constituents present in citrus juice is responsible for improving the cleaning effect, but a synergistic effect is suspected by combining one or more of the constituents present in the citrus juice with the active system used in the agent according to the invention.

In addition to the necessary components of the liquid cleaning agent according to the invention described above, it may optionally contain further, unnecessary materials. Such optional ingredients are e.g. other surfactants, other than those of the first and second class of the organic synthetic surfactant system, builder salts that can be added to aid in cleaning and soil removal performance of the surfactant of the composition, e.g. Phosphates, polyphosphates, phosphonates, carbonates, polyacetates and polycarboxylates, foam promoters, such as coconut fatty acid diethanolamide, hydrotropes and solubilizing agents, such as the lower alkanols with 2-4 carbon atoms, especially ethanol, urea, sodium or potassium toluenesulfonate and sodium or Potassium xylene sulfonate, which generally5

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NEN to be added to promote the phase stability especially of agents with high concentrations of surfactants, preservatives, fragrances and colorants. If desired, acidic or alkaline substances for pH adjustment and abrasives can also be incorporated into the cleaning agent according to the invention.

Preferred agents are those containing 10-50 percent by weight of the organic synthetic surfactant system described above, 5-25 percent by weight of lemon or lime juice and about 15-75 percent by weight of water. Those with an active detergent content of more than 35 percent by weight are particularly preferred.

The invention is further illustrated by the following examples:

Examples I-III

The following agents were made:

Medium I II III A B

Percent by weight

Sodium dodecylbenzenesulfo

29.0

29.0

29.0

29.0

29.0

nat

Sodium lauryl (ethoxy) 3-sulfate

14.0

14.0

14.0

14.0

14.0

Sodium citrate

-

-

-

-

1.0

Lemon juice

1.25

2.5

5.0

0.25

0.25

(Quadruple concentrate)

Ethanol

5.5

5.5

5.5

8.0

7.0

urea

5.5

5.5

5.5

7.5

8.0

water and

44.75

43.5

41.0

41.25

40.75

Preservative

The following half-plate comparison test method was used to determine the relative ease of cleaning baked-on dirt from substrates after soaking:

Dirty substrates in the form of square enamel plates (10x10 cm) are immersed in solutions of the test products (1 liter) at a concentration of 0.15%. The solution is at 45 ° C at the start of the test and is reheated when it drops to 40 ° C (using a small immersion heater). The plates are checked for the first signs that the dirt has softened on one of them, and then all are removed from the test solution and cleaned (the immersion time varies between 5 and 50 minutes). The cleaning is done for 30 s with a Brillo-Swish sponge, which is immersed in the appropriate test solution.

Dirt and pollution process:

The tests were carried out using fruit cake filling (cherry and apricot) and a mixture of flour and fruit cake filling (1: 4). The pie filling was made into a fine pulp by pressing through a 240 µm sieve, and a fine paste was made from the flour / pie filling mixture.

The dirt is screen printed onto the substrate in two steps. It is then baked in the middle of a large oven (Gallenkamp oven model OV330) for 4 minutes. Before placing the contaminated substrates in the oven, the temperature should be 250 ° C and it is desirable to push them quickly into the oven to avoid the temperature from dropping below 220 ° C.

Results:

The results are fully shown in Table 1 below. The assessment was carried out by a group of technicians who assessed the degree of dirt removal on the following basis:

0 = completely clean

1 = still slightly dirty

2 = moderately dirty

3 = very dirty

4 = no visible cleaning

The ratings were averages of 8 results for each product and control. Product A was used as a control.

Table 1

average difference

Evaluation control / sample

Product in 5 ° h in 26 ° H in 5 ° H in 26 ° H

Water water water water

I.

2.13

2.93

+ 0.81

+ 0.81

Control (A)

2.94

3.74

II

1.25

3.31

+ 0.44

+ 0.32

Control (A)

1.69

3.63

III

1.00

2.18

+ 0.88

+ 0.44

Control (A)

1.88

2.62

B

0.75

2.62

-0.12

-0.37

Control (A)

0.63

2.25

It is clear from the above results that agents I, II and III with lemon juice according to the invention are superior to agents A and B outside the invention.

Example IV

The influence of pH was examined by evaluating the performance of the following agent in a soaking test.

Average weight%

Sodium dodecylbenzenesulfonate 29.0

Ci2-alkyl ether sulfate with 3 ethylene oxide 14.0

Lemon juice 10.0

Ethanol 5.5

Urea 5.5

Water and preservatives 36.0

Comparisons were made using standard 10x10 cm enamel plates soiled with apricot pie filling / flour and baked as in Examples I-III. Half-plate comparisons in water of 11.3 ° German hardness were carried out at 45 ° C.

Test products were tested statistically and all tests were carried out twice ".

pH adjustments were made at 45 ° C using dilute sulfuric acid (0.1 m) and dilute sodium hydroxide solution (0.1 m), and the pH was also measured at the end of each test.

A product of the above nominal composition without lemon juice was used as a control.

The assessment was carried out by a group of technicians to determine the degree of dirt remaining on each half-board using the following assessments:

0 = completely clean

1 = still slightly dirty

2 = moderately dirty

3 = very dirty

4 = no visible cleaning.

From these ratings, the average was averaged (6 results for each test product and control

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pH value), and a dirt difference between the control and the test product was calculated.

Table 2

Results of the soaking test - a comparison of the product with and without 10% lemon juice dH

product

Reviews by

difference

cut

Control/

sample

5.5

lemon

1.5 2.5 1.0 0.5 1.0 0.5 1.17

+ 0.75

control

2.5 3.0 1.5 1.5 2.0 1.0 1.92

7.0

lemon

3.0 3.5 2.5 0 0 0 1.5

+ 0.67

control

3.5 4.0 3.0 0.5 1.0 0.5 2.17

8.5

lemon

0.5 0.5 0.5 0.5 1.0 0.5 0.58

+ 1.42

control

1.5 2.0 1.0 2.5 3.0 2.0 2.0

10.0

lemon

1.5 2.5 1.0 1.5 2.5 1.0 1.67

+ 0.50

control

3.0 3.0 1.5 2.0 2.5 1.0 2.17

The table above shows that the agent according to the invention always shows superiority in pH 5.5.7.0, 8.5 and 10.0, the results at pH 8.5 being particularly good.

Example V

The following agents were evaluated:

medium

Wt. 'C

> / o Vi

Vi

V3

"V4

Vs

Release

Sodium dodecyl

29.0

29.0

29.0

29.0

29.0

29.0

29.0

benzenesulfonate

Lauryl-3-etho-

14.0

14.0

14.0

14.0

14.0

14.0

14.0

xysulfate

Lemon juice

0.25

1.25

2.5

3.75

5.0

6.25

12.5

(Quadruple conc

kicked)

Ethanol

10.0

10.0

10.0

10.0

10.0

10.0

10.0

urea

10.0

10.0

10.0

10.0

10.0

10.0

10.0

Water and too too too too too

Preservation

100

100

100

100

100

100

100

material

Lemon juice

1

5

10th

15

20th

25th

50

Nominal salary

The method used was as follows:

1. Egg contamination was made by carefully mixing dried egg powder and water in a 1: 1 ratio.

2. A 5 cm dirt strip was screen printed onto the center of a 30 x 25 cm glass plate.

3. The plates were baked at 200 ° C for 30 minutes. Then five evaluations could be carried out on the plate. At least two control evaluations were carried out on each plate.

4. Five "wells" of 5 cm were formed on the plate with plasticine strips (plasticine). 6 ml solution (0.15%) was placed in each well. Using a J-trade covered head and 1.5 kg weight, the number of rubs to clean the 5 cm streak was recorded.

5. Results of the test solution were calculated as a percentage of the performance of the closest control on the plate.

The results of the tests using water from 5CH are tabulated below:

medium

% Lemon juice average Performance as% of control

Control (C)

1

100

Vi

5

89

V2

10th

61

v3

15

70

v4

20th

73

v5

25th

68

Va

50

60.5

The above results clearly show the superior performance of agents Vi to Vs according to the invention containing 5-50% lemon juice in cleaning stuck egg over the control.

Example VI

The following agents were compared in a standard dishwashing test for their dishwashing performance as well as a test to determine the relative ease of cleaning stubborn soil from substrates after soaking using the test method described in Examples I-III.

Medium VI Medium D

10% sodium dodecylbenzenesulfonate 15% Empilan LP 10 * 5% sodium lauryl (ethoxy) 3-sulfate 30% glycerin 5% lemon juice 5% lemon juice

2% urea 2% urea

Rest of water rest of water

* Empilan LP 10 is a non-ionic fatty amide condensate, comparable to Nopco 1179 from the Nopco Chemical Company.

The standard dishwashing tests were performed using the following test conditions:

Product concentrations 0.15 and 0.45%

Solution temperature 45 ° C

Meat sauce with 5 g / plate fat, starch, olein and

Stearic acid

The results are summarized below:

Table 3

Number of plates washed

Water hardness

5 ° H

26 ° H

Product concentration

0.15%

0.45%

0.15%

0.45%

Medium VI (pH 7)

30th

63

27th

59

Medium D (pH 5.8)

3rd

7

2nd

4th

Results of the test to determine the relative ease of cleaning baked-on dirt from substrates. The ratings were based on five results for each product at 0.75% concentration.

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Table 4

Average average rating in 5 ° H in 26 ° H water water

Difference in 5 ° H water in 26 ° H water

VI (pH 7)

0.2

2.4

D (pH 5.8)

0.7

2.4

+ 0.5

+ 0.0

VI (pH 7)

0.7

3.0

D (pH 7)

1.1

3.3

+ 0.4

+ 0.3

VI (pH 7)

2.4

D (pH 5.8)

2.7

-

+ 0.3

-

VI (pH 7)

1.5

D (pH 7)

2.1

-

+ 0.6

-

The above results clearly show the superior properties of agent VI according to the invention over agent D of the prior art both in dishwashing and in terms of performance in the case of stuck dirt.

Examples VII-IX

The following liquid dishwashing detergents are within the scope of the invention:

25th

Medium VII

% By weight

Sodium dodecylbenzenesulfonate

16.0

Nonylphenol-7-ethylene oxide

7.0

Ethanol

2.0

urea

4.0

Lemon juice

8.0

Water and preservatives too

100.0

Means VIII

% By weight

Ammonium dodecylbenzenesulfonate

32.0

Nonylphenol-10-ethylene oxide

8.0

Ethanol

3.0

urea

3.0

Sodium xylene sulfonate

9.0

Lemon juice

7.5

Magnesium sulfate

1.2

Water and preservatives too

100.0

Medium IX

% By weight

Sodium lauryl (ethoxy) 3-sulfate

24.0

Dimethyldodecylamine oxide

5.0

Lemon juice

10.0

Sodium citrate

1.0

urea

3.0

Ethanol

3.0

Water and preservatives too

100.0

G

Claims (8)

641 836 1. Aqueous, liquid cleaning agent, in particular for dishwashing, which has 5-60 percent by weight of an organic synthetic surfactant system composed of at least two different surfactants and 5-50 percent by weight of citrus juice, the organic synthetic surfactant system consisting of A. 30-90 parts by weight of the surfactant system of a first surfactant from the group of water-soluble C8_i6-alkylbenzenesulfonates, alkanesulfonates with 8-20 carbon atoms, olefin-sulfonates with 8-20 carbon atoms, di-C8_2o-alkylsulfosuccinates, di-C6_i2-alkylphenolsulfosuccinates , primary and secondary alkyl sulfates with 8-20 carbon atoms, C8_2o-alkylpolyethylene oxysulfates with 1-25 ethylene oxide groups and their mixtures and B. 70-10 parts by weight of the system of a second surfactant, which is less sensitive to Ca than the first, from the group of water-soluble, non-ionic condensation products, from 5-30 moles of ethylene or propylene oxide and one mole of an organic, hydrophobic Compound of aliphatic or alkyl aromatic nature with 8 to 24 carbon atoms and at least one reactive hydroxyl, amino, amido or carboxyl group, C8_2o-alkylsulfobetaines, amine oxides with a long-chain alkyl radical with 10-28 carbon atoms and two radicals which are either alkyl radicals or hydroxyalkyl radicals with 1 Are -4 carbon atoms, Cg_2o-alkyl-polyethylene oxysulfates with 1-25 ethylene oxide groups and mixtures thereof, wherein the surfactants of group (1) and the surfactants of group (2), which are ion-active, are in the form of their alkali metal, ammonium, lower alkanolamine, lower alkylamine salts or their mixtures, and wherein the surfactant system contains the C8-2o-alkylpolyethylene oxysulfates with 1 May contain 25 ethylene oxide groups only in one of groups 1 and 2. 2. Composition according to claim 1, whose organic, synthetic surfactant system is present in an amount of 10-50 percent by weight of the composition. 2nd PATENT CLAIMS 3. Agent according to claim 1 or 2, the citrus juice is present in an amount of 5-25 percent by weight of the agent. 4. Agent according to claim 3, the citrus juice is present in an amount of 5-10 percent by weight of the agent. 5. Agent according to one of the preceding claims, the citrus juice is lemon juice. 6. Composition according to claim 5 with a pH of 5.5-9. 7. Composition according to claim 6 with a pH of 6-8.5. 8. Agent according to one of the preceding claims, the organic surfactant system of which is present in an amount of more than 35 percent by weight but not more than 60 percent by weight.