DE2855778B2 - Liquid detergent - 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

1) about 30-90 parts by weight of the surfactant system a first, Ca-sensitive surfactant from the group of water-soluble Ce-ie-alkylbenzoisulphonates, alkanesulfonates with 8-20 carbon atoms, olefin sulfonates with 8-20 carbon atoms, di-Cs-aralkylsulfosuccinates, di-Ce-12-alkylphenolsulfosuccinates, primary and secondary Alkyl sulfates with 8-20 carbon atoms, Ce-M-alkyl polyethoxy sulfates with 1-25 Ethoxy groups and their mixtures and

2) about 70-10 parts by weight of system one second, less Ca-sensitive surfactant from the group of water-soluble, non-ionic Condensation products obtained by condensing 5 - 30 moles of an alkylene oxide, preferably ethylene or propylene oxide, with one mole of an organic, hydrophobic Compound of aliphatic or alkyl aromatic nature with 8 to 24 carbon atoms and at least one reactive hydrogen atom, in particular a reactive hydroxyl, amino, amido or carboxyl group, Ce-M-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 1-4 carbon atoms can be, Cg-20-alkyl polyethoxysulfates with Consists of 1 -25 ethoxy groups and their mixtures,

wherein the surfactants of group (1) and the ion-active surfactants of group (2) in the form of their Alkali metal, ammonium, lower alkanolamine, lower alkylamine salts or their mixtures are present.

2. Composition according to claim I, whose organic, synthetic surfactant system in an amount of - 50 percent by weight of the agent is present.

3. Composition according to claim 1 or 2, the citrus juice in an amount of 5-25 percent by weight of the Means present.

4. Agent according to claim 3, the citrus juice thereof in an amount of 5-10 percent by weight of the agent is present.

5. Agent according to one of the preceding claims, the citrus juice of which is lemon juice.

6. Composition according to claim 5 with a pH of 5.5-9.

7. Mitlei 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 in is present in an amount greater than 35 percent by weight of the composition.

The invention relates to a liquid cleaning agent with improved cleaning performance, in particular to an improved liquid cleaning agent, which is especially suitable for cleaning plates, glasses, kitchen utensils, cutlery and the like Hand suitable The liquid detergent according to the present invention contains juice of a ctrus fruit such as lemon juice Liquid detergents containing lemon juice

ίο are known in the art US Pat. No. 3,650,968 describes detergents for removing fish odor, containing 30-80 percent by weight water, 0.1-35 Contains percent by weight detergent and 0.1-15 percent by weight citrus juice (lemon juice). These liquid However, cleaning agents have only moderate dishwashing properties and can therefore not be used in a satisfactory manner for cleaning Telltr. .i, glasses, Kitchen utensils, cutlery and the like can be used.

The object of the invention is to create an effective liquid dishwashing / cleaning agent, which is also particularly effective against difficult dirt, as well as the creation of a method for Removing troublesome dirt from plates, pots, pans and other kitchen utensils.

"Difficult dirt" here means the difficult end of the dishwashing spectrum, such as baked-on proteins and dirt

H) starch base.

These and other objects of the invention which will emerge below can be accomplished Combining an organic synthetic surface-active system from at least two surface-

J5 active agents or surfactants as defined below with citrus juice in an amount of 5 . Percentage by weight, based on the total mean, are dissolved. Any citrus juice belonging to the general class of citrus fruits can be used like sweet oranges (Citrus sinensis), sour or bitter oranges (Citrus auranticum), mandarins (Citrus reticulala), grapefruits (Citrus paradisi and Citrus grandis), limes (Citrus limon), sour lime (Citrusaurantifolia), lemons (Citrus mcdica), Papeda

4) (Citrus hystrix) and three-leaved oranges (Citrus trifoliata), although lime or lemon juice in the

With regard to the fact that this is from the consumer

is well accepted, is preferred according to the invention.

Unless otherwise stated, the

Percentages of fruit juices in the present description refer to single strength fruit juices. Of the The expression "simple strength" is intended here to mean the average strength of the fruit juice squeezed out of the fruit indicate. If concentrated juices are used, these are given with the strength factor, e.g. B. "Quadruple concentrate".

The agents of the present invention are therefore particularly suitable for general use in conventional Dishwashing designed in concentrated-watery

w) form or the conventional, highly diluted Washing process can be used and combined with a good cleaning effect Consumer accepted foam content and foam stability result.

f> 5 The liquid cleaning agent according to the invention has about 5 - 60 percent by weight of an organic, synthetic surface-active system composed of at least two surface-active agents or surfactants,

as defined below, and at least 5 percent by weight of a citrus juice.

The organic, synthetic surface-active system or surfactant system consists of

1) about 30-90 parts by weight of the surfactant system of a Ca-sensitive, first surfactant from the group of water-soluble CeQs-alkylbenzenesulfonates, alkanesulfonates with 8-20 carbon atoms, olefin sulfonates with 8-20 carbon atoms, di-C ₈ -aralkylsulfosuccinates, di-C ₆ -12-alkyIphenolsulfosuccinate, primary and secondary alkyl sulphates having 8-20 carbon atoms, Cg-20 AIkylpolyäthoxysulfate with 1-25 ethoxy groups, and mixtures thereof and

2) about 70-10 parts by weight of the system of a less Ca-sensitive, second surfactant from the Group of water-soluble, non-ionic condensation products obtained by condensing 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide, with one moi organic, hydrophobic compound of aliphatic or alkyl aromatic nature with 8 - 24 Carbon atoms and at least one reactive hydrogen atom, especially one reactive Hydroxyl, amino, amido or carboxyl group, Cg -20- Alky! Sulfobetaines, amine oxides with a long-chain alkyl radical with 10-28 carbon atoms and two radicals that are either alkyl radicals or Hydroxyalkyl radicals with 1 to 4 carbon atoms can be jo, Ce-20-Alkylpolyäthoxysulfate with 1 - 25 ethylene oxide groups and their mixtures,

wherein the surfactants (1) and the icnena- ¹ tive surfactants of group (2) are present in the form of their alkali metal, ammonium, js Niederalkanolamin-, Niederalkylaminsalze or mixtures thereof.

Examples of non-ionic water-soluble condensation products, obtained by condensing 5 to 30 moles of an alkylene oxide with one mole of an organic hydrophobic compound, are the following:

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 Cn — C15-AI- alcohols condensed with 5 - 20 ethylene oxide groups; v)

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 γ, nonylphenol with 8-15 moles of ethylene oxide;

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

d) Polyäthenoxyester obtained by reacting bo 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 are;

e) the condensation products of Fettacylalkanolamiden of type C ₇ -R -alkyl-CO-NHC ₂ H ₄ OH, C ₇ -, 7-alkyl-CO-N- (CaH ₄ OH) ₂ with ethylene oxide;

f) the condensation products of Cg-ia-alkyl, Cg- | g-alkenyl- and Cg-is-alkylarylamines with Ethylene oxide.

A special bet 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 is effective in combination with citrus juice, especially lime or lemon juice, in the above specified ratios can be used to achieve the desired combined effect of good washing or cleaning performance, good foam behavior and increased performance on difficult dirt, especially caked or dried-on proteins or starch soiling, over a wide pH range from practically acidic to alkaline, z. B. from 4 - 10 to achieve. 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 above-described first and second surfactants can be used to produce the organic, synthetic surfactant system can be used in the agent according to the invention.

Typical examples of surfactant systems are

Alkylbenzenesulphonate / alkylpolyethoxysulphate

Mixtures,
Alkylbenzenesulfonate / alkylpolyethoxy-

sulphate / non-ionic material mixtures,
Alkyl sulfate / alkyl benzene sulfonate / alkyl poly

ethoxysulphate mixtures and
Alkyl sulfate / alkyl polyethoxy sulfate / amine oxide

Mixtures.

As explained above, any type of citrus juice can be used in an amount of 5 percent by weight according to the invention be used, taking juices of lemon or lime, sour lime or litnonelie, orange and the grapefruit or grapefruit are representative of the general class. There will be a minimum amount of 5 percent by weight of citrus juice, since the effect is insignificant up to with smaller amounts is practically zero. Although any proportion over 5% citric juice is used as practically possible in principle it has been found that high amounts are not necessary to achieve the desired benefit achieve. Incidentally, there is a marked drop in the increase in the improvement in performance with increasing Juice content over 10% and a rapid decrease, especially in the area of higher percentages, The use of too large amounts of juice does not justify the particularly high expenditure that occurs. Advantageously, 50%, preferably 25%, can be used as a suitable practical upper limit of a citrus juice simple strength are considered in the agent according to the invention, since at concentrations above this Percentage of citrus juice does not offer any other benefits that offset the high cost of additional citrus juice would.

One that is used in an extremely advantageous manner

The citrus juice content in the liquid cleaning agent according to the invention is between 5 and about 10 W eight percentL

Thus, the invention offers an aqueous, liquid cleaning agent which is especially suitable for dishwashing is adapted and improved cleaning performance, particularly with respect to difficult ones Dirt, and 5 to 60 percent by weight of one organic, synthetic surfactant system, consisting of at least two surfactants, as defined above, and Has 5-50 weight percent of a citrus juice

Citrus juices are available in the market. you will be either as single strength juices or as concentrates of various strengths, e.g. B. as double concentrates up to tenfold concentrates. Lemon or lime juice contains a number of different ones 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, Kefford and Chandler (1970);

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

Within each class are several different components, each separately analytical for itself can be determined. The main acid in citrus juice is citric acid, which is available in an amount of around 5 - 6 Weight percent is present.

It is not known exactly which of these are found in citrus juice existing constituents is presumed to be responsible for improving the cleaning effect but a synergistic effect through the combination of one or more of those present in citrus juice Components with the active system used in the agent according to the invention.

In addition to the necessary components of the liquid according to the invention described above Cleaning agent, it can optionally contain other unnecessary materials. Such if necessary Components contained are z. B. other surfactants, other than those of the first and second class of the organic, synthetic surfactant system, builder salts that can be added to cleanse and to aid in the soil removal performance of the detergent surfactants, e.g. B. 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 toluene sulfonate and sodium the potassium xylene sulfonal, which are generally added to ensure the "phase stability, particularly of agents with high Promote concentrations of surfactants, preservatives, fragrances and colorants. Furthermore can if desired, acidic or alkaline substances for pH adjustment as well as abrasives in the inventive Cleaning agent must be incorporated.

Preferred agents are those containing 10-50 percent by weight of the organic, synthetic described above Surfactant system, 5-25 percent by weight lemon or lime juice and about 15-75 percent by weight Contain 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 means were produced:

middle

1 I!

Weight percent III

Sodium dodecylbenzenesulfonate

Sodium lauryl (ethoxy) j-sulfate

Sodium citrate

Lemon juice (quadruple concentration)

Ethanol

urea

Water + preservatives

29.0 29.0 29.0 29.0 29.0 14.0 14.0 14.0 14.0 14.0 - - - - 1.0 1.25 2.5 5.0 0.25 0.25 5.5 5.5 5.5 8.0 7.0 5.5 5.5 5.5 7.5 8.0 44.75 43.5 41.0 41.25 40.75

To determine the relative ease of cleaning νου baked-on dirt from substrates after soaking, the following half-panel comparative test method was used:

Soiled substrates in the form of square enamel plates (10 × 10 cm) are immersed in solutions of the test products (1 liter) at a concentration of 0.15%. The solution is check at the start of the test at 45 ° C and is heated again when it falls to 4O ⁰ C (using a small immersion heater). The Plattpn be tested for the first signs that the dirt ^f au has a softening of them, and then all be removed from the test solution and cleaned (the immersion time varies from 5 to '50 min). Cleaning is done for 30 s with a Brillo Swish sponge dipped in the appropriate test solution.

Dirt and pollution process

The tests were done using fruit tart filling (cherry and apricot) and a mixture made of flour and fruit tart filling (1: 4). The pie filling was made by forcing it through a 240 µm sieve into a fine pulp, and the flour / pie filling mixture became a fine paste manufactured.

The dirt is going to be seen in rwp \

Operations applied to the substrate. It is then baked in the middle of a large oven for 4 minutes. Prior to introducing the soiled substrates in the oven the temperature of 25O ° C should be, and it is desirable to push them rapidly into the furnace in order to avoid that the temperature drops below 220 ⁰ C.

Results

The results are given in full in Table I below. The assessment was carried out by a group of technicians who determine the degree of dirt removal assessed on the following basis:

0 = completely clean

1 = still slightly soiled

2 = moderately soiled

3 = 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 (A) Average
valuation
in 5 Il in 2t H
water water 2.93
3.74 difference
(Control - sample)
in 5 "Il in 26ΊΙ
water water + 0.81 product (A) 2.13
2.94 3.31
3.63 + 0.81 + 0.32 I.
control (A) 1.25
1.69 2.18
2.62 + 0.44 + 0.44 Il
control (A) 1.00
1.88 2.62
2.25 + 0.88 -0.37 III
control 0.75
0.63 -0.12 B.
control

From the above results it is clear that the means 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 comparing the performance of the following agent in one Soak test was rated.

middle 29.0% Sodium dodecylbenzenesulfonate Cu-alkyl ether sulfate with 14.0% 3 ethylene oxide 10.0% Lemon juice 5.5% Ethanol 5.5% urea 36.0% Water + preservatives

Comparisons were made using the standard enamel plates (10 × 10 cm) made with apricot pie filling / flour soiled 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 statistically tested and all tests were performed in duplicate.

pH adjustments were made at 45 ° C using dilute sulfuric acid (0.1M) and dilute Soda Run "; (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 evaluation was made by a group of technicians to determine what remained on each half-panel Degree of dirt using the following ratings:

0 = completely pure

1 = still slightly soiled

2 = moderately soiled

3 = heavily soiled

4 = no visible cleaning.

These ratings were averaged (6 results for each test product and the Control at each pH), and a soil difference between the control and the test product got calculated.

Table 2

Soak test results - a comparison of the product with and without 10% lemon juice

pH product reviews 2.5
3.0 1.0
13th XnXn 1.0
2.0 03
1.0 By
cut difference
Control-
sample 5.5 lemon
control 13th
23 33
4.0 U) K)
Ό Xn 0
03 0
1.0 0
03 1.17
1.92 + 0.75 7.0 lemon
control 3.0
3.5 03
2.0 03
1.0 03
23 1.0
3.0 03
2.0 13th
2.17 + 0.67 83 lemon
control - O
Xn Xn 23
3.0 1.0
13th 2.0 23
23 1.0
1.0 038
2.0 + 1.42 10.0 lemon
control 13th
3.0 1.67
2.17 + 030

The table above shows that the agent according to the invention is always superior at pH 53, 7.0, 83 and 10.0 shows, the results being particularly good at pH 83.

rated: 28 55 10.0 V ₁ 5 778 V) 10 V ₄ V, V ₆ 9 10.0 29.0 29.0 29.0 29.0 29.0 B e i s ρ i 14.0 el V 14.0 14.0 14.0 14.0 The following remedies were made 1.25 3.75 5.0 6.25 12.5 middle Weight percent 10.0 10.0 10.0 10.0 10.0 C. 10.0 V ₂ 10.0 10.0 10.0 10.0 Sodium dodecylbenzenesulfonate 29.0 to 100.0 to 100X 29.0 to 100.0 to 100.0 to 100.0 to 100.0 Lauryl 3-ethoxy sulfate 14.0 I. 14.0 15th 20th 25th 50 Lemon juice (quadruple concentrate) 0.25 2.5 Ethanol 10.0 urea 10.0 Water + preservative ) to 100.0 Nominal lemon juice content 10

The method used was as follows:

1. Egg contamination was detected by careful> o Mixing of dried egg powder and water in a ratio of 1: 1.

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

3. The plates were baked at 200 ° C for 30 minutes. Then there were five ratings on the plate be performed. At least two control evaluations were made on each panel. Kl

4. Five "wells" of 5 cm were formed on the plate with strips of plasticine (Plaatilin). In 6 ml of solution (0.15%) were placed in each well. Using one with J-tissue covered head and a weight of 1.5 kg r> was the number of rubbing movements Cleaning of the 5 cm dirt strip recorded.

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

The results of the tests using water at 5 ° H are tabulated below:

middle % Lemon juice Diirchschniüliche Performance as% of Konirolle Control (C) 1 100 V, 5 89 V> 10 61 V, 15th 70 V ₁ 20th 73 Vi 25th 68 V ,. 50 60.5

The above results clearly show the superior performance of the compositions V _t to V ₆ according to the invention, which contain 5-50% lemon juice, in cleaning hard-baked eggs over the Jer control.

Example Vl

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

Means VI

Medium D

10% sodium dodecylbenzenesulfonate

5% sodium lauryl (ethoxy) sulfate 5% lemon juice 2% urea rest water

15% non-ionic Fatty amide condensate

30% glycerin

5% lemon juice 2% urea Rest water

The standard 1 egg wake tests were performed using the following test conditions:

Product concentrations: Temperature of the solution:

0.15 and 0.45%
45 ° C gravy soiling with
5 g / plate:

Fat, starch, oleic 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) Medium D (pH 5.8)

30th
3

63
7th

27 2

59 4

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

Il

Table 4

MiUeI avg. valuation

in 5 ° H in 26 ° H
water water

difference

5 ° M in 26 ° H

in water

water

VI (pH 7)

D (pH 5.8)

Vl (pH 7)

D (pH 7)

Vl (pH 7)

D (pH 5.8)

Vl (pH 7)

D (pH 7)

0.7 0.7

2.4 2.7

1.5 2.1

2.4 2.4

3.0 3.3

+ 0.5 + 0.4 + 0.5 + 0.6

+ 0.0

+ 0.3

The above results clearly show the superior properties of the agent VI according to the invention compared to the agent D of the prior art both in dishwashing and in terms of Efficiency with caked-on dirt.

Examples VII-IX

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

Means VII

Sodium Dodecylbcn / .olsilfonat

Nonylphenol-7-ethylene oxide

Ethanol

urea

Lemon juice

Water + preservatives

Means VIII

Ammonium dodecylbenzenesulfonate

Nonylphenol-IO-ethylene oxide

Ethanol

urea

Sodium xylene sulfonate

Lemon juice

Magnesium sulfate

Means IX

Sodium lauryl (ethoxy) i-stilfate

Dimethyldodecylamine oxide

Lemon juice

Sodium citrate

urea

Ethanol

Water + preservatives

Weight percent

16.0 7.0 2.0 4.0 8.0 to 100.0

Weight percent 32.0

8.0

3.0

3.0

9.0

7.5

1.2 VM! 00.0

Weight percent

24.0

5.0 10.0

1.0

3.0

3.0 to 100.0

Claims (1)

Patent claims: 1. Aqueous detergent, especially for dishwashing, the 5-60 percent by weight of a organic synthetic surfactant system of at least two surface-active agents or surfactants and 5-50 percent by weight of citrus juice, wherein the organic synthetic surfactant system from