SE442019B - Aqueous DETERGENT 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

7813213-1 2 context the difficult part of the washing spectrum, e.g. fixed- baked protein and starch dirt.

These and other objects of the invention will become more apparent of the following, can be achieved in such a way that one combines an organic synthetic surfactant system consisting of of at least two surfactants as defined below together with 5 - 50% by weight of citrus juice, based on the total composition. Each juice of a citrus fruit belonging to the general class of citrus fruits may be used, for example the following: Sweet oranges (citrus sinensis); sura or bitter oranges (citrus auranticum); mandarins (citrus reticulata); grapefruit (citrus paradisi); pumelos (citrus grandis); lemons (citrus 1imon); limes (citrus aurantifolia); lemons (citrus medica); papeda _ (citrus hystrix) and trifoliata oranges (citrus trifoliata), although lemon juice is preferred according to the invention on due to its established acceptance among consumers.

Unless otherwise stated, the percentages of fruit juices refer to below are fruit juices of simple strength. With the expression "Simple strength" in the present context means the mean strength in the fruit juice squeezed out of the fruit. If concentrated juices were used, this is stated by stating the strength factor, for example "4x concentrate".

The compositions according to the invention are thus particularly suitable. for general use in conventional dishwashing, which can be used in the concentrated aqueous form or in the conventionally highly diluted dishwashing to obtain a good cleaning effect in combination with a foam level acceptable to the consumer and foam stability small.

Accordingly, a liquid detergent composition contains according to the invention from 5 to 60% by weight of an organic. Synthetic surfactant system containing at least two different surfactants x šmeans as defined below and 5 - 50% by weight 7813213-'5 of a citrus juice.

The organic synthetic surfactant system is made of l) 2) 90 parts by weight of the surfactant system, which consists of a Ca-sensitive first surfactant selected from the group consisting of water-soluble C8-C16-alkylbenzene- sulfonates, alkane sulfonates having 8 to 20 carbon atoms, finesulfonates having 8 to 20 carbon atoms, di-C8-20 alkylsulfonates succinates, di-C 6-12 alkylphenol sulfosuccinates, pri- mar and secondary alkyl sulphates with 8 - 20 carbonate, C 8 -C 20 alkyl polyethoxy sulfates having 1 to 25 ethoxy groups and mixtures thereof, and 70 - 10 parts by weight of said system of a smaller Ca other surfactant selected from the group consisting of water-soluble nonionic condensation products obtained by condensation of 5 - 30 mol of an alkylene oxide, preferably ethylene or propylene oxide, with one mole of an organic hydrophobic compound, aliphatic or alkylaromatic in nature, containing 8 to 24 carbon atoms and at least one reactive hydrogen atom, in particular a reactive hydroxyl, amino, amido or carboxyl group; C 8-20 alkylsulfobetaines; amine oxides containing a long chain alkyl moiety with 10 - 28 carbon atoms and two parts which may be either alkyl groups or hydroxyalkyl groups having 1 to 4 carbon atoms; C8_2O- alkyl polyethoxy sulfates having 1 to 25 ethylene oxide groups, and mixtures thereof, wherein the surfactants (1) and the ionic surfactants from group (2) are present in the form of their alkali metal salts, ammonium salts, lower alkanolamine salts, lower alkylamine salts or mixtures thereof.

Examples of nonionic water-soluble condensation products obtained by condensation of 5 to 30 mol of an alkylene oxide with one mole of an organic hydrophobic compound are the following: a) Condensate of ethylene oxide with aliphatic straight chain or branched chain, primary or secondary alcohols with more than 8 carbon atoms such as those derived from tallow in QUALITY i 7815213-1 4 or coconut fatty acids, containing 5 to 20 ethylene- oxide groups, as well as branched chain C11-C15 alcohols sera with 5 - 20 ethylene oxide groups. b) Condensates of ethylene oxide and alkylphenols, wherein phenol- na may be mono- or polyalkylated and the total the number of carbon atoms in the side chain or side chains is - Specific examples are condensates of one mole of nonyl phenol with 8 - 15 moles of ethylene oxide. c) Condensate of ethylene oxide with fatty acid esters, preferably monofatty acid esters of sugar alcohols, sorbitol and mannitol. d) Polyethyleneoxy esters obtained by reaction of ethylene oxide and carboxylic acids, the latter being natural fatty acids or synthetic fatty acids made from oxidized paraffin wax having 8 to 20 carbon atoms or alkyl benzoic acids or naphthenic acids having 5 to 18 carbon atoms in alkyl chain no e) Condensation products of fatty acylalkanolamides of types C7-17 alkyl-CO-NHC2H4OH, C7-17 alkyl-CO-N (C2H40H) 2 with ethylene oxide. f) Condensation products of C8-18 alkyl-, C8-18 alkylene- and C 8-18 alkylarylamines with ethylene oxide. A speci- fict example is the condensation product of one mole of one dodecylamine with 9-12 moles of ethylene oxide.

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

It has been found that the surfactant system defined above can be used effectively in combination with citrus juice, especially lemon juice, in the proportions given above, to obtain it desired combined effect of good washing ability, good foaming properties and improved effect on heavy dirt, in particular baked or dried dirt of proteins or starches material, within a wide pH range from practically acidic pH to alkaline pH, e.g. 4 - 10. A preferred pH interval for the composition according to the invention is approx 7813213-1 , 5 - 9, especially 6 - 8.5, most preferably 7 - 8.5.

Each combination of the first and second surfactants described above the substances can be used for the production of the organic synthesis the surfactant system in the composition of the invention.

Typical examples of surfactants are alkylbenzenesulfonate / - alkyl polyethoxy sulfate blends; alkylbenzenesulfonate / alkyl- polyethoxy sulfate / nonionic blends; alkyl sulphate / alkyl- benzenesulfonate / alkyl polyethoxy sulfate blends and alkyl sulfate / alkyl polyethoxy sulfate / amine oxide blends. K As explained above, any type of citrus juice can be used in a content of from 5% by weight in the practice of the invention, juices of lemon, lime, orange and grapefruit are sentative for the general class. The lower limit of 5 percent citrus juice is stated because at lower levels becomes the effect is insufficient to practically absent. Also if any proportion exceeding 5% citrus juice is practically possible and in principle can be used, it has been shown that higher levels are not necessary in order to obtain the desired making effect. In addition, there is a clear reduction in the increase of the improvement with increasing juice content over one value of 10% and a rapid decrease especially within the higher part of the percentage range, why the use of too high levels of juice do not justify the resulting larger the cost. Advantageously, 50%, preferably 25%, can be taken as a suitable practical upper limit for single citrus juice strength in the composition according to the invention, since in concentrations above these percentages the citrus juice does not give some additional benefits that could compensate them higher the cost of additional citrus juice.

A content of citrus juice most suitably used in the liquid the detergent composition of the invention is from 5 to about 10% by weight. 7813213-1 6 According to the invention, an aqueous liquid is provided detergent composition, which is particularly suitable for washing dishes and has improved cleaning ability especially with regard to difficult dirt, comprising 5 to 60% by weight of an organic synthesis surface surfactant system consisting of at least two surfactants as defined above and 5 to 50% by weight of a citrus juice.

Citrus juices are available in the market. They occur completely generally either as simple strength juices or in the form of concentrate with different strength, ie. from Zx concentrate up to 10x concentrate. Lemon juice contains a number of different classes of chemical compounds including acids, sugars, amino acids acids, oils and trace elements. Analytical data on citrus juices can be found in the following references: l) "Chemical Constituents of Citrus Fruits", Supp. 2 (1970) by Kefford and Chandler; 2) "Biochemistry of Fruits and their Products", vol. 1 (1970) by A.C. Hulme.

Within each class there are a number of different constituents parts, each of which can be determined analytically. The main acid in The citrus juice is citric acid, which is present in a content of about 5 - 6% by weight.

It is not known exactly which of the ingredients in citrus juice who are responsible for improving the cleansing effect, but it is assumed that a synergistic effect is formed by of one or more constituents present in .citrus juice and the active system used in the composition tion according to the invention.

In addition to the essential components described above in the the detergent composition of the invention, it may may contain other non-essential materials. Such optional components include additional surfactants in addition to those listed above as the first and second surfactants the substances in the organic synthetic surfactant system; _ 7813213-1 7 build-up salts can be added to promote cleaning and the efficiency of soil removal for acid the factors in the composition, e.g. phosphate, polyphosphate, phospho- nate, carbonate, polyacetate and polycarboxylate; foaming promotion agents such as coconut fatty acid diethanolamide; hydrotropic substances and solubilizing agents such as the lower alkanol containing 2 to 4 carbon atoms, in particular ethanol, urea, sodium or potassium toluenesulfonate and sodium or potassium xylene sulfonate, which is generally added to promote phase stability, especially in compositions with high concentrations surfactants; preservative; perfumes and colors substances. In addition, as desired, it can be acidic or alkaline substances are added for pH adjustment and also scrubbing agents may be present in the detergent composition of the invention ningen.

Preferred compositions are those containing 10 to 50% by weight. percent of the above-described organic synthetic surfactants system, 5 - 25% by weight of lemon juice and about 15 - 75 weight percent water. Particularly preferred are the compositions containing a content of active detergents exceeding 35% by weight percent.

The invention is further illustrated by the following examples.

Examples 1-3.

The following compositions were prepared: Composition l 2 3 A B weight percent Sodium dodecylbenzene sulfonate 29.0 29.0 29.0 29.0 29.0 Sodium laury1- (ethoxy) 3- sulfate 14.0 14.0 14.0 14.0 14.0 Sodium citrate - - - - 1.0 Lemon juice (4x concentrate) 1.25 2.5 5.0 0.25 0.25 Ethanol 5.5 5.5 5.5 8.0 7.0 Urea 5.5 5.5 5.5 7.5 8.0 jjyatten + preservative 44.75 43.5 41.0 41.25 40.75 7813213-'1 8 In order to determine the relative ease with respect to the purity making solid dirt from substrates after leaching was used following comparison test using a half tile Dirty substrates in the form of square enamelled tiles plates (10 x 10 cm) were immersed in solutions of test products. (1 liter) at concentrations of 0.15 2. The solution had at the beginning of the test the temperature was 4500 and was reheated when it dropped to 40cC (use of a small immersed coil).

The plates were checked for the first ind *? = - that the dirt on any of them had softened and after, all were taken out of the test solution and cleaned ( the lowering times varied between 5 and 50 minutes). Clean- the operation was performed for 30 seconds using a mushrooms of the type "Brillo Swish" dipped in the substance in question: solution.

Dirt and soiling method: The tests were performed using fruit pie filling (cherries) and apricot) and currently a mixture of flour and fruit pie filling (1: 4). The pie filling was transferred to finely divided form on so way that it was pressed through a sieve with a mesh size of 240 nicrons and a fine paste was obtained from the mixture of flour and pie filling. ning.

The dirt was applied to the substrate by screen printing using reversal of two passages. The dirt was then baked in the center of a large oven (type "Gallenkamp Oven Model 07330) under 4 minutes. The temperature would be ZSOOC before it got dirty the substrate was introduced into the furnace and the rate of introduction into the furnace was desirable to avoid the temperature falling below 22000.

Results: The results are given in Table I below.

Assessment was made by a panel of technicians, who assessed the degree lv dirt removal on the following basis: 0 = completely clean 1 = still slightly soiled 7813213-1 9 2 = moderately dirty 3 = significantly soiled 4 = no visible cleaning The assessments averaged 8 results for each product and control. Product A was used as a control.

Table I.

Mean assessment Difference (control test) i 5 ° H i 26% i 5% 1 26%: Product water water water water l 2.13 2.93 + 0.8l + 0.8l control (A) 2.94 3.74 2 1.25 3.31 +0.44 + 0.32 control (A) 1.69 3.63 3 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 From the above results it appears that the lemon juice compositions 1, 2 and 3 according to the invention were superior to compositions A and B outside the scope of the invention.

Exemgel 4.

The effect of pH was examined by assessing the effect of the following liquid composition in a leaching text.

POOR nuAuTv s 7813213-1 Composition IJ Vs ~ (f » Sodium dodecylbenzenesulfonate C 1-4 alkyl ether sulfate containing 3 ethylene- oxide groups 14.0, Lemon juice 10.2 r 'tanol 5.5 Q Urea 5.5% Water + preservative 36.0 2 Comparisons were made using the standardized ones (10 x 10 cm) enamelled plates soiled with apricot pie filling flour and baked as described in Examples 1 to 3. plate comparison in water with 11.3 ° H was performed at 45 ° C.

The test products were examined at random and all tests were duplicated. cerades. The pH adjustments were performed at 45 ° C using dilute sulfuric acid (0.1 M) and dilute sodium hydroxide (0.1 M) and determination of pH at the end of each test was also performed.

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

Assessment was made by a technician panel to determine the degree residual dirt on each half-plate using the following assessment: O = completely clean l = still slightly soiled 2 = moderately dirty 3 = significantly soiled 4 = no visible cleaning These assessments were transferred to averages (6 results for each test product and control at each pH) and a dirt difference between the control and the test product was calculated. 7813213-1 ll Table II.

Results of leaching test ~ a comparison between product: med and without 10% lemon juice. åkillnaä Hedel ~ control p fl Product Reviews tal -pro " , 5 lemon 1.5 2.5 1.0 0.5 1.0 0.5 1.1 / +1, "5 control 2.5 3.0 1.5 1.5 2.0 1.0 1.0 1.92 7.0 lemon 3, o 3.5 2.5 o o 0 '1.5 + o, 67 control 3.5 4.0 3.0 0.5 1.0 0.5 2.17 8.5 lemon 0.5 0.5, 5 0.5 1, 0.5 0.58 +], 42 control 1.5 2.0 1, 2.5 3, 2.0 2.0 .0 lemon 1.5 2.5, 1.5 2.5 1.0 1.67 +0.50 control 3.0 3.0 1.5 2.0,, 2, 7 The table above shows that the composition according to the invention has a persistent superiority at pH 5.5, 7.0, 8.5 and 10.0, each the results at pH 8.5 are particularly good.

Example 5.

The following compositions were evaluated: Weight percent ÉÉÉEQÉÉÉÉÉÉÉ C V1 V2 V3 V4 V: V5- Sodium dodecyl- benzenesulfonate 29.0 29.0 29.0 29.0 39.0 29.0 29.0 Laury1-3-ethoxy- sulfate 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Lemon juice (4x concentrate) 0.25 1.25 2.5 3.75 5.0 6.25 12.5 Ethanai 10.0 10.0 10.0 10.0 10.0 io, o 1o, o Urea 10.0 19.0 10.0 1o, o 10.0 10.0 10.0 Water + to to to to to to to to preservatives 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Nominal halt lemon juice l 5 10 15 20 25 50 '815213-1 12 The method used was as follows: l. Egg dirt was prepared by thoroughly mixing dried egg powder and water in the ratio lzl. 2. A 5 cm strip of dirt was screen printed in the middle of one glass plate measuring 30 x 25 cm. 3. The plates were baked for 30 minutes at ZLLOC.

Five assessments could then be performed across each plate. At least two control assessments were performed on each plate. f 4. Five 5 cm ditches were built across the slab using plasticine strips. 6 ml of solution (0.15 à) in carried in a ditch. When using a head covered with a J-cloth and a weight corresponding to 1.5 kg was determined the number of rubs required to clean it cm wide strip of dirt.

. The results of the test solution were calculated as a percentage of speech of the effect of the closest control on the plate.

Test results using hardness water SOH is given in the table below: Composition% lemon juice Medium effect such as% control Control (C) l 100 V1 5 89 V2 10 61 V3 15 70 V4 20 73 V5 - 25 6? V6 50 60.5 The results above clearly show the superior effect of the the positions V1 - V6 according to the invention containing 5% resp. 50% lemon juice in relation to the control when cleaning fried egg.

Example 6.

The following compositions were prepared in a standardized plate washing test for washing effect: as well as with .Vñíï i uuALnv 7813213-1 l3 with regard to the determination of the relative ease with which making took place of baked dirt from substrates after lakninç with using the test method described in Examples 1-3.

Komgosition Q Komgositiøn D % sodium dodecylbenzene - 15% "Empilan (É9LP 10" * sulfonate % sodium lauryl (ethoxy) 3-30 z glyccrol ~ sulfate % lemon juice 5 2 lemon juice 2% urea 2% urea water remained water remained "Empilan LP 10" is a nonionic fatty acid amide condensate, comparable to "Nopco ll79" from Nopco Chemical Company.

"Empilan" is a registered trademark of Marchon Products Ltd.

Standardized plate washing tests were performed using of the following test conditions: Product concentrations: 0.15 and 0.45% Temperature of the solution: 45 ° C Standardized sauce dirt, grease, starch, g / plate: oleic acid and stearic acid.

The results are given in the table below: Table III.

Number of washed plates water heat s ° H 260m _ Product concentration 0.55% 0.45 E 0.5% 0.45% Composition 6 (pH 7) 30 63 27 59 Composition D (pH 5.8) 3 7 2 4 The test results indicate the relative ease with which making of baked dirt takes place from substrates. The assessments was calculated from 5 results for each product at 0.75 i QUALITY 7813213-T 14 concentration.

Table IV.

Mean assessment Difference i 5 ° H 1 2s ° H 1 5 ° H 1 2s ° H Composition water water water water 6 (pH 7) 0.2 2.4 D (pa 5.8) 0.7 2.4 * ° '5 * °' ° 6 (pH 7) 0.7 3.0 n (PH 7) 1,1 3,3 * ° '4 * °' 3 6 (PH 7) 2.4 ._ +03 _ ..

D (pH 5.8) 2.7 (PH 7) 1.5 D (pa 7) 2.1 "* ° '6' The results above clearly show the superiority of composition 6 according to the invention in relation to composition D according to state of the art both in terms of washing and removal of baked dirt.

Examples 7 - 9.

The following liquid detergent compositions within the scope of the finding was prepared: Composition 7 1% by weight Sodium dodecylbenzenesulfonate 16.0 Nonylphenol-7 ethylene oxide 7.0 Ethanol 2.0 Crea 4.0 Lemon juice 8.0 Water + preservative to 10,0,0 Püöl \\ fl üALlçy 7813213-1 Composition 8 ï¿; tpercent 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 + preservative to l00.0 Composition 9 yektprocegg Sodium lauryl (ethoxy) 3-sulfate 24.0 Dimethyl dodecylamine oxide 5.0 Lemon juice 10.0 Sodium citrate 1.0 Urea 3.0 Ethanol 3.0 Water + preservative to 100.0

Claims (8)

7813213-1 16 CLAIMS 1. Aqueous detergent composition, particularly suitable for washing, containing an organic surfactant and a citrus juice, characterized in that it contains 5-60% by weight of an organic synthetic surfactant system consisting of at least two different surfactants and 5-50% by weight of a citrus juice, the organic synthetic surfactant system consisting of: 1) 2) 30-90 parts by weight of the surfactant system consisting of a Ca-sensitive first surfactant selected from the group consisting of of water-soluble C 8-16 alkylbenzenesulfonates; alkane sulfonates having 8-20 carbon atoms; olefin sulfonates having 8-20 carbon atoms; di-C 8-20 alkylphenol sulfosuccinates; primary and secondary alkyl sulfates having 8-20 carbon atoms; C 8-20 alkyl polyethoxy sulfates having 1-25 ethoxy groups and mixtures thereof, and alkyl sulfosuccinates; di-C 6-12 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 condensation of 5-30 moles of an alkylene oxide, preferably ethylene or propylene oxide, with a moles of an organic hydrophobic compound, aliphatic or alkylaromatic in nature, having 8 to 24 carbon atoms and at least one reactive hydrogen atom, in particular a reactive hydroxyl, amino, amido or carboxyl group; C8-20 alkyl sulfobetaines; amine oxides containing a long chain alkyl moiety having 10-28 carbon atoms and two moieties which may be either alkyl groups or hydroxy-E alkyl groups having 1-4 carbon atoms; C8-20 alkyl polyethoxy sulphates having 1-25 ethoxy groups, and mixtures thereof, 2, said surfactants from group (1) and the ionic: surfactants from group (2) being present in the form of their alkali metal salts, ammonium salts, lower alkanolamine salts, lower alkylamine salts or mixtures thereof. ”Tíííis E '_J QUALITY 7813215-1 17 2. A composition according to claim 1, characterized in that the organic synthetic surfactant system is present in an amount of 10-50% by weight of the composition. 3. A composition according to claim 1, characterized in that the citrus juice is present in an amount of 5-25% by weight of the composition. 4. A composition according to claim 3, characterized in that the citrus juice is present in an amount of 5-10% by weight of the composition. Composition according to any one of claims 1-4, characterized in that the citrus juice consists of lemon juice. 6. A composition according to claim 5, characterized in that it has a pH of 5.5-9. 7. A composition according to claim 6, characterized in that the pH value is 6-8.5. Composition according to any one of the preceding claims, characterized in that the organic surfactant system is present in an amount of more than 35% by weight of the composition.