Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds

Definitions

• the present invention relates to liquid dishwashing compositions and more particularly to such compositions which contain an anionic tenside, a combination of specific amphoteric surface active compounds and an alkyl polyglycoside.
• dishwashing compositions are primarily intended for hand dishwashing and are as a rule aqueous solutions containing anionic ten-sides, such as alkyl sulfonates and alkyl ether sulfates, as essential component. These dishwashing agents are entirely satisfactory with regard to cleaning effect, foam forming effect and foam stability. However, the dishwashing compositions based on this type of anionic surface active agents are not satisfactory with regard to mildness to skin, since they have a certain irritating and allergy causing effect. There is thus a great interest in producing dishwashing compositions which are mild to the skin and at the same time give a good cleaning effect.
• anionic ten-sides such as alkyl sulfonates and alkyl ether sulfates
• nonionic alkyl polyglycosides have become of commercial interest for use in dishwashing formulations and other cleaning formulations.
• These nonionic surface active compounds which are products based on natural raw materials, are advantageous for use in dishwashing and other cleaning compositions in that they are mild to the skin, have high biodegradability and good compatibility with other types of surfactants.
• Alkyl polyglycosides are per se well-known compounds and extensively disclosed. Their use as surfactants in combination with other types of surfactants is also well-known.
• the European patent application 0341071 discloses detergent compositions which are particularly useful for manual dishwashing and which contain an alkyl polyglycoside surfactant, an anionic surfactant, a surface active betaine and/or amine oxide.
• dishwashing compositions are obtained when anionic tensides are used together with an alkyl polyglycoside and together with a combination of certain amphoteric compounds.
• Liquid dishwashing compositions containing anionic surface active agents, alkyl polyglycoside and the combination of specific amphoteric compounds have extremely good mildness to skin and good foaming properties and they further give a low biological load and are more efficient than a dishwashing composition based on anionic tenside, an alkyl polyglycoside and an amphoteric alkyl betaine surfactant.
• Dishwashing compositions according to the present invention are particularly suitable for manual washing, of glass, china, kitchen utensils etc, thanks to their mildness.
• amphoteric surface active compounds of type a) can be characterized by the general formula (I) wherein R is a hydrocarbon group having from 7 to 22 carbon atoms, n is 0 or 1, A is a carbonyl group [C(O)], a group (OCH2CH2) z or (OCH2CH2CH2) z wherein z is an integer of from 1 to 5, R1 is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer of 0 to 4, Q is the group -R2COOM wherein R2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium and B is hydrogen or a group Q as defined.
• R is a hydrocarbon group having from 7 to 22 carbon atoms
• n is 0 or 1
• A is a carbonyl group [C(O)], a group (OCH2CH2)
• Amphoteric compounds of the above type are per se known and used in cleaning compositions and shampoo compositions. They are for example described in the European patent applications 160507, 162600 and 214868.
• R is a hydrocarbon group having from 7 to 22 carbon atoms and suitably from 11 to 22 carbon atoms.
• the hydrocarbon group R can be straight or branched, saturated or unsaturated and optionally contain substituents such as hydroxyl groups.
• the group R can also be a cycloalkyl-alkyl group, an aralkyl or aralkenyl group where the alkyl or alkenyl group contains at least 6 carbon atoms.
• R is preferably an alkyl or alkenyl group and it is particularly preferred that R is a hydrocarbon group originating from coco, tallow or oleic fatty acid.
• the amphoteric compounds of formula (I) can, as indicated, contain a group A which is a carbonyl group or one or several ethoxy- or propoxy-groups. When A is ethoxy or propoxy groups ethoxy groups are preferred and A is then especially one such group. Compounds which do not contain a group A, ie in which n is 0, are preferred.
• R1 in the given formula is hydrogen or a lower alkyl group, suitably with 1 to 6 carbon atoms and is preferably hydrogen or a methyl group.
• x is 2 or 3 and y is suitably 2, 3 or 4 and preferably 2 or 3.
• the group R2 is suitably a methylene or an ethylene group, preferably a methylene group.
• M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium or substituted ammonium such as for example mono-, di- or trihydroxyethylammonium. M is preferably a sodium ion.
• Preferred compounds of the formula (I) have the formula (II): wherein Q is CH2-COOM or CH2CH2COOM, y is 1, 2 or 3 and wherein M, R, x and B have the above given meanings. x is suitably 3 and all groups B are suitably groups Q.
• R in these compounds suitably originates from tallow, oleic or coco fatty acid.
• amphoteric compounds of the above given formulae are used in combination with amphoteric compounds containing a carbonyl group.
• These amphoteric compounds, of type b), are either such which can be characterized by the general formula (III) or amido betaines as shown in formula (IV). Mixtures of these two types of amphoteric compounds can also be used.
• Compounds of formula (III) are wherein R, y, Q and B have the same meaning as given for compounds of formula (I), whereby, however, one group B is the group -CH2CHR'OH, wherein R' is H or CH3.
• the suitable and preferred definitions for R and for M in the group Q are as given for compounds of formula (I).
• Most suitable are compounds of formula (III) wherein y is 1 and Q is the group -CH2COOM.
• Amphoteric compounds of formulae IIIa and IIIb are commercially available as mixtures and usually with a weight ratio of compounds of formula IIIa to compounds of formula IIIb within the range of 1:10 to 10:1.
• Amphoteric compounds of the amido betaine type containing a carbonyl group can be characterized by the general formula (IV) wherein R is a longer hydrophobic hydrocarbon group, which suitably is a saturated or unsaturated, straight or branched, aliphatic hydrocarbon group with at least 7 carbon atoms. R suitably has from 7 to 21 carbon atoms and preferably is an alkyl or alkenyl group with from 11 to 17 carbon atoms, R' is an alkyl or hydroxyalkyl group with from 1 to 4 carbon atoms. Most suitably both groups R' are methyl groups, and n is 1 or 2. M is preferably hydrogen or a sodium ion.
• amphoteric compounds of type a) act primarily as detoxifying tensides while those of type b) act primarily as tensides, viscosity modifiers and suds formers.
• Suitable weight ratios between amphoteric compounds of type a) and type b) is within the range of from 1:10 to 10:1 and preferably within the range of from 1:5 to 5:1.
• the total amount of the defined amphoteric compounds in the dishwashing compositions is suitably from 1 to 20 per cent by weight and preferably from 1.5 to 15 per cent by weight.
• Amphoteric compounds of the above given formulae are commercially available and sold under the trade name Ampholak (R) by Berol Nobel AB, Sweden.
• the above combination of amphoteric compounds can partly replace anionic tensides and be used in liquid dishwashing compositions together with an alkyl polyglycoside to give very mild and efficient compositions with good foaming properties.
• the mildness which is obtained is dependent not only on the use of the alkyl polyglycoside but also on an efficient detoxification of anionic tensides through formation of mixed micelles of the anionic surface active compounds and the specific amphoteric surface active compounds.
• the very low critical micelle concentration for the specific amphoteric compounds is hereby utilized. The desired effect is thus obtained with very small amounts of amphoteric compound, particularly of those of the above given formulae I and II.
• the alkyl polyglycosides, or sugar ethers, which are used in the present compositions are per se known nonionic surface active compounds which have a hydrophilic polysaccharide head group and a hydrophobic hydrocarbon substituent.
• the hydrophilic saccharide units can for example be fructoside or glucoside units, glucoside units being preferred.
• the alkyl polyglycosides suitably contain an average of from 1 to 5 saccharide units and preferably from 1.2 to 1.5 units.
• the hydrophobic hydrocarbon group, an alkyl or alkenyl group, preferably an alkyl group suitably has from about 8 to about 20 carbon atoms and preferably from 10 to 18 carbon atoms.
• alkyl polyglycosides are commercially available, for example from Henkel under the trade name Plantaren (R) APG.
• the amount of alkyl polyglycosides in the present compositions is suitably from 1 to 15 per cent by weight and preferably from 1.5 to 4 per cent by weight.
• an alkyl polyglycoside and anionic tensides which normally are water soluble sulfonates or sulfates, in liquid dishwashing compositions, the latter can be replaced to a certain extent and hereby a dishwashing composition is obtained which is advantageous from a biological point of view and advantageous with regard to mildness at use.
• the present compositions also make it possible to substantially reduce the total amount of active components for obtaining the same dishwashing performance as with known compositions based on solely anionic tensides and as with compositions containing anionic tenside, an alkyl betaine amphoteric compound and an alkyl polyglycoside.
• anionic tensides of the above mentioned types are also present, but in lower amounts than usual.
• the total amount of amphoteric, nonionic and anionic surface active agents at most 90 per cent by weight are anionic tensides.
• the amount of anionic tenside is suitably within the range of from 85 to 30 per cent by weight, based on the total amount of amphoteric surface active compounds, nonionic alkyl polyglycoside and anionic surface active compounds, and is particularly within the range of from 85 to 60 per cent by weight.
• the anionic tensides are, as indicated above, water soluble sulfates or sulfonates, and then particularly alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, wherein the alkyl group usually contains from 8 to 22 carbon atoms.
• alkyl group usually contains from 8 to 22 carbon atoms.
• alkyl group usually contains from 8 to 22 carbon atoms.
• anionic tensides containing ether groups these are usually ethylene oxide groups and the compounds normally contain between 1 and 10 such groups per molecule.
• the cations are usually alkali metals, alkaline earth metals, ammonium or amines such as mono-, di- and triethanol amine cations.
• anionic tensides can be mentioned sodium lauryl sulfonate, sodium lauryl ether sulfate with two or three ethylene oxide groups, the corresponding ammonium or ethanol amine salts, sodium or other salts of dodecyl benzene sulfonic acid and alkyl benzene sulfonic acid wherein the alkyl group contains an average of from 11 to 13 carbon atoms. At least two different anionic tensides are often used in the dishwashing compositions.
• the present dishwashing compositions are liquid and the main component for this is of course preferably water.
• Water used in liquid dishwashing compositions is often deionized but other types of water can also be used.
• Other liquid solvents can of course be included, such as for example lower alcohols and glycols and lower alkyl ethers of the glycols. These types of solvents are normally present, if at all present, in minor amounts. As some specific examples can be mentioned ethanol, isopropanol, ethylene glycol etc.. Solvents are sometimes included mainly for preservation.
• One advantage of the present compositions is, however, that since they contain amphoteric compounds of the type according to formula (I) no solvent is required in order to obtain preservative effect.
• the present dishwashing compositions can be prepared in per se conventional manner by simple mixing of the components and they can of course also be used in conventional manner. Normal dosage is about 0.2 g/l dish liquor of a dishwashing composition with a total dry content of from about 10 to about 45 per cent by weight.
• the dishwashing compositions can of course also contain other conventionally used additives for improvement of different properties such as thickeners, antibacterial agents, colorants, pigments, perfumes etc..
• Other amphoteric compounds can also be present if desired, such as betaines, and also other nonionic tensides.
• the compositions should be essentially free from cationic surface active agents.
• the dishwashing compositions of the present invention have good foam properties and no special foam booster or foam stabilizing compounds are thus necessary.
• foam boosting compounds can of course be included in the present compositions and as examples of such can be mentioned amides and amine oxides containing at least one longer hydrophobic hydrocarbon group, ie a fatty acid residue having at least 7 carbon atoms and suitably up to 22 carbon atoms.
• Dishwashing compositions were prepared as follows (all amounts given are as 100% active substance): Composition I - Reference: 11.2 g of sodium salt of linear alkyl benzene sulfonate with C12 to C18 alkyl groups, 5.6 g of sodium lauryl ether sulfate with 3 ethylene oxide groups, 2.1 g of alkyl polyglycoside, 2.1 g of a C12/C14 alkyl dimethyl betaine sold under the name Amphoteen 24 and 79 g of water.
• Composition II According to the invention: 11.2 g of sodium salt of linear alkyl benzene sulfonate with C12 to C18 alkyl groups, 5.6 g of sodium lauryl ether sulfate with 3 ethylene oxide groups, 2.1 g of a mixture of two different amphoteric compounds, a 1:2 mixture of amphoteric compounds sold under the trade marks Ampholak (R) 7TX and Ampholak (R) XCO-30, respectively, - the first mentioned amphoteric compound can chemically be characterized as tallowampho polycarboxyglycinate and falls under the definition of compounds according to formula II and the last mentioned one can chemically be characterized as cocoamphocarboxyglycinate and contains a carbonyl group and comprises a mixture of compounds defined in formulae IIIa and IIIb -, 2.1 g of alkyl polyglycoside and 79 g of water.
• Composition III Reference: 11.2 g of alkane (C12-C18) sulfonate, 5.6 g of sodium lauryl ether sulfate with 3 ethylene oxide groups, 2.1 g of alkyl polyglycoside, 2.1 g of alkyl dimethyl betaine and 79 g of water.
• Composition IV According to the invention: 11.2 g of alkane C12-C18 sulfonate, 5.6 g of sodium lauryl ether sulfate with 3 ethylene oxide groups, 2.1 g of the same mixture of two amphoteric compounds as in Composition II, 2.1 g of alkyl polyglycoside and 79 g of water.
• the alkyl polyglycoside in all compositions was an alkyl polyglycoside sold under the name Plantaren (R) APG 600 by Henkel. It has an average number of saccharide units of 1,4 and a C12-14-16 hydrocarbon group.
• the alkyl dimethyl betaine used in reference compositions I and III was a C12-C14 alkyl dimethyl betaine sold under the name of Amphoteen (R) 24 by Berol Nobel AB.
• composition Efficiency Index I Composition Efficiency Index I - Reference 1 II - According to the invention 1 III - Reference 1.25 IV - According to the invention 1.8
• Composition II according to the invention had the same efficiency index as the reference but for Composition IV according to the invention a considerably better efficiency was obtained in comparison with the reference Composition III.
• Dishwashing performance of the compositions was assessed by the practical dishwashing tests. 1 ml beef tallow with an iodine number of 55.1 was applied on each plate and the plates were allowed to dry over one night at ambient temperature. 8 l of water with a concentration of 0.2 g/l of each tested composition and with a hardness of 20°dH were used at a temperature of 45+-2°C. After the initial generation of foam the dried plates covered with beef tallow were cleaned with a brush until the foam collapsed. The results were recorded as the number of washed plates and set in relation to the results obtained with composition 1. Composition Number of washed plates Dishwashing performance % I - Ref. 8 100 II - Invention 10 125 III - Ref. 16 200 IV - Invention 20 250
• composition according to the invention was prepared: 8.98 g of sodium lauryl ether sulfate with 2 ethylene oxide groups, 2 g of alkyl polyglycoside Plantaren (R) APG 600, 6.67 g of cocoamido betaine, 3.32 g of Ampholak (R) 7TX and 79.03 g of water.

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Citations (4)

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• 1991
  • 1991-04-09 SE SE9101058A patent/SE468252B/sv not_active IP Right Cessation
• 1992
  • 1992-03-11 ES ES92200679T patent/ES2073238T3/es not_active Expired - Lifetime
  • 1992-03-11 EP EP92200679A patent/EP0508507B1/fr not_active Expired - Lifetime
  • 1992-03-11 DE DE69202807T patent/DE69202807T2/de not_active Expired - Fee Related
  • 1992-03-11 AT AT92200679T patent/ATE123519T1/de not_active IP Right Cessation
  • 1992-03-11 DK DK92200679.6T patent/DK0508507T3/da active
  • 1992-04-06 JP JP4112337A patent/JPH0765071B2/ja not_active Expired - Lifetime
  • 1992-04-08 NO NO921369A patent/NO178898C/no unknown

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