FI87086C - RIKLIGT LOEDDRANDE FLYTANDE DISKMEDELSKOMPOSITION - Google Patents

Abstract

High sudsing liquid detergent compositions contain anionic surfactant and polymeric surfactant which contains ether linkages, the anionic surfactant forming stable complexes with the polymeric surfactant for improved grease handling.

Description

1 c 7 π '·'

O / ϋ ϋ O

Highly foaming liquid dishwashing detergent composition

The invention relates to aqueous high-foaming liquid detergent compositions containing the amounts and types of surfactants defined below and which are particularly useful for washing dishes, kitchen utensils and other hard surfaces.

The compositions of this invention have excellent fat handling ability.

The behavior of the detergent composition in cleaning dishes and utensils is evaluated based on its grease handling capacity. The detergent solution should easily degrease and minimize re-precipitation.

There is a continuing need for better compositions and methods that can be used to wash dishes to improve the appearance of kitchen utensils and objects. Such compositions and methods should provide improved degreasing in conventional dishwashing soil removal procedures while retaining the foaming properties of an acceptable dishwashing detergent composition.

The present invention relates to a high-foaming liquid detergent composition comprising by weight: (a) 5% to 50% of an anionic surfactant; (b) 0.1 to 10% of a polymeric surfactant containing polymerized ethylene oxide and / or propylene oxide groups and having a molecular weight of 400 to 60,000; : - (c) 0% to 10% of a foam stabilizing nonionic surfactant selected from fatty acid amides, trialkylamine oxides and mixtures thereof; 2 8 7 C £ 6 (d) 0% to 10% of a detergent builder selected from inorganic phosphates, inorganic polyphosphates, inorganic silicates and inorganic carbonates, organic carboxylates, organic phosphonates and mixtures thereof; (e) 0% to 15% alkanol containing 1 to 6 carbon atoms; and (f) 20% to 90% water, characterized in that said polymeric surfactant is selected from compounds of formula 1) [R 'R'OU 2 OJJ ^ R 4] wherein R 1 is hydrogen, each R 2 and R 3 is an alkylene group having two to six carbon atoms, wherein up to 90% of the molecule contains R 2 or R 3 groups having two carbon atoms, and the (R 20) and (R 30) groups are interchangeable, R 4 is selected from 1 ) alkylene groups having 1 to 18 carbon atoms, ii) poly (hydroxyalkylene oxide) groups in which each alkylene group contains 3 to 8 carbon atoms and is joined by 1 to 6 hydroxy groups and having: 2 to 50 hydroxyalkylene oxide groups and 2 to 50 hydroxy groups -. 25 groups, "; iii) (= NR 2 N =) and -: iv) = n (r 2 nh) x, n is 0 to 500, m is 0 to 500, n + m is 5 to 1000, x is 2 to 50 and y is 2 to 50 and equal to the number of valencies of R 4; 2) R 1 (OCH 2 CH 2) X R 2 (OCH 2 CH 2) y OR 3, wherein R 1 is H, CH 3 or CH 3 (CH 2) n where n is 1 to 17, or an unsaturated analog, x and y are each 2 to 500; 35 and R 2 is -O (CH 2) 2, where z is 1 to 18, or a saturated analog thereof, wherein the molecule has less than 90% CH3 3) R3R4 (OCH2CH) aR4R3, where R3 is sulphate or sulphonate, R4 is absent or is (OCH2CH2) b, A is 5 to 500 and B <A / 2; O 0 4) CH3 (OCH2CH2); ) xOC (CH2) yCO (CH2CH2O) xCH3, where X is 8 and Y is 4 or 14, or X is 17 and Y is 10, or CH3 (OCH2CH2) xO (C1-Q2) -COCH2CH2O ) y (CH 2 CH 2 O) x CH 3 wherein X is 7.5 or 16 and Y is 2.75, wherein the pH of said composition is greater than six when the composition contains C 10 -C 20 alkyl polyethoxylate surfactant surfactant containing an average of 0, 25 -10 ethoxy groups per molecule and has a viscosity greater than 0.1 Pa * s and said composition is substantially free of a nonionic surfactant alkyl polyethoxylate detergent when the amount of anionic surfactant is less than 20%, said anionic surface the active ingredient being a C10-C20 alkyl polyethoxylate sulfate surfactant containing an average of 0.5 to 10 ethoxy groups per molecule in the absence of! no magnesium ions or betaine surfactants.

Glassware and other tableware and kitchen utensils are washed in aqueous solutions of the detergent composition at a concentration of about 0.05 to 0.4% by weight of the composition at a temperature of about 15 to about 50 ° C.

Optional ingredients can be added to diversify behavior and produce aesthetic qualities.

"35 The liquid dishwashing compositions of this invention contain two essential ingredients: (a) an anionic surfactant which, in the absence of betaine surfactant, is either a magnesium salt and / or an alkyl polyethoxylate sulfate containing an average of 1/2 to 10 ethoxy groups per molecule, said average being calculated herein such that any alkyl sulfate surfactant has been treated as an ethoxy group-containing alkyl polyethoxylate sulfate to provide good foaming and preferably low interfacial tension; and (b) a polymer p; an active substance that improves the handling of fat.

Optional ingredients can be used to provide various potency-15 properties and aesthetic properties.

Anionic Surfactant The compositions of this invention contain from 5 to 50% by weight of an anionic surfactant or mixtures thereof, preferably containing at least about 8% and most preferably more than about 10% alkyl polyethoxylate (polyethylene oxide) sulfate. having from about 10 to about 20, preferably from about 10 to about 16 carbon atoms. ; atoms in the alkyl group and containing an average of 1/4 to .25 10, preferably about 1 to about 8, most preferably about 1 to about 6 ethoxy groups. Preferred compositions contain from about 20% to about 40% by weight of anionic surfactant.

Most anionic detergents can be broadly described as water-soluble salts of organic sulfur reaction products, especially alkali metal, alkaline earth metal, ammonium or amine salts having an alkyl radical in the molecular structure containing from about 8 to about 22 carbon atoms and a radical selected from ,; 35 consisting of sulfonic acid and sulfuric acid ester radicals. The term "alkyl" includes the alkyl moiety of acyl radicals. Examples of anionic synthetic detergents which may form a surfactant component of the compositions of the present invention include alkyl sulfates of salts of suitable cations, e.g. sodium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, potassium and / or especially magnesium cations. with, especially those obtained by sulfation of higher (C8-C18 carbon) alcohols, alkyl-10-benzene or alkyltoluene, sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms and the alkyl radical is either a straight or branched aliphatic chain; with paraffin sulfonates or olefin sulfonates in which the alkyl or alkenyl group contains from about 15 to about 20 carbon atoms; with sodium C10-20 alkylglyceryl ether sulfonates, in particular ethers of alcohols derived from tallow and coconut oil; with coconut oil fatty acid monoglyceride sulfates and sulfonates; with alkylphenol polyethylene oxide ether sulfates having an average of about 1 to about 20 ethylene oxide units in the molecule, wherein the alkyl radicals contain from 8 to about 12 carbon atoms; with reaction products of fatty acids esterified with an ionic thionic carboxylic acid, wherein the fatty acids are exemplified; 25 kiksi coconut oil derivatives; with methyl tauride fatty acid pyramids, wherein the fatty acids are derived from, for example, coconut oil; and with β-acetoxy or β-acetamidoalkanesulfonates having 8 to 22 carbon atoms in the alkane.

Specific examples of alkyl sulfate salts that can be used in the present detergent compositions include sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, and magnesium lauryl sulfates, stearyl sulfates, palm-sulfate, 35-sulfate sulfate. myristyl sulfates, 6,87086 -talalkyl sulfates, coconut alkyl sulfates, -C12-15 alkyl sulfates, and mixtures of these surfactants Preferred alkyl sulfates include C12-15 alkyl sulfates.

Suitable alkylbenzene or alkyltoluenesulfonates include alkali metal (lithium, sodium and / or potassium), alkaline earth metal (preferably magnesium), ammonium and / or straight chain alkylbenzene or alkyltoluenesulfonic acids. or alkanolammonium salts. Alkylbenzenesulfonic acids useful as precursors for these surfactants include decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetrapropylene benzene bisulfonic acid. Preferred sulfonic acids as precursors for alkyl benzene sulfonates useful in these compositions are those in which the alkyl chain is linear and averages about 11 to 13 carbon atoms in length.

Preferred anionic surfactants herein which are essential in the absence of magnesium ions or betaine surfactant are alkyl polyethoxylate sulfates of the formula R0 (C2H40) xSO3M,. Wherein R is an alkyl or alkenyl group of about 10 to about 20 carbon atoms, x is on average 1/2 to 10, wherein the alkyl sulfates are treated as if they had 0 ethoxy groups, preferably x is 1/2 to about 8, most preferably about 1 - about 6, and M is a water-soluble suitable cation as described above. Alkyl polyethoxylate sulfates useful in the composition of the invention are sulfates of the condensation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. Preferably R contains 10 to 16 carbon atoms. Alcohols; 35 may be derived from natural fats, e.g. coconut oil or tallow, or may be synthetic. Such alcohols can be reacted with about 1/2 to about 20, especially about 1 to about 14, and more particularly about 1 to about 8 molar proportions of ethylene oxide, and the resulting molecular species mixture is sulfated and neutralized.

Such molecules containing 1 to 10 ethoxylate groups should be present in an amount of greater than about 10%, preferably greater than about 15%, calculated as a percentage of the total anionic surfactant in the composition. When these molecules are mixed with alkyl sulfates treated with 0 ethoxylate groups, the calculated average degree of ethoxylation should be greater than about 0.5, preferably greater than about 0.6. A similar approach can be used to calculate the minimum desired amount of alkyl polyethoxylate sulfate that should be present when mixed with any anionic surfactant. For example, the second anionic surfactant can be treated as if it were an alkyl sulfate to calculate the average degree of ethoxylation.

Specific examples of alkyl polyethoxylate sulfates useful in the composition of the invention include sodium coconut alkyl polyethoxylate (3) ether sulfate, magnesium C 12-15 alkyl polyethoxylate (3) -25 ether sulfate, and sodium thalalkyl polyethoxylate (6). A particularly preferred example is water-soluble (e.g. magnesium) C12-13 alkyl polyethoxylate (1) ether sulfate. Preferred alkyl polyethoxylate sulfates are those containing a mixture of individual compounds, said mixture having an average alkyl chain length of about 10 to 16 carbon atoms and an average degree of ethoxylation of about 1 to about 8 moles of ethylene oxide.

For use in completely soft water composition; 35 should contain magnesium ions and / or at least 8,87086 about 10%, preferably at least about 15% by weight of the anionic surfactant of the preferred alkyl polyethoxylate sulfates described above. It is preferred that the compositions of the invention, including those containing preferred alkyl polyethoxylate sulfates, also contain magnesium and / or calcium ions, most preferably magnesium ions to act as cations for a portion of the anionic surfactant. If the composition is to be used mainly in water with a hardness of approximately 2 grains / gallon (34.2 g / m3), added magnesium is not necessary. From about 10% to about 100%, preferably from about 20% to about 90% of the anionic surfactant, a magnesium salt should be used.

The manufacturing formula for anionic, surfactant, interfacial stress reducing systems 15 can be well designed by the author of a standard detergent manufacturing guide. For purposes of this invention, the surfactant system minus the polymeric surfactant should reduce the interfacial tension to less than about 2 1/2 dynes / cm, preferably less than about 2 dynes / cm as measured relative to triolein at 0.2% concentration and temperature. 115 ° F (46 ° C) on a tensiometer with a drop around the axle. Any surfactant reduces the surface tension, but performance can be improved by selecting surfactants with longer alkyl chain lengths using cations such as magnesium that minimize charge effects when used. anionic surfactants, and using anionic surfactants in combination with co-surfactants such as trialkylamine oxides which form complexes with the anionic surfactant. A more complete description of such effects is given in Milton J. Rosen, Surfac-'35 tants and Interfacial Phenomena, 149-173 (1978), which is incorporated herein by reference.

I; 9 87066

Polymeric surfactant

The compositions of the invention contain from 0.1% to 10%, preferably from about 0.5% to about 4%, and most preferably from about 0.5% to about 2% of the above polymeric surfactant of formula 1, 2 , 3, 4 or 5.

Particularly preferred examples of compounds of formulas 2 and 3 are the following: (i) H (OCH 2 CH 2) x O (CH 2) 2 (OCH 2 CH 2) y H, CH 3 (ii) NaO 3 S (OCH 2 CH) ASO 3 Na, CH 3 (iii) NaO 3 S (OCH 2 CH 2) B (OCH 2 CH) A (OCH 2 CH 2) BSO 3 Na, wherein x, y, z, A and B are as defined above.

Without wishing to be bound by this theory, it is believed that the polymeric surfactant works by forming complexes with the hydrophilic portions of the anionic surfactants, thereby minimizing the ability of the anionic surfactants to leave the micelle or other once formed interfacial tension zone. Therefore, long terminal hydrocarbon groups are not preferred and are not acceptable when the formula is of type BA, where B is a hydrophobic moiety and A is a hydrophilic moiety. Long terminal hydrocarbon groups draw the polymer into any oil phase, thereby minimizing the number of stabilized anionic surfactant molecules. Similarly, if the hydrophilic portion of the molecule is too hydrophilic, the molecule enters too far into the aqueous phase. The molecule should be in equilibrium between hydrophobicity and hydrophilicity, and should have sufficient ether and / or amine bonds throughout its structure to complex the anionic surfactant. The anionic surfactant must also be such that it forms a complex. Magnesium cations, ether bonds and amine or ammonium groups form stable complexes with polymeric surfactants.

The surfactant preferably contains a hydrophilic group containing polyethylene oxide and / or ethyleneimine groups containing from about 1 to about 500 ethylene oxide and / or ethyleneimine derivative moieties.

Sulfonate or sulfate groups may also be present. The polymeric surfactant also contains at least one hydrophobic group, preferably comprising polyalkylene oxide groups in which the alkylene contains 3 to about 6, most preferably 3, carbon atoms, and a molecular weight of 400 to 15 to 60,000. Alkylene groups containing from about 7 to about 18, preferably from about 10 to about 18 carbon atoms, may also be used, but the polymeric surfactant preferably branches only short-chain, relatively insignificantly oil-seeking alkyl or acyl groups containing less than about 10 carbon atoms.

Preferred surfactants are block copolymers comprising one or more hydrophilic groups containing predominantly: ethylene oxide groups, and one or more hydrophobic groups containing predominantly propylene oxide groups attached to a residue from a compound containing: one or more hydroxy or amine groups to which the corresponding alkylene oxides were polymerized, said polymers having molecular weights of 400 to 60,000 and an ethylene oxide content of about 10 to about 90% by weight and a propylene oxide content of about 10 to about 90% by weight.

Preferred surfactants are those in which propylene oxide is condensed with an amine, for example ethylenediamine, to give a hydrophobic base compound having a molecular weight of about 350 to about 55,000, preferably about 500 to about 40,000. This hydrophobic parent compound is then condensed with ethylene oxide to produce about 10% to about 90%, preferably about 20% to about 80% ethylene oxide. Reverse structures in which ethylene oxide is first condensed are also desired. These structures are particularly easy to form into the desired single-phase liquid compositions.

Similar structures in which ethylenediamine is replaced by a polyol, especially propylene glycol or glycerol or glycerol condensation products, are also desirable.

In similar compositions, the polypropylene glycol moiety may be replaced with an alkyl or alkylene group containing from about 5 to about 18, preferably from about 8 to about 16 carbon atoms, and the polyethylene oxide groups may be replaced either completely or preferably in part by other water solubilizing groups, especially sulfate and sulfonate groups.

20 Foam stabilizing non-ionic surfactant

The compositions of the invention contain 0% to 10%, preferably about 1% to about 8% of a foam stabilizing nonionic surfactant or mixtures thereof. There are two basic types of foam stabilizing nonionic surfactants in the present compositions: fatty acid amides and nonionic semipolar trialkylamine oxides.

Amide-type nonionic surfactants include ammonium, monoethanol and diethanolamides of fatty acids having an acyl group of from about 8 to about 18 carbon atoms and having the general formula R 1 -CO-N (H) n (R 2 OH) 2 .m i2 87086 wherein R 1 is a saturated or unsaturated aliphatic hydrocarbon radical containing from 7 to 21, preferably from 11 to 17 carbon atoms; R2 is a methylene or ethylene group; and m is 1 or 2. Specific examples of said amides include coconut fatty acid monoethanolamide and dodecyl fatty acid diethanolamide. These acyl groups can be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be synthetic derivatives, e.g., by oxidizing petroleum 10 or hydrogenating carbon monoxide to Fischer.

Obtained in the Tropsch process. Monoethanolamides and diethanolamides of C12-14 fatty acids are preferred.

Nonionic semipolar amine surfactants include compounds and mixtures of compounds of formula 15; R 2 R 1 (C 2 HMO) n NR 0 R 3 wherein R 1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy respectively contain 8 to 18 carbon atoms, R 2 and R 3 is each a methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl-25 or 3-hydroxypropyl radical and n is 0 to 10. Particularly preferred are amine oxides of the formula: R 2 is R to N —O R3

30 R

wherein R 1 is C 10-14 alkyl and R 2 and R 3 are methyl or ethyl.

The preferred foaming properties of the compositions of the invention are such that they provide the user of the product with an indication of the cleaning performance of the dishwashing solution.

II

to g 7 fi '' r

13 o / U u O

ability. Dirt released during dishwashing acts as a defoamer and the presence or absence of foam on the surface of the dishwashing liquid is a suitable product manual. Mixtures of anionic surfactants and foam stabilizing nonionic surfactants are used in the compositions of the invention due to their high foam-forming properties, their foam stability in the presence of food debris and their ability to accurately demonstrate a reasonable level of product use in the presence of dirt.

In preferred embodiments of the invention, the ratio of anionic surfactants to foam stabilizing nonionic surfactants in the composition is in a molar ratio of about 11: 1 to about 1: 1, and more preferably about 8: 1 to about 3: 1.

Other possible surfactants

The compositions of the invention may, if desired, contain optional surfactants, in particular ampholytic and / or zwitterionic surfactants. However, when the level of anionic surfactant is less than about 20%, the composition should not contain a substantial amount of a conventional nonionic surfactant, e.g., alkyl polyethoxylate, in addition to the polymeric surfactant. Large amounts of conventional nonionic surfactants, e.g., greater than about 3-4%, tend to impair the foaming ability of the composition.

When larger amounts (> 20%) of anionic surfactants are present, it is sometimes good to have a small amount of conventional nonionic surfactants, up to 5%; "conventional" surfactants are, for example, C8-18 alkyl polyethoxylates (4-15) or C8-15 alkylphenol polyethoxylates (4-15).

Ampholytic surfactants can be generally described as derivatives of aliphatic amines, which contain a long chain of about 8 to 18 carbon atoms and an anionic water-soluble group, e.g. a carboxylate, sulfonate or sulfate group. Examples of compounds classified in this definition include sodium 3-dodecylaminopropanesulfonate and dodecyldimethylammonium hexanecarboxylate.

Zwitterionic surfactants in the present composition are generally described as internally neutralized derivatives of aliphatic quaternary ammonium and phosphonium and tertiary sulfonium compounds in which the aliphatic radical may be straight or branched and in which one of the aliphatic a carbon atom and the other contains an anionic water-solubilizing group, e.g. a carboxy, sulfo, sulfate, phosphate or phosphono group.

Highly preferred are washable surfactants, which act synergistically with the polymeric surfactant to provide an improvement in fat handling.

Washing surfactant betaine

Betaine surfactant has the general formula (+) (-)

25 R-N (R6) 2R7COO

wherein R is a hydrophobic group selected from the group consisting of alkyl groups having about 10 to 22, preferably about 12 to 18 carbon atoms, and alkylaryl-30 and aralkyl groups containing the same number of carbon atoms when the benzene ring is considered equivalent to about two carbon atoms, and groups having a similar structure having amido or ether bonds as chain members; R6 is an alkyl group having 1 to 3 carbon atoms and R7 is an alkylene group having 1 to about 6 carbon atoms.

is 87086

Examples of preferred betaines are dodecyl-amidopropyldimethylbetaine; dodekyylidimetyylibeta-amine; tetradekyylidimetyylibetaiini; setyylidimetyylibe-taiini; cetylamidopropyldimethylbetaine, tetrade-5-yldimethylbetaine, tetradecylamidopropyldimethylbetaine and docosyldimethylammonium hexanecarboxylate and mixtures thereof.

Betaine surfactants are unique ingredients. which provide exceptional benefits. When pin-10 ta-active betaine and a polymeric surfactant are combined with any anionic surfactant in the presence or absence of magnesium ions, excellent advantageous fat retention properties are produced.

Betaines containing C12-14 alkyl provide a much better benefit when combined with a polymeric surfactant than when used as such.

Betaine is preferably present in a concentration of about 0.5% to about 15% by weight of the composition, preferably about 20% to about 10%, most preferably about 1% to about 8%. The ratio of anionic surfactants to betaine is from about 1 to about 80, preferably from about 1 to about 40, more preferably from about 2 to about 40.

When betaines are present, the ratio of betaine in the composition to the polymeric surfactant should preferably be greater than 7: 1, preferably greater than 9: 1.

solvents

Alcohols such as ethyl alcohol, and hydrotropes such as sodium and potassium toluenesulfonate, sodium and potassium xylene sulfonate, trisodium sultosuccinate and the like (described, e.g., in U.S. Patent 3,915,903, incorporated herein by reference) and urea are incorporated herein by reference. can be used to achieve the desired phase stability and viscosity of the product. Alkanols containing 1 to about 6, especially two, carbon atoms, and especially ethyl alcohol may be present. Ethyl alcohol at a level of 0% to about 15%, preferably about 1% to about 6%, and potassium and / or sodium toluene, xylene and / or cumene sulfonates at a level of about 1% to about 6% may be used in the compositions of the invention. The viscosity should be greater than about 100 mPa * s, more preferably greater than 150 mPa * s, more preferably greater than about 200 mPa * s to achieve consumer acceptance.

However, the polymeric surfactant can be used to reduce viscosity and achieve phase stability, e.g., when either the preferred alkyl polyethoxylate sulfate or magnesium ions are present in the composition. To reduce the viscosity, the percentage of ethylene oxide in the polymer should be less than about 70%, preferably less than about 50%. Preferred compositions contain less than about 2% alcohol and less than about 3% hydrotrope-20 and preferably substantially no when the viscosity is maintained in the range of about 150 to about 500 mPa * s, preferably about 200 to about 400 mPa * s. If a reduction in viscosity is not desired, the percentage of ethylene oxide in the polymer should be greater than about 50%, preferably greater than about 70%. The polymeric surfactant reduces the viscosity of all water-soluble, anionic surfactants.

Other possible ingredients

The compositions according to the invention may contain up to 10% by weight of other detergent builders of either the organic or inorganic type. Examples of water-soluble inorganic building materials 35 useful alone or in admixture with each other or with organic basic complexing salts include alkali metal carbonates, phosphates, polyphosphates 17 q η p o and silicates. Specific examples of such salts include sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate and potassium tripolyphosphate. Examples of organic structural salts which may be used alone or in admixture with each other or with the inorganic basic structural salts set forth above include alkali metal polycarboxylates, e.g., water-soluble citrates, tartrates, etc., such as sodium and potassium citrate and sodium and potassium tartrate. In general, however, these structural salts have limited value in detergent compositions and their use at concentrations above 10% could limit the flexibility of the formulation in liquid compositions due to solubility and phase stability considerations. It is preferred that any structural salt used is relatively specific to control calcium as opposed to magnesium. Citrates, tartrates, malates, maleates, succinates and malonates are particularly preferred.

The detergent compositions of the invention may, if desired, contain any of the usual excipients, diluents and additives, for example perfumes, electrolytes, enzymes, dyes, anti-tarnish agents. antimicrobial agents and the like without departing from the preferred properties of the compositions. Alkali sources and pH buffering agents such as monoethanolamine, triethanolamine and alkali metal hydroxides can also be used.

When the anionic surfactant is a surfactant sulfate or alkyl polyethoxylate sulfate, the pH should be above 6, preferably above 7, to avoid ester bond hydrolysis. For safety reasons, it is also desirable that the composition be substantially free of bactericidal agents such as N-trichloromethylthio-4-35 cyclohexene-1,2-dicarboximide.

18 87086

Small amounts of bactericidal agents that inhibit the growth of bacteria, molds, etc. in the product but have no substantial effect in use may be desirable, especially if small amounts of alcohol are present.

All percentages and ratios shown herein are by weight unless otherwise indicated.

The following examples are provided to illustrate the compositions of the invention.

In the following examples, the compounds are as defined below. E represents an ethoxylate group and P represents a propoxylate group.

Name Formula MB HLB

Tetronic 504 (EgP8 5) 4 (= NCH2CH2N =) 3400 15.5 15 Tetronic 702 (E ,, CH N =) 4000 7

Tetronic 704 (E12 ^ ^ (rNCH ^ H ^) 5500 15

Tetronic 707 ^ 47 ^ 14 ^ 4 ^^ 2 ^ 2 ^ 12000 27

Tetronic 902 * (EgP ^ J ^ NCHjCH ^) 5300 6.5

Tetronic 904 * (E17P17) ,, (= NCH2CH2N =) 7500 14.5 20 Tetronic 907 * (E ^ P ^^ NCl ^ CH ^) 13900 26

Tetronic 908 lE91P17 V = NCH2CH2N = 1 20000 30.5

Tetronic 1307 (E74P24) 4 (= NCH2CH2N =) 18600 23.5

Tetronic 1502 * (EjqP ^) 4 (= NCH2CH2N =) 9000 5

Tetronic 1504 (E28 5p31) 4 ^ nCH2CH2N =) 12500 13 25 Tetronic 70R4 (pmEi2 5) 4 (= NCH2CH2N =) 5500 * Prepared by mixing other commercially available substances.

Tetronic is a registered trademark of Union Carbide Co.-30 ki.

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Name Definition

Compound A Polyethyleneimine (MP = 600) condensed with 42 moles of polypropylene oxide followed by 42 moles of polyethylene oxide.

5 Compound B Polyethyleneimine (MP = 600) condensed with 14 moles of polypropylene oxide Compound C Polyethyleneimine (MP = 600) condensed with 42 moles of polypropylene oxide Compound D Polyethyleneimine (MP = 600) condensed with 98 10 moles of polypropylene oxide

Compound E Plunoric 81 disulfated and NH 4 OH neutralized

Compound F H0-fC9H2O2f ^ g20 ^ C2H4 ° ^ 18H

PPG 4000 Polypropylene glycol MP = 4000 15 PEG 6000 Polyethylene glycol MP = 6000

Compound G Polyethyleneimine (MP = 189) acylated with 2 moles of whole fatty acid and condensed with 80 moles of ethylene oxide Name Formula 20 Compound H Polyethyleneimine (MP = 189) condensed with 105 moles of ethylene oxide Compound I Methyl-terminated with oxy - - 25 Compound J Triethanolamine condensed with 15 moles of ethylene oxide

Compound K Triethanolamine condensed with 33 moles of ethylene oxide 30 CH3 ^ CH2 ^ 8-10-10-^ CH2CH2 ° ^ 1 0 ^? Hr -1

Compound M C 13 H 27 CH-CH 2 -CH 2 -H

0 I

/ ch2ch2oh qc L n Jn.8

Jo V

CH2CH2OH

Compound N CH7 (CH_) O-CH-CH-

OH OH

20 8 70 36

The parent compound contains about 5% magnesium C12-13 alkyl sulfate, about 23% mixed magnesium and ammonium C12-13 alkyl polyethoxylate (1) sulfate, about 2.7% C12-13 alkyl dimethylamine oxides, about 5 5% ethyl alcohol, about 3% sodium toluene sulfate about 60% water with the remainder being inorganic salts, minor constituents, etc.

In the following examples, "fat consumption" is determined by the following experiment. Inside a pre-weighed 250 cm3 po-10 lypropylene cup, 3 cm3 of molten beef fat is placed at the bottom. When the fat has solidified, the cup is weighed again. A 0.4% aqueous solution of the test composition is then added to the cup, completely filling it. The temperature of the aqueous solution is 46 ° C. After 15 minutes, the cup is emptied and rinsed with distilled water. The cup is dried and then reweighed to determine the amount of fat removed. The quantity removed by the basic product is entered as 100.

In the following examples, the "fat value" is determined by adjusting the above fat consumption test using 10 ml of an easier to remove fat, an 80/20 mixture of solid vegetable fat and liquid vegetable fat, reducing the detergent content to about 2% and soaking for 30 minutes at equilibrium. reaching-25 sex.

In the examples means a significant difference and: · the numbers in parentheses under the headings "fat value" and "fat consumption" are the numbers of repeated experiments in which the averages of the results obtained in the experiments are given. 30 examples.

In all examples, the viscosity of the composition is greater than about 150 mPa * s and less than about 500 mPa * s.

87086

Example I

This experiment shows the improvement in fat values and fat consumption obtained with different Tetronics products.

Fat- Fat 5 value consumption Total (6) (5)

Basic product 100 100 200 "+ 1.3% Tetronic 504 108 * 116 * 224 *" + 1.3% Tetronic 702 113 * 113 * 226 * 10 "+ 1.3% Tetronic 707 108 * 111 * 219 * 11 + 1 .3% Tetronic 902 120 * 104 224 * "+ 1.3% Tetronic 904 108 * 99 207" + 1.3% Tetronic 907 113 * 108 * 221 * M + 1.3% Tetronic 1502 111 * 108 * 219 * 15 "+ 1.3% Tetronic 1504 106 * 111 * 217" + 1.3% Tetronic 1307 108 * 97 205 LSD1q 6 8 10

IIB

Fat- The value of fat 20 consumption Total

Replays (3) (2)

Basic product 100 100 200 "+ 1.3% Tetronic 908 121 * 87 208 .. 25 LSD10 '» 13 15

Example II

This example demonstrates that reversing the order of addition of ethylene oxide and propylene oxide to create a hydrophilic center and hydrophobic ends produces compounds that are exactly as effective as Tetronics products.

Fat- Fat value consumption Total (4) (4); 35 Basic product 100 100 200 "+ 1.3% Tetronic 704 131 * 99 230 *" + 1.3% Tetronic 70R4 129 * 96 225 * LSD10 * 9 12 22 87036

Example III

This example demonstrates that a polymeric surfactant with a somewhat hydrophilic center, two or more moderately hydrophobic groups, and hydrophilic end groups provides almost the same advantages as Tetronics products.

Fat- Fat value consumption Total (9) (5)

Basic product 100 100 200 "+ 1.3% Tetronic 70 * 1 111 * 98 210 *" + 1.3% Compound A 116 * 100 216 * LSD10 6 9 10

15 Example IV

This example demonstrates that a compound having a hydrophilic chain grafted with hydrophobic polypropylene oxide chains can provide fat value and fat consumption benefits in accordance with the invention.

20 Fat- Fat Value Consumption Total (5) (A)

Basic product 100 100 200 "+ 1.3% Compound B 111 * 92 203 25" + 1.3% Compound C 109 * 92 201 '"+ 1.3% Compound C 116 * 107 223 * LSD10 7 10 12

Example V

30 This example shows that similar structures in which anionic groups are at least partially replaced. . polyethoxylate groups, or alkylene chains are at least partially replaced by polypropoxylate groups, provide advantages in accordance with this invention.

| i 23 87086

Fat- Fat value consumption Total (7) (5)

Basic product 10o 100 200 "+ 1.3% Compound E 97 211 * ^" + 1.3% Compound F 110 * 98 209 LSD10 7 9 11

Example VI

This example demonstrates that mixtures and individual substances of polypropylene glycol-10 and polyethylene glycol do not provide advantages.

Fat- Fat value _ consumption Total (2) (2) 15 Basic product 100 100 200 "+ 0,65% PPG 4000 (A) 102 106 208» + 0,65% PEG 6000 (B) 91 101 i92 "+ 0, 65% A + 0.65% B 99 101 200 "+ 1.3% A 95 104 199 20" + 1.3% B 89 98 187 LSD10 12 13 18

Example VII

This example demonstrates that overly water-soluble compounds and compounds that are more similar to conventional surfactants and contain oil-seeking, hydrophobic end groups do not provide advantages.

. ; ' Fat- Fat value consumption Total (6) (4). . 30 Basic product 100 100 200 '· + 1.3% Compound G 102 98 200 "+ 1.3% Compound H 102 93 195” + 1.3% Compound I 93 97 195 "+ 1.3% Compound J 99 93 35 "+ 1.3% Compound K 94 93 187 *" + 1.3% Compound L 93 95 188 „LSD10 7 9 11

Example VIII

This example is a continuation of Example VII.

24 870- ''

Fat- Fat value consumption Total 5 (3) (3)

Basic product 100 100 200 "+ 1.3% Methocel Al5LV 103 103 206" + NHm C12_13E12SO4 96 98 194 "+ 1.3% NH4Cl2-13SO4 102 99 201 10" + 1.3% C12_13N (CH3) 2— »O 101 106 207 ”+ -1.3% Gelatin (type A) 106 96 202 LSD1q 10 11 15

Example IX

15 This example also demonstrates that conventional surfactants do not provide benefits.

Fat- Fat value consumption Total (5) (3) 20 Basic product 100 100 200 "+ 1.3% C- | 2_i 3Glucoside (2) 102 100 202" + 1.3% Cn monoethanolamide 104 101 205 "+ 1.3 % Compound M 101 100 201 "+ 1.3% Lexaine LM 100 100 200 25 M + 1 ij3% Compound N 99 10 & 199 LSC> 10 7 11 12 25 8 7 Ο ε 6

Example X

This example demonstrates the effect of the added Tetronic surfactant. Above about 4%, there is a loss that becomes significant before about 9% 5 level is reached.

Fat- Fat Value Consumption Total (3) {3}

Basic product 100 100 200 10 "+ 0.25% Tetronic 704 112 * 121 * 233 *" + 0.50% Tetronic 704 118 * 119 * 237 * "+ 1.0% Tetronic 704 119 * 120 * 239 *" + 4 .0% Tetronic 704 136 * 96 232 * "+ 8.0% Tetronic 704. 168 * 74 * 242 * 15" + 16.0% Tetronic 704 221 * 47 * 268 * LSD10 10 11 15

Comparative Example XI

This example shows the effect obtained by using twice the amount of commercial detergents. The fat value and fat consumption increase, but at a much higher cost compared to the results obtained with the invention.

"· Fat- The value of 25 fat consumption Total

Replays (4) (4)

Basic product 100 100 200

Basic product (used twice 140 * 130 * 270 * 30 LSD1q 8 10 13 26 87086

Example XII

Viscosity reduction

5% reduction in your viscosity

Ethoxylate (mPas)

Basic product (viscosity - 270 mPas) Basic part "+ i% Tetronic 1302 20 -42" + i% Tetronic 1304 40 -32 10 "+ i% Tetronic 1307 70 -15 This example shows the large viscosity reductions obtained by adding a polymeric surfactant The viscosity can be readjusted by reducing the levels of alcohol and / or hydrotropes As can be seen, the higher the proportion of ethoxylate groups in the polymers, the smaller the decrease in viscosity.

Description of other substances

Other polymeric surfactants not specified above are as follows:

Name Formula MB HLB

Tetronic 1302 (Eg (= NCH2CH2N =) 7800 5 ^ 5

Tetronic 1304 (Ε2ή P ^) ^ (= NCH2CH2N =) 10500 13.5

: 25 Example XIII

In this example, a different test was used to demonstrate a way to control the grease handling ability of a detergent composition. In most cases, this test gives the compositions a sequence of values similar to the overall index shown in the examples above.

This test determines the effectiveness or strength of a fat emulsion produced by a detergent by measuring the level of presence of fat formations on the hydrophobic surface:. after the surface has been exposed to a detergent solution to which grease has been added. This test 27 87086 describes practical situations in which grease re-deposits on the surface of an object to be washed later, in particular plastic.

The experiment was maintained at 3.79 L (2 gallons) of medium hard water (6 grains / gallons) at 41 ° C (105 ° F), the usual final temperature of the dishwashing water. A 0.1% detergent solution was prepared and gentle mixing was started. To the solution was added 6 ml portions of liquid vegetable oil. With total volumes of 18 ml, 36 ml and 54 ml, 10 plastic pieces (3 for each fat level, 9 in total) were successively immersed in water. After drying, the average weight gain of the plastic piece per unit area was calculated and indexed relative to the reference product.

The reference product used here is the basic product. The poly-15 polymeric surfactant was added at a concentration of 1% to the base product.

The label shows a statistically significant (LSD05) decrease in the formation of fat formations compared to the base product.

In this experiment, compounds P to T of formula 4: 0 0 CH3 (OCH2CH2) XOC (CH2) yCO (CH2CH2O) xCH3 were studied, in which compounds /..f 25 PX = 8 Y = 4 QX = 8 Y = 14 RX = 43 Y = 4 SX = 43 Y = 14 tx = i7 y = ίο 30 and compounds U and V of formula 5:

• P

0'o _ 0:! CH3 (OCH2CH2) xO (C- / Q> -COCH2CH2O) y (CH2CH2O) xCH3 28 87 086 wherein in the compounds U X = 16 Y = 2.75 V X = 7.5 Y = 2.75

Formation Index 5 -

Basic product 1Q0 "+ 1% Tetronic 704 107" + 1% Methocel A15LV 88 "+ 1% Compound E 84 *" + 1% PPC 4000 64 * 10 "+ 1% Compound F 89" + 1% Compound P 84 * "+ 1% Compound Q 80 * "+ 1% Compound R 107, _" + 1% Compound S 117 15 "+ 1% Compound T 85 *" + 1% Compound U 71 * "+1% Compound V 53 *

It should be noted that Tetronic 704 and Compound F did not prove advantageous in this experiment, but performed well in the experiments presented above. Again, the Methocel polymer does not provide a sufficient advantage.

Also, certain ABA-type compounds (compounds R and S) with a very high molecular weight do not produce •; 25 highlight the benefits.

Claims (9)

29 8 7 0 8 6 A high foaming liquid dishwashing detergent composition comprising by weight: 5 (a) 5% to 50% of an anionic surfactant; (b) 0.1 to 10% of a polymeric surfactant containing polymerized ethylene oxide and / or propylene oxide groups and having a molecular weight of 400 to 60,000; (C) 0% to 10% of a foam stabilizing nonionic surfactant selected from fatty acid amides, trialkylamine oxides and mixtures thereof; (d) 0% to 10% of a detergent builder selected from inorganic phosphates, inorganic polyphosphates, inorganic silicates and inorganic carbonates, organic carboxylates, organic phosphonates and mixtures thereof; (e) 0% to 15% alkanol containing 1 to 6 carbon atoms; and (f) 20% to 90% water, characterized in that said polymeric surfactant is selected from compounds of formula iii) (= NR 2 N =) and iv) = N (R 2 NH) x, n is 0 - 500, m is 0 to 500, n + m is 5 to 1000, x is 2 to 550 and y is 2 to 50 and the same as the number of valencies of R 4; Composition according to Claim 1, characterized in that it contains 0.1 to 7%, preferably 0.5 to 4%, of a polymeric surfactant. 2. R 1 (OCH 2 CH 2) x R 2 (OCH 2 CH 2 J 1 OR 1, wherein R 1 is H, CH 3 or CH 3 (CH 2) n, wherein n is 1 to 17, or an unsaturated analog thereof, x and y are each 2 to 500 and R 2 is - O (CH2) 2, where z is 1 to 18, or an unsaturated analog thereof, wherein the molecule has less than 90% - (OCH2CH2} groups; CH3 3) R3R4 (OCH2CH) AR4R3, wherein R3 is a sulfate or sulfonate, R4 is absent or is (OCH 2 CH 2) B, A is 5 to 500 and B <A / 2; OO 20 4) CH 3 (OCH 2 CH 2) x OC (CH 2) y CO (CH 2 CH 2 O) x CH 3 where X is 8 and Y is 4 or 14, or X is 17 and Y is 10; or o_ o. wherein said composition has a pH greater than six when the composition contains a C10-C20 alkyl poly-30 polyethoxylate sulfate surfactant having an average of 0.25 to 10 ethoxy groups per molecule and a viscosity o-: greater than 0.1 Pa * s and said composition is essential: ·. free of a nonionic surfactant alkyl poly (C) -2020 ethoxylate detergent when the amount of the anionic surfactant is less than 20%, said anionic surfactant being a C10-C20 alkyl surfactant. 87086 polyethoxylate sulfate containing an average of 0.25 to 10 ethoxy groups per molecule in the absence of magnesium ions or betaine surfactants. Composition according to Claim 1 or 2, characterized in that the anionic surfactant is chosen from the group consisting of alkyl sulphates having 8 to 18 carbon atoms, alkyl benzene sulphonates in which the alkyl group contains 9 to 15 carbon atoms and alkyl polyethoxylate sulphates, wherein the alkyl group contains 10 to 20 carbon atoms and the ethoxylate groups have an average of 0.5 to 10, sodium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, potassium and magnesium salts and mixtures thereof. Composition according to any one of Claims 1 to 3, characterized in that it contains less than 2% of polymeric surfactant and 10 to 100% of anionic surfactant is in the form of a magnesium salt. Composition according to any one of Claims 1 to 3, characterized in that it contains at least 8% of alkyl polyethoxylate sulphate containing 10 to 16 carbon atoms in the alkyl group and an average of 0.5 to 8 ethoxylates; wherein 20 to 90% of the anionic surfactant is a magnesium salt. Composition according to any one of Claims 1 to 4, characterized in that the anionic surfactant contains at least 10% of alkyl polyethoxylate sulphate, in which the alkyl group contains from about 10 to about 20 carbon atoms and which contains an average of: 1-6 ethoxylate, alkyl sulfates containing from 8 to 18 carbon atoms, and mixtures thereof, and the foam stabilizing nonionic surfactant is a semipolar nonionic surfactant amine oxide containing compounds of the formula 8 7 086 R 2 R 1 -C 2 H-, n-O-R 3 5 wherein R 1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy groups contain 8 to 18 carbon atoms, R 2 and R 3 are each a methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxy-10 propyl or 3-hydroxypropyl radical and n is 0 to 10. Composition according to Claims 3 and 4, characterized in that the anionic surfactant is selected from mixtures of alkylbenzenesulfonates having 9 to 15 carbon atoms in the alkyl group and alkyl polyethoxylate sulphates having from 15 to 16 carbon atoms in the alkyl group and containing on average 0.5 to 6 ethoxylates, and the stabilizing nonionic surfactant is a fatty acid amide of the general formula R1-CO-N (H) n (R2OH) 2. "Wherein R1 is a saturated or unsaturated aliphatic hydrocarbon radical having 7 *: - 21 carbon atoms, R2 is me- · '. a ethylene or ethylene group, and m is 1 or 2 and said fatty acid amide is 2 to 8%. Composition according to any one of Claims 1 to 3, characterized in that it contains 0.5 to 4% of a polymeric surfactant in which the amount of ethylene oxide is less than 70% by weight and less than 2% of al-30 cananol, and less than 3% hydrotrope and has a viscosity of 0.15 to 0.5 Pa * s. Composition according to Claim 8, characterized in that it contains less than 2% of polymeric surfactant, in which the amount of ethylene oxide 35 is less than 50% by weight and has a viscosity of 0.2 to 0.4 Pa * s. 33 8 70 8