US3912662A

US3912662A - Liquid detergent composition containing an ampholytic betaine-type detergent

Info

Publication number: US3912662A
Application number: US419857A
Authority: US
Inventors: Eva Margareta Martinsson; Karl Martin Edvin Hellsten; Anna Kristina Sterky
Original assignee: Modokemi AB
Current assignee: Nouryon Surface Chemistry AB
Priority date: 1972-11-30
Filing date: 1973-11-28
Publication date: 1975-10-14
Anticipated expiration: 1992-10-14
Also published as: GB1460286A; US3954845A; ATA1006173A; CA1006534A; FR2327310B1; NL161500C; DE2359234C2; NL161500B; ATA1006273A; CH590917A5; BE807895A; DE2359155A1; GB1459806A; DE2359155B2; DE2359234A1; CA1003723A; NL7316356A; NL7316355A; FR2208976B1; AT330932B

Abstract

Aqueous liquid detergent compositions that remain clear and liquid over a wide range of temperatures are provided comprising an ampholytic betaine-type detergent, a nonionic surfactant, and a complexing agent. The ampholytic betaines that are employed in the liquid detergent compositions of the invention have the formula:

wherein: 1. R represents an aliphatic or cycloaliphatic group having from about six to about 22 carbon atoms or an aromatic group linked to the oxygen of the OR group via a carbon of the aromatic nucleus and having from one to six alkyl groups totalling from about four to about 18 carbon atoms in the alkyl groups, each alkyl group having from one to about 18 carbon atoms; 2. R1 and R2 are selected from the group consisting of alkyl groups having from one to about three carbon atoms; 3. N1, N2 AND N3 REPRESENT THE NUMBER OF CARBON ATOMS IN EACH UNIT, AND ARE WITHIN THE RANGE FROM ABOUT 2 TO ABOUT 4; 4. M1, M2 AND M3 REPRESENT THE NUMBER OF OXYALKYLENE UNITS, AND ARE WITHIN THE RANGE FROM 0 TO ABOUT 10; AND 5. N4 REPRESENTS THE NUMBER OF CARBON ATOMS IN THE UNIT, AND IS WITHIN THE RANGE FROM 1 TO ABOUT 4.

Description

United States Patent Martinsson et a1.

[ 1 Oct. 14, 1975 LIQUID DETERGENT COMPOSITION CONTAINING AN AMPHOLYTIC BETAINE-TYPE DETERGENT Inventors: Eva Margareta Martinsson,

Stenungsund; Karl Martin Edvin Hellsten, Odsmal; Anna Kristina Sterky, Spanga, all of Sweden Assignee: Modokemi Aktiebolag, Stenungsund,

Sweden Filed: Nov. 28, 1973 Appl. No.: 419,857

Foreign Application Priority Data Nov. 30, 1972 Sweden 15647/72 [56] References Cited UNITED STATES PATENTS 2,217,846 10/1940 Orthner 260/501.13 3,116,125 12/1963 Bartlett 252/153 X 3,351,557 11/1967 Almstead 252/546 X 3,555,079 1/1971 Marumo 260/501.13 3,619,115 11/1971 Diehl 8/137 3,623,988 11/1971 Weimer 252/89 3,634,271 l/1972 Friedman 252/545 3,647,868 3/1972 Ernst 260/534 M 3,689,470 9/1972 Shachat 260/501.l3

FOREIGN PATENTS OR APPLICATIONS 92,940 5/1972 Germany 252/546 Primary Examiner-Ralph S. Kendall Assistant Examiner-Dennis L. Albrecht [57] ABSTRACT Aqueous liquid detergent compositions that remain clear and liquid over a wide range of temperatures are provided comprising an ampholytic betaine-type detergent, a nonionic surfactant, and a complexing agent.

17 Claims, No Drawings LIQUID DETERGENT COMPOSITION CONTAINING AN AMPIIOLYTIC BETAINE-TYPE DETERGENT Many types of liquid detergent formulations have been proposed, but it has not been possible until now to formulate a liquid detergent composition that remains clear and liquid over a wide range of temperatures, and has a washing effectiveness comparable to the solid detergent formulations. The principal problem is in selecting an efficient surfactant that is suffrciently water-soluble and compatible with complexing agents to enable the formulation of a highly concentrated liquid detergent of good washing effectiveness.

In accordance with the invention, aqueous liquid de tergent compositions are provided having good washing effectiveness and high water solubility and that remain clear and liquid over a wide range of temperatures, comprising as the surfactants an ampholytic betaine having a 2-hydroxy propylene ether group attached to the nitrogen atom of the betaine, and a nonionic surfactant; and a complexing agent, in solution in water as the liquid phase. In addition to these ingredients, which are the essential ingredients, there can also optionally be added an alkylene glycol which tends to reduce foaming, and other surfactants.

The ampholytic betaines that are employed in the liquid detergent compositions of the invention have the formula:

wherein:

l. R represents an aliphatic or cycloaliphatic group having from about six to about 22 carbon atoms or an aromatic group linked to the oxygen of the OR group via a carbon of the aromatic nucleus and having from one to six alkyl groups totalling from about four to about 18 carbon atoms in the alkyl groups, each alkyl group having from one to about 18 carbon atoms;

2. R and R are selected from the group consisting of alkyl groups having from one to about three carbon atoms;

3. n n and n represent the number of carbon atomsin each unit, and are within the range from about 2 to about 4;

4. m m and m represent the number of oxyalkylene units, and are within the range from O to about 10, it being understood that there can be differing numbers of oxyalkylene groups in various molecules in admixture, and that therefore m m and m represent average numbers, and need not be in tegers. The sum of m m and m is a maximum of about and 5. n, represents the number of carbon atoms in the unit, and is within the range from 1 to about 4.

These compounds are quite soluble in water, and

have a good detergent effect. The foaming properties good washing characteristics, and can be adapted to any kind of use. Especially good properties are shown by those ampholytic betaine compounds in accordance with the invention in which both the nitrogen atom and the carboxylic group of the betaine are linked to a single carbon atom, i.e. n is 1. Those compounds in which.

n n and 11 are 2 and at least one of m m and m is 1 or 2 are preferred, as also are those compounds in which m m and m are 0.

Exemplary R aliphatic groups include alkyl such as hexyl, isohexyl, heptyl, isoheptyl, 2-ethylhexyl, n-octyl, isooctyl, tertiary-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, myristyl, palmityl, stearyl, and eicosyl, as well as alkenyl, dienyl, and trienyl groups such as oleyl, ricinoleyl, linoleyl, linolenyl, decenyl, nonenyl, octenyl, hexenyl and heptenyl.

Exemplary R cycloaliphatic groups include cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, dimethylcyclohexyl, octylcyclohexyl, octadecyclohexyl, trimethylcyclohexyl, tetramethylcyclohexyl, diethylcyclohexyl, decylcyclohexyl, dodecylcyclohexyl, myristylcyclohexyl, palmitylcyclohexyl, oleylcyclohexyl, and dodecycyclohexyl.

Exemplary alkyl-substituted aromatic groups include dipropyl phenyl, dibutyl naphthyl, octyl naphthyl, diethyl phenyl, octyl phenyl, dodecyl phenyl, polypropylene phenyl, keryl phenyl, triethyl phenyl, butyl phenyl, dibutyl phenyl, and octadecyl phenyl.

Exemplary oxyalkylene units include oxyethylene, oxypropylene-l,2 and -l,3, and oxybutylene-1,2,-l,4- 2,3 and -l,3. These can be used in combinations of two or three thereof, such as mixed oxyethyleneoxypropylene, oxyethylene-oxybutylene, oxypropylene-oxybutylene, and oxyethylene-oxypropyleneoxybutylene.

Exemplary alkylene units intermediate the nitrogen and carboxylic groups of the betaine include methylene, ethylene, propylene, 1,2-propylene and butylene.

Exemplary R and R alkyl groups include methyl, ethyl, propyl and isopropyl.

The ampholytic betaines in accordance with the invention can be prepared starting from an aliphatic or cycloaliphatic alcohol having from about six to about 22 carbon atoms, where R is aliphatic or cycloaliphatic, or from an aromatic phenol having a total of from about 10 to about 24 carbon atoms and one or more alkyl groups having a total of from about four to about 18 carbon atoms in the alkyl groups.

If oxyalkylene units are to be present in the ampholytic betaine, the aliphatic or cycloaliphatic alcohol or aromatic phenol is first reacted with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide and mixtures thereof, to introduce from about one to about ten oxyalkylene units. Propylene oxide-1,3 and propylene oxide-1,2 can be used, as well as butylene oxide-1,3,- 1,4,-l,2,-2,3 and -l,3. The condensation product with alkylene oxide contains a terminal hydroxyl group, and is thus reacted in the same manner as the aliphatic or cycloaliphatic alcohol with epichlorohydrin.

The 2-hydroxy propylene group is introduced into this compound by reaction with epichlorohydrin to form the corresponding chloroglyceryl ether. The resulting chloroglyceryl ether can be converted to the be- In order to avoid quaternization of the amine reaction product during the amination, the molar ratio of dialkyl amine to chloroglyceryl ether'should be at least 3, and the reaction temperature should not be below taine either in two stages, by reaction with a dialkyl 5 about 140C. The reaction temperature can be reduced amine and then a monohalogenated carboxylic acid, or to as low as 100C if even higher molar ratios of dialkyl in one stage, by reaction with an amino carboxylic acid. min to hlorogly eryl ether are d, Th h preparatlon 1s in accordance i h h f llow- The quaternization of the tertiary amine with the hamg scheme: logenated carboxylic acid is effected in a neutralized z", )m,( i,., 2,. Z

(3H R0 C.,H2.,0 C.,H..,0 C.,H..,oh, ZC -CHZCI N-H i 2 (|)H R0 C.,H1..,0 m,(c., ..,0)m,(C.,,H..,0)..,CH2CHc N N H COOH R, R R R Reaction (2) is preferred, because the reaction product is primarily the ampholytic betaine in accordance with the invention. In reaction (1 the amount of glyceryl ether must be carefully controlled, in order to avoid the production of an undesirable quaternary compound in the reaction between the chloroglyceryl ether and the dialkyl amine.

It is surprising that the amino acid reacts with the chloroglyceryl ether in good yield. Normally, fatty acid chlorides react only slowly with amino acids. It is possible that the chloroglyceryl ether reacts with the amino acid by way of an epoxide intermediate.

The reaction between the hydroxy] compound and the epichlorohydrin is carried out at an elevated temperature within the range from about 50 to about 150C in the presence of a catalyst. As catalysts, stannic chloride, boron trifluoride and perchloric acid give excellent results, and provide a fast and easily controllable reaction. Other acid catalysts can be used, such as toluene sulphonic acid and sulfuric acid. In order to ensure a quantitative conversion of the hydroxy compound, the epichlorhydrin can be added in excess.

The reaction between the chloroglyceryl ether and the secondary amine is carried out at an elevated temperature within the range from about 100 to about 150C in the presence of an alkaline hydroxide catalyst such as an alkali metal hydroxide, for example, sodium hydroxide, potassium hydroxide or lithium hydroxide, or an alkaline earth metal hydroxide, such as calcium hydroxide, barium hydroxide and strontium hydroxide. This reaction can be carried out in the presence of a polar solvent such as water or a low molecular weight alcohol or glycol, such as methanol or ethanol, ethylene glycol, monoethyl ether of ethylene glycol, diethylene glycol, diethyl ether of ethylene glycol, and triethylene glycol.

aqueous solution, at a reaction temperature within the range from about 50 to about 150C, for a reaction time within the range from about 2 to about 6 hours. If the tertiary amine is only slightly soluble in water, such as when it contains hydrocarbon groups having more than about 14 carbon atoms, it may be desirable to add a solvent that is miscible with water, such as ethylene glycol, to increase the solubility of the amine in the reaction mixture, and to lower the viscosity of the reaction mixture.

The reaction of the chloroglyceryl ether with an amino acid is also carried out in an aqueous solution at a temperature within the range from about 50 to about C and for a reaction time within the range from about 15 minutes to about 3 hours. The pH is neutral or slightly basic, within the range from about 7 to about 10. A polar solvent miscible with water also can be added, as in the case of the amination, such as a lower molecular weight alcohol, such as methanol or ethanol, or a glycol such as monoethyl ether of ethylene glycol, diethylene glycol, diethyl ether of ethylene glycol, and ethylene glycol.

In addition to the above reaction procedures, other reactions can be used. Thus, the chloroglyceryl ether can be reacted with ammonia or a primary amine having a methyl or ethyl substituent, and additional alkyl substituents thereupon introduced into the resulting amine, using for example, an alkyl halide such as methyl, ethyl, or propyl chloride, or a dialkyl sulfate such as dimethyl, diethyl or dipropyl sulfate.

It is also possible to use a monoalkyl-substituted amino acid, which is reacted with the chloroglyceryl ether and quaternization of the resulting tertiary amine then carried out with an alkyl halide or dialkyl sulfate, as indicated above. These reactions may however results in a larger amount of by-product, and a lower total yield.

tures derived by hydrogenation from the naturallyoccurring fatty acids or fatty acid esters derived from vegetable oils, animal oils, or fats, such as coconut oil, palm oil, soya bean oil, cottonseed oil, corn oil, castor oil, linseed oil, tallow, grapeseed oil, tung oil, lard, safflower seed oil, fish oil and whale oil. Synthetic alcohol mixtures can also be used, prepared according to the Ziegler process or the 0x0 process, the latter producing highly branched alcohols and alcohol mixtures.

In addition to the aliphatic alcohols, cycloaliphatic alcohols which can be used include cyclohexanol, cyeloheptanol, cyclooctanol, cyclododecanol, cyclohexyldecanol, methylcyclohexanol, diethylcycloheptanol, octadecylcyclooctanol, and decylcyclohexanol.

Alkyl-substituted phenols which can be used include octylphenol, nonylphenyl, dodecyl phenol, hexadecyl phenol, dibutylphenol, dioctylphenol and dinonylphenol, keryl phenol, polypropylene phenol, the polypropylene group having from 12 to about 15 carbon atoms, and octadecyl phenol.

Suitable dialkyl amines include dimethylamine, diethylamine, dipropylamine and diisopropylamine.

The nonionic surfactant employed in the liquid detergent compositions in accordance with the invention has the formula:

R is a hydrocarbon group, and can be selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon groups having from eight to twenty carbon atoms, and monoand dialkyl phenyl groups having from about four to about 18 carbon atoms in the alkyl groups.

m is a number within the range from about 5 to about 30, and represents an average number, since different molecules in admixture can have different numbers of oxyethylene groups.

It will be apparent that these nonionic surfactants are adducts of ethylene oxide with aliphatic or cycloaliphatic alcohols 0r monoalkyl or dialkyl phenols.

Exemplary nonionic surfactants falling within this class are the ethylene oxide adducts of decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, oleyl alcohol, octyl alcohol, isooctyl alcohol, palmityl alcohol, linoleyl alcohol, ricinoleyl alcohol and linolenyl alcohol, cyclooctanol, cyclododecanol, cyclohexadecanol, octylphenol, nonylphenol, dodecyl phenol, hexadecyl phenol, octadecyl phenol, dibutylphenol, dioctylphenol, and dinonyphenol.

The complexing agent, which is the third essential component of the liquid detergent compositions of the invention, is preferaby inorganic and an alkali metal polyphosphate, such as sodium or potassium pyrophosphate, sodium orthophosphate, pentasodium tripolyphosphate, pentapotassium tripolyphosphate, sodium hexametaphosphate, and potassium hexametaphosphate. However, the organic complexing agents also can be used, and these include the alkene phosphates, alkali metal salts of aminocarboxylic acids such as ethylene diamine tetraacetic acid, nitrilotriacetic acid, hydroxyethyl ethylene diamine triacetic acid, hydroxyethyl imino diacetic acid, and diethylene triaminepentaacetic acid; alkali metal salts of oxycarboxylic acids such as citric acid, oxydiacetic acid, and gluconic acid, an alkali metal salts of polycarboxylic acids such as polymaleic acid, polyitaconic acid and polyacrylic acid.

The proportions of the ampholytic betaine, nonionic surfactant and complexing agent can be varied within wide limits. Excellent results are obtained with liquid detergent compositions containing these ingredients in the following proportions:

Over-all Range Preferred Range Component 7: by Weight 7? by Weight Ampholytic betaine 4 to 25 6 to 20 Nonionic surfactant 1 to 20 2 to 15 Complexing agent 1 to 15 I to 10 Water and 40 to 80 45 to Alkylene glycol 0 to 30 5 to 20 In this formula, n is within the range from 2 to 4, preferably 2 or 3, and m is a number within the range from 1 to 10, preferably 1 to 5, and can represent an average number since there can be different numbers of oxyalkylene units in the molecule in admixture. The alkylene glycol, in addition to a foam-reducing effect, may also aid in solubilizing the nonionic surfactant, if it is difficultly soluble in water. The alkylene glycol is in an amount within the range from about 5% to about 20% of the total composition.

The liquid detergent compositions of the invention are easily prepared by simple admixture of the components. The components can be blended in any order. It is usually convenient to blend the ampholytic betaine, nonionic surfactant, and complexing agent, and alkylene glycol, if present, and then add the water, with stirring until the ingredients are dissolved. The mixture may be moderately heated, to increase the rate of dissolution.

In addition to the essential ingredients and the optional ingredients referred to above, the liquid detergent compositions of the invention also can contaimadditional surfactants, as well as any of the adjuncts and additives ordinarily employed in liquid detergent compositions.

Since the essential components of the liquid detergent compositions include nonionic and ampholytic surfactants, any additional surfactant should be an anionic or cationic surfactant.

The anionic sulfate or sulfonate ester surfactants constitute a well known class of anionic surfactants. The alkyl aryl sulfonates are defined by the formula where R is alkyl having from eight to about eighteen carbons, n is a number from one to three, and M is hydrogen or an alkali metal, ammonium or organic amine cation. One example thereof is sodium dodecyl benzene sulfonate.

Another example are the sulfonated phenyl polypropylene alkanes, characterized by the branched chain structure of polypropylene and tertiary alkyl carbon at the benzene ring, and having the following general structure:

i l, 503M where M is hydrogen, an alkali metal, ammonium, or an organic amine cation, R and R are alkyl, of the type formula C,,l-l and at least one R is a polypropylene group, the whole alkyl group containing preferably 12 to 15 carbon atoms. These are known compounds, whose preparation and properties are set forth in US.

Pat. No. 2,477,383, to Lewis, issued July 26, 1949;

they are available in commerce under the trade names Oronite, Ultrawet, and Neolene.

Other water-soluble alkyl aromatic sulfonic acids include those prepared by alkylating benzene or naphthalene with a kerosene fraction, followed by sulfonation to aromatic sulfonic acids, such as sodium keryl benzene sulfonate.

Another class of useful anionic surfactants are the amido-alkane sulfonates, which are characterized by the following structure:

where A is hydrogen or an alkali metal, i.e. ammonium, sodium or potassium, n is a small whole number from 1 to about 5, preferably 2 or 3, R is hydrogen or an alkyl, aryl, or cycloaliphatic group, such as methyl, and R is an alkyl or alkylene radical, such as myristyl, palmityl, oleyl and stearyl. Sodium palmitic tauride, sodium palmitic methyl tauride, sodium myristic methyl tauride, sodium palmitic stearic methyl tauride, and sodium palmitic methyl amidopropane sulfonate are typical examples thereof.

These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an organic aliphatic aminosulfonic acid, such as taurine, NH CH CH SO H, and various N-substituted taurines, such as N-methyl taurine or aminopropane sulfonic acid, NH (CH SO H.

Other anionic surfactants include esters of sulfuric acid with aliphatic alcohols of to 18 carbon atoms, particularly oleic acid, tall oil, turkey red oil, and acids derived by the reduction of the fatty acids derived from coconut oil, palm oil, sperm oil andthe like long-chain fatty acids, sulfonated castor oil, esters and ethers of isethionic acid, long-chain fatty acid esters and longchain alkyl ethers of 2,3-dihydroxy-propane sulfonic acid and sulfuric acid esters of monoglycerides and glycerol monoethers.

The sulfated alkoxylated derivatives of the formula below also are useful anionic surfactants:

where M is hydrogen or an alkali metal or an organic amine cation, where R is hydrogen or a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to 26 carbon atoms or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from six to 24 carbon atoms attached to the aryl nucleus, and at tached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups, R, and R are hydrogen or methyl, n is a number from 1 to 4, the total number of carbon atoms in each unit is from one to four, and the various R units in the chain can be the same or different, and x is a number from 2 to 50. R can, for example, be a straight or branched chain alkyl group, such as octyl, nonyl, decyl, lauryl, myristyl, cetyl, or stearyl, or an alkylaryl group such as octylphenyl, nonylphenyl, decylphenyl, stearylphenyl, etc. In this formula, H could also be replaced by the group -(C H O),,,H, where m is a number rang ing from 1 to 10.

Where R is alkyl it will be evident that the wetting agent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide, propylene oxide or butylene oxide. Typical of this type of alkyl product are the condensation products of oleyl or lauryl (dode cyl) alcohol, or mercaptan, or oleic or lauric acid, with from 8 to 17 moles of ethylene oxide, such as Emulfor ON. Typical alkyl esters are Renex (polyoxyethylene ester of tall oil acids) and Neutronyl 331 (higher fatty acid ester of polyethylene glycol).

Where R is aralkyl, the wetting agent can be derived from an alkyl phenol or thiophenol.

Another class of anionic surfactants are the polyoxyalkylene phosphate esters described by the following formula:

R and R are alkyl or alkyl phenyl groups having from about eight to about twenty carbon atoms in the alkyl chain, and one of R and R may also be hydrogen. R and R can be the same or different.

A preferred class of the phosphate esters are those in which one or both of R and R is a radical containing a polyoxyalkylene ether group, and no more than one of R and R is hydrogen. The radical containing polyoxyalkylene ether is of the form:

in which n has a value greater than 0, up to about 30, and preferably is within the range from about 1 to about 10, and denotes the average number of oxyalkylene units in the chain. It will be understood that there will be present in admixture species having n values both higher and lower than the average value for n. R, and R are hydrogen, methyl or ethyl.

R is a primary or secondary straight or branched chain saturated or unsaturated aliphatic radical having from about ten to about 24 carbon atoms, preferaby from about twelve to about 22 carbon atoms, or a mono, di, or trialkyl-substituted phenyl radical having from about six to about 24 carbon atoms, and preferably from about eight to about 18 carbon atoms in the alkyl portion. I

M is hydrogen or a water-soluble salt-forming cation such as an alkali metal, such as, for instance, sodium or potassium; ammonia; or an organic amine, such as an alkanolamine or an alkylamine radical, for example, monoethanolamine, diethanolamine, triethanolamine, butylamine, octylamine, or hexylamine.

These polyoxyalkylene phosphate esters are known compounds, and are described in U.S. Pat. Nos. 3,294,693 and 3,235,627 and the disclosure thereof in these patents is hereby incorporated by reference. Additional polyoxyalkylene phosphate esters are described in US. Pat. No. 3,400,148, at column 17, and in the Mayhew & Krupin article in Soap and Sanitary Chemicals, referred to above.

Examples of ampholytic surfactants are those of the betaine or sulfobetaine type, having one of the formulae:

In these formulae, R R and R are selected from the group consisting of alkyl having from one to about 22 carbon atoms, and alkyl phenyl, wherein the alkyl has from one to about 18 carbon atoms, and R is a bivalent hydrocarbon group having from one to about 22 carbon atoms, preferably with only up to eight carbon atoms in the carbon chain linking the nitrogen and carboxylic or sulfonic groups, and preferably not more than two carbon atoms in this linking chain. Examples are of the betaine type dimethyldodecylbetaine and of the sulfobetaine type the reaction product derived from dimethyldodecylamine and l,3-propansulfone, that is R, R CH R dodecyl and R CH -CI-l g-CHg-n Also suitable ampholytic surfactants are the amino monocarboxylic acids and amino dicarboxylic acids having the general formulae:

In the above formulae, R is an alkyl group having from about ten to about twenty carbon atoms, or an alkyl phenyl group in which the alkyl has from one to about eighteen carbon atoms; R and R are bivalent hydrocarbon groups containing from one to about eight carbon atoms; and M is hydrogen or a salt-forming cation, such as a monovalent metal cation (for instance sodium, potassium and lithium); ammonium; or an organic amine cation such as triethylamine, tributyl amine, monoethanolamine, diethanolamine and triethanolamine. Examples thereof are N-dodecylglycine, N- tetradecylglycine, N-dodecyl-2-aminopropionic acid and dodecyliminodiacetic acid.

In addition, the liquid detergent compositions of the invention can include other components which are customary in liquid detergent compositions, such as corrosion inhibitors, alkaline builder salts, neutral builder salts, soil-suspending agents, optical brightening agents, coloring agents and pigments, perfumes, foam suppressants, and biocidal agents.

Alkaline inorganic and organic builder salts or sequestrants are added in order to improve soil-removal power, particularly for heavily soiled articles. The amount of the alkaline builder salt is usually within the range from about 10 to about by weight of the total solids of the composition, preferably from 20 to 60% by weight. The alkali metal polyphosphates are particularly advantageous in contributing heavy duty performance and in improving detergent properties in hard water. Such polyphosphates include pentasodium tripolyphosphate, sodium acid tripolyphosphate, pentapotassium tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, sodium tetraphosphate, sodium hexametaphosphate and pentaammonium tripolyphosphate.

The alkali metal silicates, borates, and carbonates also can be employed, alone or in admixture with polyphosphates as alkaline builder salts. Examples are the sodium metasilicates, borax, and sodium carbonate.

Soil-suspending agents also can be added, particularly for heavy duty formulations. Suitable soilsuspending agents are sodium carboxymethyl cellulose, sodium cellulose sulfate, lower alkyl and hydroxy alkyl cellulose ethers, such as ethyl hydroxyethyl cellulose, ethyl hydroxypropyl cellulose, hydroxyethyl cellulose, as well as polyvinyl alcohol and polyvinylpyrrollidone. Soil-suspending agents are usually used, it at all, in amounts of from about 0.05 to about 5%, preferably from 0.1 to 2% by weight of the total solids.

The liquid detergent compositions in accordance with the invention are useful for any washings or cleaning purposes, such as for washing textiles, metals, plastics, leather, wood, stone, glass, china, porcelain, painted surfaces, and so forth, both in the household and in industry. Since the compositions are lowfoaming, they are especially suitable for use in automatic laundering and dish-washing machines and other applications where low foaming is desired.

The following Examples, in the opinion of the inventors, represent preferred methods for preparing the ampholytic betaines used in the liquid detergent compositions of the invention:

EXAMPLE A Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 200 grams (1 mol) of a mixture of 55% lauryl alcohol and 45% myristyl alcohol. The alcohols were heated to 75C, and there was then added 2 grams of stannic chloride SnCl and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to 125C, with continued stirring, and the mixture held at this temperature for 2 hours. Residual epichlorohydrin was removed by vacuum distillation. The residual product was a slightly yellow liquid.

To this product there was added 1200 ml of a 14% solution of dimethylamine in ethanol, corresponding to 3 mols of dimethylamine. The resulting mixture was then heated to 150C in an autoclave, with stirring, and held at this temperature for 1 hour. The reaction mixture was then cooled, and 40 grams (1 mol) of sodium hydroxide was added. Excess dimethylamine and the ethanol were then separated by vacuum distillation at 50C. The product obtained was analyzed by titration with perchloric acid in glacial acetic acid, and was found to contain solely the mixed lauryl-myristyl oxy-2- hydroxy propylene dimethylamine.

One part by weight of this product, corresponding to 0.5 mol tertiary amine, was stirred into 6 parts by weight of water, and the solution brought to 70C. Then, at 70C over minutes 0.6 mol monochloroacetic acid was added, in the form of a 20% aqueous solution neutralized with sodium hydroxide to pH 7. The reaction was allowed to proceed at 70C for two hours, and was then continued for another 2 hours at 90C. The course of the reaction was followed by titration of the liberated chloride ions with silver nitrate solution.

At the end of the reaction the product was a clear aqueous solution having good foaming and detergent properties of ampholytic betaine having the formula:

The yield calculated on the amount of added alcohol was 96%.

EXAMPLE B Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 200 grams (1 mol) of a mixture of 55% lauryl alcohol and 45% myristyl alcohol. The alcohols were heated to 75C, and there was then added 2 grams of stannic chloride SnCL, and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to 125C with continued stirring, and the mixture held at this temperature for 2 hours. Residual epichlorohydrin was removed by vacuum distillation. The residual product was a slightly yellow liquid.

To this product there was added 340 grams of a 40% aqueous solution of dimethylamine, corresponding to 3 mols of dimethylamine. The resulting mixture was then heated to 150C in an autoclave with stirring and held at this temperature for 1 hour. The reaction mixture was then cooled and 40 grams (1 mol) of sodium hydroxide was added. The mixture was allowed to separate in a separatory funnel, and the top phase containing the amine so removed. Excess dimethylamine was then separated by vacuum distillation at 50C. The product was the mixed lauryl myristyl oxy-2-hydroxy propylene dimethylamine.

One part by weight of this product corresponding to 0.5 mol tertiary amine was stirred into 1.5 parts by weight of water, and then 0.6 mol monochloroacetic acid was added at C over 1 hour in the form of a 40% water solution neutralized with sodium hydroxide to pH 7. The reaction was allowed to proceed at 70C for another hour, and was then continued for 2 hours at 90C. At the end of the reaction the product was a clear aqueous solution having good foaming and detergent properties of ampholytic betaine having the formula:

The yield calculated on the amount of added alcohol was 97%.

EXAMPLE C Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 418 grams (1 mol) of cetyl tetraoxyethylene alcohol adduct having the formula: C l-l O(C H O).,H. The alcohol was heated to C, and there was then added 2 grams of stannic chloride and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to 125C with continued stirring, and the mixture held at this temperature for 2 hours. Residual epichlorohydrin was then removed by vacuum distillation. The residual product was a slighly yellow liquid.

To 510 grams (1 mol) of this product there was added 340 g of a 40% aqueous solution of dimethylamine, corresponding to 3 mols of dimethylamine. The resulting mixture was then heated to 150C. in an autoclave with stirring, and held at this temperature for 1 hour. The reaction mixture was then cooled and 40 grams (1 mol) of sodium hydroxide was added. The mixture was allowed to separate in a separatory funnel, and the top phase containing the amine removed. Excess dimethylamine was then separated by vacuum distillation at 50C. The product obtained was cetyl tetraoxyethylene oxy-2-hydroxy propylene dimethylam- One part by weight of this product corresponding to 0.5 mol tertiary amine was stirred into 0.5 part by weight ethylene glycol and one part by weight of water. The mixture was heated to 70C, and 0.6 mol of monochloroacetic acid added at 70C over 1 hour in the form 'of a 40% water solution neutralized with sodium hydroxide to pH7. The reaction was allowed to proceed at 70C for another hour and was then continued for 2 hours at C. 1

By addition of sodium hydroxide, the pH was maintained between about 9 and 10. The product mixture was fluid and clear. Analysis of the chloride content showed conversion of chloroacetate, and 98% of the tertiary amine had reacted. The product was:

OH CH EXAMPLE D Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 246 grams lmol) of octyloxy propylene oxide adduct containing 2 mols propylene oxide: C H, O(C H O) H. The alcohol was heated to 75C, and there was then added 2 grams of stannic chloride and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to 125C with continued stirring, and the mixture held at this temperature for 2 hours. Residual epichlorohydrin was then removed by vacuum distillation. The residual product was a slightly yellow liquid.

To 338 grams of this product there was added 340 g of a 40% aqueous solution of dimethylamine, corresponding to 3 mols of dimethylamine. The resulting mixture was then heated to 150C in an autoclave with stirring, and held at this temperature for 1 hour. The reaction mixture was then cooled and 40 grams (1 mol) of sodium hydroxide was added. The mixture was allowed to separate in a separatory funnel, and the top phase containing the amine removed. Excess dimethyl' amine was then separated by vacuum distillation at 50C. The product obtained was octyltetraoxy propylene-oxy-2-hydroxy propylene dimethylamine.

One part by weight of this product corresponding to 0.5 mol tertiary amine was stirred into 0.5 part by weight diethylene glycol and one part by weight of water. The mixture was heated to 70C, and 0.6 mol monochloroacetic acid added at 70C over one hour in the form of a 40% water solution neutralized with sodium hydroxide to pH 7. The reaction was allowed to proceed at 70C for another hour, and was then continued for 2 hours at 90C. At the end of the reaction the product was a clear aqueous solution of ampholytic betaine having the formula:

The yield calculated on the amount of added alcohol was 96%.

EXAMPLE E Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 308 grams (1 mol) of nonyl phenol-ethylene oxide adduct C H C H O(C H O) H. The alcohol was heated to 75C and there was then added 2 grams of stannic chloride and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to 125C with continued stirring, and the mixture held at this temperature for 2 hours. Residual epichlorohydrin was then removed by vacuum distillation. The residual product was a slightly yellow liquid.

80 grams of this product (0.2 mol) was mixed with 67.5 grams of 40% aqueous solution of dimethylamine (0.6 mol). The reaction mixture was allowed to stand for 2 hours at 150C. Hydrochloric acid which formed was neutralized with 8.32 grams of sodium hydroxide, after which the mixture was transferred to a separatory funnel, and the top phase containing the tertiary amine was separated.

Dimethylamine dissolved in the tertiary amine phase was removed by vacuum distillation. The product was analyzed by titration with perchloric acid in glacial acetic acid and with sodium lauryl sulfate at pH 1 1, and was found to consist of 95% tertiary amine, but no quaternary compounds.

58 grams of this tertiary amine was dissolved in 61 grams of water and 26 grams of diethylene glycol. The mixture was heated to C and then a 40% aqueous solution of monochloroacetic acid neutralized with so dium hydroxide was added dropwise over 1 hour, so that the total quantity of monochloroacetic acid added amounted to 15.7 grams. The reaction mixture was then held another hour at 70C after which the temperature was increased to C and held at this temperature for 3 hours. At the conclusion of this time 97% of the tertiary amine had reacted and 99% of the theoretical amount of chloride ions had formed. The product had the formula:

This product had a syrupy consistency at room temperature, and displayed good cleansing properties.

EXAMPLE F Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 200 grams (1 mol) of a mixture of 55% lauryl alcohol and 45% myristyl alcohol. The alcohols were heated to 75C and there was then added 2 grams of stannic chloride and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to C, with continued stirring, and the mixture held at this temperature for 2'hours. Residual epichlorohydrin was removed by vacuum distillation. The residual product was a slightly yellow liquid.

Sodium dimethylglycine (134 grams) and monoethyleneglycol (344 grams) were mixed, and brought to 125C, whereupon the chloroglyceryl ether was added dropwise over 25 minutes. The reaction was continued at 125C for a further ten minutes, and then halted. The mixture, which essentially consisted of sodium chloride and the ampholytic betaine product, was hot-filtered, obtaining a clear yellowish liquid. The conversion of the chloroglyceryl ether with dimethylglycine was 98%. The final product had the formula:

EXAMPLE G Into a glass flask provided with stirrer, heating means and reflux condenser was introduced 348 grams (1 mol) of C,,H O(C H O(C I-I O(C H O) H. The alcohol was heated to 75C, and there was then added 2 grams of stannic chloride and 101 grams (1.1 mol) of epichlorohydrin over a period of about 1 hour. The temperature was then raised to 125C, with continued stirring, and the mixture held at this temperature for 2 hours. Residual epichlorohydrin was then removed by vacuum distillation. The residual product was a slightly yellow liquid.

To 440 grams of this product there was added 340 g of a 40 aqueous solution of dimethylamine, corresponding to 3 mols of dimethylamine. The resulting mixture was then heated to 150C in an autoclave with stirring, and held at this temperature for 1 hour. The reaction mixture was then cooled, and 40 grams (1 mol) of sodium hydroxide was added. The mixture was allowed to separate in a separatory funnel and the top phase containing the amine removed. Excess dimethylamine was then separated by vacuum distillation at "50C. The product obtained was octyl mono oxybutylene monooxypropylene dioxyethylene oxy-2-hydroxypropylene dimethylamine.

One part by weight of this product corresponding to 0.5 rnol tertiary amine was stirred into 0.5 part by weight diethylene glycol and one part by weight of water. The mixture was heated to 70C, and 0.6 mol monochloroacetic acid added at 70C over one hour in the form of a 40% water solution neutralized with sodium hydroxide to pH 7. The reaction was allowed to proceed at 70C for another hour, and was then continued for another 2 hours at 90C. At the end of the reaction the product was a clear aqueous solution showing good cleaning properties of ampholytic betaine having the formula:

The yield calculated on the amount of added alcohol was 95%.

The following Examples, in the opinion of the inventors, represent preferred embodiments of the liquid detergent compositions of the invention:

EXAMPLE 1 A liquid detergent composition was prepared having the following formulation:

The detergent components were mixed together, and the water then added, and the composition stirred until a clear solution had formed. This composition was a quite mobile fluid, and remained clear over the range of temperatures from 4C to 45C.

The foam stability of this composition was then de termined in apparatus described by Fries in Seifen-Ole- Fette-Wachse, No. 25/65, pp. 913-917, Messmethode zur Testung gesteuerter Schaume. This equipment simulates the mechanical working of a detergent solu tion in an automatic laundering machine. 0.5% detergent solutions were used.

For comparison purposes, two control compositions were also tested; Control I was a commercial detergent composition especially formulated for washing at 60C. and Control II was an ampholytic betaine surfactant composition without the nonionic surfactant but otherwise similar to the liquid detergent composition of the invention. These compositions had the following formulations:

Mixed deeyllaurylmyristyl- OCH CH(OH)CH l 1(CH -CH CO6 l2 Tetrapotassium pyrophosphate 12 Water 76 The following results were obtained:

TABLE I Height of foam, millimeters Control I Control 11 Temp. Commercial Composition of Example 1 C Product Example 1 without nonionic surfactant In this test, if the foam level exceeds 250 mm, there is a considerable risk of foam overflow from the automatic washer. Consequently, Control 11 is unacceptable. Control I is better, but the results for Example 1 show that the liquid detergent composition in accordance with the invention is lower foaming, especially at elevated temperatures, which makes it well suited for automatic machine laundering.

The three test compositions were also tested in respect to their detergent effectiveness in dissolving fat. In this experiment, test swatches of polyester cotton fabric were soaked with isotope-marked glyceryl trioleate. The cotton swatehes after drying were washed in a Terg-O-Tometer. The content of glyceryl trioleate of the test swatches was determined both before and after washing by analysis of the radioactivity of the test swatch. The following results were obtained:

TABLE II Concen' tration Washing Water of washeffect hardness ing agent 7r washed Composition (dh) ('72.) off Control I Commercial 2.8 0.5 660 product 16.8 l.0 77.0 Example 1 2.8 0.5 85.1 l6.8 1.0 83.l Control I] Example l without 2.8 0.5 78.5 nonionic surfactant l6.8 l O 78.6

From these results, it is apparent that the composition according to the invention had a substantially greater cleaning effectiveness than the two control compositions.

The washing effectiveness of Contorl I, the commercial detergent composition, and the liquid detergent composition in accordance with the invention was tested in terms of effectiveness in removing silicates; the washing tests were carried out using the Terg-O' Tometer at 40C in water of 2.8 degrees of hardness and a concentration of detergent of 5 grams per liter. The test swatches were of artificially-soiled cotton fabric from Waschereiforschung, Krefeld, West Germany. The reflectance of the fabric was measured before and after washing, and the measurements were converted according to Kubelka-Munks formula: K/S (l- R) /2R, wherein R is the reflectance. See also W. G. Catler and R. C. Davis; Detergency, Theory and Test Method, part 1, New York 1972, p. 387-392. The washing effect was expressed as the relative reduction of K/S, and the following results were obtained:

TABLE III Composition Washing Effect Control I Commercial product 47.2% Example I 50.8%

TABLE IV Composition Washing Effect Control I Commercial product 23.0% Example 1 26.5%

The results show that the liqiud detergent compositon in accordance with the invention was more effective than the commercial product.

EXAMPLE 2 A liquid detergent composition was prepared having the following formulation:

Parts Ingredients by weight Ampholytic betaine surfactant DccylOCH Cl-l(OH )CH N(CH;) CH COO 2 Ampholytic betaine surfactant The detergent components were mixed together and the water then added, and the composition stirred until a clear solution had formed. This composition was quite mobile and remained clear over the range of temperatures from -4C to 45C.

The washing effectiveness of the liquid detergent composition was then evaluated in terms of removal of silicates. Washing tests were carried out using the Terg- O-Tometer at 40C in water of 2.8 degrees of hardness and a concentration of detergent of 5 grams per liter. The test swatches were of artificially-soiled cotton fabric from Waschereiforschung, Krefeld, West Germany. The reflectance of the fabric was measured before and after washing, and the measurements were converted according to Kubelka-Munks formula: K/S l- R) /2R, wherein R is the reflectance. See also W. G. Catler and R. C. Davis: Detergency, Theory and Test Method, part 1, New York 1972, pp. 387-392. The washing effect was expressed as the relative reduction of K/S, and the following results were obtained:

TABLE V Composition Washing Effect Example 2 (Control I Agent Washing Effect Ampholytic composition according to invention (Control I The results show that the liquid deterg'eiitcomposition in accordance with the invention was quite effective.

EXAMPLE 3 A liquid detergent composition in accordance with the invention was prepared according to the following formulation:

Ingredients Parts Weight Ampholytic betaine surfactan H,CH(OH )cn mcun cu coo The detergent components were mixed together and the water then added, and the composition stirred until a clear solution had formed. This composition was quite mobile and remained clear over the range of temperature from 4C to 45C.

The washing effectiveness of the liquid detergent composition was then evaluated in terms of removal of silicates. Washing tests were carried out using the Terg- O-Tometer at 40C in water of 2.8 degrees of hardness and a concentration of detergent of 5 grams per liter. The test swatches were of artificially-soiled cotton fabric from Waschereiforschung, Krefeld, West Germany.

Composition Washing Effect Example 3 51.2% (Control 1 47.2%)

Thus, the liquid detergent composition in accordance with the invention was quite effective in removing inorganic silicates.

A comparative washing experiment was also carried out at 60C using cotton fabric soiled with cocoa. This fabric was obtained from Eidgenossische Material-- prufungsanstalt in St. Gallen, Switzerland. The following results were obtained:

Composition Washing Effect Example 3 28.1% (Control I 23.0%)

The results show that the liquid detergent composition in accordance with the invention was quite effective.

Having regard to the foregoing disclosure, the following is claimed as the inventive and patentable embodiments thereof:

1. An aqueous liquid detergent composition that remains clear and liquid over a wide range of temperatures comprising:

a. from about 2 to about 25% by weight of an ampholytic betaine. surfactant having the formula:

wherein:

R is selected from the group consisting of aliphatic and cycloaliphatic groups having from six to about 22 carbon atoms and aromatic groups linked to the oxygen of the OR group via a carbon of the aromatic nucleus and having from one to six alkyl groups totalling from about four to about 18 carbon atoms in the alkyl groups, each alkyl group having from one to about 18 carbon atoms;

R, and R are selected from the group consisting of alkyl groups having from one to about three carbon atoms;

n n and n represent the number of carbon atoms in each unit, and are within the range from about 2 to about 4;

m m and m represent the number of oxyalkylene units, and are within the range from 0 to about 10. at least one of m m and m is 1, and the sum of m,, m and m is within the range from 1 to about 10;

n.; represents the number of carbon atoms in the unit, and is within the range from 1 to about 4.

b. from about 1 to about 20% by weight of a nonionic surfactant having the formula:

wherein:

R is selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon groups having from eight to 20 carbon atoms, and monoand dialkyl phenyl groups having from about four to about 18 carbon atoms in the alkyl groups;

m is a number within the range from about 5 to about 30; and

c. from about 1 to about 15% by weight of a complexing agent,

said components (a), (b) and (0) being dissolved in an amount of an aqueous medium sufficient to provide a clear liquid formulation.

2. An aqueous liquid detergent composition in accordance with claim 1, in which n, is 1, so that both the nitrogen atom and the carboxylic group of the betaine surfactant are linked to a single carbon atom.

3. An aqueous liquid detergent composition in accordance with claim 1, in which m, n and n;, are 2 and at least one of m m and m is 1 or 2.

4. An aqueous liquid detergent composition in accordance with claim 1, in which m m and m;; are 1.

5. An aqueous liquid detergent composition in accordance with claim 1, in which R is an aliphatic group.

6. An aqueous liquid detergent composition in accordance with claim 1, in which R is a cycloaliphatic group.

7. An aqueous liquid detergent composition in accordance with claim 1, in which R is an alkyl-substituted aromatic group.

8. An aqueous liquid detergent composition in accordance with claim 1, in which R and R are each methyl and n is l.

9. An aqueous liquid detergent composition in accordance with claim 1, in which the nonionic surfactant is an adduct of ethylene oxide with an aliphatic alcohol.

10. An aqueous liquid detergent composition in accordance with claim 1, in which the nonionic surfactant is an adduct of ethylene oxide with a monoalkyl or dialkyl phenol.

11. An aqueous liquid detergent composition in accordance with claim 1, in which the complexing agent is an inorganic polyphosphate.

12. An aqueous liquid detergent composition in accordance with claim 1, in which the complexing agent is selected from the group consisting of alkene phosphates, salts of aminocarboxylic acids, salts of oxycarboxylic acids, and salts of polycarboxylic acids.

13. An aqueous liquid detergent composition in accordance with claim 1, in which the water is in an amount within the range from about 40 to about 80% by weight.

14. An aqueous liquid detergent composition in accordance with claim 13, comprising from 0 to about 30% of an alkylene glycol having the formula: n 2n )m H wherein n is within the range from about 2 to about 4, and

m is a number within the range from about 1 to about 10.

15. An aqueous liquid detergent composition in accordance with claim 14, in which the alkylene glycol is in an amount within the range from about 5% to about 20%.

16. An aqueous liquid detergent composition in accordance with claim 1, comprising a noncomplexing alkaline builder salt in an amount within the range from about 10 to about by weight of the total solids of the composition.

17. An aqueous liquid detergent composition in accordance with claim 1, comprising a soil-suspending agent in an amount within the range from about 0.05

to about 5% by weight of the total solids LBS-O06 UNITED STATES PATENT'OFFICE 1 2 CERTIFICATE OF CORRECTION Patent No. 3,?722. 662 Dated October 14, 1975 O Inventofls) Eva. Margareta Martinsson et 211.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 0

Column 4, lirm 67-68 "results" should be "result 6 Column 8, line 64 "R should be R Column 9, line 32 "Pat" should be -Pats-- QOlumn line 64 1 R1 R; CH3. R3 dodccyl and R,

--CH i should be R R2 ='CH3, R3 dodccyl and R CH2-CH ,--Cl*l a Column 10, line 54 "it should be ii- Column 10, line 59 "washings" should be --washing--' Column 17, line 20 "Contorl I" should be -Contro]. 1--

Column 17, line 31 m: (U l) {2R,

should be 8 K/s (l-RF/ZRJ Page 2 of 2 LBS-03E UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIGN Patent 20. 3,912,662 I Dated October 14, 1975 Inventor(s) Eva Margareta Martinsson et 211 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 17, line 61 "liqiud" should be -liquid- .1

Column 17, line 61 "compositon" should be -compositionshould be (LEV/2R4 Column 18, line 40 "(Control I i 47.2%" should be --(Control I 47.2%)-- Z o lumn 19, line 24 RFQR;

should be K/S (FRY/2K! Column 20, line 12 after "from" please insert -about Signed end Scaled this fifteenth Day f June 1976 {SEAL} Arrest:

RUTH C. MASON C. MARSHALL DANN Altsting Officer 7 Commissioner of Parems and Trademarks

Claims

1. AN AQUEOUS LIQUID DETERGENT COMPOSITION THAT REMAINS CLEAR AND LIQUID OVER A WIDE RANGE OF TEMPERATURES COMPRISING: A. FROM ABOUT 2 TO ABOUT 25% BY WEIGHT OF AN AMPHOLYTIC BETAINE SURFACTANT HAVING THE FORMULA:

2. An aqueous liquid detergent composition in accordance with claim 1, in which n4 is 1, so that both the nitrogen atom and the carboxylic group of the betaine surfactant are linked to a single carbon atom.

3. An aqueous liquid detergent composition in accordance with claim 1, in which n1, n2 and n3 are 2 and at least one of m1, m2 and m3 is 1 or 2.

4. An aqueous liquid detergent composition in accordance with claim 1, in which m1, m2 and m3 are 1.

8. An aqueous liquid detergent composition in accordance with claim 1, in which R1 and R2 are each methyl and n4 is 1.

14. An aqueous liquid detergent composition in accordance with claim 13, comprising from 0 to about 30% of an alkylene glycol having the formula: HO(Cn H2n O)m H wherein n5 is within the range from about 2 to about 4, and m5 is a number within the range from about 1 to about 10.

16. An aqueous liquid detergent composition in accordance with claim 1, comprising a noncomplexing alkaline builder salt in an amount within the range from about 10 to about 80% by weight of the total solids of the composition.

17. An aqueous liquid detergent composition in accordance with claim 1, comprising a soil-suspending agent in an amount within the range from about 0.05 to about 5% by weight of the total solids.