US2985592A

US2985592A - Detergent composition

Info

Publication number: US2985592A
Application number: US560280A
Authority: US
Inventors: John Wayne L St
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1956-01-20
Filing date: 1956-01-20
Publication date: 1961-05-23
Anticipated expiration: 1978-05-23
Also published as: GB811902A; DE1041189B; CH354880A

Description

United States Patent 2,985,592 DETERGENT COMPOSITION Wayne L. St. John, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporalion of Ohio No Drawing. Filed Jan. 20, 1956, Ser. No. 560,280

11 Claims. (Cl. 252-137) The present invention relates to detergent compositions containing an additive which imparts to these detergent compositions improved sudsing characteristics and more particularly to improvements in the sudsing and suds stability characteristics of detergent compositions containing sulfated and sulfonated anionic detergents.

Synthetic detergents of the anionic sulfated and sulfonated types are known to have excellent detersive properties. Often, however, for purposes of consumer appeal, it is thought to be desirable to increase and improve the sudsing characteristics of these detergent compositions, particularly in regard to products designed primarily to be used for washing dishes, and other kitchen utensils. To the average housewife, the suds floating on a washing solution serves as an indication of the remaining washing power and as a means for covering from sight the solution itself which may take on an unpleasant appearance after being in use a short time. Greasy materials and scraps of food are often carried into the washing solution. The addition of an alkali metal tripolyphosphate to the anionic sulfated and sulfonated detergents is known to improve the sudsing characteristics of these detergents as well as to impart to the compositions thus formed other improvements, in respect to economy, detergency, and mildness. However, even with these improved compositions, as well as with anionic sulfa-ted and sulfonated detergent compositions which do not contain tripolyphosphate there may be a tendency to wastefuly add to a dishwashing solution the detergent composition in an amount, based on the quantity of suds formed, greater than that necessary to achieve adequate detergency.

It is an object of the present invention to provide detergent compositions which display improved sudsing characteristics.

It is a further object to provide, as additives for detergent compositions containing sulfated and sulfonated anionic detergents, a class of compounds having an exceptional ability to increase and improve these detergent compositions in respect to sudsing and suds stability characteristics.

It is another object to provide a means for overcoming the disadvantages referred to in connection with the washing of dishes, kitchen utensils, etc.

Further objects and advantageous features will appear from the following detailed description.

In general, the present invention relates to the recognition of the alkylurea glycosides as a class of compounds which when present in minor amounts, impart to the active detergent in a detergent composition greatly improved sudsing and suds stability characteristics, especially when these compositions are used at customary dishwashing and laundering temperatures.

The following structural formulas will serve to indicate the range of compounds included within the scope of my invention:

wherein R is a higher alkyl radical having from about ten to about fifteen carbon atoms and R is either a monosaccharide or a reducing oligosaccharide. The structural formulas indicated that I include compounds in which the carbohydrate moiety is attached to either of the nitrogen atoms of the urea moiety. 1 Either or both of the hydrogen atoms can be substituted by low molecular weight alkyl or alkylol groups such as methyl, ethyl, propyl, methylol, ethanol, propanol and dihydroxy propyl. The lower alkyl and the lower alkylol groups should not contain in excess of three carbon atoms each, and the lower alkylol groups may be monoor polyhydroxy in structure. The polyalkyl and polyalkylol derivatives of the alkylurea glycosides may be symmetrical or unsymmetrical.

Specific examples and structural formulae of compounds which come within the scope of the above generalformula and which may be employed in the practice of the present invention are:

( l) Dodecylurea-N-glucoside CHzO H (2) Dodecylurea-N-glucoside I (llHnOH H ,t H

H a t It be HzNC O-NC11H15 3 Pentadecylurea-N'-galactoside (6) N-dodecyl-N,N-dimethylurea-N-lactoside CH2OH OHzOH 3 (7) N-dodecyl-N-ethano1u.rea-N'-glucoside onion CHiCHnOH r bomoumn I ornoHioH on It will be understood that when either a specific alkylurea glycoside or the alkylurea glycosides as a class is referred to, both the alpha and beta substituted ring forms are intended to be encompassed. The alpha and beta forms of the alkylurea glycosides may be exemplified by the following structural formulae of alpha and beta dodecylurea-N-glycoside:

Alpha (P114013 0 n .i 111 H NHCONHC Hn l H on Beta onion o 11 NI-IOONHCmHn HO F f n I I H on Methods for the preparation of the alkyl ureas, alkylalkylol ureas, mixed polyalkyl ureas, etc. arenurnerous and are well known in the art. Several means of preparing alkylurea glycosides are known in the art; one method may be illustrated by the preparation of dodecylurea-N'- glucoside: A mixture of 22.8 g. of dodecylurea, 19.8 g. of glucose, 2.5 g. of concentrated hydrochloric acid and 200 ml. of 95% ethyl alcohol is stirred and heated at 50 C. for 100 hours, then cooled and filtered. The product is washed successively with water and hot benzene.

All monosaccharides and reducing oligosaccharides can condense with the alkylureas to form al kylurea glycosides. In order for the condensation to proceed it is necessary that there be present a monosaccharide or an oligosaccharide having a monosaccharide residue with unsubstituted hemiacetal hydroxyls. When such unsubstituted hemiacetal hydroxyls are present, the oligosaccharides reduce alkaline copper-salt solutions, mutarotate, and form glycosides as dothe monosaccharides. In the absence of a reducing group, none of these reactions are exhibited.

The term oligosaccharides is used to differentiate the di, triand tetrasaccharides from the monosaccharides. The following oligosaccharides, since they do not contain unsubstituted hemiacetal hydroxyls, will not condense with the alkylureas to give the desired alkylurea glycosides: sucrose, trehalose, melizitose, raffinose, gentianose, labiose, and stachyose. Examples of oligosaccharides which", because of the presence of'unsubstituted hemiacetal hydroxyls, are reducing carbohydrates, and which will condense with the alkylureas to form alkylurea glycosides are as follows: maltose, lactose, cellobiose, melibiose, etc.

Water soluble salts of sulfonic acids which exhibit detergent effect, such as the higher alkylated benzene sulfonic acids (eJg. potassium. salt of the sulfonic acid derived from the condensation product of benzene and a chlorinated kerosene fraction containing predominantly twelve carbon atoms per molecule, or the sodium salt of the sulfonic acid derived from the condensation product of benzene and polypropylenes having from 9 to 15 carbon atoms and averaging 12 carbon atoms) are greatly improved in respect to their sudsing properties by addition thereto of a smaller amount of the substituted amides mentioned above. Also, water soluble salts of higher mono fatty acid esters of 1,Z-dihydroxypropane-3-sulfonic acid (sodium salt of the coconut oil fatty acid monoester of this sulfonic acid is a specific example) will find use in the practice of this invention. In addition, water soluble salts of higher fatty acid monoesters of lower molecular weight hydroxy alkyl sulfonic acids (e.g. oleic acid ester of the sodium salt of isethionic acid) and of the higher fatty acid amides of lower molecular amino alkyl sulfonic acids (e.g. ammonium salt of oleic acid amide of N-rnethyltaurine) can be employed. Likewise.

detergent compositions which display improved sudsing characteristics in the practice of my invention can be prepared from synthetic detergents such as the water soluble salts of the higher alcohol esters of sulfocarboxylic acids (e.g. sodium salt of the lauryl alcohol ester of sulfoacetic acid) and others of high molecular alcohols and lower hydroxy sulfonic acids (e.g. monolauryl ether of l,2-dihydroxy propane-B-sodium sulfonate).

Other synthetic detergents which are useful in the practice of my invention include the water soluble salts of high molecular aliphatic sulfuric acid esters such as the alkali metal, ammonium and substituted ammonium salts of sulfuric acid esters of normal primary aliphatic alcohols having twelve to eighteen carbon atoms, particularly those whose principal active ingredient is a water-soluble salt of lauryl sulfuric acid or oleyl sulfuric acid. Specific examples are the sodium alkyl sulfate obtained from the mixed higher alcohols produced by the reduction of coconut oil, palmkernel oil, or other oils of the coconut oil group (a group of tropical nut oils characterized by their high content of combined fatty acids having 10 to 15 carbon atoms), tallow or sperm oil. Also, water soluble salts of sulfuric acid esters of higher fatty acid monoglycerides (e.g. sodium salt of the coconut oil fatty acid monoester of 1,2-dihydroxy propane-B-snlfuric acid ester) and of the sulfated higher fatty acid alkylolamides (eg. sodium salt of sulfated coconut oil fatty acid ethanolamide) may be employed. Included among these synthetic detergents are the water soluble salts of higher alkyl polyethylene oxide sulfuric acid esters (eg. the sulfated and neutralized reaction product of about three moles of ethylene oxide with one mole of the higher alcohols produced by the reduction of coconut oil fatty acids having 10-14 carbon atoms).

7 Any of the above detergents may be used either alone or in admixture.

The above examples-are merely specific illustrations of the numerous detergents which, with or without the addition of an alkali metal tripolyphosphate, can be rendered more efiicient in their sudsing characteristics when used inconjunction with the alkylurea glycosides in accordance with my invention, and I do not wish to be limited thereto. The concentration of these detergents in the cleansing and laundering compositions of the present invention is generally from about 12% to about 50% by weight of total product and'preferably from about 12% to about 30% by weight of total product.

\ These detergents maybe used singly or in combination with auxiliary materials, which may include any of the. substances customarily employed by the art, in admixture with sulfated and/or sulfonated organic synthetic detergents. The various alkali metal phosphates (e.g. tripolyphosphate and higher polyphosphates, hexametaphosphate, pyrophosphate, and orthophosphate), the alkali metal silicates, sulfates, carbonates, etc. are illustrative but not exhaustive examples of these auxiliary materials.

When it is considered desirable to incorporate an alkali metal tripolyphosphate into the detergent compositions of the present invention, the optimum ratio of the tripolyphosphate to active synthetic detergent is from about 2.5:1 to about 3:1. However, improved sudsing per formance, attributable to the above designated suds building additives, can be demonstrated when the ratio of the tripolyphosphate to active synthetic is from about 1:1 to about 5:1.

The alkylureas, which have been heretofore suggested for use in detergent compositions as suds-builders and detergency additives (Ross, 2,708,183) are characterized by their limited Water solubility. The substitution of a monosaccharide or a reducing oligosaccharide for an amino hydrogen on the urea moiety of an alkyl urea re sults in a distinctly different class of compounds, the members of which have considerably greater Water-solubility than the alkylureas and which are greatly superior to the alkylureas in respect to suds-building performance. These alkylurea glycosides contain in their molecular structure both hydrophobic (higher alkyl) and hydrophilic (carbohydrate) groupings.

Dodecylurea-N'-glucoside may be considered to be representative of the alkylurea glycosides which form a part of the present invention. Dodecylurea may likewise be considered to be representative of the alkylureas. Dodecylurea-N-glucoside has been found to be greatly superior to dodecylurea as a suds builder. In the following tabulation the monoethanol amide of coconut oil fatty acids, hereafter designated as coconut ethanolamide, has been selected as a standard for comparison since it is one of the most widely known and commonly used organic suds builders. The percentages in the following table are relative to coconut ethanolamide at 100%. All three detergent compositions contain 175% alkyl benzene sulfonate, 32.5% sodium sulfate, 47% sodium tripolyphosphate, and 3% of the specified organic suds-builder.

In the dishwashing test, dishes were washed by hand in a dishpan containing 115 F. water to which a standardized amount of a detergent composition was added. As increasing numbers of plates soiled with equal amounts of a standardized simulated soil are Washed, the height of the suds over the solution decreases. The results of the dishwashing test are expressed in terms of comparative average suds endurance in the presence of soil, based on decrease in suds height, in tests run on these soiled plates. The results expressed in the column headed Laundry Test were obtained by washing standardized swatches soiled With a standardized synthetic soil in a laundry test using 140 F. water. In both the dishwashing and laundry tests the water contained 7 grains of hardness per gallon.

When either the dishwashing test or the laundry test is used as a criterion for suds building performance, do-' decylurea-N'-glucoside is markedly superior to dodecylurea or coconut ethanolamide, according to the results tabulated in Table I.

In the improved detergent compositions of the present invention, the amount by weight of the alkylurea glycoside suds building additives employed is sufiicient to increase the sudsing performance of the detergent composition and is at least V2% of the total product, but usually is not greater than the amount by weight of active detergentpresent. Thus, it has been found that the proportion of active detergent to alkylurea glycoside in the compositions of the present invention will be within the range of about :1 to about 1:1. For example, in those improved detergent compositions which contain from about 12% to about 50% by weight of active detergent, based on the total product, from about /2% to about 12% by weight, based on total product, of the alkylurea glycoside or the lower alkyl and/or alkylol nitrogen substituted alkylurea glycosides Will preferably be used. Particularly effective high suds building performance is achieved when such alkylurea glycosides constitute from about 1% to about 6% by weight of the total product in such detergent compositions.

The following samples are additional-1y illustrative of the nature of the present invention, and it will be understood that the invention is not limited thereto. Parts shown are by Weight.

Example I To 50 parts of commercial sodium alkyl benzene sulfonate (the sodium salt of the sulfonic acid of the conden-. sation product of benzene and a mixture of polypropylenes I Example II A detergent composition similar to that set forth in Example I with, however, sodium myristyl sulfate substituted in whole or in part for alkyl benzene sulfonate displays a similar improved sudsing performance.

Example III Another detergent composition which shows improved sudsing performance is prepared by compounding 17% of the monoglyceride sulfate of the higher alcohols derived from coconut oil, 31% sodium sulfate, 40% sodium tripolyphosphate, and 12% tetradecylurea-N-glucoside.

Other detergent compositions which possess surprisingly improved sudsing characteristics are as follows.

Example IV 17.5% of alkyl benzene sulfonate of-polypropylenes having from 9 to 15 carbon atoms and averaging 12 car-' bon atoms, 32.5% sodium sulfate, 47 sodium 'tripolyphosphate, and 3% dodecylurea-N-galactoside.

Example V 15% of the sodium salt of the monosulfuric acid ester of the higher alcohols derived from coconut oil and having predominantly 10 to 14 carbon atoms, 22% sodium sulfate, 62% sodium tripolyphosphate and 1% dodecylurea-N-lactoside.

Example VI 40% of alkyl benzene sulfonate of polypropylenes having from 9 to 15 carbon atoms and averaging 12 carbonatoms, 57% sodium sulfate and 3% dodecylurea-N'-' position in any of the forms in which such compositions" are manufactured. The glycosides may be mechanically mixed in; they may be crutched into the detergent composition in the formof a slurry, and they may be dis solved in a solution: of: the detergent composition; While such: ready-for-use mixtures. may. be manufactured and may be preferable for. many purposes, it is likewise within the scope of' the present invention to add the glycosides to water prior to the adding of the detergent alone or detergent and alkali metal tripolyphosphate or vice versa, or to adddetergent and alkylurea-N-glycoside, or detergent, alkylurea-N'-glycoside and alkali metal tripolyphosphate simultaneously but separately to the water.

While the present invention has been described with reference to specific examples and formulations, I do not Wish' to be limited thereto. Modifications and variations of these specific examples and formulations will be readily apparent to those skilled in the art and it is not intended that the specific examples and formulations contained herein should limit the scope of the invention.

Havingthus described my invention, what is claimed 1. A cleansing and launderingzcomposition having improved sudsing power at dishwashing temperatures, consisting essentially of at least one synthetic organic detergent component selected from the group consisting of the water-soluble anionic sulfate and sulfonate detergents as the essentialv cleansing agent and as a suds-promoting agent an alkylurea glycoside selected from the group consisting of H R-I ICO1 I-R and H R HI \I-o1 I-R' wherein R is a higher alkyl radical of about to about carbon atoms and R is a carbohydrate selected from the group consisting of monosaccharides and reducing disaccharides, the amount by weight of said alkylurea glycoside being not greater than the amount of the detergent but sufficient to increase the sudsing performance thereof.

2. The cleansing and laundering composition of claim 1 containing an alkali metal tripolyphosphate in an amount by weight. of'from about one to about five times the amount by weight of active detergent.

3. A. cleansing and laundering composition having improved. sudsing power at dishwashing temperatures consisting essentially of at least one synthetic organic detergent component selected from the group consisting of the water-soluble anionic sulfate and sulfonate detergents as the essential cleansing agent and as a suds-promoting agent about /2 to about 12% by weight, based on total product, of alkylurea glycoside selected from the group consisting of III R 5. A cleansing and laundering composition having improved sudsing power' at dishwashing temperatures consisting essentially of at least one synthetic organic detergentcomponent selected from the group consistingof the watersoluble anionic sulfate and sulfonate detergents as 8 the essential cleansing agent and asa suds promoting agent an alkylurea glycoside selected from the group consisting of wherein R is a higher alkyl radical of about 10 to about 15 carbon atoms and R is a carbohydrate selected from the group consisting of monosaccharides and reducing disaccharides, the ratio by weight of said detergent to said alkylurea glycoside being from about :1 to about 1:1 and being sufiicient to increase the sudsing performance of said cleansing and laundering composition.

6. The cleansing and laundering composition of claim 5 containing an alkali metal tripolyphosphate in an amount by weight of from about one to about five times 8-. The cleansing, and laundering composition of claim 7 containing an alkali metal tripolyphosphate in an amount by weight of from about one to about five timesthe amount by weight of active detergent.

9. A cleansing and laundering composition having improved sudsing power at dishwashing temperatures consisting essentially of a synthetic organic detergent component selected from the group consisting of the Watersoluble anionic sulfate and sulfonate detergents as the essential cleansing agent and as a suds-promoting agent about /2 to about 12% by weight based on total prod net, of a lower alkyl and loweralleylol nitrogen-substituted alkylurea glycoside selected from the group con wherein R is a higher alkyl radical'of about 10 to about 15 carbon atoms, R is a carbohydrate selected from the group consisting of monosaccharides and reducing disaccharides, the amount of said lower alkyl and lower alkyl- 01 nitrogen-substituted alkylurea glycoside being sufficient' to increase the sudsing performance of said cleansing and laundering composition.

10. A cleansingand laundering composition having improved sudsing power at' dishwashing temperatures consisting essentially of a synthetic organic detergent componentfselected from the group consisting of the watersoluble anionic sulfate and sulfonate detergents-as the essential cleansing agent and as a suds-promoting agentabout 1% to about 6% of an alkylurea glycosideselected 9 wherein R is a higher alkyl radical and R is a carbohydrate selected from the group consisting of monosacchar-ides and reducing disaccharides, the amount of said alkylurea glycoside being sufficient to increase the sudsing performance of said cleansing and laundering composition.

11. A cleansing and laundering composition having im proved sudsing power at dishwashing temperatures consisting essentially of a water-soluble alkyl benzene sulfonate as the essential cleansing agent and as a suds-promoting agent about 1% to 6% by weight, based on total product, of an alkylurea glycoside selected from the group consisting of:

| i" HN-CONR wherein R is a higher alkyl radical of about 10 to 15 carbon atoms and R is a carbohydrate selected from the group consisting of monosaccharides and reducing disaccharides.

and

References Cited in the file of this patent UNITED STATES PATENTS May 23 1961 Patent No. 2 985 592 Wayne L. St. John hat error appears in the above numbered pat- It is hereby certified t that the said Letters Patent should read as ent requiring correction and corrected below.

Column 2, lines 40 to 46, formula (3) should appear as shown below instead of as in the patent:

cn on NHCONHC H line 24, for "average" read averaging ember 1961.

column 6,

Signed and sealed this 7th day of Nov (SEAL) Attest:

DAVID L. LADD ERNEST W. SWIDER Commissioner of Patents Attesting Officer

Claims

1. A CLEANSING AND ALUNDERING COMPOSITION HAVING IMPROVED SUDSING POWER AT DISHWASHING TEMPERATURES, CONSISTING ESSENTIALLY OF AT LEAST ONE SYNTHETIC ORGANIC DETERGENT COMPONENT SELECTED FROM THE GROUP CONSISTING OF THE WATER-SOLUBLE ANIONIC SULFATE AND SULFONTE DETERGENTS AS THE ESENTIAL CLEANSING AGENT AND AS A SUDS-PROMOTING AGENT AN ALKYLUREA GLYCOSIDE SELECTED FROM THE GROUP CONSISTING OF