US2927081A - Detergent composition containing n-tris (methylol) methyl amides - Google Patents

Description

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United States Patent DETERGENT COMPOSITION CONTAINING N-TRIS (METHYLOL) METHYL AMIDES Charles H. Schramm, Hillsdale, NJ., assignor to Lever Bfrtglhers Company, New York, N.Y., a corporation 0 ame No Drawing. Application January 31, 1956 Serial No. 562,602

17 Claims. (Cl. 252-137) There are two general types of detergent compositions available on the market: light duty and heavy duty detergents. Heavyduty detergents have the ability to remove st-ubborn soil and prevent soil redeposition in laundering. .:These are allpurpose detergents, usually are available in powdered form, and contain polyphos- However, these detergents by virtue of their ,polyphosphatecontent and their strong detergency tend to irritate sensitive skin and therefore are less favored by the housewife for dishwashing and fine laundering. To compete with soap for these purposes, light duty detergents have been formulated. These lack the polyphosphate builders but have a detergency which is adequate for dishwashingand light laundering, and are not as hard on the skin. 1

Many light duty detergents have been made available in liquid form, as solutions of synthetic detergents containing a high concentration of the active detergent. Such detergents possess special properties, and are quite attractive to the housewife because there is no need to dissolve the detergent. A washing solution is obtainable simply upon dilution of an easily measured portion of the concentrated liquid with water.

An important feature of both heavy and light duty detergents is their sudsing power. Most housewives still rely upon the. sudsing of the washing solution to tell them when the .detergencyis sufiicient, and when it has been exhausted. .This is particularly so in dishwashing, and the standardized dishwashing tests are based upon this principle; the end point of the usual dishwashing test is the time when the suds no longer completely cover the surface of the washing solution. As is well known, most synthetic detergents are deficient in sudsing power, and this difficulty is usually overcome by incorporating an ingredient which enhances suds. It is essential that the added ingredient be soluble in the washing solution to a sufficient extent to permit the preparation of solu- Many such agents are Also, the agent should tions of washing concentrations. very sparsely soluble in water. be stable to bleach if it is to be useful in heavyduty detergents.

In accordance with the invention, synthetic detergent compositions are provided which contain an N-tris- (methylol) methyl amide and an organic nonsoap detergent, as the essential ingredients. The nonsoap detergent is referred to hereinafter as a syndet. When the detergent compositions of the invention are primarily intended for light duty purposes, these are the only essential components of the composition. If the light duty composition is to be in liquid form, a solvent for the syndet and the N-tris(methylol) methyl amide will of course be present in an amount to completely dissolve them. When the detergent composition is formu t the invention:

2,927,081 Patented Mar. 1, 196.0

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lated for heavy duty, detergent polyphosphates and supplemental builders also will be present.

The N-tris(rnethylol) methyl amides of the invention have the formula:

' onion where R is an aliphatic hydrocarbon radical, which can be saturated or unsaturated, and can have a straight or branched chain, and which has from nine to .fifteen carin which the acid is given as illustrative:

CHiOH CHaOH I n GHzOH CHrOH The following illustrates the procedure: 200 grams oflauric acid was heated with 121 grams of tris-(hydroxymethyl)methyl amine, bot-hjof which are available commercially, at to 200 C. for 5 hours. The resulting product was then refluxed with a large excess of water to give a quantitative yield of N- tris-(hydroxymethyl)-methyl lauramide. Recrystallization fro-m chloroform yielded a pure product melting .at l15.21l5.8 C.

The following N-tris(rnethylol) methyl amides are typical, and can be used in the detergent compositions of onion ctnao onn-o-ornon CHzOH CHzOH CnHzaC ONH-C-CHzOH HgOH GHrOH 01.11.10 ONH-Q-C'HaOHI onion The N-tris(methylol) methyl amide can be combined with any syndet to give a detergent composition- 3 well known in the art under this name. They have the general structure where R is a straight or branched chain hydrocarbon radical having from 1 to about 24 carbon atoms, at least one R having 8 to 24 carbon atoms, x is a number from 1 to 5, and may be an average number, and M is hydrogen, an alkali metal such as sodium, potassium and ammonium, such as ethanolamine, diethanolamine, triethanolamine, and hexylamine (a more extensive list is given infra). R can for example be methyl, ethyl, hexyl, isohexyl, octyl, tert-octyl, isooctyl, nonyl, decyl, dodecyl, or octadecyl.

One example thereof are the sulfonated polypropylene benzene alkanes, having an alkyl radical characterized by thebranched chain structure of polypropylene and attached by a tertiary alkyl carbon to the benzene ring, and having the following general structure:

IMCHCHgR:

where M is hydrogen, an alkali metal or an organic amine cation, and R and R are alkyl, of the type formula C,,H and at least one R is a straight or branched chain'polypropylene group, the whole alkyl group con- 7 are the Nacconols.

.The alkyl sulfates are characterized by the structure RSO M, where M is hydrogen or an alkali metal, i.e., ammonium, sodium, or potassium, or an organic amine cation, and R is a straight or branched chain saturated or unsaturated hydrocarbon radical, suchas myristyl, palmityl, oleyl, stearyl, and lauryl, as well as the mixed alkyl radicals derived from fatty oils, such as coconut oil fatty alkyl, tallow fatty alkyl, cottonseed oil fatty alkyl and fish oil fatty alkyl radicals. R usually has from eight to eighteen carbon atoms, preferably from twelve to sixteen carbon atoms.

Another class of anionic syndets are the sulfated oxyethylated alkyl phenols, which have the following general formula:

where R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, A is oxygen, sulfur, a carbonamide or thiocarbonamide group or a carboxylic or thiocarboxylic ester group, x is a number from three to eight, and M is hydrogen or an alkali metal, e.g., sodium, potassium, and ammonium, or an organic amine cation. R can, for example, be a straight or branched chain octyl, nonyl, decyl, dodecyl, tetradecyI or octadecyl group. When the ammonium or organic amine salts are used, somewhat higher concentrations of detergent can usually be incorporated in aqueous solution.

In addition to these there may be mentioned sulfonated castor oil, .esters and ethers of isethionic acid, 1,2-dihy- Where M is hydrogen or an alkali metal, i.e., ammonium, sodium, or potassium, or an organic amine cation, n is a small Whole number from one to about five, preferably two or three, 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, olelyl and stearyl. Sod1um palmitic tauride, sodium palmitic methyl tauride, sodium myristic methyl tauride, sodium palmiticstearic methyl tauride and sodium palmitic methyl amidopropane sulfonate have been found to be particularly suitable for use in the comopsitions of the invention.

The anionic syndets can be used in the form of the free acid, which can be neutralized in situ in the liquid detergent solution by addition of an organic amine or ammonium hydroxide. They are also readily available as the alkali metal salts, such as sodium, potassium and ammonium, and these would generally be used. However, the ammonium or organic amine salts may be more soluble, and in this event would be preferred, particularly from the standpoint of increasing the detergent concentration to a maximum. The amine can be any of those listed hereinafter.

There may also be used, either alone or in admixture with the anionics, nonionic syndets such as polyoxyalkylene ethers, which retain the terminal OH groups, as the glycols, and in which the terminal OH groups are substituted, as the mono and diethers thereof, such as the polyoxyalkylene alkyl phenols, polyoxyalkylene fatty acid amides, and alkyl polyoxyalkylene oxyand thioether and oxyand thioester nonionic detergents.

Many polyoxyalkylene glycol ether syndets have the following general formula:

Where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an aralkyl' group having a straight or sulfur, carboxylic ester and thiocarboxylic ester groups, R and R are hydrogen or methyl, and x is ,a numberfrom eight to twenty. R can for example be a straight or branched .chain octyl, nonyl, decyl, octadecyl, dodecyl,

tetradecyl, or hexadecyl group, or an alkyl aryl group such as octylbenzene, nonylbenzene, decylbenzene, octadecylbenzene, etc.

When R is .alkyl it will be evident that the syndet can be regarded as der ved from an alcohol, mercaptan, oxy or thio fatty acid of highmolecular weight, by condensation with ethylene oxide, 2,3-butylene oxide or 1,2-propylene oxide. Typical of this type of alkyl ether are the condensation products of oleyl or dodecyl alcohol or mercaptan with from eight to seventeen moles of ethylene oxide, such as Emulfor ON, Nonic 218 and Sterox SE and SK. Typical alkyl esters are G1226 and Renex (polyoxyethylene ester of tall oil acids), Sterox CD, Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol). I

When R is aralkyl, the syndets can be derived from an alkyl phenol or thiophenol.

The polyoxyalltylene alkyl phenols and thiopheno'ls havethe following general formula:

a tona'onwononn'cn-won oxide, available commercially under the trade names NIW, Antarox A-400, lgepal CA and C0, Triton X-100, Neutronyx 600 and Tergitol NPX.

Another class of nonionic syndets are Pluronics, which have the structure:

These are fully described in U.S. Patent No. 2,674,619

to L. G. Lundsted, dated April 6, 1954; see especially column 3, lines 55 to 71. See also U.S. Patent No. 2,677,700 to D. R. Jackson etaL, dated May 4, 1954.

m and m represent the average number "of oxyethylene units, and n the average number of oxypropylene units. See U.S. Patent No. 2,674,619. The sum of m and m preferably is within the range from to 41, and n preferably is within the range from 17 to 3'1.

For light duty purposes, the detergent composition need not contain detergent polyphosphates or supple mental builders. Because of solubilityproblems, they will usually not be incorporated in liquid detergent solutions. However, these can be added if desired to the powders for heavy duty or other special purposes such as for use in certain waters. In the presence of polyphosphates, the N-tris(methylol) methyl amides improve the detergency of the 'syndct as well'a's'the sudsing.

Detergent polyphosphates are well known. The alkali metal, e.g., sodium, potassium and ammonium, salts are water-soluble. Sodium, potassium, and ammoniumpyrophosphates, tripolyphosphates and t'etraphosphat'es are exemplary.

Typical supplemental builders are the alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates, metaphosphates, and orthophosphates, such as sodium silicate, magnesium sulfate, sodium tetraborate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, disodium orthophosphate, sodium metaphosphate, calcium sulfate, calcium chloride, sodium chloride, sodium borate and potassium metaphosphate. i

In addition to or instead of the above-mentioned supplement-al inorganic salts, organic materials such as starch, polyethylene glycols, polyvinyl alcohols, ethylhydroxyethyl cellulose, and salts of carboxymethylcellulose andcellulose sulfuric acid esters can be used as supplemental builders. It has been found that between about 0.1 and 1% of such materials is useful.

The ibuider mixture is so chosen that the. composition obtained in an aqueous 0.14% solution has a pH of 7 or above. Preferably, its pH lies within the range from 7 to about 10 since solutions which are more alkaline may be irritating to the skin and tend to weaken some fabrics, particularly woolens.

The powdered detergent composition is prepared by conventional methods, as by blending the ingredients thereof in an aqueous solution 'or slurry and then drying the resulting mixture in a spray or drum dryer at elevated temperatures. The N tris"(methylol) methyl amide may "be added to the detergent composition at any stage of its manufacture, or to the finished powder.

In the case of liquid detergents the ingredients may be dissolved in warm water, or water-and-alcohol, or a1 cohol; they may be dissolved separately in alcohol or water, and then these solutions are mixed. Thereafter, the solution may be diluted to the desired concentration. The amount of solvent should be suflicient to dissolve all of the solid components, and furnish a detergent solution which does not cloud or form a precipitate at temperatures as low as 45 F. The amount of total solids inthe composition is variable and is limited only by the solubility of the components in the solvent. Usually, it is desirable to have the syndet concentration as high as possible, and inasmuch as the N-tris (methylol) methyl amide improves the sudsing of the depending upon-solubilityw Of this, the syndet should be within the range from about 23 to about 42% and the concentration of the N-tri(methylol) methyl amide should be within the range from about 8 to about 12%. --Wa'ter is the preferred solvent. When the solid syndet; and N-tris(methylol) methyl amide are "not sufliciently soluble in water alone to produce the desiredlow cloud point their solubility may be improved by the use of a mixture of water and a water-miscible lo'wer aliphatic alcohol,'such as ethyl or methyl alcohol, watermiscible glycols, such as ethylene glycol and diethylene glycol, as well as the a'lkylolamines. The latter solvents also make .it possible to control the pH, which usually should be within the range from about 7 to about 10 for optimum detergency.

pH control also can be obtained by incorporating an inorganic base, such as sodium, potassium or ammonium hydroxide, in the detergent, as well as organic amines, such as methylamine, butylamine, hexylamine, and the like. The amount of the base is not critical, but it is desirable-to have sufficient base present to neutralize all free acids, including detergent acids and any free inorganic acid contaminants therewith, plus an excess amount to buffer acids encountered in washing and maintain a reserve of alkalinity in the wash solution. In addition to this, of course the amine may have solvent properties and be relied upon in part for this function.

Exemplifying the amines useful for these purposes, as well as for preparing salts of the anionic syndets supra, are water-soluble, strongly basic amines such as triethanol amine, diethanolamine, monoethanolarnine, ethylenediamine, .diethylenetriamine, tetraethanol ammonium hydroxide, morpholine, mixed isopropanolamines, monoiso: propanolamine, diethylene glycol amine,'and amino ethyl ethanolamine. The alk-ylolamines, ether mono-, dior tri-, are preferred. 7'

"It may be noted that lower alcohols such as ethyl alco 1101 and polyethylene 'glycols of low molecular weight may reduce the viscosity of the solution when used in small amounts. On the other hand, polyethylene glycols of higher molecular weight may tend to increase viscosity even when employed in small amounts. Polyethylene glyco'ls having a molecular weight within the range from to 60 00 are preferred, but as indicated the chain length is notcritical; those having lower molecular weights aim bf used, for example, diethylene glycol and triethylene g yco The composition may also contain dyestuffs and perfumes to suit the housewifes desire. It is customary to mask the odor of organic amines, and those skilled in the art are aware of perfumes which meet this need.

The following examples illustrate the invention.

In the examples the Dexter suds were determined using a Dexter twin-tub washing machine, model 507 EPIDQ This is a vertical type agitator or washing machine. The.

machine has a capacity of 16 gallons. Tests are con;

ducted on compositions containing 3 and 6 ounces of detergent per 16 gallons of water. .The machine is filled with the 16 gallons of water and the temperature adjusted to 120 F. The required amount of concentrated hard water stock solution is added to achieve the desired hardness. Thereafter, the detergent is added, and 1 minute later 1 ounce of vacuum cleaner dust which has been dispersed in about 200 ml. of water by a motor driven stirrer is added and agitation continued for 1 minute to insure thorough dispersion throughout the wash water.

Six pounds of clean dry cotton load cloth are added to the washer with the agitator not running, to be sure that the load pieces are carefully distributed throughout the machine and pushed below the surface of the washing solution before the washing action is started. The machine is run for 20 minutes during which time the suds are observed for volume and'quantity. Readings are taken at 1 and 20 minutes. The highest rating at any one time is 4, according to the following suds condition:

- No suds The total suds rating is the sum of all of these, or amaximum possible total of 32.

The dishwashing test data were obtained using standardstainlesssteel dishpans. The dinner plates. are circular, 9 inches in diameter. About to 5.5 grams of standard dishwashing soil are. spread evenly over the top of each plate with a spatula. This soil is composed of 9. parts by weight of Covo, emulsifier-free, to which is added 8 parts by weight of Pillsburys bread flour and 1.25 ml. of green coloring for each pound of flour used, all thoroughly mixed.

4 The detergent composition is dissolved in 6 quarts of water of the desired hardness and at the desired detergent concentration. The test solution is brought to a temperature of 116 F. The plates are then washed by hand using freshly laundered dish cloths and washing is continued until the suds in the pan or solution no longer completely cover the surface of the water.

The Terg-O -Tometer detergency and sudsing were determined using the Terg-O-Tometer apparatus. The water bath temperature is adjusted to 124 to 128 F., to bracket the standardized 125 F. washing temperature. The paddle oscillation is brought to 90 complete cycles per minute and the paddle should oscillate through 320 of are.

With the agitators in position on the machine the detergent is added to the washpot of the machine. From 1 to 4 grams of detergent to 1250 ml. of water usually is used. 1250 ml. of water of desired hardness is added to the washpot containing the detergent after which the machine is started and the solution agitated until the detergent is dissolved. Eight pieces of soiled cloth approximately 4 /2" by 6" and four pieces of white unsoiled cloth of the same quality and size are added. Washing is continued for 20 minutes, after which the test swatches are removed from the solution and hand-squeezed. The washpot is refilled with clear rinse water of the same hardness used for washing at a temperature of about 130 F. and with the agitators running the cloths are rinsed for 1 minute. The cloths then are removed, hand squeezed and ironed dry. The reflectance of the soil cloths and of the white redeposition cloths is measured with a Hunter reflectometer using the green filter.

The results are calculated in this way: the average reflectance of the eight soiled test swatches'after Washing is taken. From this is subtracted the average of the soiled cloths before washing. The difference is the number of detergency units or DU. The reflectances of the four white redeposition pieces are averaged after washing, and this average is the number of redeposition units or RU. The tests usually are run at 3 ounce and 6 ounce concentration levels in and 180 p.p.m. hardness water.

The sudsing test in the Terg-O-Tometer is run in a way similar to that in the Dexter washing machine. A 10 and 15 and a 20 minute reading is taken. Bleach is added at 15 minutes so that a decrease in the readings between 15 and 20 minutes indicates susceptibility of the product to bleach. An approximation between the total Dexter and total Terg-O-Tometer suds can be obtained with the following formula using the total 10 and 20 minute readings at both levels in both waters. Dexter suds equals 1.26XTerg-O-Tometer suds-l-4'.

EXAMPLES 1 TO 12 A group of twelve compositions were prepared by slurrying the following ingredients in the amounts indi- 'cated in water and then drum drying.

Table I Percent by weight Control Examples Sodium -Oronite (sodium phenyl polypropylene sulfonate, polypropylene alkyl having an average of 12 to 15 carbon atoms) p 18 13 N-tris(methylol) methyl amide indicated in 1 Table TI 2 to 5 Sodium toluene sulionate 2. 5 2. 5 Tetrasodium pyrophosphate 30 30 Pentasodinm tripolyphosphatd, 15 16 R. U. Silicate (Na O'2 48102) 6 e Sodium carbonate 3 3 Sodium carboxymethylcellulos 0. 5 0. 5 Sodium sulfate and miscellaneous.. 14. 5 14. 5

These were tested for suds by the standard Dexter test and for dishwashing by the standardized dishwashing testdescribed above, and compared with the control composition containing no trimethylol methyl amide.

The suds ratings wiven in the table below are the total of the Dexter suds readings at 3 and 6 ounce concentrations in both 50 and 180 p.p.m. hardness water. The numberof dishes washed is the total of the results at both 10 and 30 gram concentrations inboth 50 and 180 p.p.m. hardness Water.

Table II N-tris(methylol) methyl amide CHsOH R-C ONH-(iJ-CHzOH CHzOH Example Percent Dexter Total N o. by R derived from- Total Dishes weight Suds Gontrol None 1O 96 1 3. 5 Tallow fatty acids..- 8 89 3. 5 Hardened tallow fatty acids 5 89 3. 5 Steario acid 4% 68 3. 5 Oapric acid 13% 136 3. 5 Coconut oil fatty acids 16% 141 3. 5 Coconut oil bottoms fatty acids (Palruitic-olelc mixture) 14% 3. 5 Laurie acid.-. 20 164 3. 5 \dyristic acid. 21 148 2.0 18 148 3. 0 21% 163+ 3. 5 20% 161 4. 0 21% 167+ 6.0 22% 170+ 1 Predominantly palmitic, small amount of oleio.

newest 9 The above :resul'ts :show that an enhanced sudsin'g is obtainedwith N-tristmethylol) methyl amides in which the R :radical has from nine to fifteen carbon atoms. The laurie, myristi'c and mixed lauricmyristic composi- 10 The data show that the addition of 2% N-tris(methylol) methyl lauramide .gives a noticeable boost in both sudsing and dishwashing. 4% of the amide gives a-substantial boost in these properties. At the 4% level the tions .are the best. The vN-tris(methylol.) methyl amide 5 N-tris'(methylol) methyl mixed lauric an'd myristic derived from stearic acid is relatively poor, and so are amides is about equal to the N-tris(methylol) methyl those derived from .tallow, and .harden'e'dtallow, probably .lauramide both .in dishwashing and in sudsing. The 4% due to their eighteen carbon atom acid content. The N-tris(methylol) methyl palmitic-oleic amide is less satis- N-ti'is (metliylol) methyl amides derived fr'orn capric, factory in di'shwashing, although satisfactory in 'sudsing. coconut oil and coconut oil bottoms acids are inter- These .N-tris(methylol) .inethyl amides can be used mediate. in conjunction with other suds boosters, such as coconut The results for the mixed lauric and rn-yristic N-tris oil fatty acids glycine and coconut oil fatty acids a t (methylol) methyl amides show that 3 /2 parts of the amide. 'The former formulations are not susceptible to N=tris('m'ethylol) methyl amide by weight of the combleach as is the coconut oil fatty acid glycine alone. position is sufficient, and that while more may be used Thecoconut-oil fatty acid aoetamide is deficient in dishno advantage is obtained using larger amounts. washing but .in combination with. an N-t-sistmethyf-lol.)

methyl amide this deficiency is overcome.

EXAMPLES 13 TO 16 EXAMPLES 17 AND 18 A group of compositions was made up by slurrying 0 Samples were prepared by slurrying the following inthe named ingredients in water and drum drying: "g'redien't's in Water anddrum "drying.

iTable JV Control Control coma Example; central ns'am'pie A B 0 17 D 18 Pereentby weight I. Sodium bronite (sodium phenyl polypro pylene sulfonate, polypropylene alkyl hav- H ing an average of 12 17015 carbon atoms)....; 18 i i 18 B i 9 Sodium tallow sulfate -1 7 7 Ntris(methylol) methyl lauramide-xii'ytistamide. "as 1 Sodium toluene sulfonate 2. 5 2. 5 2,5 I 1 Tetzasodiurn 'pyrupliosphate..- 30 J 1 .30. 30 30 Pe'utasodiumt'ri olyphosphate. 15 a 15 1'5 15 15 R. U. Silieate( a,0;2.4sio,) s 6 s s a s is Sodium carbonate 3 3 3 31. y 3 3 Sodium carboxymethylcellulose 0. 5 -0. 5 0.5 0. 5 055- 0.5 Sodium sulfate and miscellaneous.-. 14.5 14.5 14. 53 1435 11.5 14.15

These formulations were tested .for sudsi-ng and de- Ingredient Perceu t tergency by the standardized Terg-O-Tometer tests and i dishwashing tests described above.

Sodium om ts (sodium phenyl polypropylene sulfonate i s plolyprfipygene 31th]? ha tvifig mp: 121trot15 carbo'n atoms) 2 Table .V 0 111m at one a o wa yac su ae N-trismisthylbn methyl amide (See Table III)- 0to4 -T METERSUDS geutasogium tripolypholsp liate etraso 111111 pyrop osp 8. 8...... R.U. silicate (NmOtSiOz 1:2.4) 6.0 v P-DJII- 0 ppm. Sodium carb h a; itiggrffiffi MW 7; 0 so. a m, Sodium sulfate and miscellaneous Balance 59 10' 15 20' 10' 15' 20' 10' 15' 201 10' 15' 20' Suds data were obtained by the Dexter washing mal chine test and by the dishwa'sh-i-ng test described above. -Gontrol.A-.- -0 0 0 0 0 0 0 0 o In the tablewhich follows the suds tatingsare the totals -i .8 g 8 8 8 8 g g g g of the Dexter washing machine suds ratings at the 3 and Gontrolieh 0 0 o :5 :4 :/z 0 0 0 1A s 6 ounce levels in 50 and 180 p.p.m. hard water and 2 /2 the dishwashing ratings are the total of the number of ""{i/ 1A 1% 1% }4 y 1 1 1 dishes washed at the 10 and 30 gram levels in 50 and Controliil- 2 g g g 180 p.p.m. hard water. A 25+ /2 9 0 1 60 0 AM-t 1 Table III N-tris(m'ethylol) methyl amide CHQOH TERG-O-TOMETER DETERGENCJY R-OONH-G-GH on 2 .50 p.p.m. 180 p.p.m. CHrOH I Composition 3 'oz. 6 oz. 3 oz. 6 oz. Exlaqmple Percent Ra l a DBltte!" Dlsh- V i h weight ewe DU RU DU RU DU RU DU RU N 28.9 79.3. 28.8 82.0 27.6 79.0 28.3 81.9 gonml Laurie BGICL. 26.5v 79.7 25.5 80.4 23.8 79.5 25.0 -6 4 .-.-"do.l-t 27.1 80.3 25.3 78.8 26.9 '79.7 26.6 79.1; 4 W3 5???- 21 at a; 3% a; as as. 22-; 4 c

9% sodium Oronite, 7% sodium tallow sulfate. 7 '7 11 12 DISHWASHING The results show that all of the amides tested have some boosting effect, as shown both in the dishwashing. and [Average of two runs] v Dexter sudsmg tests. However, none of the materials 50 180 mm are in any way as effective as the N-tris(met hy1'ol) meth- Composition Total 5 yl lauramide (Example 23) m accordance with the invention. g 30g. 10g 30 g.

I EXAMPLES 24 AND '25 COHtYOlA g g g 3 3 Three detergent compositions were prepared by mixa 11 5 9 30 10 ing the ingredients named in the table below in the f fig 8+ 2g amounts indicated in an aqueous slurry and drum drying. 34 17 32 9s Table VII The improvement obtained using the N tris(methylol) 15 methyl amide of the invention in Examples 17 and 18 is evident. Control Example No,

I I EXAMPLES 19 to 23 I 24 25 A group of formulations were made up containing Sodium Q -o 1t d1um phenyipoly. ropylene s lfonate, polypropylene N t r1s(methylol) methyl amide and analogous alkanol g kyl gua average of 12 to 15 amides for comparison purposes. These amides were cgrhon atoms) u 9,0 9.0 9, So lurn tallo ftt cl su ate 8.0 8.0 8.0 ncorporated individually indrum dried formulations hav fl z laummide 4 0 mg the following cOmPOSlUOIl: 25 Nqnonoethanol lam-amide 4.0 gentasolilum trlpolgpholspliate g g g e raso um pyron 051) a e sod; o t 1 I perclem by lwelght g3 sl1icatte)(N?1O 24s10--- $8 3. 2.

mm rom e so 1um p eny po ypropy ene su o um car onae fonate p yp py alkyl having an average of I iigigr f.fifl ii ffi flff i i-122: 313 313 $23 12 to 15 carbon atoms) 18.0 Sodium sulfate and mls to 100.0 to 100.0 to 100.0 Alkanol amide I I 3.5 Sodium toluene sulfonate 2,5 Mlsc. includes inert materials introduced with raw material. Tetrasodium tripolyphosphate ,I15.0 v Tetrasodium pyrophosphate 30.0 The compositions were tested in accordance with the R.U. Silicate (NagO:2.4SiO 6.0] 'Dexter sudsing test with the following results: Sodium carbona 3.0 Sodium carboxymethylcellulose 0.5 T

l able VIII Sodium sulfate and misc. 14.5 H O 7.0

a I I I Example No. Misc. includes tree tatty acid introduced with the raw 40 control materials.

The alkanol amides used are listed in the table below. 1% 1, 2% 2 1% The formulations were evaluated by the Dexter sudsing momma-50 "l 2 2611 2 test and the dishwashing test described above.

Table VI Dexter Sudslng Test Dlshwashlng Test Example No; Alkanol Amide p.p.m; 180 p.p.m. 50 p.p.m. 180 p.p.m.

7 30:. 602. 302. 602. 10 gm. 30 gm. 10 gm. 30 gm.

Control No amide $6.16 2, 2 x, at 2,2 s 40 7 41 I CHIOH 1a c,,11,,-c 1-r-rn---o--cm I 114,114 214,215 1%, 114 214.2% 11 60 18 so CHgOH 20 C1lHu-CINHCHCHIOH 1,1 214,2: 54,1 295.2% 12 52 12 52 CHIOH 21 C11Hn- -('IJNH-C-C;Hg 1%, 1% 2%, 2% 1%, 1% 2%, 2% 15 53 16 55 I CHzOH 22 C11H;1C-NH-CHCH1OH 1%, 1% 2%, 2% 1%, 1% 2%, 2% 17 18 60+ GHaOH I 23 CnHfl-(f-NH-C-CHgOH 2, 2% 3,11% 2,2 3,35 21 60+ 22 60+ CHzOH 1 Average 01 2 W8.

13 The above :data shows that the N-tris(methylol) methyl lauramide of the invention is superior tothe lauric :monoethanol amide, The latteris no better than the control.

EXAMPLE 26 The ingredients mentioned below were mixed in a slurry and drum dried.

1 Misc. includes free fatty acid material.

These formulations were tested in the Dexter sudsing and dishwashing tests described above with the following results:

The results show that the N-tris(methylol) methyl lauric and myristic amide is effective as a booster in com bination with the sulfated detergent. There is no significantly increased sudsin and dishwashing. capacity at the high usage levels (6 ounce level in sudsing and 30 gm. level in dishwashing in both 50 ppm. and 180 ppm. hard water).

EXAMPLES 27 AND 28 These are examples of highly concentrated liquid detergents.

Percent by weight Example No. Control Phenyl polypropylene sulfonic acids (alkyl of 12 to 15 carbon polypropylene, 100% active.) 26 5 25. 5 25. 5 Antaron K460 A (ammonium salt of sulfated oxyethylated nonyl phenol, prepared from condensation of nonyl phenol with five moles of ethylene oxide, 57%

active) 15.0 15.0 15. N -tris (methylol) methyl lauramide-myristamide 1:1 10.0 N-trisunet ylol) methyl capramide 10.0 Ethyl alcohol 15.0 15.0 15.0 Potassium hydroxide (86.4% alkali). 5. 0 5. 0 5.0 Water, perfume, ctc 39. 29. 5 29. 5

6 gms 33, 34

14 These compositions remain clear at .tcmperatures as low as 35 and have a pH of 7.2 at 26 C. In place of potassium hydroxide, ammonium hydroxide or triethanolamine could be used.

These formulations have excellent dishwashing capacity, as the following data show:

Plates washed in 120 ppm. at- Control Example No.

All parts and percentages in the specification and claims are by weight, and when with reference to components of the detergentcomposition are based on the weight of the composition unless otherwise indicated.

I claim:

1. A nonsoap detergent composition consisting essentially of an amount of a synthetic organic nonsoap detergent selected from the group consisting of anionic nonsoap and nonionic nonsoap detergents to impart detergency to the compisition and an amount from 0.5 to about 15% of the total composition and suflicient to enhance the sudsing of the synthetic detergent of an N-tris(methylol) methyl amide having the formula:

where R is an aliphatic hydrocarbon radical having from nine to fifteen carbon atoms.

2. A nonsoap detergent composition in accordance with claim 1 in which the N-tris(methylol) methyl amide is N- tris(methylol) methyl lauramide.

3. A nonsoap detergent composition in accordance with claim 1 in which the N-tris(methylol) methyl amide is N-tris(methylol) methyl myristamide.

4. A nonsoap detergent composition in accordance with claim 1 in whichthe N-tris(methylol) methyl amide is N-tris(methylol) methyl coconut oil fatty amide.

5. A nonsoap detergent composition in accordance with claim 1 in which the synthetic detergent is an anionic synthetic detergent.

6. A nonsoap detergent composition in accordance with claim 1 in which the synthetic detergent is a nonionic synthetic detergent.

7. A nonsoap detergent composition in accordance with claim 5 in which the anionic synthetic detergent is an alkyl aryl sulfonate.

8. A nonsoap detergent composition in accordance with claim 5 in which the anionic synthetic detergent is an alkyl sulfate.

9. A nonsoap detergent composition in accordance with claim 5 in which the anionic synthetic detergent is a detergent sulfated polyoxyalkylene alkyl phenol.

10. A nonsoap detergent composition in accordance with claim 6 in which the nonionic synthetic detergent is a detergent polyoxyalkylene ether.

11. A nonsoap detergent composition in accordance with claim 6 in which the nonionic synthetic detergent is a polyoxyalkylene ether glycol.

12. A nonsoap detergent composition in accordance with claim 6 in which the nonionic synthetic detergent is a polyoxyalkylene alkyl phenol.

13. A concentrated light duty nonsoap liquid detergent composition which remains clear and uniform without separation of solid materials at low temperatures consisting essentially of a solvent, a synthetic organic nonsoap detergent selected from the group. consisting of anionic nonsoap and nonionic nonsoap detergents in an amount to impart detergency to the solution and an amount from 0.5 to about 15% of the total composition 15 and sufiicient to enhance the sudsing of the synthetic detergent of an N-tris(methylol) methyl amide having the formula:

. omoH R-CONHCCH2OH CHQOH where R is an aliphatic hydrocarbon radical having from nineto fifteen carbon atoms.

14. A heavy duty nonsoap detergent composition con sisting essentially of an amount of a synthetic organic non- :soap detergent selected from the group consisting of anionic nonsoap and nonionic nonsoap detergents to impart detergency to the composition, a detergent polyphosphate, and an amount from 0.5 to about 15% of the total composition and sufficient to enhance the detergency and slidsing of the synthetic detergent of an N-tris(methv ylol) methyl amide having the formula:

OHJOH RC ONH-C-CHzOH V HaOH References Cited in the file of this patent UNITED STATES PATENTS Weisberg Nov. 23, 1943 2,334,852 2,527,076 Preston Oct. 24, 1950 2,587,546 Matuszak Feb. 26, 1952 2,607,740 Vitale Aug. 19, 1952 2,757,143 Katzman July 31, 1956 FOREIGN PATENTS 414,403 Great Britain July 30. 1934 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,927 ,081 March 1, 1960 Charles H. Schramm It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5 line 24,- in the formula, for "m'' second occurrence read m column 8, line 45 for "when" read given column 10, line 56, Table V,v Example N0. 17, seventh column thereof, under the heading "5O p. p,m." and subheadings "6 02,-" and "20 "3 for "V read 1 same Example N0. 17, line 56, tenth column thereof under the heading "180 p. p.m.-" and subheadings, 3 oz. and "20 5 for 1" read V column 13 line 30, Table X in the heading, for "Deuter" read Dexter column 14 line 24 for compisi tion" read composition Signed and sealed this 30th day of August 1960.

(SEAL) Attest:

ERNEST W. SWIDER ROBERT C. WATSON Attesting Officer Commissioner of Patents

Claims (1)

14. A HEAVY DUTY NONSOAP DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF AN AMOUNT OF A SYNTHETIC ORGANIC NONSOAP DETERGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC NONSOAP AND A NONIONIC NONSOAP DETERGENTS TO IMPART DETERGENCY TO THE COMPOSITION, A DETERGENT POLYPHOSPHATE, AND AN AMOUNT FROM 0.5 TO ABOUT 15% OF THE TOTAL COMPOSITION AND SUFFICIENT TO ENHANCE THE DETERGENCY AND SUDSING OF THE SYNTHETIC DETERGENT OF AN N-TRIS(METHYLOL) METHYL AMIDE HAVING THE FORMULA: