US2932617A - Detergent composition containing 2-alkyl-4, 4-bis (hydroxymethyl) oxazolines - Google Patents

Description

UnitedStates Patent nstant Vincent Lamberti,.Hackensaclt, and Mark D. Konort, Fort Lee, N.J., assignors to Lever Brothers Company, New York, .N.Y., a corporation of Maine v 4N0 Drawing. Application February 29,1956 Serial No. 568,433

2 claims." C1. 252 137 This invention relates todetergent compositions which can be formulated from slurries or solutions as heatdried powders and which contain a small amount of a 2-alkyl-4,4-bis(hydroxymethyl) oxazoline to improve the sudsing and,- in-some instances, the detergency of the compositions. t

There are two general types of detergent compositions available on the market: light duty and heavy duty detergents. Heavy duty detergents have the ability to remove stubborn soil and prevent sail redeposition in laundering. These are all-purpose detergents, usually are available in powdered form, and contain polyphosphates as builders. However, these detergents by virtue of their polyphosphate content 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 deter- V gents have been formulated. These lack the polyphosphate builders but have a detergency which is adequate for dishwashing and light laundering, and are not as hard on the skins 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 detergency is suflicient, 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 thetime when the suds no longer completely coverthe surface of the washing solution. As is well known, most synthetic detergents are deficient in sudsing power, and this difliculty is usually overcome by incorporating an ingredient which enhances suds. It iseSsentiaIthat the added ingredient be soluble in the washing solution to a sufiicient extent to permit the preparation of solu-' Many such agents are,

tions of washing concentrations.

very sparsely solublein water. Also, the agent should be stable to bleach'if it is tobe useful in heavy duty.

detergents. In accordance with the invention, synthetic detergent compositions are provided which contain a 2-alkyl-4,4- bis phosphates and supplemental builders alsowillbe present,

The 2-alhy1-4,4-bis(hydroxymethyl) ,oxazolines of the invention have the formula:

2,932,617 Patented Apr, 12, 1960 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 about thirteen carbon atoms, preferably about eleven carbon atoms. Thus, R can be nonyl, decyl, unde'cyl, dodecyl and tri" decyl. These limits are critical. 2-heptadecyl-4,4-bis ('hydroxymethyl) oxazoline, in which R has seventeen carbon atoms, actually is a suds depressant (see Example 3,.below). 1

These are prepared by refluxing molar proportions ofi t-ris(hydroxymethyl) amino methane with the correspond ing fatty acid in Xylene solution until two moles'of water per mole of reactant are collected in the water trap, J. Am. Chem. Soc. 73, 2598 (1951). 1

The following 2-alkyl-4,4-bis(hydroxymethyl) oxazolines are typical, and can be used in the detergent compositions of the invention:

(hydroxymethyl) oxazoline and an organic nonsoap de-..

Melting t Point (C.)

CHQOH CHsOH l "l l ornon V l l earn,- n, oo.e-1o1.4

CHrOH The 2-alkyl-4,4-bis(hydroxymethyl) oxazoline can combined with any sync let to give-a detergent composition. Anionic, nonionic and cationic syndetsand mixtures thereof can be used. The alkyl aryl sulfonat'es and the'; alkyl sulfates are especially preferred. The oxazolines of the invention are effective sudsaboosters with dodecyl benzene sulfonate when the compositionsare formulated as mechanical mixtures, or as heat-dried formulations, which, as the term is used herein and in the claims, re-

fers to formulations prepared from aqueous solutions;

and/or slurries. However, in the caseof other anionic;-

nonionic and cationic syndets, the oxazolines evidence their suds-boostingproperties only in the heat-dried" formulations, apparently because those properties are developed in the axazoline in the crutcher or in the drying operation. The term oxazoline" as used herein and in the claims is inclusive of the heat-dried material.

Enough of the oxazoline would be used to enhanceaqueous solutions of washing concentrations. from 0.5%.to 5% is adequate.

The alkyl aryl-sulfonatcs are a class of anionic syndets wen'known a 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 am'-.

. SOaM 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 containing preferably twelve to fifteen carbon atoms. These are known compounds,,whose preparation and properties are set forth in US. Patent No. 2,477,383 to Lewis, issued July 26, 1949; they are available in commerce under the trade names Oronite," Ultrawet" and Neo1ene."

Another example thereof are the alkyl aryl sulfonates made by chlorinating a keryl hydrocarbon, and condensing this with benzene, followed by, sulfonating. These are-the Nacconols.

The alkyl sulfates are characterized by the structure RSO M, where M ishydrogen 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, such 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. V

Another, class'of anionic syndets are the sulfated oxye'thylated alkyl phenols, which have the following general formula: I

R snomommfomomosom 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 carbon-amideor thiocarbonamide group or a. carboxylic or thiocarboxylic ester group, x is a numher 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, tetradecyl 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 others of isothionic acid, l,2-dihydroxy propane-3-sulfonic acid, and sulfuric acid esters of monoglyceride and glycerol monoethers. The salts of these acids are usually employed.

Another class of useful. anionic syndets are the amidoa'lkane sulfonates which are characterized by the following structure:

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, oleyl and stearyl. Sodium palmitic tauride, sodium palrnitic methyl tauride, sodium myristic methyl tauride, sodium palmiticstearic methyl tauride and sodium palrnitic methyl amidopropane sulfona-te have been found to be particularly suitable for use in the compositions of the invention.

The anionic syndets can be used in the form of the free acid, which can be neutralized in sim in the detergent solution or slurry before drying by addition of an organic amine or ammonium hydroxide. amines useful for preparing salts of the anionic syndets supra, are water-soluble, strongly basic amines such as triethanolamine, ethylenediarnine, diethylenetriamine, tetraethanol am,- monium hydroxide, morpholine, mixed isopropanolamines, monoisopropanolamine, diethylene glycol amine, and amino' ethyl ethanolamine. The alkylolamines, either mono-, dior tri-, are-preferred. They are also readilyavailable as the alkali metal salts, such as sodium, potassium andammonium, and these would generally be used. However, the ammonium or organic amine salts may be more soluble, and in this event may be preferred.

There may also be used, either alone or in admixture with the anionics, nonionic syndets such as polyoxy alkylene-ethers', which retain thetermi-nal OH groups, as the glycols, and in which the terminal OH groups are substituted, as the mono and diethers thereof, such as the polyoxya-lkylene' alkyl phenols, polyoxyalkylene fatty acid amides, and alkyl polyoxyalkylenc oxyand t-hio ether and oxyand thioester nonionic detergents.

Many Ipolyoxyalkylene glycol ether syndets have the following general formula:

where R is a straight or branched chain saturatedor unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an alkyl aryl group having a straight or branched saturated or unsaturated hydrocarbon group of from eight to eighteen carbon atoms attachedtothe ary-l nucleus, and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiccarboxylic ester groups. R and R are hydrogen or" or thio fatty acid of high molecu-lar weigh-t, by condensa tion with ethylene oxide, 2,3-butylene oxide or 1,2-propyle'ne onide. Typicalof this type of alkylether are the condensation products of oleyl or dodecyl alcohol or mercaptan with from eight to seventeen moles ofethylene oxide, such as Emulfor ON,'Nonic'218 and Sterox SE and SK. Typical alkyl esters are 61226 and Renex (polyoxyethylene ester of tall oil acids), Sterox CD, Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).

Exemplifying the idiethanolamine, monoethanolamine,

The polyoxyalkylene alkyl phenols and thiophenols have the following general formula:

A-{OHRCHEV'O},CHR'OHR"OH where R is a straight or branched saturated, or unsaturated hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, R and R" are hydrogen or methyl, A is oxygen or sulfur and x is a number from eight to twenty. R can, for example, bestraight or branched chain octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl 'or octadecyl. Typical are the condensation products of octyl and nonyl phenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names N=IW, Antarox A-400, 'Igepal CA and CO, Triton X-100, Neutronyx 600 and Tergitol NPX.

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

. 2,677,700 to D. R. Jackson et al., dated May 4, 1954.

m and mrepresent the average number of oxyethylene units, and n the average number of oxypropylene units.

See US. Patent No. 2,674,619. The sum of m and m preferably is within the range from 15 to 41, and n preferably is within the range from 17 to 31. t

For light duty purposes, the detergent composition need not contain detergent polyphosphates or supplemental builders. However, t-hese can be included if desired in the compositions for heavyduty or other special purposes, such as for use in certain waters.

Detergent polyphosphates are well known. The akali metal, e.g. sodium, potassium and ammonium, salts are water-soluble. Sodium, potassium, and ammonium pyrophosphates, tripolyphosphates and tetraphosphates are exemplary.

Typical supplemental builders are the alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates, met-aphosphates, 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 meta-- phosphate. 1 i

In addition to or instead of the above-mentioned supplemental inorganic salts, organic materials such as starch, polyethylene glycols, polyvinyl alcohols, ethylhydroxyethyl cellulose, and salts of carboxymethylcellulose and cellulose 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 builder mixture'is so chosen that the composition 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 morealkaline 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.2-alkyl-4,4-bis(hydroxymethyl) oxazoline preferably is added to the solution or slurry of the detergent composition before drying but it can also 65 be added to thefinished powder when the syndet is a dodecyl benzene sulfonate.

The following examples illustrate the invention.

In the examples, the dishwashing test was carried out using circular dinner plates, 9 inches in diameter. About 5 to 5.5 grams of standard dishwashing soil was spread evenly over the top of each plate with a spatula. This soil is composed of 9 parts by weight of Covo, emulsifierfree, 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 using a Hobart Mixer,

Model C-210.

The detergent composition is dissolved in 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 sudsing is determined using the Terg-O-Tometer apparatus. The sudsing test in the Tergo Tometer is run in this way. One liter of water of the desired hardness (50 ppm. or 180 ppm.) is added at a temperature slightly above the washing temperature (120 F.) to compensate for the temperature drop in the wash pot. A 1.32 gram portion of detergent, equivalent in concentration to 3 oz./l6 gallons, is then dissolved in the water nad 1.76 grams of vacuum cleaner dust soil is added and agitated one minute. Twelve pieces of clean desized cotton sheeting approximately 4 /2 x 6 inches are added one by one and the agitation is restarted. When the detergent is to be tested for stability in the presence of hypochlorite bleach, 4.4 ml. of conventional household hypochlorite bleach is added immediately after restarting the agitation. At the end of 10 minutes, the amount of suds is estimated, and a point value is assigned for the suds as follows:

Percent Coverage of Surface of Liquid in Terg-O-To meter Beaker Point Value 0 Zero coverage.

5 Trace25% coverage.

25%50% coverage. 50%l00% coverage. Complete coverage.

To obtain minute differences in these ratings, a plus or minus may be applied to agiven grading.

EXAMPLES 1 TO 3 A series of detergents were made up according to the following formulation bysIurrying the named components in water and drum drying:

Percent by weight Sodium Oronite (sodium phenyl polypropylene sulfonate, polypropylene alkyl having an average The oxazolines used, of the formula in column 1, supra, had the R radical listedin the table below.

These formulations were tested for sudsing and dishwashing, with the following results:

Table l Terg-o-Tometer Sudsing 50 p.p.m. water 180 p.p.m. water Example R'in Oxaz- No. oliue' 3 oz. 602. 3 oz. 6 oz.

'ii" 1''''1" y y i i iy y V 3 i i n ecy 2 2 2 z 1 2 v z 2 Pentadecyh. 0 0 0 P 3 2 0 0 0 14 14 $6 HeptadecyL 0 0 0 Y2 $6 0 0 0 0 $6 Hypoohlorite bleach added at 15 minutes.

The above formulations were subjected to the stand:. ardized dishwashing test, with the following results:

4 s 6 7 s 9 ,10 11 12 1a 14 Dishwashing: Number of plates washed by 10 g. in 50 p.p.rn. water- 4 8 13 15 4 16 19 I6. 6. 15 '24.

Table II D h 'ashin 18 u v g Example No. p.p.m. 180 p.p.m.

10 g. 30 g. 10 g. 36 g.

The test data show that the undecyl oxazolineis a very effective suds booster, particularly at the lower usage levels. The pentadecyl andfthe heptadecyl oxazolines show that the suds boosting properties diminish strikingly as the number of carbon atoms in the R EXAMPLES 4 TO 14 The formulations described herein were mechanical mixtures of the ingredients. conforming to the composition indicated in the table below.

Table III The test data show that the oxazoline enhances strong-.

ly' both the sudsing and dishwashing ability of the detergent, in both the built and unbuilt formulations.

All parts and percentages in the specification and claims are by weight, and when with reference to come pone nts of the detergent compositionare basedon the weight of the composition unless otherwise indicated.

W claim:

1. A detergent composition consisting essentially ofan alkali metal dodecyl benzene sulfonate in an amount to impart detergency to the composition and an amount.

of from about 0.5 to about 5% to enhance the sudsing and detergency of the sulfonate of a 2-alkyl-4,4-bis(hydroxymethyl) oxazoline having the formula:

CH2OH I\CH:OH CH2 where R is an aliphatic hydrocarbon radicalhaving from I:

nine, to thirteen carbon atoms.

2. A heavy duty detergent composition consisting'essentiallyof an alkali metal do'decyl benzene sulfonate in an amount to impart detergency to the composition, a detergent polyphosphate and an amount of from about Percent by Weight Built Formulations Unbuilt Formulations Sodium Dodecylbenzenesultonate 2-Undecy1-4,4-Bis(Hydroxymethyl) Oxazol Pentas odium Tripolyphosphate Tetrasodium- Pyrophosph ate Sodium Tetraph0sphate Sodium Carbonate; 3 RU Silicate (1Naz01.2.4 SiO;,) 6 Sodium Carboxymethylcellulose 0.?

Crabcotw Queen Water V Sodium Sulfate-FMiscellaue'ous; 20.

eel-- aommoc con- Omen cow- 1 omooo crummy;

9 0.5 to about 5% to enchance the sudsing and detergency of the sulfonate of a 2-alkyl-4,4-bis(hydroxymethyl) oxazoline having the formula:

CHaOH where R is an aliphatic hydrocarbon radical having from m nine to thirteen carbon at oms.

UNITED STATES PATENTS Orelup Nov. 6, 1945 Wampner June 25, 1946 Valko Feb. 25, 1947 Lewis July 26, 1949 Preston Oct. 24, 1950 Brandner Apr. 21, 1953

Claims (1)

1. 2. A HEAVY DUTY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF AN ALKALI METAL DODECYL BENZENE SULFONATE IN AN AMOUNT TO IMPART DETERGENCY TO THE COMPOSITION, A DETERGENT POLYPHOSPHATE AND AN AMOUNT OF FROM ABOUT O.5 TO ABOUT 5% TO ENCHANCE THE SUDSING AND DETERGENCY OF THE SULFONATE OF A 2-ALKYL-4,4-BIS(HYDROXYMETHYL) OXAZOLINE HAVING THE FORMULA: