US3278444A - Detergent composition - Google Patents

Description

United States Patent 3,278,444 DETERGENT COMPOSITION Louis McDonald, Altadena, Califi, assignor, by mesne assignments, to Kelite Chemicals Corporation, Los Angeles, Calif., a corporation of Delaware No Drawing. Filed Mar. 30, 1961, Ser. No. 99,369 1 Claim. (Cl. 252-121) The present invention relates to a detergent composition and it particularly relates to a bar detergent compo- SlOn.

Considerable difficulty has been experienced in preparing soap detergent bars by combining together various types of synthetic surface active organic non-soap detergents of the anionic or non-ionic types and frequently it has been necessary to utilize a wide variety of adhesives which do not enhance the property of the detergent bar.

In some instances where the additive is a long chain fatty acid water soluble soap considerable difiiculty is experienced due to the fact that such soap whether used by itself or combined with other detergent materials, lathers poorly in hard water, is not effective in salt solution, and will form insoluble lime soap curds in the form of scums which are not effectively dispersed by the dilute soap solutions.

Furthermore, such scums tend to deposit upon the skin in case of personal cleaning or upon fabrics that are washed therein and can not be readily rinsed. The scum or curd also forms a diificult to remove annular deposit on the wash bowl or bath tub, requiring supplemental cleansing and washing operations.

On the other hand, where organic non-soap detergents are employed, such as dodecyl benzene sodium sulfate, or lauryl alcohol ammonium sulfate or sulfated monoglycerol ester of lauric acid, or nonyl phenoxy-polyoxyethylene ethanol, or polypropylene glycol-ethylene oxide condensates or combinations thereof, the solid detergent materials show rather poor physical properties and deteriorate rapidly when exposed to water during use.

The same difiiculty occurs when the bars are made of a combination of fatty acid soda soaps and organic nonsoap detergents. These non-soap detergents, when used by themselves or with soda soaps, tend to form a gel in the presence of water or tend to release the more active non-soap detergent components when permitted to stand in a dish or other receptacle containing small amounts of water or which may receive drippage or seepage or splash of water.

For example, this loss of detergent material, which is called sloughing may readily be measured by determining a loss of weight of a non-soap detergent bar material or a combination of soap and a non-soap detergent material which is permitted to stand in water of a specified depth at 75 F. for an interval of about 12 hours.

It has been found that these difficulties can not be readily remedied by merely including an inert filler or polymeric thickening agents.

It is among the objects of the present invention to produce a physically stable bar primarily composed of synthetic detergent materials which will have high resistance to sloughing and which will also have the ability to reharden and assume normal physical properties after exposure to moisture.

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It is another object of the present invention to provide an improved bar detergent containing large quantities of non-soap organic detergents which will exhibit superior ability to lather in hard water and which will suppress the formation of lime soap curds and which will effectively disperse any lime soaps that may be formed if any fatty acid soaps are present.

Still further objects of the present invention is to provide non-ionic or anionic non-soap detergent bars with or without inclusion of fatty acid soda soaps which will be highly stable against sloughing when exposed to water over long periods of time and which will produce abundant lather in hard water and will not be subject to deterioration or precipitation in water containing soluble inorganic salts.

Still further objects and advantages will appear in the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration and explanation only and not by way of limitation, since various change-s therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

It has now been found that most effective and satisfactory bar detergent compositions may be prepared containing substantial or major quantities of non-soap organic detergents in which there is included an alkyl, aryl or alkyl-aryl grouping which is a polymerizable monomer provided with a strong polar group such as an inorganic acid group of the nature of a sulfonic acid group, a sulfate group, a phosphonate group or a carboxylate group. These polymerizable monomers which form a long central chain are desirably terminated by alkyl, aryl or alkyl-aryl groupings which also contain polar acid groups. These polymers, which have an average molecular weight ranging from 50,000 to 10,000,000, or more, preferably from 70,000 to 5,000,000, will be anionic in character and may be used in a proportion of about 0.05 to 55% of the total weight of the bar with a preferred proportion of 0.1 to 5%. These compounds will have the general formula:

Polyvinyl toluene sodium sulfonate. Polystyrene sodium sulfonate. Styrene hetero polymer of maleic acid. Polyvinyl sodium sulfate.

Polyvinyl sodium sulfonate. Polystyrene sodium phosphonate. Polyvinyl toluene calcium sulfonate.

The sodium, ammonium, potassium, calcium or magnesium salts of these polymeric compounds or the free acids of the polymeric compounds may also be used. J

These compounds appear to be particularly effective in controlling and preventing sloughing even when used in such small quantities as 0.05 to 2% of the total bar.

Among the preferred compounds which may be employed are 0.5 to 1% of polystyrene sodium or calcium sulfonate or mixtures thereof or other polystyrene or polyvinyl or even polyethylene, sodium, potassium, calcium or strontium sulfates or sulfonates. These small amounts may be added to a detergent bar containing 5 to 50% of non-ionic detergents such as nonylphenoxypolyoxyethylene ethanols and anionic detergents such as alkyl aryl sodium sulfonate, dodecyl benzene sodium sulfonate or sodium salts of sulfated esters of alkyl phenoxypolyoxyethylene ethanol.

In addition the bar may also contain 5095% of fatty acid soda soaps. Under some conditions it is also possible to include .05 to .5 of emulsified water insoluble ethyl, benzyl, or propyl cellulose. These cellulosic compounds should be water insoluble and they are emulsified before addition to the bar composition.

It is also possible to include water soluble cellulose derivatives such as hydroxy ethyl cellulose, methyl cellulose, or carboxy cellulose in amounts ranging from 2 to These latter water soluble celluloses may be replaced in part or whole with protective colloids, such as dextrin, agar, pectin, locus bean gum, gum tragacanth, gum arabic and the like. Preferably the non-soap detergent composition may be made up primarily, that is from 50 to 90% of alkyl aryl sulfonates or alkane sulfonates such as dodecyl benzene sodium sulfonates.

The total bar may contain from 25 to 75% of non-soap organic detergents, such as alkyl aryl sodium sulfonates or dodecyl benzene sodium sulfonates.

A particularly desirable effect of the inclusion of strongly anionic water soluble or water dispersable polymers such as polystyrene sodium sulfonate and/or polystyrene calcium sulfonate or mixtures of the sodium and calcium salts thereof results in the elimination of any tendency of the preferred non-soap organic detergents leaving a sticky residue upon the skin or causing undesirable drying out or roughening of the epidermal outer layer of the skin.

Surprisingly, even with as high as 10-50% by weight of dodecyl benzene sodium sulfonate or alkyl aryl sodium sulfonate, there is no sticky residue left upon the skin agd the detergent material is readily removed by rinsing o To show the high effectiveness in controlling sloughing by the use of 0.1 to 1% of polyvinyl toluene sodium sulfonate and polyvinyl toluene calcium sulfonate the following example is given:

EXAMPLE I A bar detergent is made up of the following composition:

Material 1 Preferred Range O in Orb- H on CNN 0 COO 1 All in parts by weight.

Test specimen 1 x 2 x 2" Area exposed to water 7.0 in.

Volume of water per test specimen 50 cc. Temperature-75 F.

Time of exposure to water 14.5 hrs.

Test bars of known constant weight were immersed in distilled water to a depth of 0.375 for the 14.5 hour test period. Gelled or exuded materials were then scraped from the bar.

The bar was next allowed to come to constant weight at room ambient condition (75 F. 30% RH) and the weight of soap and organic detergent lost by sloughing was estimated by difference. Losses by sloughing of other bars were estimated under the same conditions for purposes of comparisons.

The bar of the above composition lathers profusely in soft, hard or sea water. Despite the high concentration of dodecyl benzene sodium sulfonate present, it rinses readily and does not leave a sticky film or residue on the skin.

While the above combination is preferred from the viewpoint of cost and performance many other organic non-soap detergents may be employed with or without fatty acid soda soaps in conjunction with the anionic polymeric additives to produce physically stable bars that exhibit good detergency and rinsibility.

As examples of other non-soap detergents which may be employed the following compounds are set forth:

Sodium lauryl sulfate.

Sodium sulfate of monolauryl glycerol ester.

Polypropylene-polyethylene condensate.

Oleyl methyl tauride.

Sorbitan monopalmitate-polyoxyalkylene derivative.

Alkyl sodium sulfonates.

Alkyl phenoxy polyoxyethylene ethanols.

Sulfated ester of alkylphenoxy polyoxyethylene ethanols.

Alkyl aryl sodium sulfonates.

Alkylolamides.

To give a general formulation in parts by Weight:

Composition II Parts by weight Soda soap 20 to Nonionic and/ or anionic non-soap detergent 10 to 50 Polymonomer (vinyl or styrene) aryl metal salt 0.1 to 2 Water 5 to 30 In the above composition the soda soap may be tallow or cocoanut oil soap or a combination of both. The anionic component is desirably 2 to 3 times the proportion of the non-ionic component of the non-soap detergent.

Desirably equal parts of sodium and calcium salts may be employed as the polymonomer although the calcium salt may range from 25-75% of the composition. The metal salt is desirably a strong mineral acid residue and the aryl group may be phenyl, toluyl, xylyl or benzyl. Less preferably, groups such as naphthyl or anthracyl may be used.

It is also possible in some instances to use aluminum or zinc salts in connection with the polymonomer. Desirably the polymonomer consists of a linked chain including one or more of the following groups:

-CH=CH CH C=CH -C H C=CH- --C3H7C=CH- Less preferably it is possible to use epoxy chains such as -cH--oH- -C CHaCH- These detergent bars may be made up in crutchers, soap chip dryers, amalgamators, mills, plodders and tablet presses. The procedures using vacuum plodding without milling can also be employed. Further, it is possible to produce aerated or floating bars by framing after crutching with final pressing into tablets. Continuous methods such as are commonly used for making floating bars from fatty acid soda soaps may also be followed.

The non-soap organic detergents, polymer additives and fatty acid soda soaps (when employed) can be mixed to a homogenous mass in a crutcher prior to processing steps for making bars or the components can be pre-mixed in an amalgamator and then milled in a conventional four roll soap mill until a homogenous mixture is obtained.

The following are further examples in which fatty acid soda soaps and organic non-soap detergents are combined:

EXAMPLE III Preferred Material Preferred Range Active Parts by Weight Kettle soap (made from 80 parts tallow and 20 parts cocoanut oil) containing 35% moisture"- 86 50-120 56 Sulfated ester of alkylphenoxypolyoxyethylene ethanols 10 to 20 4 Nonylphcnoxy polyoxyeth'ylene ethanol 2 1 to 2 Dodecylbenzene sodium sulfonate 40% active 59.0 25 to 75 22. 5 Ethyl cellulose ether emulsion (25% ethyl cellulose 47.549% cthoxyl. 22 cps.) 1 0.1 to 2 0. 25 Polyvinyl toluene sodium sulfonate 13. 6 5 to 0. 34 Polyvinyl toluene calcium sulfonate 10.8 5 to 15 0. 27

With the kettle soap slowly agitating in a crutcher at l40160 F. the other components are added in the order shown.

The mass is agitated until a homogenous mixture results. The mixture is then flowed to the feeder trough of a set of chilling rolls to produce ribbons of 0.005 to 0.015" in thickness. The ribbons are conveyed to a conveyor dryer such as a "Proctor and Schwartz dryer where the moisture content is adjusted to the order of 6 to 18%.

A drying temperature of 160 F. and a cycle of 20 minutes is used. Following drying the ribbons are cooled to ambient temperature and then milled through a 4 roll soap mill.

The milled ribbons are then plodded and the plodder bars are cut to size and pressed into cakes or bars.

In the event floating bars are wanted, the crutcher mixture is agitated at higher speed until air is stabilized in the mixture. The mass is then poured into soap frames and allowed to cool and dry to the desired level of moisturei.e. the order of 16-18%.

Following drying the slabs of the detergent mixture are cut into unfinished bars and then pressed into finished bars.

EXAMPLE IV Plrxefgrred Material Parts by Range 6 We Parts by Welgh Weight Soda soap (from fallow-20 cocoanut oil) (35% moisture)-. 116. 0 50 to 150 40 Sulfated ester of nonyl phenoxypolyoxyethylene ethanol 12. 5 5 to 20 5 Nonyl phenoxypolyoxyethylene ethanol 4. 0 1 to 10 4 Dodecyl benzene sodium sulfon- & 75. 0 25 to 125 33 Polystyrene sodium sulfouate (120 000 average MW) 10.0 2 to 15 0. 25 Polystyrene calcium sulfonate (120,000 average MW) 6.0 2 to 15 0.15 Water 17. 6 5 1:0 25 17.6

EXAMPLE V Bars are made almost entirely of organic non-soap detergents and can be produced from the following composition:

Preferred Range of Material Parts by Parts by Weight Weight Water 7. 0 2.0 to 12.0 Magnesium trisilicate 10.0 0.0 to 5.0 Di-g1ycolstearate 2.0 1.0 to 10.0 Lauryl alkylolamide 6. 25 1.0 to 8.0 Dodtecyl) benzene sodium sulfonate 64. 00 20.0 to 80.0

ac 1ve Sodium lauryl sulfate 5.00 3.0 to 40.0 Nonylphenoxy polyoxyethyleue ethanol.-. 5. 00 3.0 to 10.0 Polyvinyl toluene sodium sulfonate (aver- 0. 50 0.25 to 2.0

age molecular wt. 120,000). Polyvinyl toluene calcium sulionate (aver- 0. 25 0.0 to 2.0

age molecular wt. 450,000).

With the exception of water, magnesium silicate, polyvinyl toluene sodium sulfonate and polyvinyl calcium sulfonate, all the components are charged in an amalgamator and mixed for 5 minutes.

In a liquid mixing vessel equipped with an impeller agitator a slurry is made of the magnesium trisilicate, water, polyvinyl toluene sodium sulfonate and polyvinyl toluene, calcium sulfonate.

This slurry is added to the amalgamator along with color and/or perfume materials and the entire batch is mixed for an additional 5 minutes.

The amalgamated batch is then transferred to a 4 roll mill and is subjected to two passes through the mill. Following milling the milled ribbons are fed to a plodder. The extruded plodder bars are then cut and pressed into finished bars. The bars exhibit good physical stability, abundant lather and rinse freely.

It is possible to considerably vary the soda soap and organic non-soap detergent components in respect to amount and kind used and still produce a satisfactory bar. Similarly, minor but effective amounts of anionic polymers other than, for example, polyvinyl toluene sulfonates can be used.

Lau'ryl alkylolamide can be used to replace or supplement nonylphenoxypolyoxyethylene ethanol, or sodium lauryl sulfate to replace or supplement dodecyl-benzene sodium sulfonate, or glycerylmonolauro-sulfate to replace or supplement sulfated alkylphenoxypolyoxy-ethylene ethanol,

Also, polyvinyl sodium sulfate or styrene-hetero polymerof maleic acid may replace or supplement polyvinyl toluene sulfonates or polystyrene sulfonates.

Furthermore, fillers other than magnesium trisilicate may be used, such as talc, silica, starch or nacre.

While there has been herein described a preferred form of the invention, it should be understood that the same may be altered in details and in relative arrangement of parts within the scope of the appended claim.

Having now particularly described and ascertained the nature of the invention, and in what manner the same is to be performed.

What is claimed is:

A bar soap composition resistant to sloughing and capable of being effectively used in salt, acid, and alkaline solution consisting essentially of 5 to 50% by weight of an organic non-soap anionic detergent, .05 to 5% by weight of a metal salt of a linear organic polymer containing acid groups in the molecule, having a molecular weight in the range of 70,000 to 5,000,000, said polymer selected from the group consisting of polyvinyl toluene and polystyrene, sodium and calcium sulfonates, and 50 to 95% by weight of a soap selected from the group consisting of a sodium salt of tallow and a sodium salt of coconut oil fatty acids.

References Cited by the Examiner UNITED STATES PATENTS LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, Examiner.

I. T. FEDIGAN, Assistant Examiner.