US2555285A

US2555285A - Detergent composition

Info

Publication number: US2555285A
Authority: US
Publication date: 1951-05-29
Anticipated expiration: 1968-05-29

Description

Patented May 29, 1951 DETERGENT COMPOSITION Eldridge J. Black, Levittown, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 27, 1948, Serial No. 67,565

4 Claims.

This invention relates to novel, dry detergent compositions having as their base a liquid, nonionic polyglycol ether type surface active agent.

Most soap and other organic detergent products are now available in dry flake, powder or pellet form. In producing such dry detergent compositions, soap or other synthetic organic detergents are customarily mixed with an alkali metal salt, often sodium sulfate or other alkalies commonly employed in detergent compositions, and the mixture then dried, either on drum driers to produce a flake product or by a. spray drying process wherein a slurry of the organic detergent and inorganic alkali metal salt is atomized into a spray drying chamber where it falls through a current of hot air and is formed into small hollow spherical beads or pellets. However, the organic detergents which are commonly employed in producing dry flake, powder or beaded detergents are all solids at room temperature. In addition to the usual fatty acid alkali metal soaps, such normally solid synthetic organic detergents as the sodium salts of alkylaryl sodium sulfonates, sodium salts of fatty alcohol. sulfates and the like have been employed in producing such dry detergent compositions.

Non-ionic, polyglycol ether type surface active agents are well known in the art and have found considerable application as detergents, wetting agents and emulsifiers. However, many of these polyglycol ether type surface active agents are liquids at ordinary conditions and it has heretofore been impossible to produce dry powdered or beaded, free-flowing cleaning and similar compositions Which contained any substantial amount of these liquid, non-ionic, polyglycol ether type surface active agents. While these non-ionic, polyglycol ether type surface active agents have been mixed with a variety of inorganic or organic powders to give flowable mixtures, for instance as suggested in U. S. Patent No. 2,213,477, it has been found that most solid materials ordinarily employed in detergents, wetting and dispersing compositions will tolerate only relatively small amounts of the liquid, poly-glycol ether type surface active agents before the composition becomes a paste rather than a dry composition. The amount of such liquid, non-ionic, polyglycol ether type surface active agents which may be mixed with the various solid materials, such as inorganic alkalies, commonly used in detergent compositions will vary with the particular nonionic, polyglycol ether type surface active agent and the particular alkali. Flor example, the water soluble polyglycol ether obtained by con- 2 densing about mols of ethylene oxide with 1 mol of diamyl phenol can be mixed with sodium sulfate to the extent of only about 5% to give a mixture which can still be considered a dry product rather than a paste; while sodium pyrophosphate will tolerate greater amounts of this non-ionic, polyglycol ether type detergent, i. e. up to about 18% before the mixture would be considered a paste rather than a dry product. However, all of these known mixtures are dense, wet-looking products with relatively poor appearance, and, in addition, when stored in paper containers at room temperature for a few days or at even a slightly elevated temperature (50 C.) for a few hours, a large percentage of the liquid, non-ionic, polyglycol ether detergent leaks out, staining the container. Such mixtures obviously have very little sales appeal and, in addition, are apt to cause damage to painted surfaces,

20 linoleum and the like with which the packages may come in contact. They have therefore frequently been prepared for sale as concentrated aqueous solutions in which form they must be protected from freezing, and in any event have had to be packed in liquidtight containers such as jars or cans; all of which substantially increases the packaging and transportation costs and consequently the sales price of such mixtures.

It is therefore an object of any present invention to provide dry powdered, flake or beaded detergent compositions containing a substantial amount of a normally liquid, non-ionic, polyglycol ether type surface active agent which presents a pleasing appearance and from which the polyglycol ether type detergent does not separate.

Briefly stated, the present invention resides in the discovery that if a small amount of a dispersing agent comprising an alkali metal salt of the condensation product of formaldehyde with naphthalene sulfonic acids is incorporated in a normally liquid, non-ionic, polyglycol ether type surface active agent, the thus obtained mixture of the sodium salt of the formaldehydealkyl naphthalene sulfonic acid and the normally liquid, non-ionic, polyglycol ether type surface active agent can be slurried with an inorganic alkali metal salt and the slurry dried by suitable means to produce a dry composition in flake, powder or beaded form in which the liquid, nonionic, polyglycol ether type detergent is firmly incorporated so that on storage, even at elevated temperatures, there is no leakage of the non-ionic detergent from the composition. The novel compositions of the present invention thus comprise a mixture of three essential components: l, a normally liquid, non-ionic polyglycol ether type detergent; 2, an alkali metal salt of a formaldehyde naphthalene sulfonic acid; and 3, an inorganic alkali metal salt of the class commonly used in detergent compositions.

A number of dispersing agents comprising the alkali metal salts, usually the sodium salt, of the condensation product of formaldehyde and naphthalene sulfonic acids, particularly alkyl naphthalene sulfonic acids, are available'on themarket and all of these known dispersing agents of this type 'may be employed in practicing the present invention. Such dispersing agents of this type are available under such trade names as Tamol (Rohm & Haas), Daxad (Dewey 8: Almy), Darvan (R. T. Vanderbilt), etc., andsince-they are known in the artthey are not described in detail in this specification. It has been found that an amount of such sodium salts. of naphthalene sulfonic acid-formaldehyde. condensation products equal to at least and preferably equal to about 50% by weight of the non-ionic, polyglycol ether type surface active agent which is employed, is effective for producing the novel compositions of this invention. Substantially larger amounts thereof may be used but generally are not economically justified. The optimum amount for any particular composition may readily be determined by preliminary test.

As examples of alkali metal salts which may be employed in producing the novel compositions of this invention may be mentioned sodium sulfate and other inorganic alkaline detergent agents such as sodium carbonate, borax, sodium triphosphate, sodium hexametaphosphate, sodium pyrophosphate, sodium silicate, sodium sesquisilicate and similar inorganic alkali salts, for instance the corresponding potassium salts, com monly employed in detergent compositions either as builders for fillers or as active ingredients. Such inorganic alkaline agents are preferably employed in an amount equal to the amount of liquid, non-ionic, polyglycol ether type surface active agent which is employed, and are generally employed in an amount greater than the liquid, non-ionic, polyglycol ether type detergent-up to ten times the amount by weight.

The liquid, non-ionic, polyglycol ether type surface active agents which are useful for producing the novel compositions of this invention are the normally liquid, non-ionic, surfaceactive agents obtained by condensing alkylene oxides with water insoluble organic compounds containing at least six carbon atoms and having an active hydrogen, such as organic hydroxy compounds, i. e. alcohols, phenols, thiols, primary and secondary amines, carboxylic and sulfonic acids and their amides. Compounds of this type are well known in the art and are disclosed along with suitable methods for their preparation, in U. S. Patents Nos. 1,970,578 and 2,213,477. They may be represented by the following general formula:

wherein R represents the residue of an organic compound containing an active hydrogen and the R represent hydrogen or lower alkyl and n represents an integer of from 3 to 100 or higher, and usually from 6 to 50. These compounds may readily be obtained as disclosed in the above mentioned patents by condensing a polyglycol ether containing the required number of alkenoxy groups or an alkylene oxide, usually ethylene oxide (although propylene or butylene oxides may be employed if desired) with a water insoluble organic compound containing at least 6 carbon atoms and having an active hydrogen. The amount of alkylene oxide condensed with the water insoluble organic compound having an active hydrogen, i. e. the length of the polyglycol ether chain, will depend primarily on the particular compound with which it is condensed. As

a convenientrule of thumb, approximately 1 mol valuable in detergent compositions, and, therefore, the poly-alkylene oxide derivatives of such phenolic compounds are a preferred type of nonionic surface active agents which are employed in the compositions of the present invention. Numerous compounds of this type, i. 'e. polyalkylene oxide derivatives of phenolic compounds containing one or more alkyl substituents, which may be employed in the compositions of the present inventionare described in U. s. Patent No. 2,213,477, and 11 preferably employ the water soluble poly-alkylene oxide derivatives of alkyl phenolic compounds in which the total number of alkyl carbon atoms is between 6 and 18. As examples of such phenolic compounds may be mentioned the isomeric, dibutyl and diamyl phenols and cresols, tripropyl phenol and cresol, secondary or tertiary isomeric heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, cetyl, oleyl, octadecyl and the like phenols and cresols. Of particular valueare the poly-alkylene oxide derivatives of secondary and tertiary alkyl substituted phenols and cresols obtained by condensing olefines of the type obtained in petroleum refining withphenols or cresols. In, the case of products obtained by condensing phenol or cresol with olefines of from 3 to 5 carbon atoms such as propylene, butylene and amylene, it is desirable to employ the di-alkylated phenols or cresols, while in the case of compounds obtained by condensing a phenol or cresol with an olefine containing8or more carbon atoms, the monosubstituted derivatives are preferred. Particularly desirable derivatives can be obtained from the phenols and cresols containing a substituent derived fromolefines containing from 8 to 18 carbon atoms, such as di-isobutylene and other 'alkylenes as nonylene, decylene, undecylene and dodecylene, pentadecylene, ,octadecylene and mixtures thereof, and may advantageously be the dimers and trimers obtained by polymerization of such low molecular weight olefines as propylene, butylene, amylene or mixtures thereof. However, the water, solublepoly-alkylene oxide derivatives of other Water insoluble organic compounds containing at least 6 carbon atoms and having an active hydrogenmay be employed in the compositions of the present invention. Thus, the poly-alkylene oxide derivatives, described in U. S. Patent No. 1,970,578, of aliphatic organic hydroxy compounds, carboxy compounds and amino compounds, as well as phenoli c compounds, may be employed if desired. As examples of water insoluble higher fatty acids whose polyalkylene oxide derivatives may be employed may be mentioned lauric, oleic, ricinoleic, palmitic and stearic acid, and the like, or mixtures thereof, such as the mixtures obtained from animal and vegetable fats and oils or by the oxidation of such petroleum fractions as paraflin wax. There may also be employed poly-alkylene oxide derivatives of water insoluble aliphatic hydroxy compounds such as higher aliphatic alcohols, i. e. the alcohols corresponding to the fatty acids specified immediately above, particularly the alcohols obtainable by hydrogenation of the fatty acids or glycerides present in animal or vegetable oils and waxes such as cocoanut oil, castor oil and the like. There may also be used polyalkylene oxide derivatives of higher molecular weight amines such as octyl amine, cetyl amine, oleyl amine, naphthyl amines, alkyl anilines, etc.; also the poly-alkylene oxide derivatives of organic mercapto compounds such as the products described in U. S. Patent 2,205,021, i. e. the polyalkylene oxide derivatives of such mercapto compounds as dodecyl mercaptan, oleyl mercaptan, cetyl mercaptan, decyl mercaptan and thiophen- 01s, thionaphthols, benzo-mercaptan, etc.; also the poly-alkylene oxide derivatives, such as those described in U. S. Patent No. 2,085,706, of carboxylic acid amides and of sulfonamides of the type described in U. ,8. Patent No. 2,002,613, or the poly-alkylene oxide derivatives, described in U. S. Patent No. 2,266,141, of sulfonic acids may be employed if desired.

' While the novel dry detergent compositions of the present invention thus comprise a mixture of three essential components, it will be apparent that other normally solid compositions which are frequently included in detergent compositions may be incorporated in the products of this invention if desired. Among the normally solid materials commonly employed in detergent compositions which may be included in the compositions of this invention may be mentioned the usual alkali metal soaps of fatty acids, alkylaryl sulfonates and fatty alcohol sulfates. Such mixtures of organic anionic active detergents and the novel compositions of the present invention are particularly valuable for the production of non-foaming detergent compositions for use in automatic washing machines, either dishwashing or laundry machines, wherein the production of foam is not desired. Such compositions are disclosed in the copending application of Arthur L. Fox, Serial No. 659,661, now Patent No. 2,543,744 issued on March 6, 1951. In addition, the various cation active surface active agents such as pyridinium chloride and the like may be incorporated in the compositions of the present invention and particularly valuable compositions of the present invention may be produced by incorporating a sufiicient amount of a cation active quaternary ammonium type bactericide to produce a germicidal detergent composition. Thus, the principals of the present invention may advantageously be applied to the germicidal detergent compositions of the type disclosed in copending applications of J. M. Lambert, Serial No. 737,- 437 or J. J. Ayo, Serial No. 789,765.

In producing the novel compositions of the present invention, the three essential components in all compositions of the present invention, i. e. the liquid, non-ionic, polyglycol ether type surface active agent, the alkali metal salt of the alkyl naphthalene sulfonic acid-formaldehyde condensation product and the inorganic alkali are advantageously mixed by slurrying in water and the resultant slurry then dried in any man: ner. A satisfactory, dry, somewhat fibrous material in chip or flake form can be made by the use of a drum drier. However, a more attractive product may be obtained by spray drying. By varying the spray drying conditions, such as the slurry concentration, temperature, etc., the density of the resultant hollow beaded pellets may be controlled so that products having densities ranging from 0.05 to 0.7 may be obtained. All the dry products, whether beaded or in flake or chip form, are dry in appearance and free flowing and unaffected by storage so that they may be stored at ordinary or slightly elevated conditions without any leakage of the liquid, non-ionic, polyglycol ether type surface active agent therefrom.

The following specific examples illustrate in detail preferred specific compositions of the present invention. The parts are by weight.

Example I A slurry was made up by mixing in 10 parts of water, 1.5 parts of the liquid, non-ionic, polyglycol ether type surface active agent obtained by condensing about 10 molar proportions of ethylene oxide with 1 molar proportion of 2,4- diamyl phenol, .7 part of a dispersing agent sold under the trade name of Tamol NNO, comprising the sodium salt of formaldehyde-alkyl naphthalene sulfonic acid, 2.5 parts of tetrasodium pyrophosphate and 5.3 parts of sodium sulfate. The diamyl phenol-ethylene oxide condensation product was first dissolved in water and the dry powders then added gradually with stirring. A thick, homogeneous slurry resulted, which was then spray dried at about 400 C. A hollow beaded, dry product, with a density of .3, was obtained. This material, on storage in paper containers at 50 C. for one week, showed no leakage or liquid separation of the diamyl phenolethylene oxide condensation product. The product was perfectly dry and free flowing and had a pleasing appearance. By varying the spray drying conditions, such as the slurry concentration and temperature, similar compositions have been spray dried to obtain well beaded, dry, freefiowing products with densities ranging from 0.05 to 0.7, all of which were unaffected by storage.

Under similar conditions, but with the sodium salt of the formaldehyde-alkyl naphthalene sulfonic acid omitted, when the resulting slurry was sprayed into a drying tower under identical conditions as that employed with the composition given in the preceding paragraph, no beading took place. Rather, a sticky, wet mass fell to the bottom of the tower and also stuck to the walls of the tower. A. wide variety of drying conditions were tried, higher and lower temperatures, pressures, slurry concentration and temperature, but no acceptable product could be made without the product known as Tamol NNO or a similar product, such as Daxad 11 or Darvan 1, i. e. a sodium salt of a formaldehyde-alkyl naphthalene sulfonic acid.

Example II A slurry, similar to that described in the first paragraph of Example I, was prepared and was then drum dried on a 72 inch drum dryer at 100 p. s. i. steam pressure and about 10 R. P. M. A dry, somewhat fibrous, free-flowing product was obtained in flake form. Storage of this product 75 at 50 C. for one Week in a paper container resulted in no leakage of the liquid detergent into the paper container, L p v When thesame slurry, from which the sodium salt of the formaldehyde-alkyl naphthalene sulfonic acid was omitted and replaced by an equal amount of sodium sulfatawas dried on a drum dryer, the slurry broke on the rolls and a wet,

sticky product was obtained. No variations in the drying conditions would give a dry product.

An apparently dry, free-flowing powder was obtained by spraying 1.5 parts of the liquid, nonionic surface activeagent obtained by con densing about 10 molar proportions of ethylene oxide with 1 molar proportion of diamyl phenol onto 8.5 parts of; ignited borax and mixing until a dry, free-flowing powder was obtained. However, on storage of this composition in a paper carton at 50 C., approximately 50% of the liquid detergent leaked out into the paper container during the course of a week: Likewise, in a similar manner, the apparently dry, dense powder obtained by mixing .5 part of the liquid, polyglycol ether type surface-active agent, obtained by condensing about 10 molar proportions of ethylene oxide with 1 molar proportion of diamyl phenol, with 9.5 parts of sodium sulfate; upon storage at 50 C. for 24; hours, approximately 50% of the liquid detergent leaked out into the paper container.

Whilethe non-ionic, polyg'lycol ether type surface active agent, obtained by condensing about molar proportions of ethylene oxide with 1 molar proportion of diamyl phenol, was employed in the compositions described in detail above-it should be understood that this particular normally liquid, non-ionic, polyg ly col ether type surface active agent has been specified solely for the purposes of illustrating the'prsent invention and that similar comp'ositionsmaybe obtained by employing in place thereof other normally liquid, no'n-ioni polyglyool ether type surface active agents of thetype previously described. It will alsobe understood that the progames 8' V nortiqnsi i ie s s epi d in ih xama e ma b v ith h r n e r t or i en. However, for any particular ingredient those skilled in the art can 7 readily determine satisfactory proportions and produce a balanced fomula by simple preliminary tests.

l m= 1. a solid dry detergent eomposition from which there is no liquid separation on storage, on i t es ntia f m 1 i919. P ris. W e g t. -ia ino i alkali det nt. alt partby weightoff a normally liquid watersoluble non-i onic surface active agent which containsa polyoxyalkylene ether chain having at least 3 lk ii re ps a 0- to. about 0- art by weight of an alkali metal salt of a formaldehyde; alkylnaphthalene sulfonic acid condensation product. I) p I .2-.'. .h p t 9n as efin n a m.. wherein the inorganic detergent salt is sodium sulfate. V n v I 3; The composition as, defined in claim 1 wherein the non-ionic detergent specified is a polyglycol ether of an alkyl phenol. 4. The composition as defined in claim 3 wherein the inorganic alkali detergent salt specified is sodium sulfate.

ELDRIDGE J. BLACK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Date

Claims

1. A SOLID DRY DETERGENT COMPOSITION FROM WHICH THERE IS NO LIQUID SEPARATION ON STORAGE, CONSISTING ESSENTIALLY OF FROM 1 TO 10 PARTS BY WEIGHT OF AN INORGANIC ALKALI DETERGENT SALT, 1 PART BY WEIGHT OF A NORMALLY LIQUID WATER SOLUBLE NON-IONIC SURFACE ACTIVE AGENT WHICH CONTAINS A POLYOXYALKYLENE ETHER CHAIN HAVING AT LEAST 3 ALKENOXY GROUPS, AND 0.2 TO ABOUT 0.5 PARTS BY WEIGHT OF AN ALKALI METAL SALT OF A FORMALDEHYDEALKYLNAPHTHALENE SULFONIC ACID CONDENSATION PRODUCT.