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Publication numberUS3350319 A
Publication typeGrant
Publication dateOct 31, 1967
Filing dateJan 18, 1966
Priority dateJan 18, 1966
Publication numberUS 3350319 A, US 3350319A, US-A-3350319, US3350319 A, US3350319A
InventorsSchonfeldt Nikolaus Augustin
Original AssigneeMo Och Domsjoe Ab
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Aqueous detergent-inorganic builder concentrates
US 3350319 A
Abstract  available in
Images(6)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent ()fifice 3,350,319 AQUEOUS DETERGENT-INORGANIC BUILDER CONCENTRATES Nikolaus Augustin Schonfeldt, Molndal, Sweden, assignor to M Qch Domsjo Aktiebolag, Ornskoldsvik, Sweden, a limited company of Sweden No Drawing. Filed Jan. 18, 1966, Ser. No. 521,437 16 Claims. (Cl. 252-138) This application is a continuation-in-part of application Ser. No. 214,505, filed Aug. 3, 1962, which application has been now abandoned.

This invention relates to clear aqueous polyoxyalkylene ether detergent-inorganic builder concentrates.

Polyoxyalkylene glycol ethers are now Widely used as wetting agents and detergents, in which use they are characterized by a rather limited solubility in water. These compounds are valuable because of their good surfaceactive properties, combined with their nonionic character, but they have the disadvantage, when in the form of aqueous concentrates, of being precipitated in the presence of even small amounts of electrolytes or inorganic builders such as salts or alkali. Also, when aqueous solutions or aqueous concentrates of these ethers are heated, the ethers precipitate with the loss of water. These disadvantages considerably limit the field of use of these compounds, and they have not come into as wide a use as would be expected, despite their advantageous failure to form curds when in use in hard water, and their resistance to decomposition in the presence of acids and alkali. As the result of their precipitation in hot aqueous solutions or in the presence of certain inorganic builders, they cannot be employed in high concentrations in built washing and detergent compositions. They cannot, for example, be employed in conjunction with caustic alkali solutions such as are used for cleaning purposes, as for instance in the cleaning of chemical equipment or barrels, because they are salted out at such concentrations of caustic.

The polyoxyalkylene glycol ethers having long alkylene oxide chains have a greater solubility in water than those having short chains, but this improvement in solubility is usually not sufiicient to overcome the salting out effect. Moreover, the extension of the polyoxyalkylene chain upsets the hydrophilic-lipophilic balance in the ether, and reduces the efiiciency of the ether as a detergent or wetting agent. Solvents such as low molecular weight aliphatic alcohols and the like can be employed in conjunction with compositions containing these polyoxyalkylene glycol ethers, but these do not have surface-active properties, and hence serve merely as diluents for the product, increasing the manufacturing cost without improving the functional properties.

Heavy liquid detergents, as is well known, are based on a combination of a detergent and an inorganic builder which considerably enhances the ability of the detergent to cut into grease and heavy dirt of like character, and may contain additional ingredients to aid in preventing redeposition of the dirt which is taken up in the washing solution. Such detergents are normally available in powdered form, because of the great difliculty of formulating them as liquids, and it is only recently that heavy duty liquid detergents in concentrated form have been made available. The problem in such liquid detergent formulations is the compatibility of the various components, which prevents the formation of clear solutions that remain clear under all atmospheric temperature conditions which might be encountered. The special problem of compatibility of inorganic builders or electrolytes with polyoxyalkylene glycol ethers has heretofore made it impossible to employ the latter components in heavy duty liquid detergents of this type.

I 3,359,319 Patented Oct. 31, 1967 Light duty liquid detergents have been formulated in a variety of ways. Such liquids do not contain inorganic builders. Typical light duty liquid compositions are disclosed in U.S. Patent No. 2,874,126 to Epstein et al., dated Feb. 17, 1959, No. 2,978,416 to Fein et al., dated April 4, 1961, No. 3,000,832 to Kooijman, dated Sept. 19, 1961, and No. 2,913,416 to Fineman et al., dated Nov. 17, 1959.

U.S. Patent No. 2,877,186 to Krumrei, dated Mar. 10, 1959, discloses heavy duty detergents containing an anionic synthetic detergent, a phosphate builder, and a sodium silicate builder, and resolves the problem of salting-out of the anionic detergent from such compositions by incorporating a water-soluble alkali metal salt of an alkyl glyceryl ether sulfonate. These components in addition inhibit the redeposition of soil from washing solutions of such detergents. These compositions do not contain polyoxyalkylene glycol ethers.

No. 3,101,324 to Wixon, dated Aug. 20, 1963, describes a heavy duty detergent concentrate comprising an alkali metal higher alkyl aryl sulfonate detergent and a potassium polyphosphate, with a saturated monohydric alcohol, such as ethanol, propanol, or isopropanol, as one solubi'lizer, together with an alkali metal sulfonate salt having a lower alkyl group, up to about six carbon atoms, such as aryl sulfonates containing such groups, as a supplemental solubilizing agent, in promoting the compatibility of these ingredients. These formulations also do not include polyoxyalkylene ethers.

In accordance with the invention, it has been determined that water-soluble sulfonated and sulfated alkyl phenols in small amounts can inhibit the precipitation or salting-out of polyoxyalkylene glycol ethers from aqueous concentrates in the presence of inorganic builders such as salts or alkali. The reason for this effect is not understood, but it appears that it may be due to solubilization of the polyoxyalkylene glycol ether in some Way.

In accordance with the instant invention, a clear aqueous detergent-inorganic builder concentrate is provided consisting essentially of an inorganic builder, a polyoxyalkylene glycol ether precipitatable from the concentrate in the presence of the inorganic builder, an alkylphenol having an S0 group, in an amount sufiicient to prevent precipitation of the polyoxyalkylene glycol ether from the aqueous concentrate, and Water.

The alkyl phenols effective in this way have at least one-S0 group, either in the phenol ring or in the alkyl side chain. In the former case, the S0 group is present as a sulfonate group, attached to a carbon atom of the ring, and in the latter case, the 50;, group is present in the form of a sulfate ester of the corresponding alkylol group, attached thereto through the oxygen atom of the alkylol group. Thus, the alkyl phenols employed in accordance with the invention will have the structure:

( 1)! (SOHBDn This generic structure includes both of the following two specific structures.

(ii) H) p In these structure, R is a straight or branched chain alkyl group having from about six to about twelve carbon atoms, m represents the number of alkyl groups on the phenol ring, SO M represents the sulfonate group, R OSO M represents the sulfated alkyl group, n the number of such groups, p the number of hydroxyl groups, and R is a straight or branched chain alkylene group having from six to twelve carbon atoms.

The total of m, n, and p in each structure is six, and each is an integer ranging from 1 to 4.

M is a monovalent cation such as hydrogen, an inorganic cation such as sodium, potassium or ammonium or an organic cation such as a highly basic amine, for ex ample, triethanolamine, diethanolamine, monoethanolamine or tributylamine.

Additional organic sulfonate and sulfates can be employed with the alkyl phenol sulfonates and sulfates. Such sulfonates and sulfates do not themselves have the property of inhibiting precipitation of the polyoxyalkylene glycol ether in the presence of electrolytes, but they enhance the action of the alkylphenol sulfonate and sulfate in such inhibition. These compounds are therefore referred to a supplementary organic sulfonates and sulfates, and among the compounds thus included as a class are the alkyl sulfates, alkylaryl sufonates, alkyl sulfonates, aryl sulfonates, and sulfated fatty oils and acids. Also useful are the sulfated derivatives of the polyoxyalkylene glycol ethers whose precipitation is inhibited in accordance with the invention, and the amidoalkane sulfonates.

The alkyl sulfonates are defined by the structure RSO M where R represents a long chain saturated or unsaturated aliphatic group having from eight to eighteen carbon atoms, such as the mixed sodium alkane sulfonates derived from petroleum, sodium decane sulfonate, sodium dodecane sulfonate and sodium octadecane sulfonate.

The alkyl sulfates are the sulfated long chain alkyl alcohols having the formula ROSO M such as sodium lauryl sulfate, sodium palmityl sulfate, sodium octadecyl sulfate, sodium decyl sulfate and sodium octyl sulfate.

The aryl sulfonates and alkyl aryl sulfonates contain an aromatic ring having sulfonate groups attached to one or more of the ring carbon atoms. The alkyl aryl sulfonates have in addition an alkyl group having from one to sixteen carbon atoms. Both are defined by the chemical structure:

where R can be hydrogen or an alkyl group having from one to sixteen carbon atoms and m is the number of such groups and has a value from one to about four. Typical are sodium benzene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate, sodium dodecyl benzene sulfonate, and sodium lauryl benzene sulfonate. One group of these compounds, the sodium polypropylene benzene sulfonates, is described in United States Patent No. 2,477,383 to Lewis. Also useful are the sodium keryl benzene sulfonates.

The amidoalkane sulfonates are characterized by the structure of an amide, of which the nitrogen is attached through an alkylene group to the sulfonate radical, and have the structure:

a-co-N- onansoaM n is a small whole number from 1 to about 5, preferably 2 or 3, 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 palmitic methyl tauride, sodium myristic methyl tauride, sodium palmitic-stearic methyl tauride and sodium palmitic methyl amidopropane sulfonate are typical examples thereof.

The sulfonated acids and esters of organic acids also are useful, particularly the sulfuric acid esters of aliphatic acids of ten to eighteen carbon atoms, particularly oleic acid, tall oil acids, turkey red oil acids, and acids derived by the reduction of the fatty acids derived from coconut oil, palm oil, sperm oil and the like long-chain fatty acids, sulfonated castor oil, esters and ethers of isethionic acid (beta hydroxyethylene sulfuric acid) and the esters and ethers of the acid sulfate of isethionic acid, i.e., ethionic acid, such as for example lauroylcycloimidiniuml-ethyoxy-ethionic acid-Z-ethionic acid, long-chain fatty acid esters and long-chain alkyl ethers of 2,3-dihydroxypropane sulfonic acid, and sulfuric acid esters of monoglycerides and glycerol monoethers.

The sulfated polyoxyalkylene glycol ethers have the- 0 pounds are in every respect the same as the polyoxyalkylene glycol ethers of the invention, with the addition of the sulfate group OSO M.

In all of the above formulae, it will be understood that M represents hydrogen, or a monovalent inorganic cation such as sodium, potassium or ammonium, or a monovalent organic cation such as a highly basic amine, for example triethanolamine, diethanolamine, monoethanolamine or tributylamine.

The polyoxyalkylene glycol ethers which are held in solution in accordance with the invention can be defined by the following general formula:

wherein R is a straight or branched chain saturated or unsaturated hydrocarbon group having from about eight to about twenty-four carbon atoms, or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from about eight to about twelve carbon atoms attached to the aryl nucleus, the aralkyl group being attached to A through the aryl nucleus. A is selected from the group consisting of ethereal oxygen and sulfur, amino, carboxylic ester and thio carboxylic ester groups. Y represents a straight or branched chain alkylene group having from two to four carbon atoms and x is a number from about 8 to about 20.

R can for example be a straight or branched chain alkyl group, such as octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl; an alkylene group, such as hexenyl, dodecenyl, oleyl, linoleyl, ricinoleyl, or linolenyl; or an alkyl aryl group, such as octyl phenyl, nonyl phenyl, decyl phenyl, dodecyl phenyl, or isooctyl phenyl. Y can be ethylene, 1 methylethylene, 1,2-diethylethylene,1,1diethylmethylene, 1,3-propylene and l-butylene.

When R is alkyl, it will be evident that the polyovyalkylene glycol ether can be regarded as derived from an alcohol, mercaptan, amine, or an oxy or fatty acid of high molecular Weight, by condensation with an alkylene oxide, for example, ethylene oxide, 1,2-propylene oxide, 2,3-butylene oxide or 1,2-butylene oxide. Typical of this type of product are the condensation products of oleyl, stearyl, lauryl, palmityl, and myristic alcohol, mercaptan or amine or oleic, lauric, palmitic, myristic or stearic acid, with from 8 to 1 moles of ethylene oxide such as Emulfor-ON, Nonic 218, Sterox SE and Sterox SK. Typical alkyl esters are Renex (polyoxyethylene ester of tall oil acids) and Neutronyx 330, and 331, higher fatty acid of polyethylene glycol.

When R is aralkyl the polyoxyalkylene glycol ether can be derived from an alkyl phenol or thiophenol.

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

Where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from about eight to about eighteen carbon atoms, A is oxygen or sulfur, and x is a number from 8 to 20. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from 8 to 17 moles of ethylene oxide, available commercially under the tradenames Igepal CA and CO, NIW, Antarox A 400, Triton X-100, Neutronyx 600 and Tergitol NFX.

The aqueous concentrate of the invention will usually contain polyphosphates as the principal inorganic builder. Other builders which can be used with or without the polyphosphates, include alkali metal and alkaline earth metal sulfates, chlorides, silicates, hydroxides, borates, carbonates, metaphosphates and orthophosphates, such as sodium silicate, magnesium sulfate, sodium carbonate, sodium sulfate, sodium hydroxide, potassium hydroxide, trisodium orthophosphate, potassium carbonate, sodium dihydrogen orthophosphate, sodium metaphosphate, calcium orthophosphate, calcium sulfate, calcium chloride, sodium chloride, sodium borate, potassium metaphosphate, and magnesium chloride. The builders should be water soluble.

As the polyphosphate, any of the alkali metal polyphosphates as a class can be employed, such as the tripolyphosphates including pentasodium tripolyphosphate, and pentapotassium tripolyphosphate, the pyrophosphates such as tetrasodium pyrophosphate and tetra-potassium pyrophos-phate, the hexametaphosphates, such as sodium hexametaphosphate and potassium hexametaphosphate, and the tetrapolyphos-phates such as hex-asodium tetrapolyphosphate and hexapotassium tetrapolyphosphate.

In addition to, or instead of the above-mentioned builder materials, organic materials such as starch, polyethylene glycols, polyvinyl alcohol and salts of carboxymethylcellulose may be used as builders. Between about 0.1 and 1% of an alkali metal carboxymethyl cellulose increases detergency and sudsing.

For use in hard water, or in Water of high salt content that might produce stains, such as iron salts, the inorganic builder can include a chelating agent or scquestrant such as a salt of an aminoacetic acid compound. Only small amounts are needed. Amounts within the range from about 0.015 to about 5% by weight of the total aqueous concentrate are usually sufficient, but more can of course be used, if salt contents so require.

The aminoacetic acid compounds that can be used with the inorganic builders herein are defined by the following formula:

wherein R is selected from the group consisting of CHR CHR OH, v

CHRoCHR7OH CHRgC O 0 R10, CH2CH2N CHBBCHR'IOH CHRaCOORm CHZCHPN CHzCHzN 01112601131011 cnmco 01m and a polymeric chain of 11 units of [Grimm-N :ICHRsCOOR: HRaOOORio n where n is an integer from 1 to 7, and a polymeric chain of n units of l: CHzCH2-N CHRsCOORs CHR3CH2OH u where n is an integer from 1 to 7; and wherein R R R R R and R are selected from the group consisting of hydrogen, alkyl groups of from one to three carbon atoms; and at least one of R R R and R are selected from the group consisting of hydrogen, ammonium and alkali metals, such as sodium, potassium and lithium, and the remainder of R R R and R are selected from the group consisting of hydrogen, ammonium and alkali metals, such as sodium, potassium and lithium, aliphatic, cycloaliphatic, aromatic and heterocyclic groups, having from one to about eighteen carbon atoms. R R R R R and R can, for example, be methyl, ethyl, propyl, isopropyl, CH OH, CH CH OH, CH CH CH OH and CHzCHOHzOH R R R and R can be for example, straight and branched chain alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, lauryl, decyl, nonyl, octadecyl, isopropyl, isobutyl, tertiary butyl; cycloalkyl groups such as cyclo propyl, cyclohexyl, cyclopentyl and hexahydrotolyl; aryl groups such as phenyl and naphthyl; aralkyl and alkaryl groups such as tolyl, xylyl and benzyl. These may include inert substituents such as hydroxyl, amido, mercapto,

' thio and halogen groups, among others.

R and R may be taken together or With R to form an N-heterocyclic ring, as with an alkylene group, for example, ethylene and propylene, or an arylene group, such as phenylene or Exemplary of the aminoacetic acid compounds which can be used are ethylene diamine tetraacetic acid, the mono, di-, triand tetra-sodium, potassium, lithium and ammonium salts of ethylene diamine tetraacetic acid; the tri-sodium, potassium, lithium, or ammonium salts of monomethyl, monoethyl, monopropyl, monoisopropyl, monobutyl, monopentyl, monohexyl, monobenzyl, monoamyl, monoallyl, monoethylene and monophenylene esters of ethylene diamine tetraacetic acid; as well as nitrolotriacetic (triglycollamic), hydroxyethylethylenediamine triacetic, hydroxyethyliminodiacetic, diethylene triamine pentaacetic, and tetraethylenepentamineheptaacetic acids, the mono-, dior tri-s0dium, potassium, lithium, and ammonium salts of such acids and the disodium, potassium, lithium or ammonium salts of the methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, benzyl, amyl, and allyl monoesters of such acids.

When employed with such inorganic builders, the polyoxyalkylene glycol ethers are not precipitated from the aqueous concentrate or in the washing solution, as might be expected, due to the presence of the alkyl phenol sulfate or sulfonate.

The aqueous detergent-inorganic builder concentrate of the invention contains from about 3.5% to about 55% and preferably from about 28 to about 50% by Weight total detergent-inorganic builder. The detergent contains the polyoxyalkylene glycol ether as the active detergent in an amount from about 1 to about 40% and preferably from about 5 to about 20% by Weight. An inorganic builder that is neutral or of low alkalinity is present in the aqueous concentrate in an amount from about 0.015

to about 50% and preferably from about 20 to about 35% by weight. A strongly alkaline builder would be used in a nondeleterious amount; 2% is a suitable amount.

It is to be understood that the polyoxyalkylene glycol ether can be supplemented with, if desired, other detergents of the anionic or nonionic type.

Quite small amounts of the alkyl phenol sulfate or sulfonate in the concentrate are effective to prevent precipitation of the polyoxyalkylene glycol ether in such concentrates. As little as 0.5% by weight of the concentrate of the alkyl phenol is sufficient in most instances. However, the amount of alkyl phenol sulfate or sulfonate is proportionate to the amount or concentration of polyoxyalkylene glycol ether in the aqueous concentrate, and to the amount of inorganic builder that is present, and at high concentrations of inorganic builder compound, amounts considerably higher than this may be necessary. In most instances, amounts within the range from 0.5 to 10% of the concentrate are adequate. As much as 20% by weight of the phenol can be employed without deleterious effects upon the desired wetting or detergent properties of the polyoxyalkylene glycol ether.

The aqueous concentrates of the invention incorporat ing a polyoxyalkylene ether and a sulfonated or sulfated alkyl phenol are heavy duty liquid deteregnts, due to their inorganic builder content. They are accordingly useful in any of the ways in which heavy duty detergents are used, and form washing solutions upon simple dilution with water to a washing concentration. They can, for instance, be added to detergent compositions or to their washing solutions.

Such compositions are prepared by conventional methods, as by blending the ingredients thereof in an aqueous concentrate or slurry.

The following examples in the opinion of the inventor represent preferred embodiments of his invention.

Example I A clear aqueous detergent-inorganic builder concentrate was prepared containing 18% by weight of sodium metasilicate pentahydrate, 5% by weight of a polyoxyalkylene glycol ether obtained by condensation of 12 moles of ethylene oxide and 1 mole of nonylphenol, 4.8% by weight of the sodium salt of sulfonated nonylphenol, and the rest water. This concentrate could be heated to boiling but did not show cloudiness at this temperature.

In contrast, a concentrate prepared exactly as described but without the sodium nonylphenol sulfonate did not produce a clear concentrate at room temperature.

Example II A clear aqueous detergent-inorganic builder concentrate was prepared from 7.5% by weight of the sodium salt of sulfonated nonylphenol, 18% by weight of sodium metasilicate pentahydrate, by weight of the condensation product of 12 moles of ethylene oxide and 1 mole of nonylphenol, and the rest water. The cloud point of this concentrate was 55 C.

A similar concentrate containing 6.5% instead of 7.5% of the sodium salt of sulfonated nonylphenol produced a concentrate which was clear at room temperature but whose cloud point was 40 C., thus showing the efiect of the amount of sodium nonylphenol sulfonate on the precipitation of the polyoxyethylene nonylphenol ether.

Example III A clear aqueous detergent-inorganic builder concentrate was prepared containing 15% by weight of potassium pyrophosphate, 10% by weight of sodium metasilicate pentahydrate, 3% by weight of the condensation product of 12 moles of ethylene oxide and 1 mole of nonylphenol, and 6% by weight of the sodium salt of sulfonated nonylphenol, the remainder being water. This concentrate showed no cloudiness, eve nwhen heated at 100 C.

8 Example IV A clear aqueous detergent-inorganic builder concentrate was prepared containing 18% by weight of sodium metasilicate pentahydrate, 5% by weight of the condensation product of 10 moles of ethylene oxide with 1 mole of octylphenol, 5% by weight of the sodium salt of sulfonated octylphenol, and the rest water. This concentrate showed a cloud point of 40 C.

Example V A clear aqueous detergent-inorganic builder concentrate was prepared containing 18% by weight of sodium metasilicate pentahydrate, 5% by weight of the condensation product of 20 moles of ethylene oxide with 1 mole of mixed oleyl and cetyl alcohols, 8% by weight of the sodium salt of sulfonated octylphenol, and the rest water. The cloud point of this concentrate was 60 C.

Example VI A clear aqueous detergent-inorganic builder concentrate was prepared containing 18% by weight of sodium metasilicate pentahydrate, 6.5% by weight of the condensation product of 15 moles of ethylene oxide and 1 mole of tall oil acid, 4% by weight of the sodium salt of sulfonated nonylphenol, and the rest water. This concentrate did not become cloudy even when heated at 100 C.

Example VII A clear aqueous detergent-inorganic builder concentrate was prepared containing 18% by weight of sodium metasilicate pentahydrate, 6.5% by weight of the condensation product of 7 moles of ethylene oxide and 1 mole of lauryl alcohol, 4% by weight of the potassium salt of sulfonated dodecylphenol, and the rest water. The cloud point of this concentrate was found to be 55 C.

Example VIII An aqueous concentrate was prepared containing 2% sodium hydroxide (pellets) and 1% by weight of the condensation product of 20 moles of ethylene oxide and one mole of mixed oleyl and cetyl alcohol. This concentrate when heated to 100 C. became cloudy. To the concentrate was then added 0.5% by weight of the sodium salt of sulfonated nonylphenol. The concentrate became clear, and continued heating at 100 C. failed to produce any cloudiness.

Example IX A clear aqueous detergent-inorganic builder concentrate was prepared containing 18% by weight of sodium metasilicate pentahydrate, 4% by weight of the sodium salt of sulfonated nonylphenol, 6.5% by weight of the condensation product of 12 moles of ethylene oxide and one mole of nonylphenol, and the rest water. This concentrate had a cloud point of 51 C. To the concentrate was added 13% by weight of the sodium salt of toluene sulfonic acid. The resulting concentrate was then heated at 100 C. but did not become cloudy. Similar results were obtained employing sodium xylene sulfonate, sodium benzene sulfonate, sodium castor oil sulfate, and sodium lauryl sulfate, in corresponding amounts.

Example X The following is an example of a detergent formulation incorporating the concentrate of the invention.

Percent Condensation product of 12 moles of ethylene oxide Sodium sulfate 14.5

Having regard to the foregoing disclosure, the following is claimed as the inventive and patentable embodiments thereof:

1. A clear aqueous detergent-inorganic builder concentrate consisting essentially of from about 3.5% to about 55% by weight total detergent-inorganic builder consisting essentially of an inorganic builder selected from the group consisting of neutral builders and builders of low alkalinity, in an amount within the range from about 0.015 to about 50% by weight of the concentrate, and builders of high alkalinity in an amount within the range from about 0.015 to about 2% by weight of the concentrate from about 1 to about 40% by weight of a polyoxyalkylene glycol ether precipitatable from the concentrate in the presence of the inorganic builder, and having the formula:

wherein R is a hydrocarbon gnoup having from about eight to about twenty-four carbon atoms, selected from the group consisting of alkyl and aralkyl hydrocarbon groups, A is selected from the group consisting of ethereal oxygen and sulfur; amino; carboxylic ester; and thiocarboxylic ester groups, Y is an alkylene group having from about two to about four carbon atoms, and x is a number within the range from about 8 to about 20; an alkylphenol having an S group, the alkyl group having from about six to about twelve carbon atoms, and the S0 group being present as a member selected from the group consisting of sulfonate groups attached to a carbon atom of the phenol ring, and sulfate ester groups attached to an alkyl group attached to the phenol ring and having from about six to about twelve carbon atoms, in an amount within the range from about 0.5 to about 20% by weight suflicient to prevent precipitation of the polyoxyalkylene glycol ether and water.

2. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 which contains a total detergent-inorganic builder concentration of at least about 28% by weight.

3. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the alkylphenol having an S0 group is an alkylphenol sulfonate.

4. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the alkylphenol having an S0 group is an alkylphenol sulfate.

5. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the polyoxyalkylene glycol ether is a condensation product of ethylene oxide with an alkylphenol.

6. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the polyoxyalkylene glycol ether is a condensation product of an aliphatic alcohol and ethylene oxide.

7. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 comprising in addition an alkyl benzene sulfonate having an alkyl group of from one to sixteen carbon atoms in an amount to enhance the action of the alkylphenol in preventing precipitation of the polyoxyalkylene glycol ether.

8. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 7 comprising in addition a sulfuric acid ester of a fatty acid having from ten to eighteen carbon atoms in an amount to enhance the action of the alkylphenol in preventing precipitation of the polyoxyalkylene glycol ether.

9. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 comprising in addition a benzene sulfonate in an amount to enhance the action of the alkylphenol in preventing precipitation of the polyoxyalkylene glycol ether.

10. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 comprising in addition a sulfated fatty alcohol having from eight to eighteen carbon atoms in an amount to enhance the action of the alkylphenol in preventing precipitation of the polyoxyalkylene glycol ether.

11. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the inorganic builder is sodium metasilicate pentahydrate.

12. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the inorganic builder is a mixture of potassium pyrophosphate and sodium metasilicate pentahydrate.

13. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the inorganic builder is sodium hydroxide used in an amount of about 2% by weight of the concentrate.

14. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the inorganic builder is a mixture of pentasodium tripolyphosphate, sodium silicate, sodium carbonate, and sodium sulfate.

15. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 1 in which the concentrate also contains an aminoacetic acid compound chelating agent.

16. A clear aqueous detergent-inorganic builder concentrate in accordance with claim 14 in which the inorganic builder includes sodium carboxymethyl hydroxyethylcellulose.

References Cited UNITED STATES PATENTS 2,249,757 7/1941 Flett 252161 X 2,267,725 12/ 1941 Flett. 2,693,479 11/1954 Ross. 2,874,126 2/ 1959 Epstein et al 25216l 2,978,416 4/1961 Fein et al. 252-161 3,000,832 9/1961 Kooyman et al. 252--161 3,144,412 8/1964 Inamorato 252--138 LEON D. ROSDOL, Primary Examiner.

J. T. FEDIGAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,350,319 October 31, 1967 Nikolaus Augustin Schonfeldt It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, .line 7, for "structure" read structures column 4, line 60, for "poly0vy" read polyoxyline 69, for "8 to 1" read 8 to 17 column 5, lines 72 to 75, the right-hand formula should appear as shown below instead of as in' the patent:

CHR COOR CH CH N CHR COOR column 7, line 26, for "deteregnts" read detergents line 75, for "eve nwhen" read even when column 10,

lines 41 and 42, for inorganic builder includes" read concentrate also contains Signed and sealed this 24th day of December 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR.

EDWARD J. BRENNER Attesting Officer Commissioner of Patents

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US2874126 *Feb 8, 1956Feb 17, 1959Emulsol Chemical CorpHair shampoo
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US3652422 *Aug 5, 1970Mar 28, 1972Agnes M HughesCleaner for wigs
US3874927 *Aug 16, 1973Apr 1, 1975Caw Ind IncMethod of washing soiled culinary articles
US3893943 *Dec 20, 1972Jul 8, 1975Caw Ind IncNovel catalyst and process for preparing the same
US3915738 *Aug 20, 1973Oct 28, 1975Caw IndMethod of cleaning glass windows and mirrors
US3923456 *Aug 20, 1973Dec 2, 1975Caw Ind IncMethod of washing textile materials with surface-active agent and catalyst-containing micelles
US4024078 *Mar 31, 1975May 17, 1977The Procter & Gamble CompanyLiquid detergent composition
US4067712 *Dec 10, 1976Jan 10, 1978Caw Industries, Inc.Method of growing plants in soil
US4067713 *Dec 10, 1976Jan 10, 1978Caw Industries, Inc.Method of improving the fertility of soil and the soil thus prepared
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Classifications
U.S. Classification510/424, 510/425, 510/490, 510/423
International ClassificationC11D3/00, C11D17/00, C11D1/02, C11D1/72, C11D1/22
Cooperative ClassificationC11D1/22, C11D1/72, C11D3/08, C11D3/10
European ClassificationC11D1/72, C11D1/22, C11D3/08, C11D3/10