US2584056A - Preparation of stable, solid, watersoluble, surface-active compositions containing urea and a quaternary ammonium compound - Google Patents
Preparation of stable, solid, watersoluble, surface-active compositions containing urea and a quaternary ammonium compound Download PDFInfo
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- US2584056A US2584056A US13084A US1308448A US2584056A US 2584056 A US2584056 A US 2584056A US 13084 A US13084 A US 13084A US 1308448 A US1308448 A US 1308448A US 2584056 A US2584056 A US 2584056A
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- quaternary ammonium
- urea
- ammonium compound
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0052—Cast detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
- C11D3/323—Amides; Substituted amides urea or derivatives thereof
Definitions
- This invention relates to improvements in granular, water-soluble, surface-active compositions containing effective proportions of watersoluble, surface-active quaternary ammonium compounds.
- water-soluble, surfaceactive quaternary ammonium compounds are known.
- these compounds are substituted ammonium salts in which all four of the hydrogens of the ammonium radical are substituted by organic radicals at least one of which contains a chain of eight to sixteen carbon atoms.
- organic radicals at least one of which contains a chain of eight to sixteen carbon atoms.
- the cost of the special raw materials required makes the cost of such compounds prohibitive in terms of commercial application.
- such compounds may be described as solids, they frequently exhibit an oiliness or greasiness which causes them to agglomerate rapidly when originally flaked or granulated.
- cocoanut oil is a low cost raw material for the production of a particularly valuable group of such quaternary ammonium compounds, the distribution in length of the carbon chains of the constituent fatty acids being such that the quaternary ammonium compounds formed by conversion of the mixed fatty acids to amines followed by methylation and reaction with benzyl chloride are unusually effective surface-active and bactericidal agents.
- these compounds are normally either an oily liquid or a greasy solid.
- water-soluble, surface-active quaternary ammonium compounds include a lauryl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium bromide, heptadecyl trimethyl ammonium chloride, lauryl pyridinium chloride, octadecyl pyridinium bromide, decyl chlorobenzyl diethyl ammonium chloride, undecyl benzyl diethyl ammonium bromide, and the like.
- quaternary ammonium compounds are effective in dilutions of as little as 1 s%, 100% or even /1ono%. for example in sanitizing vessels and utensils used in connect on with food and drink, and are commonly used in aqueous solutions of such concentrations. For this reason, and the further reasonthat they are conveniently prepared in aqueous solution, these compounds are commonly manufactured and distributed as aqueous solutions containing from about to about of the quaternary ammonium compound.
- any such solid product must be of the same order of solubility as the quaternary ammonium compound itself if its practical value is to be maintained.
- This invention relates particularly to improvements in granular, water-soluble, surface-active compositions containing effective proportions of a water-soluble, surface-active quaternary ammonium compound and urea.
- a mixture of urea in major proportion and such quaternary ammonium compounds in minor but effective proportion can be fused to produce a homogeneous melt, but the temperature required to obtain a homogeneous fusion from such simple mixtures usually exceeds 110-115 C. and such temperatures initiate the curio'i s decomposition previously mentioned.
- the decomposition products include ammon a and more odoriferous reaction products and the decomposition reaction,
- mixtures of urea comprising not more than about 80% by weight on the total of urea, about 12%-22% by weight on the urea of such water-soluble. surface-active quaternary ammonium compounds and about ift-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate can be fused to produce a homogeneous melt at temperatures above normal atmospheric temperature but not exceeding about 110 0., usually at about 95100 C.. and that at such temperatures the decomposition previously mentioned does not occur. Some negligible decomposition may occur but it does not continue after the melt is cooled and solidified.
- the granular product of our invention com prises urea, but not more than about 80% by weight on the total product of urea, about 12 /;-22% by weight on the urea of a water-soluble. surface-active quaternary ammonium compound and about 4%-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate.
- This product may contain as much as by weight on the total of urea, quaternary ammonium compound and sodium acetate of water.
- the quaternary ammonium compound may be supplied to the fusion operation. for example, as an aqueous solution containing 50% by weight of the quaternary ammonium compound.
- the direct product of such fusions will, within the stated limits, be stable solids.
- the quaternary ammonium compound may be dehydrated. partially or to substantially anhydrous condition, before being supplied to the fusion operation.
- the melt produced by fusing a concentrated aqueous solution of the quaternary ammonium compound with the urea and sodium acetate may be dehydrated after solidification.
- temperatures involving decomosition are to be avoided.
- One particularly advantageous product of our invention comprises urea, but not more than about 80%, by weight on the total product of urea, about 12%22% by weight on the urea of a water-soluble, surfaceactive uaternary ammonium compound, about ice-6.5% by weight on the total of urea and quaternary ammonium compound of sodium aceta te and about 8.5 %-14% by weight on the total of urea, quaternary ammonium compound and sodium acetate of water.
- the proportions stated are important. If the proportion of urea is increased, higher temperatures are required to produce a clear, homogeneous melt. If the proportion of quaternary ammonium compound, or that of water, is increased, the products do not solidify satisfactorily, in particular the products do not flake or granulate readily. If the proportion of sodium acetate is decreased, the fusion temperature required tends to increase and the products do not solidify satisfactorily, in particular the products do not flake or granulate readily. If the proportion of sodium acetate is increased, the products become hygroscopic and tend to deliquesce and to-agglomerate.
- Example I A water-soluble, surf ace-active quaternary ammonium compound was derived from cocoanut -oil fatty acids, by conventional processing, by
- Example II 20 parts of the same solution of the quaternary ammonium compound, 75 parts of urea and 5 parts of anhydrous sodium acetate were fused to a clear melt at a temperature of -100 C. in a stainless steel oil jacketed pan.
- the film on the roll had a, temperature of about 21 C. as it was removed from the roll and was about 0.040" thick.
- About 33 lbs. of the flake product were recovered per square foot of roll surface per hour. The product was odorless and. remained granular on prolonged exposure to air at 80 F. with a relative humidity of 68%.
- Other materials may be compounded with the product of our invention.
- other surface-active materials such as sodium lauryl sulfate, potassium mono-naphthalene sulfonate and alkyl aryl polyether alcohols, and alkylol amides, sodium carbonate, sodium bicarbonate, normal and acid orthophosphates, polyphosphates such as triphosphate and tetraphosphate.
- polymetaphosphates, pyrophosphates and borates including borax may be included in the composition.
- the products of our invention may also include, for example, 2%-5% by weight on the total of urea and quaternary ammonium compound of glacial acetic acid, concentrated sulfuric acid or syrupy phosphoric acid.
- the process of our invention is, in a broader aspect, applicable to the production of homogeneous, solid products comprising urea and such water-soluble, surface-active quaternary ammonium compounds in cast shapes, for example, rather than in granular form. If the product is not to be granular, the proportions of quaternary ammonium compound on the urea may be varied over wider limits than those previously stated for granular products. For the production of such non-granular solid products, the
- proportion of the quaternary ammonium compound may range from 3% to 35% by weight on the urea.
- a method of compounding stable, solid, water-soluble, surface-active compositions which comprises fusing together urea, in major proportion but not more than 80% by weight on the total composition of urea, and 12 %-22% by weight on the urea
- a water-soluble, surfaceactive quaternary ammonium salt in which all four hydrogens ofthe ammonium radical are substituted by organic radicals at least one of which contains a chain of 8 to 16 carbon atoms and 4%-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate at a temperature above normal atmospheric temperature and not exceeding 110 C. and cooling and solidifying the fusion.
- a method of compounding stable, solid, water-soluble, surface-active compositions which comprises fusing together urea, in major propor- 6 tion but not more than 80% by weight on the total composition of urea, and 3%-35% by weight on the urea of a water-soluble, surface-active quaternary ammonium salt in which all four hydrogens of the ammonium-radical are substituted by organic radicals at least one of which contains a chain of 8 to 16 carbon atoms and 4%-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate at a temperature above normal atmospheric temperature and not exceeding 110 C. and cooling and solidifying the fusion.
Description
Patented Jan. 29, 1952 PREPARATION OF STABLE, SOLID, WATER- SOLUBLE,
SURFACE-ACTIVE COMPOSI- TIONS CONTAINING UREA AND A QUA-. TERNARY AMMONIUM COMPOUND Edward (J. Soule and William H.
Sheltmirc,
Niagara Falls, N. assignors to Mathicson Chemical Corporation, a corporation of Virginia No Drawing. Application March 4, 1948, Serial No. 13,084
2 Claims. 1 This invention relates to improvements in granular, water-soluble, surface-active compositions containing effective proportions of watersoluble, surface-active quaternary ammonium compounds.
A large number of water-soluble, surfaceactive quaternary ammonium compounds are known. In general, these compounds are substituted ammonium salts in which all four of the hydrogens of the ammonium radical are substituted by organic radicals at least one of which contains a chain of eight to sixteen carbon atoms. While it is possible to produce such watersoluble, surface-active quaternary ammonium compounds which are solids at ordinary atmospheric temperatures, the cost of the special raw materials required makes the cost of such compounds prohibitive in terms of commercial application. Further, although such compounds may be described as solids, they frequently exhibit an oiliness or greasiness which causes them to agglomerate rapidly when originally flaked or granulated.
For example, cocoanut oil is a low cost raw material for the production of a particularly valuable group of such quaternary ammonium compounds, the distribution in length of the carbon chains of the constituent fatty acids being such that the quaternary ammonium compounds formed by conversion of the mixed fatty acids to amines followed by methylation and reaction with benzyl chloride are unusually effective surface-active and bactericidal agents. However, even when substantially anhydrous, these compounds are normally either an oily liquid or a greasy solid. I
Other known water-soluble, surface-active quaternary ammonium compounds include a lauryl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium bromide, heptadecyl trimethyl ammonium chloride, lauryl pyridinium chloride, octadecyl pyridinium bromide, decyl chlorobenzyl diethyl ammonium chloride, undecyl benzyl diethyl ammonium bromide, and the like.
These quaternary ammonium compounds are effective in dilutions of as little as 1 s%, 100% or even /1ono%. for example in sanitizing vessels and utensils used in connect on with food and drink, and are commonly used in aqueous solutions of such concentrations. For this reason, and the further reasonthat they are conveniently prepared in aqueous solution, these compounds are commonly manufactured and distributed as aqueous solutions containing from about to about of the quaternary ammonium compound.
In general, the ultimate consumer would prefer, for a variety of practical reasons, to receive such quaternary ammonium compounds as a granular solid, but for the oily or greasy characteristic previously mentioned. Further, since these compounds depress the freezing point of their solutions very little, containers in which such aqueous solutions are shipped, stored or handled must be protected against freezing to avoid losses resulting from resultant container damage. Of course, any such solid product must be of the same order of solubility as the quaternary ammonium compound itself if its practical value is to be maintained.
This problem has been recognized. for some time and various expedients for dealing with it have been suggested. Probably the most effective of such proposals has been that of fusing the quaternary ammonium compound with urea.
In some proportions, reasonably dry solids canbe thus prepared but a fusion temperature upwards of about 110-115 C. is usually required to obtain a homogeneous product and such temperatures initiate a curious decomposition that continues for an indefinite period even after the fusion is solidified and cooled to ordinary atmospheric temperatures. Such decomposition not only involves substantial losses of the effective agent but also renders the product ob jectionable during handling and in use.
Proposals involving the admixture of some inorganic salt with the quaternary ammonium compound, to take up any water present, have been less than successful for the reason that the difficulties involved are not to be solved merely by removing or binding the water present. The product remains an oily or greasy product tending to agglomerate.
This invention relates particularly to improvements in granular, water-soluble, surface-active compositions containing effective proportions of a water-soluble, surface-active quaternary ammonium compound and urea.
A mixture of urea in major proportion and such quaternary ammonium compounds in minor but effective proportion can be fused to produce a homogeneous melt, but the temperature required to obtain a homogeneous fusion from such simple mixtures usually exceeds 110-115 C. and such temperatures initiate the curio'i s decomposition previously mentioned. The decomposition products include ammon a and more odoriferous reaction products and the decomposition reaction,
decomposition products for a lon -period. This I decomposition is not arrested by cooling and solidifiying the fusion or melt.
We have discovered that mixtures of urea comprising not more than about 80% by weight on the total of urea, about 12%-22% by weight on the urea of such water-soluble. surface-active quaternary ammonium compounds and about ift-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate can be fused to produce a homogeneous melt at temperatures above normal atmospheric temperature but not exceeding about 110 0., usually at about 95100 C.. and that at such temperatures the decomposition previously mentioned does not occur. Some negligible decomposition may occur but it does not continue after the melt is cooled and solidified. This surprising effect enables us to produce a stable, granular, water-soluble homogeneous surface-active composition comprising an effective proportion of the quaternary ammonium compound by producing a fusion in this manner and then cooling the fusion and either flaking or granulating the fusion as it cools and solidifies or grinding the solidified melt.
The granular product of our invention com prises urea, but not more than about 80% by weight on the total product of urea, about 12 /;-22% by weight on the urea of a water-soluble. surface-active quaternary ammonium compound and about 4%-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate. This product may contain as much as by weight on the total of urea, quaternary ammonium compound and sodium acetate of water. The quaternary ammonium compound may be supplied to the fusion operation. for example, as an aqueous solution containing 50% by weight of the quaternary ammonium compound. The direct product of such fusions will, within the stated limits, be stable solids. Or, the quaternary ammonium compound may be dehydrated. partially or to substantially anhydrous condition, before being supplied to the fusion operation. Again, the melt produced by fusing a concentrated aqueous solution of the quaternary ammonium compound with the urea and sodium acetate may be dehydrated after solidification. In any dehydration of the quaternary ammonium compounds or products containin them, temperatures involving decomosition are to be avoided. One particularly advantageous product of our invention comprises urea, but not more than about 80%, by weight on the total product of urea, about 12%22% by weight on the urea of a water-soluble, surfaceactive uaternary ammonium compound, about ice-6.5% by weight on the total of urea and quaternary ammonium compound of sodium aceta te and about 8.5 %-14% by weight on the total of urea, quaternary ammonium compound and sodium acetate of water.
The proportions stated are important. If the proportion of urea is increased, higher temperatures are required to produce a clear, homogeneous melt. If the proportion of quaternary ammonium compound, or that of water, is increased, the products do not solidify satisfactorily, in particular the products do not flake or granulate readily. If the proportion of sodium acetate is decreased, the fusion temperature required tends to increase and the products do not solidify satisfactorily, in particular the products do not flake or granulate readily. If the proportion of sodium acetate is increased, the products become hygroscopic and tend to deliquesce and to-agglomerate.
The following examples will illustrate the practice and the products of our invention. In these examples. all parts are parts by weight.
Example I A water-soluble, surf ace-active quaternary ammonium compound was derived from cocoanut -oil fatty acids, by conventional processing, by
conversion of the fatty acids to the corresponding cocoa amines, methylation to form dimethyl cocoa amines and treatment with benzyl chloride to produce cocoa dimethyl benzyl ammonium chloride in the form of a 50% by weight aqueous solution.
20 parts 01' this solution of the quaternary ammonium compound, 75 parts of urea and 5 parts of anhydrous sodium acetate were fused, with stirring, to a homogeneous melt at a temperature of 103 (3., fusion being carried out in an oil bath. This fusion was cooled, solidified and granulated and this granular product was air dried to a total water content of about 1% by weight. The product had no ammoniacal odor and it remained granular and free flowing on prolonged exposure to air at F. with a relative humidity of 68%. Glasses rinsed in a solution of the product containing 400 parts per million of the quaternary ammonium compound were free of odor.
Example II 20 parts of the same solution of the quaternary ammonium compound, 75 parts of urea and 5 parts of anhydrous sodium acetate were fused to a clear melt at a temperature of -100 C. in a stainless steel oil jacketed pan. A stainless steel roll, cooled by internal circulation of water at 10 C., dipped into the fusion in the pan, was slowly revolved while the film formed on the. roll was scraped off. The film on the roll had a, temperature of about 21 C. as it was removed from the roll and was about 0.040" thick. About 33 lbs. of the flake product were recovered per square foot of roll surface per hour. The product was odorless and. remained granular on prolonged exposure to air at 80 F. with a relative humidity of 68%.
Other materials may be compounded with the product of our invention. For example, other surface-active materials such as sodium lauryl sulfate, potassium mono-naphthalene sulfonate and alkyl aryl polyether alcohols, and alkylol amides, sodium carbonate, sodium bicarbonate, normal and acid orthophosphates, polyphosphates such as triphosphate and tetraphosphate. polymetaphosphates, pyrophosphates and borates including borax may be included in the composition.
The products of our invention may also include, for example, 2%-5% by weight on the total of urea and quaternary ammonium compound of glacial acetic acid, concentrated sulfuric acid or syrupy phosphoric acid.
The process of our invention is, in a broader aspect, applicable to the production of homogeneous, solid products comprising urea and such water-soluble, surface-active quaternary ammonium compounds in cast shapes, for example, rather than in granular form. If the product is not to be granular, the proportions of quaternary ammonium compound on the urea may be varied over wider limits than those previously stated for granular products. For the production of such non-granular solid products, the
proportion of the quaternary ammonium compound may range from 3% to 35% by weight on the urea. I
We claim:
1. A method of compounding stable, solid, water-soluble, surface-active compositions which comprises fusing together urea, in major proportion but not more than 80% by weight on the total composition of urea, and 12 %-22% by weight on the urea Of a water-soluble, surfaceactive quaternary ammonium salt in which all four hydrogens ofthe ammonium radical are substituted by organic radicals at least one of which contains a chain of 8 to 16 carbon atoms and 4%-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate at a temperature above normal atmospheric temperature and not exceeding 110 C. and cooling and solidifying the fusion. a
2. A method of compounding stable, solid, water-soluble, surface-active compositions which comprises fusing together urea, in major propor- 6 tion but not more than 80% by weight on the total composition of urea, and 3%-35% by weight on the urea of a water-soluble, surface-active quaternary ammonium salt in which all four hydrogens of the ammonium-radical are substituted by organic radicals at least one of which contains a chain of 8 to 16 carbon atoms and 4%-6.5% by weight on the total of urea and quaternary ammonium compound of sodium acetate at a temperature above normal atmospheric temperature and not exceeding 110 C. and cooling and solidifying the fusion.
' EDWARD C. SOULE.
WILLIAM H. SHELTMIRE.
REFERENCES CITED OREIGN PATENTS Country Date Great Britain Mar. 6, 1936 Number
Claims (1)
1. A METHOD OF COMPOUNDING STABLE, SOLID, WATER-SOLUBLE, SURFACE-ACTIVE COMPOSITIONS WHICH COMPRISES FUSING TOGETHER UREA IN MAJOR PROPORTION BUT NOT MORE THAN 80% BY WEIGHT ON THE TOTAL COMPOSITION OF UREA, AND 12%-22% BY WEIGHT ON THE UREA OF A WATER-SOLUBLE, SURFACEACTIVE QUATERNARY AMMONIUM SALT IN WHICH ALL FOUR HYDROGENS OF THE AMMONIUM RADICAL ARE SUBSTITUTED BY ORGANIC RADICALS AT LEAST ONE OF WHICH CONTAINS A CHAIN OF 8 TO 16 CARBON ATOMS AND 4%-6.5% BY WEIGHT ON THE TOTAL OF UREA AND QUATERNARY AMMONIUM COMPOUND OF SODIUM ACETATE AT A TEMPERATURE ABOVE NORMAL ATMOSPHERIC TEMPERATURE AND NOT EXCEEDING 110* C. AND COOLING AND SOLIFYING THE FUSION.
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| Application Number | Priority Date | Filing Date | Title |
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| US13084A US2584056A (en) | 1948-03-04 | 1948-03-04 | Preparation of stable, solid, watersoluble, surface-active compositions containing urea and a quaternary ammonium compound |
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| Application Number | Priority Date | Filing Date | Title |
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| US13084A US2584056A (en) | 1948-03-04 | 1948-03-04 | Preparation of stable, solid, watersoluble, surface-active compositions containing urea and a quaternary ammonium compound |
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| US2584056A true US2584056A (en) | 1952-01-29 |
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| US13084A Expired - Lifetime US2584056A (en) | 1948-03-04 | 1948-03-04 | Preparation of stable, solid, watersoluble, surface-active compositions containing urea and a quaternary ammonium compound |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2702774A (en) * | 1950-06-16 | 1955-02-22 | California Research Corp | Process of preparation of free flowing composition containing quaternary ammonium compound |
| US2727007A (en) * | 1950-07-08 | 1955-12-13 | Drew & Co Inc E F | Detergent-germicide composition |
| US2927900A (en) * | 1951-07-10 | 1960-03-08 | Gen Aniline & Film Corp | Solid detergent composition and process for preparation thereof |
| US3216944A (en) * | 1961-09-11 | 1965-11-09 | Procter & Gamble | Stabilized fabric softener composition |
| US3256180A (en) * | 1962-08-14 | 1966-06-14 | Little Inc A | Fabric softener compositions |
| US3351483A (en) * | 1963-02-14 | 1967-11-07 | Little Inc A | Method of softening textile fabrics |
| US4601954A (en) * | 1984-03-30 | 1986-07-22 | Servicemaster Industries, Inc. | Disinfectant formulation |
| US4624713A (en) * | 1984-11-15 | 1986-11-25 | Economics Laboratory, Inc. | Solid rinse aids and methods of warewashing utilizing solid rinse aids |
| US5674831A (en) * | 1993-12-30 | 1997-10-07 | Ecolab Inc. | Method of making urea-based solid cleaning compositions |
| US6060444A (en) * | 1993-12-30 | 2000-05-09 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
| US6124250A (en) * | 1993-12-30 | 2000-09-26 | Ecolab Inc. | Method of making highly alkaline solid cleaning compositions |
| US6164296A (en) * | 1993-12-30 | 2000-12-26 | Ecolab Inc. | Method of removing waxy/fatty soils from ware with a combination of a nonionic silicone surfactant and a nonionic surfactant |
| US6369021B1 (en) | 1999-05-07 | 2002-04-09 | Ecolab Inc. | Detergent composition and method for removing soil |
| US6673765B1 (en) | 1995-05-15 | 2004-01-06 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
| US11214763B2 (en) | 2018-01-26 | 2022-01-04 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
| US11377628B2 (en) | 2018-01-26 | 2022-07-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
| US11655436B2 (en) | 2018-01-26 | 2023-05-23 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB443795A (en) * | 1933-10-10 | 1936-03-06 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of shaped washing and cleansing agents |
-
1948
- 1948-03-04 US US13084A patent/US2584056A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB443795A (en) * | 1933-10-10 | 1936-03-06 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of shaped washing and cleansing agents |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2702774A (en) * | 1950-06-16 | 1955-02-22 | California Research Corp | Process of preparation of free flowing composition containing quaternary ammonium compound |
| US2727007A (en) * | 1950-07-08 | 1955-12-13 | Drew & Co Inc E F | Detergent-germicide composition |
| US2927900A (en) * | 1951-07-10 | 1960-03-08 | Gen Aniline & Film Corp | Solid detergent composition and process for preparation thereof |
| US3216944A (en) * | 1961-09-11 | 1965-11-09 | Procter & Gamble | Stabilized fabric softener composition |
| US3256180A (en) * | 1962-08-14 | 1966-06-14 | Little Inc A | Fabric softener compositions |
| US3351483A (en) * | 1963-02-14 | 1967-11-07 | Little Inc A | Method of softening textile fabrics |
| US4601954A (en) * | 1984-03-30 | 1986-07-22 | Servicemaster Industries, Inc. | Disinfectant formulation |
| US4624713A (en) * | 1984-11-15 | 1986-11-25 | Economics Laboratory, Inc. | Solid rinse aids and methods of warewashing utilizing solid rinse aids |
| US6489278B1 (en) | 1993-12-30 | 2002-12-03 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US20060040841A1 (en) * | 1993-12-30 | 2006-02-23 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US6060444A (en) * | 1993-12-30 | 2000-05-09 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
| US6124250A (en) * | 1993-12-30 | 2000-09-26 | Ecolab Inc. | Method of making highly alkaline solid cleaning compositions |
| US6164296A (en) * | 1993-12-30 | 2000-12-26 | Ecolab Inc. | Method of removing waxy/fatty soils from ware with a combination of a nonionic silicone surfactant and a nonionic surfactant |
| US7199095B2 (en) | 1993-12-30 | 2007-04-03 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US5674831A (en) * | 1993-12-30 | 1997-10-07 | Ecolab Inc. | Method of making urea-based solid cleaning compositions |
| US5698513A (en) * | 1993-12-30 | 1997-12-16 | Ecolab Inc. | Urea-based solid cleaning compositions free from or containing minor amounts of water |
| US6956019B2 (en) | 1993-12-30 | 2005-10-18 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US6664219B1 (en) | 1993-12-30 | 2003-12-16 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US20040254090A1 (en) * | 1993-12-30 | 2004-12-16 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US6767884B2 (en) | 1993-12-30 | 2004-07-27 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
| US6673765B1 (en) | 1995-05-15 | 2004-01-06 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
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| US11655436B2 (en) | 2018-01-26 | 2023-05-23 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| US11834628B2 (en) | 2018-01-26 | 2023-12-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
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