US2571690A - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
US2571690A
US2571690A US3374A US337448A US2571690A US 2571690 A US2571690 A US 2571690A US 3374 A US3374 A US 3374A US 337448 A US337448 A US 337448A US 2571690 A US2571690 A US 2571690A
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Prior art keywords
soap
water
particles
alkali metal
fatty acid
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US3374A
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Dobbel Petrus Bernardus Maria
Bertram Simon Hendrik
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Dobbelman NV
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Dobbelman NV
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D271/00Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/081,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/08Water-soluble compounds
    • C11D9/10Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/08Water-soluble compounds
    • C11D9/10Salts
    • C11D9/12Carbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/26Organic compounds, e.g. vitamins containing oxygen

Definitions

  • This invention relates to a detergent composi- 7 tion and process for using the same. More particularly, it deals with a composition containing a fatty acid soap which may be used for producing suds in hard water, including sea water.
  • Another object is to provide a reliable method for using such a composition.
  • foaming produced by a fatty acid soap in hard water or sea water is insured by first dissolving in the hard or sea water a substance capable of combining with the cations which cause hardness in the water to form substantially little or non-ionized products, before the fatty acid soap is dissolved in the water and has a chance to react with these cations.
  • a substance capable of combining with the cations which cause hardness in the water to form substantially little or non-ionized products before the fatty acid soap is dissolved in the water and has a chance to react with these cations.
  • the special additives or substances are ones which combine with the cations of the group consisting of calcium, magnesium, ferrous iron, aluminum and manganese which cause hardness in the water.
  • These additives must be readily water soluble and either be dissolved first or be more soluble than the detergent employed in the composition. This may be insured by physically combining the additive with the detergent, such as coating it on the detergent particles, mixing Thus the composition of this invention 7 2 it therewith as-smaller sized particles than the particles of the detergent, or by adding the additive to the hard water first and separately from the detergent.
  • the additive will be the first of the two substances to dissolve in the hard water, or at least it will be the first of the two substances to react with these cations causing hardness to form products which will not react with the detergent,
  • fatty acid soaps included vention comprises at least about 50% by weight of a fatty acid soap and preferably more, but minor amounts of other and chemical washing agents which may contain small quantities of the silicates, phosphates, and/or persalts of sodium may be used.
  • composition as a whole should be substantially free from soluble (such as alkali metal) metasilicates and carbonates particularly sodium carbonate, although minor percentages of these compounds may be tolerated 'in the detergent composition.
  • the amount of special additive in the detergent composition of this invention is not based on the equivalent quantity of fatty acid but is preferably based upon the degree of hardness of the water, while the amount of fatty acid soap is proportioned to the amount of suds or foaming which'is to be made.
  • amount of fatty acid soap is proportioned to the amount of suds or foaming which'is to be made.
  • additive such as sodium fluoride or its equivalent
  • the water softening additive must bedissolved, or at least react with the cations causing hardness of the water, before the soap is dissolved in the hard water and reacts with these cations.
  • the most effective way of doing this is to separately dissolve the additive in the water before the soap is dissolved in the water, and practically speaking of the package or containers for the detergent composition may thus contain two separate compartments, one containing the additive which is to be used first and the other containing the soap detergent. These packages may be so physically arranged that when they are opened the additive will first be poured into the Water before the soap detergent.
  • Another way of insuring the additive to be dissolved first in the hard water is to use a granular composition in which the particles of soap are coated with a layer of the additive (which may be carried or deposited on another layer of a harmless salt such as sodium sulfate)
  • a third method is to use a mixture of particles of soap detergent and additive, wherein the size of the additive particles is considerably smaller than the size of the particles of the soap detergent so that the smaller particles will be the first to dissolve when both are added simultaneously to water.
  • both the additive and the detergent are added simultaneously to the hard water in which washing is to take place, but because of the physical relationship between the two substances of the composition the additive will always dissolve before the soap.
  • EXAMPLE I One percent of a detergent composition consisting of: (l) 500 grs. of coarse dry granular soap consisting of 60% palm oil fatt acid, 10% tallow fatty acid, and coconut fatty acid, and (2) 500 grs. of finely powdered sodium fluoride was added to water having approximately 100 German hardness (G. H.) and sufiicient suds were produced for effective washing.
  • EXAMPLE H Two percent of a detergent composition consisting of: (1) 500 grs. of dry coarse granular coconut fatty acid soap, and (2) 1500 grs. of finely powdered sodium fluoride (or oxalate) was found suitable for washing in sea water.
  • a coated granular detergent composition according to this invention was prepared in the following manner: Dry coconut soap powder was covered with a layer of molten anhydrous sodium sulfate about equal in weight tothat of the soap, then the resulting coated soap particles were coated with wet sodium fluoride (or oxalate). This was accomplished by suspending the sodium fluoride (or oxalate) in a little water to form a super saturated aqueous solution of sodium fluoride (or oxalate) containing an equivalent amount of sodium fluoride (or oxalate) by weight to that of the soap to be used.
  • the salt coated soap was then mixed in this NaFsuspension and allowed to solidify, or this suspension was atomized on the coated soap particles in a rotating drum.
  • the resulting product was then dried and contained a film or additional coating of sodium fluoride (or oxalate) which product was suitable for washing in hard water having 20 German hardness, consisting of 15 calcium and 5 magnesium hardness.
  • EXAMPLE V The advantage of sodium fluoride and oxalate over previously employed soluble phosphate and sodium carbonate water softeners is shown by comparative tests, the results of which are given in Table II below: In each test 0.25% coconut fatty acid soap was employed, and the cubic centimeters of foam were recorded after shaking in hard water having a German hardness of 20, (15 Ca and 5 Mg) with different amounts of each of the additives disclosed in the table. In each test the additive was dissolved in the water before the soap was added. For comparison 0.25 of the same coconut soap was shaken in water having 0 German hardness, and 210 cubic centimeters of foam was produced.
  • a detergent composition for producing suds in hard water comprising particles of a suds-producing fatty acid soap, and a water soluble layer of an alkali metal fluoride covering the particles of soap, the alkali metal fluoride of the layer covering the particles of soap being adapted to dissolve in the water before the water contacts the soap and to react with the cations in the water which cause its hardness and to form substantially non-ionized compounds therewith, thereby preventing the reaction of such cations with the soap.
  • a detergent composition as claimed in claim 1 characterized in that the alkali metal fluoride is sodium fluoride.
  • a detergent composition as claimed in claim 1 characterized in that the particles of fatty acid soap are powdered soap in which the particles of soap are covered with a layer of said fluoride.
  • a detergent composition for producing suds in hard water comprising particles of a sudsproducing fatty acid soap, and a layer of water soluble material covering the particles of soap consisting of an alkali metal compound selected from the group consisting of alkali metal fluorides, oxalates and ferrocyanides, the alkali metal compound of the layer covering the soap particles being adapted to dissolve in the water before the water contacts the soap of the covered particles and to react with the cations in the water which cause its hardness and to form substantially nonionized compounds therewith, thereby preventing the reaction of such cations with the soap.
  • a detergent composition as claimed in claim 4 characterized in that the particles of fatty acid soap are powdered soap in which the particles of 6 soap are covered with a layer of said water soluble material.
  • a detergent composition for producing suds in hard water comprising particles of a sudsproducing fatty acid soap, and a water-soluble layer of an alkali metal oxalate covering the particles of soap, the alkali metal oxalate of the layer covering the soap being adapted to dissolve in the water before the water contacts the soap of the particles and to react with the cations in the water which causes its hardness and to form substantially non-ionized compounds therewith, thereby preventing the reaction of such cations with the soap.
  • a detergent composition as claimed in claim 6 characterized in that the alkali metal oxalate is sodium oxalate.
  • a detergent composition as claimed in claim 6 characterized in that the particles of fatty acid soap are powdered soap in which the particles of soap are covered with a layer of said water soluble material.

Description

Patented Oct. 16, 1951 DETERGENT COMPOSITION Petrus Bernardus Hubertus Maria Dobbelmann, Nimeguen, and Simon Hendrik Bertram, The Hague, Netherlands, assignors to Dobbelman N. V., Nimeguen, Netherlands No Drawing. Application January 20, 1948, Se-
rial No. 3,374. In the Netherlands January 20,
8 Claims. (01. 252-433) This invention relates to a detergent composi- 7 tion and process for using the same. More particularly, it deals with a composition containing a fatty acid soap which may be used for producing suds in hard water, including sea water.
Previously, compounds such as sodium carbonate and alkali metal. phosphates, silicates, pyrophosphates, and the like, have been used to soften hard waters before washing therein with fatty acid soaps. The effect of these water softeners is generally too small to render soap usable in hard water unless uneconomically large quantities of the softeners are added to the water, and it is not always certain that these softeners produce insoluble calcium salts. It has been found that the addition of these softeners with soap in hard water leads to only a small amount of suds or foam formation suitable for washing, and even the addition of sodium carbonate or sodium metasilicate to the hard water before the soap is added produces very little foaming.
Accordingly it is an object to this invention to produce a new, effective, efficient, economical and quickly acting detergent composition which may be used for washing in hard water or sea water.
Another object is to provide a reliable method for using such a composition.
According to this invention, foaming produced by a fatty acid soap in hard water or sea water is insured by first dissolving in the hard or sea water a substance capable of combining with the cations which cause hardness in the water to form substantially little or non-ionized products, before the fatty acid soap is dissolved in the water and has a chance to react with these cations. comprises two essential ingredients, first a special type of additive to soften the hard water, and second a detergent comprising at least about 50% of a fatty acid soap to produce the desired amount of suds.
The special additives or substances are ones which combine with the cations of the group consisting of calcium, magnesium, ferrous iron, aluminum and manganese which cause hardness in the water. These additives must be readily water soluble and either be dissolved first or be more soluble than the detergent employed in the composition. This may be insured by physically combining the additive with the detergent, such as coating it on the detergent particles, mixing Thus the composition of this invention 7 2 it therewith as-smaller sized particles than the particles of the detergent, or by adding the additive to the hard water first and separately from the detergent. In anyone of these three manners the additive will be the first of the two substances to dissolve in the hard water, or at least it will be the first of the two substances to react with these cations causing hardness to form products which will not react with the detergent,
and particularly the fatty acid soaps included vention comprises at least about 50% by weight of a fatty acid soap and preferably more, but minor amounts of other and chemical washing agents which may contain small quantities of the silicates, phosphates, and/or persalts of sodium may be used.
The composition as a whole should be substantially free from soluble (such as alkali metal) metasilicates and carbonates particularly sodium carbonate, although minor percentages of these compounds may be tolerated 'in the detergent composition.
The amount of special additive in the detergent composition of this invention, is not based on the equivalent quantity of fatty acid but is preferably based upon the degree of hardness of the water, while the amount of fatty acid soap is proportioned to the amount of suds or foaming which'is to be made. For example, for each German hardness (1 is equivalent to .0112 gr. per'liter of salts producing hardness in the water) about 0.5% by weight of additive, such as sodium fluoride or its equivalent, is required. Thus, if one wishes to wash in water having a 100 Ger man hardness with a 0.5% soap concentration, a 1% mixture of 50 parts soap and 50 parts sodium fluoride or oxalate should be used; and if one wishes to wash with a 1% soap concentration in the same water, 1.5% of a mixture of 100 parts soap and 50 parts sodium fluoride or oxalate should be used.
a As previously stated, it is essential to this invention that the water softening additive must bedissolved, or at least react with the cations causing hardness of the water, before the soap is dissolved in the hard water and reacts with these cations. The most effective way of doing this is to separately dissolve the additive in the water before the soap is dissolved in the water, and practically speaking of the package or containers for the detergent composition may thus contain two separate compartments, one containing the additive which is to be used first and the other containing the soap detergent. These packages may be so physically arranged that when they are opened the additive will first be poured into the Water before the soap detergent. Another way of insuring the additive to be dissolved first in the hard water is to use a granular composition in which the particles of soap are coated with a layer of the additive (which may be carried or deposited on another layer of a harmless salt such as sodium sulfate) A third method is to use a mixture of particles of soap detergent and additive, wherein the size of the additive particles is considerably smaller than the size of the particles of the soap detergent so that the smaller particles will be the first to dissolve when both are added simultaneously to water. In either one of the latter two methods, both the additive and the detergent are added simultaneously to the hard water in which washing is to take place, but because of the physical relationship between the two substances of the composition the additive will always dissolve before the soap.
The following examples illustrate the effectiveness of this invention:
EXAMPLE I One percent of a detergent composition consisting of: (l) 500 grs. of coarse dry granular soap consisting of 60% palm oil fatt acid, 10% tallow fatty acid, and coconut fatty acid, and (2) 500 grs. of finely powdered sodium fluoride was added to water having approximately 100 German hardness (G. H.) and sufiicient suds were produced for effective washing.
EXAMPLE H Two percent of a detergent composition consisting of: (1) 500 grs. of dry coarse granular coconut fatty acid soap, and (2) 1500 grs. of finely powdered sodium fluoride (or oxalate) was found suitable for washing in sea water.
EXAMPLE III Table I 0.35% of composition=0.25% of soap+ 0.1% of NaF in water of 20 German Hardness 0.25% of soap in water of 20 German Hardness 0.25% of soap in dist. water C'mj Cm.
From Table I, no washing action is obtained in the hard Water of 20 G. H. if no sodium fluoride is added, but when sodium fluoride is added a washing action about equal to that of the soap alone in distilled water is obtained.
EXAMPLE IV In order to insure that the sodium fluoride and/or sodium oxalate is dissolved in the water before the soap, a coated granular detergent composition according to this invention was prepared in the following manner: Dry coconut soap powder was covered with a layer of molten anhydrous sodium sulfate about equal in weight tothat of the soap, then the resulting coated soap particles were coated with wet sodium fluoride (or oxalate). This was accomplished by suspending the sodium fluoride (or oxalate) in a little water to form a super saturated aqueous solution of sodium fluoride (or oxalate) containing an equivalent amount of sodium fluoride (or oxalate) by weight to that of the soap to be used. The salt coated soap was then mixed in this NaFsuspension and allowed to solidify, or this suspension was atomized on the coated soap particles in a rotating drum. The resulting product was then dried and contained a film or additional coating of sodium fluoride (or oxalate) which product was suitable for washing in hard water having 20 German hardness, consisting of 15 calcium and 5 magnesium hardness.
EXAMPLE V The advantage of sodium fluoride and oxalate over previously employed soluble phosphate and sodium carbonate water softeners is shown by comparative tests, the results of which are given in Table II below: In each test 0.25% coconut fatty acid soap was employed, and the cubic centimeters of foam were recorded after shaking in hard water having a German hardness of 20, (15 Ca and 5 Mg) with different amounts of each of the additives disclosed in the table. In each test the additive was dissolved in the water before the soap was added. For comparison 0.25 of the same coconut soap was shaken in water having 0 German hardness, and 210 cubic centimeters of foam was produced.
Both detrimental calcium hardness and magnesium hardness are prevented by the addition of soluble fluorides and/or oxalates according to this invention.
While there is described above the principles of this invention in connection with specific compositions, it is to be clearly understood that this description is made only by way of example and not as a limitation to the scope of this invention.
What is claimed is:
1. A detergent composition for producing suds in hard water, comprising particles of a suds-producing fatty acid soap, and a water soluble layer of an alkali metal fluoride covering the particles of soap, the alkali metal fluoride of the layer covering the particles of soap being adapted to dissolve in the water before the water contacts the soap and to react with the cations in the water which cause its hardness and to form substantially non-ionized compounds therewith, thereby preventing the reaction of such cations with the soap.
2. A detergent composition as claimed in claim 1 characterized in that the alkali metal fluoride is sodium fluoride.
3. A detergent composition as claimed in claim 1 characterized in that the particles of fatty acid soap are powdered soap in which the particles of soap are covered with a layer of said fluoride.
4. A detergent composition for producing suds in hard water, comprising particles of a sudsproducing fatty acid soap, and a layer of water soluble material covering the particles of soap consisting of an alkali metal compound selected from the group consisting of alkali metal fluorides, oxalates and ferrocyanides, the alkali metal compound of the layer covering the soap particles being adapted to dissolve in the water before the water contacts the soap of the covered particles and to react with the cations in the water which cause its hardness and to form substantially nonionized compounds therewith, thereby preventing the reaction of such cations with the soap.
5. A detergent composition as claimed in claim 4 characterized in that the particles of fatty acid soap are powdered soap in which the particles of 6 soap are covered with a layer of said water soluble material.
6. A detergent composition for producing suds in hard water, comprising particles of a sudsproducing fatty acid soap, and a water-soluble layer of an alkali metal oxalate covering the particles of soap, the alkali metal oxalate of the layer covering the soap being adapted to dissolve in the water before the water contacts the soap of the particles and to react with the cations in the water which causes its hardness and to form substantially non-ionized compounds therewith, thereby preventing the reaction of such cations with the soap.
7. A detergent composition as claimed in claim 6 characterized in that the alkali metal oxalate is sodium oxalate.
8. A detergent composition as claimed in claim 6 characterized in that the particles of fatty acid soap are powdered soap in which the particles of soap are covered with a layer of said water soluble material.
PETRUS BERNARDUS HUBERTUS MARIA DOBBELIVIANN. SIMON HENDRIK BERTRAM.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 586,231 Boynton July 13, 1897 1,722,137 Frischer July 23, 1929 1,854,235 Stoddard Apr. 19, 1932 1,935,663 Phair Nov. 21, 1933 FOREIGN PATENTS Number Country Date 441,379 Great Britain Jan. 9, 1936 OTHER REFERENCES Washing, Cleaning and Polishing Materials, Bureau of Standards Circular C424 (1939), PD.

Claims (1)

  1. 4. A DETERGENT COMPOSITION FOR PRODUCING SUDS IN HARD WATER, COMPRISING PARTICLES OF A SUDSPRODUCING FATTY ACID SOAP, AND A LAYER OF WATER SOLUBLE MATERIAL COVERING THE PARTICLES OF SOAP CONSISTING OF AN ALKALI METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL FLUORIDES, OXALATES AND FERROCYANIDES, THE ALKALI METAL COMPOUND OF THE LAYER COVERING THE SOAP PARTICLES BEING ADAPTED TO DISSOLVE IN THE WATER BEFORE THE WATER CONTACTS THE SOAP OF THE COVERED PARTICLES AND TO REACT WITH THE CATIONS IN THE WATER WHICH CAUSE ITS HARDENESS AND TO FORM SUBSTANTIALLY NONIONIZED COMPOUNDS THEREWITH, THEREBY PREVENTING THE REACTION OF SUCH CATIONS WITH THE SOAP.
US3374A 1947-01-20 1948-01-20 Detergent composition Expired - Lifetime US2571690A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL129869 1947-01-20
NL136587 1947-12-05

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US2571690A true US2571690A (en) 1951-10-16

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US (1) US2571690A (en)
BE (2) BE494704A (en)
CH (1) CH280191A (en)
FR (1) FR959841A (en)
GB (1) GB656248A (en)
LU (1) LU30039A1 (en)
NL (2) NL67413C (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2907649A (en) * 1957-08-05 1959-10-06 Commw Products Inc Aluminum cleaning composition
US4051055A (en) * 1976-12-21 1977-09-27 The Procter & Gamble Company Cleansing compositions
US4299739A (en) * 1976-03-25 1981-11-10 Lever Brothers Company Use of aluminum salts in laundry detergent formulations
US5180511A (en) * 1989-09-14 1993-01-19 J.M. Huber Corporation Flotation aid and process for removal of impurities from silicate minerals

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US586231A (en) * 1897-07-13 Edward s
US1722137A (en) * 1927-01-21 1929-07-23 Western Boiler Compound And Ch Method of treating water and materials used in connection therewith
US1854235A (en) * 1930-01-18 1932-04-19 Conover Company Detergent composition
US1935663A (en) * 1928-06-16 1933-11-21 Kohnstamm & Co Inc H Laundering method
GB441379A (en) * 1934-02-24 1936-01-09 Electric Smelting And Aluminum Improvements in or relating to a process of washing or laundering

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US586231A (en) * 1897-07-13 Edward s
US1722137A (en) * 1927-01-21 1929-07-23 Western Boiler Compound And Ch Method of treating water and materials used in connection therewith
US1935663A (en) * 1928-06-16 1933-11-21 Kohnstamm & Co Inc H Laundering method
US1854235A (en) * 1930-01-18 1932-04-19 Conover Company Detergent composition
GB441379A (en) * 1934-02-24 1936-01-09 Electric Smelting And Aluminum Improvements in or relating to a process of washing or laundering

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2907649A (en) * 1957-08-05 1959-10-06 Commw Products Inc Aluminum cleaning composition
US4299739A (en) * 1976-03-25 1981-11-10 Lever Brothers Company Use of aluminum salts in laundry detergent formulations
US4051055A (en) * 1976-12-21 1977-09-27 The Procter & Gamble Company Cleansing compositions
US5180511A (en) * 1989-09-14 1993-01-19 J.M. Huber Corporation Flotation aid and process for removal of impurities from silicate minerals

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CH280191A (en) 1952-01-15
GB656248A (en) 1951-08-15
BE494704A (en)
NL67413C (en)
LU30039A1 (en)
BE479650A (en)
FR959841A (en) 1950-04-06
NL66550C (en)

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