US2152520A - Bleaching, washing, cleansing, and rinsing agents - Google Patents

Bleaching, washing, cleansing, and rinsing agents Download PDF

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US2152520A
US2152520A US36117A US3611735A US2152520A US 2152520 A US2152520 A US 2152520A US 36117 A US36117 A US 36117A US 3611735 A US3611735 A US 3611735A US 2152520 A US2152520 A US 2152520A
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compositions
acid
sodium
cleansing
parts
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US36117A
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Lind Otto
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds

Definitions

  • This invention relates to compositions suitable as bleaching, washing, cleansing and rinsing agents, particularly for the treatment of textiles and other fibrous materials, and also, to processes of employing the same.
  • An object of the invention is to provide compositions possessing outstanding technical advantages including the power of removing yellow discoloration from textiles and also of preventing yellow discoloration due to the use of iron-containing water in the cleaning or other treatment of fibrous materials.
  • Another object is to provide compositions for the household and for industrial use which besides accomplishing a bleaching action upon fabrics treated therewith also simultaneously eil'ect a thorough cleansing action.
  • compositions which contain in combination essentially one part of an oxygen-yielding compound, one to three parts of a water soluble salt of a phosphoric acid poorer in molecularly combined water than ortho-phosphoric acidand one to three. parts of an inorganic salt adapted to react alkaline when in aqueous solution, all parts being by weight.
  • compositions which contain also strong detergent powers there is added to the above composition a suitable quantity of a foaming agent, preferab y from two to six parts by weight.
  • a foaming agent preferab y from two to six parts by weight.
  • the o ygen-yielding compounds suitable for use in the compositions of the present. invention include adm lrw hemansommnnds. e p oxides as well as the per salts. There may be used, for example, sodiumperoxide and the following per salts: perborates, percarbonates, persulfates, per-phosphates and perpyrophosphates...
  • alkali metal salts for example, the sodium salts of these compounds are preferred but other readfly soluble salts mayalso be used.
  • a suitable amount of a stabilization agent such as, for example, water glass or various magnesium compounds, this addition being considered within the.comprehension of the present invention.
  • the salts of phosphoric acids which contain less molecularly combined water than orthophosphoric .acid suitable in the practice of the invention include in general the water soluble salts of pyrophosphoric acid, metaphosphoric acid and polyphosphoric acids.
  • the alkali metal pyrophosphates for example, tetrasodium pyrophosphate, and especially the neutral pyrophosphates produce excellent compositions.
  • the alkali metal metaphosphates may also be used, and as well those which exist in the polymeric form, for example, hexameric sodium meta-phosphate.
  • the water soluble polyphosphates are suitable, the alkali metal phosphates being particularly desirable, such as NasPaOm and NMPlOlJ for example.
  • the alkali metal subphosphates for example, sodium subphosphate, may also be employed.
  • the alkali metal salts of these phosphoric acids are preferred, other salts may be used with considerable advantage, for example, the ammonium salts, and the salts obtained by the use of organic bases, as triethanolairline, cyclohexylamine, aminopropandiols and the like. In certain instances it has been found that mixtures of the above mentioned salts may be employed with better results.
  • Alkaline reacting inorganic salts in general are suitable in the compositions of the present invention, but the alkali metal carbonates suchas soda, the alkali metal phosphates like trisodium phosphate, the alkali metal silicates like sodium metasilicate and the alkali metal box-ates like borax, are preferred.
  • the invention comprehends the use of foaming agents of the most varied character and includes as one embodiment, the ,use of soap, and as a second important embodiment certain soap-like compounds.
  • soap commercial grades in general are suitable.
  • soap-like materials there are used with excellent results the alkali metal or other soluble salts of sulfonated higher molecular iatty alcohols and in particular the sodium salts of the sulfuric acid esters of the aliphatic alcohols or hydrocarbons havin more than 8 carbon atoms, preferably from 12 to 22 carbon atoms, such alcohols being producible from natural oils and waxes or from suitable mineral oil fractions by oxidation or other suitable treatment.
  • the alkali metal salts of sulfonated oils may also be used with advantage.
  • all those capillary active compounds in general may be used which possess a high molecular radical on the one hand and a radical im- Examiner parting water solubility on the other hand, for example, the sodium salt of oleyl methyl taurine.
  • the bleaching, washing, cleansing and rinsing agents of the present invention above described may be supplemented by the addition of any one or more of a number of other substances which are generally or sometimes used in rinsing. washing and cleansing agents.
  • an additional wetting agent may be added such as is exemplified by the sodium salt of isopropyl naphthalene sulfonic acid.
  • As a softening or soaking agent there may be added an enzyme of the nature of pancreatin.
  • agents may be added which increase the penetrating, emulsifying and dispersing power of the composition. The properties may be improved in some.
  • hydrocarbons of the nature of benzene or of its derivatives like the halogenated hydrocarbons for example, trichlorethylene and carbon tetrachloride.
  • the addition of alcohols may be used with advantage.
  • a suitable quantity of a superlatting agent for example, wool fat, or a polishing and scouring agent. for example, sand or other abrasive.
  • compositions of the present invention do not constitute any part of the present invention for in general all methods known for the production of washing agents on an industrial scale are suitable.
  • the compositions may be prepared according to known methods in agitating or stirring apparatus of common construction, in ball mills and in other equivalent apparatus.
  • the various ingredients may be brought together in any suitable order.
  • the alkali pyrophosphate or other equivalent salt is mixed with the soap to form a paste after which the mixture is ground and mixed with the proper proportions of sodium perborate and soda or other equivalent compounds.
  • the sodium pyrophosphate or other salt may be initially mixed with the desired quantities of sodium perborate and soda or equivalent materials.
  • compositions can be manufactured ready for use or can be mixed wholly or in part at the place of use.
  • liquids are to be included in the composition, the various solid ingredients may be separately or-simultaneously dissolved in a single body of liquid, or separate solutions of the compounds may be formed and then mixed together.
  • novel bleachingTwashing, cleansing and rinsing agents of the present invention may be marketed in solid form, for example, as a powder,
  • compositions in flakes, in granules or in strip form.
  • compositions may be manufactured in liquid form by dissolving the same in liquids, or they may be prepared in dough form or in paste or cream form.
  • Excellent wuhing, bleaching and cleansing agents may be formed by incorporating together, by anyone of the methods hereinbefore described, the following substances, all parts being by weight:
  • Example 2 Parts 60% soap 60' Tetrasodium pyrophosphate 11 Sodium perborate 9 Trisodium phosphate 8 Sodium metasilicate 12
  • Example 3 Parts Mixture of the sodium salts of the acid sulfuric acid esters of the fatty alcohols 40 Tetrasodium pyrophosphate Borax J 30 Sodium perborate 10
  • Example 4 Parts 60% soap 50 Sodium polyphosphate of the formula The following products are used with particular advantage in the rinsing of fabrics or textiles treated in laundries, all parts being by weight:
  • Example 7 Parts Tetrasodium pyrophosphate 50 Sodium perborate 17 Calcined soda 34
  • Example 8 Parts Tetrasodium pyrophosphate 27 Sodium perborate 23
  • Example '9 Parts Sodium perborate 20 Sodium polyphosphate of the formula NacP4O1a 40 Calcined soda 40
  • Example 10 Y, Parts Sodium perborate Tetra-sodium pyrophosphate 50 Trisodium phosphate 25
  • Example 11 Parts Sodium perpyrophosphate 25 Sodium polyphosphate of the formula NasPiOu 25 Sodium metasilicate 50 l A a p L .i ⁇ 252. cowosmows.
  • Example 12 phoric acid salt being-present in a proportion Parts constituting not less than 20% by weight of the Sodium perborate 20 s aid mixture.
  • Sodium hexametaphosphate 20 2.
  • the two to six parts of a saponaceous foaming agent, present compositions may be used with advantage said parts being by weight, said phosphoric acid in the household as well as in places like launbeing present in a proportion constituting not dries, hospitals and the like for the washing less than 10% by weight of the said mixture. 15 and cleaning of dresses, underwear and other 3.
  • the present compositions may be used with is sodium perborate. special advantage where only iron-containing 4.
  • the combination of substances described in water is available, for in such case the absorption claim 1 wherein the water soluble salt of phos- 20 of iron by the fiber is prevented.
  • phoric acid is of pyrophosphoric acid.
  • the combination of substances described in and caused by the presence of iron compounds claim 1 wherein the water soluble salt of phosmay be removed by the compositions of the presphoric acid is tetrasodium pyrophosphate. ent invention.
  • the compositions are also suitable 6.
  • the combination of substances described in u for other fibrous materials and other articles enclaim 1 wherein the water soluble salt of phoscountered in domestic life and in industrial purphoric acid is of metaphosphoric acid. suits. 'l.
  • the combination of substances described in Whereas the advantages of the compositions of claim 1 wherein the water soluble salt of phosthe present invention are generally obtained to phoric acid is sodium hexametaphosphate. so the most effective degree when the proportions 8.
  • ter soluble salt oi. a phosphoric acid containing less molecularly combined water than crthophosphoric acid, and of from 1 to 3 parts of an alkali ,ssmmetalssalhadaptediaiormjnsaqueons alkaline,

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Patented Mar. 28, 1939 UNITED STATES Cress PATENT OFFICE,
BLEACHING, WASHING, CLEANSING, AND RINSING AGENTS No Drawing. Application August 14, 1935, Serial No. 38,117. In Germany August 22, 1934 15 Claims.
This invention relates to compositions suitable as bleaching, washing, cleansing and rinsing agents, particularly for the treatment of textiles and other fibrous materials, and also, to processes of employing the same.
An object of the invention is to provide compositions possessing outstanding technical advantages including the power of removing yellow discoloration from textiles and also of preventing yellow discoloration due to the use of iron-containing water in the cleaning or other treatment of fibrous materials.
Another object is to provide compositions for the household and for industrial use which besides accomplishing a bleaching action upon fabrics treated therewith also simultaneously eil'ect a thorough cleansing action.
In accordance with the preferred embodiment of the invention, the above objects are accomplished through the provision of compositions which contain in combination essentially one part of an oxygen-yielding compound, one to three parts of a water soluble salt of a phosphoric acid poorer in molecularly combined water than ortho-phosphoric acidand one to three. parts of an inorganic salt adapted to react alkaline when in aqueous solution, all parts being by weight. Detailed tests have shown that such compositions can be very advantageously used in the bleaching, washing, cleansing and rinsing of fibrous materials.
Where it is desired to provide compositions which contain also strong detergent powers, there is added to the above composition a suitable quantity of a foaming agent, preferab y from two to six parts by weight. The products produced in this manner possess additional advantages, for example. they do not deposit or precipitate out in iron-containing water.
The o ygen-yielding compounds suitable for use in the compositions of the present. invention include adm lrw hemansommnnds. e p oxides as well as the per salts. There may be used, for example, sodiumperoxide and the following per salts: perborates, percarbonates, persulfates, per-phosphates and perpyrophosphates...
The alkali metal salts, for example, the sodium salts of these compounds are preferred but other readfly soluble salts mayalso be used. In special instances, or for particular uses, it is sometimes more advantageous to use together with the oxygen-yielding compound a suitable amount of a stabilization agent such as, for example, water glass or various magnesium compounds, this addition being considered within the.comprehension of the present invention.
The salts of phosphoric acids which contain less molecularly combined water than orthophosphoric .acid, suitable in the practice of the invention include in general the water soluble salts of pyrophosphoric acid, metaphosphoric acid and polyphosphoric acids. The alkali metal pyrophosphates, for example, tetrasodium pyrophosphate, and especially the neutral pyrophosphates produce excellent compositions. The alkali metal metaphosphates may also be used, and as well those which exist in the polymeric form, for example, hexameric sodium meta-phosphate. Also, the water soluble polyphosphates are suitable, the alkali metal phosphates being particularly desirable, such as NasPaOm and NMPlOlJ for example. The alkali metal subphosphates, for example, sodium subphosphate, may also be employed. Although the alkali metal salts of these phosphoric acids are preferred, other salts may be used with considerable advantage, for example, the ammonium salts, and the salts obtained by the use of organic bases, as triethanolairline, cyclohexylamine, aminopropandiols and the like. In certain instances it has been found that mixtures of the above mentioned salts may be employed with better results.
Alkaline reacting inorganic salts in general are suitable in the compositions of the present invention, but the alkali metal carbonates suchas soda, the alkali metal phosphates like trisodium phosphate, the alkali metal silicates like sodium metasilicate and the alkali metal box-ates like borax, are preferred.
The invention comprehends the use of foaming agents of the most varied character and includes as one embodiment, the ,use of soap, and as a second important embodiment certain soap-like compounds. Where soap is used, commercial grades in general are suitable. As soap-like materials there are used with excellent results the alkali metal or other soluble salts of sulfonated higher molecular iatty alcohols and in particular the sodium salts of the sulfuric acid esters of the aliphatic alcohols or hydrocarbons havin more than 8 carbon atoms, preferably from 12 to 22 carbon atoms, such alcohols being producible from natural oils and waxes or from suitable mineral oil fractions by oxidation or other suitable treatment. The alkali metal salts of sulfonated oils-may also be used with advantage. In fact all those capillary active compounds in general may be used which possess a high molecular radical on the one hand and a radical im- Examiner parting water solubility on the other hand, for example, the sodium salt of oleyl methyl taurine.
The bleaching, washing, cleansing and rinsing agents of the present invention above described may be supplemented by the addition of any one or more of a number of other substances which are generally or sometimes used in rinsing. washing and cleansing agents. For example, an additional wetting agent may be added such as is exemplified by the sodium salt of isopropyl naphthalene sulfonic acid. As a softening or soaking agent, there may be added an enzyme of the nature of pancreatin. Furthermore, agents may be added which increase the penetrating, emulsifying and dispersing power of the composition. The properties may be improved in some. cases by the addition of hydrocarbons of the nature of benzene or of its derivatives like the halogenated hydrocarbons, for example, trichlorethylene and carbon tetrachloride. In certain cases, the addition of alcohols may be used with advantage. Furthermore, there may be incorporated in the compositions a suitable quantity of a superlatting agent, for example, wool fat, or a polishing and scouring agent. for example, sand or other abrasive.
The method by which the compositions of the present invention are compounded does not constitute any part of the present invention for in general all methods known for the production of washing agents on an industrial scale are suitable. The compositions may be prepared according to known methods in agitating or stirring apparatus of common construction, in ball mills and in other equivalent apparatus. The various ingredients may be brought together in any suitable order. For example, when a product containing soap is to be formed, the alkali pyrophosphate or other equivalent salt is mixed with the soap to form a paste after which the mixture is ground and mixed with the proper proportions of sodium perborate and soda or other equivalent compounds. When compositions free of soap are to be produced, the sodium pyrophosphate or other salt may be initially mixed with the desired quantities of sodium perborate and soda or equivalent materials. A satisfactory mixture can also be obtained by grinding all of the materials together in a dry condition to form a powder. The compositions can be manufactured ready for use or can be mixed wholly or in part at the place of use. Where liquids are to be included in the composition, the various solid ingredients may be separately or-simultaneously dissolved in a single body of liquid, or separate solutions of the compounds may be formed and then mixed together.
The novel bleachingTwashing, cleansing and rinsing agents of the present invention may be marketed in solid form, for example, as a powder,
in flakes, in granules or in strip form. Furthermore, the compositions may be manufactured in liquid form by dissolving the same in liquids, or they may be prepared in dough form or in paste or cream form.
Excellent wuhing, bleaching and cleansing agents may be formed by incorporating together, by anyone of the methods hereinbefore described, the following substances, all parts being by weight:
Example 2 Parts 60% soap 60' Tetrasodium pyrophosphate 11 Sodium perborate 9 Trisodium phosphate 8 Sodium metasilicate 12 Example 3 Parts Mixture of the sodium salts of the acid sulfuric acid esters of the fatty alcohols 40 Tetrasodium pyrophosphate Borax J 30 Sodium perborate 10 Example 4 Parts 60% soap 50 Sodium polyphosphate of the formula The following products are used with particular advantage in the rinsing of fabrics or textiles treated in laundries, all parts being by weight:
Example 7 Parts Tetrasodium pyrophosphate 50 Sodium perborate 17 Calcined soda 34 Example 8 Parts Tetrasodium pyrophosphate 27 Sodium perborate 23 Trisodium phosphate 20 Sodium metasilicate 30 Example '9 Parts Sodium perborate 20 Sodium polyphosphate of the formula NacP4O1a 40 Calcined soda 40 Example 10 Y, Parts Sodium perborate Tetra-sodium pyrophosphate 50 Trisodium phosphate 25 Example 11 Parts Sodium perpyrophosphate 25 Sodium polyphosphate of the formula NasPiOu 25 Sodium metasilicate 50 l A a p L .i\ 252. cowosmows. W Examiner Example 12 phoric acid salt being-present in a proportion Parts constituting not less than 20% by weight of the Sodium perborate 20 s aid mixture. Sodium hexametaphosphate 20 2. In compositions for bleaching, washing, Sodium metasilicate 20 cleansing and rinsing, the combination oi sub- 5 calcined soda. 40 stances consisting of one part of an oxygenylelding compound, one to three parts of a water Bleaching, washing, cleansing and rinsing soluble salt of a phosphoric acid poorer in moagents prepared in accordance with the above lecularly combined water than orthophosphoric examples excel to a considerable degree and in acid, one to three parts of an alkaline metal salt 10 many respects mixtures heretofore known and adapted to form an aqueous alkaline solution and proposed for the above mentioned purposes. The two to six parts of a saponaceous foaming agent, present compositions may be used with advantage said parts being by weight, said phosphoric acid in the household as well as in places like launbeing present in a proportion constituting not dries, hospitals and the like for the washing less than 10% by weight of the said mixture. 15 and cleaning of dresses, underwear and other 3. The combination of substances described in textiles. claim 1 wherein the oxygen-yielding compound The present compositions may be used with is sodium perborate. special advantage where only iron-containing 4. The combination of substances described in water is available, for in such case the absorption claim 1 wherein the water soluble salt of phos- 20 of iron by the fiber is prevented. Furthermore, phoric acid is of pyrophosphoric acid. the yellow discoloration generally so common 5. The combination of substances described in and caused by the presence of iron compounds claim 1 wherein the water soluble salt of phosmay be removed by the compositions of the presphoric acid is tetrasodium pyrophosphate. ent invention. The compositions are also suitable 6. The combination of substances described in u for other fibrous materials and other articles enclaim 1 wherein the water soluble salt of phoscountered in domestic life and in industrial purphoric acid is of metaphosphoric acid. suits. 'l. The combination of substances described in Whereas the advantages of the compositions of claim 1 wherein the water soluble salt of phosthe present invention are generally obtained to phoric acid is sodium hexametaphosphate. so the most effective degree when the proportions 8. The combination of substances described in are as hereinbefore disclosed, it should be underclaim 1 wherein the water soluble salt of phosstood that m ny of th vant es may be obphoric acid is of a polyphosphoric acid. tained through the use of compositions of difler- 9. The composition oil matter described in em D D o p the P p o o claim 1 wherein the inorganic salt adapted to 35 an alkaline reacting inorganic salt may be inform an alkaline aqueous solution is soda. creased or d creased to uit ny p i ular pur- 10. The combination of substances described in p se req i in Particular alkalinity for most claim 2 wherein the foaming agent is soap. fective results. It should be understood further 11, The binat of t nc described that the invention is to be given a broad interin claim 2 wherein the water soluble salt of phos- 40 pretation commensurate in scope with that of the phoric acid is of pyrophosphoric acid, terms mployed in h l im ppended hereto. 12. The combination of substances described in Furthermore, the claims should be interpreted "claim 2 wherein the water soluble salt of phosas including the equivalents of the substances phoric acid is of metaphosphoric acid. specified therein. 13. The combination of substances described in I claim: claim 2 wherein the water soluble salt of phos- 1. In compositions for bleaching, washing. phoric acid is of a polyphosphoric acid. cleansing and rinsing, the combination of sub- 14. The combination of substances described in stances consisting of one part of an oxygenclaim 2 wherein the inorganic salt adapted to yielding compound, one to three parts of a waform an alkaline aqueous solution comprises soda. w
ter soluble salt oi. a phosphoric acid containing less molecularly combined water than crthophosphoric acid, and of from 1 to 3 parts of an alkali ,ssmmetalssalhadaptediaiormjnsaqueons alkaline,
solution, said parts being by weight, said phos- 15. The combination of substances described in claim 2 wherein the alkaline reacting inorganic salt is soda and the foaming agent is soap.
OTIOLIND.
US36117A 1934-08-22 1935-08-14 Bleaching, washing, cleansing, and rinsing agents Expired - Lifetime US2152520A (en)

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DE2152520X 1934-08-22
GB25140/34A GB443731A (en) 1934-08-22 1934-08-31 Improvements in or relating to bleaching, washing, and cleansing agents, particularly for use in water containing iron

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NL (1) NL74422C (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2477492A (en) * 1943-12-03 1949-07-26 Monsanto Chemicals Agglomerated water treating composition and method of producing same
US2576205A (en) * 1945-08-25 1951-11-27 Colgate Palmolive Peet Co Denture cleansing composition
US2693454A (en) * 1951-10-26 1954-11-02 Olin Mathieson Dry, stable, powdered bleaching composition
US2927840A (en) * 1955-07-08 1960-03-08 Degussa Process for the treatment of fibrous materials
US2931776A (en) * 1955-09-01 1960-04-05 Reckitt & Colman Ltd Denture cleanser composition
US2937998A (en) * 1954-10-22 1960-05-24 Henkel & Cie Gmbh Process for preparing stable peroxidecontaining borates
US2980621A (en) * 1956-08-07 1961-04-18 Bittenfield Morris Spotting composition
US3519570A (en) * 1966-04-25 1970-07-07 Procter & Gamble Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions
US3519379A (en) * 1967-04-28 1970-07-07 Procter & Gamble Soaking and laundering process
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
US6306811B1 (en) * 1996-03-27 2001-10-23 Solvay Interox Compositions containing sodium percarbonate

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2437253A (en) * 1940-01-08 1948-03-09 Lever Brothers Ltd Detergent composition
DE751038C (en) * 1940-08-14 1952-07-21 Benckiser Gmbh Joh A Paste-shaped hand cleansers and body care products
DE746848C (en) * 1942-03-08 1944-08-25 Boehme Fettchemie G M B H Skin cleanser
ZA670520B (en) * 1966-02-26
AU413469B2 (en) * 1966-03-09 1971-05-24 Knapsack Ag Process forthe manufacture of detergent compositions

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2477492A (en) * 1943-12-03 1949-07-26 Monsanto Chemicals Agglomerated water treating composition and method of producing same
US2576205A (en) * 1945-08-25 1951-11-27 Colgate Palmolive Peet Co Denture cleansing composition
US2693454A (en) * 1951-10-26 1954-11-02 Olin Mathieson Dry, stable, powdered bleaching composition
US2937998A (en) * 1954-10-22 1960-05-24 Henkel & Cie Gmbh Process for preparing stable peroxidecontaining borates
US2927840A (en) * 1955-07-08 1960-03-08 Degussa Process for the treatment of fibrous materials
US2931776A (en) * 1955-09-01 1960-04-05 Reckitt & Colman Ltd Denture cleanser composition
US2980621A (en) * 1956-08-07 1961-04-18 Bittenfield Morris Spotting composition
US3519570A (en) * 1966-04-25 1970-07-07 Procter & Gamble Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions
US3519379A (en) * 1967-04-28 1970-07-07 Procter & Gamble Soaking and laundering process
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
US3714050A (en) * 1968-03-07 1973-01-30 Colgate Palmolive Co Stain removal
US6306811B1 (en) * 1996-03-27 2001-10-23 Solvay Interox Compositions containing sodium percarbonate

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BE410581A (en) 1935-08-31
BE410601A (en) 1935-08-31
FR792904A (en) 1936-01-13
NL74422C (en) 1954-04-15
FR46658E (en) 1936-07-24
GB443731A (en) 1936-03-02

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