US3192166A - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

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Publication number
US3192166A
US3192166A US68652A US6865260A US3192166A US 3192166 A US3192166 A US 3192166A US 68652 A US68652 A US 68652A US 6865260 A US6865260 A US 6865260A US 3192166 A US3192166 A US 3192166A
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US
United States
Prior art keywords
potassium
detergent
sodium
alkyl
total
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US68652A
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English (en)
Inventor
Norman R Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE610313D priority Critical patent/BE610313A/xx
Priority to NL271301D priority patent/NL271301A/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US68652A priority patent/US3192166A/en
Priority to DEP28221A priority patent/DE1218647B/de
Priority to FR878772A priority patent/FR1305229A/fr
Priority to GB40742/61A priority patent/GB948396A/en
Application granted granted Critical
Publication of US3192166A publication Critical patent/US3192166A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • This invention relates to opaque built liquid detergents of themedium-duty and heavy-duty type. More particularly, it relates to such liquid detergents which contain a unique opacifying agent and have improved sudsing and detergent characteristics.
  • a built detergent is one which contains, in addition to at least one organic surface active agent, a soluble salt capable of sequestering'calcium and magnesium ions of hard water and also capable of increasing the level of detergent effectiveness of the surface active agent.
  • built liquid detergents have, to some extent, replaced built granular detergents for various reasons. These reasons include: complete freedom from dustiness, compact package and convenience in pouring and measuring.
  • liquid detergents oifer relative simplicity in'manufacturing techniques.
  • the primary problem which has to be overcome in formulating built liquid detergents which are homogeneous in nature is that of incorporating sufiicient surface active agent and builder into the same solution.
  • Bo homogeneous as used herein is meant free from a precipitate of detergent actives.
  • anionic sulfated or sulfonated compounds are ordinarily used as surface active agents, and potassium pyrophosphate is used as the builder.
  • Various surface active agents, hydrotr-opes and solvents are employed to increase their compatibility.
  • the fact that the builder may corrode non-ferrous metals such as aluminum, may, depending on the use for which the product is intended, lead the manufacturer to include sodium silicate in the formulation as a corrosion inhibitor.
  • sodium silicate special measures have to be taken to prevent the loss of homogeneity of the liquid formulation. For example, limitations on the pH of the formulation or the addition of agents designed to achieve compatibility among its constituents is usually required.
  • compositions thus formulated are generally clear liquids of relatively low viscosity.
  • percentages refer to weight percent of the total formula unless otherwise indicated.
  • the alkali metal salts may be used interchangeably, since in an aqueous system it is for the most part immaterial how a particular ion is introduced, there being a substantially complete and continuous exchange of ions among the comborate decahydrate (borax, sodium borate, U.S.P. XIII),
  • formulations such as the following comprise the invention: 1) from about 2% to about 15% of an alkali metal salt of a borate anion, the said salt having a solubility in water of not more than 5% at 25 C. and being sufficient to yield an opaque solution having a viscosity of at least about 350 centipoises at F.; (2) from about 3% to about 10% of an aliphatic tertiary amine oxide; (3) from about 3% to about 15% of a non-soap synthetic detergent of the sulfated or sulfonated type; (4) from about 3% to about 10% of a soluble hydrotrope; and (5) from about 10% to about 30% of a soluble pyrophosphate salt.
  • the organic detergent actives, hydrotrope and phosphate are dissolved in an aqueous vehicle and the borate salts are added to the solution.
  • the borate salts are added to the solution.
  • the alkali metal borates which find utility in this invention have a solubility of 5% or less in water at 25 C. Borates of greater solubility do not yield compositions having the opaque, viscous character desired in the practice of this invention.
  • sodium tetra- Na B O -10H O or Na O'2B O -10H O and potassium pentaborate KB O -4H O or K O-5B O -8H O are especially efiicacious.
  • the borate salt must comprise from about 2% to about 15% by weight of the total composition. Less than 2% of this component will not yield the preferred degree of opacity and viscosity, i.e., the solution will be clear or translucent rather than opaque and will have a viscosity of less than 350 centipoises at 75 F. Amounts greater than 15% will adversely affect the stability and homogeneity of the solution. Preferably, this component should comprise from about 4% to about 10% by weight of the total composition.
  • Amine oxides which are essential components of the detergent compositions of this invention, are compounds of the general formula R R R N o.
  • the arrow is a conventional representation of a semipolar bond. They are generally prepared by the direct oxidation of the appropriate tertiary amine. When R is a much longer chain than R 'and R amine oxides have surface activity.
  • R is an alkyl radical of from about 10 to about 16 carbon atoms. Desirable surface active properties are lost if R is substantially less than 10 carbon atoms, and solubility in the formulation of this invention is too low if R is greater than 16 carbon atoms.
  • R is a dodecyl radical or a mixture of dodecyl with decyl, tetradecyl and hexadecyl radicals, such that at least 50% of the radicals are dodecyl radicals.
  • a convenient source of the preferred mixture of alkyl radicals designated R is the middle cut of coconut fatty alcohol which has the approximate chain length composition: 2%C10, 66%C12, 23%C14, and 970- 5.
  • R and R are each selected from the group consisting of methyl and ethyl radicals.
  • R and R are methyl radicals.
  • the amine oxide is used at from about 3% to about of the total formula. Less than about 3% amine oxide adversely affects the performance of the formulations and more than about 10% amine oxide interferes with achieving homogeneity between builder and .detergent when present in the liquid formulation in, sufficient amounts.
  • Soluble pyrophosphate salts are suitable builders in the liquid detergent compositions of this invention. They complex the calcium and magnesium ions of hard water; and, when the calcium ions of hard water are present in excess, have an additional water softening effect by precipitating calcium pyrophosphate. They also serve to increase the level of detergency obtainable with synthetic non-soap surface active agents. Potassium, sodium,
  • ethanolammonium, diethanolammonium, and triethanolammonium are suitable salts of the pyrophosphate anion in the practice of this invention.
  • Potassium pyrophosphate is especially preferred.
  • the soluble salt of pyrophosphate is employed at a level of from about 10% to about 30%.
  • the pyrophosphate salts like various other sequestering agents, are corrosive towards aluminum. If the detergent solution is to contact this metal repeatedly or for prolonged periods of time, especially at elevated temperatures, acorrosion inhibitor should be desirably included.
  • Soluble silicates are highly'effective inhibitors and can be added to the formulas of this invent on at levels of from about 3.5% to about 6%.
  • Potassium, or preferably sodium silicates having a Weight ratio of SiO /M O of from about 1.0 to about 2.6 and preferably from about 1.6 to about 2.6 can be used.
  • M in this ratio refers to sodium or potassium.
  • Suitable hydrotropes to increase the compatibility of the ingredients in the formulations of this invention are the aryl sulfonates. More specifically, they are soluble salts of the hydrotrope anions.
  • Preferred salts of hydro 'trope anions are benzene sulfonate, xylene sulfonate and toluene sulfonate. They are used as the soluble salts such as:' ethanolammonium, diethanolammonium, and triethanol-ammonium and especially as the alkali metal, potassium or sodium, salts. Sodium or potassium toluene sulfonate is especially preferred.
  • the hydrotrope salt is added at levels 'offrom about 3% to about 10% and sufficient to achieve homogeneity in the detergent solution. Levels of from about 4% to about 6% are preferred. The upper limit of about 10% is dictated by the dilution effect on the product of an ingredient which-is substantially inert so far as sudsing and detergency are concerned. The lower limit is the amountrequired toachieve a homogeneous solution. Itwill be appreciated that it is necessary that the formulations of this invention should be liquid at somewhat higher and somewhat lower temperatures than usual room temperature.
  • the amount of hydrotrope salt'used is preferably the minimum amount which will prevent precipitation of the detergent actives throughout the temperature ranges to which the product is likely to be subjected.
  • anionic detergent which have been found beneficial for purposes of this invention are: alkyl benzene sulfonate, alkyl ethylene oxide ether sulfate wherein there are from 1 to 5 ethylene oxide residues per alkyl group, and alkyl sulfate.
  • the anions of these anionic deter-gents may be represented,
  • R80 the alkyl chain (R) will contain from about 9 to about 16 carbon atoms and preferably about 12 carbon atoms.
  • Mixtures of alkyl radicals of different chain lengths are preferably used since they are readily soluble and available from a synthetic source such as a mixture containing tri-, tetra-, and pentapolypropylene polymers and averaging about 12 carbon atoms obtained from petroleum hydrocarbons or from natural sources, such as the mixture of fatty alcohols derived from coconut oil.
  • These detergents are,'of course, used in the form of their water soluble salts; specifically, they are used as sodium, potassium, ethanolammonium, diethanolammonium, and triethanolammonium salts. The sodium and tri-ethanolammonium salts are preferred.
  • alkyl benzene sulfonate and alkyl sulfate are especially preferred, other non-soap anionic synthetic detergents, containing alkyl radicals as specified above, can be usefully employed in the compositions of this invention if they have the following characteristics: their salts, as specified above, are soluble to the extent of at least 3% in an aqueous solution consisting of a mixture of 3% dimethyld-odecylamine oxide, 3% potassium toluene sulfonate, 10% potassium pyrophosphate, and 2% potassium borate; and they are stable against hydrolysis in alkaline solution.
  • An example is the potassium salt of the sulfated condensation product of four moles of ethylene oxide with a mole of nonyl phenol.
  • the compositions of this invention suds so well in the laundry and dishpan that no suds builder is required.
  • the alkyl sulfate and alkyl benzene sulfonate make a particular contribution to sudsing in the compositions of this invention.
  • Alkyl benzene sulfonate as hereinbefore defined is particularly favored for this purpose because in most circumstances it reduces the cost of the formula.
  • the anionic detergent can tend to improve the mildness of the formulations, alkyl benzene sulfonate being partic ularly noteworthy in this respect.
  • Anionic detergents also permit the incorporation of higher levels of active ingredients in a given amount of solvent (water) while still maintaining homogeneity of the liquid composition, i.e., the compositioncan be made more concentrated.
  • compositions of this invention will include two anionic detergents, for example, C -alkyl benzene sulfonate and coconut alkyl sulfate in approximately equal quantities. If more of one detergent is used, preferably less of another is used. To maintain the homogeneous character of the product, the sum of anionic detergent and amine oxide is preferably kept in the range. of from about 10% to about 25% by weight of the total composition.
  • the inorganic builder content is preferably raised as the total synthetic detergent content is loweredg'so that the sum of builder and detergent iskept within the range of about 25% to about 40% by weight of the total composition. It has been found that if these limitations are obborate" selected from the group consisting of sodium tetraborate decahydrate and potassium pentaborate;
  • R being an alkyl radical containing about 9 to about 6 carbon atoms, and mixtures thereof;
  • silicate solids having an SiO /M O ratio of from about 16:1 to about 2.621 where M is selected from the group consisting of sodium and potassium;
  • the cations of-the salts of the said detergent anions, of the salts of the said hydrotrope anions, and of the salts of the said pyrophosphate anion being selected from the roup consisting of potassium, sodium, e-thanolammonium, diethanolainmonium, and triethanolammonium, the mole ratio of the total of potassium and alkanolarnmonium cations to sodium cations being greater than about 3:1.
  • An opaque viscous liquid detergent composition consisting essentially of:
  • R being an alkyl radical containing about 9 to about 16 carbon atoms, and mixtures thereof;
  • An opaque viscous liquid detergent composition consisting essentially of:
  • An opaque viscous liquid detergent composition consisting essentially of: (a) from about 4% to about 10% of sodium tetraborate decahydrate; (b) from about 3% to about 10% or" coconut dimethyl amine oxide; (c) from about 3% to about 15% of a member selected from the group consisting of sodium dodecyl benzene sulfonate, sodium coconut sulfate and mixtures thereof; (d) from about 4% to about 6% of potassium toluene sulfonate; (e) from about 10% to about 30% of potassium pyrophospate; and the balance substantially; (f) water.
  • An opaque viscous liquid detergent composition consisting essentially of:

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  • Chemical & Material Sciences (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)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US68652A 1960-11-14 1960-11-14 Liquid detergent composition Expired - Lifetime US3192166A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE610313D BE610313A (en, 2012) 1960-11-14
NL271301D NL271301A (en, 2012) 1960-11-14
US68652A US3192166A (en) 1960-11-14 1960-11-14 Liquid detergent composition
DEP28221A DE1218647B (de) 1960-11-14 1961-11-13 Dickfluessiges undurchsichtiges Waschmittel
FR878772A FR1305229A (fr) 1960-11-14 1961-11-13 Nouvelles compositions détersives
GB40742/61A GB948396A (en) 1960-11-14 1961-11-14 Liquid detergent composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US68652A US3192166A (en) 1960-11-14 1960-11-14 Liquid detergent composition

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US3192166A true US3192166A (en) 1965-06-29

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US (1) US3192166A (en, 2012)
BE (1) BE610313A (en, 2012)
DE (1) DE1218647B (en, 2012)
GB (1) GB948396A (en, 2012)
NL (1) NL271301A (en, 2012)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3440171A (en) * 1964-06-29 1969-04-22 Union Carbide Corp Surface active compositions
US3462240A (en) * 1966-07-12 1969-08-19 Shell Oil Co Acoustic apparatus for examining a pipeline for leaks
US3898186A (en) * 1973-04-09 1975-08-05 Procter & Gamble Dishwashing compositions containing gel forming gelatin
US3928249A (en) * 1972-02-07 1975-12-23 Procter & Gamble Liquid detergent composition
US3944506A (en) * 1973-08-17 1976-03-16 Barnes-Hind Pharmaceuticals, Inc. Abradant skin cleanser containing a borate salt
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
US4029591A (en) * 1974-09-27 1977-06-14 Lion Fat & Oil Co., Ltd. Liquid detersive bleaching composition
US4048123A (en) * 1973-08-17 1977-09-13 Barnes-Hind Pharmaceuticals, Inc. Abradant skin cleanser
DE2746843A1 (de) * 1977-10-19 1979-04-26 Benckiser Gmbh Joh A Verfahren zum maschinellen spuelen von geschirr
US4244840A (en) * 1977-05-10 1981-01-13 Colgate-Palmolive Company Self-opacified liquid hard surface cleaning compositions
US4259216A (en) * 1979-10-11 1981-03-31 The Lion Fat & Oil Co., Ltd. Process for producing liquid detergent composition
US4788005A (en) * 1987-05-15 1988-11-29 The Clorox Company Thickened aqueous abrasive cleanser exhibiting no syneresis
US20060228323A1 (en) * 2005-03-31 2006-10-12 Andrew Novelle Compositions for treating and removing noxious materials malodors and microbes, and methods of use and preparation thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4436653A (en) 1981-04-06 1984-03-13 The Procter & Gamble Company Stable liquid detergent compositions
US4438024A (en) 1982-05-10 1984-03-20 The Procter & Gamble Company Stable liquid detergent compositions
GB8513293D0 (en) * 1985-05-28 1985-07-03 Procter & Gamble Ntc Ltd Cleaning compositions
ATE103970T1 (de) * 1986-09-29 1994-04-15 Akzo Nv Verdickte, waesserige reinigungsmittel.
JPS6390586A (ja) * 1986-09-29 1988-04-21 リ−・フア−マス−テイカルズ・インコ−ポレイテツド 改良された接着タブ系
NO170944C (no) * 1987-01-24 1992-12-30 Akzo Nv Fortykkede, vandige preparater, samt anvendelse av slike
WO1994028108A1 (en) 1993-06-01 1994-12-08 Ecolab Inc. Thickened hard surface cleaner

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1753395A (en) * 1928-04-05 1930-04-08 Wilkes Frederic Cleaning compound
US2169976A (en) * 1934-01-26 1939-08-15 Ig Farbenindustrie Ag Process of producing assistants in the textile and related industries
US2581677A (en) * 1952-01-08 Phosphate detergent composition in
GB800706A (en) * 1955-09-06 1958-09-03 Colgate Palmolive Co Liquid detergent compositions
US2999068A (en) * 1959-04-27 1961-09-05 Procter & Gamble Personal use detergent lotion
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581677A (en) * 1952-01-08 Phosphate detergent composition in
US1753395A (en) * 1928-04-05 1930-04-08 Wilkes Frederic Cleaning compound
US2169976A (en) * 1934-01-26 1939-08-15 Ig Farbenindustrie Ag Process of producing assistants in the textile and related industries
GB800706A (en) * 1955-09-06 1958-09-03 Colgate Palmolive Co Liquid detergent compositions
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
US2999068A (en) * 1959-04-27 1961-09-05 Procter & Gamble Personal use detergent lotion

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3440171A (en) * 1964-06-29 1969-04-22 Union Carbide Corp Surface active compositions
US3462240A (en) * 1966-07-12 1969-08-19 Shell Oil Co Acoustic apparatus for examining a pipeline for leaks
US3928249A (en) * 1972-02-07 1975-12-23 Procter & Gamble Liquid detergent composition
US3898186A (en) * 1973-04-09 1975-08-05 Procter & Gamble Dishwashing compositions containing gel forming gelatin
US3944506A (en) * 1973-08-17 1976-03-16 Barnes-Hind Pharmaceuticals, Inc. Abradant skin cleanser containing a borate salt
US4048123A (en) * 1973-08-17 1977-09-13 Barnes-Hind Pharmaceuticals, Inc. Abradant skin cleanser
US4029591A (en) * 1974-09-27 1977-06-14 Lion Fat & Oil Co., Ltd. Liquid detersive bleaching composition
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
US4244840A (en) * 1977-05-10 1981-01-13 Colgate-Palmolive Company Self-opacified liquid hard surface cleaning compositions
DE2746843A1 (de) * 1977-10-19 1979-04-26 Benckiser Gmbh Joh A Verfahren zum maschinellen spuelen von geschirr
US4259216A (en) * 1979-10-11 1981-03-31 The Lion Fat & Oil Co., Ltd. Process for producing liquid detergent composition
US4788005A (en) * 1987-05-15 1988-11-29 The Clorox Company Thickened aqueous abrasive cleanser exhibiting no syneresis
US20060228323A1 (en) * 2005-03-31 2006-10-12 Andrew Novelle Compositions for treating and removing noxious materials malodors and microbes, and methods of use and preparation thereof

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Publication number Publication date
BE610313A (en, 2012)
GB948396A (en) 1964-02-05
NL271301A (en, 2012)
DE1218647B (de) 1966-06-08

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