US3461074A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
US3461074A
US3461074A US502558A US3461074DA US3461074A US 3461074 A US3461074 A US 3461074A US 502558 A US502558 A US 502558A US 3461074D A US3461074D A US 3461074DA US 3461074 A US3461074 A US 3461074A
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United States
Prior art keywords
detergent
sodium
alkali metal
dried
heat
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US502558A
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English (en)
Inventor
Lawrence L Schwalley
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US Borax Inc
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United States Borax and Chemical Corp
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Classifications

    • 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
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0086Laundry tablets
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • 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
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • C11D3/062Special methods concerning phosphates
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the detergent composition consists of a heat-dried mix- DETERGENT COMPOSITIONS Lawrence L. Schwalley, Whittier, Califl, assignor to United States Borax & Chemical Corporation, Los Angeles, Calif., a corporation of Nevada No Drawing. Filed Oct. 22, 1965, Ser. No. 502,558 Int. Cl. Cll'd 9/34, 7/36 U.S. Cl. 252-109 12 Claims ABSTRACT OF THE DISCLOSURE Detergent compositions especially useful for forming laundry tablets.
  • compositions are heterogeneous mixtures of a heat-dried mixture, a nonionic synthetic detergent and alkali metal polyphosphate high in Form I.
  • the heat-dried portion contains additional alkali metal polyphosphate which is low in Form I and an anionic synthetic detergent or soap.
  • This invention relates to novel detergent compositions which are particularly useful for forming laundry tablets.
  • Detergent tablets have become increasingly popular within the last few years primarily because of the convenience in using them.
  • One problem, however, which has been difiicult to overcome is control of the rate of dissolving the tablet in the washing solution.
  • the present invention provides an improvement in detergent compositions useful for laundry tablets in which the tablets are readily formed, will dissolve at a controlled rate in the washing solution, and have excellent detergency properties.
  • a still further object of this invention is to provide improved laundry tablets utilizing such improved detergent compositions.
  • This invention provides detergent compositions for forming laundry tablets comprising a heterogeneous mixture of (a) About 22 to about 70 percent by weight of a heat-dried mixture comprising about one part by weight of a low Form I alkali metal polyphosphate and about 0.3 to about one part by weight of a member of the group consisting of the anionic synthetic detergents and soaps;
  • the invention also provides a process for producing said detergent compositions and improved laundry tablets utilizing said detergent compositions.
  • novel detergent compositions of the present invention can be used to form improved detergent tablets, with excellent properties.
  • Laundry washing tablets utilizing the detergent compositions of this invention are readily formed, will dissolve in the laundry washing solution at a preferred rate, have the desirable degree of hardness so as to stand up under packaging and handling conditions, and have excellent fabric washing properties.
  • detergent tablets incorporating the detergent compositions of the present invention have excellent solubility and high soil removal efficiency in washing solutions. Also, they are readily formed and have exceptional integrity, without resorting to the use of binders or surface hydration such as by spraying with water vapor.
  • the heat-dried portion represents about 35 to about 60 percent of the composition.
  • the term heat-dried is to be understood as having the meaning generally understood in the detergent art, that is, the components are mixed together, generally as an aqueous slurry, and then either spraydried into particulate form or drum-dried followed by reduction of the product to the desired particle size.
  • the polyphosphates useful in the heat-dried compositions are the low Form I (or high Form II) content alkali metal polyphosphates such as the sodium, potassium and lithium tripolyphosphates.
  • Sodium tripolyphosphate is the presently preferred phosphate and, when used to prepare the heat-dried portion of the composition, should be low in Form I, that is containing less than about 5% Of Form I Naspaow.
  • anionic synthetic detergents or soaps well known to the art.
  • Particularly useful anionic synthetic detergents are the water-soluble salts of higher aliphatic and aromatic sulfuric acids such as the sodium salts of alkylbenzenesulfonic acids and long chain alkylsulfates.
  • anionic synthetic detergents include sodium octyl-, nonyl-, dodecyl-, decyl-, and tetradecylbenzenesulfonates, sodium diisopropylnaphthalene sulfonate, sodium isopropylnaphthalene sulfate, long chain alkylsulfates such as sodium lauryl-and stearylsulfates, the mahogany and petroleum sulfonates, long chain alkyloxyethylene sulfates such as sodium or potassium laurylpolyoxyethylene sulfate, sodium la lrnonooxyethylene sulfate, sodium octadecylpolyoxyethylene sulfate and sodium cetylpolyoxyethylene sulfate, long chain alkylaryloxyethylene sulfates such as ammonium, sodium or potassium nonyl-, octyl-, and tridecylphenol monoand poly
  • soaps which can be employed in the heatdried mixture there can be enumerated the water-soluble salts of myristic, palmitic, stearic, behenic, oleic, lauric, abietic,
  • the weight ratio of anionic synthetic detergent and/or soap to polyphosphate is from about 0.3 to about 1:1, with a preferred ratio in the range of from about 0.4 to 0.7: 1.
  • a small amount, such as up to about 0.2 part, of nonionic synthetic detergent can also be included in the heatdried portion, and is preferred for reducing sticking in tablet pressing.
  • the heat-dried component is readily prepared using procedures and apparatus well known to those skilled in the detergent art.
  • the ingredients are made up in the desired proportions as an aqueous slurry and then heat-dried, as for example, by spray-drying into particulate form or by drum-drying followed by reduction of the product to the desired particle size such as through a 16 mesh screen.
  • the presently preferred heat-drying procedure is spray-drying and the preferred particle size is predominantly about 30 to about mesh, with not more than about 10% through 200 mesh.
  • the resulting heat-dried material is a homogeneous mixture suitable for incorporation in the novel detergent compositions of this invention.
  • the novel detergent compositions of this invention contain from about 1 to about 12 percent and preferably from about 3 to 9 percent, by weight of a nonionic synthetic detergent, preferably a liquid nonionic detergent.
  • a nonionic synthetic detergent preferably a liquid nonionic detergent.
  • these include the ethylene oxide condensation products with alkylphenols, such as nonylphenol, octylphenol, and diamylphenol.
  • the phenols are condensed with 6 to 20 or more moles of ethylene oxide.
  • esters of the sugar alcohols such as sorbitan and mannitan
  • the polyethyleneoxy esters of tall oil acids such as ethoxylated alkanols such as ethoxylated lauryl alcohol, ethylene oxidefatty acid condenstates, and propylene glycol-ethylene oxide condensates.
  • the detergent compositions also contain about 18 to about 77 percent by weight of non-hydrated powdered or granular alkali metal polyphosphate in addition to that in the heat-dried portion of the mixture.
  • the compositions contain from about 30 to about 64 percent by weight of sodium tripolyphosphate.
  • the polyphosphate is powdered or granular with a particle size range of from about 16 to +200 mesh, preferably in the range of about 30 to +100 mesh. The following is a typical analysis of a sodium tripolyphosphate suitable for this portion of the composition.
  • the polyphosphate in this portion of the composition is high in Form I Na P O that is it should contain from about 20 to 40% or higher of Form I, the form which hydrates more rapidly.
  • additives such as fillers, builders, optical brighteners, perfumes, coloring agents, bacteriostats, corrosion inhibitors, anti-redeposition agents, sequestering agents, etc.
  • desirable additives such as fillers, builders, optical brighteners, perfumes, coloring agents, bacteriostats, corrosion inhibitors, anti-redeposition agents, sequestering agents, etc.
  • these additives are sodium tetraborate, sodium sulfate, sodium carbonate, sodium metasilicate, sodium carboxymethyl cellulose, ethylenediamine tetraacetic acid, fluorescent or optical pigments, talc, trichlorocarbanilide, hexachlorophene, trichlorosalicylanilide, etc.
  • These additives can be incorporated in the heat-dried portion prior to heat-drying or they can be added to the composition during the preparation of the final heterogeneous mixture.
  • novel detergent compositions of this invention are readily prepared merely by intimately mixing the components, such as at about room temperature, in suitable mixing or blending apparatus, in such proportions as to give a final product having the desired percentage of each component.
  • the resulting product is a heterogeneous mixture of the components, which is especially useful for compression into laundry tablets.
  • a portion of the nonionic detergent is added first to the heat-dried portion and the mixture allowed to cure before combining with the additional polyphosphate and remaining nonionic. Curing requires merely standing with slight agitation or tumbling in a slowly rotating mixer so as to allow the heat-dried portion to absorb the wet nonionic. Alternatively, curing usually is not required if a portion of the additional polyphosphate is added immediately in order to thereby coat the wet particles.
  • Example I The following materials were combined as a slurry in water and then spray-dried to give a granular detergent composition as follows:
  • Part I The above composition (39.93 parts by weight), which is referred to as Part I, was combined with 1.8 parts by weight of nonoylphenoxypoly(ethyleneoxy)ethanol and the mixture cured by intimately mixing in a slowly rotating drum for up to about 72 hours. The cured mixture was then blended with the following ingredients (referred to as Part Ii) in which said parts are by weight.
  • Pentasodium tripolyphosphate about 34% Form Nonylphenoxypoly(ethyleneoxy)ethanol 4.20 Sodium carboxymethyl cellulose (65% active) 2.50 Optical brightener a- 0.12 Perfume M 0.05
  • the detergent composition When pressed into tablets, the detergent composition had excellent tablet forming properties, dissolved completely in three minutes, and had outstanding clothes washing efficiency.
  • Example H Part I (spray-dried composition) was prepared as described in Example I and 39.39 parts were intimately mixed with 1.80 parts of nonylphenoxypoly(ethylenoxy) ethanol. Powdered high Form I pentasodium tripolyphosphate (5.0 parts) was then added to the mixture, thereby coating the particles coated with the nonionic detergent. The resultant mixture was then blended with Part II, hav- The resultant detergent formulation can be used to form excellent laundry washing tablets.
  • the detergent compositions can be used to form laundry tablets according to procedures well known to the art.
  • Multipurpose laundry tablets containing a bleach core can be prepared by procedures described in Speak et al. U.S. Patent No. 3,154,494.
  • the bleach material is first compacted and then coated with the detergent composition.
  • the coating can be preformed in two separate halves, each having a cavity therein, the bleach can be compressed to the desired shape and then deposited in the cavity formed in one half of the coating and the other half of the preformed coating can be pressed on top, forming a finished composition having a core of bleach and a coating contiguous therewith and completely enclosing the same.
  • the tablet is to form one half of the coating with a cavity, fill the cavity with bleach powder, put the rest of the coating material on top and then press the entire mass to the desired shape.
  • the detergent composition is used to make a multipurpose tablet with a bleach core, it should be substantially dry, that is it should have a maximum of about 2% moisture and volatile matter.
  • the compositions can also be used to produce the usual single layer detergent tablets without a bleach core.
  • a superior detergent formulation for laundry detergent tablets containing alkali metal polyphosphate, anionic detergent (including soap), and nonionic detergent in which the anionic detergent has been combined with a portion of of the alkali metal polyphosphate and a heat dried mixture formed, which is then combined with the nonionic detergent and the remaining alkali metal polyphosphate, which must be a high Form I polyphosphate.
  • the process for producing a detergent composition suitable for forming laundry tablets which comprises (a) forming an aqueous slurry containing about one part by weight of a low Form I alkali metal polyphosphate containing less than about 5% Form I and about 0.3 to one part by weight of a member of the group consisting of the sulfonate and sulfate anionic synthetic detergents and water-soluble salts of higher fatty acid soaps, (b) heat-drying said slurry to form a homogeneous mixture, and (c) intimately mixing said homogeneous mixture with a liquid nonionic detergent and additional alkali metal polyphosphate containing at least about Form I in such proportions as to provide a heterogeneous mixture containing about 22 to 70 percent by weight of said homogeneous mixture, about 1 to 12 percent by weight of said liquid nonionic detergent and about 18 to about 77 percent by weight of said additional alkali metal polyphosphate.
  • said alkali metal polyphosphate is sodium tripo
  • the process for producing a detergent composition suitable for forming laundry tablets which comprises (a) forming an aqueous slurry containing about one part by weight of a low Form I alkali metal polyphosphate containing less than about 5% Form I and from about 0.4 to about 0.7 part by weight of a member of the group consisting of the sulfonate and sulfate anionic synthetic detergents and water-soluble salts of higher fatty acid soaps,
  • alkali metal polyphosphate in the heat-dried homogeneous mixture is sodium tripolyphosphate containing less than about 5% of Form I Na P O and said additional alkali metal polyphosphate is sodium tripolyphosphate containing at least about 20% of Form I Na P O 7.
  • said slurry is spray-dried.

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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)
  • Detergent Compositions (AREA)
US502558A 1965-10-22 1965-10-22 Detergent compositions Expired - Lifetime US3461074A (en)

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US50255865A 1965-10-22 1965-10-22

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US3461074A true US3461074A (en) 1969-08-12

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Country Status (9)

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US (1) US3461074A (fr)
BE (1) BE688505A (fr)
CA (1) CA789508A (fr)
CH (1) CH482827A (fr)
DE (1) DE1617212A1 (fr)
FR (1) FR1500509A (fr)
GB (1) GB1103675A (fr)
NL (1) NL6614720A (fr)
ZA (1) ZA666332B (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886098A (en) * 1971-03-15 1975-05-27 Colgate Palmolive Co Manufacture of free flowing particulate detergent composition containing nonionic detergent
US4006110A (en) * 1971-11-30 1977-02-01 Colgate-Palmolive Company Manufacture of free-flowing particulate heavy duty synthetic detergent composition
DE2753573A1 (de) * 1976-12-06 1978-06-08 Colgate Palmolive Co Tablettenfoermiges wasch- und reinigungsmittel
US4099912A (en) * 1974-05-15 1978-07-11 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components
US4131558A (en) * 1975-02-14 1978-12-26 The Procter & Gamble Company Process for preparing an orthophosphate-silicate detergent product
US4278571A (en) * 1980-05-28 1981-07-14 The Procter & Gamble Company Surfactant cake compositions
US4362641A (en) * 1980-03-12 1982-12-07 Occidental Chemical Corporation Composition of an STPP product for dishwasher detergent formulations and method of preparation
US5078301A (en) * 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5481799A (en) * 1988-09-09 1996-01-09 Metcal, Inc. Process for producing a self-heating auto regulating connector
EP0839906A1 (fr) * 1996-11-01 1998-05-06 Unilever Plc Composition détergente
EP1099487A2 (fr) * 1999-11-09 2001-05-16 BeviClean GmbH Procédé, dispositif et additif détergent pour le nettoyage chimique de conduites
US6472362B1 (en) * 1997-10-22 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions in tablet form

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6328951B1 (en) 1999-12-21 2001-12-11 International Flavors & Fragrances Inc. Water-soluble solid-phase ironing aid freshening composition tablets consisting of same for use in the steam chamber of an iron and process for preparing and utilizing the same
EP2527156A1 (fr) 2011-05-25 2012-11-28 RLS Merilna Tehnika D.O.O. Appareil et procédé pour inscrire un motif dans un substrat

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2622068A (en) * 1948-06-04 1952-12-16 Procter & Gamble Process of making heat dried detergent compositions containing form ii sodium triphosphate
US2961410A (en) * 1957-04-02 1960-11-22 Procter & Gamble Process for preparing detergent compositions
US2961409A (en) * 1957-04-02 1960-11-22 Procter & Gamble Process for preparing detergent compositions
US3081267A (en) * 1959-12-31 1963-03-12 Procter & Gamble Detergent tablet and process for making same
US3154494A (en) * 1961-08-07 1964-10-27 United States Borax Chem Fabric laundry compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2622068A (en) * 1948-06-04 1952-12-16 Procter & Gamble Process of making heat dried detergent compositions containing form ii sodium triphosphate
US2961410A (en) * 1957-04-02 1960-11-22 Procter & Gamble Process for preparing detergent compositions
US2961409A (en) * 1957-04-02 1960-11-22 Procter & Gamble Process for preparing detergent compositions
US3081267A (en) * 1959-12-31 1963-03-12 Procter & Gamble Detergent tablet and process for making same
US3154494A (en) * 1961-08-07 1964-10-27 United States Borax Chem Fabric laundry compositions

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886098A (en) * 1971-03-15 1975-05-27 Colgate Palmolive Co Manufacture of free flowing particulate detergent composition containing nonionic detergent
US4006110A (en) * 1971-11-30 1977-02-01 Colgate-Palmolive Company Manufacture of free-flowing particulate heavy duty synthetic detergent composition
US4099912A (en) * 1974-05-15 1978-07-11 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components
US4131558A (en) * 1975-02-14 1978-12-26 The Procter & Gamble Company Process for preparing an orthophosphate-silicate detergent product
DE2753573A1 (de) * 1976-12-06 1978-06-08 Colgate Palmolive Co Tablettenfoermiges wasch- und reinigungsmittel
US4362641A (en) * 1980-03-12 1982-12-07 Occidental Chemical Corporation Composition of an STPP product for dishwasher detergent formulations and method of preparation
US4278571A (en) * 1980-05-28 1981-07-14 The Procter & Gamble Company Surfactant cake compositions
US5078301A (en) * 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5481799A (en) * 1988-09-09 1996-01-09 Metcal, Inc. Process for producing a self-heating auto regulating connector
EP0839906A1 (fr) * 1996-11-01 1998-05-06 Unilever Plc Composition détergente
US6472362B1 (en) * 1997-10-22 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions in tablet form
EP1099487A2 (fr) * 1999-11-09 2001-05-16 BeviClean GmbH Procédé, dispositif et additif détergent pour le nettoyage chimique de conduites
EP1099487A3 (fr) * 1999-11-09 2003-04-02 BeviClean GmbH Procédé, dispositif et additif détergent pour le nettoyage chimique de conduites

Also Published As

Publication number Publication date
ZA666332B (fr)
DE1617212A1 (de) 1971-02-25
CA789508A (en) 1968-07-09
CH482827A (de) 1969-12-15
NL6614720A (fr) 1967-04-24
GB1103675A (en) 1968-02-21
FR1500509A (fr) 1967-11-03
BE688505A (fr) 1967-04-19

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