EP0313143A2 - Phosphatfreie Reinigungs- und Bleichmittel - Google Patents

Phosphatfreie Reinigungs- und Bleichmittel Download PDF

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Publication number
EP0313143A2
EP0313143A2 EP88202243A EP88202243A EP0313143A2 EP 0313143 A2 EP0313143 A2 EP 0313143A2 EP 88202243 A EP88202243 A EP 88202243A EP 88202243 A EP88202243 A EP 88202243A EP 0313143 A2 EP0313143 A2 EP 0313143A2
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
composition
acid
sodium
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.)
Withdrawn
Application number
EP88202243A
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English (en)
French (fr)
Other versions
EP0313143A3 (de
Inventor
Wiliam Derek Emery
Stephen George Barnes
Peter Stanford Sims
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.)
Unilever PLC
Original Assignee
Unilever PLC
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
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of EP0313143A2 publication Critical patent/EP0313143A2/de
Publication of EP0313143A3 publication Critical patent/EP0313143A3/de
Withdrawn legal-status Critical Current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
    • C11D3/08—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/395—Bleaching agents

Definitions

  • This invention relates to non-phosphorus detergent bleach compositions.
  • it relates to aluminosilicate built laundry detergent bleach compositions having improved cleaning and stain-removal performances.
  • Water-insoluble aluminosilicates commonly known as zeolites, have been used in detergent compositions as important alternative builders to phosphates (see, for example, GB-A-­1429143; GB-A-1470250; GB-A-1504211; GB-A-1529454 and US-A-­4064062).
  • aluminosilicate built detergent compositions which contain 0.01-4% by weight of a polyphosphonate sequestering agent and 5-25% by weight of citric acid or citrates as pH-regulating agent. These compositions are unsatisfactory when used for washing at the low temperature region of 40°C and below.
  • organic peroxyacids as a class are effective bleaching agents in the lower temperature region of, say, 40°-60°C. Bleaching experiments have indicated that organic peroxyacids, e.g. 1,2-diperoxydodecanedioic acid, provide effective bleaching and stain removal at 40°C in a phosphate-­built detergent formulation but, remarkably, they are much less effective in a non-phosphate, aluminosilicate built detergent composition.
  • non-­phosphorus detergent bleach composition comprising at least one detergent-active material and :
  • composition of the invention contains at least one detergent-active material which can be an organic soap or synthetic detergent surfactant material.
  • an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, soap, or mixtures thereof is included.
  • Many suitable detergent-active compounds are commercially available and are fully described in literature, for example in US-A-4222905 and US-A-4239659 and in "Surface Active Agents and Detergents", Vol. I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds which can be used are synthetic anionic, soap and nonionic compounds.
  • the first-mentioned are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
  • suitable synthetic, anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol-­alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; al
  • Suitable soaps are the alkali metal salts of long chain C8-C22 fatty acids such as the sodium soaps of tallow, coconut oil, palmkernel oil, palm oil or hardened rapeseed oil fatty acids or mixtures thereof.
  • the preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium (C16-C18) alkyl sulphates.
  • nonionic detergent compounds examples include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
  • alkylene oxides usually ethylene oxide
  • alkyl (C6-C22) phenols generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule
  • condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide generally 6 to 30 EO
  • nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • detergent-active compounds for example mixed anionic or mixed anionic and nonionic compounds
  • Amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the compositions of the invention, but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic, detergent-active compounds are used, it is generally in small amounts in the compositions based on the much more commonly used synthetic anionic and/or nonionic detergent-active compounds.
  • the detergent composition of the invention also contains a water-insoluble aluminosilicate cation-exchange material in an amount of from 15% to about 40% by weight, preferably from 20% to 35% by weight.
  • the aluminosilicate can be crystalline or amorphous in character, preferred materials having the unit cell formula I M z [(AlO2) z (SiO2) y ] xH2O I wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is from about 1.0 to about 0.5 and x is at least 5, preferably from about 7.5 to about 276, more preferably from about 10 to about 264.
  • the aluminosilic­ate materials are in hydrated form and are preferably crystalline containing from about 10% to about 28%, more preferably from about 18% to about 22% water.
  • the aluminosilicate ion-exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns, preferably from about 0.2 micron to about 4 microns.
  • particle size diameter herein represents the average particle size diameter of a given ion-­exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the aluminosilicate ion-exchange materials herein are usually further characteri­zed by their calcium ion-exchange capacity, which is at least about 200 mg.
  • aluminosilicate ion- exchange materials herein are still further characterized by their calcium ion-­ exchange rate which is at least about 2 grains Ca++/gallon/­minute/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/­gallon/minute/gram/gallon to about 6 grains/gallon/minute/­gram/gallon, based on calcium ion hardness.
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion-­exchange rate of at least about 4 grains/gallon/minute/gram/­gallon.
  • Aluminosilicate ion-exchange materials useful in the practice of this invention are commercially available and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion-exchange materials is discussed in US-A-3985669.
  • Preferred synthetic crystalline aluminosilicate ion-exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the crystalline aluminosilicate ion-exchange material is Zeolite A and has the formula Na12[AlO2)12 (SiO2)12] xH2O wherein x is from about 20 to about 30, especially about 27.
  • Zeolite X of formula Na86 [(AlO2)86)(SiO2)106] .276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(AlO2)6 (SiO2)6] 7.5 H2O).
  • the detergent composition of the invention further contains an alkali metal citrate or citric acid in an amount of from about 1% to about 15%, preferably from 2 to 10%, by weight of the composition.
  • a preferred alkali metal citrate is sodium citrate, particularly trisodium citrate, i.e. C6H5O7.Na3.2H2O.
  • a further essential component of the compositions herein is from about 1% to about 15% by weight, preferably from 2% to 8% by weight of a solid organic peroxyacid compound.
  • the organic peroxyacid compounds used in the present invention are solid at room temperature and should preferably have a melting point of at least 50°C.
  • Such peroxyacid compounds are the organic peroxyacids and water-soluble salts thereof having the general formula: HO-O- -R-Y, wherein R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms, and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
  • Y groups can include, for example: wherein M is H or a water-soluble, salt-forming cation.
  • the organic peroxyacids and salts thereof usable in the present invention can contain either one, two or more peroxy groups and can be either aliphatic or aromatic.
  • the unsubstituted acid may have the general formula: HO-O- -(CH2) n -Y wherein Y can be H, -CH3, -CH2Cl, and n can be an integer from 6 to 20.
  • Peroxydodecanoic acids, peroxytetradecanoic acids and peroxyhexadecanoic acids are the most preferred compounds of this type, particularly 1,2-diperoxy-dodecanedioic acid, 1,14-diperoxytetradecanedioic acid and 1,16-diperoxyhexadeca­ nedioic acid.
  • Examples of other preferred compounds of this type are diperoxyazelaic acid, diperoxyadipic acid and diperoxysebacic acid.
  • the unsubstituted acid may have the general formula: HO-O- -C6H4-Y wherein Y is, for example, hydrogen, halogen, alkyl,
  • Y is, for example, hydrogen, halogen, alkyl
  • the percarboxy and Y groupings can be in any relative position around the aromatic ring.
  • the ring and/or Y group (if alkyl) can contain any non-interfering substituents such as halogen or sulphonate groups.
  • aromatic peroxyacids and salts thereof include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-­cholorodiperoxyphthalic acid, diperoxyisophthalic acid, m-­chloroperoxybenzoic acid, p-nitroperoxybenzoic acic, and peroxy-alpha-napthoic acid.
  • a preferred aromatic peroxyacid is diperoxyisophthalic acid.
  • a particularly preferred peroxyacid for use in the present invention is 1,12-diperoxydodecanedioic acid.
  • Suitable salts of peroxyacids are preferably the magnesium salts, such as are described in EP-A-0105689.
  • the detergent composition herein can contain any of the conventional additives and adjuncts in the amounts in which such materials are normally employed in fabric washing compositions.
  • additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel and coconut fatty acids; lather depressants such as alkyl phosphates, silicones and waxes; anti-­redeposition agents such as sodium carboxymethyl cellulose (SCMC), polyvinyl pyrrolidone (PVP) and the cellulose ethers such as methylcellulose and ethyl hydroxyethyl cellulose; stabilizers such as ethylene diamine tetraacetate; fabric softening agents; inorganic salts such as sodium sulphate and sodium carbonate; and - usually present in very minor amounts - fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases; germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamide
  • Polycarboxylate polymers though not essential, may also be included as desired in amounts of e.g. from about 0.5% to 6% by weight of the total composition.
  • the polycarboxylate polymers herein are preferably selected from co-polymeric polycarboxylic acids and their salts derived from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid or mesaconic acid as a first monomer and ethylene, methyl vinyl ether, acrylic acid or metacrylic acid as a second monomer, the co-polymer comprising at least about 10 mole%, preferably at least about 20 mole% of polycarboxylic acid units and having weight average molecular weights of at least about 10,000, preferably at least about 30,000; homopolyacrylates and homopolymethacrylates having a weight average molecular weight of from about 1000 to about 80,000, preferably from about 5000 to about 50,000; and mixtures thereof.
  • the detergent bleach compositions of the invention are alkaline and will advantageously give a solution pH (2-10 g/1) of from 8-10.5, with an optimal pH of between 8 and 9.
  • buffering agents such as borax, may be necessary.
  • compositions may optionally include an inorganic peroxide compound, such as the alkali metal perborates, percarbonates, and persilicates, the perborates, particularly sodium perborate tetra- and monohydrates, being preferred because of their commercial availability.
  • an inorganic peroxide compound such as the alkali metal perborates, percarbonates, and persilicates, the perborates, particularly sodium perborate tetra- and monohydrates, being preferred because of their commercial availability.
  • the detergent compositions of the invention are preferably presented in free-flowing particulate, e.g. powdered or granular form, and can be produced by any of the known techniques commonly employed in the manufacture of such washing compositions, but preferably by spray-drying an aqueous slurry comprising the surfactant(s), the alumino-­silicate and the alkali metal citrate or citric acid to form a detergent base powder, to which the heat-sensitive ingredients, including the organic peroxyacid, peroxide compound, enzymes and optionally some other ingredients as conveniently desirable are added.
  • the alkali metal citrate does not form part of the base powder and is separately dry-mixed with the spray-dried base powder. It is preferred that the process used to form the compositions should result in a product having a moisture content of up to about 15%, more preferably from about 7% to about 14% by weight.
  • composition A Parts by weight Sodium linear alkylbenzene sulphonate 9.0 Fatty alcohol-7 ethoxylate 1.5
  • Maleic acid/acrylic acid copolymer Sokalan ® CP5 ex BASF
  • 4.0 Sodium aluminosilicate Zeolite A 24.0 Sodium sulphate (anhydrous) 0.3 Sodium carboxymethyl cellulose 0.5 Sodium ethylenediamine tetraacetate (EDTA) 0.2 Sodium carbonate (Na2CO3) 2.0 Water and fluorescer (0.13) 7.6
  • Composition (B) Sodium perborate monohydrate 8.0 Anti-foaming agent 2.5
  • Proteolytic enzyme Sevinase®ex NOVO
  • DPDA Diperoxydodecanedioic acid
  • Table I ⁇ R values Tea Wine Detergency Protein stains Composition A/B + 0% citrate 11.0 30.1 17.1 10.1 " + 1% citrate 13.1 32.5 18.8 9.6 " + 2% citrate 14.2 34.3 18.5 14.1 " + 3% citrate 14.8 35.1 18.4 14.1 " + 5% citrate 16.2 37.4 19.4 21.6 " + 10% citrate 16.4 38.2 18.2 24.3
  • composition A1 is Composition A without Sokalan CP5 co­polymer.
  • composition A/B + citrate of Example I compares with a conventional good quality sodium triphosphate built detergent powder including DPDA of the following composition: Composition Parts by weight Sodium linear alkylbenzene sulphonate 6.0 Nonionic fatty alcohol-7 ethoxylate 7.0 Alkaline sodium silicate 6.0 Sosium triphosphate 25.0 Sodium sulphate 40.1 EDTA 0.1 Sodium carboxymethyl cellulose 0.5 Polymer 1.0 Fluorescer 0.3 Anti-foaming agent 1.0 Water 7.0 Diperoxy dodecanedioic acid 6.0 III) Tergotometer wash, 8 gram/litre dosage, 24°FH water, 40°C, buffered at pH 8.5, 30 min.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP88202243A 1987-10-23 1988-10-07 Phosphatfreie Reinigungs- und Bleichmittel Withdrawn EP0313143A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB878724899A GB8724899D0 (en) 1987-10-23 1987-10-23 Detergent bleach compositions
GB8724899 1987-10-23

Publications (2)

Publication Number Publication Date
EP0313143A2 true EP0313143A2 (de) 1989-04-26
EP0313143A3 EP0313143A3 (de) 1989-10-18

Family

ID=10625799

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88202243A Withdrawn EP0313143A3 (de) 1987-10-23 1988-10-07 Phosphatfreie Reinigungs- und Bleichmittel

Country Status (8)

Country Link
EP (1) EP0313143A3 (de)
JP (1) JPH01146996A (de)
KR (1) KR920001656B1 (de)
AU (1) AU607268B2 (de)
BR (1) BR8805449A (de)
GB (1) GB8724899D0 (de)
NO (1) NO884699L (de)
TR (1) TR23816A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0456315A3 (en) * 1990-05-08 1992-02-05 The Procter & Gamble Company Low ph granular laundry detergent compositions containing aluminosilicate citric acid and carbonate builders
EP0569066A1 (de) * 1992-04-16 1993-11-10 Unilever N.V. Desinfizierende Zusammensetzungen
GB2292564A (en) * 1994-08-11 1996-02-28 Procter & Gamble Detergent Composition
US5583098A (en) * 1993-11-24 1996-12-10 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
EP0816481A3 (de) * 1996-06-26 1999-02-10 Unilever N.V. Zitronensäuremonohydrat enthaltende Persäuregranulate zwecks verbesserter Auflösbarkeit
EP0843716A4 (de) * 1995-07-25 1999-11-17 Procter & Gamble Waschmittel enthaltend hydroxycarbonsäuren
US6262013B1 (en) 1999-01-14 2001-07-17 Ecolab Inc. Sanitizing laundry sour

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9006171D0 (en) * 1990-03-19 1990-05-16 Unilever Plc Detergent compositions
JPH04277599A (ja) * 1991-03-05 1992-10-02 Unilever Nv 洗剤組成物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT337325B (de) * 1973-08-31 1977-06-27 Henkel & Cie Gmbh Verfahren zum waschen, bleichen oder reinigen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuhrung des verfahrens
DE3121242A1 (de) * 1981-05-29 1983-01-05 Degussa Ag, 6000 Frankfurt Verfahren zum bleichen und desinfizieren von textilien und mittel zur durchfuehrung des verfahrens
US4374035A (en) * 1981-07-13 1983-02-15 The Procter & Gamble Company Accelerated release laundry bleach product
JPS6031880A (ja) * 1983-08-01 1985-02-18 Kubota Ltd 加圧浮上濃縮装置
JPS60221496A (ja) * 1984-04-17 1985-11-06 ライオン株式会社 漂白性洗浄剤組成物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0456315A3 (en) * 1990-05-08 1992-02-05 The Procter & Gamble Company Low ph granular laundry detergent compositions containing aluminosilicate citric acid and carbonate builders
EP0569066A1 (de) * 1992-04-16 1993-11-10 Unilever N.V. Desinfizierende Zusammensetzungen
US5583098A (en) * 1993-11-24 1996-12-10 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
GB2292564A (en) * 1994-08-11 1996-02-28 Procter & Gamble Detergent Composition
EP0843716A4 (de) * 1995-07-25 1999-11-17 Procter & Gamble Waschmittel enthaltend hydroxycarbonsäuren
EP0816481A3 (de) * 1996-06-26 1999-02-10 Unilever N.V. Zitronensäuremonohydrat enthaltende Persäuregranulate zwecks verbesserter Auflösbarkeit
US6262013B1 (en) 1999-01-14 2001-07-17 Ecolab Inc. Sanitizing laundry sour

Also Published As

Publication number Publication date
NO884699D0 (no) 1988-10-21
JPH01146996A (ja) 1989-06-08
TR23816A (tr) 1990-09-13
AU2400888A (en) 1989-04-27
AU607268B2 (en) 1991-02-28
NO884699L (no) 1989-04-24
KR890006802A (ko) 1989-06-16
GB8724899D0 (en) 1987-11-25
EP0313143A3 (de) 1989-10-18
BR8805449A (pt) 1989-06-27
KR920001656B1 (ko) 1992-02-21

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