EP0219314A2 - Granulierte Reinigungsmittel mit Löslichkeit - Google Patents

Granulierte Reinigungsmittel mit Löslichkeit Download PDF

Info

Publication number
EP0219314A2
EP0219314A2 EP86307799A EP86307799A EP0219314A2 EP 0219314 A2 EP0219314 A2 EP 0219314A2 EP 86307799 A EP86307799 A EP 86307799A EP 86307799 A EP86307799 A EP 86307799A EP 0219314 A2 EP0219314 A2 EP 0219314A2
Authority
EP
European Patent Office
Prior art keywords
composition according
surfactant
sulfate
alkali metal
ply
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.)
Granted
Application number
EP86307799A
Other languages
English (en)
French (fr)
Other versions
EP0219314B2 (de
EP0219314A3 (en
EP0219314B1 (de
Inventor
Brett Alan Evans
George John Kaminsky
Richard Hansen
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25137068&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0219314(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0219314A2 publication Critical patent/EP0219314A2/de
Publication of EP0219314A3 publication Critical patent/EP0219314A3/en
Application granted granted Critical
Publication of EP0219314B1 publication Critical patent/EP0219314B1/de
Publication of EP0219314B2 publication Critical patent/EP0219314B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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

Definitions

  • the present invention relates to granular detergent compositions containing a specific mixture of alkylben­zene sulfonate surfactant, alkyl sulfate surfactant, alkali metal silicate and water-soluble sulfate.
  • the compositions are prepared by drying, preferably by spray-drying, an aqueous slurry comprising the above components. While the compositions preferably also contain detergent builder materials, there should be relatively little or no pyrosphosphate or anhydrous Form 1 tripolyphosphate builder in that portion of the composition prepared by drying the slurry comprising the sulfonate and sulfate surfactants, silicate and sulfate.
  • alkylbenzene sulfonate and alkyl sulfate surfactants are desired for optimum detergency perform­ance. However, such mixtures tend to gel on contact with water. This can result in poor solubility of granules having high levels of alkylbenzene sulfonate and alkyl sulfate surfactants, particularly when such granules are incorporated in dense detergent compositions.
  • soluble granular detergent compositions containing high levels of alkyl­benzene sulfonate and alkyl sulfate surfactants can be obtained by drying an aqueous slurry comprising the surfactants, silicate in a weight ratio of surfactant to silicate within the range of from 1.5:1 to 6:1, sulfate and relatively little or no pyrophosphate or anhydrous Form 1 tripolyphosphate detergent builder material.
  • these soluble detergent granules are admixed or agglomerated with builders and other optional detergent ingredients.
  • compositions are obtained by admixing the soluble granules with builders, compacting the admix at relatively low pressures (e.g., 137.9 kPa to 1379 kPa and optionally admixing additional builders and other ingredients to provide finished granular detergent compositions.
  • the compositions can also contain 0-20% of other surfactants such as alkylbenzene sulfonates.
  • Spray-dried detergents containing mixtures of alkylbenzene sulfonate and alkyl ethoxy sulfate surfactants, silicate and builders are exemplified.
  • the particles are mixed with spray-dried base granule containing about 27% of a mixture of alkylbenzene sulfonate and alkyl ethoxy sulfate surfactants, 18% silicate and about 22% sodium tripolyphosphate.
  • Japanese OPI 106509 published August 21, 1979, discloses spray-dried granular detergents containing 15-40% surfactant, 5-20% silicate and no more than 12% phosphate.
  • the compositions are said to have good physical properties and to cause less deposition of insolubles on clothes.
  • Japanese OPI 72998 and 72999 published April 25, 1985, disclose dense granular detergents formed by high shear mixing of alkylbenzene sulfuric acid and alkyl sulfuric acid with sodium carbonate and water to cause neutralization, admixing other ingredients such as builders, and then crushing and granulating the mixture.
  • This invention relates to a granular detergent composition prepared by: (1) forming base granules comprising, by weight:
  • the granular detergent compositions of the present invention contain from 30% to 85%, preferably from 35% to 60 %, more preferably from 40% to 50%, by weight of a mixture of C11-C13 alkylbenzene sulfonate surfactant and C12-C16 alkyl sulfate surfactant in a weight ratio of sulfonate sur­factant to sulfate surfactant of from 4:1 to 1:4, preferably from 3:1 to 1:3, more preferively from 2:1 to 1:2.
  • Sulfonate surfactants useful herein are the water­soluble salts, particularly the alkali metal, ammonium and alkanolammonium (e.g., monoethanolammonium or triethanolammonium) salts of alkylbenzene sulfonates in which the alkyl group contains from 11 to 13 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • alkali metal, ammonium and alkanolammonium e.g., monoethanolammonium or triethanolammonium
  • Useful alkyl sulfate surfactants are the water-­soluble salts, particularly the alkali metal, ammonium and alkanolammonium (e.g., monoethanolammonium or triethanolammonium) salts of C12-C16 linear or branched alkyl sulfates. Preferred are those containing a C12-C15, especially C14-C15, linear alkyl group.
  • compositions herein can also contain minor amounts (generally less than about 30%, but preferably less than about 15%, by weight of the above sulfonate and sulfate surfactants) of other detergent surfactants known in the art.
  • minor amounts can include anionic, nonionic, cationic, ampholytic and zwitterionic surfactants, such as those disclosed in U.S. Patent 3,919,678, Laughlin, et al, issued December 30, 1975.
  • compositions of the present invention also contain an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from 1.0 to 3.2, preferably from 1.6 to 2.4.
  • the alkali metal silicates can be purchased in either liquid or granular form. Silicate solutions or slurries can conveniently be used to avoid having to dissolve the dried form in the aqueous slurry (e.g., crutcher mix) of the components herein.
  • aqueous slurry e.g., crutcher mix
  • the weight ratio of the alkylbenzene sulfonate plus alkyl sulfate surfactants herein to the alkali metal silicate should be from 1.5:1 to 6:1, preferably from 2:1 to 4:1, more preferably from 2:5:1 to 3.5:1.
  • compositions further contain from 10% to 60%, preferably from 20% to 50%, by weight of a water-soluble (preferably sodium) sulfate.
  • a water-soluble (preferably sodium) sulfate is usually formed during the sulfation/sulfonation and neutralization steps in the production of the alkylbenzene sulfonate and alkyl sulfate surfactants herein.
  • compositions herein prepared by drying an aqueous slurry comprising the components.
  • the slurry generally contains from 25% to 70%, preferably from 40% to 60%, water, whereas the dried granules initially contain from 1% to 10%, preferably from 1% to 3%, water.
  • the drying operation can be accomplished by any convenient means, such as by using spray-drying towers, both counter-current and co-current, fluid beds, flash-drying equipment, or industrial microwave or oven-drying equipment. These are more fully described in U.S. Patent 4,019,998, Benson et al, issued April 26, 1977 (particularly from Column 14, line 19 to Column 15, line 9).
  • the granular detergents herein are very soluble in the wash water even though they contain high levels of alkylbenzene sulfonate and alkyl sulfate surfactants. Good solubility is obtained when the weight ratio of total sulfonate plus sulfate surfactant to silicate is within the 1.5:1 to 6:1 range specified above. While not intending to be limited by theory, it is believed that this relatively high level of silicate provides structure and helps to maintain integrity of the high surfactant granules and that this minimizes gelling when the surfactants contact the wash water.
  • silicate level becomes too high (e.g., a surfactant to silicate ratio of 1:1), overall solubility can suffer due to the formation of silicate insolubles.
  • granules having a surfactant to silicate ratio of, for example, 8:1 have insufficient structure and tend to be too mushy at these high surfactant levels.
  • the amount of detergent pyrophosphate or anhydrous Form 1 tripolyphosphate builder material in the portion of the granular detergent obtained by drying an aqueous slurry of the essential components herein should also be minimized.
  • the compositions can contain from 0% to 20%, preferably from 0% to 15%, more preferably from 0% to material in the portion of the granular detergent obtained by drying an aqueous slurry of the essential components herein should also be minimized.
  • the compositions can contain from 0% to 20%, preferably from 0% to 15%, more preferably from 0% to 10%, by weight of such detergent builder material or mixtures thereof.
  • the compositions are substantially free of such detergent builder (e.g., they contain less than 5%, preferably less than 3%, by weight of such builder).
  • compositions can contain up to 60% preferably from 1% to 45% by weight of other detergent builders including any of those described in U.S. Patent 3,925,262, Laughlin et al, issued December 9, 1975.
  • Builders are generally selected from the various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, (Form 11 or hydrated Form 1), polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-­triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176; and 3,400,148.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, and tetraborate decahydrate.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Polymeric polycarboxylate builders are also described in U.S. Patent 3,308, 067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • polycarboxylates are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al.
  • polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution and converted to the corresponding salt.
  • a preferred phosphate builder is Form 11 sodium tripolyphosphate preferably anhydrous.
  • a preferred builder for use in compositions that are substantially free of phosphate builders is sodium citrate.
  • the builders herein should have the same particle size as the remainder of the composition, as described hereinafter.
  • the above granular detergent compositions can be used as is as finished detergent compositions or as detergent additive compositions. However, they are preferably used as (and hereinafter referred to as) detergent base granules which are then admixed or agglomerated with builder material and with other optional ingredients to provide finished detergent compositions exhibiting good solubility.
  • Such finished compositions can comprise by weight from 5% to 50%, preferably from 10% to 40%, more preferably from 12% to 25%, of the alkylbenzene sulfonate and alkyl sulfate surfactants herein and from 5% to 95%, preferably from 10% to 85%, more preferably from 15% to 75%, of detergent builder material, such as described above.
  • the amount of pyrophosphate and anhydrous Form 1 tripolyphosphate should be minimised i.e. the finished compositions preferably contain from 0% to 20% preferably from 0% to 10% of such material or mixtures thereof.
  • compositions can also contain minor amounts, generally less than 30%, preferably less than 20%, by weight of other ingredients usually included in detergent compositions.
  • auxiliary detergent surfactants color speckles, bleaching agents, and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, enzymes, enzyme-stabilizing agents and perfumes.
  • Agglomeration can be accomplished by agitating in the presence of a suitable binder (e.g., in a fluidized bed, tumble mixer, or a rotating drum or pan) or by mechanically mixing under pressure (e.g., extruding, pressing, milling, compacting or pelletizing). Final sizing can then be achieved by grinding and screening.
  • a suitable binder e.g., in a fluidized bed, tumble mixer, or a rotating drum or pan
  • pressure e.g., extruding, pressing, milling, compacting or pelletizing
  • the detergent base granules are admixed with from 0% to 300%, preferably from 25% to 200%, more preferably from 50% to 150%, by weight of the base granules, of a detergent builder material such as described above.
  • the resulting admix is then preferably compacted at a relatively low pressure of from 137.9 to 1379 preferably from 275.8 to 1034 more preferably from 344.8 to 689.4 kilo Pascals (kPa).
  • the composition is then preferably admixed with an additional 0% to 300%, preferably from 25% to 200%, more preferably from 50% to 150%, by weight of the base granules, of a detergent builder material.
  • the above levels and types of builder material and compaction pressure are preferably selected so that the final detergent composition has a bulk density of from 0.55 to 1.2, preferably from 0.65 to 1.1, more preferably from 0.70 to 0.9 g/cc and an average particle size of from 20 to 1500 microns, preferably from 50 to 1200 microns, more preferably from 100 to 800 microns.
  • the above compaction step is preferably accomplished by using equipment that applies a relatively uniform compaction pressure, for example, by using compaction rollers with smooth (i.e., noncorrugated) surfaces.
  • the composition is preferably granulated and screened to provide an average particle size similar to that desired for the final composition.
  • the following granular detergent composition was prepared.
  • the base granules were produced by spray-drying an aqueous crutcher mix of the components on a 305 cm tower using a crutcher temperature of 93°C a size 3-1/2 nozzle to make fine granules, and silicone deaeratants. If the base granules contained more than 2% moisture, a second drying stage on a continuous fluid bed was performed to reduce moisture to 2%.
  • the base granules were then admixed with powdered STP hexahydrate to form the preblend.
  • the preblend was compacted at 344.8 kPa roll pressure on a 10 cm by 25 cm chilsonator, and screened to select a -14(1168 microns)/+65(208 microns) particle size cut (Tyler mesh).
  • Oversized particles were collected and granulated on a Fitzmill using a 1168 microns screen and low rpm's. This was screened to select a -20(833 microns)/+ 48(295 microns) particle size cut. Both materials were dedusted by blowing off fines in a fluid bed dryer using ambient air.
  • the admix was prepared at 181.5 kg per batch in a drum mixer. Carbonate, granular STP (with dye sprayed-on), brightener, enzymes, and suds suppressor prills were blended with the compacted mainstream product cut and regranulated overs. The ratio of mainstream product cut to overs was 7 to 1. Mineral oil was sprayed on the final admix in 13.6 to 18.1 kg batches at a 1% level using a Forberg Mixer.
  • Example 1 is preferably incorporated into a laminated laundry product formed from two plies of water insoluble tissues, at least one of which is water permeable, which are laminated together. At least one of the plies has cup like depressions, surrounded by rims and the other ply being attached to the first ply at the rims to physically separate the cups.
  • the laminate is made with plies of the tissue paper described by Trokhan in U.S. Patent 4,529,480, issued July 16, 1985.
  • the tissue had good air permeability as set forth in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
  • Example 1 When the composition of Example 1 is incorporated in said laminated laundry product, it exhibits superior solubility.
  • the following granular detergent composition can be prepared and used according to Example I.

Landscapes

  • 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)
EP19860307799 1985-10-09 1986-10-09 Granulierte Reinigungsmittel mit Löslichkeit Expired - Lifetime EP0219314B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78593185A 1985-10-09 1985-10-09
US785931 1985-10-09

Publications (4)

Publication Number Publication Date
EP0219314A2 true EP0219314A2 (de) 1987-04-22
EP0219314A3 EP0219314A3 (en) 1988-11-09
EP0219314B1 EP0219314B1 (de) 1993-08-04
EP0219314B2 EP0219314B2 (de) 1999-06-23

Family

ID=25137068

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860307799 Expired - Lifetime EP0219314B2 (de) 1985-10-09 1986-10-09 Granulierte Reinigungsmittel mit Löslichkeit

Country Status (6)

Country Link
EP (1) EP0219314B2 (de)
JP (1) JPH07116477B2 (de)
AU (1) AU597909B2 (de)
CA (1) CA1337041C (de)
DE (1) DE3688820T3 (de)
NZ (1) NZ217875A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217340A (en) * 1988-04-14 1989-10-25 Unilever Plc Preparation of a granular detergent composition
EP0352892A2 (de) * 1988-07-28 1990-01-31 Kao Corporation Granulöses Waschmittelkonzentrat von hoher Dichte
US5030379A (en) * 1988-05-06 1991-07-09 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing high bulk density detergent powders admixed with zeolite and coated with nonionic surfactant
US5298183A (en) * 1990-06-06 1994-03-29 Lever Brothers Company, Division Of Conopco, Inc. Soap powder compositions
EP0889117A1 (de) * 1996-03-11 1999-01-07 Kao Corporation Waschmittelzusammensetzung fur kleidung
US6191096B1 (en) 1995-01-18 2001-02-20 Henkel Kommanditgesellschaft Auf Aktien Spray-dried amorphous alkali metal silicate compound and its use in detergent compositions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1275019A (en) * 1985-10-09 1990-10-09 The Procter & Gamble Company Granular detergent compositions having improved solubility
NL194729C (nl) * 1986-10-13 2003-01-07 Novartis Ag Werkwijze voor de bereiding van peptidealcoholen via vaste fase.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0084657A1 (de) * 1981-12-28 1983-08-03 Henkel Kommanditgesellschaft auf Aktien Starkschäumendes, körniges Waschmittel mit erhöhter Kornstabilität und Verfahren zu dessen Herstellung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA767282B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Laundry detergent composition and use
JPS6157700A (ja) * 1984-08-29 1986-03-24 花王株式会社 水溶性フイルムを用いた単位包装洗剤製品

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0084657A1 (de) * 1981-12-28 1983-08-03 Henkel Kommanditgesellschaft auf Aktien Starkschäumendes, körniges Waschmittel mit erhöhter Kornstabilität und Verfahren zu dessen Herstellung

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217340A (en) * 1988-04-14 1989-10-25 Unilever Plc Preparation of a granular detergent composition
US5030379A (en) * 1988-05-06 1991-07-09 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing high bulk density detergent powders admixed with zeolite and coated with nonionic surfactant
EP0352892A2 (de) * 1988-07-28 1990-01-31 Kao Corporation Granulöses Waschmittelkonzentrat von hoher Dichte
EP0352892A3 (en) * 1988-07-28 1990-03-28 Kao Corporation High-density granular concentrated detergent composition
US5298183A (en) * 1990-06-06 1994-03-29 Lever Brothers Company, Division Of Conopco, Inc. Soap powder compositions
US6191096B1 (en) 1995-01-18 2001-02-20 Henkel Kommanditgesellschaft Auf Aktien Spray-dried amorphous alkali metal silicate compound and its use in detergent compositions
US6458755B2 (en) 1995-01-18 2002-10-01 Henkel Kommanditgesellschaft Auf Aktien Amorphous alkali metal silicate compound
EP0889117A1 (de) * 1996-03-11 1999-01-07 Kao Corporation Waschmittelzusammensetzung fur kleidung
EP0889117A4 (de) * 1996-03-11 2000-03-08 Kao Corp Waschmittelzusammensetzung fur kleidung
US6114297A (en) * 1996-03-11 2000-09-05 Kao Corporation Detergent composition for clothing

Also Published As

Publication number Publication date
NZ217875A (en) 1990-02-26
CA1337041C (en) 1995-09-19
JPS62161898A (ja) 1987-07-17
EP0219314B2 (de) 1999-06-23
DE3688820T2 (de) 1994-03-10
AU6359486A (en) 1987-04-16
EP0219314A3 (en) 1988-11-09
JPH07116477B2 (ja) 1995-12-13
DE3688820T3 (de) 2000-01-13
AU597909B2 (en) 1990-06-14
EP0219314B1 (de) 1993-08-04
DE3688820D1 (de) 1993-09-09

Similar Documents

Publication Publication Date Title
EP0220024B1 (de) Granulierte Reinigungsmittel mit Löslichkeit
US4715979A (en) Granular detergent compositions having improved solubility
EP0715652B1 (de) Verfahren zur herstellung von detergensagglomeraten von hoher dichte
US5366652A (en) Process for making high density detergent agglomerates using an anhydrous powder additive
US4487710A (en) Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid
EP0656825B1 (de) Verfahren zum herstellen von kompakten waschmittelzusammensetzungen
JPS63286496A (ja) 粒状洗剤組成物の製造方法
JPH0678558B2 (ja) 洗剤組成物の製造方法
CA1337513C (en) Detergent compositions and process for preparing them
EP0510746A2 (de) Verfahren zur Herstellung verdichteter Reinigungsmittelgranulate
US5663136A (en) Process for making compact detergent compositions
PL184656B1 (pl) Sposób wytwarzania kompozycji detergentowej lub jej komponentu
EP0578871A1 (de) Verfahren zur Herstellung von kompakten Reinigungsmitteln
US5736502A (en) Process for preparing detergent compositions
EP0219314B1 (de) Granulierte Reinigungsmittel mit Löslichkeit
EP0436240B2 (de) Verfahren zur Herstellung von Reinigungsmitteln hoher Dichte mit verbesserten Verteilungseigenschaften
US5998356A (en) Process for making granular detergents
CA2231577C (en) Process for making granular detergents
WO1992018603A1 (en) Agglomeration of high active pastes to form surfactant granules useful in detergent compositions
EP1550712A1 (de) Verfahren zur Herstellung eines granularen anionischen Tensids
EA003404B1 (ru) Способ получения гранулированных моющих составов
CA1221289A (en) Granular, free-flowing detergent component and method for its production
MXPA98000047A (en) Procedure for preparing a detergent composition of free flow particles that have better solubility

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19890513

17Q First examination report despatched

Effective date: 19901119

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB IT

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

REF Corresponds to:

Ref document number: 3688820

Country of ref document: DE

Date of ref document: 19930909

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

Effective date: 19940427

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19990623

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR GB IT

ET3 Fr: translation filed ** decision concerning opposition
ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20041004

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20041029

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050914

Year of fee payment: 20

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20051013

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20061008

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060630

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20