EP0883678B1 - Procede de production de granules detergents de haute densite - Google Patents

Procede de production de granules detergents de haute densite Download PDF

Info

Publication number
EP0883678B1
EP0883678B1 EP96908611A EP96908611A EP0883678B1 EP 0883678 B1 EP0883678 B1 EP 0883678B1 EP 96908611 A EP96908611 A EP 96908611A EP 96908611 A EP96908611 A EP 96908611A EP 0883678 B1 EP0883678 B1 EP 0883678B1
Authority
EP
European Patent Office
Prior art keywords
amount
carbonate
microns
particle size
process according
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
EP96908611A
Other languages
German (de)
English (en)
Other versions
EP0883678A1 (fr
Inventor
Donald Scott Adams
Burce Albert Yeazell
Eric Fitzgerald Riddick
Junan Kao
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=22254790&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0883678(B1) "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 EP0883678A1 publication Critical patent/EP0883678A1/fr
Application granted granted Critical
Publication of EP0883678B1 publication Critical patent/EP0883678B1/fr
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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the invention involves a process for making built high active detergent agglomerates having improved free flow properties.
  • Laundry detergent granules comprise one or more surfactants (usually of the anionic type) and one or more detergency builders ( typically phosphates, carbonates, zeolites, etc.)
  • Detergent granules are typically made by preparing a paste of the detergent ingredients, and spray drying the paste to form granules. Such products also can be made by agglomerating a mixture of the surfactant and builder in a mixer. In an agglomeration process, the anionic surfactant in its neutralized form can be used or it can be introduced into the agglomeration process in its acid form and be neutralized in situ by alkaline materials (e.g. sodium carbonate) as described in EP-A-0 555 622.
  • alkaline materials e.g. sodium carbonate
  • Optional detergent materials such as brighteners, soil release agents, etc. can be agglomerated along with the surfactant and builder or can be mixed with the agglomerates after they are formed. Generally, agglomeration provides the ability to produce higher density detergent products than those which are produced by spray drying.
  • flow aids such as clay, talc, zeolites or silica are typically used.
  • the object of the present invention is to provide a process for producing detergent agglomerates having high surfactant levels and improved free flow characteristics.
  • the present invention is directed to a process comprising the steps of:
  • anionic detergent agglomerates having high anionic surfactant content i.e., 20% or above
  • carbonate and, optionally, phosphate builders improved free flow characteristics can be achieved if at least 40% of the total (i.e., combined) amount of particulate carbonate/phosphate used in preparing the agglomerates meets a specification of 97% particles less than 40 ⁇ m (microns) and a median particle size of 5 to 20 ⁇ m (microns)
  • Anionic surfactant is an essential component of compositions prepared by the present process.
  • Such surfactants are well known in the art.
  • the anionic surfactants useful in the subject invention are preferably the alkali metal (i.e., sodium and potassium) salts of alkylbenzene sulfonates or alkyl sulfates or mixtures thereof.
  • examples of other anionic surfactants which are also useful are the alkali metal salts of paraffin sulfonates, alkyl glyceryl ether sulfonates and alkyl ether sulfates, all having 8 to 1.8 carbon atoms in their alkyl chains.
  • the anionic surfactant raw materials preferably have a moisture content of less than 1.0%, more preferably less than 0.5%. Based on the total weight of raw materials added during the process of the subject invention, the amount of anionic surfactant is from 20% to 35%, preferably from 20% to 30%.
  • Preferred alkylbenzene sulfonates useful in the subject process include those with an alkyl portion which is straight chain or branched chain, preferably having from 8 to 18 carbon atoms, more preferably from 10 to 16 carbon atoms.
  • the alkyl chains of the alkylbenzene sulfonate preferably have an average chain length of from about 11 to about 14 carbon atoms.
  • Alkylbenzene sulfonate which includes branched chain alkyl is termed ABS.
  • Alkylbenzene sulfonate which is all straight chain is preferred because it is more easily biodegraded; it is termed LAS.
  • Preferred alkyl sulfates useful in the subject process include those with an alkyl portion which is straight chain or branched chain, preferably having from 8 to 24 carbon atoms, more preferably from 10 to 20 carbon atoms, more preferably still from 12 to 18 carbon atoms.
  • the alkyl chains of the alkyl sulfates preferably have an average chain length of from 14 to 16 carbon atoms.
  • the alkyl chains are preferably linear.
  • Alkyl sulfates are typically obtained by sulfating fatty alcohols produced by reducing the glycerides of fats and/or oils from natural sources, especially from tallow or coconut oil.
  • Preferred anionic surfactants useful in the subject invention process may also be combinations of alkylbenzene sulfonates and alkyl sulfates, whether mixed together or added during the process separately. Combinations having a ratio of alkylbenzene sulfonate to alkyl sulfate of from 20:80 to 80:20 are preferred; those having a ratio of from 40:60 to 60:40 are more preferred. Additional disclosure of anionic synthetic surfactants can be found in U.S. Pat. 3,664,961, Norris, issued May 23, 1972.
  • phosphates are used as builders in compositions made according to the process herein.
  • the phosphate builder raw materials useful in the subject invention process are in particulate form and consist essentially of the water-soluble salts (e.g., the sodium and potassium salts) of polyphosphates (e.g., tripolyphosphate, hexametaphosphate, etc.) or pyrophosphates or mixtures thereof.
  • the phosphate builder raw materials preferably have a moisture content of less than 2%, more preferably less than 1%. Based on the total weight of raw materials added during the process of the subject invention, the amount of phosphate builder is typically from 5% to 65%, preferably from 15% to 55%, more preferably from 25% to 45%.
  • Phosphate builder raw materials are typically supplied from their manufacturers in powder form, usually having a median particle size of from 25 ⁇ m (microns) to 50 ⁇ m (microns).
  • Carbonate raw materials are typically supplied from their manufacturers in granular form, usually having a particle size of from 25 ⁇ m (microns) to 150 ⁇ m (microns) "As is" median particle size for polyphosphate and carbonate varies for supplies obtained in different geographies as well as by supplier.
  • the polyphosphate builder and/or carbonate are ground to a particle size such that at least 40% of the total amount of particles of phosphate/carbonate used in the process meet a particle size specification of 97% of particles less than 40 ⁇ m (microns) and median particle size of 5 to 20 ⁇ m (microns) preferably 10 to 20 ⁇ m (microns).
  • a particle size specification 97% of particles less than 40 ⁇ m (microns) and median particle size of 5 to 20 ⁇ m (microns) preferably 10 to 20 ⁇ m (microns).
  • Either the carbonate, phosphate or both can be ground to achieve the specified amount of total phosphate/carbonate particles within the required size requirements.
  • Preferably at least 70% of the particles should meet the required specification.
  • all of the particles of phosphate and carbonate used in the process will be within an overall size range of 5 to 300 ⁇ m (microns).
  • Grinding can be accomplished in conventional powder grinding equipment such as an ACM Classifier Mill (Hosokawa Micron Powder Systems). During grinding, or after grinding, if necessary, the particles are classifed to assure that the ground particles to be used are within the required specification. For classification, a Micron Pulsaire Classifier (Hosokawa Powder Systems) can be used.
  • ACM Classifier Mill Hosokawa Micron Powder Systems
  • a preferred phosphate builder useful in the subject process is sodium tripolyphosphate (STPP); STPP can be obtained commercially from, for example, FMC Corp.
  • STPP sodium tripolyphosphate
  • TSPP tetrasodium pyrophosphate
  • TSPP can be obtained commercially from, for example, FMC Corp.
  • the subject invention process utilizes particulate alkali metal carbonate preferably consisting essentially of sodium carbonate or potassium carbonate or a mixture thereof as builders.
  • An acid precursor of anionic surfactant is used in the process and the carbonate also functions as a neutralizing agent to convert the acid precursor to the alkali metal salt.
  • the alkali metal carbonate raw materials preferably have a moisture content of less than 2%, more preferably less than 1%. Based on the total weight of raw materials added to the process of the subject invention, the amount of alkali metal carbonate is from 6% to 60%, preferably from 10% to 50%, more preferably from 30% to 40%.
  • the amount of carbonate fed to the process is at least 2 times that theoretically needed to neutralize the acid.
  • the amount of carbonate will be from 4 times to 12 times, more preferably still from 6 times to 12 times, the amount needed to neutralize the acid precursor.
  • substantially the only water present in the materials as they go through the process is the minor amounts of moisture present in the raw materials and the water generated by neutralization of acid precursor of anionic surfactant.
  • the maximum amount of water in the materials being processed is preferably 10%, more preferably 7%, more preferably still 5%, still more preferably 3%.
  • the detergent agglomerates produced by the process may be somewhat hygroscopic and pick up moisture from the atmosphere.
  • the detergent agglomerates from the process of the subject invention typically have an average particle size of from 200 ⁇ m (microns) to 800 ⁇ m (microns), more preferably from 300 ⁇ m (microns) to 700 ⁇ m (microns), more preferably still from 400 ⁇ m (microns) to 600 ⁇ m (microns).
  • An advantage of the process of the invention is that the use of flow aids such as silicas, clays, diatomaceous earth, aluminosilicates (e.g., zeolites), perlite, and calcite can be substantially reduced or eliminated.
  • flow aids such as silicas, clays, diatomaceous earth, aluminosilicates (e.g., zeolites), perlite, and calcite can be substantially reduced or eliminated.
  • the subject invention can be carried out in a continuous or batch manner. Continuous processing is preferred. A description of the subject process conducted in a continuous manner is as follows:
  • the first step of the process is preferably carried out in a high-speed, high-shear mixer.
  • Suitable mixers for this step include, for example, the Loedige CB®, the Shugi Granulator®, and the Drais K-TTP®.
  • the preferred mixer for the first step is the Loedige CB®.
  • the high-speed mixer has a substantially cylindrical mixing chamber which is from 0.3m to 1m in diameter and from 1m to 3.5m in length.
  • Preferred mixers for the first step have a central shaft, with mixer blades attached, which preferably rotates at a speed of from 300 rpm to 1800 rpm, more preferably from 350 rpm to 1250 rpm, more preferably still from 400 rpm to 1000 rpm, the speed generally being lower for larger mixers.
  • the high-speed mixer preferably is water-jacketed to permit cooling water to flow through the mixer jacket, in order to remove heat generated by the neutralization reaction.
  • the essential raw materials i.e., surfactant acid precursor; carbonate; and phosphate, if used
  • the typical average throughput rate is from 0.2 kgs -1 (kg/sec) to 17 kgs -1 (kg/sec), especially from 2 kgs -1 (kg/sec) to 13 kgs -1 (kg/sec), the higher throughput rates generally being achieved using larger mixers.
  • the average residence time of materials in the first-step mixer is preferably from 2 seconds to 30 seconds, more preferably from 5 seconds to 20 seconds, more preferably still from 10 seconds to 15 seconds.
  • Much of the neutralization of the acid by the carbonate occurs in the first step of the process.
  • substantially all of the neutralization takes place in the first step.
  • the neutralization reaction may be completed after the mixture discharges from the first-step mixer.
  • the acid is substantially completely neutralized during the process. Cooling water at a temperature of from 5°C to 25°C is preferably fed to the water jacket of the high-speed mixer.
  • the temperature of the mixture at the discharge from the high-speed mixer is typically from 35°C to 70°C, preferably from 45°C to 55°C.
  • the materials discharged from the first-step mixer are typically fed substantially immediately into the second-step mixer.
  • the average residence time for materials between the mixers is preferably less than 5 minutes, more preferably less than 1 minute.
  • the second step of the process of the subject invention is preferably carried out in a moderate-speed mixer.
  • Suitable mixers for this step include plowshare mixers, for example, the Loedige KM® and the Drais K-T®.
  • the Loedige KM® is the preferred mixer for the second step of the subject invention process.
  • the moderate-speed mixer has a substantially cylindrical mixing chamber which is from 0.6m to 2m in diameter and from 2m to 5m in length.
  • the preferred mixers have a central shaft, with mixer blades attached, which preferably rotates at a speed of from 40 rpm to 160 rpm, more preferably from 45 rpm to 140 rpm, more preferably still from 50 rpm to 100 rpm, the speed generally being lower for larger mixers.
  • the moderate-speed mixer preferably is water-jacketed to permit water to flow through the mixer jacket, in order to maintain the temperature of product in the moderate-speed mixer at about its incoming temperature.
  • the temperature of the mixture at the discharge of the moderate-speed mixer is typically from 35°C to 70°C, preferably from 45°C to 55°C.
  • the agglomerates produced by the process herein can be used "as is" for detergent purposes.
  • materials normally included in detergent compositions can be included in the agglomerates per se or combined with the agglomerates in one or more subsequent mixing steps.
  • Such materials include organic polymeric builders such as polycarboxylates (see U.S.Patent 4,144,226 Diehl), phosphonic acid builders such as disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,442,137; 3,400,176; and 3,400,148, alkali metal silicates, zeolite builders as disclosed in U.S. Patent 4,605,509, bleaches, bleach activators, soil suspending agents, enzymes, perfumes, chelating agents, and additional surfactants such as alkyl polyethoxylates, ethoxylated fatty amines, etc.
  • Compostion A was made according to the process of the present invention, utilizing acid precursor of the alkylbenzene sulfonate surfactant.
  • a Loedige CB mixer was used in Step 1 and a Loedige KM mixer in Step 2. All materials were added in Step 1, except that 20% of the zeolite (i.e., 1.44 parts) was added in Step 2. All of the sodium carbonate which, "as received” had a particle size of 97% less than approximately 200 ⁇ m (microns) and a median particle size of 50 ⁇ m (microns) was ground and classified to meet a specification of 97% less than 40 ⁇ m (microns) and a median particle size of 10 ⁇ m (microns).
  • the tripolyphosphate had an "as received" particle size of 97% less than 200 ⁇ m (microns) and a median particle size of 50 ⁇ m (microns).
  • the tripolyphosphate was not ground and classified prior to use.
  • 44 parts carbonate which is 67% of the total amount phosphate and carbonate used to prepare the composition was pretreated to meet the particle size specification required by the invention.
  • Composition B was made in the same manner as Composition A, except that both the carbonate and phosphate were used with their "as received" particle size. Also, in Composition B, 90% of the zeolite was added in Step 1 and 10% (i.e., 1.52 parts) was added in Step 2.
  • Composition A had excellent free flow characteristics, whereas Composition B had poor free flow characteristics.
  • compositions were subjected to an "arch test".
  • an agglomerate product to form an arch under pressure can be used to determine potential flowability problems in conveying equipment and storage silos.
  • the agglomerate product is pressed into the form of an arch in a cylindrical vessel, and the stickiness of the product is assessed by measuring the force required to break the arch. The stickier the product, the greater the force required. 1.5 kg force was required for Composition A and 3-5 kg was required for Composition B.

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)

Claims (7)

  1. Procédé de préparation d'agglomérats détergents comprenant les étapes consistant à :
    (a) mélanger des composants détergents dans un mélangeur, lesdits composants comprenant :
    (1) 20 % à 35 % d'un précurseur acide d'un tensioactif anionique ;
    (2) 0 % à 65 % d'un adjuvant phosphate particulaire choisi dans le groupe constitué par le polyphosphate, le pyrophosphate, et leurs mélanges ; et
    (3) 6 % à 60 % d'un carbonate particulaire choisi dans le groupe constitué par le carbonate de sodium, le carbonate de potassium, et leurs mélanges ; dans lequel la quantité de carbonate est au moins deux fois celle qui est suffisante pour neutraliser l'acide tensioactif ; et
    (b) agglomérer le mélange de l'étape (a) dans un mélangeur à vitesse modérée pour produire des agglomérats détergents dans lesquels le précurseur acide a été sensiblement neutralisé,
       caractérisé en ce qu'au moins 40 % de la quantité totale des composants (2) et (3) satisfait à une dimension de particule de 97 % de particule inférieures à 40 µm (microns) et une dimension moyenne de particule de 5 à 20 µm (microns).
  2. Procédé selon la revendication 1, dans lequel au moins 67 % de la quantité totale des composants (2) et (3) a la dimension de particule mentionnée dans la revendication 1.
  3. Procédé selon la revendication 1 ou 2, dans lequel la quantité de composant (3) est de quatre à douze fois la quantité nécessaire pour neutraliser le composant (1).
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de composant (2) est de 5 à 65 %.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de composant (2) est 15 à 55 % et la quantité de composant (1) est 20 à 30 %.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité du carbonate particulaire est au moins 10 %.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de carbonate particulaire est au moins 30 %.
EP96908611A 1996-02-29 1996-02-29 Procede de production de granules detergents de haute densite Expired - Lifetime EP0883678B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/002848 WO1997032003A1 (fr) 1996-02-29 1996-02-29 Procede de production de granules detergents de haute densite

Publications (2)

Publication Number Publication Date
EP0883678A1 EP0883678A1 (fr) 1998-12-16
EP0883678B1 true EP0883678B1 (fr) 2004-05-19

Family

ID=22254790

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96908611A Expired - Lifetime EP0883678B1 (fr) 1996-02-29 1996-02-29 Procede de production de granules detergents de haute densite

Country Status (10)

Country Link
EP (1) EP0883678B1 (fr)
JP (1) JP2898102B2 (fr)
AR (1) AR006032A1 (fr)
AT (1) ATE267240T1 (fr)
AU (1) AU5179496A (fr)
CZ (1) CZ273098A3 (fr)
DE (1) DE69632549T2 (fr)
EG (1) EG21214A (fr)
WO (1) WO1997032003A1 (fr)
ZA (1) ZA971381B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5914307A (en) * 1996-10-15 1999-06-22 The Procter & Gamble Company Process for making a high density detergent composition via post drying mixing/densification
WO1998020104A1 (fr) * 1996-11-06 1998-05-14 The Procter & Gamble Company Procede de neutralisation destine a la fabrication de granules agglomerees de detergent
CN100419056C (zh) * 1999-08-20 2008-09-17 花王株式会社 制备高堆积密度洗涤剂组合物的方法
DE10258011A1 (de) * 2002-12-12 2004-07-08 Henkel Kgaa Trockenneutralisationsverfahren
DE102005005499A1 (de) * 2005-02-04 2006-08-17 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8817386D0 (en) * 1988-07-21 1988-08-24 Unilever Plc Detergent compositions & process for preparing them
GB8922018D0 (en) * 1989-09-29 1989-11-15 Unilever Plc Detergent compositions and process for preparing them
ES2104884T3 (es) * 1992-02-14 1997-10-16 Procter & Gamble Procedimiento para elaborar granulos de detergente por neutralizacion de acidos sulfonicos.
EP0578871B1 (fr) * 1992-07-15 1998-05-27 The Procter & Gamble Company Procédé et compositions pour détergents sous forme compacte
US5486303A (en) * 1993-08-27 1996-01-23 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive

Also Published As

Publication number Publication date
WO1997032003A1 (fr) 1997-09-04
ZA971381B (en) 1997-08-28
CZ273098A3 (cs) 1998-12-16
AR006032A1 (es) 1999-07-21
JPH10505631A (ja) 1998-06-02
DE69632549D1 (de) 2004-06-24
JP2898102B2 (ja) 1999-05-31
ATE267240T1 (de) 2004-06-15
AU5179496A (en) 1997-09-16
EP0883678A1 (fr) 1998-12-16
EG21214A (en) 2001-02-28
DE69632549T2 (de) 2005-05-12

Similar Documents

Publication Publication Date Title
US4925585A (en) Detergent granules from cold dough using fine dispersion granulation
US5080848A (en) Process for making concentrated surfactant granules
EP0451894B2 (fr) Compositions détergentes granulaires à haute densité apparente et leur procédé de préparation
EP0715652B1 (fr) Procede de fabrication d'agglomerats detersifs de masse volumique elevee
EP0390251B1 (fr) Compositions détergentes et procédé pour leur préparation
US5164108A (en) Process for preparing high bulk density detergent compositions
CA2164106C (fr) Constituant detergent renfermant un surfactif anionique; methode de preparation
US5573697A (en) Process for making high active, high density detergent granules
PL184924B1 (pl) Sposób wytwarzania granulowanej detergentowej lub czyszczącej kompozycji albo jej składnika
PL184656B1 (pl) Sposób wytwarzania kompozycji detergentowej lub jej komponentu
US5736502A (en) Process for preparing detergent compositions
WO1998020104A1 (fr) Procede de neutralisation destine a la fabrication de granules agglomerees de detergent
CA2140285C (fr) Compositions detergentes
EP0349200B1 (fr) Procédé de fabrication de granules de détergent concentrés
EP0883678B1 (fr) Procede de production de granules detergents de haute densite
US6207635B1 (en) Process for manufacture of high density detergent granules
CA2245962C (fr) Procede de production de granules detergents de haute densite
EP0323659B1 (fr) Procédé de préparation d'un produit détergent granulaire
EP0723581A1 (fr) Procede continu pour produire un detergent granulaire a haute densite
JP2965905B2 (ja) 改良された流動特性を有する凝集化洗剤組成物の製造法
JPH11509263A (ja) 改善された流動性を有する凝集洗剤組成物の製法
MXPA97009168A (en) Procedure for manufacturing detergent highly active and high densi granules
CN1217019A (zh) 高密度洗涤剂颗粒的生产方法

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

17P Request for examination filed

Effective date: 19980921

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 20010509

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

AK Designated contracting states

Kind code of ref document: B1

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

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040519

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040519

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20040519

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040519

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040519

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040519

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040519

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69632549

Country of ref document: DE

Date of ref document: 20040624

Kind code of ref document: P

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040819

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040819

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040819

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

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040830

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LU

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

Effective date: 20050228

Ref country code: IE

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

Effective date: 20050228

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050222

EN Fr: translation not filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: PT

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

Effective date: 20041019

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

Ref country code: DE

Payment date: 20120229

Year of fee payment: 17

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

Ref country code: GB

Payment date: 20120127

Year of fee payment: 17

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130228

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69632549

Country of ref document: DE

Effective date: 20130903

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 NON-PAYMENT OF DUE FEES

Effective date: 20130228

Ref country code: DE

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

Effective date: 20130903