EP0633310B1 - Vorformulierung für Waschmittelzusammensetzung auf der Basis von Polyimid und einem Silikat - Google Patents

Vorformulierung für Waschmittelzusammensetzung auf der Basis von Polyimid und einem Silikat Download PDF

Info

Publication number
EP0633310B1
EP0633310B1 EP94401434A EP94401434A EP0633310B1 EP 0633310 B1 EP0633310 B1 EP 0633310B1 EP 94401434 A EP94401434 A EP 94401434A EP 94401434 A EP94401434 A EP 94401434A EP 0633310 B1 EP0633310 B1 EP 0633310B1
Authority
EP
European Patent Office
Prior art keywords
weight
silicate
order
preformulation
polyimide
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
EP94401434A
Other languages
English (en)
French (fr)
Other versions
EP0633310A1 (de
Inventor
Gilles Guerin
Arnaud Ponce
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.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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 Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP0633310A1 publication Critical patent/EP0633310A1/de
Application granted granted Critical
Publication of EP0633310B1 publication Critical patent/EP0633310B1/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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the present invention relates to a preformulation "buider or” cobuilder " biodegradable for detergent composition, based on a polyimide and silicate mixture.
  • Builder or “cobuilder” means any constituent which improves the performance of surfactants of a detergent composition.
  • tripolyphosphates have been the most frequently used in detergent compositions and detergents. However, they are partly responsible for the eutrophication of the lakes and waters slow flow when not sufficiently eliminated by treatment plants waters ; so we are looking to replace them partially or completely.
  • Copolymers of acrylic acid and maleic anhydride have been proposed (EP 25,551) as incrustation inhibitors. They have the disadvantage of not being biodegradable in a natural environment.
  • agent title "builder” or “cobuilder” for detergent composition a new range of compounds, peptide polymers and more specifically polymers or amino acid copolymers.
  • sodium polyaspartates and polyglutamates which are useful for their high biodegradability, testify to a good builder or co-builder activity (US 4,428,749). It has been shown to be the negatively charged form of these compounds which is the active form in the detergent formulation.
  • polyimides have the advantage of being stable in detergent formulations for extended durations.
  • the object of the present invention is precisely to optimize the character biodegradable from this type of compound.
  • a particular formulation has been developed according to the invention of it, such that it simultaneously satisfies the following two imperatives: it remains stable in the detergent formulation and in a humid environment it brought into contact with an aqueous medium of non-alkaline pH in at least one species water-soluble biodegradable and naturally endowed with an activity within the detergent formulation. Optimization of the biodegradable character is not acquired for costs of stability in detergent formulation nor of the subsequent generation of the active species.
  • non-alkaline pH is meant in the context of the present invention, a pH unfavorable to the hydrolysis of the polyimide to its water-soluble salts.
  • a pH unfavorable to the hydrolysis of the polyimide to its water-soluble salts are notably covered by this definition the pH of natural aqueous media, such as river water which have values close to neutrality.
  • the subject of the present invention is a "builder” or “cobuilder” preformulation for a detergent composition
  • a detergent composition comprising at least one polyimide polymer mixed with at least one silicate, characterized in that it is capable of generating at least one polypeptide species water-soluble biodegradable when it comes into contact with an aqueous medium of non-alkaline pH and in that the polyimide and the silicate are present therein in a weight ratio polyimide / silicate varying between approximately 40/60 and 55/45.
  • polyimide polymer is meant according to the invention a polyimide biopolymer whose charge density COO - is likely to increase in the detergent bath.
  • polymers can be homopolymers derived from racide as well aspartic or glutamic, as copolymers derived from aspartic racide and glutamic acid in any proportions, or copolymers derived from the acid aspartic and / or glutamic and other amino acids (for example up to 15% in weight, preferably less than 5% by weight, of other amino acids).
  • copolymerizable amino acids there may be mentioned glycine, alanine, valine, leucine, isoleucine, phenylalanine, methionine, trypotophan, histidine, proline, lysine, arginine, serine, threonine, cysteine ...
  • Said polyimide biopolymers can have a weight-average molecular mass of the order of 2000 to 10 7 and generally of the order of 3.500 to 60,000.
  • polyimides derived from aspartic or glutamic acid can be prepared by thermocondensation of said amino acid (s) in a substantially anhydrous medium, as described in JACS, 80 , 3361 (1958), J. Med. Chem. 16 , 893 (1973), Polymer 23 , 1237 (1982) or in U.S. Patent No. 3,052,655.
  • Said polyimides preferably have a COO charge density - zero; however, they can be partially hydrolyzed (by opening a few imide rings with the formation of alkali or ammonium carboxylates).
  • alkali metal silicates can be used general those already used as adjuvants in detergency formulation.
  • the most advantageous silicates in this application are those having a SiO 2 / M 2 O molar ratio of between 1.6 and 3.5. They are sold either in the form of concentrated solutions at around 30-60% by weight of dry extract, or in the form of silicate powder, atomized and optionally compacted.
  • said silicate has a SiO 2 / M 2 O molar ratio of the order of 1.6 to 3.5 and more particularly of the order of 1.8 to 2.6.
  • Said silicate can be mixed with the polyimide polymer in a form any, structured (powder, granules ...) or not.
  • it is an aqueous solution at approximately 30-60%, preferably approximately 35-60% by weight of dry extract of a silicate of an alkali metal, in particular of SiO 2 / M 2 O ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, preferably with M representing a sodium atom.
  • the preformulation claimed may contain in addition to polyimide and silicate, an alkali metal carbonate.
  • an alkali metal carbonate may contain in addition to polyimide and silicate.
  • the presence of a carbonate within the preformulation is particularly advantageous in terms of humidity stability.
  • the carbonate content of said preformulation varies according to the content of silicate.
  • the carbonate percentages presented below will always be expressed relative to the total weight of carbonates and silicates.
  • the carbonate content varies between 20% and 75%, expressed by relative to the total weight of silicates and carbonates.
  • Said polyimide / silicate mixture with, if appropriate, carbonate can be prepared by bringing into contact (by adsorption and / or absorption) of a concentrated aqueous solution of an alkali metal silicate with a molar ratio SiO 2 / M 2 O of 1 '' from 1.6 to 3.5, preferably of the order of 1.8 to 2.6, and having a dry extract of the order of 30 to 60%, preferably of the order of 35 to 60%, with said polyimide polymer and, where appropriate, said carbonate, and drying.
  • the contacting operation can be carried out by simple addition, or else by spraying said concentrated solution of silicate onto the polyimide throughout known mixer with high shear, in particular of the LODIGE® type, or in the tools for granulation (drum, plate ...), at a temperature of around 20 ° C.
  • the particles of the mixture obtained can be ground, if desired, so as to obtain an average diameter of the order of 200 to 800 micrometers.
  • the densified cogranules are then dried by any known means.
  • a method particularly effective is drying in a fluidized bed using an air stream at a temperature of the order of 40 to 150 ° C, preferably 40 to 100 ° C. This operation is carried out for a period depending on the air temperature, the water content of the cogranules at the outlet of the granulation device and that desired dried cogranules, as well as fluidization conditions; the skilled person knows adapt these different conditions to the desired product.
  • the present invention covers the use of the preformulation for composition detergent claimed in detergent compositions in all proportions. These in fact vary widely depending on the specificity of detergent formulations incorporating it.
  • detergent composition generally refer to any detergent formulation, powder or liquid, intended for use both in a washing machine laundry, dishwasher only for household cleaning in general.
  • the quantities put work can be of the order of 1 to 60%, and preferably of the order of 3 to 40% of the weight of said compositions (these quantities are expressed in preformulation weight relative to the weight of the detergent composition).
  • these values are not provided for information only in the context of the present invention and are in no way limiting.
  • the detergent composition Besides the preformultaion which is the subject of the invention, is present in the detergent composition at least one surfactant in an amount which can range from 8 to 20%, preferably of the order of 10 to 15% of the weight of said composition.
  • the equipment is a PARMILLEUX ® dryer made up of two tanks connected by a tube. The first is in an air circulation oven, it has an inlet argon. The second is connected to a vacuum pump.
  • a first "builder” A preformulation was carried out with 150 g of PSI from Example 1 and 320 g of silicate solution with a ratio of 2 to 58% of extract dry, or an excess of silicate.
  • a HENRY ® grinder at temperature ambient, the powder + liquid mixture very quickly becomes a paste then goes through a liquid step before giving a sticky powder.
  • This powder is then passed into a high pressure extruder.
  • the cogranules obtained are dried in a fluidized bed.
  • the composition of the cogranules determined by calcination at 950 ° C for 3 h, is 44% silicate, 35% PSI and 21% water.
  • a second "builder" B preformulation was prepared, according to the operating mode described in example 2, starting from 50 g of PSI of example 1 and 114.8 g of solution of silicate with a ratio of 2 to 54% of dry extract, an excess of silicate.
  • the powder, obtained at the outcome of the reaction is dried overnight in air and then ground in a HENRY® mill. After sieving, the section is recovered between 800 and 200 ⁇ m.
  • the composition of cogranules determined by calcination is: 34% PSI; 43% dry silicate; 23 % water. Chemical analysis of total carbon and silica gives: 35% PSI; 41% dry silicate; 24% water.
  • a third "builder" C preformulation was prepared with 105 g of carbonate sodium, 233.5 g sodium silicate solution 45% dry extract and 290 g PSI of example 1.
  • the carbonate and the PSI are stirred for 5 minutes in a mixer LODIGE®.
  • the silicate is added in small nets and the mixing is continued until obtaining a moist and homogeneous powder.
  • the product is dried in a cold fluid bed first then at 60/70 ° C.
  • the carbonates / carbonates + silicates ratio is 1/2.
  • the inlay is evaluated by washing reference textiles in the washing machine: cotton testfabric 405 and cotton / polyamide krefeld 12A. After 20 wash cycles at 75 ° C followed by drying, the different samples are burned at 950 ° C for 3 hours, the mineral inlay is calculated from the ash rate expressed in relation to that obtained without additive.
  • builder A is less sensitive to humidity than CP5 or sodium polyaspartate. It is very good under 56% relative humidity and remains better than the other two at 90% relative humidity.

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)
  • Biological Depolymerization Polymers (AREA)

Claims (15)

  1. Vorformulierung "Builder" oder "Cobuilder" in Pulverform für Waschmittel-Zusammensetzungen, umfassend mindestens ein Polyimid-Polymer in Mischung mit mindestens einem Silicat, dadurch gekennzeichnet, daß sie fähig ist, mindestens eine wasserlösliche, biodegradable Polypeptid-Form zu erzeugen, wenn sie in Kontakt mit einem wäßrigen Medium von nicht alkalischem pH-Wert tritt, und dadurch, daß das Polyimid und das Silicat darin in einem Gewichtsverhältnis Polyimid/Silicat anwesend sind, das zwischen 40/60 und 55/45 variiert.
  2. Vorformulierung nach Anspruch 1, dadurch gekennzeichnet, daß das genannte Polyimid-Biopolymer geeignet ist, von der Polykondensation von Aminodisäuren oder Vorläufern der genannten Aminodisäuren zu stammen.
  3. Vorformulierung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das genannte Polyimid-Biopolymer geeignet ist, von der Polykondensation von Asparaginsäure und/oder Glutaminsäure oder von Vorläufern der genannten Säur(n) zu stammen.
  4. Vorformulierung nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das genannte Polyimid-Biopolymer eine mittlere Molekularmasse in Gewicht in der Größenordnung von 2.000 bis 107 aufweist.
  5. Vorformulierung nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das genannte Polyimid-Biopolymer eine mittlere Molekularmasse in Gewicht in der Größenordnung von 3.500 bis 60.000 aufweist.
  6. Vorformulierung nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Silicat ein molares Verhältnis SiO2/M2O zwischen 1,6 und 3,5, vorzugsweise in der Größenordnung von 1,8 bis 2,6 aufweist.
  7. Vorformulierung nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie geeignet ist, ausgehend von einer Lösung eines Silicates von einem Alkalimetall, insbesondere von Natrium oder Kalium, des molaren Verhältnisses SiO2/M2O zwischen 1,6 und 3,5, vorzugsweise in der Größenordnung von 1,8 bis 2,6, die 30 Gew.-% bis 60 Gew.-%, vorzugsweise 35 Gew.-% bis 60 Gew.-% Trockenextrakt enthält, durch In-Kontakt-Bringen der genannten Lösung mit dem genannten Polyimid-Polymer und Trocknen erhalten zu werden.
  8. Vorformulierung nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie außerdem ein Alkalimetallcarbonat enthält.
  9. Vorformulierung nach vorstehendem Anspruch, dadurch gekennzeichnet, daß das Carbonat in einem Gewichtsverhältnis in der Größenordnung von 20 % bis 75 % vorliegt, ausgedrückt durch das Verhältnis im Gesamtgewicht an Silicaten und Carbonaten.
  10. Vorformulierung nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß sie geeignet ist, ausgehend von einer Lösung eines Silicates von einem Alkalimetall, insbesondere von Natrium oder Kalium, des molaren Verhältnisses SiO2/M2O zwischen 1,6 und 3,5, vorzugsweise in der Größenordnung von 1,8 bis 2,6, die 30 Gew.-% bis 60 Gew.-%, vorzugsweise 35 Gew.-% bis 60 Gew.-% Trockenextrakt enthält, durch In-Kontakt-Bringen der genannten Lösung mit dem genannten Polyimid-Polymer und dem genannten Carbonat und Trocknen erhalten zu werden.
  11. Vorformulierung nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie die folgenden Charakteristiken aufweist:
    einen Gehalt an Polyimid-Polymer in der Größenordnung von 5 Gew.-% bis 35 Gew.-%,
    einen Gehalt an Silicat in der Größenordnung von 40 Gew.-% bis 60 Gew.-%,
    einen Gehalt an Wasser von 10 Gew.-% bis 30 Gew.-%.
  12. Vorformulierung nach Anspruch 11, dadurch gekennzeichnet, daß sie die folgenden Charakteristiken aufweist:
    einen Gehalt an Polyimid-Polymer in der Größenordnung von 35 Gew.-%,
    einen Gehalt an Silicat in der Größenordnung von 45 Gew.-%,
    einen Gehalt an Wasser von 20 Gew.-%.
  13. Vorformulierung nach Anspruch 11 oder 12, dadurch gekennzeichnet, daß sie außerdem einen Gehalt an Carbonat in der Größenordnung von 20 Gew.-% bis 30 Gew.-% aufweist, ausgedrückt durch das Verhältnis im Gesamtgewicht an Silicaten und Carbonaten.
  14. Vorformulierung nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie in Form von Co-Granulaten vorliegt.
  15. Verwendung der Vorformulierung, die den Gegenstand von irgendeinem der vorstehenden Ansprüche bildet, in einer Waschmittel-Zusammensetzung.
EP94401434A 1993-07-08 1994-06-24 Vorformulierung für Waschmittelzusammensetzung auf der Basis von Polyimid und einem Silikat Expired - Lifetime EP0633310B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9308385 1993-07-08
FR9308385A FR2708279B1 (fr) 1993-07-08 1993-07-08 Agent pour formulation détergente à base d'un polyimide et d'un silicate.

Publications (2)

Publication Number Publication Date
EP0633310A1 EP0633310A1 (de) 1995-01-11
EP0633310B1 true EP0633310B1 (de) 2000-03-01

Family

ID=9449051

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94401434A Expired - Lifetime EP0633310B1 (de) 1993-07-08 1994-06-24 Vorformulierung für Waschmittelzusammensetzung auf der Basis von Polyimid und einem Silikat

Country Status (12)

Country Link
US (1) US5643863A (de)
EP (1) EP0633310B1 (de)
JP (1) JP2914478B2 (de)
KR (1) KR100278211B1 (de)
CN (1) CN1057559C (de)
BR (1) BR9402654A (de)
CA (1) CA2127626C (de)
DE (1) DE69423144T2 (de)
DK (1) DK0633310T3 (de)
ES (1) ES2142915T3 (de)
FR (1) FR2708279B1 (de)
TW (1) TW287197B (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5902782A (en) * 1995-01-20 1999-05-11 Procter & Gamble Company Detergent compositions comprising stabilised polyamino acid compounds
US7494816B2 (en) * 1997-12-22 2009-02-24 Roche Diagnostic Operations, Inc. System and method for determining a temperature during analyte measurement
FR2774388B1 (fr) * 1998-02-02 2002-12-13 Rhodia Chimie Sa Systeme comprenant une matiere active organique hydrophobe encapsulee dans un polymere organique solide alcali-hydrosoluble et susceptible d'etre liberee en milieu alcalin
FR2774311B1 (fr) * 1998-02-02 2000-03-17 Rhodia Chimie Sa Granules dispersables dans l'eau comprenant une matiere active hydrophobe
DE19842053A1 (de) * 1998-09-15 2000-03-23 Bayer Ag Verwendung von Polyasparaginsäuren in Reinigerformulierungen mit abrasiver Wirkung
DE19907014A1 (de) * 1999-02-18 2000-08-24 Bayer Ag Formulierung von Wasch- und Reinigungsmittel-Compounds mit Polyasparaginsäuren und/oder Iminodisuccinaten
US6152150A (en) * 1999-08-03 2000-11-28 Odorpro, Inc. Method of stain removal using a dry zeolite containing composition
DE10027624A1 (de) * 2000-06-02 2001-12-06 Zschimmer & Schwarz Mohsdorf G Verfahren zur Nachreinigung von gefärbten oder bedruckten polyesterhaltigen textilen Produkten und Mischung zur Durchführung des Verfahrens
US20060019859A1 (en) * 2004-07-23 2006-01-26 Melani Duran Powder dilutable multi-surface cleaner
JP7065179B2 (ja) * 2018-03-30 2022-05-11 三井化学株式会社 再付着防止剤及び洗剤組成物
CN115198545A (zh) * 2022-03-16 2022-10-18 杭州桑瑞斯新材料有限公司 一种纤维织物净洗加工工艺

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8519046D0 (en) * 1985-07-29 1985-09-04 Unilever Plc Detergent compositions
US4911856A (en) * 1988-11-30 1990-03-27 Ecolab Inc. Low acid, soluble salt containing aqueous-organic softening agents for detersive systems
FR2675153B1 (fr) * 1991-04-15 1994-07-22 Rhone Poulenc Chimie Composition detergente contenant un biopolymere polyimide hydrolysable en milieu lessiviel.
EP0561452A1 (de) * 1992-03-20 1993-09-22 Unilever N.V. Zusammensetzung für Geschirrspülmaschinen, die Polyaminosäuren als Gerüststoffe enthalten
US5266237A (en) * 1992-07-31 1993-11-30 Rohm And Haas Company Enhancing detergent performance with polysuccinimide
US5393868A (en) * 1992-10-13 1995-02-28 Rohm And Haas Company Production of polysuccinimide by thermal polymerization of maleamic acid
EP0628655B1 (de) * 1993-06-11 2001-05-16 Ciba SC Holding AG Bleichhilfsmittel

Also Published As

Publication number Publication date
JP2914478B2 (ja) 1999-06-28
KR100278211B1 (ko) 2001-04-02
DE69423144D1 (de) 2000-04-06
US5643863A (en) 1997-07-01
JPH0770592A (ja) 1995-03-14
TW287197B (de) 1996-10-01
FR2708279A1 (fr) 1995-02-03
BR9402654A (pt) 1995-04-04
ES2142915T3 (es) 2000-05-01
DK0633310T3 (da) 2000-06-05
CA2127626C (fr) 2002-01-01
EP0633310A1 (de) 1995-01-11
FR2708279B1 (fr) 1995-09-01
CN1100136A (zh) 1995-03-15
KR960014320A (ko) 1996-05-22
DE69423144T2 (de) 2000-11-16
CN1057559C (zh) 2000-10-18
CA2127626A1 (fr) 1995-01-09

Similar Documents

Publication Publication Date Title
EP0511037B1 (de) Im Waschverfahren hydrolysierbares Polyimidbiopolymer enthaltende Waschmittelzusammensetzung
EP0561656B1 (de) Builder auf Basis von Silikat und anorganischer Verbindung
EP0488868B1 (de) Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen
EP0633310B1 (de) Vorformulierung für Waschmittelzusammensetzung auf der Basis von Polyimid und einem Silikat
JPH04227696A (ja) 安定なパーオキシカルボン酸顆粒
MX2007015067A (es) Composicion detergente.
CA1051741A (fr) Compositions solides pour le lavage, le nettoyage et le blanchiment et procedes pour leur fabrication et leur utilisation
FR2460997A1 (fr) Compositions de blanchiment particulaires
CA2114382C (fr) Composition detergente solide contenant au moins un polymere polycarboxylique biodegradable et non hygroscopique
CA2107815A1 (fr) Composition detergente incorporant un biopolymere polyimide hydrolysable en milieu lessiviel
EP0572288B1 (de) Verwendung von amorphen Siliko-Aluminaten als Wirtsgitter von Kalcium-enthaltenden Niederschlägen
EP0139547B1 (de) Granulierte Reinigungsmittel mit geringem Phosphatgehalt und Verfahren zu deren Herstellung
WO1996012784A1 (fr) Compositon d'adjuvant de detergence sans zeolithes ni phosphates
JPH10505874A (ja) ケイ酸塩顆粒及びその製造方法
WO1996029386A1 (fr) Composition d'adjuvant de detergence diminuant les incrustations calciques
LU85925A1 (fr) Composition detergente organique synthetique non ionique en particules renforcee par des adjuvants de detergence et ses procedes de fabrication
FR2732032A1 (fr) Composition d'adjuvant de detergence diminuant les incrustations calciques, son utilisation dans des compositions detergentes et ces compositions detergentes
FR2712896A1 (fr) Composition détergente contenant un polyimide biodégradable ou un hydrolysat dudit polyimide.
FR2796389A1 (fr) Procede de lavage contenant de l'acide arabinonique et/ou l'un, au moins, de ses sels
FR2837832A1 (fr) Adjuvant de detergence a base d'ammonium quaternaire et d'un produit mouillant
BE846439A (fr) Composition detergente avec adjuvants a base d'ortho- et de pyrophosphates hydrosolubles
FR2741887A1 (fr) Polymere silicie supporte et agent alcalin protecteur du verre et de la vaisselle a base dudit polymere silicie supporte
FR2715165A1 (fr) Produit utilisable en détergence comprenant du silicate vitreux hydraté.

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: 19940701

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE DK ES FR GB IT NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHODIA CHIMIE

17Q First examination report despatched

Effective date: 19980810

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE DK ES FR GB IT NL SE

ITF It: translation for a ep patent filed

Owner name: D. PERROTTA & C. S.A.S.

REF Corresponds to:

Ref document number: 69423144

Country of ref document: DE

Date of ref document: 20000406

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2142915

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20000511

EN Fr: translation not filed
EN4 Fr: notification of non filing translation in an earlier bopi is erroneous
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
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: SE

Payment date: 20030604

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20030610

Year of fee payment: 10

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

Ref country code: DK

Payment date: 20030613

Year of fee payment: 10

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

Ref country code: GB

Payment date: 20030618

Year of fee payment: 10

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

Ref country code: ES

Payment date: 20030619

Year of fee payment: 10

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

Ref country code: NL

Payment date: 20030630

Year of fee payment: 10

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

Ref country code: DE

Payment date: 20030707

Year of fee payment: 10

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

Ref country code: BE

Payment date: 20030902

Year of fee payment: 10

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: 20040624

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 NON-PAYMENT OF DUE FEES

Effective date: 20040625

Ref country code: ES

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

Effective date: 20040625

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

Ref country code: DK

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

Effective date: 20040630

Ref country code: BE

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

Effective date: 20040630

BERE Be: lapsed

Owner name: *RHODIA CHIMIE

Effective date: 20040630

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 NON-PAYMENT OF DUE FEES

Effective date: 20050101

Ref country code: DE

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

Effective date: 20050101

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

EUG Se: european patent has lapsed
EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20040624

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: 20050228

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: IT

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

Effective date: 20050624

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20040625