EP0165136B1 - Kopolymere auf Basis von Polyoxyäthylen und Polyoxyalkylen enthaltende Reinigungsmittelzusammensetzungen die als Antivergrauungsmittel verwendet werden und Verfahren zu deren Herstellung - Google Patents

Kopolymere auf Basis von Polyoxyäthylen und Polyoxyalkylen enthaltende Reinigungsmittelzusammensetzungen die als Antivergrauungsmittel verwendet werden und Verfahren zu deren Herstellung Download PDF

Info

Publication number
EP0165136B1
EP0165136B1 EP85400956A EP85400956A EP0165136B1 EP 0165136 B1 EP0165136 B1 EP 0165136B1 EP 85400956 A EP85400956 A EP 85400956A EP 85400956 A EP85400956 A EP 85400956A EP 0165136 B1 EP0165136 B1 EP 0165136B1
Authority
EP
European Patent Office
Prior art keywords
copolymer
copolymers
compositions according
polyoxyethylene
zeta potential
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
Application number
EP85400956A
Other languages
English (en)
French (fr)
Other versions
EP0165136A1 (de
Inventor
Robert Gresser
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
Rhone Poulenc Chimie SA
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
Priority claimed from FR8408009A external-priority patent/FR2564852B1/fr
Priority claimed from FR8505125A external-priority patent/FR2579988A2/fr
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Priority to AT85400956T priority Critical patent/ATE41030T1/de
Publication of EP0165136A1 publication Critical patent/EP0165136A1/de
Application granted granted Critical
Publication of EP0165136B1 publication Critical patent/EP0165136B1/de
Expired 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/3726—Polyurethanes
    • 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
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones

Definitions

  • the present invention relates to polyoxyalkylene-based copolymers used as anti-deposition agents in the washing of textiles.
  • copolymers are used more particularly as an antiredepositing agent for washing in aqueous medium of polymeric, organic and synthetic materials.
  • the present invention which has overcome all these technical problems relates to detergent compositions according to claim 1 below.
  • zeta potential is understood to mean the absolute value of this parameter.
  • copolymers which meet the definition of the invention all preferably have a molecular weight less than or equal to 150,000 and even more preferably between 2000 and 150,000 and even more particularly between 4000 and 100,000.
  • the copolymers according to the invention preferably comprise an amount by weight of ethylene oxide relative to the polymer of between 10% and 90% and even more preferably an amount between 30 and 90% and very particularly an amount between 40 and 70%.
  • the ethylene oxide groups constitute the hydrophilic part of the copolymer and therefore allow the solubilization of the copolymer in water which is essential for a detergency application in an aqueous medium.
  • the alkylene oxide groups constitute the hydrophobic part of the copolymers and allow the adsorption of the copolymer on the fiber made up of synthetic organic polymers. This adsorption of the copolymer on the fiber will allow the desired effect, that is to say the anti-deposition.
  • composition for dry cleaning is known, based in particular on an ethylene-propylene polyglycol in solution in a solvent of the hydrocarbon type.
  • compositions for dry cleaning in a solvent medium and not for washing in an aqueous medium relate to compositions for dry cleaning in a solvent medium and not for washing in an aqueous medium.
  • a first group of anti-depositing copolymers used in the prior art consists of copolymers composed of linear or branched polyoxyethylene and polyoxyalkylene blocks of alkylene oxide containing in particular from 3 to 6 carbon atoms per alkylene group.
  • the alkylene groups are preferably propylene or butylene groups.
  • copolymers marketed under the brand name "PLURONICS”" are prepared in a known manner, for example according to the process described in US Patent No. 2,674,619. They are used for the most part and essentially for polyoxyethylene-polyoxyalkylene copolymers as removal agent dirt, according to US Patent No. 4,276,205, for example, which relates to compositions based on an amine oxide, an ethoxylated alcohol or an ethoxylated alkylphenol and a condensation product d alkylene oxides - C 2- C 4 .
  • compositions are presented as having a significant soil removal effect, in particular for greases, the amine oxide promoting the liquefaction of these.
  • the polyoxyalkylene groups are preferably chosen from polyoxypropylene and polyoxybutylene.
  • the copolymers of formula (I) can optionally be made ionizable by quaternizing the nitrogen atom (s). This quaternization can be carried out for example by a hydrogen atom or by an alkyl group.
  • copolymers of formula (II) sold are prepared in a manner known per se, for example described in US Patent No. 2,970,150, Example 16.
  • polyoxyalkylenes can be chosen in particular from polyoxypropylenes.
  • French Patent No. 2,308,646 describes polyurethanes having an anti-redeposition action for polyester-cotton fibers.
  • copolymers of formula (III) mention may be made of those for which A represents a hexamethylene, toluylene, isophorone, diphenylalkane radical.
  • copolymers of formula (III) those which have: a molecular mass of between 4000 and 40,000 and very particularly between 4000 and 25,000, a weight amount of ethylene oxide of between 40 and 50%, polyoxyethylene blocks with molecular weights less than 3500 and even more preferably between 550 and 1600 and polyoxyalkylene blocks with molecular masses less than 4000 and preferably between 500 and 2000.
  • copolymers of formula (III) are obtained for example by condensation of polyoxyethylene, of polyoxyalkylene of alkylene oxide of 3 to 6 carbon atoms or of block copolymers of polyoxyethylene-polyoxyalkylene with diisocyanates chosen from hexamethylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes, in an anhydrous medium in the presence of tin salt.
  • diisocyanates chosen from hexamethylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes
  • copolymers obtained by condensation of the homopolymers with diisocyanates have markedly improved anti-depositing properties.
  • copolymers described above can be used according to the invention as anti-depositing agents when they lower the zeta potential of the textile fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber.
  • This decrease in zeta potential is a function of the amount of copolymer adsorbed. This amount must be greater than 0.02 mg / g.
  • the quantity adsorbed is measured by bringing a sample of fabric made of polymeric, organic, synthetic material (TERGAL "type) of a mass close to 3.5 g fixed on a metal support, with 100 ml of a NaCl solution. (3 g / l) containing the polymer, in a cell thermostatically controlled at 25 ° C. The medium is stirred When the adsorption equilibrium is reached, the quantity adsorbed is determined by an assay of the concentration of polymer remaining in solution according to the method described by BALEUX (CR Acad. Sc., 274 series C, (1972), 1617).
  • the zeta potential of the fiber is measured before contact with the copolymer and after contact.
  • zeta potential or electrokinetic potential
  • the variation of the potential difference at the ends of the buffer as a function of the pressure applied to the solution makes it possible to determine the zeta potential of the fibers (JS STANLEY J. Phys. Chem. 58, (1954), 533).
  • the tissue washers Before measuring the electrokinetic potential, the tissue washers are brought into contact for 24 hours with a polymer solution in NaCl 3 g / l medium, so as to adsorb the copolymer on the fibers. After this adsorption phase, the tissue washers are placed in the filter of the apparatus and the copolymer solution used during the adsorption period circulates under the effect of a pressure through the tissue pad.
  • the anti-depositing effect of the copolymer can be measured by a series of different tests in the presence of dirt.
  • the anti-depositing effect is achieved when the zeta potential of the fiber on which the copolymer is adsorbed is equal to or less than 0.5 times that of the bare fiber.
  • This reduction in zeta potential is achieved for amounts of adsorbed copolymer equal to or greater than 0.02 mg / g of tissue.
  • the preferred amount of adsorbed copolymer varies with the type of adsorbed copolymer.
  • the preferred amount of adsorbed copolymer is between 0.05 and 5 mg / g of tissue.
  • the anti-depositing efficacy of an additive is evaluated by carrying out five cumulative “Terg-O-Tometer” washing cycles (United States Testing Company Inc. Hobokin, NJ) in the presence of “complete” soiling.
  • the total soil concentration used is 50 g / I for each wash cycle.
  • the fabric samples used during our washing tests are polyester samples ("DACRON" 54 "from TESTFABRIC) washed beforehand at 60 ° C in a machine supplied with fresh water and in the absence of detergent.
  • the concentration of anti-depositing additive used is 50 mg / 1.
  • the redeposition is quantified by the difference AR (measured by a GARDNER photometer "", filter Y) between the reflectance of the initially clean fabric and that of the fabric after five washing cycles.
  • the anti-depositing agent is all the more effective when ⁇ R is low.
  • an additive has a significant anti-depositing effect if the value of AR is reduced by at least 3 points in the presence of the polymer compared to the value of AR measured in the absence of additive.
  • Examples 1 to 14 were carried out using copolymers obtained by condensation of PLURONICS "by means of hexamethylene diisocyanate (HDI) at a temperature between 80 and 105 ° C. in the optional presence of a catalyst such as dilaurate dibutyltin Tests 1 to 14 are reported in Table 1a.
  • a catalyst such as dilaurate dibutyltin Tests 1 to 14 are reported in Table 1a.
  • Examples 15 to 39 were carried out using copolymers obtained by condensation of polyoxyethylene and another polyoxyalkylene in the presence of hexamethylene diisocyanate. Tests 15 to 39 are reported in Table 1b, 1c and 1d.
  • the invention also relates to the preparation of detergent compositions comprising the copolymers of the type described above, a simple and effective preparation process has been developed.
  • the process for the preparation of detergent compositions of the type of the invention is characterized in that the anti-depositing copolymer is added to a slurry comprising other constituents of the compositions, the mixture thus obtained is then dried.
  • copolymer thus introduced retains all of these properties in the composition obtained. This is an advantageous advantage because the copolymers of the invention can be used without appreciably modifying the conventional methods of preparation of detergent compositions.
  • the preparation of the slurry is done in a manner known per se.
  • the copolymer is added thereto with stirring.
  • the mixture obtained is then dried by any suitable means.
  • Any dry additive used in detergent compositions can be mixed with the dry product thus obtained: bleaching agents, anti-foaming agent, perfumes, dyes, enzymes for example.
  • the amount of copolymer added is such that it represents in particular approximately 0.2 to 5% and preferably between 1 and 2% by weight of the final composition.
  • the copolymer When added to the slurry, the copolymer can be presented in different forms.
  • a first possibility consists in presenting the copolymer in the form of a solution in water.
  • the concentration of copolymer in the solution is between 5 and 20% and preferably 10 to 15%.
  • Another possibility is to prepare a solution of the copolymer in a water-alcohol mixture.
  • an aliphatic alcohol such as for example ethanol or a compound which can be used in detergency as a nonionic surfactant such as for example polyoxyethylenated alkylphenols, polyoxyethylenated aliphatic alcohols, glycols and polyglycols.
  • a nonionic surfactant such as for example polyoxyethylenated alkylphenols, polyoxyethylenated aliphatic alcohols, glycols and polyglycols.
  • a suitable silica can be used as support, for example a silica of the TIXOSIL "38A type.
  • copolymer and of sulfonic acids such as for example arylsulfonic, alkylsulfonic, alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.
  • sulfonic acids such as for example arylsulfonic, alkylsulfonic, alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.
  • a slurry is prepared comprising LABS and sodium sulfate, stearate, silicate and tripolyphosphate, with stirring for 20 minutes at 85-90 ° C.
  • the antiredepositing agent according to the invention is not added to the formulation.
  • the slurry is then dried at 4 hours at 150 ° C. and then mixed with the other constituents of the composition.
  • an antiredeposition agent is added with stirring for 15 minutes at 80 ° C. in the form of a 10% solution in water according to the invention.
  • This agent is that corresponding to Example 20 (copolymer obtained by condensation of polyoxyethylene and polyoxyalkylene in the presence of hexamethylene diisocyanate).
  • the slurry thus prepared is mixed after drying (4 hours at 150 ° C) with the other components of the composition.
  • the amount of anti-depositing agent used represents 1% of the total weight of the composition.
  • the concentration of the washing composition is 6 g / l.
  • the reflectance Ry of the textile is evaluated after washing. The higher the reflectance Ry, the lower the redeposition. The results are given below:
  • the invention is in no way limited to the embodiments described which have been given only by way of examples.
  • it includes all the means constituting technical equivalents of the means described as well as their combinations if these are used in the context of protection as claimed.

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)
  • Detergent Compositions (AREA)

Claims (13)

1. Waschmittelgemische, die ein Wiederablagerungen verhinderndes Copolymer enthalten und zum Waschen synthetischer, organischer, polymerer Werkstoffe dienen, dadurch gekennzeichnet, daß das genannte Polymere aus Blockcopolymeren besteht, die durch Verkettung von Einheiten der allgemeinen Formel (III)
Figure imgb0014
gebildet werden, in der
- R9 und R10 Homopolymere von Ethylenoxid oder von Alkylenoxid mit 3 bis 6 gerad- oder verzweigtkettigen Kohlenstoffatomen oder verzweigte oder unverzweigte Blockcopolymere dieser Polyoxyethylen-Polyoxyalkylene, und
- A einen ggf. substituierten Alkylen- oder Phenylenrest bedeuten,
und die das Zetapotential eines Gewebes aus einem synthetischen, organischen, polymeren Werkstoff auf einen Wert kleiner oder gleich dem 0,5-fachen des Zetapotentials der unbehandelten Faser verringert, wobei das Zetapotential durch Kontakt des Gewebes mit einer NaCI-Lösung von 3 g/l und pH-Wert 7 und unter solchen Bedingungen gemessen wird, daß die Menge des pro Gramm des Gewebes adsorbierten Copolymeren mindestens 0,02 mg beträgt.
2. Gemische nach Anspruch 1, dadurch gekennzeichnet, daß die Polyoxyalkylene Polyoxypropylene sind.
3. Gemische nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß die Copolymere ein Molekulargewicht zwischen 4000 und 25 000 haben.
4. Gemische nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Copolymeren einen Ethylenoxidanteil von 40 bis 50 Gew.% haben.
5. Gemische nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Copolymere Polyoxyethylensequenzen eines Molekulargewichts kleiner als 3500 und vorzugsweise zwischen 550 und 1600 aufweisen.
6. Gemische nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Copolymeren Polyoxyalkylensequenzen aus Alkylenoxid mit 3 bis 6 Kohlenstoffatomen eines Molekulargewichts kleiner als 4000 und vorzugsweise zwischen 500 und 2000 aufweisen.
7. Gemische nach Anspruch 1, dadurch gekennzeichnet, daß das Copolymere das Zetapotential der Faser, gemessen bei pH = 7 in einer NaCI-Lösung von 3 g/I und unter solchen Bedingungen, daß die Menge adsorbierten Copolymeren zwischen 0,05 und 5 mg/g liegt, auf einen Wert kleiner als das 0,5-fache des Zetapotentials der unbehandelten Faser, verringert.
8. Verfahren zur Herstellung von Waschmittelgemischen nach irgendeinem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das Wiederablagerungen verhindernde Copolymere einem Brei hinzugefügt wird, der andere Bestandteile des Gemisches enthält, und daß die erhaltene Mischung anschließend getrocknet wird.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Copolymere dem Brei in Form einer wäßrigen Lösung zugefügt wird.
10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Copolymere dem Brei in Form einer Lösung in einem Alkohol-WasserGemisch zugefügt wird.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß als Alkohol eine Verbindung verwendet wird, die als nicht-ionisches Tensid verwendbar ist.
12. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das zugefügte Copolymere auf einem Siliciumdioxid-Träger vorliegt.
13. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das zugefügte Copolymer in Form einer Mischung mit einer Verbindung aus der Gruppe der Sulfonsäuren zugegeben wird.
EP85400956A 1984-05-23 1985-05-15 Kopolymere auf Basis von Polyoxyäthylen und Polyoxyalkylen enthaltende Reinigungsmittelzusammensetzungen die als Antivergrauungsmittel verwendet werden und Verfahren zu deren Herstellung Expired EP0165136B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85400956T ATE41030T1 (de) 1984-05-23 1985-05-15 Kopolymere auf basis von polyoxyaethylen und polyoxyalkylen enthaltende reinigungsmittelzusammensetzungen die als antivergrauungsmittel verwendet werden und verfahren zu deren herstellung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8408009A FR2564852B1 (fr) 1984-05-23 1984-05-23 Compositions detergentes comprenant des polymeres oxyde d'ethylene-oxyde d'alkylene a titre d'agents antiredeposants.
FR8408009 1984-05-23
FR8505125 1985-04-04
FR8505125A FR2579988A2 (en) 1985-04-04 1985-04-04 Process for the preparation of detergent compositions comprising copolymers based on polyoxyethylene and polyoxyalkylene

Publications (2)

Publication Number Publication Date
EP0165136A1 EP0165136A1 (de) 1985-12-18
EP0165136B1 true EP0165136B1 (de) 1989-03-01

Family

ID=26223980

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85400956A Expired EP0165136B1 (de) 1984-05-23 1985-05-15 Kopolymere auf Basis von Polyoxyäthylen und Polyoxyalkylen enthaltende Reinigungsmittelzusammensetzungen die als Antivergrauungsmittel verwendet werden und Verfahren zu deren Herstellung

Country Status (9)

Country Link
US (1) US4724095A (de)
EP (1) EP0165136B1 (de)
DE (1) DE3568455D1 (de)
DK (1) DK227385A (de)
ES (3) ES8702485A1 (de)
FI (1) FI80472C (de)
GR (1) GR851258B (de)
NO (1) NO163866C (de)
PT (1) PT80513B (de)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3536530A1 (de) * 1985-10-12 1987-04-23 Basf Ag Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
US4904359A (en) * 1985-10-31 1990-02-27 The Procter & Gamble Company Liquid detergent composition containing polymeric surfactant
EP0222557B1 (de) * 1985-10-31 1993-10-13 The Procter & Gamble Company Flüssige Reinigungsmittelzusammensetzung
DE3643791A1 (de) * 1986-12-20 1988-06-23 Basf Ag Waessrige polyurethan-klebstoff-dispersion
DE3712069A1 (de) * 1987-04-09 1988-10-20 Basf Ag Verwendung von pfropfpolymerisaten auf basis von polyestern, polyesterurethanen und polyesteramiden als vergrauungsinhibitoren in waschmitteln
US4839942A (en) * 1988-01-15 1989-06-20 Damp James B Fish scaling apparatus
US5049303A (en) * 1988-11-09 1991-09-17 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing a mixture of an ethylene oxide/propylene oxide block copolymer and a polycarboxylate
US20050204477A1 (en) * 2004-03-22 2005-09-22 Casella Victor M Fabric treatment for stain release
US20030192130A1 (en) * 2002-04-09 2003-10-16 Kaaret Thomas Walter Fabric treatment for stain release
US7893014B2 (en) * 2006-12-21 2011-02-22 Gregory Van Buskirk Fabric treatment for stain release
US10822577B2 (en) 2002-04-09 2020-11-03 Gregory van Buskirk Fabric treatment method for stain release
US10900168B2 (en) * 2002-04-09 2021-01-26 Gregory van Buskirk Fabric treatment for stain repellency
US20050058515A1 (en) * 2003-09-12 2005-03-17 Markusch Peter H. Geotextile/polymer composite liners based on waterborne resins
US20050229327A1 (en) * 2004-04-20 2005-10-20 Casella Victor M Fabric treatment for stain release
EA016304B1 (ru) * 2006-11-10 2012-04-30 Басф Се Способ сульфинилирования производной пиразола
EP2081908B1 (de) 2006-11-10 2013-04-24 BASF Agro B.V., Arnhem (NL), Zürich Branch Verfahren zur sulfinylierung eines pyrazolderivats
CA2667562A1 (en) 2006-11-10 2008-05-15 Basf Se Process for the sulfinylation of a pyrazole derivative
DK2349987T3 (da) 2008-10-02 2013-03-11 Basf Se Fremgangsmåde til fremstilling og oprensning af trifluormethansulfinsyre
JP2018505320A (ja) 2015-01-14 2018-02-22 バスカーク、 グレゴリー ヴァン しみ抜きのための改善された布地の処理方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806001A (en) * 1952-12-05 1957-09-10 Fong Willie Polyethyleneglycols as laundering aids
CH1277169D (de) * 1969-08-22
FR2308646A1 (fr) * 1975-04-23 1976-11-19 Rhone Poulenc Ind Polyurethanne hydrophile et son application
US4028313A (en) * 1975-06-25 1977-06-07 Bayer Aktiengesellschaft Process for the production of water-dispersible polyhydroxyl compounds
CA1066984A (en) * 1976-05-21 1979-11-27 Harold D. Deshon Drycleaning detergent solution
US4347152A (en) * 1976-12-02 1982-08-31 Colgate-Palmolive Company Phosphate-free concentrated particulate heavy duty laundry detergent
US4201824A (en) * 1976-12-07 1980-05-06 Rhone-Poulenc Industries Hydrophilic polyurethanes and their application as soil-release, anti-soil redeposition, and anti-static agents for textile substrates
FR2407980A1 (fr) * 1977-11-02 1979-06-01 Rhone Poulenc Ind Nouvelles compositions anti-salissure et anti-redeposition utilisables en detergence
US4276205A (en) * 1980-02-04 1981-06-30 The Procter & Gamble Company Detergent compositions containing amine oxide and nonionic surfactants and polyethylene glycol
DE3165042D1 (en) * 1980-06-17 1984-08-30 Procter & Gamble Detergent composition containing low level of substituted polyamines
US4383079A (en) * 1981-04-09 1983-05-10 Minnesota Mining And Manufacturing Company Extension of polyurethane hydrogel cure time
US4493773A (en) * 1982-05-10 1985-01-15 The Procter & Gamble Company Low phosphate, softening laundry detergent containing ethoxylated nonionic, alkylpolysaccharide and cationic surfactants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.S.Stanley, J.Phys.Chem. 58 (1954), pp. 533-536 *

Also Published As

Publication number Publication date
ES8702485A1 (es) 1986-12-16
NO163866C (no) 1990-08-01
FI80472B (fi) 1990-02-28
PT80513B (fr) 1987-04-06
NO163866B (no) 1990-04-23
EP0165136A1 (de) 1985-12-18
PT80513A (fr) 1985-06-01
US4724095A (en) 1988-02-09
NO852017L (no) 1985-11-25
ES543378A0 (es) 1986-12-16
FI80472C (fi) 1990-06-11
FI852050L (fi) 1985-11-24
DK227385D0 (da) 1985-05-22
GR851258B (de) 1985-11-25
FI852050A0 (fi) 1985-05-22
ES556897A0 (es) 1988-01-01
DE3568455D1 (en) 1989-04-06
ES8801365A1 (es) 1988-01-01
ES8801366A1 (es) 1988-01-01
ES556898A0 (es) 1988-01-01
DK227385A (da) 1985-11-24

Similar Documents

Publication Publication Date Title
EP0165136B1 (de) Kopolymere auf Basis von Polyoxyäthylen und Polyoxyalkylen enthaltende Reinigungsmittelzusammensetzungen die als Antivergrauungsmittel verwendet werden und Verfahren zu deren Herstellung
CA1070890A (fr) Polyurethane hydrophile et son application
CH640565A5 (fr) Composition anti-salissure et anti-redeposition, utilisable en detergence.
EP1345970B1 (de) Verwendung von amphoteren polysacchariden zur behandlung von gegenständen aus textilfasern
EP0279134B1 (de) Latex gegen Wiederverschmutzung beim Waschen von Textilien
FI91079C (fi) Segmenttipolyestereitä ja niiden kaltaisia yhdisteitä käytettäviksi lianirrotusaineina pesuainekoostumuksissa
EP0882117B1 (de) Schmutzabweisendes mittel und verfahren zur behandlung von gewebten baumwollartikeln
AU687213B2 (en) Soft surface cleaning composition with hydrogen peroxide
BE1001724A4 (fr) Composition de pre-detachage et son procede d'utilisation pour le detachage et le lavage de tissus.
EP1360364B1 (de) Verwendung von nicht-ionischen polysacchariden in einer zusammensetzung zur pflege von textilprodukten
CA1091843A (fr) Polyurethannes hydrophiles utilisables dans les compositions detergentes
FR2634799A1 (fr) Composition aqueuse pour l'assouplissement de textiles, et procede utilisant cette composition
CA2426695C (fr) Utilisation d'une composition a base de polysaccharide anionique pour le soin du linge
CH619001A5 (de)
EP1969025B1 (de) Klare und verdickend wirkende wässrige zusammensetzungen, verwendung davon in sauren wässrigen formulierungen und resultierende formulierungen
LU86428A1 (fr) Polyamides antistatiques d'acides trialkylacetiques et de polyamines,composition detergente les contenant et procedes pour laver et/ou traiter le linge les utilisant
BE1003814A3 (fr) Composition detergente liquide antistatique et son procede d'utilisation pour laver du linge.
FR2585362A1 (fr) Composition detergente antistatique de blanchissage et compositions assouplissantes la contenant
FR2564852A1 (fr) Compositions detergentes comprenant des polymeres oxyde d'ethylene-oxyde d'alkylene a titre d'agents antiredeposants.
FR2571756A1 (fr) Compositions de detergent assouplissant pour cycle de lavage en eau chaude
JPH0475957B2 (de)
FR2569717A1 (fr) Composition de detergent-assouplissant pour cycle de lavage
FR2784391A1 (fr) Composition detergente ou rincante protectrice des fibres textiles
EP0666897A1 (de) Verfahren und zusammensetzung zur entfettung der oberfläche eines gegenstandes
FR2824841A1 (fr) Utilisation, dans une composition pour le traitement des articles en fibres textiles, d'un polyorganosiloxane a fonctions(s) piperidinyle (s) comme agent anti-salissure ("soil release")

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

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

17P Request for examination filed

Effective date: 19851123

17Q First examination report despatched

Effective date: 19861009

D17Q First examination report despatched (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHONE-POULENC CHIMIE

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 41030

Country of ref document: AT

Date of ref document: 19890315

Kind code of ref document: T

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

Ref document number: 3568455

Country of ref document: DE

Date of ref document: 19890406

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

Ref country code: FR

Payment date: 19910422

Year of fee payment: 7

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

Ref country code: GB

Payment date: 19910514

Year of fee payment: 7

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

Ref country code: SE

Payment date: 19910517

Year of fee payment: 7

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

Ref country code: AT

Payment date: 19910522

Year of fee payment: 7

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910531

Year of fee payment: 7

Ref country code: DE

Payment date: 19910531

Year of fee payment: 7

Ref country code: CH

Payment date: 19910531

Year of fee payment: 7

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

Ref country code: LU

Payment date: 19910607

Year of fee payment: 7

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

Ref country code: BE

Payment date: 19910628

Year of fee payment: 7

EPTA Lu: last paid annual fee
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: 19920515

Ref country code: GB

Effective date: 19920515

Ref country code: AT

Effective date: 19920515

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

Ref country code: SE

Effective date: 19920516

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

Ref country code: LI

Effective date: 19920531

Ref country code: CH

Effective date: 19920531

Ref country code: BE

Effective date: 19920531

BERE Be: lapsed

Owner name: RHONE-POULENC CHIMIE

Effective date: 19920531

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

Ref country code: NL

Effective date: 19921201

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

Effective date: 19920515

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930129

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: DE

Effective date: 19930202

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 85400956.0

Effective date: 19921204