EP0219048B1 - Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres - Google Patents

Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres Download PDF

Info

Publication number
EP0219048B1
EP0219048B1 EP86113884A EP86113884A EP0219048B1 EP 0219048 B1 EP0219048 B1 EP 0219048B1 EP 86113884 A EP86113884 A EP 86113884A EP 86113884 A EP86113884 A EP 86113884A EP 0219048 B1 EP0219048 B1 EP 0219048B1
Authority
EP
European Patent Office
Prior art keywords
weight
vinyl acetate
oxide
graft copolymer
graft copolymers
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
EP86113884A
Other languages
German (de)
French (fr)
Other versions
EP0219048A3 (en
EP0219048A2 (en
Inventor
Alexander Dr. Kud
Guenther Dr. Schulz
Wolfgang Dr. Trieselt
Heinrich Dr. Hartmann
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to AT86113884T priority Critical patent/ATE53065T1/en
Publication of EP0219048A2 publication Critical patent/EP0219048A2/en
Publication of EP0219048A3 publication Critical patent/EP0219048A3/en
Application granted granted Critical
Publication of EP0219048B1 publication Critical patent/EP0219048B1/en
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
    • C11D3/3788—Graft 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • the present invention has for its object to provide graying inhibitors for detergents and graying inhibitors for the aftertreatment of textile material containing synthetic fibers.
  • graft copolymers which can be obtained by grafting a) polyalkylene oxides having a molecular weight (by number average) from 2000 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide with b) vinyl acetate in the weight ratio a): b ) from 1: 0.2 to 1:10 and their acetate groups are optionally saponified up to 15%, as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.
  • the products to be used according to the invention are known (cf. DE-PS 10 77 430). They are obtainable by grafting polyalkylene oxides with vinyl acetate, the graft copolymerization being initiated by free radicals. For this purpose, one can either use conventional polymerization initiators, which break down into radicals under the polymerization conditions, or initiate the polymerization by high-energy radiation.
  • Suitable polyalkylene oxides are polymers based on ethylene oxide, propylene oxide and / or butylene oxide, which have a number-average molecular weight of 2,000 to 100,000, preferably 4,000 to 50,000.
  • the alkylene oxide units can be randomly distributed in the polymer or in the form of blocks, e.g. Block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and butylene oxide and block copolymers of ethylene oxide, propylene oxide and butylene oxide.
  • the polyalkylene oxides in question are either dissolved in vinyl acetate and polymerized continuously or batchwise after addition of a polymerization initiator.
  • a semi-continuous mode of operation is also possible, in which a part, e.g. 10% of the mixture of polyalkylene oxide, vinyl acetate and initiator to be polymerized is introduced, heated to the polymerization temperature and, after the polymerization has started, the rest of the mixture to be polymerized is added as the polymerization progresses.
  • the graft copolymers can also be obtained by introducing polyalkylene oxide, heating to the polymerization temperature and adding vinyl acetate and starter either all at once, batchwise or, preferably, continuously.
  • Particularly suitable polymerization initiators are organic peroxides, such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbonate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, t-butyl perisobutyrate, t-butyl peracetate, di-t-amyl peroxide, t-butyl hydroperoxide and mixtures of initiators.
  • organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide
  • the polymerization can take place to 200 ° C in the temperature range from the 50th
  • the graft copolymerization is preferably carried out at 70 to 140 ° C. It can also take place under pressure.
  • the graft copolymerization can be carried out in the manner of a solution polymerization in a solvent.
  • Suitable solvents are, for example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, and glycols, such as propylene glycol, ethylene glycol and butylene glycol, and the methyl or Ethyl ether of the dihydric alcohols and dioxane.
  • the graft copolymerization is preferably carried out in the presence of water as the solvent. When using water as a solvent, there is initially a solution that is dependent on the amount of added ben vinyl acetate into a dispersion. If necessary, emulsifiers can also be used in this production method.
  • graft copolymer or polyalkylene oxide and vinyl acetate Per 100 parts by weight of the graft copolymer or polyalkylene oxide and vinyl acetate, 5 to 100, preferably 10 to 50 parts by weight of a solvent or else a solvent mixture, e.g. a mixture of isopropanol and water or a mixture of ethylene glycol and ethanol.
  • a solvent mixture e.g. a mixture of isopropanol and water or a mixture of ethylene glycol and ethanol.
  • the weight ratio of polyalkylene oxide to vinyl acetate in the graft copolymer is 1: 0.2 to 1:10, preferably 1: 0.5 to 1: 6.
  • Polyethylene oxide with a molecular weight (number average) of 2,000 to 100,000, in particular 4,000 to 50,000, is preferably used as the graft base.
  • Up to 15% of the acetate groups of the graft copolymer can optionally be saponified.
  • the saponification of the graft copolymers, which then leads to graft copolymers containing vinyl alcohol units, is carried out by adding a base, such as NaOH or KOH, or by adding acids, and optionally heating the mixture.
  • the graft copolymers to be used according to the invention as graying inhibitors generally have a K value according to H. Fikentscher of 10 to 200, preferably 20 to 100 (determined in a 1% strength by weight solution in ethyl acetate at 25 ° C.).
  • the graft copolymers described above are used in detergents with a reduced phosphate content (this should be understood to mean a phosphate content of less than 25% by weight sodium triphosphate) or in phosphate-free detergents.
  • the graft copolymers to be used according to the invention are added to commercially available detergent mixtures in an amount of 0.1 to 3, preferably 0.3 to 2% by weight, based on the detergent mixture.
  • the graft copolymers can be added to the detergent formulation in the form of a paste, a highly viscous mass or as a solution in a solvent.
  • the products can also be adsorbed on the surface of agents such as Na 2 S0 4 or builders (zeolites) and solid auxiliaries in the detergent formulation. It is also possible to add the products in finely divided form to the detergent formulation.
  • the commercial detergent containing except phosphates (as a builder) surfactants for example C s - to C1 2 alkylphenol ethoxylates, from C 12 - to C 2 o-alkanol ethoxylates, block copolymers of ethylene oxide and propylene oxide, which optionally end are closed, anionic surfactants such as Cs to C 12 alkylbenzenesulfonates, C 12 to C 16 alkanesulfonates, C1 2 to C 16 alkyl sulfates, C 12 to C16 alkyl sulfosuccinates, sulfated ethoxylated C 12 / C 16 alkanols, and optionally also 0.5 to 3% by weight.
  • anionic surfactants such as Cs to C 12 alkylbenzenesulfonates, C 12 to C 16 alkanesulfonates, C1 2 to C 16 alkyl sulfates, C 12 to C16 al
  • an incrustation inhibitor such as polymaleic acid, maleic acid / acrylic acid copolymers, polyacrylic acid or salts thereof, and also phosphate substitutes, such as zeolites in an amount of 5 to 30% by weight, 3 to 25% by weight of a bleaching agent, such as sodium perborate, optionally bleach activators, 10 to 30% by weight of adjusting agents, such as sodium sulfate, soap, alkalis, such as soda, plasticizers and defoamers, perfume, optical brighteners and optionally enzymes.
  • a bleaching agent such as sodium perborate
  • bleach activators 10 to 30% by weight of adjusting agents, such as sodium sulfate, soap, alkalis, such as soda, plasticizers and defoamers, perfume, optical brighteners and optionally enzymes.
  • the graft copolymers are also suitable as an additive in the aftertreatment of textile material containing synthetic fibers.
  • they are added to the last rinsing bath of a washing machine cycle, the addition either being carried out together with a fabric softener usually used at this point or, if a fabric softener is not desired, used alone instead of the fabric softener.
  • the amounts used are 0.01 to 0.3 g / l wash liquor.
  • the use of the graft copolymers in the last rinsing bath of a washing machine cycle has the advantage that the laundry is soiled much less during the next washing cycle than without the addition of the graying inhibitor.
  • the parts given in the examples are parts by weight, the percentages relate to the weight of the substances.
  • the molecular weights (number average) of the polyether diols used were calculated from the OH number.
  • the graft copolymers were prepared according to DE-PS 10 77 430 by grafting the parts of vinyl acetate shown in Table 1 to 100 parts of a polyethylene oxide with the molecular weight (number average) also given in the table.
  • the K values of the graft copolymers are also given in Table 1.
  • This graft copolymer was prepared by completely saponifying the graft copolymer 4 with NaOH.
  • the graying inhibitor was added in an amount of 0.5%, based on the test detergent.
  • the test vessels each contained 15 g test fabric (5 g polyester, 5 g polyester-cotton blend and 5 g cotton fabric) and 10 g dirt fabric. Cotton dirt from the Krefeld laundry research institute was used as the dirt fabric, namely WFK 10D.
  • the detergent used had the following composition:
  • Table 2 shows the increase in the reflectance of polyester and polyester / cotton blended fabrics after the addition of 0.5% of the products according to the invention, based on the weight of the detergent used, compared to the washing test without addition and to the addition of a graying inhibitor according to EP-PS 87 671.
  • the table shows that, on the one hand, the effect decreases when the polyethylene glycol chosen as the starting material for the graft copolymers drops below a molecular weight of approx. 2000, on the other hand, the effect is maximum when the polyethylene glycol / vinyl acetate ratio is about 1: 2 to 1: 2.5.
  • the copolymers of vinyl acetate described in EP-PS 087 671 are clearly exceeded by the products according to the invention.
  • the table also shows that water-dispersed polyvinyl acetate alone and polyethylene glycol alone have practically no graying-inhibiting effect, as does a graft copolymer whose acetate groups have been completely saponified.

Abstract

Detergents contain added graft copolymers which have an antiredeposition action and are obtainable by grafting polyalkylene oxides having a number average molecular weight of from 2000 to 100,000 with vinyl acetate in a weight ratio of from 1:0.2 to 1:10, and up to 15% of whose acetate groups may be hydrolyzed.

Description

Aufgrund gesetzgeberischer Maßnahmen ist es in vielen Ländern erforderlich, den Gehalt an Phosphaten in Waschmitteln stark herabzusetzen bzw. phosphatfreie Waschmittel anzubieten. Reduziert man jedoch den Gehalt an Phosphaten in Waschmitteln, so wird dadurch die Waschwirkung der Produkte verschlechtert. Phosphate wirken nicht nur als Sequestriermittel für Erdalkalimetall-lonen, sondem auch als Inkrustierungs- und Vergrauungsinhibitoren. Während man das Problem der Inkrustierung, d.h. der Ablagerungen mineralischer Herkunft auf dem Waschgut durch Ersatz der Phosphate in Waschmitteln durch andere Stoffe in den Griff bekommen kann, ist dies bei dem Problem der Vergrauung, d.h. des Wiederanschmutzens der Wäsche mit Schmutzteilchen und Fetten beim Waschen noch verbesserungsbedürftig. Das Problem der Vergrauung tritt vor allem bei Synthesefasern enthaltendem Gewebe auf, insbesondere bei Polyester enthaltenden Textilien.Legislative measures have made it necessary in many countries to greatly reduce the phosphate content in detergents or to offer phosphate-free detergents. However, if the phosphate content in detergents is reduced, the washing effect of the products is impaired. Phosphates not only act as sequestrants for alkaline earth metal ions, but also as incrustation and graying inhibitors. While addressing the problem of incrustation, i.e. of deposits of mineral origin on the laundry by replacing the phosphates in detergents with other substances, this is the problem of graying, i.e. the re-soiling of the laundry with dirt particles and fats during washing still needs improvement. The problem of graying occurs particularly in the case of fabrics containing synthetic fibers, in particular in the case of textiles containing polyester.

Aus der EP-PS 87 671 ist die Verwendung von Copolymerisaten, die als Monomereneinheiten

  • a) 50 bis 90 Gew.% mindestens eines Vinylesters von C1- bis C4-aliphatischen Carbonsäuren,
  • b) 5 bis 35 Gew.% mindestens eines N-Vinyllactams,
  • c) 1 bis 20 Gew.% mindestens eines basische Gruppen enthaltenden Monomeren oder dessen Salze oder Quaternierungsprodukte und
  • d) 0 bis 20 Gew.% mindestens eines mit den Monomeren a), b) und c) copolymerisierbaren sonstigen von Carboxylgruppen und basischen Gruppen freien Monomeren mit der Maßgabe einpolymerisiert enthalten, daß sich die Prozentzahlen jeweils auf 100 ergänzen,
    als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von synthetische Fasern enthaltendem Textilgut bekannt.
EP-PS 87 671 describes the use of copolymers as monomer units
  • a) 50 to 90% by weight of at least one vinyl ester of C 1 to C 4 aliphatic carboxylic acids,
  • b) 5 to 35% by weight of at least one N-vinyl lactam,
  • c) 1 to 20% by weight of at least one monomer containing basic groups or its salts or quaternization products and
  • d) 0 to 20% by weight of at least one copolymerized with the monomers a), b) and c) of other monomers free of carboxyl groups and basic groups, with the proviso that the percentages each add up to 100,
    known as graying inhibitors in the washing and aftertreatment of textile material containing synthetic fibers.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Vergrauungsinhibitoren für Waschmittel und Vergrauungsinhibitoren zum Nachbehandeln von Synthesefasern enthaltendem Textilgut zur Verfügung zu stellen.The present invention has for its object to provide graying inhibitors for detergents and graying inhibitors for the aftertreatment of textile material containing synthetic fibers.

Die Aufgabe wird erfindungsgemäß gelöst durch Verwendung von Pfropfcopolymerisaten, die erhältlich sind durch Pfropfen von a) Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 2000 bis 100.000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid mit b) Vinylacetat im Gewichtsverhältnis a):b) von 1:0,2 bis 1:10 und deren Acetatgruppen gegebenenfalls bis zu 15 % verseift sind, als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von Synthesefasern enthaltendem Textilgut.The object is achieved according to the invention by using graft copolymers which can be obtained by grafting a) polyalkylene oxides having a molecular weight (by number average) from 2000 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide with b) vinyl acetate in the weight ratio a): b ) from 1: 0.2 to 1:10 and their acetate groups are optionally saponified up to 15%, as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.

Die erfindungsgemäß zu verwendenden Produkte sind bekannt (vgl. DE-PS 10 77 430). Sie sind erhältlich durch Pfropfen von Polyalkylenoxiden mit Vinylacetat, wobei die Pfropfcopolymerisation radikalisch initiiert wird. Hierfür kann man sich entweder üblicher Polymerisationsinitiatoren bedienen, die unter den Polymerisationsbedingungen in Radikale zerfallen oder die Polymerisation auch durch energiereiche Bestrahlung initiieren. Als Polyalkylenoxide kommen Polymerisate auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid in Betracht, die ein Molekulargewicht (Zahlenmittel) von 2000 bis 100.000, vorzugsweise 4000 bis 50.000 haben. Die Alkylenoxid-Einheiten können im Polymerisat statistisch verteilt sein oder in Form von Blöcken vorliegen, z.B. Blockcopolymerisate aus Ethylenoxid und Propylenoxid, Blockcopolymerisate aus Ethylenoxid und Butylenoxid sowie Blockcopolymerisate aus Ethylenoxid, Propylenoxid und Butylenoxid.The products to be used according to the invention are known (cf. DE-PS 10 77 430). They are obtainable by grafting polyalkylene oxides with vinyl acetate, the graft copolymerization being initiated by free radicals. For this purpose, one can either use conventional polymerization initiators, which break down into radicals under the polymerization conditions, or initiate the polymerization by high-energy radiation. Suitable polyalkylene oxides are polymers based on ethylene oxide, propylene oxide and / or butylene oxide, which have a number-average molecular weight of 2,000 to 100,000, preferably 4,000 to 50,000. The alkylene oxide units can be randomly distributed in the polymer or in the form of blocks, e.g. Block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and butylene oxide and block copolymers of ethylene oxide, propylene oxide and butylene oxide.

Zur Herstellung der Pfropfcopolymerisate werden die in Betracht kommenden Polyalkylenoxide entweder in Vinylacetat gelöst und nach Zugabe eines Polymerisationsinitiators kontinuierlich oder diskontinuierlich polymerisiert. Ebenso ist eine halbkontinuierliche Arbeitsweise möglich, bei der man einen Teil, z.B. 10 % des zu polymerisierenden Gemisches aus Polyalkylenoxid, Vinylacetat und Initiator vorlegt, auf Polymerisationstemperatur erhitzt und nach dem Anspringen der Polymerisation den Rest der zu polymerisierenden Mischung nach Fortschritt der Polymerisation zugibt. Die Pfropfcopolymerisate können auch dadurch erhalten werden, daß man Polyalkylenoxid vorlegt, auf die Polymerisationstemperatur erwärmt und Vinylacetat und Starter entweder auf einmal, absatzweise oder vorzugsweise kontinuierlich zufügt.To prepare the graft copolymers, the polyalkylene oxides in question are either dissolved in vinyl acetate and polymerized continuously or batchwise after addition of a polymerization initiator. A semi-continuous mode of operation is also possible, in which a part, e.g. 10% of the mixture of polyalkylene oxide, vinyl acetate and initiator to be polymerized is introduced, heated to the polymerization temperature and, after the polymerization has started, the rest of the mixture to be polymerized is added as the polymerization progresses. The graft copolymers can also be obtained by introducing polyalkylene oxide, heating to the polymerization temperature and adding vinyl acetate and starter either all at once, batchwise or, preferably, continuously.

Als Polymerisationsinitiatoren eignen sich vor allem organische Peroxide, wie Diacetylperoxid, Dibenzoylperoxid, Succinylperoxid, Di-tert.-butylperoxid, tert.-Butylperbenzoat, tert.-Butyl-perpivalat, tert.-Butyl-permaleinat, Cumolhydroperoxid, Diisopropyl-peroxidicarbonat, Bis-(o-toluoyl)-peroxid, Didecanoylperoxid, Dioctanoylperoxid, Dilauroylperoxid, t-Butylperisobutyrat, t-Butylperacetat, Di-t-amylperoxid, t-Butylhydroperoxid sowie Mischungen von Initiatoren. Die Polymerisation kann in dem Temperaturbereich von 50 bis 200°C erfolgen. Vorzugsweise wird die Pfropfcopolymerisation bei 70 bis 140°C vorgenommen. Sie kann auch unter Druck stattfinden. Die Pfropfcopolymerisation kann nach Art einer Lösungspolymerisation in einem Lösemittel vorgenommen werden. Geeignete Lösemittel sind beispielsweise Alkohole, wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, sec.-Butanol, tert.-Butanol, n-Hexanol und Cyclohexanol sowie Glykole, wie Propylenglykol, Ethylenglykol und Butylenglykol sowie die Methyl- oder Ethylether der zweiwertigen Alkohole sowie Dioxan. Die Pfropfcopolymerisation wird vorzugsweise in Gegenwart von Wasser als Lösemittel durchgeführt. Bei Verwendung von Wasser als Lösemittel liegt zunächst eine Lösung vor, die in Abhängigkeit von der Menge des zugegebenen Vinylacetats in eine Dispersion übergeht. Bei dieser Herstellmethode können gegebenenfalls auch Emulgatoren verwendet werden.Particularly suitable polymerization initiators are organic peroxides, such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbonate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, t-butyl perisobutyrate, t-butyl peracetate, di-t-amyl peroxide, t-butyl hydroperoxide and mixtures of initiators. The polymerization can take place to 200 ° C in the temperature range from the 50th The graft copolymerization is preferably carried out at 70 to 140 ° C. It can also take place under pressure. The graft copolymerization can be carried out in the manner of a solution polymerization in a solvent. Suitable solvents are, for example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, and glycols, such as propylene glycol, ethylene glycol and butylene glycol, and the methyl or Ethyl ether of the dihydric alcohols and dioxane. The graft copolymerization is preferably carried out in the presence of water as the solvent. When using water as a solvent, there is initially a solution that is dependent on the amount of added ben vinyl acetate into a dispersion. If necessary, emulsifiers can also be used in this production method.

Pro 100 Gew.-Teile des Pfropfcopolymerisats bzw. Polyalkylenoxid und Vinylacetat, verwendet man 5 bis 100, vorzugsweise 10 bis 50 Gew.-Teile eines Lösemittels oder auch eines Lösemittelgemisches, z.B. eine Mischung aus Isopropanol und Wasser bzw. einer Mischung aus Ethylenglykol und Ethanol.Per 100 parts by weight of the graft copolymer or polyalkylene oxide and vinyl acetate, 5 to 100, preferably 10 to 50 parts by weight of a solvent or else a solvent mixture, e.g. a mixture of isopropanol and water or a mixture of ethylene glycol and ethanol.

Das Gewichtsverhältnis von Polyalkylenoxid zu Vinylacetat im Pfropfcopolymerisat beträgt 1:0,2 bis 1:10, vorzugsweise 1:0,5 bis 1:6. Als Pfropfgrundlage wird vorzugsweise Polyethylenoxid eines Molekulargewichts (nach dem Zahlenmittel) von 2000 bis 100.000, insbesondere 4000 bis 50.000 verwendet. Bis zu 15 % der Acetatgruppen des Pfropfcopolymerisats können gegebenenfalls verseift sein. Die Verseifung der Pfropfcopolymerisate, die dann zu Vinylalkohal-Einheiten enthaltenden Pfropfcopolymerisaten führt, wird durch Zugabe einer Base, wie NaOH oder KOH, bzw. durch Zugabe von Säuren, und gegebenenfalls Erwärmen der Mischung vorgenommen. Die erfindungsgemäß als Vergrauungsinhibitoren einzusetzenden Pfropfcopolymerisate haben in der Regel einen K-Wert nach H. Fikentscher von 10 bis 200, vorzugsweise 20 bis 100 (bestimmt in 1 gew%iger Lösung in Essigsäureethylester bei 25°C).The weight ratio of polyalkylene oxide to vinyl acetate in the graft copolymer is 1: 0.2 to 1:10, preferably 1: 0.5 to 1: 6. Polyethylene oxide with a molecular weight (number average) of 2,000 to 100,000, in particular 4,000 to 50,000, is preferably used as the graft base. Up to 15% of the acetate groups of the graft copolymer can optionally be saponified. The saponification of the graft copolymers, which then leads to graft copolymers containing vinyl alcohol units, is carried out by adding a base, such as NaOH or KOH, or by adding acids, and optionally heating the mixture. The graft copolymers to be used according to the invention as graying inhibitors generally have a K value according to H. Fikentscher of 10 to 200, preferably 20 to 100 (determined in a 1% strength by weight solution in ethyl acetate at 25 ° C.).

Die oben beschriebenen Pfropfcopolymerisate werden in Waschmitteln mit reduziertem Phosphatgehalt (darunter soll ein Phosphatgehalt von weniger als 25 Gew.% Natriumtriphosphat verstanden werden) oder in phosphatfreien Waschmitteln verwendet. Die erfindungsgemäß zu verwendenden Pfropfcopolymerisate werden handelsüblichen Waschmittelmischungen in einer Menge von 0,1 bis 3, vorzugsweise 0,3 bis 2 Gew.%, bezogen auf die Waschmittelmischung zugesetzt. Die Pfropfcopolymerisate können dabei in Form einer Paste, einer hochviskosen Masse oder als Lösung in einem Lösemittel der Waschmittelformulierung zugesetzt werden. Die Produkte können auch an der Oberfläche von Stellmitteln, wie z.B. Na2S04 oder Gerüststoffen (Zeolithe) sowie festen Hilfsstoffen der Waschmittelformulierung adsorbiert werden. Weiterhin ist es möglich, die Produkte in feinverteilter Form der Waschmittelformulierung hinzuzusetzen.The graft copolymers described above are used in detergents with a reduced phosphate content (this should be understood to mean a phosphate content of less than 25% by weight sodium triphosphate) or in phosphate-free detergents. The graft copolymers to be used according to the invention are added to commercially available detergent mixtures in an amount of 0.1 to 3, preferably 0.3 to 2% by weight, based on the detergent mixture. The graft copolymers can be added to the detergent formulation in the form of a paste, a highly viscous mass or as a solution in a solvent. The products can also be adsorbed on the surface of agents such as Na 2 S0 4 or builders (zeolites) and solid auxiliaries in the detergent formulation. It is also possible to add the products in finely divided form to the detergent formulation.

Die handelsüblichen Waschmittel enthalten außer Phosphaten (als Gerüststoff) Tenside, z.B. Cs- bis C12-Alkylphenolethoxylate, C12- bis C2o-Alkanolethoxylate, Blockcopolymerisate des Ethylenoxids und Propylenoxids, die gegebenenfalls Endgruppen verschlossen sind, anionische Tenside, wie Cs- bis C12-Alkylbenzolsulfonate, C12- bis C16-Alkansulfonate, C12- bis C16-Alkylsulfate, C12- bis C16Alkylsulfosuccinate, sulfatierte ethoxylierte C12/C16-Alkanole, sowie gegebenenfalls noch 0,5 bis 3 Gew.% eines Inkrustierungsinhibitors, wie Polymaleinsäure, Maleinsäure-Acrylsäure-Copolymerisate, Polyacrylsäure bzw. deren Salze, außerdem Phosphatersatzstoffe, wie Zeolithe in einer Menge von 5 bis 30 Gew.%, 3 bis 25 Gew.% eines Bleichmittels, wie Natriumperborat, gegebenenfalls Bleichaktivatoren, 10 bis 30 Gew.% Stellmittel, wie Natriumsulfat, Seife, Alkalien, wie Soda, Weichmacher und Entschäumer, Parfüm, optische Aufheller und gegebenenfalls Enzyme.The commercial detergent containing except phosphates (as a builder) surfactants, for example C s - to C1 2 alkylphenol ethoxylates, from C 12 - to C 2 o-alkanol ethoxylates, block copolymers of ethylene oxide and propylene oxide, which optionally end are closed, anionic surfactants such as Cs to C 12 alkylbenzenesulfonates, C 12 to C 16 alkanesulfonates, C1 2 to C 16 alkyl sulfates, C 12 to C16 alkyl sulfosuccinates, sulfated ethoxylated C 12 / C 16 alkanols, and optionally also 0.5 to 3% by weight. % of an incrustation inhibitor, such as polymaleic acid, maleic acid / acrylic acid copolymers, polyacrylic acid or salts thereof, and also phosphate substitutes, such as zeolites in an amount of 5 to 30% by weight, 3 to 25% by weight of a bleaching agent, such as sodium perborate, optionally bleach activators, 10 to 30% by weight of adjusting agents, such as sodium sulfate, soap, alkalis, such as soda, plasticizers and defoamers, perfume, optical brighteners and optionally enzymes.

Die Pfropfcopolymerisate eignen sich außerdem als Zusatz beim Nachbehandeln von synthetische Fasern enthaltendem Textilgut. Sie werden zu diesem Zweck dem letzten Spülbad eines Waschmaschinenzyklus zugesetzt, wobei der Zusatz entweder zusammen mit einem an dieser Stelle üblicherweise angewendetem Wäscheweichspülers erfolgen kann, oder - falls ein Weichspüler nicht erwünscht ist - allein anstelle des Weichspülers eingesetzt. Die Einsatzmengen betragen 0,01 bis 0,3 g/l Waschflotte. Die Verwendung der Pfropfcopolymerisate im letzten Spülbad eines Waschmaschinenzyklus hat den Vorteil, daß die Wäsche beim nächsten Waschzyklus weit weniger angeschmutzt wird als ohne den Zusatz des Vergrauungsinhibitors.The graft copolymers are also suitable as an additive in the aftertreatment of textile material containing synthetic fibers. For this purpose, they are added to the last rinsing bath of a washing machine cycle, the addition either being carried out together with a fabric softener usually used at this point or, if a fabric softener is not desired, used alone instead of the fabric softener. The amounts used are 0.01 to 0.3 g / l wash liquor. The use of the graft copolymers in the last rinsing bath of a washing machine cycle has the advantage that the laundry is soiled much less during the next washing cycle than without the addition of the graying inhibitor.

Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe. Die K-Werte der Pfropfcopolymerisate wurden nach H. Fikentscher, Cellulose Chemie 13, 58-64 und 71-74 (1932) in 1 %iger Lösung in Essigsäureethylester bei einer Temperatur von 25°C gemessen; dabei bedeutet K = k•103. Die Molekulargewichte (Zahlenmittel) der eingesetzten Polyetherdiole wurden aus der OH-Zahl errechnet.The parts given in the examples are parts by weight, the percentages relate to the weight of the substances. The K values of the graft copolymers were measured according to H. Fikentscher, Cellulose Chemie 13, 58-64 and 71-74 (1932) in 1% solution in ethyl acetate at a temperature of 25 ° C; where K = k • 10 3 . The molecular weights (number average) of the polyether diols used were calculated from the OH number.

Folgende Produkte wurden verwendet:The following products were used:

Pfropfcopolymerisate 1 bis 13Graft copolymers 1 to 13

Die Pfropfcopolymerisate wurden nach der DE-PS 10 77 430 durch Aufpfropfen der in Tabelle 1 angegebenen Teile Vinylacetat auf jeweils 100 Teile eines Polyethylenoxids mit dem ebenfalls in der Tabelle angegebenen Molekulargewicht (Zahlenmittel) hergestellt. Die K-Werte der Pfropfcopolymerisate sind ebenfalls in der Tabelle 1 angegeben.

Figure imgb0001
The graft copolymers were prepared according to DE-PS 10 77 430 by grafting the parts of vinyl acetate shown in Table 1 to 100 parts of a polyethylene oxide with the molecular weight (number average) also given in the table. The K values of the graft copolymers are also given in Table 1.
Figure imgb0001

Pfropfcopolymerisat 14Graft copolymer 14

Dieses Pfropfcopolymerisat wurde durch vollständige Verseifung des Pfropfcopolymerisates 4 mit NaOH hergestellt.This graft copolymer was prepared by completely saponifying the graft copolymer 4 with NaOH.

Die vergrauungsinhibierende Wirkung der oben angegebenen Pfropfcopolymerisate wurde folgendermaßen geprüft:

  • Polyesterprüfgewebe und Polyester/Baumwoll-Mischgewebe wurden zusammen mit einem Standard-Schmutzgewebe einer Reihe von 3 Wäschen unterzogen. Das Schmutzgewebe wird nach jeder Wäsche erneuert, wobei das Testgewebe nach jeder Wäsche stärker anschmutzt. Der Weißgrad des Testgewebes nach der dritten Wäsche dient zur Beurteilung des Anschmutzungsgrades, die Werte werden durch mehrfache Wiederholung und Mittelwertsbildung gesichert. Es wurde in % Remission mit einem Elrepho (Zeiss) Filter 8 gemessen.
The graying-inhibiting effect of the graft copolymers indicated above was tested as follows:
  • Polyester test fabric and polyester / cotton blend fabric were subjected to a series of 3 washes together with a standard dirt fabric. The dirty fabric is renewed after each wash, the test fabric becoming more soiled after each wash. The degree of whiteness of the test fabric after the third wash serves to assess the degree of soiling, the values are secured by repeated repetition and averaging. It was measured in% remission using an Elrepho (Zeiss) filter 8.

Prüfbedingungen:

  • Prüfgerät: Launder-D-meter
  • Wasserhärte: 3,5 µmol Ca/I, Ca: Mg = 3:2
  • Flottenmenge: 250 ml
  • Flottenverhältnis:1:10
  • Versuchstemperatur: 35 bis 60°C
  • Versuchsdauer: 30 Minuten (mit Aufheizzeit)
  • Waschmittelkonzentration: 8 g/I
Test conditions:
  • Tester: Launder-D-meter
  • Water hardness: 3.5 µmol Ca / I, Ca: Mg = 3: 2
  • Amount of liquor: 250 ml
  • Fleet ratio: 1:10
  • Test temperature: 35 to 60 ° C
  • Test duration: 30 minutes (with heating up time)
  • Detergent concentration: 8 g / l

In den Beispielen wurde der Vergrauungsinhibitor in einer Menge von 0,5 %, bezogen auf das Testwaschmittel zugesetzt. Die Prüfgefäße enthielten jeweils 15 g Testgewebe (5 g Polyester-, 5 g Polyester-Baumwollmisch-und 5 g Baumwollgewebe) und 10 g Schmutzgewebe. Als Schmutzgewebe diente Baumwollschmutzgewebe der Wäschereiforschungsanstalt Krefeld, und zwar WFK 10D.In the examples, the graying inhibitor was added in an amount of 0.5%, based on the test detergent. The test vessels each contained 15 g test fabric (5 g polyester, 5 g polyester-cotton blend and 5 g cotton fabric) and 10 g dirt fabric. Cotton dirt from the Krefeld laundry research institute was used as the dirt fabric, namely WFK 10D.

Das verwendete Waschmittel hatte folgende Zusammensetzung:

Figure imgb0002
The detergent used had the following composition:
Figure imgb0002

Es handelt sich also um ein phosphatreduziertes Waschmittel, wie es nach Inkrafttreten der 2. Stufe der Phosphathöchstmengenverordnung zum deutschen Waschmittelgesetz seit Januar 1984 im Handel anzutreffen ist.It is therefore a phosphate-reduced detergent, as has been on the market since January 1984 after the entry into force of the second stage of the Ordinance on Maximum Phosphate in the German Detergent Act.

Tabelle 2 zeigt die Erhöhung der Remission von Polyester- und Polyester/Baumwollmischgewebe nach Zusatz von 0,5 % der erfindungsgemäßen Produkte, bezogen auf das Gewicht des eingesetzten Waschmittels, im Vergleich zu dem Waschversuch ohne Zusatz und zu einem Zusatz eines Vergrauungsinhibitors gemäß EP-PS 87 671.

Figure imgb0003
Table 2 shows the increase in the reflectance of polyester and polyester / cotton blended fabrics after the addition of 0.5% of the products according to the invention, based on the weight of the detergent used, compared to the washing test without addition and to the addition of a graying inhibitor according to EP-PS 87 671.
Figure imgb0003

Die Tabelle zeigt, daß einerseits ein Absinken der Wirkung eintritt, wenn das als Ausgangsmaterial für die Pfropfcopolymeren gewählte Polyethylenglykol unter ein Molekulargewicht von ca. 2000 absinkt, zum anderen ein Maximum in der Wirkung bei einem PolyethylenglykoWinylacetat-Verhältnis von etwa 1:2 bis 1:2,5. Gleichzeitig ist ersichtlich, daß die in der EP-PS 087 671 beschriebenen Copolymeren des Vinylacetats von den erfindungsgemäßen Produkten deutlich übertroffen sind. Außerdem zeigt die Tabelle, daß in Wasser dispergiertes Polyvinylacetat allein sowie Polyethylenglykol allein praktisch keine vergrauungsinhibierende Wirkung besitzt, ebenso wie ein Pfropfcopolymerisat, dessen Acetatgruppen vollständig verseift worden sind.The table shows that, on the one hand, the effect decreases when the polyethylene glycol chosen as the starting material for the graft copolymers drops below a molecular weight of approx. 2000, on the other hand, the effect is maximum when the polyethylene glycol / vinyl acetate ratio is about 1: 2 to 1: 2.5. At the same time it can be seen that the copolymers of vinyl acetate described in EP-PS 087 671 are clearly exceeded by the products according to the invention. The table also shows that water-dispersed polyvinyl acetate alone and polyethylene glycol alone have practically no graying-inhibiting effect, as does a graft copolymer whose acetate groups have been completely saponified.

Claims (6)

1. Use of a graft copolymer which is obtainable by grafting (a) a polyalkylene oxide having a number average molecular weight of from 2000 to 100,000 and based on ethylene oxide, propylene oxide and/or butylene oxide with (b) vinyl acetate in a weight ratio (a):(b) of from 1:0.2 to 1:10, and up to 15% of whose acetate groups may be hydrolyzed, as an antiredeposition agent in the washing of textile materials containing synthetic fibers.
2. Use of a graft copolymer as claimed in claim 1, which is obtainable by grafting (a) a polyalkylene oxide having a number average molecular weight of from 4000 to 50,000 with (b) vinyl acetate in a weight ratio of from 1:0.5 to 1:6.
3. Use of a graft copolymer as claimed in claims 1 and 2, which has a K value according to H. Fikentscher of from 10 to 200 (determined in 1% strength by weight solution in ethyl acetate at 25°C).
4. Use of a graft copolymer as claimed in claim 1, which is obtainable by grafting (a) a polyethylene oxide having a number average molecular weight of from 2000 to 50,000 with (b) vinyl acetate in a weight ratio of from 1:0.5 to 1:6 and has a K value of from 10 to 200 (determined in 1% strength solution in ethyl acetate at 25°C).
5. Use of a graft copolymer as claimed in any of claims 1 to 4, wherein the graft copolymer is added to the final rinse of a washing machine cycle.
6. A detergent based on surfactants, builders, bleaches and conventional additives, which contains, as an added antiredeposition agent, from 0.1 to 3% by weight of added antiredeposition agent, from 0.1 to 3% by weight of a graft copolymer which is obtainable by grafting (a) a polyalkylene oxide having a number average molecular weight of from 2000 to 100,000, based on ethylene oxide, weight of from 2000 to 100,000, based on ethylene oxide, propylene oxide and/or butylene oxide with (b) vinyl acetate in a weight ratio (a):(b) of from 1:0.2 to 1:10, and up to 15% of whose acetate groups may be hydrolyzed.
EP86113884A 1985-10-12 1986-10-07 Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres Expired - Lifetime EP0219048B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86113884T ATE53065T1 (en) 1985-10-12 1986-10-07 USE OF GRAFT COPOLYMERS OF POLYALKYLENE OXIDES AND VINYL ACETATE AS GRAYING INHIBITORS IN THE WASHING AND AFTER-TREATMENT OF TEXTILE PRODUCTS CONTAINING SYNTHETIC FIBERS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3536530 1985-10-12
DE19853536530 DE3536530A1 (en) 1985-10-12 1985-10-12 USE OF POLYALKYLENE OXIDES AND VINYL ACETATE GRAFT COPOLYMERISATS AS GRAY INHIBITORS IN THE WASHING AND TREATMENT OF TEXTILE GOODS CONTAINING SYNTHESIS FIBERS

Publications (3)

Publication Number Publication Date
EP0219048A2 EP0219048A2 (en) 1987-04-22
EP0219048A3 EP0219048A3 (en) 1988-08-10
EP0219048B1 true EP0219048B1 (en) 1990-05-23

Family

ID=6283495

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86113884A Expired - Lifetime EP0219048B1 (en) 1985-10-12 1986-10-07 Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres

Country Status (7)

Country Link
US (1) US4746456A (en)
EP (1) EP0219048B1 (en)
JP (1) JPH0765073B2 (en)
AT (1) ATE53065T1 (en)
CA (1) CA1269013A (en)
DE (2) DE3536530A1 (en)
ES (1) ES2014962B3 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6812200B2 (en) 2000-12-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Process for coating detergent tablets
WO2007115381A2 (en) 2006-04-10 2007-10-18 K.U. Leuven Research And Development Solid dispersion of poorly soluble drugs in graft copolymers
US7867963B2 (en) 2007-06-12 2011-01-11 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7919449B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Detergent composition with hydrophilizing soil-release agent and methods for using same
US7919073B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US8293699B2 (en) 2007-06-12 2012-10-23 Rhodia Operations Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US8993506B2 (en) 2006-06-12 2015-03-31 Rhodia Operations Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate

Families Citing this family (201)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3711298A1 (en) * 1987-04-03 1988-10-13 Basf Ag USE OF GASKET POLYMERISATS BASED ON POLYALKYLENE OXIDES AS GRAY INHIBITORS IN THE WASHING AND TREATMENT OF TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
DE3711296A1 (en) * 1987-04-03 1988-10-13 Basf Ag USE OF ALKOXYLATED CARBOXYL GROUPS OF POLYMERISATS IN DETERGENTS
DE3711318A1 (en) * 1987-04-03 1988-10-20 Basf Ag USE OF GRAFT POLYMERISATS BASED ON POLYALKYLENE OXIDES AS GRAY INHIBITORS IN THE WASHING AND POST-TREATING OF TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
DE3711319A1 (en) * 1987-04-03 1988-10-20 Basf Ag USE OF GRAFT POLYMERISATS BASED ON POLYALKYLENE OXIDES AS GRAY INHIBITORS IN THE WASHING AND POST-TREATING OF TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
DE3712069A1 (en) * 1987-04-09 1988-10-20 Basf Ag USE OF GRAFT POLYMERISATS BASED ON POLYESTERS, POLYESTERURETHANES AND POLYESTERAMIDES AS GRAYING INHIBITORS IN DETERGENTS
GB8821035D0 (en) * 1988-09-07 1988-10-05 Unilever Plc Detergent compositions
GB8821032D0 (en) * 1988-09-07 1988-10-05 Unilever Plc Detergent compositions
GB8821034D0 (en) * 1988-09-07 1988-10-05 Unilever Plc Detergent compositions
US5049302A (en) * 1988-10-06 1991-09-17 Basf Corporation Stable liquid detergent compositions with enchanced clay soil detergency and anti-redeposition properties
US4908150A (en) * 1989-02-02 1990-03-13 Lever Brothers Company Stabilized lipolytic enzyme-containing liquid detergent composition
US5082585A (en) * 1989-02-02 1992-01-21 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic liquid detergent compositions containing nonionic copolymeric stabilizing agents for included lipolytic enzymes
DE3915070A1 (en) * 1989-05-09 1990-11-15 Basf Ag ISOPROPANOL SOLUBLE COPOLYMERISATES, MONOMERS CONTAINING POLYALKYLENE OXIDE BLOECKE, INCLUDED IN POLYMERIZED, THEIR PREPARATION AND THEIR USE
CA2029631A1 (en) * 1989-11-22 1991-05-23 Kathleen A. Hughes Graft polymers as biodegradable detergent additives
IT1236317B (en) * 1989-11-24 1993-02-09 Danieli Off Mecc SIMPLIFIED HYDRAULIC HAMMERING MACHINE
GB2239249A (en) * 1989-12-22 1991-06-26 Basf Corp Copolymers from polyalkylene oxides containing an allyl glycidyl ether reactive double bond and vinyl acetate
US5070140A (en) * 1989-12-22 1991-12-03 Basf Corporation Copolymers of vinyl acetate and allyl glycidyl ether capped C12 -C.sub.
DE4016002A1 (en) * 1990-05-18 1991-11-21 Basf Ag USE OF WATER-SOLUBLE OR WATER-DISPERSIBLE PEPPER PROTEINS AS ADDITION TO WASHING AND CLEANING AGENTS
EP0551390B1 (en) * 1990-09-28 1995-11-15 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5156906A (en) * 1991-09-30 1992-10-20 Basf Corporation Method of pretreating fabrics in impart soil release properties thereto
US5266166A (en) * 1992-05-18 1993-11-30 Betz Paperchem, Inc. Methods for controlling the deposition of organic contaminants in pulp and papermaking processes using a polyalkylene oxide/vinyl acetate graft copolymer
ATE175993T1 (en) * 1992-08-25 1999-02-15 Clariant Gmbh USE OF POLYVINYL ALCOHOL AS A DETERGENT ADDITIVE
US5514288A (en) * 1993-12-28 1996-05-07 Basf Corporation Method of pretreating fabrics to impart soil release properties thereto using polymers of vinyl ethers
US5733856A (en) * 1994-04-08 1998-03-31 Basf Corporation Detergency boosting polymer blends as additives for laundry formulations
GB2294268A (en) 1994-07-07 1996-04-24 Procter & Gamble Bleaching composition for dishwasher use
DE4424818A1 (en) 1994-07-14 1996-01-18 Basf Ag Low-viscosity mixtures of amphiphilic nonionic graft copolymers and viscosity-reducing additives
EP0693549A1 (en) 1994-07-19 1996-01-24 The Procter & Gamble Company Solid bleach activator compositions
FR2723858B1 (en) 1994-08-30 1997-01-10 Ard Sa PROCESS FOR THE PREPARATION OF SURFACTANTS FROM WHEAT BY-PRODUCTS AND NOVEL ALKYL XYLOSIDES
GB2297978A (en) 1995-02-15 1996-08-21 Procter & Gamble Detergent compositions containing amylase
DE69617035T2 (en) * 1995-09-04 2002-04-18 Unilever Plc DETERGENT COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF
DE19532717A1 (en) 1995-09-05 1997-03-06 Basf Ag Use of modified polyaspartic acids in detergents
EP0778342A1 (en) 1995-12-06 1997-06-11 The Procter & Gamble Company Detergent compositions
US5750483A (en) * 1995-12-06 1998-05-12 Basf Corporation Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide
US6066612A (en) 1996-05-03 2000-05-23 The Procter & Gamble Company Detergent compositions comprising polyamine polymers with improved soil dispersancy
US5919697A (en) * 1996-10-18 1999-07-06 Novo Nordisk A/S Color clarification methods
ES2183929T3 (en) 1996-10-31 2003-04-01 Procter & Gamble BLOSSOMING WATERPROOF LIQUID COMPOSITIONS AND PRE-TREATMENT PROCEDURE.
GB9711829D0 (en) 1997-06-06 1997-08-06 Unilever Plc Detergent compositions
DE19814739A1 (en) * 1998-04-02 1999-10-07 Basf Ag Solubilizing agents useful in pharmaceutical, cosmetic and food compositions
EP1065262A1 (en) 1999-06-29 2001-01-03 The Procter & Gamble Company Bleaching compositions
JP4523126B2 (en) * 1999-07-30 2010-08-11 株式会社日本触媒 Scale inhibitor
US6315835B1 (en) * 2000-04-27 2001-11-13 Basf Corporation Anti-spotting and anti-filming hard surface cleaning formulations and methods
DE10021726A1 (en) * 2000-05-04 2001-11-15 Henkel Kgaa Nanoparticles are used for loosening dirt and/or reducing resoiling of hard surface or textile, especially in a textile finish, washing, pretreatment or after-treatment agent
DE10026334A1 (en) * 2000-05-26 2001-12-06 Henkel Kgaa Detergent tablets with graft copolymer coating
US6511952B1 (en) 2000-06-12 2003-01-28 Arco Chemical Technology, L.P. Use of 2-methyl-1, 3-propanediol and polycarboxylate builders in laundry detergents
JP2002003890A (en) * 2000-06-20 2002-01-09 Kao Corp Detergent composition
DE10042815A1 (en) * 2000-08-30 2002-03-14 Basf Ag Use of grafted polyalkylene oxides as graying inhibitors in washing
GB2366797A (en) * 2000-09-13 2002-03-20 Procter & Gamble Process for making foam component by pressurising/depressurising
DE10050958A1 (en) * 2000-10-13 2002-04-18 Basf Ag Use of vinyl ester/polyether (especially polyethylene glycol or capped polyalkylene oxide) graft polymers to give water-soluble or -dispersible coatings or packaging films for detergents
BR0114910B1 (en) 2000-10-27 2013-05-28 stabilized aqueous liquid detergent composition.
ATE431844T1 (en) * 2002-02-11 2009-06-15 Rhodia Chimie Sa DETERGENT WITH BLOCK COPOLYMER
KR100587429B1 (en) * 2004-08-30 2006-06-09 한국산노프코 주식회사 Graft polymer and method for preparing the graft polymer
GB0424777D0 (en) * 2004-11-10 2004-12-08 Ciba Spec Chem Water Treat Ltd Graft polymers
WO2006066059A1 (en) * 2004-12-17 2006-06-22 The Procter & Gamble Company Hydrophobically modified polyols for improved hydrophobic soil cleaning
CA2589395A1 (en) * 2004-12-17 2006-06-22 The Procter & Gamble Company Hydrophilically modified polyols for improved hydrophobic soil cleaning
DE102005003122A1 (en) * 2005-01-21 2006-07-27 Henkel Kgaa Anti-adhesive polymers to prevent the adhesion of microorganisms to textiles and to prevent laundry odor
RU2394879C2 (en) * 2005-05-31 2010-07-20 Дзе Проктер Энд Гэмбл Компани Polymer-containing detergent compositions and use thereof
FR2887448B1 (en) * 2005-06-23 2009-04-17 Rhodia Chimie Sa COSMETIC COMPOSITION COMPRISING AN AMPHOLYTE COPOLYMER
FR2887450B1 (en) * 2005-06-23 2007-08-24 Rhodia Chimie Sa CONCENTRATED INGREDIENT FOR THE TREATMENT AND / OR MODIFICATION OF SURFACES, AND ITS USE IN COSMETIC COMPOSITIONS
FR2894585B1 (en) * 2005-12-14 2012-04-27 Rhodia Recherches Et Tech COPOLYMER COMPRISING ZWITTERIONIC UNITS AND OTHER UNITS, COMPOSITION COMPRISING THE COPOLYMER, AND USE
EP2024479B2 (en) * 2006-05-31 2015-02-25 The Procter & Gamble Company Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
US7465701B2 (en) * 2006-05-31 2008-12-16 The Procter & Gamble Company Detergent composition
EP1876227B2 (en) * 2006-07-07 2020-08-12 The Procter and Gamble Company Detergent Compositions
FR2903595B1 (en) * 2006-07-11 2008-08-22 Rhodia Recherches & Tech COSMETIC COMPOSITIONS COMPRISING A THERMOPLASTIC MATERIAL POWDER
GB0618542D0 (en) † 2006-09-21 2006-11-01 Unilever Plc Laundry compositions
JP2010531384A (en) 2007-06-29 2010-09-24 ザ プロクター アンド ギャンブル カンパニー Laundry detergent composition comprising an amphiphilic graft polymer based on polyalkylene oxide and vinyl ester
WO2009014821A2 (en) * 2007-07-20 2009-01-29 Rhodia Inc. Method for recovering crude oil from a subterranean formation
KR101533858B1 (en) * 2007-08-03 2015-07-03 바스프 에스이 Associative thickener dispersion
US8232356B2 (en) * 2007-11-14 2012-07-31 Basf Se Method for producing a thickener dispersion
RU2470069C2 (en) 2008-01-04 2012-12-20 Дзе Проктер Энд Гэмбл Компани Laundry detergent composition containing glycosyl hydrolase
WO2009092698A1 (en) 2008-01-22 2009-07-30 Basf Se Coated polyoxymethylenes
EP2083067A1 (en) 2008-01-25 2009-07-29 Basf Aktiengesellschaft Use of organic complexing agents and/or polymeric compounds containing carbonic acid groups in a liquid washing or cleaning agent compound
BRPI0908073A2 (en) 2008-02-06 2015-08-25 Basf Se Coated polyoxymethylene molding, process for producing coated polyoxymethylene molding, and polyoxymethylene molding composition
MY150244A (en) 2008-02-13 2013-12-31 Basf Se Coated polyoxymethylenes
US20090253612A1 (en) 2008-04-02 2009-10-08 Symrise Gmbh & Co Kg Particles having a high load of fragrance or flavor oil
EP2135931B1 (en) 2008-06-16 2012-12-05 The Procter & Gamble Company Use of soil release polymer in fabric treatment compositions
GB0810881D0 (en) 2008-06-16 2008-07-23 Unilever Plc Improvements relating to fabric cleaning
TW201031743A (en) 2008-12-18 2010-09-01 Basf Se Surfactant mixture comprising branched short-chain and branched long-chain components
US8900328B2 (en) 2009-03-16 2014-12-02 The Procter & Gamble Company Cleaning method
WO2011003904A1 (en) 2009-07-10 2011-01-13 Basf Se Surfactant mixture having short- and long-chained components
EP2302026A1 (en) * 2009-09-15 2011-03-30 The Procter & Gamble Company Detergent composition comprising surfactant boosting polymers
US8334250B2 (en) * 2009-12-18 2012-12-18 The Procter & Gamble Company Method of making granular detergent compositions comprising amphiphilic graft copolymers
US20110152161A1 (en) * 2009-12-18 2011-06-23 Rohan Govind Murkunde Granular detergent compositions comprising amphiphilic graft copolymers
US20110166370A1 (en) 2010-01-12 2011-07-07 Charles Winston Saunders Scattered Branched-Chain Fatty Acids And Biological Production Thereof
EP2534234B1 (en) 2010-02-12 2015-01-14 Basf Se Use of a copolymer as a thickener in liquid detergents having lower graying tendency
WO2011120799A1 (en) 2010-04-01 2011-10-06 Unilever Plc Structuring detergent liquids with hydrogenated castor oil
MX2012013145A (en) 2010-05-14 2013-10-30 Sun Products Corp Polymer-containing cleaning compositions and methods of production and use thereof.
CA2802277C (en) 2010-06-17 2015-08-04 Basf Se Polymers with saccharide side groups and their use
CN102971453B (en) 2010-07-02 2015-08-12 宝洁公司 Comprise their method of the long filament of non-flavorants activating agent, nonwoven web and preparation
CA2803629C (en) 2010-07-02 2015-04-28 The Procter & Gamble Company Filaments comprising an active agent nonwoven webs and methods for making same
MX2012015187A (en) 2010-07-02 2013-05-09 Procter & Gamble Method for delivering an active agent.
RU2543892C2 (en) 2010-07-02 2015-03-10 Дзе Проктер Энд Гэмбл Компани Production of films from nonwoven webs
MX345026B (en) 2010-07-02 2017-01-12 Procter & Gamble Web material and method for making same.
WO2012009660A2 (en) 2010-07-15 2012-01-19 The Procter & Gamble Company Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof
US8883698B2 (en) 2010-07-15 2014-11-11 The Procter & Gamble Co Compositions comprising a near terminal-branched compound and methods of making the same
MX345554B (en) * 2010-11-10 2017-02-03 Colgate Palmolive Co Fabric conditioners containing soil releasing polymer.
EP2654731B1 (en) 2010-12-23 2016-07-27 AbbVie Deutschland GmbH & Co. KG Solid retard formulations based on solid dispersions
CA2827658A1 (en) 2011-02-17 2012-08-23 The Procter & Gamble Company Bio-based linear alkylphenyl sulfonates
EP2678410B1 (en) 2011-02-17 2017-09-13 The Procter and Gamble Company Composiitons comprising mixtures of c10-c13 alkylphenyl sulfonates
EP2495300A1 (en) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuring detergent liquids with hydrogenated castor oil
FR2973034B1 (en) 2011-03-21 2014-05-02 Ard Sa NOVEL POLYESTER OLIGOMER COMPOSITIONS AND USE AS SURFACTANTS
EP2476743B1 (en) 2011-04-04 2013-04-24 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Method of laundering fabric
EP2522715A1 (en) 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Aqueous concentrated laundry detergent compositions
EP2522714A1 (en) 2011-05-13 2012-11-14 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Aqueous concentrated laundry detergent compositions
BR112013028716A2 (en) 2011-05-13 2017-01-24 Unilever Nv aqueous concentrated liquid laundry detergent, composition, method of washing polyester fabrics and their use
WO2012171849A1 (en) 2011-06-15 2012-12-20 Basf Se Branched polyesters with sulfonate groups
US8846599B2 (en) 2011-06-15 2014-09-30 Basf Se Branched polyesters with sulfonate groups
US20140141126A1 (en) 2011-06-29 2014-05-22 Solae Llc Baked food compositions comprising soy whey proteins that have been isolated from processing streams
AR088442A1 (en) 2011-09-20 2014-06-11 Procter & Gamble DETERGENT COMPOSITIONS THAT INCLUDE PRIMARY SURFACTANT SYSTEMS THAT INCLUDE SURFACTANTS BASED ON HIGHLY RAMIFIED ISOPRENOIDS AND OTHER SURFACTANTS
US20130072414A1 (en) 2011-09-20 2013-03-21 The Procter & Gamble Company Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants
EP2758503A2 (en) 2011-09-20 2014-07-30 The Procter and Gamble Company Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants
AR088757A1 (en) 2011-09-20 2014-07-02 Procter & Gamble DETERGENT COMPOSITIONS WITH HIGH FOAM THAT INCLUDE SURFACTANTS WITH ISOPRENOID BASE
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013070559A1 (en) 2011-11-11 2013-05-16 The Procter & Gamble Company Surface treatment compositions including shielding salts
CN106906573B (en) 2012-01-04 2019-08-27 宝洁公司 The fibre structure containing active material of multiple regions with different densities
EP2800803A1 (en) 2012-01-04 2014-11-12 The Procter and Gamble Company Active containing fibrous structures with multiple regions
PL2822981T3 (en) 2012-03-09 2016-11-30 Continuous process for the synthesis of graft polymers based on polyethers
US9068023B2 (en) 2012-03-09 2015-06-30 Basf Se Continuous process for the synthesis of graft polymers based on polyethers
IN2014DN06969A (en) 2012-03-09 2015-04-10 Procter & Gamble
WO2013139702A1 (en) 2012-03-21 2013-09-26 Unilever Plc Laundry detergent particles
MX2015000924A (en) 2012-07-26 2015-04-10 Procter & Gamble Low ph liquid cleaning compositions with enzymes.
DE102012220241A1 (en) * 2012-11-07 2014-05-08 Henkel Ag & Co. Kgaa Polymers with polar groups as soil release assets
DE102012221198A1 (en) * 2012-11-20 2014-05-22 Henkel Ag & Co. Kgaa Anti-adhesive polymers for microbial-repulsive textile finishing
AU2014241193B2 (en) 2013-03-28 2016-10-20 The Procter And Gamble Company Cleaning compositions containing a polyetheramine
EP2832843B1 (en) 2013-07-30 2019-08-21 The Procter & Gamble Company Method of making granular detergent compositions comprising polymers
PL2832842T3 (en) 2013-07-30 2019-09-30 The Procter & Gamble Company Method of making granular detergent compositions comprising surfactants
JP6431087B2 (en) 2013-12-09 2018-11-28 ザ プロクター アンド ギャンブル カンパニー Fiber structure containing activator and printed graphics
US20150210964A1 (en) 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer Product Compositions
EP2963100B1 (en) 2014-07-04 2018-09-19 Kolb Distribution Ltd. Liquid rinse aid compositions
EP2979682B1 (en) 2014-07-30 2018-09-05 Symrise AG A fragrance composition
FR3024736B1 (en) 2014-08-06 2016-08-26 Snf Sas USE IN DETERGENT COMPOSITIONS OF POLYMERS OBTAINED BY LOW-CONCENTRATION REVERSE EMULSION POLYMERIZATION WITH A LOW RATE OF NEUTRALIZED MONOMERS
EP2987848A1 (en) 2014-08-19 2016-02-24 The Procter & Gamble Company Method of laundering a fabric
US9617502B2 (en) 2014-09-15 2017-04-11 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
WO2016106167A1 (en) 2014-12-23 2016-06-30 Lubrizol Advanced Materials, Inc. Laundry detergent compositions
EP3237594B1 (en) 2014-12-23 2018-05-16 Lubrizol Advanced Materials, Inc. Laundry detergent compositions stabilized with an amphiphilic rheology modifier crosslinked with an amphiphilic crosslinker
TWI525110B (en) 2014-12-24 2016-03-11 財團法人工業技術研究院 Polymer, and pharmaceutical composition employing the same
WO2016155993A1 (en) 2015-04-02 2016-10-06 Unilever Plc Composition
US10639251B2 (en) 2015-10-28 2020-05-05 Symrise Ag Method for inhibiting or masking fishy odours
WO2017097434A1 (en) 2015-12-06 2017-06-15 Symrise Ag A fragrance composition
EP3190167B1 (en) 2016-01-07 2018-06-06 Unilever PLC Bitter pill
WO2017133879A1 (en) 2016-02-04 2017-08-10 Unilever Plc Detergent liquid
US10081783B2 (en) 2016-06-09 2018-09-25 The Procter & Gamble Company Cleaning compositions having an enzyme system
BR112018075524A2 (en) 2016-06-09 2019-03-19 Unilever N.V. detergent composition, system for a user to formulate custom-made on-demand laundry products and apparatus for providing laundry products
WO2017211700A1 (en) 2016-06-09 2017-12-14 Unilever Plc Laundry products
EP3272850A1 (en) 2016-07-19 2018-01-24 Henkel AG & Co. KGaA Easy ironing/anti-wrinkle/less crease benefit of fabric treatment compositions with the help of soil release polymers
US10421932B2 (en) 2016-07-21 2019-09-24 The Procter & Gamble Company Cleaning composition with insoluble quaternized cellulose particles and non-anionic performance polymers
WO2018036625A1 (en) 2016-08-20 2018-03-01 Symrise Ag A preservative mixture
US20180119065A1 (en) 2016-11-01 2018-05-03 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
EP3535362A1 (en) 2016-11-01 2019-09-11 The Procter and Gamble Company Leuco colorants as bluing agents in laundry care compositions, packaging, kits and methods thereof
BR112019006576A2 (en) 2016-11-01 2019-07-02 Milliken & Co leuco dyes as bleaching agents in laundry care compositions
US10752868B2 (en) 2016-11-09 2020-08-25 Henkel IP & Holding GmbH Unit dose detergent composition
EP3327106A1 (en) 2016-11-25 2018-05-30 Henkel AG & Co. KGaA Easy ironing/anti-wrinkle/less crease benefit by use of cationic polymers and its derivatives
EP3327108A1 (en) 2016-11-25 2018-05-30 Henkel AG & Co. KGaA Easy ironing/anti-wrinkle/less crease benefit of detergents with the help of bentonite or its derivatives
DE102016015429A1 (en) * 2016-12-23 2018-06-28 Henkel Ag & Co. Kgaa Graying inhibition when washing clothes
US11421048B2 (en) 2017-05-04 2022-08-23 Lubrizol Advanced Materials, Inc. Dual activated microgel
WO2018224379A1 (en) 2017-06-09 2018-12-13 Unilever Plc Laundry liquid dispensing system
US20210085579A1 (en) 2017-08-09 2021-03-25 Symrise Ag 1,2-alkanediols and a process for their production
WO2019038186A1 (en) 2017-08-24 2019-02-28 Unilever Plc Improvements relating to fabric cleaning
WO2019038187A1 (en) 2017-08-24 2019-02-28 Unilever Plc Improvements relating to fabric cleaning
DE112018004365T5 (en) 2017-09-29 2020-09-24 Unilever N.V. Laundry products
WO2019068473A1 (en) 2017-10-05 2019-04-11 Unilever Plc Laundry products
EP3694972A1 (en) 2017-10-12 2020-08-19 The Procter and Gamble Company Leuco colorants as bluing agents in laundry care composition
BR112020006988A2 (en) 2017-10-12 2020-10-06 The Procter & Gamble Company white dyes in combination with a second bleaching agent as bleaching agents in laundry care compositions
TWI715878B (en) 2017-10-12 2021-01-11 美商美力肯及公司 Leuco colorants and compositions
US20190194579A1 (en) 2017-10-12 2019-06-27 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
BR112020008476B1 (en) 2017-11-01 2023-11-21 Milliken & Company LEUCO COMPOUND
US11814607B2 (en) 2018-03-02 2023-11-14 Conopco, Inc. Laundry additive composition comprising a soil release polymer/silicone mixture
EP3759206B1 (en) 2018-03-02 2024-04-03 Unilever IP Holdings B.V. Method of softening a laundry composition
US11326129B2 (en) 2018-06-26 2022-05-10 The Procter & Gamble Company Fabric care compositions that include a graft copolymer and related methods
EP3824058A1 (en) 2018-07-18 2021-05-26 Symrise AG A detergent composition
MX2021003248A (en) 2018-09-20 2021-05-12 Symrise Ag Compositions comprising odorless 1,2-pentanediol.
MX2021005418A (en) 2018-11-08 2021-07-06 Symrise Ag An antimicrobial surfactant based composition.
US20220183937A1 (en) 2019-03-11 2022-06-16 Symrise Ag Method for improving the performance of a fragrance or a fragrance mixture
PL3969554T3 (en) 2019-05-16 2023-07-17 Unilever Ip Holdings B.V. Laundry composition
WO2021043585A1 (en) 2019-09-04 2021-03-11 Symrise Ag A perfume oil mixture
RU2737709C1 (en) * 2019-09-24 2020-12-02 АО "КИФ плюс" Detergent composition for washing and cleaning of solid surfaces
CN114728254A (en) 2019-10-16 2022-07-08 西姆莱斯股份公司 Polyurea microcapsules and liquid surfactant system containing the same
CN114728092A (en) 2019-11-29 2022-07-08 西姆莱斯股份公司 Edge block with improved odor performance
US11186805B2 (en) 2019-12-20 2021-11-30 The Procter & Gamble Company Particulate fabric care composition
WO2021228352A1 (en) 2020-05-11 2021-11-18 Symrise Ag A fragrance composition
EP4162016A1 (en) 2020-06-05 2023-04-12 The Procter & Gamble Company Detergent compositions containing a branched surfactant
EP3978589A1 (en) 2020-10-01 2022-04-06 The Procter & Gamble Company Narrow range alcohol alkoxylates and derivatives thereof
EP4237498A1 (en) 2020-10-27 2023-09-06 Milliken & Company Compositions comprising leuco compounds and colorants
WO2022136270A1 (en) 2020-12-21 2022-06-30 Unilever Ip Holdings B.V. A laundry treatment composition
CN116964186A (en) 2021-03-03 2023-10-27 西姆莱斯股份公司 Toilet edge block with smell change
BR112023018460A2 (en) 2021-03-22 2023-10-10 Symrise Ag COMPOSITION OF LIQUID DETERGENT
EP4323489A1 (en) 2021-04-14 2024-02-21 Unilever IP Holdings B.V. Fabric conditioner compositions
WO2022218696A1 (en) 2021-04-14 2022-10-20 Unilever Ip Holdings B.V. Fabric conditioner compositions
EP4083050A1 (en) 2021-05-01 2022-11-02 Analyticon Discovery GmbH Microbial glycolipids
EP4134421A1 (en) * 2021-08-12 2023-02-15 The Procter & Gamble Company Detergent composition comprising detersive surfactant and graft polymer
WO2023088551A1 (en) 2021-11-17 2023-05-25 Symrise Ag Fragrances and fragrance mixtures
WO2023147874A1 (en) 2022-02-04 2023-08-10 Symrise Ag A fragrance mixture
WO2023160805A1 (en) 2022-02-25 2023-08-31 Symrise Ag Fragrances with methoxy acetate structure
WO2023213386A1 (en) 2022-05-04 2023-11-09 Symrise Ag A fragrance mixture (v)
WO2023232243A1 (en) 2022-06-01 2023-12-07 Symrise Ag A fragrance mixture (v)
WO2023232245A1 (en) 2022-06-01 2023-12-07 Symrise Ag Fragrances with cyclopropyl structure
WO2023232242A1 (en) 2022-06-01 2023-12-07 Symrise Ag Fragrance mixture
EP4306628A1 (en) 2022-07-11 2024-01-17 The Procter & Gamble Company Laundry detergent composition containing two graft copolymer
WO2024027922A1 (en) 2022-08-05 2024-02-08 Symrise Ag A fragrance mixture (ii)
WO2024037712A1 (en) 2022-08-17 2024-02-22 Symrise Ag 1-cyclooctylpropan-2-one as a fragrance
EP4331564A1 (en) 2022-08-29 2024-03-06 Analyticon Discovery GmbH Antioxidant composition comprising 5-deoxyflavonoids
WO2024051922A1 (en) 2022-09-06 2024-03-14 Symrise Ag A fragrance mixture (iii)
WO2024078679A1 (en) 2022-10-10 2024-04-18 Symrise Ag A fragrance mixture (vi)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755252A (en) * 1956-07-17 Partially-acetylated polyvinyl alco-
FR1222944A (en) * 1958-04-15 1960-06-14 Hoechst Ag Graft polymers and their preparation process
DE1077430B (en) * 1958-04-15 1960-03-10 Hoechst Ag Process for the production of graft polymers of polyvinyl esters
US3284364A (en) * 1963-01-25 1966-11-08 American Cyanamid Co Soil anti-redeposition agents
US4088610A (en) * 1972-07-12 1978-05-09 Lever Brothers Company Detergent compositions
JPS5335566B2 (en) * 1973-03-22 1978-09-28
FR2308646A1 (en) * 1975-04-23 1976-11-19 Rhone Poulenc Ind HYDROPHILIC POLYURETHANNE AND ITS APPLICATION
DE3206883A1 (en) * 1982-02-26 1983-09-15 Basf Ag, 6700 Ludwigshafen USE OF COPOLYMERISATES CONTAINING BASIC GROUPS AS GRAY INHIBITORS FOR WASHING AND TREATING TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
US4490271A (en) * 1983-06-30 1984-12-25 The Procter & Gamble Company Detergent compositions containing polyethylene glycol and polyacrylate
EP0165136B1 (en) * 1984-05-23 1989-03-01 Rhone-Poulenc Chimie Detergent compositions containing copolymers based on polyoxyethylene and polyoxyalkylene used as antisoil redeposition agents, and process for their preparation

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6812200B2 (en) 2000-12-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Process for coating detergent tablets
WO2007115381A2 (en) 2006-04-10 2007-10-18 K.U. Leuven Research And Development Solid dispersion of poorly soluble drugs in graft copolymers
US8993506B2 (en) 2006-06-12 2015-03-31 Rhodia Operations Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate
US7867963B2 (en) 2007-06-12 2011-01-11 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7919449B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Detergent composition with hydrophilizing soil-release agent and methods for using same
US7919073B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US8268765B2 (en) 2007-06-12 2012-09-18 Rhodia Operations Mono-, di- and polyol phosphate esters in personal care formulations
US8293699B2 (en) 2007-06-12 2012-10-23 Rhodia Operations Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces

Also Published As

Publication number Publication date
CA1269013A (en) 1990-05-15
DE3536530A1 (en) 1987-04-23
EP0219048A3 (en) 1988-08-10
DE3671470D1 (en) 1990-06-28
ES2014962B3 (en) 1990-08-01
JPS6295399A (en) 1987-05-01
ATE53065T1 (en) 1990-06-15
EP0219048A2 (en) 1987-04-22
US4746456A (en) 1988-05-24
JPH0765073B2 (en) 1995-07-12

Similar Documents

Publication Publication Date Title
EP0219048B1 (en) Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres
EP0285935B1 (en) Use of graft polymers on the base of polyalkylenoxides as greyness inhibitors by washing and aftertreatment of synthetic fibres containing textile goods
EP0285038B1 (en) Use of graft polymers of polyalkylene oxides as anti-redeposition agents in the washing and after-treatment of textiles containing synthetic fibres
EP0285037B1 (en) Use of graft polymers of polyalkylene oxides as anti-redeposition agents in the washing and after-treatment of textiles containing synthetic fibres
EP0457205B1 (en) Use of water-soluble or water-dispersible grafted proteins as detergent and cleaning agent additives
EP0286019B1 (en) Use of graft polymers on the base of polyester, polyesterurethanes and polyesteramides as greyness inhibitors in washing agents
EP0116930B1 (en) Copolymers, their preparation and their use in washing and cleaning compositions
DE3915070A1 (en) ISOPROPANOL SOLUBLE COPOLYMERISATES, MONOMERS CONTAINING POLYALKYLENE OXIDE BLOECKE, INCLUDED IN POLYMERIZED, THEIR PREPARATION AND THEIR USE
WO2002018526A1 (en) Use of grafted polyalkylene oxides as greying inhibitors when washing
DE2814287A1 (en) Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive
DE3206883A1 (en) USE OF COPOLYMERISATES CONTAINING BASIC GROUPS AS GRAY INHIBITORS FOR WASHING AND TREATING TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
EP0610846B1 (en) Use of copolymers comprising vinyl/monomers and carbonamide as detergent additive
DE3711299C2 (en) Use of graft polymers based on polyvinylpyrrolidone as graying inhibitors in the washing and aftertreatment of textile fibers containing synthetic fibers
EP1513916B1 (en) Use of copolymers containing alkylene oxide units, as an additive in dishwashing compositions
WO1991019778A1 (en) Use of graft copolymers in washing and cleaning products
EP0584736B1 (en) Use of polyvinyl alcohols as detergent additive
WO2014177423A1 (en) Comb polymers as detergency boosters for washing and cleaning agents
EP0801165A2 (en) Pretreatment of textiles
DE2910133A1 (en) Builders for washing and cleaning agents - comprising a mixt. of a copolymer of (meth)acrylic! acid and an acrylic! acid, hydroxy alkyl ether! and poly maleic acid
EP0541588B1 (en) Use of polymerizates containing n-(alkyloxy-polyalkoxymethyl)carbonamide groups as additives to washing and cleaning agents
DE2616261C3 (en) Detergents and cleaning agents which contain copolymers containing carboxyl and hydroxyl groups
DE2646803B2 (en) Copolymers containing hydroxyl and carboxyl groups

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

17P Request for examination filed

Effective date: 19880630

17Q First examination report despatched

Effective date: 19890315

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 ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 53065

Country of ref document: AT

Date of ref document: 19900615

Kind code of ref document: T

ITF It: translation for a ep patent filed

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

REF Corresponds to:

Ref document number: 3671470

Country of ref document: DE

Date of ref document: 19900628

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
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
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 86113884.0

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

Ref country code: SE

Payment date: 19990927

Year of fee payment: 14

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

Ref country code: AT

Payment date: 19991004

Year of fee payment: 14

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

Ref country code: CH

Payment date: 19991005

Year of fee payment: 14

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

Ref country code: NL

Payment date: 19991007

Year of fee payment: 14

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

Ref country code: ES

Payment date: 19991013

Year of fee payment: 14

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

Ref country code: BE

Payment date: 19991020

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20000915

Year of fee payment: 15

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

Ref country code: GB

Payment date: 20001003

Year of fee payment: 15

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

Ref country code: AT

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

Effective date: 20001007

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 NON-PAYMENT OF DUE FEES

Effective date: 20001008

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

Ref country code: DE

Payment date: 20001014

Year of fee payment: 15

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

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20001030

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

Ref country code: LI

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

Effective date: 20001031

Ref country code: CH

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

Effective date: 20001031

Ref country code: BE

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

Effective date: 20001031

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 20001031

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: 20010501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed

Ref document number: 86113884.0

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

Effective date: 20010501

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: 20011007

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 20011018

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Effective date: 20011007

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: 20020628

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20011113

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;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: 20051007