EP0219048A2 - 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

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Publication number
EP0219048A2
EP0219048A2 EP86113884A EP86113884A EP0219048A2 EP 0219048 A2 EP0219048 A2 EP 0219048A2 EP 86113884 A EP86113884 A EP 86113884A EP 86113884 A EP86113884 A EP 86113884A EP 0219048 A2 EP0219048 A2 EP 0219048A2
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EP
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Prior art keywords
graft copolymers
vinyl acetate
weight
oxide
washing
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EP86113884A
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German (de)
French (fr)
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EP0219048B1 (en
EP0219048A3 (en
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Alexander Dr. Kud
Guenther Dr. Schulz
Wolfgang Dr. Trieselt
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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    • 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

  • graying inhibitors in the washing and aftertreatment of textile material containing synthetic fibers.
  • 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 (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 in the temperature range from 50 to 200.degree.
  • 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 can be carried out 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 water is used as the solvent, there is initially a solution which, depending on the amount of vinyl acetate added, becomes 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 a solvent mixture, e.g. a mixture of isopropanol and water or a mixture of ethylene glycol and ethanol.
  • a solvent or 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 have a K value according to H. Fikentscher of 10 to 200, preferably 20 to 100 (determined in 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 adsor on the surface of agents such as Na2SO4 or builders (zeolites) as well as solid additives in the detergent formulation beers. It is also possible to add the products in finely divided form to the detergent formulation.
  • the commercial detergents contain, in addition to phosphates (as builders), surfactants, e.g. C8- to C12-alkylphenol ethoxylates, C12- to C20-alkanol ethoxylates, block copolymers of ethylene oxide and propylene oxide, which are optionally end groups, anionic surfactants, such as C8- to C12-alkylbenzenesulfonates, C12- to C16-alkanesulfonates, C12- to C1 , C12- to C16alkylsulfosuccinates, sulfated ethoxylated C12 / C16 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 one Amount of 5 to 30% by weight, 3 to 25% by weight of
  • 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.
  • 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 whiteness of the test fabric after the third wash is used 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.
  • Test conditions: Tester: Launder-O-meter Water hardness: 3.5 ⁇ mol Ca / l, 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
  • 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 selected 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 approximately 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 also shows Table that water-dispersed polyvinyl acetate alone and polyethylene glycol alone has practically no graying-inhibiting effect, as does a graft copolymer whose acetate groups have been completely saponified.

Abstract

Verwendung von Pfropfcopolymerisaten, die erhältlich sind durch Pfropfen von Polyalkylenoxiden eines Molekulargewichts (Zahlenmittel) von 2000 bis 100.000 mit Vinylacetat im Gewichtsverhältnnis 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. Use of graft copolymers which are obtainable by grafting polyalkylene oxides having a molecular weight (number average) from 2000 to 100,000 with vinyl acetate in a weight ratio of 1: 0.2 to 1:10 and whose acetate groups are optionally saponified up to 15%, as graying inhibitors during washing and aftertreatment of textile material containing synthetic fibers.

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-Ionen, sondern 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 greases 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,
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 C₁ to C₄ 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,

als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von syntheti­sche Fasern enthaltendem Textilgut bekannt.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 (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 in the temperature range from 50 to 200.degree. 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 can be carried out 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 water is used as the solvent, there is initially a solution which, depending on the amount of vinyl acetate added, becomes 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 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 Vinylalkohol-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 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 have a K value according to H. Fikentscher of 10 to 200, preferably 20 to 100 (determined in 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. Na₂SO₄ oder Gerüststoffen (Zeolithe) sowie festen Hilfsstoffen der Waschmittelformulierung adsor­ biert 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 adsor on the surface of agents such as Na₂SO₄ or builders (zeolites) as well as solid additives in the detergent formulation beers. 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. C₈- bis C₁₂-Alkylphenolethoxylate, C₁₂- bis C₂₀-­Alkanolethoxylate, Blockcopolymerisate des Ethylenoxids und Propylen­oxids, die gegebenenfalls Endgruppen verschlossen sind, anionische Ten­side, wie C₈- 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 detergents contain, in addition to phosphates (as builders), surfactants, e.g. C₈- to C₁₂-alkylphenol ethoxylates, C₁₂- to C₂₀-alkanol ethoxylates, block copolymers of ethylene oxide and propylene oxide, which are optionally end groups, anionic surfactants, such as C₈- to C₁₂-alkylbenzenesulfonates, C₁₂- to C₁₆-alkanesulfonates, C₁₂- to C₁ , C₁₂- to C₁₆alkylsulfosuccinates, sulfated ethoxylated C₁₂ / C₁₆ 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 one 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 setting agent, 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 · 10³. 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:The graying-inhibiting effect of the graft copolymers indicated above was tested as follows:

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.
Prüfbedingungen:
Prüfgerät: Launder-O-meter
Wasserhärte: 3,5 µmol Ca/l, Ca: Mg = 3:2
Flottenmenge: 250 ml
Flottenverhältnis: 1:10
Versuchstemperatur: 35 bis 60°C
Versuchsdauer: 30 Minuten (mit Aufheizzeit)
Waschmittelkonzentration: 8 g/lPolyester 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 whiteness of the test fabric after the third wash is used 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.
Test conditions:
Tester: Launder-O-meter
Water hardness: 3.5 µmol Ca / l, 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 Polyethylenglykol/Vinylacetat-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, deren Acetatgruppen voll­ständig verseift worden sind.The table shows that, on the one hand, the effect decreases when the polyethylene glycol selected 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 approximately 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 also shows Table that water-dispersed polyvinyl acetate alone and polyethylene glycol alone has practically no graying-inhibiting effect, as does a graft copolymer whose acetate groups have been completely saponified.

Claims (5)

1. 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.1. Use of graft copolymers which can be obtained by grafting (a) polyalkylene oxides with a molecular weight (in 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. 2. Verwendung von Pfropfcopolymerisaten gemäß Anspruch 1, dadurch gekennzeichnet, daß sie erhältlich sind durch Pfropfen von (a) Po­lyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 4000 bis 50.000 mit (b) Vinylacetat im Gewichtsverhltnis 1:0,5 bis 1:6.2. Use of graft copolymers according to claim 1, characterized in that they are obtainable by grafting (a) polyalkylene oxides with a molecular weight (by number average) from 4000 to 50,000 with (b) vinyl acetate in a weight ratio of 1: 0.5 to 1: 6 . 3. Verwendung von Pfropfcopolymerisaten gemäß den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie einen K-Wert nach H. Fikentscher von 10 bis 200 haben (bestimmt in 1 gew.%iger Lösung in Essigsäureethyl­ester bei 25°C).3. Use of graft copolymers according to claims 1 and 2, characterized in that they have a K value according to H. Fikentscher of 10 to 200 (determined in 1% by weight solution in ethyl acetate at 25 ° C). 4. Verwendung von Pfropfcopolymerisaten gemäß Anspruch 1, dadurch gekennzeichnet, daß sie erhältlich sind durch Pfropfen von (a) Po­lyethylenoxid eines Molekulargewichts (nach dem Zahlenmittel) von 2000 bis 50.000 mit (b) Vinylacetat im Gewichtsverhältnis 1:0,5 bis 1:6 und einem K-Wert von 10 bis 200 haben (bestimmt in 1 %iger Lösung in Essigsäureethylester bei 25°C).4. Use of graft copolymers according to claim 1, characterized in that they can be obtained by grafting (a) polyethylene oxide having a molecular weight (by number average) from 2000 to 50,000 with (b) vinyl acetate in a weight ratio of 1: 0.5 to 1: 6 and have a K value of 10 to 200 (determined in 1% solution in ethyl acetate at 25 ° C.). 5. Waschmittel auf der Basis von Tensiden, Gerüststoffen, Bleichmitteln und üblichen Zusätzen, dadurch gekennzeichnet, daß sie als vergrau­ungsinhibierenden Zusatz 0,1 bis 3 Gew.% von Pfropfcopolymerisaten enthalten, 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.5. Detergents based on surfactants, builders, bleaches and conventional additives, characterized in that they contain 0.1 to 3% by weight of graft copolymers as graying-inhibiting additive, which can be obtained by grafting (a) polyalkylene oxides having a molecular weight (according to the 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 optionally saponified up to 15% are.
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)

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CA1269013A (en) 1990-05-15
DE3536530A1 (en) 1987-04-23
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