EP0285038A2 - Use of graft polymers of polyalkylene oxides as anti-redeposition agents in the washing and after-treatment of textiles containing synthetic fibres - Google Patents

Use of graft polymers of polyalkylene oxides as anti-redeposition agents in the washing and after-treatment of textiles containing synthetic fibres Download PDF

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Publication number
EP0285038A2
EP0285038A2 EP88104889A EP88104889A EP0285038A2 EP 0285038 A2 EP0285038 A2 EP 0285038A2 EP 88104889 A EP88104889 A EP 88104889A EP 88104889 A EP88104889 A EP 88104889A EP 0285038 A2 EP0285038 A2 EP 0285038A2
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Prior art keywords
graft polymers
graft
weight
polyalkylene oxides
monomers
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EP88104889A
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German (de)
French (fr)
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EP0285038B1 (en
EP0285038A3 (en
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Alexander Dr. Kud
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

  • the object of the present invention is to provide other graying inhibitors for detergents and graying inhibitors for the aftertreatment of textile goods containing synthetic fibers.
  • the polyalkylene oxides of molecular weight (number average) from 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide given under a) above serve as the graft base.
  • Homopolymers of ethylene oxide or copolymers having an ethylene oxide content of 40 to 99 mol% are preferably used.
  • the proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference.
  • Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers.
  • copolymers of ethylene oxide and propylene oxide for example, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide are suitable.
  • the ethylene oxide content of the copolymers is preferably 40 to 99 mol%, the propylene oxide content 1 to 60 mol% and the proportion Butylene oxide in the copolymers 1 to 30 mol%.
  • straight-chain, branched homopolymers or copolymers can also be used as the graft base.
  • Branched copolymers are prepared, for example, by working on polyhydric low molecular weight alcohols, e.g. Trimethylolpropane, pentoses or hexoses, ethylene oxide and optionally also propylene oxide and / or butylene oxides.
  • the alkylene oxide units can be randomly distributed in the polymer or in the form of blocks.
  • N-vinylpyrrolidone is grafted onto the polyalkylene oxides as the monomer of component (b).
  • component (c) vinyl esters are used which are derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, as well as methyl acrylate, ethyl acrylate, methyl methacrylate, methyl methacrylate and mixtures of the aforementioned monomers. Suitable vinyl esters are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl i-valerate and vinyl caproate. Of the monomers of group (c), vinyl acetate, vinyl propionate, methyl acrylate or mixtures of vinyl acetate and methyl acrylate are preferably used.
  • the polyalkylene oxides of component (a) which are considered are grafted with the monomers of component (b) in the presence of initiators which form free radicals or by the action of high-energy radiation, which should also be understood to mean the action of high-energy electrons.
  • This can be done by dissolving the polyalkylene oxide in at least one monomer of group (b) and polymerizing the mixture after adding a polymerization initiator.
  • the graft polymerization can also be carried out semi-continuously by initially introducing a portion, for example 10%, of the mixture of polyalkylene oxide to be polymerized, at least one monomer from group (b) and / or (c) and initiator, heating to the polymerization temperature and after the light-off Polymerization adds the rest of the mixture to be polymerized as the polymerization progresses.
  • the graft polymers can also be obtained by placing the polyalkylene oxides of group (a) in a reactor, heating to the polymerization temperature and at least one monomer from group (b) and / or (c) and polymerization initiator either all at once, batchwise or preferably continuously adds and polymerizes.
  • the weight ratio of components (a): (b): (c) is from 1: 0.3: 1 to 1: 5: 30 and is preferably in the range from 1: 0.5: 1.5 to 1: 4 : 25.
  • the order in which the monomers (b) and (c) are grafted onto the polymer (a) can be chosen as desired. For example, N-vinylpyrrolidone is first grafted onto the polymer (a) and then a monomer (c) or a mixture of monomers from group (c).
  • the graft polymers are preferably used, in the production of which first N-vinylpyrrolidone and then vinyl acetate were grafted onto the graft base.
  • 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 peroxidic o-tamoyl (bis) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide and mixtures of the initiators, redox initiators and azo starters mentioned.
  • organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succ
  • the graft polymerization takes place in the temperature range from 50 to 200, preferably 70 to 140 ° C. It is usually carried out under atmospheric pressure, but can also take place under reduced or elevated pressure. If desired, the graft polymerization described above can also 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 ethylene glycol, propylene glycol and butylene glycol, and the methyl or Ethyl ether of dihydric alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane.
  • the graft polymerization can also be carried out in water as a solvent.
  • the emulsifiers used are, for example, ionic or nonionic surfactants whose HLB value is in the range from 3 to 13.
  • HLB value For the definition of the HLB value, reference is made to the publication by WC Griffin, J. Soc. Cosmetic Chem., Volume 5, 249 (1954).
  • the amount of surfactants, based on the graft copolymer is 0.1 to 5% by weight.
  • solutions or dispersions of the graft polymers are obtained. If solutions of the graft polymer are prepared in an organic solvent or in mixtures of an organic solvent and water, 5 to 200, preferably 10 to 100 parts by weight of the organic solvent or solvent mixture are used per 100 parts by weight of the graft polymer .
  • the weight ratio of components a) to b) to c) in the graft polymer is 1: 0.3: 1 to 1: 5: 30, preferably 1: 0.5: 1.5 to 1: 4:25.
  • the graft polymers have a K value of 5 to 200, preferably 5 to 50 (determined according to H. Fikentscher in dimethylformamide at 25 ° C. and a polymer concentration of 2% by weight).
  • the graft polymer can optionally be subjected to a partial hydrolysis, in which up to 15 mol% of the grafted monomers of component (c) are hydrolyzed.
  • the hydrolysis of graft polymers leads to graft polymers containing vinyl alcohol units.
  • the hydrolysis can be carried out, for example, by adding a base, such as sodium hydroxide solution or potassium hydroxide solution, or else by adding acids and, if appropriate, heating the mixture.
  • the graft polymers described above are used in detergents with a reduced phosphate content (this is to be understood as meaning a phosphate content of less than 25% by weight sodium triphosphate) or in phosphate-free detergents.
  • the graft polymers described above are added to commercial detergent formulations in an amount of 0.1 to 5, preferably 0.3 to 3,% by weight, based on the detergent mixture.
  • the graft polymers can be added to the detergent formulation in the form of granules, a paste, a highly viscous mass, as a dispersion or as a solution in a solvent.
  • the graft polymers can also be adsorbed on the surface of fillers, for example sodium sulfate or builders (zeolites) and other solid auxiliaries in the detergent formulation.
  • phosphate content is below 25% by weight or detergents which are free of phosphate at all contain surfactants as an essential component, e.g. C8 to C12 alkylphenol ethoxylates, C12 to C20 alkanol ethoxylates, and block copolymers of ethylene oxide and propylene oxide.
  • the polyalkylene oxides are solid substances at room temperature up to temperatures of 50 ° C. to 60 ° C. and are readily soluble or dispersible in water. These are linear or branched reaction products of ethylene oxide with propylene oxide and / or isobutylene oxide, which have a block structure or which can also have a statistical structure.
  • the end groups of the polyalkylene oxides can optionally be closed. This should be understood to mean that the free OH groups of the polyalkylene oxides can be etherified and / or esterified and / or aminated and / or reacted with isocyanates.
  • Anionic surfactants such as C8 to C12 alkyl benzene sulfonates, C12 to C16 alkane sulfonates, C12 to C16 alkyl sulfates, C12 to C16 alkyl sulfosuccinates and sulfated ethoxylated C12 to C16 alkanols are also suitable as constituents of powder detergents.
  • Powdered detergents usually contain 5 to 20% by weight of a surfactant or a mixture of surfactants.
  • the powder detergents may also optionally contain polycarboxylic acids or their salts, for example tartaric acid or citric acid.
  • incrustation inhibitors are, for example, homopolymers of acrylic acid, methacrylic acid and maleic acid or copolymers, e.g. Copolymers of maleic acid and acrylic acid, copolymers of maleic acid and methacrylic acid or copolymers of a) acrylic acid and / or methacrylic acid with b) acrylic acid esters, methacrylic acid esters, vinyl esters, allyl esters, itaconic acid esters, itaconic acid, methylene malonic acid, methylene malonic acid esters, crotonic acid and crotonic acid esters.
  • homopolymers of acrylic acid, methacrylic acid and maleic acid or copolymers e.g. Copolymers of maleic acid and acrylic acid, copolymers of maleic acid and methacrylic acid or copolymers of a) acrylic acid and / or methacrylic acid with b) acrylic acid esters, methacrylic acid esters, vinyl esters, allyl
  • copolymers of olefins and C1 to C4 alkyl vinyl ethers come into consideration.
  • the molecular weight of the homo- and copolymers is 1,000 to 100,000.
  • the incrustation inhibitors are used in an amount of 0.5 to 10% by weight in detergents.
  • compositions of the detergent mixture can also be corrosion inhibitors, monomeric, oligomeric and polymeric phosphonates, ether sulfonates based on unsaturated fatty alcohols, for example oleyl alcohol ethoxylate butyl ether and their alkali metal salts.
  • Powdery Detergents can optionally also contain zeolites, for example in an amount of 5 to 30% by weight.
  • the detergent formulations can optionally also contain bleaches. If bleaching agents are used, the amounts usually used are 3 to 25% by weight. The best known bleach is, for example, sodium perborate.
  • the detergent formulations may also contain bleach activators, plasticizers, defoamers, perfumes, optical brighteners and enzymes. Detergents, such as sodium sulfate, can optionally be present in an amount of 10 to 30% by weight.
  • the graft polymers described above can also be used as an additive to liquid detergents.
  • the liquid detergents contain, as a mixing component, liquid or solid surfactants which are soluble or at least dispersible in the detergent formulation.
  • the surfactant content of liquid detergents is usually in the range from 15 to 50% by weight. Suitable surfactants for this are the products which are also used in powder detergents, and liquid polyalkylene oxides or polyalkoxylated compounds.
  • a small amount of solubilizers e.g. Water or a water-miscible organic solvent, e.g. Prepare a homogeneous mixture of isopropanol, methanol, ethanol, glycol, diethylene glycol or triethylene glycol.
  • the graft polymers 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 normally used at this point or — if a fabric softener is not desired — alone instead of the fabric softener.
  • the amounts used are 0.01 to 0.3 g / l wash liquor.
  • the use of the graft polymers in the last rinsing bath of a washing machine cycle has the advantage that the laundry is soiled less by detached dirt particles that are present in the washing liquor during the next washing cycle than without the addition of the graying inhibitor in the previous washing.
  • the parts given in the examples are parts by weight, the figures in percent relate to the weight of the substances.
  • the molecular weights (number average) of the polyalkylene oxides a) used were calculated from the OH number.
  • graft polymers were prepared in such a way that first N-vinylpyrrolidone and then vinyl acetate or a mixture of vinyl acetate and methyl acrylate at 105 ° C. using 2.25% by weight, based on the polyethylene oxide given in Table 1 the monomers used in the graft copolymerization polymerized onto dibenzoyl peroxide.
  • the K values of the graft polymers obtained are also given in Table 1.
  • M n number average molecular weight
  • PEO polyethylene oxide
  • VP N-vinyl pyrrolidone
  • VAc vinyl acetate
  • MA methyl acrylate
  • the graft copolymers 6 and 7 were hydrolyzed to 15 mol%.
  • the graying-inhibiting effect of the above-mentioned graft copolymers was tested as follows: polyester test fabric and polyester / cotton blend fabric were used together with a standard dirt fabric subjected to a series of 3 washes. 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 3rd wash is used to assess the degree of soiling. The values are secured by repeated repetition and averaging. The photometric measurement of the reflectance in% was measured in the present case on the Elrepho 2000 (Datacolor) at the wavelength of 460 nm (barium primary white standard according to DIN 5033).
  • the graying inhibitor was added in each case in an amount of 0.5%, based on the test detergent.
  • the test vessels each contained 15 g of 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 test detergent used had the following composition: C12 alkyl benzene sulfonate 6.25% Tallow fatty alcohol reacted with 11% 4.7% ethylene oxide Soap 2.8% Na triphosphate (90% degree of conservation) 20% Na perborate (tetrahydrate) 20% Na2SO4 24% Sodium disilicate 6% Mg silicate 1.25% Carboxymethyl cellulose (CMC), Na salt 0.6% Tetrasodium salt of ethylenediaminetetraacetic acid 0.2% Rest of water to 100%.
  • CMC Carboxymethyl cellulose
  • Table 2 shows the increase in reflectance of polyester and polyester / cotton blended fabrics after addition of 0.5% of the products to be used according to the invention, based on the weight of the test detergent used. Table 2 also shows the results of comparative examples.
  • Table 2 shows that the homopolymers PEO, PVP and PVac and the fully saponified graft polymers 9 and 10 have practically no activity as a graying inhibitor.

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Abstract

Use of graft copolymers which are obtainable by grafting (a) polyalkylene oxides of a molecular weight (according to the number average) of 300 to 100,000 based on ethylene oxide, propylene oxide and/or butylene oxide with (b) N-vinylpyrrolidone and (c) a vinyl ester which is derived from a saturated monocarboxylic acid containing 1 to 6 C atoms and/or a methyl or ethyl ester of acrylic acid or methacrylic acid in the weight ratio (a) : (b) : (c) of 1:0.3:1 to 1:5:30, where the addition sequence of the monomers (b) and (c) in the graft copolymerisation is arbitrary and up to 15 mol % of the grafted monomers (c) can be hydrolysed.

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 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 US-PS 4,444,561 ist bekannt, Copolymerisate, die als charakteristische Monomere

  • 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 einpolymerisiert enthalten,
als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von synthetische Fasern enthaltendem Textilgut zu verwenden.From US Pat. No. 4,444,561 it is known to use copolymers as characteristic monomers
  • 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,
to be used as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.

Aus der nicht vorveröffentlichten DE-Patentanmeldung P 35 36 530.7 ist bekannt, Pfropfpolymerisate, die erhältlich sind durch Pfropfen von

  • a) Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 2.000 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 sein können,
als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von Synthese­fasern enthaltendem Textilgut zu verwenden.From the unpublished DE patent application P 35 36 530.7 it is known to graft polymers which are obtainable by grafting
  • a) polyalkylene oxides with a molecular weight (number average) of 2,000 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide,
  • b) vinyl acetate in the weight ratio a): b) from 1: 0.2 to 1:10 and their acetate groups can optionally be saponified up to 15%,
to be used as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.

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

Die Aufgabe wird erfindungsgemäß gelöst, wenn man als Vergrauungs­inhibitoren beim Waschen und Nachbehandeln von Synthesefasern enthaltendem Textilgut Pfropfpolymerisate einsetzt, die erhältlich sind durch Pfropfen von

  • (a) Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 300 bis 100.000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid
  • (b) N-Vinylpyrrolidon und
  • (c) einem Vinylester, der sich von einer gesättigten 1 bis 6 C-Atome enthaltenden Monocarbonsäure ableitet, und/oder einem Methyl- oder Ethylester der Acrylsäure oder Methacrylsäure
im Gewichtsverhältnis (a) : (b) : (c) von 1 : 0,3 : 1 bis 1 : 5 : 30, wobei die Reihenfolge der Zugabe der Monomeren (b) und (c) bei der Pfropfcopolymerisation beliebig ist und bis zu 15 Mol-% der aufgepfropften Monomeren (c) hydrolisiert sein können.The object is achieved according to the invention if, as graying inhibitors in the washing and aftertreatment of textile material containing synthetic fibers, graft polymers are used which can be obtained by grafting
  • (a) Polyalkylene oxides with a molecular weight (number average) of 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide
  • (b) N-vinyl pyrrolidone and
  • (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, and / or a methyl or ethyl ester of acrylic acid or methacrylic acid
in the weight ratio (a): (b): (c) from 1: 0.3: 1 to 1: 5: 30, the order of addition of the monomers (b) and (c) being arbitrary in the graft copolymerization and up to 15 mol% of the grafted monomers (c) can be hydrolyzed.

Als Pfropfgrundlage dienen die oben unter a) angegebenen Polyalkylenoxide eines Molekulargewichts (nach dem Zahlenmittel) von 300 bis 100.000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid. Vorzugsweise verwendet man Homopolymerisate des Ethylenoxids oder Copolymerisate, mit einen Ethylenoxidanteil von 40 bis 99 Mol.%. Für die bevorzugt einzusetzenden Ethylenoxidpolymerisate beträgt somit der Anteil an einpolymerisiertem Ethylenoxid 40 bis 100 Mol.%. Als Comonomer für diese Copolymerisate kommen Propylenoxid, Butylenoxid und/oder Isobutylenoxid in Betracht. Geeignet sind beispielsweise Copolymerisate aus Ethylenoxid und Propylenoxid, Copolymerisate aus Ethylenoxid und Butylenoxid sowie Copolymerisate aus Ethylenoxid, Propylenoxid und mindestens einem Butylenoxid. Der Ethylenoxidanteil der Copolymerisate beträgt vorzugsweise 40 bis 99 Mol.%, der Propylenoxidanteil 1 bis 60 Mol.% und der Anteil an Butylenoxid in den Copolymerisaten 1 bis 30 Mol.%. Neben geradkettigen können auch verzweigte Homo- oder Copolymerisate als Pfropfgrundlage verwendet werden.The polyalkylene oxides of molecular weight (number average) from 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide given under a) above serve as the graft base. Homopolymers of ethylene oxide or copolymers having an ethylene oxide content of 40 to 99 mol% are preferably used. The proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference. Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers. For example, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide are suitable. The ethylene oxide content of the copolymers is preferably 40 to 99 mol%, the propylene oxide content 1 to 60 mol% and the proportion Butylene oxide in the copolymers 1 to 30 mol%. In addition to straight-chain, branched homopolymers or copolymers can also be used as the graft base.

Verzweigte Copolymerisate werden hergestellt, indem man beispielsweise an mehrwertige niedrigmolekulare Alkohole, z.B. Trimethylolpropan, Pentosen oder Hexosen, Ethylenoxid und gegebenenfalls noch Propylenoxid und/oder Butylenoxide anlagert. Die Alkylenoxid-Einheiten können im Polymerisat statistisch verteilt sein oder in Form von Blöcken vorliegen. Vorzugsweise verwendet man als Komponente a) Polyethylenoxide eines Molekulargewichts (nach dem Zahlenmittel) von 1.000 bis 50.000.Branched copolymers are prepared, for example, by working on polyhydric low molecular weight alcohols, e.g. Trimethylolpropane, pentoses or hexoses, ethylene oxide and optionally also propylene oxide and / or butylene oxides. The alkylene oxide units can be randomly distributed in the polymer or in the form of blocks. Preferably used as component a) polyethylene oxides with a molecular weight (number average) of 1,000 to 50,000.

Auf die Polyalkylenoxide wird als Monomer der Komponente (b) N-Vinylpyrrolidon aufgepfropft. Als Komponente (c) werden Vinylester eingesetzt, die sich von einer gesättigten 1 bis 6 C-Atome enthaltenden Monocarbonsäure ableiten, sowie Acrylsäuremethylester, Acrylsäureethylester, Methacrylsäuremethylester, Methacrylsäureethylester und Mischungen der vorstehend genannten Monomeren. Geeignete Vinylester, sind beispielsweise Vinylformiat, Vinylacetat, Vinylpropionat, Vinylbutyrat, Valeriansäurevinylester, i-Valeriansäurevinylester und Capronsäurevinylester. Von den Monomeren der Gruppe (c) verwendet man vorzugsweise Vinylacetat, Vinylpropionat, Methylacrylat oder Mischungen aus Vinylacetat und Methylacrylat.N-vinylpyrrolidone is grafted onto the polyalkylene oxides as the monomer of component (b). As component (c), vinyl esters are used which are derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, as well as methyl acrylate, ethyl acrylate, methyl methacrylate, methyl methacrylate and mixtures of the aforementioned monomers. Suitable vinyl esters are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl i-valerate and vinyl caproate. Of the monomers of group (c), vinyl acetate, vinyl propionate, methyl acrylate or mixtures of vinyl acetate and methyl acrylate are preferably used.

Zur Herstellung der Pfropfpolymerisate werden die in Betracht kommenden Polyalkylenoxide der Komponente (a) mit den Monomeren der Komponente (b) in Gegenwart von Radikale bildenden Initiatoren oder durch Einwirkung energiereicher Strahlung, worunter auch die Einwirkung energiereicher Elektronen verstanden werden soll, gepfropft. Hierbei kann man so vorgehen, daß man das Polyalkylenoxid in mindestens einem Monomer der Gruppe (b) löst und nach Zugabe eines Polymerisationsinitiators die Mischung auspolymerisiert. Die Pfropfpolymerisation kann auch halb­kontinuierlich durchgeführt werden, indem man zunächst einen Teil, z.B. 10 % des zu polymerisierenden Gemisches aus Polyalkylenoxid, mindestens einem Monomeren der Gruppe (b) und/oder (c) und Initiator vorlegt, auf Polymerisationstemperatur erhitzt und nach dem Anspringen der Polymerisation den Rest der zu polymerisierenden Mischung nach Fortschritt der Polymerisation zugibt. Die Pfropfpolymerisate können auch dadurch erhalten werden, daß man die Polyalkylenoxide der Gruppe (a) in einem Reaktor vorlegt, auf die Polymerisationstemperatur erwärmt und mindestens ein Monomer der Gruppe (b) und/oder (c) und Polymerisationsinitiator entweder auf einmal, absatzweise oder vorzugsweise kontinuierlich zufügt und polymerisiert.To prepare the graft polymers, the polyalkylene oxides of component (a) which are considered are grafted with the monomers of component (b) in the presence of initiators which form free radicals or by the action of high-energy radiation, which should also be understood to mean the action of high-energy electrons. This can be done by dissolving the polyalkylene oxide in at least one monomer of group (b) and polymerizing the mixture after adding a polymerization initiator. The graft polymerization can also be carried out semi-continuously by initially introducing a portion, for example 10%, of the mixture of polyalkylene oxide to be polymerized, at least one monomer from group (b) and / or (c) and initiator, heating to the polymerization temperature and after the light-off Polymerization adds the rest of the mixture to be polymerized as the polymerization progresses. The graft polymers can also be obtained by placing the polyalkylene oxides of group (a) in a reactor, heating to the polymerization temperature and at least one monomer from group (b) and / or (c) and polymerization initiator either all at once, batchwise or preferably continuously adds and polymerizes.

Das Gewichtsverhältnis der Komponenten (a) : (b) : (c) beträgt von 1 : 0,3 : 1 bis 1 : 5 : 30 und liegt vorzugsweise in dem Bereich von 1 : 0,5 : 1,5 bis 1 : 4 : 25. Bei der Herstellung der Pfropfpolymerisate kann die Reihenfolge, in der die Monomeren (b) und (c) auf das Polymerisat (a) aufgepfropft werden, beliebig gewählt werden. Beispielsweise pfropft man zunächst N-Vinylpyrrolidon auf das Polymerisat (a) auf und danach ein Monomer (c) oder eine Mischung von Monomeren der Gruppe (c). Man kann jedoch auch zunächst die Monomeren der Gruppe (c) und danach N-Vinylpyrrolidon auf die Pfropfgrundlage polymerisieren oder eine Monomerenmischung aus (b) und (c) in einem Schritt auf (a) aufpfropfen. Vorzugsweise werden jedoch die Pfropfpolymerisate verwendet, bei deren Herstellung zunächst N-Vinylpyrrolidon und anschließend Vinylacetat auf die Pfropfgrundlage aufgepfropft wurden.The weight ratio of components (a): (b): (c) is from 1: 0.3: 1 to 1: 5: 30 and is preferably in the range from 1: 0.5: 1.5 to 1: 4 : 25. In the preparation of the graft polymers, the order in which the monomers (b) and (c) are grafted onto the polymer (a) can be chosen as desired. For example, N-vinylpyrrolidone is first grafted onto the polymer (a) and then a monomer (c) or a mixture of monomers from group (c). However, it is also possible first to polymerize the monomers of group (c) and then N-vinylpyrrolidone onto the graft base or to graft a monomer mixture of (b) and (c) onto (a) in one step. However, the graft polymers are preferably used, in the production of which first N-vinylpyrrolidone and then vinyl acetate were grafted onto the graft base.

Als Polymerisationsinitiatoren eignen sich vor allem organische Peroxide, wie Diacetylperoxid, Dibenzoylperoxid, Succinylperoxid, Di-tert.-butyl­peroxid, tert.-Butylperbenzoat, tert.-Butylperpivalat, tert.-Butylper­maleinat, Cumolhydroperoxid, Diisopropylperoxidicarbamat, Bis-(o-toluoyl)-­peroxid, Didecanoylperoxid, Dioctanoylperoxid, Dilauroylperoxid, tert.-­Butylperisobutyrat, tert.-Butylperacetat, Di-tert.-Amylperoxid, tert.-­Butylhydroperoxid sowie Mischungen der genannten Initiatoren, Redox­initiatoren und Azostarter.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 peroxidic o-tamoyl (bis) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide and mixtures of the initiators, redox initiators and azo starters mentioned.

Die Pfropfpolymerisation erfolgt im Temperaturbereich von 50 bis 200, vorzugsweise 70 bis 140°C. Sie wird üblicherweise unter atmosphärischem Druck durchgeführt, kann jedoch auch unter vermindertem oder erhöhtem Druck ablaufen. Falls gewünscht, kann die oben beschriebene Pfropf­polymerisation auch in einem Lösemittel durchgeführt werden. Geeignete Lösemittel sind beispielsweise Alkohole, wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, sek.-Butanol, tert.-Butanol, n-Hexanol und Cyclohexanol sowie Glykole, wie Ethylenglykol, Propylenglykol und Butylenglykol sowie die Methyl- oder Ethylether der zweiwertigen Alkohole, Diethylenglykol, Triethylenglykol, Glycerin und Dioxan. Die Pfropf­polymerisation kann auch in Wasser als Lösemittel durchgeführt werden. In diesem Fall liegt zunächst eine Lösung vor, die in Abhängigkeit von der Menge der zugegebenen Monomeren der Komponente b) in Wasser mehr oder weniger gut löslich ist. Um wasserunlösliche Produkte, die während der Polymerisation entstehen können in Lösung zu überführen, kann man beispielsweise organische Lösemittel zusetzen, wie einwertige Alkohole mit 1 bis 3 Kohlenstoffatomen, Aceton oder Dimethylformamid. Man kann jedoch auch bei der Pfropfpolymerisation in Wasser so verfahren, daß man die wasserunlöslichen Pfropfpolymerisate durch Zugabe üblicher Emulgatoren oder Schutzkolloide, z.B. Polyvinylalkohol, in eine feinteilige Dispersion überführt. Als Emulgatoren verwendet man beispielsweise ionische oder nichtionische Tenside, deren HLB-Wert im Bereich von 3 bis 13 liegt. Zur Definition des HLB-Werts wird auf die Veröffentlichung von W.C. Griffin, J. Soc. Cosmetic Chem., Band 5, 249 (1954) hingewiesen.The graft polymerization takes place in the temperature range from 50 to 200, preferably 70 to 140 ° C. It is usually carried out under atmospheric pressure, but can also take place under reduced or elevated pressure. If desired, the graft polymerization described above can also 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 ethylene glycol, propylene glycol and butylene glycol, and the methyl or Ethyl ether of dihydric alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane. The graft polymerization can also be carried out in water as a solvent. In this case, there is initially a solution which, depending on the amount of the monomers of component b) added, is more or less readily soluble in water. In order to convert water-insoluble products which may arise during the polymerization into solution, it is possible, for example, to add organic solvents, such as monohydric alcohols having 1 to 3 carbon atoms, acetone or dimethylformamide. However, graft polymerization in water can also be carried out in such a way that the water-insoluble graft polymers are added by adding customary emulsifiers or protective colloids, for example polyvinyl alcohol, are converted into a finely divided dispersion. The emulsifiers used are, for example, ionic or nonionic surfactants whose HLB value is in the range from 3 to 13. For the definition of the HLB value, reference is made to the publication by WC Griffin, J. Soc. Cosmetic Chem., Volume 5, 249 (1954).

Die Menge an Tensiden, bezogen auf das Pfropfcopolymerisat, beträgt 0,1 bis 5 Gew.%. Bei Verwendung von Wasser als Lösemittel erhält man Lösungen bzw. Dispersionen der Pfropfpolymerisate. Sofern man Lösungen des Pfropfpolymerisates in einem organischen Lösemittel herstellt bzw. in Mischungen aus einem organischen Lösemittel und Wasser, so verwendet man pro 100 Gew.-Teile des Pfropfpolymerisates 5 bis 200, vorzugsweise 10 bis 100 Gew.-Teile des organischen Lösemittels oder des Lösemittelgemisches.The amount of surfactants, based on the graft copolymer, is 0.1 to 5% by weight. When water is used as the solvent, solutions or dispersions of the graft polymers are obtained. If solutions of the graft polymer are prepared in an organic solvent or in mixtures of an organic solvent and water, 5 to 200, preferably 10 to 100 parts by weight of the organic solvent or solvent mixture are used per 100 parts by weight of the graft polymer .

Das Gewichtsverhältnis der Komponenten a) zu b) zu c) im Pfropfpolymerisat beträgt 1:0,3:1 bis 1:5:30, vorzugsweise 1:0,5:1,5 bis 1:4:25. Die Pfropf­polymerisate haben einen K-Wert von 5 bis 200, vorzugsweise 5 bis 50. (bestimmt nach H. Fikentscher in Dimethylformamid bei 25°C und einer Polymerkonzentration von 2 Gew.%). Nach der Pfropfpolymerisation kann das Pfropfpolymerisat gegebenenfalls einer partiellen Hydrolyse unterworfen werden, bei der bis zu 15 Mol.% der aufgepfropften Monomeren der Komponente (c) hydrolysiert werden. So führt beispielsweise die Hydrolyse von Pfropfpolymerisaten, zu deren Herstellung als Komponente (c) Vinylester verwendet werden, zu Vinylalkohol-Einheiten enthaltenden Pfropfpolymerisaten. Die Hydrolyse kann beispielsweise durch Zugabe einer Base, wie Natronlauge oder Kalilauge oder auch durch Zugabe von Säuren und gegebenenfalls Erwärmen der Mischung vorgenommen werden.The weight ratio of components a) to b) to c) in the graft polymer is 1: 0.3: 1 to 1: 5: 30, preferably 1: 0.5: 1.5 to 1: 4:25. The graft polymers have a K value of 5 to 200, preferably 5 to 50 (determined according to H. Fikentscher in dimethylformamide at 25 ° C. and a polymer concentration of 2% by weight). After the graft polymerization, the graft polymer can optionally be subjected to a partial hydrolysis, in which up to 15 mol% of the grafted monomers of component (c) are hydrolyzed. For example, the hydrolysis of graft polymers, for the preparation of which as component (c) vinyl esters are used, leads to graft polymers containing vinyl alcohol units. The hydrolysis can be carried out, for example, by adding a base, such as sodium hydroxide solution or potassium hydroxide solution, or else by adding acids and, if appropriate, heating the mixture.

Die oben beschriebenen Pfropfpolymerisate werden erfindungsgemäß in Waschmitteln mit reduziertem Phosphatgehalt (darunter soll ein Phosphat­gehalt von weniger als 25 Gew.% Natriumtriphosphat verstanden werden) oder in phosphatfreien Waschmitteln verwendet. Zur Vergrauungsinhibierung beim Waschen werden die oben beschriebenen Pfropfpolymerisate handelsüblichen Waschmittelformulierungen in einer Menge von 0,1 bis 5, vorzugsweise 0,3 bis 3 Gew.%, bezogen auf die Waschmittelmischung, zugesetzt. Die Pfropf­polymerisate können dabei in Form eines Granulats, einer Paste, einer hochviskosen Masse, als Dispersion oder als Lösung in einem Lösemittel der Waschmittelformulierung zugegeben werden. Die Pfropfpolymerisate können auch an der Oberfläche von Stellmitteln, z.B. Natriumsulfat oder Gerüst­stoffen (Zeolithen) sowie anderen festen Hilfsstoffen der Waschmittel­formulierung adsorbiert werden.According to the invention, the graft polymers described above are used in detergents with a reduced phosphate content (this is to be understood as meaning a phosphate content of less than 25% by weight sodium triphosphate) or in phosphate-free detergents. To inhibit graying during washing, the graft polymers described above are added to commercial detergent formulations in an amount of 0.1 to 5, preferably 0.3 to 3,% by weight, based on the detergent mixture. The graft polymers can be added to the detergent formulation in the form of granules, a paste, a highly viscous mass, as a dispersion or as a solution in a solvent. The graft polymers can also be adsorbed on the surface of fillers, for example sodium sulfate or builders (zeolites) and other solid auxiliaries in the detergent formulation.

Handelsübliche, pulverförmige Waschmittel, deren Phosphatgehalt unter 25 Gew.% liegt bzw. Waschmittel, die überhaupt phosphatfrei sind, enthalten als einen wesentlichen Bestandteil Tenside, z.B. C₈- bis C₁₂-Alkylphenolethoxylate, C₁₂- bis C₂₀-Alkanolethoxylate, sowie Blockcopolymerisate des Ethylenoxids und Propylenoxids. Die Polyalkylenoxide sind bei Raumtemperatur bis zu Temperaturen von 50°C bis 60°C feste Stoffe und gut in Wasser löslich bzw. dispergierbar. Es handelt sich hierbei um lineare oder verzweigte Umsetzungsprodukte von Ethylenoxid mit Propylenoxid und/oder Isobutylenoxid, die eine Blockstruktur besitzen oder die auch statistisch aufgebaut sein können. Die Endgruppen der Polyalkylenoxide können gegebenenfalls verschlossen sein. Hierunter soll verstanden werden, daß die freien OH-Gruppen der Polyalkylenoxide verethert und/oder verestert und/oder aminiert und/oder mit Isocyanaten umgesetzt sein können.Commercial powder detergents whose phosphate content is below 25% by weight or detergents which are free of phosphate at all contain surfactants as an essential component, e.g. C₈ to C₁₂ alkylphenol ethoxylates, C₁₂ to C₂₀ alkanol ethoxylates, and block copolymers of ethylene oxide and propylene oxide. The polyalkylene oxides are solid substances at room temperature up to temperatures of 50 ° C. to 60 ° C. and are readily soluble or dispersible in water. These are linear or branched reaction products of ethylene oxide with propylene oxide and / or isobutylene oxide, which have a block structure or which can also have a statistical structure. The end groups of the polyalkylene oxides can optionally be closed. This should be understood to mean that the free OH groups of the polyalkylene oxides can be etherified and / or esterified and / or aminated and / or reacted with isocyanates.

Als Bestandteil pulverförmiger Waschmittel eignen sich auch anionische Tenside, wie C₈- bis C₁₂-Alkylbenzolsulfonate, C₁₂- bis C₁₆-Alkansulfonate, C₁₂- bis C₁₆-Alkylsulfate, C₁₂- bis C₁₆-Alkyl­sulfosuccinate und sulfatierte ethoxylierte C₁₂- bis C₁₆-Alkanole. Pulverförmige Waschmittel enthalten üblicherweise 5 bis 20 Gew.-% eines Tensids oder einer Mischung von Tensiden.Anionic surfactants such as C₈ to C₁₂ alkyl benzene sulfonates, C₁₂ to C₁₆ alkane sulfonates, C₁₂ to C₁₆ alkyl sulfates, C₁₂ to C₁₆ alkyl sulfosuccinates and sulfated ethoxylated C₁₂ to C₁₆ alkanols are also suitable as constituents of powder detergents. Powdered detergents usually contain 5 to 20% by weight of a surfactant or a mixture of surfactants.

Die pulverförmigen Waschmittel können außerdem gegebenenfalls Polycarbonsäuren bzw. deren Salze enthalten, beispielsweise Weinsäure oder Zitronensäure.The powder detergents may also optionally contain polycarboxylic acids or their salts, for example tartaric acid or citric acid.

Ein weiterer wichtiger Bestandteil in Waschmittelformulierungen sind Inkrustierungsinhibitoren. Bei diesen Stoffen handelt es sich beispiels­weise um Homopolymerisate der Acrylsäure, Methacrylsäure und Maleinsäure bzw. um Copolymerisate, z.B. Copolymerisate aus Maleinsäure und Acryl­säure, Copolymerisate aus Maleinsäure und Methacrylsäure bzw. um Copolymerisate von a) Acrylsäure und/oder Methacrylsäure mit b) Acryl­säureestern, Methacrylsäureestern, Vinylestern, Allylestern, Itaconsäure­estern, Itaconsäure, Methylenmalonsäure, Methylenmalonsäureester, Croton­säure und Crotonsäureester. Außerdem kommen Copolymere aus Olefinen und C₁- bis C₄-Alkylvinylethern in Betracht. Das Molekulargewicht der Homo- und Copolymerisate beträgt 1.000 bis 100.000. Die Inkrustationsinhibitoren werden in einer Menge von 0,5 bis 10 Gew.% in Waschmitteln verwendet.Another important ingredient in detergent formulations are incrustation inhibitors. These substances are, for example, homopolymers of acrylic acid, methacrylic acid and maleic acid or copolymers, e.g. Copolymers of maleic acid and acrylic acid, copolymers of maleic acid and methacrylic acid or copolymers of a) acrylic acid and / or methacrylic acid with b) acrylic acid esters, methacrylic acid esters, vinyl esters, allyl esters, itaconic acid esters, itaconic acid, methylene malonic acid, methylene malonic acid esters, crotonic acid and crotonic acid esters. In addition, copolymers of olefins and C₁ to C₄ alkyl vinyl ethers come into consideration. The molecular weight of the homo- and copolymers is 1,000 to 100,000. The incrustation inhibitors are used in an amount of 0.5 to 10% by weight in detergents.

Weitere Mischungsbestandteile von Waschmitteln können auch Korrosionsinhibitoren, monomere, oligomere und polymere Phosphonate, Ethersulfonate auf der Basis von ungesättigten Fettalkoholen, z.B. Oleylalkoholethoxylatbutylether und deren Alkalisalze sein. Pulverförmige Waschmittel können gegebenenfalls auch Zeolithe enthalten, z.B. in einer Menge von 5 bis 30 Gew.% enthalten. Die Waschmittelformulierungen können gegebenenfalls auch Bleichmittel enthalten. Sofern Bleichmittel eingesetzt werden, betragen die üblicherweise angewendeten Mengen 3 bis 25 Gew.%. Das bekannteste Bleichmittel ist beispielsweise Natriumperborat. Außerdem können die Waschmittelformulierungen ggf. noch Bleichaktivatoren, Weichmacher, Entschäumer, Parfum, optische Aufheller und Enzyme enthalten. Stellmittel, wie Natriumsulfat, können gegebenenfalls in einer Menge von 10 bis 30 Gew.% in Waschmitteln enthalten sein.Other constituents of the detergent mixture can also be corrosion inhibitors, monomeric, oligomeric and polymeric phosphonates, ether sulfonates based on unsaturated fatty alcohols, for example oleyl alcohol ethoxylate butyl ether and their alkali metal salts. Powdery Detergents can optionally also contain zeolites, for example in an amount of 5 to 30% by weight. The detergent formulations can optionally also contain bleaches. If bleaching agents are used, the amounts usually used are 3 to 25% by weight. The best known bleach is, for example, sodium perborate. The detergent formulations may also contain bleach activators, plasticizers, defoamers, perfumes, optical brighteners and enzymes. Detergents, such as sodium sulfate, can optionally be present in an amount of 10 to 30% by weight.

Die oben beschriebenen Pfropfpolymerisate können auch als Zusatz zu Flüssigwaschmitteln verwendet werden. Die Flüssigwaschmittel enthalten als Abmischkomponente flüssige oder auch feste Tenside, die in der Wasch­mittelformulierung löslich oder zumindest dispergierbar sind. Der Tensid­gehalt von Flüssigwaschmitteln liegt üblicherweise in dem Bereich von 15 bis 50 Gew.%. Als Tenside kommen hierfür die Produkte in Betracht, die auch in pulverförmigen Waschmitteln eingesetzt werden sowie flüssige Polyalkylenoxide bzw. polyalkoxylierte Verbindungen. Falls die Pfropfpoly­merisate mit den übrigen Bestandteilen des Flüssigwaschmittels nicht direkt mischbar sind, kann man mit Hilfe geringer Menge an Lösungs­vermittlern, z.B. Wasser oder eines mit Wasser mischbaren organischen Lösemittels, z.B. Isopropanol, Methanol, Ethanol, Glykol, Diethylenglykol oder Triethylenglykol, eine homogene Mischung herstellen.The graft polymers described above can also be used as an additive to liquid detergents. The liquid detergents contain, as a mixing component, liquid or solid surfactants which are soluble or at least dispersible in the detergent formulation. The surfactant content of liquid detergents is usually in the range from 15 to 50% by weight. Suitable surfactants for this are the products which are also used in powder detergents, and liquid polyalkylene oxides or polyalkoxylated compounds. If the graft polymers are not directly miscible with the other constituents of the liquid detergent, a small amount of solubilizers, e.g. Water or a water-miscible organic solvent, e.g. Prepare a homogeneous mixture of isopropanol, methanol, ethanol, glycol, diethylene glycol or triethylene glycol.

Die Pfropfpolymerisate 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 angewendeten Wäscheweichspüler erfolgen kann oder - falls ein Weichspüler nicht er­wünscht ist - allein anstelle des Weichspülers. Die Einsatzmengen betragen 0,01 bis 0,3 g/l Waschflotte. Die Verwendung der Pfropfpolymerisate im letzten Spülbad eines Waschmaschinenzyklus hat den Vorteil, daß die Wäsche beim nächsten Waschzyklus weit weniger von abgelösten Schmutzteilchen, die in der Waschflotte vorhanden sind, angeschmutzt wird als ohne den Zusatz des Vergrauungsinhibitors bei der vorausgegangenen Wäsche.The graft polymers 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 normally used at this point or — if a fabric softener is not desired — alone instead of the fabric softener. The amounts used are 0.01 to 0.3 g / l wash liquor. The use of the graft polymers in the last rinsing bath of a washing machine cycle has the advantage that the laundry is soiled less by detached dirt particles that are present in the washing liquor during the next washing cycle than without the addition of the graying inhibitor in the previous washing.

Die in den Beispielen angegebenen Teile sind Gew.-Teile, die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe. Die K-Werte der Pfropf­polymerisate wurden nach H. Fikentscher, Cellulosechemie, Band 13, 58-64 und 71-74 (1932) in Dimethylformamid bei einer Temperatur von 25°C und einer Polymerkonzentration von 2 Gew.% gemessen; dabei bedeutet K = k·10³. Die Molekulargewichte (Zahlenmittel) der eingesetzten Polyalkylenoxide a) wurden aus der OH-Zahl errechnet.The parts given in the examples are parts by weight, the figures in percent relate to the weight of the substances. The K values of the graft polymers were measured according to H. Fikentscher, Cellulosechemie, Vol. 13, 58-64 and 71-74 (1932) in dimethylformamide at a temperature of 25 ° C. and a polymer concentration of 2% by weight; where K = k · 10³. The molecular weights (number average) of the polyalkylene oxides a) used were calculated from the OH number.

Folgende Produkte wurden verwendet:The following products were used:

Pfropfcopolymerisate 1 bis 13Graft copolymers 1 to 13

Diese Pfropfpolymerisate wurden in der Weise hergestellt, daß man auf das jeweils in Tabelle 1 angegebene Polyethylenoxid zunächst N-Vinylpyrrolidon und danach Vinylacetat bzw. eine Mischung aus Vinylacetat und Methylacrylat bei 105°C unter Verwendung von 2,25 Gew.-%, bezogen auf die bei der Pfropfcopolymerisation eingesetzten Monomeren, an Dibenzoylperoxid aufpolymerisierte. Die K-Werte der erhalten Pfropfpolymerisate sind ebenfalls in Tabelle 1 angegeben.

Figure imgb0001
These graft polymers were prepared in such a way that first N-vinylpyrrolidone and then vinyl acetate or a mixture of vinyl acetate and methyl acrylate at 105 ° C. using 2.25% by weight, based on the polyethylene oxide given in Table 1 the monomers used in the graft copolymerization polymerized onto dibenzoyl peroxide. The K values of the graft polymers obtained are also given in Table 1.
Figure imgb0001

Die Abkürzungen in Tabelle 1 haben folgende Bedeutung:

Mn = Zahlenmittel des Molekulargewichts
PEO = Polyethylenoxid
VP = N-Vinylpyrrolidon
VAc = Vinylacetat
MA = MethylacrylatThe abbreviations in table 1 have the following meaning:

M n = number average molecular weight
PEO = polyethylene oxide
VP = N-vinyl pyrrolidone
VAc = vinyl acetate
MA = methyl acrylate

Die Pfropfcopolymerisate 6 und 7 waren zu 15 Mol-% hydrolisiert.The graft copolymers 6 and 7 were hydrolyzed to 15 mol%.

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 3. Wäsche dient zur Beurteilung des Anschmutzungsgrades. Die Werte werden durch mehrfache Wiederholung und Mittelwertbildung gesichert. Die photometrische Messung der Remission in % wurde im vorliegenden Falle am Elrepho 2000 (Datacolor) bei der Wellenlänge 460 nm gemessen (Barium-Primärweißstandard nach DIN 5033).The graying-inhibiting effect of the above-mentioned graft copolymers was tested as follows: polyester test fabric and polyester / cotton blend fabric were used together with a standard dirt fabric subjected to a series of 3 washes. 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 3rd wash is used to assess the degree of soiling. The values are secured by repeated repetition and averaging. The photometric measurement of the reflectance in% was measured in the present case on the Elrepho 2000 (Datacolor) at the wavelength of 460 nm (barium primary white standard according to DIN 5033).

Prüfbedingungen:

Prüfgerät:      Launder-O-meter
Wasserhärte:      3,5 mmol 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/lTest conditions:

Tester: Launder-O-meter
Water hardness: 3.5 mmol 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 jeweils 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 each case in an amount of 0.5%, based on the test detergent. The test vessels each contained 15 g of 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 Testwaschmittel hatte folgende Zusammensetzung:

C₁₂-Alkylbenzolsulfonat      6,25 %
Talgfettalkohol umgesetzt mit 11 Ethylenoxid      4,7 %
Seife      2,8 %
Na-triphosphat (90 % Erhaltungsgrad)      20 %
Na-perborat (Tetrahydrat)      20 %
Na₂SO₄      24 %
Natriumdisilikat      6 %
Mg Silikat      1,25 %
Carboxymethylcellulose (CMC), Na-Salz      0,6 %
Tetranatriumsalz Salz der Ethylendiamintetra­essigsäure      0,2 %
Rest      Wasser auf 100 %.The test detergent used had the following composition:

C₁₂ alkyl benzene sulfonate 6.25%
Tallow fatty alcohol reacted with 11% 4.7% ethylene oxide
Soap 2.8%
Na triphosphate (90% degree of conservation) 20%
Na perborate (tetrahydrate) 20%
Na₂SO₄ 24%
Sodium disilicate 6%
Mg silicate 1.25%
Carboxymethyl cellulose (CMC), Na salt 0.6%
Tetrasodium salt of ethylenediaminetetraacetic acid 0.2%
Rest of water to 100%.

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 erfindungsgemäß zu verwendenden Produkte, bezogen auf das Gewicht des eingesetzten Test­waschmittels. In Tabelle 2 sind außerdem die Ergebnisse von Vergleichs­beispielen angegeben.

Figure imgb0002
Table 2 shows the increase in reflectance of polyester and polyester / cotton blended fabrics after addition of 0.5% of the products to be used according to the invention, based on the weight of the test detergent used. Table 2 also shows the results of comparative examples.
Figure imgb0002

Die Tabelle 2 zeigt, daß die Homopolymeren PEO, PVP und PVac und die vollständig verseiften Pfropfpolymeren 9 und 10 praktisch keine Wirksamkeit als Vergrauungsinhibitor besitzen.Table 2 shows that the homopolymers PEO, PVP and PVac and the fully saponified graft polymers 9 and 10 have practically no activity as a graying inhibitor.

Claims (6)

1. Verwendung von Polymerisaten in Waschmitteln, dadurch gekennzeichnet, daß man als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von Synthesefasern enthaltendem Textilgut Pfropfpolymerisate einsetzt, die erhältlich sind durch Pfropfen von (a) Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) (a) von 300 bis 100.000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid mit (b) N-Vinylpyrrolidon und (c) einem Vinylester, der sich von einer gesättigten 1 bis 6 C-Atome enthaltenden Monocarbonsäure ableitet und/oder einem Methyl- oder Ethylester der Acrylsäure oder Methacrylsäure 1. Use of polymers in detergents, characterized in that graft polymers are used as graying inhibitors in the washing and aftertreatment of textile material containing synthetic fibers, which are obtainable by grafting (a) Polyalkylene oxides with a molecular weight (number average) (a) from 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide (b) N-vinyl pyrrolidone and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid im Gewichtsverhältnis (a) : (b) : (c) von 1:0,3:1 bis 1:5:30, wobei die Reihenfolge der Zugabe der Monomeren (b) und (c) bei Pfropfpolymerisation beliebig ist und bis zu 15 Mol-% der aufgepfropften Monomeren (c) hydrolysiert sein können.in the weight ratio (a): (b): (c) from 1: 0.3: 1 to 1: 5: 30, the order of addition of the monomers (b) and (c) in graft polymerization being arbitrary and up to 15 Mol% of the grafted monomers (c) can be hydrolyzed. 2. Verwendung von Pfropfpolymerisaten nach Anspruch 1, dadurch gekennzeichnet, daß sie erhältlich sind durch Pfropfen von (a) Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 1.000 bis 50.000 und einem Ethylenoxidanteil von 40 bis 100 Mol.% mit (b) N-Vinylpyrrolidon und (c) Vinylacetat. 2. Use of graft polymers according to claim 1, characterized in that they are obtainable by grafting (a) Polyalkylene oxides with a molecular weight (number average) of 1,000 to 50,000 and an ethylene oxide content of 40 to 100 mol% (b) N-vinyl pyrrolidone and (c) vinyl acetate. 3. Verwendung von Pfropfpolymerisaten nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie einen K-Wert von 5 bis 200 (bestimmt nach H. Fikentscher in Dimethylformamid bei 25°C und einer Polymer­konzentration von 2 Gew.%) haben.3. Use of graft polymers according to claims 1 and 2, characterized in that they have a K value of 5 to 200 (determined according to H. Fikentscher in dimethylformamide at 25 ° C and a polymer concentration of 2% by weight). 4. Waschmittel auf der Basis von Tensiden, Gerüststoffen und gegebenenfalls anderen üblichen Zusätzen, dadurch gekennzeichnet, daß sie als vergrauungsinhibierenden Zusatz 0,1 bis 5 Gew.% an Pfropfpoly­merisaten enthalten, die erhältlich sind durch Pfropfen von (a) Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 300 bis 100.000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid mit (b) N-Vinylpyrrolidon und (c) einem Vinylester, der sich von einer gesättigten 1 bis 6 C-Atome enthaltenden Monocarbonsäure ableitet und/oder einem Methyl- oder Ethylester der Acrylsäure oder Methacrylsäure 4. Detergents based on surfactants, builders and, if appropriate, other customary additives, characterized in that they contain 0.1 to 5% by weight of graft polymers as graying-inhibiting additives, which can be obtained by grafting (a) Polyalkylene oxides with a molecular weight (number average) of 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide (b) N-vinyl pyrrolidone and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid im Gewichtsverhältnis (a) : (b) : (c) von 1:0,3:1 bis 1:5:30, wobei die Reihenfolge der Zugabe der Monomeren (b) und (c) bei der Pfropfpolymerisation beliebig ist und bis zu 15 Mol-% der aufgepfropften Monomeren (c) hydrolysiert sein können.in the weight ratio (a): (b): (c) from 1: 0.3: 1 to 1: 5: 30, the order of addition of the monomers (b) and (c) being arbitrary in the graft polymerization and up to 15 mol% of the grafted monomers (c) can be hydrolyzed.
EP88104889A 1987-04-03 1988-03-26 Use of graft polymers of polyalkylene oxides as anti-redeposition agents in the washing and after-treatment of textiles containing synthetic fibres Expired - Lifetime EP0285038B1 (en)

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US4904408A (en) 1990-02-27
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