EP0285037B1 - 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
EP0285037B1
EP0285037B1 EP88104888A EP88104888A EP0285037B1 EP 0285037 B1 EP0285037 B1 EP 0285037B1 EP 88104888 A EP88104888 A EP 88104888A EP 88104888 A EP88104888 A EP 88104888A EP 0285037 B1 EP0285037 B1 EP 0285037B1
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oxide
weight
graft polymers
number average
molecular weight
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German (de)
French (fr)
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EP0285037A2 (en
EP0285037A3 (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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers

Definitions

  • EP-A-0 098 803 discloses water-soluble or water-dispersible graft polymers which can be prepared by grafting polyalkylene oxide adducts which contain a hydrophobic substituent with ethylenically unsaturated polymerizable sulfonic acids, carboxylic acids or their anhydrides. These graft polymers are also used, inter alia, as graying inhibitors.
  • 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 products to be used according to the invention are known for example from GB-PS 922 457.
  • the at least one end-capped polyalkylene oxides with a number average molecular weight of 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide are used as the graft base.
  • Homopolymers of ethylene oxide or ethylene oxide copolymers with an ethylene oxide content of 40 to 99 mol%, which are end group-capped at least on one side, 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.
  • Suitable comonomers for these copolymers are propylene oxide, n-butylene oxide and / or isobutylene oxide.
  • 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 up to 60 mol% and the proportion of butylene oxide in the copolymers 1 to 30 mol%.
  • branched homopolymers or copolymers which are end group-capped at least on one side can also be used as the graft base.
  • Branched copolymers are prepared, for example, by adding to polyhydric low molecular weight alcohols, for example trimethylolpropane, glycerol, pentoses or hexoses, ethylene oxide and, if appropriate, also propylene oxide and / or butylene oxides.
  • the alkylene oxide units can be randomly distributed in the polymer or in the form of blocks.
  • At least one terminal OH group of the polyalkylene oxides is end group-capped. This should be understood to mean that it is etherified, esterified, aminated or modified by reaction with an isocyanate, for example.
  • the substituents of the terminal H atoms of the hydroxyl groups of the polyalkylene oxides are alkyl groups with 1 to 18 carbon atoms, substituted alkyl groups such as the benzyl group, or also phenyl groups.
  • Polyalkylene oxides whose end groups are esterified are obtained, for example, by esterification of the polyalkylene oxides described above with carboxylic acids having 1 to 18 carbon atoms, e.g. by reaction with formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid, stearic acid, maleic acid, terephthalic acid and phthalic acid.
  • the end group capping of the polyalkylene oxides can also be carried out by reaction with the corresponding anhydrides, e.g. by reaction with maleic anhydride.
  • the polyalkylene oxides can also be reacted at least on one side by reaction with isocyanants, e.g. Phenyl isocyanate, naphthyl isocyanate, methyl, ethyl and stearyl isocyanate can be modified.
  • Aminated products are obtained by autoclaving the corresponding alkylene oxide with amines, e.g. C1 to C18 alkylamines obtained.
  • 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 above-mentioned monomers.
  • Suitable vinyl esters are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl i-valerate and vinyl caproate.
  • the graft copolymers are prepared by known processes, for example by the polyalkylene oxides of component (a) at least one end group capped with the monomers of component (b) in the presence of free radical initiators or by action grafting high-energy radiation, which should also be understood to mean the action of high-energy electrons.
  • the procedure here can be such that component (a) is dissolved in at least one monomer from group (b) and the mixture is polymerized out after addition of a polymerization initiator.
  • the graft copolymerization can also be carried out semi-continuously by first introducing a portion, for example 10%, of the mixture of end-capped polyalkylene oxide to be polymerized, at least one monomer from group (b) and initiator, heating to the polymerization temperature and, after the polymerization has started, the rest of the polymerizing mixture is added according to the progress of the polymerization.
  • the graft copolymers can also be obtained by placing the end-capped polyalkylene oxides of group (a) in a reactor, heating to the polymerization temperature and adding and polymerizing at least one monomer from group (b) and polymerization initiator either all at once, batchwise or, preferably, continuously.
  • the weight ratio of components (a) :( b) is 1: 0.2 to 1:10, preferably 1: 0.5 to 1: 6.
  • Suitable polymerization initiators are, in particular, organic peroxides, such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tertiary butyl peroxide, tertiary butyl perbenzoate, tertiary butyl perpivalate, tertiary butyl permaleinate, cumene hydroperoxide, diamopropyl peroxide, diarbamate toloyl peroxide, Dioctanoyl peroxide, dilauroyl peroxide, tertiary butyl perisobutyrate, tertiary butyl peracetate, di-tertiary amyl peroxide, tertiary butyl hydroperoxide and mixtures of the initiators, redox initiators and azo starters mentioned.
  • organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxid
  • 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 copolymerization described above can also be carried out in a solvent.
  • Suitable solvents are, for example, alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, n-hexanol and cyclohexanol, and glycols, such as ethylene glycol, propylene glycol and butylene glycol, and the methyl or ethyl ether dihydric alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane.
  • the graft polymerization can also be carried out in water as a solvent.
  • a solution which, depending on the amount of the monomers of component (b) added, is more or less readily soluble in water and can assume a disperse character.
  • organic solvents can be added, for example monohydric alcohols with 1 to 3 carbon atoms, acetone or dimethylformamide.
  • graft polymerization in water can also be carried out by converting the water-insoluble graft polymers into a finely divided dispersion by adding customary emulsifiers or protective colloids, for example polyvinyl alcohol.
  • 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. Suc. Cosmetic Chem., Vol. 5, 249 (1954).
  • the amount of surfactants, based on the graft polymer is 0.1 to 5% by weight.
  • water 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.
  • 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 (b) are hydrolyzed.
  • a partial hydrolysis in which up to 15 mol% of the grafted monomers of component (b) are hydrolyzed.
  • the hydrolysis of graft polymers the production of which was used as the preferred monomer of group (b), vinyl acetate, to graft polymers containing vinyl alcohol units.
  • the hydrolysis can be carried out, for example, by adding a base, such as sodium hydroxide solution, potassium hydroxide solution, ammonia or amines, such as triethanolamine, morpholine or triethylamine, or by adding acids, e.g. HCl, and optionally heating the mixture.
  • a base such as sodium hydroxide solution, potassium hydroxide solution, ammonia or amines, such as triethanolamine, morpholine or triethylamine
  • acids e.g. HCl
  • 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 solids at room temperature up to temperatures of 70 ° 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.
  • Powdery detergents usually contain 5 to 20% by weight of a surfactant or a mixture of surfactants.
  • the surfactant content of liquid detergents is in the range from 15 to 50% by weight.
  • the powder detergents can optionally also contain polycarboxylic acids or their salts, for example tartaric acid and 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 homopolymers 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, they being in non-neutralized form, as alkali or ammonium salt and in partially neutralized form, e.g. Neutralization of 40 to 60% of the carboxyl groups can be used.
  • Powdered detergents may 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.
  • Sodium perborate for example, is suitable as a bleaching agent.
  • 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. 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 usually 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.
  • the graft polymers were prepared by the process known from GB-PS 922 457 by grafting on the monomers (b) given in Table 1 (to 100 parts in each case of a polyalkylene oxide with the molecular weight (number average) also given in Table 1).
  • the polymers 1, 3 to 10 and 18 to 20 were etherified, in the case of the polymers 2, 11 and 12 a terminal OH group of the polyalkylene oxide was esterified, in the case of polymer 15 a terminal OH group was aminated with a C10-amine in which Polymers 16 and 17 were both both terminal OH groups of the polyalkylene oxide esterified with maleic acid and in polymer 19 one end group of the polyalkylene oxide was etherified with a C10-alkyl group while the other was esterified with maleic acid.
  • the graying-inhibiting effect of the above-mentioned graft polymers was tested as follows: polyester test fabric and polyester / cotton blend fabric were subjected to a series of 3 washes together with a standard dirt fabric. The dirty fabric is renewed after each wash, the test fabric becoming more soiled after each wash. The 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 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 ethylene oxide 4.7% Soap 2.8% Na triphosphate (90% 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 on 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

A detergent containing as grayness inhibitor in the wash and aftertreatment of textile material containing synthetic fibers graft polymers obtainable by grafting (a) a polyalkylene oxide which has a number average molecular weight of from 300 to 100,000, is based on ethylene oxide, propylene oxide and/or butylene oxide, and is end group capped at at least one end, with (b) at least on vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and/or a methyl or ethyl ester of acrylic or methacrylic acid in a weight ratio (a):(b) of from 1:0.2 to 1:10.

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 Erdalkali-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 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 charakterische 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 EP-A-0 098 803 sind wasserlösliche oder in Wasser dispergierbare Pfropfpolymerisate bekannt, die durch Pfropfen von Polyalkylenoxidaddukten, die einen hydrophoben Substituenten enthalten, mit ethylenisch ungesättigten polymerisierbaren Sulfonsäuren, Carbonsäuren oder deren Anhydriden herstellbar sind. Diese Pfropfpolymerisate werden u.a. auch als Vergrauungsinhibitoren eingesetzt.EP-A-0 098 803 discloses water-soluble or water-dispersible graft polymers which can be prepared by grafting polyalkylene oxide adducts which contain a hydrophobic substituent with ethylenically unsaturated polymerizable sulfonic acids, carboxylic acids or their anhydrides. These graft polymers are also used, inter alia, as graying inhibitors.

Aus der nicht vorveröffentlichten EP-A-0 219 048 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.EP-A-0 219 048, which has not been published beforehand, discloses graft polymers which can be obtained by grafting
  • a) polyalkylene oxides with a molecular weight (according to the 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 durch Verwendung von Pfropfpolymerisaten, die erhältlich sind durch Pfropfen von

  • a) mindestens einseitig endgruppenverschlossenen Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 300 bis 100 000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid mit
  • b) mindestens 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) von 1:0,2 bis 1:10 und deren aufgepropfte Monomere b) gegebenenfalls bis zu 15 Mol% hydrolysiert sein können, als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von Synthesefasern enthaltendem Textilgut.
The object is achieved according to the invention by using graft polymers which are obtainable by grafting
  • a) polyalkylene oxides with a molecular weight (number average) of at least one end group capped from 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide
  • b) at least one vinyl ester which is 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) from 1: 0.2 to 1:10 and whose grafted-on monomers b) can optionally be hydrolyzed up to 15 mol%, as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.

Die Aufgabe wird erfindungsgemäß außerdem mit Waschmitteln auf der Basis von Tensiden, Gerüststoffen, wasserlöslichen oder in Wasser dispergierbaren Pfropfpolymerisaten als Vergrauungsinhibitoren und gegebenenfalls anderen üblichen Zusätzen gelöst, wenn sie 0,1 bis 5 Gew.-% an Pfropfpolymerisaten aufweisen, die erhältlich sind durch Pfropfen von

  • (a) mindestens einseitig endgruppenverschlossenen Polyalkylenoxiden eines Molekulargewichts (nach dem Zahlenmittel) von 300 bis 100 000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid mit
  • (b) mindestens 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) von 1:0,2 bis 1:10 und deren aufgepfropfte Monomere (b) gegebenenfalls bis zu 15 Mol% hydrolysiert sind.The object is also achieved according to the invention with detergents based on surfactants, builders, water-soluble or water-dispersible graft polymers as graying inhibitors and, if appropriate, other conventional additives if they have 0.1 to 5% by weight of graft polymers which can be obtained by grafting from
  • (a) polyalkylene oxides of molecular weight (number average) from 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide which are end group capped at least on one side
  • (b) at least one 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 a weight ratio (a) :( b) of 1: 0.2 to 1:10 and their grafted monomers (b) are optionally hydrolyzed up to 15 mol%.

Die gemäß Erfindung zu verwendenden Produkte sind beispielsweise aus der GB-PS 922 457 bekannt. Als Pfropfgrundlage dienen die oben unter a) angegebenen mindestens einseitig endgruppenverschlossenen Polyalkylenoxide eines Molekulargewichts (Zahlenmittel) von 300 bis 100 000 auf Basis von Ethylenoxid, Propylenoxid und/oder Butylenoxid. Vorzugsweise verwendet man mindestens einseitig endgruppenverschlossene Homopolymerisate des Ethylenoxids oder Ethylenoxidcopolymerisate mit einem 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, n-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, die mindestens einseitig endgruppenverschlossen sind, als Propfgrundlage verwendet werden. Verzweigte Copolymerisate werden hergestellt, indem man beispielsweise an mehrwertige niedrigmolekulare Alkohole, z.B. Trimethylolpropan, Glycerin, 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. Mindestens eine endständige OH-Gruppe der Polyalkylenoxide ist endgruppenverschlossen. Darunter soll verstanden werden, daß sie z.B. verethert, verestert, aminiert oder durch Umsetzung mit einem Isocyanat modifiziert ist.The products to be used according to the invention are known for example from GB-PS 922 457. The at least one end-capped polyalkylene oxides with a number average molecular weight of 300 to 100,000 based on ethylene oxide, propylene oxide and / or butylene oxide are used as the graft base. Homopolymers of ethylene oxide or ethylene oxide copolymers with an ethylene oxide content of 40 to 99 mol%, which are end group-capped at least on one side, 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. Suitable comonomers for these copolymers are propylene oxide, n-butylene oxide and / or isobutylene 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 up to 60 mol% and the proportion of butylene oxide in the copolymers 1 to 30 mol%. In addition to straight-chain, branched homopolymers or copolymers which are end group-capped at least on one side can also be used as the graft base. Branched copolymers are prepared, for example, by adding to polyhydric low molecular weight alcohols, for example trimethylolpropane, glycerol, pentoses or hexoses, ethylene oxide and, if appropriate, also propylene oxide and / or butylene oxides. The alkylene oxide units can be randomly distributed in the polymer or in the form of blocks. At least one terminal OH group of the polyalkylene oxides is end group-capped. This should be understood to mean that it is etherified, esterified, aminated or modified by reaction with an isocyanate, for example.

Für die Veretherung kommen als Substituenten der endständigen H-Atome der Hydroxylgruppen der Polyalkylenoxide Alkylgruppen mit 1 bis 18 Kohlenstoffatomen, substituierte Alkylgruppen, wie die Benzylgruppe, oder auch Phenylgruppen in Betracht. Polyalkylenoxide, deren Endgruppen verestert sind, werden beispielsweise durch Veresterung der oben beschriebenen Polyalkylenoxide mit Carbonsäuren mit 1 bis 18 Kohlenstoffatomen erhalten, z.B. durch Umsetzung mit Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Malonsäure, Bernsteinsäure, Stearinsäure, Maleinsäure, Terephthalsäure und Phthalsäure. Sofern Carbonsäureanhydride zur Verfügung stehen, kann der Endgruppenverschluß der Polyalkylenoxide auch durch Umsetzung mit den entsprechenden Anhydriden durchgeführt werden, z.B. durch Umsetzung mit Maleinsäureanhydrid. Die Polyalkylenoxide können auch mindestens einseitig durch Umsetzung mit Isocyananten, z.B. Phenylisocyanat, Naphthylisocyanat, Methyl-, Ethyl- und Stearylisocyanat modifiziert werden.For the etherification, the substituents of the terminal H atoms of the hydroxyl groups of the polyalkylene oxides are alkyl groups with 1 to 18 carbon atoms, substituted alkyl groups such as the benzyl group, or also phenyl groups. Polyalkylene oxides whose end groups are esterified are obtained, for example, by esterification of the polyalkylene oxides described above with carboxylic acids having 1 to 18 carbon atoms, e.g. by reaction with formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid, stearic acid, maleic acid, terephthalic acid and phthalic acid. If carboxylic anhydrides are available, the end group capping of the polyalkylene oxides can also be carried out by reaction with the corresponding anhydrides, e.g. by reaction with maleic anhydride. The polyalkylene oxides can also be reacted at least on one side by reaction with isocyanants, e.g. Phenyl isocyanate, naphthyl isocyanate, methyl, ethyl and stearyl isocyanate can be modified.

Aminierte Produkte werden durch Autoklavenreaktion des entsprechenden Alkylenoxids mit Aminen, z.B. C₁- bis C₁₈-Alkylaminen erhalten.Aminated products are obtained by autoclaving the corresponding alkylene oxide with amines, e.g. C₁ to C₁₈ alkylamines obtained.

Als Komponente (b) 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, Valeransäurevinylester, i-Valeransäurevinylester und Capronsäurevinylester. Von den Monomeren der Gruppe (b) verwendet man vorzugsweise Vinylacetat, Vinylpropionat, Methylacrylat, Methylmethacrylat oder Mischungen der genannten Monomeren. Die Herstellung der Propfcopolymerisate erfolgt nach bekannten Verfahren, indem man beispielsweise die in Betracht kommenden mindestens einseitig endgruppenverschlossenen 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, pfropft. Hierbei kann man so vorgehen, daß man die Komponente (a) in mindestens einem Monomer der Gruppe (b) löst und nach Zugabe eines Polymerisationsinitiators die Mischung auspolymerisiert. Die Pfropfcopolymerisation kann auch halbkontinuierlich durchgeführt werden, indem man zunächst einen Teil, z.B. 10% des zu polymerisierenden Gemisches aus endgruppenverschlossenem Polyalkylenoxid, mindestens einem Monomeren der Gruppe (b) 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 die endgruppenverschlossenen Polyalkylenoxide der Gruppe (a) in einem Reaktor vorlegt, auf die Polymerisationstemperatur erwärmt und mindestens ein Monomer der Gruppe (b) und Polymerisationsinitiator entweder auf einmal, absatzweise oder vorzugsweise kontinuierlich zufügt und auspolymerisiert. Das Gewichtsverhältnis der Komponenten (a):(b) beträgt 1:0,2 bis 1:10, vorzugsweise 1:0,5 bis 1:6.As component (b), 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 above-mentioned 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 (b), preference is given to using vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate or mixtures of the monomers mentioned. The graft copolymers are prepared by known processes, for example by the polyalkylene oxides of component (a) at least one end group capped with the monomers of component (b) in the presence of free radical initiators or by action grafting high-energy radiation, which should also be understood to mean the action of high-energy electrons. The procedure here can be such that component (a) is dissolved in at least one monomer from group (b) and the mixture is polymerized out after addition of a polymerization initiator. The graft copolymerization can also be carried out semi-continuously by first introducing a portion, for example 10%, of the mixture of end-capped polyalkylene oxide to be polymerized, at least one monomer from group (b) and initiator, heating to the polymerization temperature and, after the polymerization has started, the rest of the polymerizing mixture is added according to the progress of the polymerization. The graft copolymers can also be obtained by placing the end-capped polyalkylene oxides of group (a) in a reactor, heating to the polymerization temperature and adding and polymerizing at least one monomer from group (b) and polymerization initiator either all at once, batchwise or, preferably, continuously. The weight ratio of components (a) :( b) is 1: 0.2 to 1:10, preferably 1: 0.5 to 1: 6.

Als Polymerisationsinitiatoren eignen sich vor allem organische Peroxide, wie Diacetylperoxid, Dibenzoylperoxid, Succinylperoxid, Di-tertiär-butylperoxid, Tertiär-butylperbenzoat, Tertiär-butylperpivalat, Tertiär-butylpermaleinat, Cumolhydroperoxid, Diisopropylperoxidicarbamat, Bis-(o-toluoyl)-peroxid, Didecanoylperoxid, Dioctanoylperoxid, Dilauroylperoxid, Tertiärbutyl-perisobutyrat, Tertiär-butylperacetat, Di-tertiär-amylperoxid, Tertiär-butylhydroperoxid sowie Mischungen der genannten Initiatoren, Redox-Initiatoren und Azostarter.Suitable polymerization initiators are, in particular, organic peroxides, such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tertiary butyl peroxide, tertiary butyl perbenzoate, tertiary butyl perpivalate, tertiary butyl permaleinate, cumene hydroperoxide, diamopropyl peroxide, diarbamate toloyl peroxide, Dioctanoyl peroxide, dilauroyl peroxide, tertiary butyl perisobutyrate, tertiary butyl peracetate, di-tertiary amyl peroxide, tertiary butyl hydroperoxide and mixtures of the initiators, redox initiators and azo starters mentioned.

Die Pfropfpolymerisation erfolgt in dem 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 Pfropfcopolymerisation auch in einem Lösemittel durchgeführt werden. Geeignete Lösemittel sind beispielsweise Alkohole, z.B. Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, sekundär-Butanol, tertiär-Butanol, n-Hexanol und Cyclohexanol sowie Glykole, wie Ethylenglykol, Propylenglykol und Butylenglykol sowie die Methyl- oder Ethyläther der zweiwertigen Alkohole, Diethylenglykol, Triethylenglykol, Glycerin und Dioxan. Die Pfropfpolymerisation kann außerdem 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 und dispersen Charakter annehmen kann. Um wasserunlösliche Produkte, die während der Polymerisation entstehen können, in Lösung zu überführen, kann man beispielsweise organische Lösemittel zusetzen, beispielsweise 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. Suc. Cosmetic Chem., Bd. 5, 249 (1954) hingewiesen. Die Menge an Tensiden, bezogen auf das Propfpolymerisat, 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 Gewichtsteile des Pfropfpolymerisates 5 bis 200, vorzugsweise 10 bis 100 Gewichtsteile des organischen Lösemittels oder des Lösemittelgemisches.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 copolymerization described above can also be carried out in a solvent. Suitable solvents are, for example, alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, n-hexanol and cyclohexanol, and glycols, such as ethylene glycol, propylene glycol and butylene glycol, and the methyl or ethyl ether 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 and can assume a disperse character. In order to convert water-insoluble products that can arise during the polymerization into solution, for example, organic solvents can be added, for example monohydric alcohols with 1 to 3 carbon atoms, acetone or dimethylformamide. However, graft polymerization in water can also be carried out by converting the water-insoluble graft polymers into a finely divided dispersion by adding customary emulsifiers or protective colloids, for example polyvinyl alcohol. 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. Suc. Cosmetic Chem., Vol. 5, 249 (1954). The amount of surfactants, based on the graft polymer, 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.

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 (b) hydrolysiert werden. So wird beispielsweise die Hydrolyse von Pfropfpolymerisaten, zu deren Herstellung als bevorzugtes Monomer der Gruppe (b) Vinylacetat verwendet wurde, zu Vinylalkohol-Einheiten enthaltenden Propfpolymerisaten. Die Hydrolyse kann beispielsweise durch Zugabe einer Base, wie Natronlauge, Kalilauge, Ammoniak oder Aminen, wie Triethanolamin, Morpholin oder Triethylamin, oder auch durch Zugabe von Säuren, z.B. HCl, und gegebenenfalls Erwärmen der Mischung vorgenommen werden.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 (b) are hydrolyzed. For example, the hydrolysis of graft polymers, the production of which was used as the preferred monomer of group (b), vinyl acetate, to graft polymers containing vinyl alcohol units. The hydrolysis can be carried out, for example, by adding a base, such as sodium hydroxide solution, potassium hydroxide solution, ammonia or amines, such as triethanolamine, morpholine or triethylamine, or by adding acids, e.g. HCl, and optionally 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 70°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 solids at room temperature up to temperatures of 70 ° 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. Der Tensidgehalt von Flüssigwaschmitteln liegt in dem Bereich von 15 bis 50 Gew.%.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. Powdery detergents usually contain 5 to 20% by weight of a surfactant or a mixture of surfactants. The surfactant content of liquid detergents is in the range from 15 to 50% by weight.

Die pulverförmigen Waschmittel können außerdem gegebenenfalls Polycarbonsäuren bzw. deren Salze enthalten, beispielsweise Weinsäure und Zitronensäure.The powder detergents can optionally also contain polycarboxylic acids or their salts, for example tartaric acid and 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. aus Copolymerisaten 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, wobei sie in nicht neutralisierter Form, als Alkali- oder Ammoniumsalz sowie in partiell neutralisierter Form, z.B. Neutralisation von 40 bis 60% der Carboxylgruppen, eingesetzt werden.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 homopolymers 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, they being in non-neutralized form, as alkali or ammonium salt and in partially neutralized form, e.g. Neutralization of 40 to 60% of the carboxyl groups can be used.

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. Diese Stoffe können z.B. mit Hilfe der Formel RO(CH₂CH₂O)n-C₄H₈-SO₃Na, in der n = 5 bis 40 und R = Oleyl ist, charakterisiert werden. Pulverförmige Waschmittel können gegebenenfalls auch Zeolithe enthalten, z.B. in einer Menge von 5 bis 30 Gew.%. Die Waschmittelformulierungen können gegebenenfalls auch Bleichmittel enthalten. Sofern Bleichmittel eingesetzt werden, betragen die üblicherweise angewendeten Mengen 3 bis 25 Gew.%. Als Bleichmittel kommt beispielsweise Natriumperborat in Betracht. Außerdem können die Waschmittelformulierungen gegebenenfalls noch Bleichaktivatoren, Weichmacher, Entschäumer, Parfum, optische Aufheller und Enzyme enthalten. Stellmittel, wie z.B. Natriumsulfat, können gegebenenfalls in einer Menge von 10 bis 30 Gew.% in Waschmitteln enthalten sein.Other components of the mixture of detergents can also include corrosion inhibitors, monomeric, oligomeric and polymeric phosphonates, ether sulfonates the basis of unsaturated fatty alcohols, for example oleyl alcohol ethoxylate butyl ether and their alkali salts. These substances can be characterized, for example, using the formula RO (CH₂CH₂O) n -C₄H₈-SO₃Na, in which n = 5 to 40 and R = oleyl. Powdered detergents may 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. Sodium perborate, for example, is suitable as a bleaching agent. 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. 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. 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 usually 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 bedeute K = k·10³.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.

Die Molekulargewichte (Zahlenmittel) der eingesetzten Polyalkylenoxide a) wurden aus der OH-Zahl errechnet.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:

Propfpolymerisate 1 bis 21Graft polymers 1 to 21

Die Propfpolymerisate wurden nach dem aus der GB-PS 922 457 bekannten Verfahren durch Aufpfropfen der in Tabelle 1 angegebenen Monomeren (b) (auf jeweils 100 Teile eines Polyalkylenoxids mit dem ebenfalls in Tabelle 1 angegebenen Molekulargewichts (Zahlenmittel)) hergestellt. Die Polymeren 1, 3 bis 10 und 18 bis 20 waren verethert, bei den Polymeren 2, 11 und 12 war eine endständige OH-Gruppe des Polyalkylenoxids verestert, bei Polymer 15 war eine endständige OH-Gruppe mit einem C₁₀-Amin aminiert, bei den Polymeren 16 und 17 waren jeweils beide endständigen OH-Gruppen des Polyalkylenoxids mit Maleinsäure verestert und bei Polymer 19 war eine Endgruppe des Polyalkylenoxids mit einer C₁₀-Alkylgruppe verethert, während die andere mit Maleinsäure verestert war.

Figure imgb0001
Figure imgb0002
 The graft polymers were prepared by the process known from GB-PS 922 457 by grafting on the monomers (b) given in Table 1 (to 100 parts in each case of a polyalkylene oxide with the molecular weight (number average) also given in Table 1). The polymers 1, 3 to 10 and 18 to 20 were etherified, in the case of the polymers 2, 11 and 12 a terminal OH group of the polyalkylene oxide was esterified, in the case of polymer 15 a terminal OH group was aminated with a C₁₀-amine in which Polymers 16 and 17 were both both terminal OH groups of the polyalkylene oxide esterified with maleic acid and in polymer 19 one end group of the polyalkylene oxide was etherified with a C₁₀-alkyl group while the other was esterified with maleic acid.
Figure imgb0001
Figure imgb0002

Die vergrauungsinhibierende Wirkung der oben angegebenen Pfropfpolymerisate 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 Fall am Elrepho 2000 (Datacolor) bei der Wellenlänge 460 nm gemessen (Barium-Primärweißstandard nach 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/l The graying-inhibiting effect of the above-mentioned graft polymers was tested as follows: polyester test fabric and polyester / cotton blend fabric were subjected to a series of 3 washes together with a standard dirt fabric. The dirty fabric is renewed after each wash, the test fabric becoming more soiled after each wash. The 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 460 nm (barium primary white standard according to DIN 5033. Test conditions: Tester: Launder-O-meter Water hardness: 3.5 mmol Ca / l, Ca: Mg = 3: 2 Fleet quantity: 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 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 ethylene oxide 4.7% Soap 2.8% Na triphosphate (90% 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 on 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 imgb0003
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 imgb0003

Claims (4)

  1. The use of a graft polymer which is obtainable by grafting
    a) a polyalkylene oxide which has a number average molecular weight of from 300 to 100,000, is based on ethylene oxide, propylene oxide or butylene oxide, and is end group capped at at least one end, with
    b) at least one vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms or a methyl or ethyl ester of acrylic or methacrylic acid
    in a weight ratio (a):(b) of from 1:0.2 to 1:10 and up to 15 mol % of the grafted monomers (b) of which may, if desired, be hydrolyzed, as a grayness inhibitor in the washing and aftertreatment of textiles containing synthetic fibers.
  2. A use as claimed in claim 1, wherefor component (a) is a polyalkylene oxide having a number average molecular weight of from 1,000 to 50,000 and an ethylene oxide content of from 40 to 100 mol %, and end group capped at at least one end.
  3. A use as claimed in claim 1 or 2, wherefor the graft polymer is obtainable by grafting
    a) a polyethylene oxide which has a number average molecular weight of from 1,000 to 50,000 and is capped at one or both ends with
    b) vinyl acetate
    in a weight ratio (a):(b) of from 1:0.5 to 1:6, and has a K value of from 5 to 200 (determined according to H. Fikentscher in dimethylformamide at 25°C and at a polymer concentration of 2% by weight.
  4. A detergent based on surfactants, builders, water-soluble or water-dispersible graft polymers as grayness inhibitors and optionally other customary additives, containing from 0.1 to 5% by weight of a graft polymer which is obtainable by grafting
    a) a polyalkylene oxide which has a number average molecular weight of from 300 to 100,000, is based on ethylene oxide, propylene oxide or butylene oxide and is end group capped at at least one end with
    b) at least one vinyl ester derived from a saturated monocarboxylic acid having 1 to 6 carbon atoms or a methyl or ethyl ester of acrylic or methacrylic acid,
    in a weight ratio (a):(b) of from 1:0.2 to 1:10 and up to 15 mol % of the grafted-on monomers (b) of which may be hydrolyzed.
EP88104888A 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 EP0285037B1 (en)

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JPS63260994A (en) 1988-10-27
US4846995A (en) 1989-07-11
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