EP0219048B1 - Utilisation de copolymères greffés d'oxydes de polyalkylènes et d'acétate de vinyle comme agents antiredéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques - Google Patents

Utilisation de copolymères greffés d'oxydes de polyalkylènes et d'acétate de vinyle comme agents antiredéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques Download PDF

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Publication number
EP0219048B1
EP0219048B1 EP86113884A EP86113884A EP0219048B1 EP 0219048 B1 EP0219048 B1 EP 0219048B1 EP 86113884 A EP86113884 A EP 86113884A EP 86113884 A EP86113884 A EP 86113884A EP 0219048 B1 EP0219048 B1 EP 0219048B1
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EP
European Patent Office
Prior art keywords
weight
vinyl acetate
oxide
graft copolymer
graft copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP86113884A
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German (de)
English (en)
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EP0219048A3 (en
EP0219048A2 (fr
Inventor
Alexander Dr. Kud
Guenther Dr. Schulz
Wolfgang Dr. Trieselt
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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Priority to AT86113884T priority Critical patent/ATE53065T1/de
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Publication of EP0219048A3 publication Critical patent/EP0219048A3/de
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Publication of EP0219048B1 publication Critical patent/EP0219048B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

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

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (6)

1. Utilisation de compolymères greffés qui sont préparés par greffage de (a) poly(oxydes d'alkylène) de poids moléculaire (moyenne en nombre) de 2000 à 100 000 à base d'oxyde de butylène avec (b) de l'acétate de vinyle dans un rapport en poids (a):(b) de 1:0,2 à 1:10 et dont les groupements acétate sont éventuellement saponifiés jusqu'à 15%, comme anti-redéposants dans le lavage des produits textiles contenant des fibres synthétiques.
2. Utilisation de copolymères greffés selon la revendication 1, caractérisée en ce qu'ils sont obtenus par greffage de (a) poly(oxydes d'alkylène) de poids moléculaire (moyenne en nombre) de 4000 à 50 000 avec (b) de l'acétate de vinyle dans un rapport en poids de 1:0,5 à 1:6.
3. Utilisation de copolymères greffés selon la revendication 1 ou 2, caractérisée en ce qu'ils présentent une valeur K selon H. Fikentscher de 10 à 200 (mesurée à 25°C en solution à 1% en poids dans l'acétate d'éthyle).
4. Utilisation de copolymères greffés selon la revendication 1, caractérisée en ce qu'ils sont préparés par greffage de (a) poly(oxyde d'éthylène) de poids moléculaire (moyenne en nombre) de 2000 à 50 000 avec (b) de l'acétate de vinyle dans un rapport pondéral de 1:0,5 à 1:6 et ont une valeur K de 10 à 200 (mesurée à 25°C en solution à 1% dans l'acétate d'éthyle).
5. Utilisation de copolymères greffés selon l'une des revendications 1 à 4, caractérisée en ce que les copolymères greffés sont ajoutés comme adjuvants au dernier bain de rinçage d'un cycle de machine à laver.
6. Produits de lavage à base de tensides, d'adjuvants, d'agents de blanchiment et d'additifs usuels, caractérisée en ce qu'ils contiennent comme agent anti-redéposition de 0,1 à 3% en poids de copolymères greffés qui sont préparés par greffage de (a) poly(oxydes d'alkylène) de poids moléculaire (moyenne en nombre) de 2000 à 100 000 à base d'oxyde d'éthylène, d'oxyde de propylène et/ou d'oxyde de butylène avec de l'acétate de vinyle dans un rapport en poids (a):(b) de 1:0,2 à 1:10 et dont les groupements acétate sont éventuellement saponifiés jusqu'à 15%.
EP86113884A 1985-10-12 1986-10-07 Utilisation de copolymères greffés d'oxydes de polyalkylènes et d'acétate de vinyle comme agents antiredéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques Expired - Lifetime EP0219048B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86113884T ATE53065T1 (de) 1985-10-12 1986-10-07 Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853536530 DE3536530A1 (de) 1985-10-12 1985-10-12 Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
DE3536530 1985-10-12

Publications (3)

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

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EP86113884A Expired - Lifetime EP0219048B1 (fr) 1985-10-12 1986-10-07 Utilisation de copolymères greffés d'oxydes de polyalkylènes et d'acétate de vinyle comme agents antiredéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques

Country Status (7)

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

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US6812200B2 (en) 2000-12-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Process for coating detergent tablets
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Also Published As

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

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