EP0285037B1 - Utilisation de polymères greffés à base d'oxydes de polyalkylènes comme agents antirédéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques - Google Patents

Utilisation de polymères greffés à base d'oxydes de polyalkylènes comme agents antirédéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques 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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EP
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Prior art keywords
oxide
weight
graft polymers
number average
molecular weight
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EP88104888A
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German (de)
English (en)
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EP0285037A2 (fr
EP0285037A3 (en
Inventor
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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Priority to AT88104888T priority Critical patent/ATE91499T1/de
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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
    • C11D3/0005—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)
  • Graft Or Block Polymers (AREA)

Claims (4)

  1. Utilisation de polymères de greffage, que l'on peut obtenir par le greffage de
    (a) poly(oxydes d'alkylène) bloqués au moins d'un côté par des radicaux terminaux, d'un poids moléculaire (selon la moyenne en nombre) de 300 à 100.000, à base d'oxyde d'éthylène, d'oxyde de propylène et/ou d'oxyde de butylène,
    avec
    (b) au moins un ester vinylique, qui dérive d'un acide mnocarboxylique saturé, contenant de 1 à 6 atomes de carbone et/ou un ester méthylique ou éthylique de l'acide acrylique ou de l'acide méthacrylique,
    dans le rapport pondéral (a):(b) de 1:0,2 à 1:10 et dont les monomères (b) greffés sur eux peuvent éventuellement être hydrolysés jusqu'à 15% molaires, à titre d'inhibiteurs de ternissement au cours du lavage et du traitement subséquent de matières textiles contenant des fibres synthétiques.
  2. Utilisation de polymères greffés suivant la revendication 1, caractérisée en ce que l'on utilise, à titre de composant (a), des poly(oxydes d'alkylène) bloqués au moins d'un côté par des radicaux terminaux, d'un poids moléculaire (selon la moyenne en nombre) de 1000 à 50.000 et comportant une fraction d'oxyde d'éthylène de 40 à 100% molaires.
  3. Utilisation de polymères greffés selon les revendications 1 et 2, caractérisée en ce qu'on peut les obtenir par le greffage
    (a) d'un poly(oxyde d'éthylène) bloqué d'un ou des deux côtés, d'un poids moléculaire (selon la moyenne en nombre) de 1000 à 50.000
    avec
    (b) l'acétate de vinyle
    dans le rapport pondéral (a):(b) de 1:0,5 à 1:6 et d'une valeur K de 5 à 200 (déterminée selon H. Fikentscher à 25°C, dans le diméthylformamide et à une concentration en polymère de 2% en poids).
  4. Détergents ou agents de lessivage à base de composés surfactifs ou tensioactifs, d'adjuvants de détergence, de polymères de greffage solubles dans l'eau ou dispersibles dans l'eau à titre d'inhibiteurs de ternissement et éventuellement d'autres additifs usuels, caractérisés en ce qu'ils comportent de 0,1 à 5% en poids de polymères de greffage, que l'on peut obtenir par le greffage de
    (a) poly(oxydes d'alkylène) bloqués au moins d'un côté par des radicaux terminaux, d'un poids moléculaire (selon la moyenne en nombre) de 300 à 100.000, à base d'oxyde d'éthylène, d'oxyde de propylène et/ou d'oxyde de butylène,
    avec
    (b) au moins un ester vinylique, qui dérive d'un acide mnocarboxylique saturé, contenant de 1 à 6 atomes de carbone et/ou un ester méthylique ou éthylique de l'acide acrylique ou de l'acide méthacrylique,
    dans le rapport pondéral (a):(b) de 1:0,2 à 1:10 et dont les monomères (b) greffés sur eux sont éventuellement hydrolysés jusqu'à 15% molaires.
EP88104888A 1987-04-03 1988-03-26 Utilisation de polymères greffés à base d'oxydes de polyalkylènes comme agents antirédéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques Expired - Lifetime EP0285037B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88104888T ATE91499T1 (de) 1987-04-03 1988-03-26 Verwendung von propfpolymerisaten auf basis von polyalkylenoxiden als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3711298 1987-04-03
DE19873711298 DE3711298A1 (de) 1987-04-03 1987-04-03 Verwendung von propfpolymerisaten auf basis von polyalkylenoxiden als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut

Publications (3)

Publication Number Publication Date
EP0285037A2 EP0285037A2 (fr) 1988-10-05
EP0285037A3 EP0285037A3 (en) 1990-09-19
EP0285037B1 true EP0285037B1 (fr) 1993-07-14

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EP88104888A Expired - Lifetime EP0285037B1 (fr) 1987-04-03 1988-03-26 Utilisation de polymères greffés à base d'oxydes de polyalkylènes comme agents antirédéposants pendant le lavage et le post-traitement de matières textiles contenant des fibres synthétiques

Country Status (7)

Country Link
US (1) US4846995A (fr)
EP (1) EP0285037B1 (fr)
JP (1) JP2541616B2 (fr)
AT (1) ATE91499T1 (fr)
CA (1) CA1302832C (fr)
DE (2) DE3711298A1 (fr)
ES (1) ES2041721T3 (fr)

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DE3882260D1 (de) 1993-08-19
JPS63260994A (ja) 1988-10-27
ES2041721T3 (es) 1993-12-01
DE3711298A1 (de) 1988-10-13
EP0285037A2 (fr) 1988-10-05
EP0285037A3 (en) 1990-09-19
CA1302832C (fr) 1992-06-09
US4846995A (en) 1989-07-11
ATE91499T1 (de) 1993-07-15
JP2541616B2 (ja) 1996-10-09

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