EP0476371A1 - Agent d'encollage pour des fils de fibres discontinues et de filaments continus - Google Patents

Agent d'encollage pour des fils de fibres discontinues et de filaments continus Download PDF

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Publication number
EP0476371A1
EP0476371A1 EP91114381A EP91114381A EP0476371A1 EP 0476371 A1 EP0476371 A1 EP 0476371A1 EP 91114381 A EP91114381 A EP 91114381A EP 91114381 A EP91114381 A EP 91114381A EP 0476371 A1 EP0476371 A1 EP 0476371A1
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Prior art keywords
proteins
polymerization
graft
water
monomers
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German (de)
English (en)
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EP0476371B1 (fr
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Matthias Dr. Kroner
Manfred Dr. Niessner
Heinrich Dr. Hartman
Dieter Voelker
Juergen Dr. Hartmann
Holger Dr. Schoepke
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15—Proteins or derivatives thereof

Definitions

  • the invention relates to the use of water-soluble or water-dispersible grafted proteins which can be obtained by free-radically initiated polymerization of monoethylenically unsaturated monomers in the presence of proteins as sizing agents for staple fiber and filament yarns.
  • Protein sizes have also been replaced in many of these fields of application by synthetic polymers, carboxymethyl cellulose and starch derivatives.
  • Protein sizing based on animal proteins such as casein or bone or skin glue must be mixed with softening additives such as glycerin, castor oil and its soaps or with surface-active substances in order to be used as a sizing agent at all.
  • softening additives such as glycerin, castor oil and its soaps or with surface-active substances
  • a mixture of casein and paraffins serves as an emulsion size for nylon filaments.
  • DE-AS 15 94 905 discloses the use of water-soluble sodium or ammonium salts of copolymers of acrylonitrile and acrylic acid for the sizing of staple fiber yarns.
  • water-soluble alkaline earth metal salts of copolymers of (meth) acrylic acid and (meth) acrylonitrile in a mixture with starch or starch derivatives are used as sizing agents.
  • polyester sizing which are described in U.S. Patents 3,546,008, 3,548,026 and 4,268,645.
  • the sized warp threads are freed from the size.
  • the sizing agents get into the wastewater of the textile companies. Biodegradable or non-eliminable sizing agents pollute the wastewater.
  • the object of the present invention is to provide sizing agents which are largely biodegradable or can be eliminated from the wastewater and which have improved application properties compared to the known natural material sizing agents.
  • Monoethylenically unsaturated monomers of group (a) for the preparation of the grafted proteins are, for example, C3- to C8-monoethylenically unsaturated carboxylic acids, for example acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid and vinyl acetic acid.
  • the associated anhydrides of the monomers mentioned can be used, for example maleic anhydride and itaconic anhydride.
  • acrylic acid, methacrylic acid or mixtures thereof are preferably used Production of the grafted proteins.
  • the carboxylic acids can be used in the graft copolymerization as free carboxylic acids or in the form of the salts with inorganic or organic bases.
  • sodium hydroxide solution, potassium hydroxide solution, alkaline earth metal oxides and hydroxides, ammonia, trimethylamine, triethylamine, tributylamine, triethanolamine, diethanolamine, morpholine, methylamine or dimethylamine are suitable for neutralizing the monoethylenically unsaturated carboxylic acids.
  • Mixtures of different bases can also be used for neutralization, for example sodium hydroxide solution and ethanolamine.
  • the compounds of group (a) are also the esters of the above-mentioned carboxylic acids with monohydric or polyhydric C1 to C22 alcohols.
  • Suitable alcohols which are used for the esterification of the monoethylenically unsaturated carboxylic acids described above are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, stearyl alcohol, palmityl alcohol, Decyl alcohol, dodecyl alcohol, tallow fatty alcohol, sorbitol, mannitol, glycerin, ethylene glycol, propylene glycol, butanediol.
  • esters of acrylic acid and methacrylic acid with methanol, ethanol, n-propanol, n-butanol, tert-butanol, 2-ethylhexyl alcohol, stearyl alcohol, ethylene glycol and propylene glycol are preferably used.
  • esters mentioned n-butyl acrylate, methyl methacrylate, ethylhexyl acrylate and ethyl acrylate in a mixture with acrylic acid and / or methacrylic acid are particularly preferably subjected to the graft copolymerization in the presence of proteins.
  • Suitable as monomers of group (a) are the amides of C3- to C8-carboxylic acids, which are derived from ammonia, C1- to C22-alkylamines or dialkylamines.
  • Suitable amines for the preparation of the acid amides are, for example, methylamine, dimethylamine, stearylamine, tallow fatty amine and palmitylamine.
  • the N-methylol derivatives of the amides can be used in the graft copolymerization, e.g. N-methylol acrylamide or N-methylol methacrylamide.
  • the N-methylol derivatives of the amides mentioned can also be etherified, e.g. with C1 to C22 alcohols, preferred monomers are N- (butoxymethyl) acrylamide and N- (isobutoxymethyl) acrylamide.
  • Suitable monomers (a) are the nitriles of the carboxylic acids, such as acrylonitrile or methacrylonitrile, vinyl ethers of alcohols containing 1 to 18 carbon atoms, for example vinyl methyl ether, vinyl isobutyl ether, vinyl n-butyl ether, vinyl ethyl ether and vinyl esters of saturated C1 to C Carb carboxylic acids, in particular vinyl acetate, Vinyl propionate and vinyl butyrate.
  • Other suitable monomers are styrene and alkyl styrenes.
  • the graft copolymers contain the monomers (a) in amounts of 0.5 to 90, preferably 10 to 85,% by weight in copolymerized form.
  • Proteins are used as a further essential component in the graft copolymerization. All proteins are suitable for this, of which a proportion of at least 20% by weight dissolves in the polymerization medium under the polymerization conditions. Suitable proteins are described, for example, in US Pat. No. 4,812,550 cited above. A further overview of suitable proteins can be found in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Weinheim 1980 Volume 19, 491 to 557.
  • the proteins are renewable raw materials. For example, they come from hides, supporting and connective tissue, bones and cartilage: collagen, elastin, gelatin, ossein and skin glue. Proteins from milk are whey proteins, casein and lactalbumin. Keratin comes from wool, bristles, feathers and hair.
  • Proteins from fish and eggs and from blood are also suitable as slaughterhouse waste, e.g. Blood proteins, albumin, globulin, globin, fibrinogen and hemoglobin.
  • Other suitable proteins come from plants such as corn, wheat, barley and oats: glutelin, prolamine, zein and gluten.
  • Proteins can also be obtained from seeds, e.g. from soybeans, calico seeds, peanuts, sunflowers, rapeseed, coconut, linseed, sesame, safflower, peas, beans and lentils.
  • the protein components of clover, alfalfa, grass, potatoes, cassava and yam can also be used.
  • Other protein suppliers are bacteria, fungi, algae and yeast, e.g.
  • Proteins which are preferably used as component (b) for the production of the graft copolymers are casein, gelatin, bone glue, proteins from soybeans, cereals, in particular wheat, corn and peas.
  • the proteins are obtained from the natural raw materials, for example, by dissolving, grinding, sifting and classifying. In order to convert them into a soluble form, digestion by physical, chemical or enzymatic treatment is necessary in many cases, e.g.
  • the monomers (a) are radically polymerized in the presence of proteins. All known compounds can be used as a radical donor. These initiators can be soluble or insoluble in water. Water-soluble initiators are, for example, inorganic peroxides, such as potassium, sodium and ammonium peroxodisulfate and hydrogen peroxide.
  • initiators are organic peroxides, hydroperoxides, peracids, ketone peroxides, perketals and peresters, for example methyl ethyl ketone hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-di (tert-butyl peroxy) cyclohexane, di (tert-butyl) peroxide, tert-butyloxy perpivalate, tert-butyl monoperoxy maleate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide and mixtures of peroxides.
  • organic peroxides for example methyl ethyl ketone hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-di (tert-butyl peroxy) cyclohexane, di (
  • Redox systems that contain a reducing component in addition to a peroxy compound are also suitable.
  • Suitable reducing components are, for example, cerium III and iron II salts, sodium sulfite, sodium bisulfite, sodium dithionite, ascorbic acid and sodium formaldehyde sulfoxylate.
  • Suitable initiators are preferably selected by using compounds which form free radicals and which have a half-life of less than 3 hours at the polymerization temperature chosen in each case.
  • the polymerization is first started at a lower temperature and ends at a higher temperature, it is advisable to work with at least two initiators which disintegrate at different temperatures, namely first an initiator which already disintegrates at a lower temperature and then the initiator Complete the main polymerization with an initiator that decomposes at a higher temperature.
  • the decomposition temperature can be reduced by adding heavy metal salts, for example copper, cobalt, manganese, iron, nickel and chromium salts to peroxidic catalysts.
  • Suitable initiators are also azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis- (2, 4-dimethylvaleronitrile) and dimethyl 2,2'-azobisisobutyrate.
  • Hydrogen peroxide, potassium, ammonium and sodium peroxodisulfate and tert-butyl perpivalate are particularly preferably used as initiators in the graft polymerization. Based on the monomers to be polymerized, 0.5 to 10, preferably 1 to 8,% by weight of an initiator or a mixture of polymerization initiators is used. The amount of initiator used can have a considerable influence on the graft polymer formed.
  • graft polymers with particularly advantageous properties can be obtained by first adding a water-soluble initiator for the main reaction and then for post-polymerizing and removing residual monomers from the latex.
  • a water-soluble initiator for the main reaction and then for post-polymerizing and removing residual monomers from the latex.
  • the monomers and the initiator are metered into a polymerizing mixture at the same time, it is advantageous to choose a feed time for the initiator of 10 minutes to 2 hours longer than the monomer feed time.
  • the time for the monomer feed can be 2 hours and for the initiator feed 3 hours.
  • the graft polymerization can optionally be carried out in the presence of regulators.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
  • allyl compounds such as allyl alcohol, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydroxylamine sulfate and butenols. If the graft copolymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers used in the polymerization, can be used.
  • the polymerization can be carried out in an aqueous medium or in an organic solvent in which the proteins are at least 20% by weight soluble.
  • Suitable organic solvents are, for example, acetic acid, formic acid, alcohols, such as methanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, ethers, such as tetrahydrofuran and dioxane.
  • ketones such as acetone and methyl ethyl ketone can be used as an inert diluent in graft polymerization.
  • the use of methanol, ethanol, isopropanol, acetone, tetrahydrofuran and dioxane is particularly preferred.
  • the graft polymerization can be carried out in mixtures of organic solvents and in mixtures of water and organic solvents which dissolve in water.
  • concentration of monomer and protein in the solvent used in each case is 10 to 70, preferably 15 to 60% by weight.
  • the graft polymerization is carried out in conventional devices which are provided with mixing elements, for example pistons, kettles, autoclaves and cylindrical reactors equipped with stirrers.
  • the graft polymerization can also be carried out in cascade cascades or in other polymerization devices connected to one another.
  • the polymerization can be carried out batchwise or continuously. Kneaders are also suitable as the polymerization device. If water-soluble monomers (a) are used in the graft polymerization, the polymerization can also be carried out by the reverse suspension polymerization method or by the water-in-oil emulsion polymerization method.
  • the graft polymerization is preferably carried out as solution polymerization and emulsion polymerization.
  • emulsifiers and protective colloids can also be added in amounts of up to 5% by weight. However, it is preferred to work in the absence of surface-active additives. Precipitation polymerization may be of interest for special applications.
  • the polymerization can also be initiated by the action of UV radiation or the action of high-energy rays, for example ⁇ , ⁇ or ⁇ rays.
  • the graft polymerization is carried out in the temperature range from 20 to 160, preferably 30 to 100 ° C. At temperatures that are above the boiling point of the solvent used in each case, the graft polymerization is usually carried out in apparatus designed to be pressure-tight.
  • Polymerization is preferably carried out in the absence of atmospheric oxygen in an inert gas atmosphere, for example nitrogen, argon, helium or carbon dioxide are used as the inert gases.
  • an inert gas atmosphere for example nitrogen, argon, helium or carbon dioxide are used as the inert gases.
  • the reaction temperature and the amount of initiator influence the properties of the graft polymers formed.
  • the monomers to be polymerized and the protein can be introduced together with at least one polymerization initiator and polymerized by heating to the polymerization temperature required in each case.
  • the protein (b) and initially only some of the monomers (a) and the initiator are initially introduced into the polymerization device and the remaining monomers (a) and the initiator are added continuously or batchwise in accordance with the progress of the polymerization.
  • the order in which the reactants are metered into the polymerization reactor can be varied as desired.
  • a protein solution or a dispersion of a protein in a reactor, to heat it to the required polymerization temperature and to add the monomers and initiators continuously or batchwise.
  • the individual monomers can be metered into the polymerization zone simultaneously, as a mixture or from separate metering devices.
  • water-insoluble monomers (a) it may be advantageous to prepare a mixture of water, solvents, regulators, bases and the total amounts of monomers (a) and proteins (b) and this mixture continuously or batchwise at the same time the initiator, according to the progress of the polymerization dosed into the polymerization vessel.
  • these process variants can have considerable effects on the effectiveness of the graft polymers as sizing agents.
  • the pH of the reaction medium can also have an influence on the properties of the graft polymer.
  • the solubility of the proteins below and above the isoelectric point can be used in the graft polymerization.
  • Acidic or basic monomers can be used in the form of the corresponding salts.
  • acrylic acid is used as the free acid or as the ammonium, alkali or alkaline earth salt.
  • the graft polymerization can be carried out in the pH range from 1 to 14, preferably 6 to 12.
  • the graft polymers can be precipitated from solutions, for example, by changes in pH. This can be used in the processing, cleaning and isolation of the graft copolymers. It may be advantageous to use 2 or more proteins in the graft polymerization.
  • the order of the proteins used can have favorable effects on the properties of the graft copolymers formed.
  • it is advantageous to take advantage of the emulsifying ability of a protein by first emulsifying a water-insoluble monomer with a protein and then adding another protein and subjecting the reaction mixture to graft copolymerization.
  • water-insoluble monomers e.g.
  • n-butyl acrylate, N-butoxymethylacrylamide, N-isobutoxymethyl methacrylamide, 2-ethylhexyl acrylate or methyl methacrylate can first be a three-phase mixture of monomer, water and insoluble protein, e.g. Casein.
  • alkalis e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia solution, triethylamine, alkanolamine, morpholine or other alkaline substances.
  • alkalis e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia solution, triethylamine, alkanolamine, morpholine or other alkaline substances.
  • the films obtained after the graft polymerization can be converted into a form by heating to 50 ° C. to 150 ° C., particularly well in vacuo, which is only in water then redisperse when the pH is above 7.
  • the films of the graft copolymers prepared and treated in this way are only slightly swellable or insoluble in pure water.
  • spontaneous redispersion is achieved by adding a base. This can be used to provide the yarns with a water-resistant protective cover that can only be easily removed again in an alkaline environment.
  • a casein grafted with n-butyl acrylate which is neutralized with ammonia solution and then isolated as a film by removing the solvents in vacuo and in the drying cabinet at 80 ° C. for 10 minutes was stored, just redispersed in water while the film is water-insoluble after a 1-hour dwell time at 80 ° C.
  • the film can then be stored under water for at least 1 week without losing its shape. After adding a few drops of caustic soda, it dissolves into a fine-particle emulsion that is indistinguishable from the original emulsion.
  • the proteins used in the graft polymerization can be chemically modified in various ways before or after the graft polymerization. For example, it may be advantageous to partially decompose the protein hydrolytically or enzymatically before the polymerization. Depending on the reaction conditions, a partial hydrolytic degradation of the proteins can take place during the graft polymerization.
  • the graft polymers can be modified in various ways after the graft polymerization, e.g. graft polymers of alkyl acrylates can be saponified onto proteins with the elimination of alcohol.
  • carboxylic acid derivatives e.g. Carboxylic anhydrides are implemented.
  • carboxylic anhydrides are acetic anhydride, succinic anhydride, maleic anhydride.
  • the proteins obtainable in this way, grafted with monoethylenically unsaturated monomers, which are either in dissolved or dispersed form, have K values of 10 to 200, preferably 15 to 180 (determined according to H. Fikentscher in 1% strength in water at 25 ° C. and pH 7).
  • the graft copolymers show a biodegradation corresponding to the protein content, in the elimination test according to Zahn-Wellens they can be very easily eliminated.
  • a commercial preservative is added for storage in the presence of water. In the air-dried state, the graft polymers can be stored stably even without preservatives.
  • the graft polymers described are used as sizing agents for staple fiber and filament yarns. These yarns are made of cellulose fibers such as cotton, viscose, linen, jute, ramie; and polyester / cellulose fiber blends, polyester, polyacrylonitrile, rayon rayon, wool, polyester / wool blends, acetate, triacetate and polyamide.
  • the amount of sizing agent on the yarns is usually 0.5 to 30% by weight, based on the yarns.
  • the graft polymers can be used both alone and together with other components. They can also be mixed in any ratio to create specific properties.
  • the desired hardness of the resulting films of these mixtures can be set by the mixing ratio of the hard and soft components. In this way it is possible to set specific film properties by deliberately mixing two or more graft copolymers.
  • the graft polymers to be used according to the invention are notable for their good sizing effect, at the same time having a high film hardness and thus a low tendency to stick the sized warp threads. Furthermore, they show high adhesive strength values as well as mixture stability, storage stability and do not tend to gel under processing conditions. They are also characterized by being easy to wash out before further processing of the fabrics which have been produced using the sizing agents.
  • a particular advantage is the environmentally friendly disposal of the graft polymers contained in the wastewater after washing, because the natural components of the graft polymers are biodegradable and the synthetic components can be easily eliminated.
  • a graft polymer of, for example, 40% casein and 60% n-butyl acrylate was already 93% eliminated in the Zahn-Wellens test after 2 days from the aqueous supernatant of the test solution.
  • the measurements were carried out on 1% strength by weight aqueous solutions of the graft polymers at 25 ° C. and a pH of 7. The data in% mean% by weight.
  • Proxel XL 2 in the form of a 10% strength aqueous solution was used as a preservative for the aqueous solutions and dispersions of the graft polymers.
  • a solution of 150 g of bone glue in 100 g of water is placed in a 2 l glass apparatus which is equipped with an anchor stirrer, feed devices for monomers, initiator solutions and sodium hydroxide solution, reflux condenser and nitrogen inlet and outlet and is brought to 80 ° C. under a nitrogen atmosphere warmed up.
  • 30 g of solid casein and 22 g of a 5% aqueous sodium hydroxide solution are added.
  • a viscous, homogeneous solution is obtained, to which 120 g of n-butyl acrylate are added dropwise from 2 feed vessels within 2 hours and 100 g of a 4% strength aqueous sodium peroxodisulfate solution are added dropwise over the course of 3 hours.
  • reaction mixture is stirred for a further 3 hours at 80 ° C. and then diluted by adding 300 g of water. Then 1 g of the usual preservative for casein is added and the reaction mixture is filtered. A milky emulsion with a solids content of 32% is obtained.
  • the K value of the graft polymer is 16.6.
  • the graft polymer contains 0.12% unpolymerized n-butyl acrylate.
  • 225 g of bone glue are dissolved in 160 g of water by heating to a temperature of 80 ° C under a nitrogen atmosphere.
  • 15 g of n-butyl acrylate are run into this solution within 10 minutes and at the same time 30 g of a 3% strength aqueous sodium peroxodisulfate solution are run in within 15 minutes.
  • 275 g of a 27% aqueous acrylic acid solution are simultaneously added dropwise within 2 hours and 100 g of a 4% aqueous sodium peroxodisulfate solution are added over 2.5 hours.
  • the reaction mixture is stirred for a further 3 hours at 80 ° C.
  • a solution of 170 g of 25% strength aqueous sodium hydroxide solution and 1 g of the commercially available preservative is added.
  • 370 g of water are added and a cloudy solution with a solids content of 32% is obtained.
  • the K value of the graft polymer is 86 and the residual monomer content is 0.005%.
  • graft polymers are prepared with the starting materials specified in the following table in accordance with the instructions given for the preparation of the graft polymer 3.
  • the graft polymer In the apparatus described for the production of the graft polymer 1, 200 g of bone glue are dissolved in 140 g of water at 80 ° C. under a nitrogen atmosphere. 260 g of a 23% aqueous acrylic acid solution are then added dropwise to the resulting solution over the course of 2 hours, and at the same time 100 g of a 4% aqueous sodium peroxodisulfate solution are added over 3 hours. After the addition of the initiator has ended, the reaction mixture is stirred for a further 1 hour at 80 ° C., cooled and neutralized by adding 170 g of a 20% strength aqueous sodium hydroxide solution. The polymer solution has a solids content of 31%. The graft polymer has a K value of 79.4.
  • the apparatus used for the production of the graft polymer 1 150 g of bone glue and 100 g of water are stirred under a nitrogen atmosphere and heated to a temperature of 85.degree. A mixture of 75 g of acrylic acid and 75 g of n-butyl acrylate is allowed to run into the resulting solution within 2 hours and at the same time 100 g of a 4% strength aqueous sodium peroxodisulfate solution are run in within 3 hours. After the initiator addition has ended, the reaction mixture is stirred for a further 2 hours at 80 ° C. and then neutralized by adding 170 g of a 25% strength aqueous sodium hydroxide solution.
  • the graft polymer has a residual n-butyl acrylate content of 0.03%.
  • the graft polymer has a K value of 37.7 and contains 0.002% unpolymerized methyl methacrylate.
  • the emulsion will after the initiator addition has ended, the mixture is stirred at 75 ° C. for 4 hours, diluted with 300 g of water and mixed with 1 g of the preservative. It has a solids content of 20%.
  • the K value of the graft polymer is 45.6.
  • Example 12 is repeated with the only exception that N- (isobutoxymethyl) acrylamide is now used instead of N- (n-butoxymethyl) acrylamide.
  • the K value of the graft polymer is 44.8.
  • the latices obtained according to a) and b) are mixed so that the resulting mixture contains 70% of the latex according to a) and 30% of the latex according to b).
  • the mixture is then mixed with 1 g of the preservative. It is stable for weeks.
  • the graft polymers 1 to 15 described above are used as sizing agents for staple fiber and filament yarns.
  • A) the film properties and B) the pilling values and the pseudo warp thread break values were determined as a measure of the sizing effect.
  • the film hardness of the films was tested to determine the film properties.
  • the test was carried out on the König pendulum device (DIN 53 157).
  • the sizing effect is tested on the Reutlingen weaving tester, which simulates the load on the warp yarns during the weaving process by repeatedly mechanically stressing sized yarns under a certain tension using metal pins (J. Trauter and R. Vialon, Textiltechnik International 1985, 1201).
  • the number of these stresses (number of turns) at which a certain damage to the yarn can be determined represents a measure of the quality of the sizing agent.
  • yarns made from cotton with 8% aqueous liquors and yarns made from polyester / cotton in a weight ratio of 65/35 with 14% aqueous liquors of the graft polymers given below were sized at room temperature.
  • the arbitration was carried out on a laboratory sizing machine (DE-PS 2 714 897). The sized yarns were then held at 68% relative humidity and 20 ° C for 24 hours.
  • the examples show the results of the tests (film properties and sizing effect).
  • the graft polymers 1 to 15 to be used according to the invention are viscoplastic and homogeneous and show good pilling and pseudo warp thread break values with regard to the sizing effect.
  • proteins can be modified by radical grafting with ethylenically unsaturated monomers in such a way that their properties as textile sizes are considerably improved.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Harvester Elements (AREA)
  • Power Steering Mechanism (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
EP91114381A 1990-09-15 1991-08-27 Agent d'encollage pour des fils de fibres discontinues et de filaments continus Expired - Lifetime EP0476371B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT9191114381T ATE104712T1 (de) 1990-09-15 1991-08-27 Schlichtemittel fuer stapelfaser- und filamentgarne.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4029348A DE4029348A1 (de) 1990-09-15 1990-09-15 Verwendung von wasserloeslichen oder in wasser dispergierbaren gepfropften proteinen als schlichtemittel
DE4029348 1990-09-15

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EP0476371A1 true EP0476371A1 (fr) 1992-03-25
EP0476371B1 EP0476371B1 (fr) 1994-04-20

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EP (1) EP0476371B1 (fr)
JP (1) JPH04245974A (fr)
AT (1) ATE104712T1 (fr)
CA (1) CA2050032A1 (fr)
DE (2) DE4029348A1 (fr)
ES (1) ES2063422T3 (fr)
FI (1) FI914139A (fr)
PT (1) PT98962B (fr)

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DE19936476A1 (de) 1999-08-03 2000-07-06 Ctp Papierhilfsmittel Gmbh & C Streichmasse zur Herstellung bedruckbarer Papiere
DE10066096B4 (de) * 1999-08-03 2006-04-20 Ctp Gmbh Verfahren zur Herstellung von Gelatine-Propfpolymeren und deren Verwendung zur Herstellung von Streichmassen zur Herstellung bedruckbarer Papiere

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1594905A1 (de) * 1966-02-01 1969-08-28 Basf Ag Schlichtemittel
US3578492A (en) * 1966-11-23 1971-05-11 Edgar D Bolinger Sized twestless yarns
US3651210A (en) * 1970-05-15 1972-03-21 Ashland Oil Inc Synthetic emulsion-graft copolymers further reacted with protein
US4812550A (en) * 1987-03-30 1989-03-14 Gencorp Inc. Preparation of latices

Patent Citations (4)

* Cited by examiner, † Cited by third party
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ES2063422T3 (es) 1995-01-01
PT98962A (pt) 1992-08-31
FI914139A (fi) 1992-03-16
JPH04245974A (ja) 1992-09-02
EP0476371B1 (fr) 1994-04-20
PT98962B (pt) 1999-02-26
CA2050032A1 (fr) 1992-03-16
FI914139A0 (fi) 1991-09-03
DE59101437D1 (de) 1994-05-26
ATE104712T1 (de) 1994-05-15
DE4029348A1 (de) 1992-03-19

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