Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • A—HUMAN NECESSITIES
  • A46—BRUSHWARE
  • A46D—MANUFACTURE OF BRUSHES
  • A46D1/00—Bristles; Selection of materials for bristles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/902—High modulus filament or fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2973—Particular cross section

Definitions

• the invention relates to monofilaments and bristles made of polyacrylonitrile or polyacrylonitrile copolymers which are predominantly composed of acrylonitrile building blocks and whose titers are higher than 2.5 tex, their strength is greater than 20 cN / tex and their initial modulus is greater than 700 cN / tex - based on 100 % Stretch - is.
• the shaped products were termed monofilament in the case of endless material and bristles in the case of short-cut material in order to clarify that it is not textile threads or fibers in the usual sense, but rather structures with diameters of more than 0.05 to approx 0.2 mm, corresponding to a single titer of more than 2.5 tex to about 30 tex.
• German Offenlegungsschrift 3,027,844 describes high-modulus threads and fibers made of polyacrylonitrile, the initial modulus of which is higher than 1300 cN / tex.
• the titers described in the examples of this preliminary literature are between 1.7 and 3.6 dtex.
• the titer range of about 1.5 to 15 dtex specified in the text limits the titer range to the usual range of textile spun threads and fibers, which usually ranges from 20 dtex in some cases to 20 dtex and exceptionally up to 25 dtex with a single titer of 15 dtex.
• filaments that are as similar as possible to natural human hair are also the subject of German Offenlegungsschrift 2,434,488.
• filaments in the titer range from 2 to 7 tex are produced by a wet spinning process.
• the total stretching of 1: 6 takes place in two stages in the wet state.
• No physical-physical values of the filaments produced can be found in the examples of this preliminary literature.
• reworking has shown that with the method according to DE-A-2 434 488, at best, filaments can be produced which have an initial modulus below 600 cN / tex.
• Textile fibers and threads made of polymers with a high content of acrylonitrile units are usually produced by a solution spinning process.
• the solvent which usually makes up more than 70% of the thread emerging from the nozzle, has to be removed and the thread-forming polymer has to be compacted into a compact thread.
• the removal of the solvent and the production of a compact thread are more difficult to solve, the thicker the diameter of the spun filament.
• the filaments obtained are characterized by a high initial modulus with a coarse titer over 2.5 tex. It is known that the initial module, as a measure of the force absorption of a filament at low elongation, is much more sensitive to defects in the filament structure than, for example, the tensile strength. Nevertheless, such filaments with initial moduli of e.g. Generate 1500 or 1700 cN / tex. The high stretchability of the coarse-titer filaments spun from a solution was also surprising.
• a filament drawn out of the nozzle with a calculated titer of 215 tex (based on the thread-forming substance) - or 1,200 tex, based on the spinning material used - could be 16.7-fold to a final titer of 12, 9 tex can be stretched.
• the invention therefore relates to monofilaments and bristles made of homo- or copolymers of acrylonitrile, which consist of at least 90% by weight of acrylonitrile building blocks and a titer of more than 2.5 tex.
• These filaments are characterized in that they have a tensile strength of at least 20 cN / tex, preferably more than 23 cN / tex and an initial modulus, based on 100% elongation, of more than 700 cN / tex.
• the polymer required for this should have a relative viscosity, measured as a solution of 0.5 g in 100 ml of dimethylformamide at 20 ° C., of 1.7 to 6.0.
• the filaments according to the invention preferably have a titer of up to about 30 tex. Arithmetically, assuming a circular cross section, this corresponds to diameter values of approx. 0.052 to 0.180 mm. Further features that are the subject of the subclaims, but are discussed below in connection with possible uses of such monofilaments and bristles.
• the monofilaments and bristles according to the invention are particularly suitable for the production of filament-reinforced composite materials.
• the filaments according to the invention and in particular the bristles according to the invention can be mixed into the materials to be reinforced in a much simpler, more homogeneous and in higher concentration.
• the mixtures produced in this way are characterized, for example, by lower viscosities and better flow behavior.
• the preferred titer and cut length of the filaments according to the invention depend very much on the planned area of use and the required amount of use in the composite material.
• bristles with a titre of 8 to 20 tex in concrete mixtures leads to a considerable reduction in the cracking of the hardened concrete parts, it increases the elasticity, reduces the brittleness and increases the breaking energy considerably. Similar advantages can be observed with sprayed concrete, mortar and a wide variety of plasters reinforced with bristles according to the invention.
• bristles in the titer range from 3 to 10 tex produce particularly good reinforcement results. For example, increased impact strength - in contrast to the results when using glass fibers - is maintained even at low temperatures.
• the same titer range leads e.g. when used in sealing compounds based on polymer bitumen for particularly high dimensional stability.
• the optimal titer of the bristles is very significantly influenced by the amount of bristles used, the admixing technique and, in the case of solids, by the grain size distribution of the material to be reinforced.
• the strengths of the filaments according to the invention are in each case above 20 cN / tex and preferably in the range from 25 to 60 cN / tex.
• the initial moduli of the filaments according to the invention must be over 700, preferably over 800, preferably between 1,000 and 1,800 cN / tex.
• Cutting lengths e.g. 0.5 to 30 mm, in other areas of application of the bristles cutting lengths from 100 to 150 mm.
• the short cutting lengths of the bristles in the area of 1 to 2 mm or less should preferably be used in a mixture with filaments with a longer cutting length.
• the short cutting lengths can fundamentally improve the rheological behavior of, for example, building adhesives and tile adhesives.
• the use of a higher molecular weight polymer which is preferably composed of more than 99% by weight of acrylonitrile building blocks, is advantageous because the filaments made therefrom are significantly more resistant to aggressive media than corresponding filaments made from raw materials with a higher copolymer content.
• the invention is also based on a method for producing the monofilaments or bristles by a wet spinning process, in which in addition to wet drawing, hot drawing must be carried out after drying.
• the process according to the invention is characterized in that the filaments are drawn before, during or after washing at least in a ratio of 1: 4, dried under tension, but possibly with a low degree of shrinkage, and then at least subjected to hot drawing at temperatures of at least 120 ° C. and subjected to an aspect ratio of at least 1: 2.
• the effective total drawing of the threads should be at least 1: 8, preferably 1:10 to 1:20.
• the hot stretching is preferably a stretching in the dry-hot state, the amount of heat required being transferred by contacting surface radiators or hot rollers.
• the precipitation or solution polymers prepared by the customary process can be used as polymer raw materials. Depending on the requirements for the fields of application, both homo- and copolymers of acrylonitrile can be used. The highest possible purity should be ensured for the monomers used. Suitable comonomers are all unsaturated compounds copolymerizable with acrylonitrile, of which the following should be mentioned here, for example:
• Acrylamide acrylic acid and its esters, methacrylonitrile, methacrylamide, methacrylic acid and their esters and corresponding compounds substituted on the methyl group, vinyl esters and ethers such as vinyl acetate, vinyl stearate, vinyl butyl ether, haloacetic acid vinyl esters such as bromoacetic acid vinyl ester, dichloroacetic acid vinyl ester, trichloroacetic acid halide, e.g. Vinyl chloride, vinyllylidene chloride, vinyl bromide and unsaturated compounds bearing sulfonate groups, etc.
• vinyl esters and ethers such as vinyl acetate, vinyl stearate, vinyl butyl ether
• haloacetic acid vinyl esters such as bromoacetic acid vinyl ester, dichloroacetic acid vinyl ester, trichloroacetic acid halide, e.g. Vinyl chloride, vinyllylidene chloride, vinyl bromide and unsaturated compounds bearing sulf
• Polymers can be used whose relative solution viscosities are measured as 0.5% di methylformamide solutions at 20 ° C in the range of 1.7 to 6.0. Typically, higher molecular weight polymers result in filaments with better physical properties. However, a considerably larger amount of solvent must be used and recovered for their production, which means that the production costs of such filaments are increased considerably. Good results under economical conditions are achieved with polymers which are in a viscosity range of approximately 1.85 to 3.5, particularly good results are provided by polymers in the viscosity range between 2.5 and 3.5.
• the dissolving conditions are to be selected so that spinning solutions which are as homogeneous as possible and free of gel particles are obtained.
• Scattered light measurements using a laser as the light source are particularly suitable for checking the quality of the spinning solution. Only flawless spinning solutions which show very low scattered light values enable the high draws required according to the invention.
• the spinning solutions can be prepared both continuously and discontinuously.
• Inorganic or organic additives such as matting agents, stabilizers, flame retardants, etc. can be incorporated into the spinning solutions.
• Additives such as CaC0 3 or Si0 2 in a concentration of 1 to 20% which influence the surface structure are also suitable.
• the spinning process according to the invention is distinguished by a high effective total drawing of at least 1: 8.
• the effective total drawing only the wet drawing before, during or after the washing process and the hot drawing are taken into account, but a contraction of the filaments is deducted.
• the so-called nozzle warpage is not included in the values of the total stretching; rather, the fresh spun filaments that are obtained after a wet spinning process are classified as undrawn material.
• the effective total stretching should be at least 1: 8 by the method according to the invention. Effective total draw ratios of 1:10 to 1 20 are preferred.
• the process according to the invention can be carried out on conventional filament spinning plants.
• the required effective total drawing takes place in several stages, first the spun filaments are wet-drawn before, during or after washing out the residual solvent content in one or gradually in several hot baths at least in a ratio of 1: 4.
• the temperature of the stretching bath media which generally consist of mixtures of water and the aprotic solvent used, should be kept as high as possible. Temperatures a little below the boiling point of the bath liquid are preferred. However, baths that contain other stretching bath media are also possible, e.g. Glycol or glycerin, if appropriate also in mixtures with the polymer solvent, at which stretching temperatures above 100 ° C. can also be selected.
• the filaments are prepared in a preparation bath and then freed as much as possible of adhering water by the action of rotating pairs of press rollers.
• the preparation applied in the preparation bath can influence the stretching behavior of the filaments. It should therefore be selected from known preparation compounds that shows the lowest possible thread friction.
• the filaments obtained are dried under tension on hot rollers.
• a small amount of shrinkage which often proves to be advantageous for the subsequent stretching, can be permitted;
• care must be taken that the cables always run under tension over the drying rollers.
• the temperatures of the rollers should be chosen so that the cable leaves the dryer with a very low residual moisture of less than 1%. Temperatures of the drying rollers of 140 to 240 ° C have proven to be particularly favorable, but this does not exclude the use of higher or lower temperatures. It is also possible to dry on the rollers at stepped temperatures.
• the spinning tow is stretched again using at least twice its length using dry heat.
• This stretching can also take place in one or more stages.
• the heating of the cable can be carried out according to the methods customary in the art, e.g. by rotating hot rollers, by contact via hot plates, in a hot air duct or by radiation, in particular infrared radiation. Gradual stretching, in which different heating methods are used, can also be used. Such combinations are always particularly advantageous when stretching from or between hot rolls in the first stretching stage and using one of the three other methods described in the second stage.
• the drawing temperatures are influenced by the type of polymer used and in part by the previous drawing and the drying conditions. Drying temperatures in the range from about 120 to 250 ° C. are generally suitable.
• the filaments are cooled in a conventional manner and either wound up to form continuous material or cut into bristles with the desired cutting length using known methods. If the application requires it, a special preparation, e.g. improves the spreadability or adhesion in a composite material to which monofilaments or bristles are applied.
• the measured values were recorded with an Instron tensile tester, model 1122.
• the clamping length was 200 mm, the expansion took place at a speed of 100% of the clamping length per minute.
• the initial modulus was determined in the 0.1-0.3% stretch range.
• the resulting sheet was withdrawn vertically from the nozzle at 6.3 m / min, in two successive troughs, which were filled with a mixture of 40% DMF and 60% water, stretched to 27 m / min at boiling temperature, in hot water in Countercurrent washed, finished, dried at 170, 190 and briefly 230 ° C to then first be stretched at 180 ° C to 40 m / min and then over hot plates at 180 ° C to 78 m / min.
• the total effective stretching was 1: 12.4.
• the filaments obtained had the following properties:
• An 18% spinning mass of a polymer according to Example 1 was pressed through a nozzle with 10 holes, hole diameter 0.3 mm into a precipitation bath of 40% DMF and 60% water at 39 ° C.
• the filaments were drawn off from the nozzle at 4.5 m / min, drawn to 22.5 m / min in two baths with 60% DMF and 40% water at 95 ° C., washed in hot water and after passing through an anti-aging bath to 2 Duos dried at temperatures of 150 and 190 ° C under tension. With a third duo heated to 190 ° C, the filaments were stretched to 42 m / min and then drawn off from this duo at 67.0 m / min. The total draw was 1: 14.9.
• the filaments showed the following properties:
• the total draw was 1: 16.7.
• Example 3 A dope as described in Example 3 was spun, wet drawn, washed and finished under the conditions of Example 4. The drying took place on 3 duos with a surface temperature of 150, 160 and 180 ° C. The cable was stretched to 42 m / min with a duo heated to 205 ° C. and pulled off from this duo at 59 m / min (total stretching 1: 13.1). The filaments obtained had the following values:
• the threads were with 3.5 m / min withdrawn from the nozzle, stretched in two subsequent baths of 60% DMF and 40% water at 95 ° C to 22.6 m / min, washed in hot water at 80 ° C, finished and 4 duos dried at 135, 150, 165 and 170 ° C.
• the speeds of the individual duos were: 22.5; 24.8; 24.5; and 22.5 m / min.
• the threads from the last duo were drawn off at 48.0 m / min, which means that the effective total drawing was 1: 13.7.
• the filaments obtained had the following properties:
• This example represents a reworking of the essential details of Example 1 of DE-A-2 434 488.
• a 22% solution of a polymer made from 93.6% by weight acrylonitrile, 5.8% by weight methyl acrylate and 0.6 % Sodium methallylsulfonate in DMF was spun through a 10 hole nozzle, hole diameter 0.3 mm, nozzle diameter 20 mm into a precipitation bath of 55% DMF and 45% water at 20 ° C.
• the spraying speed of the spinning mass was set to 6.0 m / min and the threads were drawn off the nozzle at 4.8 m / min (delay: 0.8).
• the initial modulus was determined in the range from 0.3 to 0.5% elongation, since the values were in the range from 0.1 to 0.3% lower.
• the titer value resulted from the individual capillary values averaged from all 10 capillaries. In this way it was not possible to achieve a titer of 4 tex. For this reason, the spinning test of Example 7 was repeated, but now the threads, after drying at 180 ° C., were wound up at 27.0 m / min. The following physical values resulted under these conditions:
• the initial modulus was determined from the 0.3 to 0.5% elongation range.

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• Textile Engineering (AREA)
• Toxicology (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Artificial Filaments (AREA)
• Road Signs Or Road Markings (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
• Woven Fabrics (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Citations (8)

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• 1984
  • 1984-02-25 DE DE19843406910 patent/DE3406910A1/de active Granted
• 1985
  • 1985-02-13 AT AT85101521T patent/ATE46548T1/de not_active IP Right Cessation
  • 1985-02-13 EP EP85101521A patent/EP0154217B1/de not_active Expired
  • 1985-02-13 DE DE8585101521T patent/DE3573142D1/de not_active Expired
  • 1985-02-20 CA CA000474751A patent/CA1246821A/en not_active Expired
  • 1985-02-22 DD DD85273483A patent/DD229723B3/de not_active IP Right Cessation
  • 1985-02-22 ZA ZA851353A patent/ZA851353B/xx unknown
  • 1985-02-22 BR BR8500775A patent/BR8500775A/pt not_active IP Right Cessation
  • 1985-02-22 JP JP60033006A patent/JPS60194111A/ja active Pending
  • 1985-02-22 NO NO850719A patent/NO171771C/no unknown
  • 1985-02-22 DK DK084085A patent/DK169727B1/da not_active IP Right Cessation
  • 1985-02-24 IL IL74435A patent/IL74435A/xx not_active IP Right Cessation
  • 1985-02-26 MX MX026628A patent/MX166827B/es unknown
• 1986
  • 1986-02-07 US US06/827,328 patent/US4719150A/en not_active Expired - Lifetime

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