EP0332919B1 - Oberflächenmodifizierte, vollaromatische Polyamidfaser und Verfahren zu ihrer Herstellung - Google Patents

Oberflächenmodifizierte, vollaromatische Polyamidfaser und Verfahren zu ihrer Herstellung Download PDF

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EP0332919B1
EP0332919B1 EP19890103472 EP89103472A EP0332919B1 EP 0332919 B1 EP0332919 B1 EP 0332919B1 EP 19890103472 EP19890103472 EP 19890103472 EP 89103472 A EP89103472 A EP 89103472A EP 0332919 B1 EP0332919 B1 EP 0332919B1
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Prior art keywords
fiber
aromatic polyamide
wholly aromatic
modified
polyamide fiber
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EP19890103472
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French (fr)
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EP0332919A2 (de
EP0332919A3 (de
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Hiroyuki Moriga
Shoji Makino
Akira Kimura
Hirosuke Watanabe
Tadashi Hirakawa
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Teijin Ltd
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Teijin Ltd
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Priority claimed from JP4756188A external-priority patent/JPH0778309B2/ja
Priority claimed from JP5494688A external-priority patent/JPH01239168A/ja
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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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • 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
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a surface-modified wholly aromatic polyamide fiber, comprising: a fiber matrix comprising a wholly aromatic polyamide material; fine inorganic particles distributed on and in a surface portion of the matrix and comprising at least one cation-exchanging inorganic material; and an additive attached to the fine inorganic particles and a method of producing same.
  • the present invention relates to a wholly aromatic polyamide fiber surface-modified with cation-exchanging inorganic fine particles and a specific additive attached to the fine particles and thus useful for fiber-reinforced rubber or synthetic resinous materials, and a method of producing the same.
  • EP-A-0 168 066 discloses a process for the improvement of the adhesion to rubber or a thermoplastic elastomer of synthetic yarns, cords or fabrics made therefrom by applying thereto an adhesive consisting of an aqueous solution or dispersion of specific polyurethane specific with ionic groups, capped isocyanate groups and groups with a Zerewitinoff-active H atom, followed by drying the product thus treated.
  • wholly aromatic polyamide fibers have an excellent heat-resistance, a superior mechanical strength, a high elastic modulus and satisfactory chemical resistance and electric property, and thus are usable for various composite materials.
  • the wholly aromatic polyamide fiber i.e., the aramide fiber
  • JP-A-62-97967 discloses a method of producing a wholly aromatic polyamide shaped article having an enhanced bonding property to an organic polymeric matrix, comprising the step of treating a surface of the wholly aromatic polyamide shaped article with an aqueous solution of a metal salt of hypochlorous acid.
  • JP-A-62-243620 discloses a surface-modified wholly aromatic polyamide shaped article in which a portion of or all of amide radicals located in a surface portion of a wholly aromatic polyamide shaped article comprising recurring units of the general formula: -NH-Ar1-CONH-A2-CO- and/or -NH-Ar3-CO-, wherein Ar1 , Ar2 , and Ar3 respectively and independently from each other represent a divalent aromatic group, are replaced at the nitrogen atoms by an aliphatic organic radical having 2 to 10 carbon atoms.
  • JP-A-62-243628 discloses a method of producing a surface-modified wholly aromatic polyamide shaped article, characterized by treating a wholly aromatic polyamide shaped article with an alkali metal salt or alkaline earth metal salt of an aromatic or aliphatic hydrocarbon to convert at least a portion of the amide radicals located in the surface portion of the article to a metal salt radical, and to cause the surface portion of the article to swell, and then treating the surface portion of the article with a polyepoxy compound having at least three epoxy radicals per polymer molecule of the polyamide.
  • the fibers when the wholly aromatic polyamide fibers are converted to a paper-like sheet or nonwoven fabric and are used as reinforcing materials for resinous shaped articles, the fibers usually exhibit a poor resistance to organic solvents for matrix resins of the shaped articles, and thus the reinforcing materials are frequently broken in the step in which the reinforcing materials are impregnated with a solution of a resinous material in the organic solvent.
  • the reinforcing materials made from the wholly aromatic polyamide fibers exhibit a poor bonding to the matrix resin, and therefore, in a resultant fiber-reinforced shaped article, the reinforcing material is easily peeled from the resinous matrix.
  • An object of the present invention is to provide a surface-modified wholly aromatic polyamide fiber having an activated surface which exhibits an enhanced bonding or adherence to another resinous material, and an improved resistance to organic solvents, and a method of producing same.
  • the above-mentioned object can be attained by the surface-modified wholly aromatic polyamide fiber of the type indicated at the outset and being characterized in that said additive as applied comprises at least one member selected from the group consisting of cationic organic compounds and organic silicone compounds having at least two different types of reactive radicals.
  • the above-mentioned surface-modified wholly aromatic polyamide fiber can be produced by the method of the present invention comprising a method of producing a surface-modified wholly aromatic polyamide fiber, comprising: converting a wholly aromatic polyamide material to a fiber through a spinning step, at least one drawing step and at least one heat-treating step; and at any stage after the spinning step, applying fine inorganic particles comprising at least one cation-exchanging inorganic material to a surface of the fiber; and treating the fine inorganic particles adhered to the surface of the fiber with an additive to cause the additive to be attached to the fine inorganic particles and being characterized in that the additive as applied comprises at least one member selected from the group consisting of cationic organic compounds and organic silican compounds having at least two different types of reactive radicals.
  • the wholly aromatic polyamide fiber can be produced from a wholly aromatic polyamide material by a usual method comprising a spinning [fiber-forming) step, at least one drawing step, and at least one heat-treating step.
  • the wholly aromatic polyamide material preferably comprises at least one wholly aromatic polyamide polymer having 80 to 100 molar% of principal recurring units of the formula (1): -NH-Ar1-NHCO-Ar2-CO- (1) wherein Ar1 and Ar2 represent, respectively and independently from each other, a member selected from the group consisting of the ingredients of the formula (A), (B) and (C): in which R1 and R2 represent respectively and independently from each other a member selected from the group consisting of halogen atoms, for example, chlorine atom and bromine atom, and a lower alkyl radical having 1 to 2 carbon atoms, for example, methyl or ethyl radical, and n represents zero or an integer of 1 to 4.
  • Ar1 and Ar2 represent, respectively and independently from each other, a member selected from the group consisting of the ingredients of the formula (A), (B) and (C): in which R1 and R2 represent respectively and independently from each other a member selected from the group consisting of halogen atoms
  • the wholly aromatic polyamide polymer may be a homopolymer or a copolymer.
  • the wholly aromatic polyamide polymer may have 0 to 20 molar% of additional recurring units, in addition to 80 to 100 molar% of the principal recurring units of the formula (1).
  • the additional recurring units may be selected from those of the formulae (2) and (3): ⁇ NH - Ar3 - CO ⁇ (2) and ⁇ NH - Ar4 - NHCO - Ar5 - CO ⁇ (3) wherein Ar3, Ar4 and Ar5, respectively and independently from each other, represent an unsubstituted or substituted divalent aromatic radical selected from those of the formulae: in which R3 represents a member selected from the group consisting of lower arkyl radicals having 1 to 3 carbon atoms, lower alkoxy radicals having 1 to 3 carbon atoms, halogen atoms and nitro radicals, and t represents zero or an integer of from 1 to 3, and Ar4 and Ar5 are different from Ar1 and Ar2.
  • the above-mentioned wholly aromatic polyamide homopolymer and copolymer can be prepared by known methods, for example is disclosed by GB-B-1,501,948, US-A-3,733,964 or JP-A-49-100322.
  • the principal recurring units of the formula (1) preferably comprise the ingredients of the formulae (A) and (B) in the total content of 80 to 100 molar% and the ingredient of the formula (B) is in a content of 10 to 40 molar%, based on the total content of the ingredients represented by Ar1 and Ar2.
  • the cation-exchanging inorganic material usable for the present invention preferably comprises at least one member selected from the group consisting of silica-alumina, silica-magnesia, bentnite, kaolin, fuller's earth, activated clay, montmorilonite, halloysite, talc and a mixture of an inorganic material comprising, as a major component, hydrated magnesium silicate and a hydrated gel-forming inorganic material.
  • the cation-exchanging inorganic compound is in the form of fine solid particles and is easily adhered on a surface of the wholly aromatic polyamide fiber.
  • the fine inorganic particles preferably have a size of 0.01 to 5 ⁇ m, more preferably, 0.01 to 3 ⁇ m.
  • the inorganic material comprising, as a major component, hydrated magnesium silicate may be talc and may preferably have a particle size of 0.01 to 3 ⁇ m.
  • the hydrated gel-forming inorganic material refers to an inorganic material which forms a substantially non-fluidable or semi-fluidable gel when hydrated with water in an amount of five times the weight of the material.
  • the hydrated gel-forming inorganic compound comprises, as a major component, aluminum silicate.
  • the fine inorganic particles are applied in an amount of 0.1% to 5% based on the weight of the fiber matrix (non-surface modified fiber).
  • the fine inorganic particles can be applied to the surface of the fiber at any stage after the spinning (fiber-forming step).
  • the fine inorganic particles can be applied to the fiber surface while the fiber is softened or plasticized, so that the particles are adhered, pierced or embedded on or in the surface portion of the fiber.
  • the fiber may be an undrawn fiber immediately after the spinning step but before complete cooling or a heated undrawn fiber.
  • the fine inorganic particles are blown toward the surface of the undrawn fiber or the undrawn fiber is immersed in an aqueous slurry containing the fine inorganic particles, to allow the fine inorganic particles to adhere to the fiber surface, and then the undrawn fiber adhered with the fine inorganic particles is dried, if necessary, and drawn at a temperature higher than the glass transition temperature of the wholly aromatic polyamide polymer, at a draw ratio, for example, of 5 or more, by using a contact type or non-contact type heater.
  • This process is effective for piercing or pushing the fine inorganic particles into the surface portion of the fiber, and for fixing the particles in the fiber surface portion.
  • the application of the fine inorganic particles can be effected to a drawn fiber surface and then a heat treatment can be applied to the fine inorganic particle-applied fiber surface at an elevated temperature.
  • the fine inorganic particles are applied in an amount of 0.1% to 5%, more preferably 0.1% to 2%, based on the weight of the fiber matrix (non-surface modified fiber).
  • the fine inorganic particles are applied onto a drawn fiber surface and the applied drawn fiber is then further drawn or heat-treated at an elevated temperature.
  • the fine inorganic particle-applied fiber is further treated with an additive comprising at least one member selected from the group consisting of cationic organic compounds and organic silicone compounds having at least two different types of reactive radicals.
  • the additive is attached to the fine inorganic particles on the fiber surface.
  • the cationic organic compounds refer to electron-donating organic compounds and include amino-radical-containing organic compounds and tert-cationic radical-containing organic compounds.
  • a silicone compound is directly applied to a fiber surface to reduce a surface friction or to increase a surface tenacity.
  • this treatment is applied to the wholly aromatic polyamide fiber surface, however, the effect of the treatment is only temporary. Also, a large amount of the silicone compound must be applied to the fiber surface. This phenomenon is due to a poor affinity of the usual silicone compound to the wholly aromatic polyamide fiber surface.
  • the fine inorganic particles fixed on the fiber surface exhibit a high affinity to the cationic organic compounds or a specific organic silicone compounds having two or more different types of reactive radicals.
  • the cationic organic compound may be a modified silicone compound having an amino radical or a tert-onium radical.
  • the organic cationic silicone compound exhibits a very high reactivity to the cation-exchanging inorganic fine particles and form a very stable and durable film on the fiber surface. That is, the film of the organic cationic silicone compounds has a high resistance to water-washing, laundering and dry cleaning, and is effective for decreasing surface friction and increasing a surface tenacity of the fiber.
  • an amino-modified silicone compound when applied in an amount of 1.0% or less based on the non-surface modified fiber, a friction between fibers is significantly decreased.
  • an amino-modified silicone polymer having a molecular weight of 10,000 or less is applied in an amount of less than 1.0% based on the non-surface modified fiber, the resultant surface-modified fiber exhibits a significantly enhanced surface tenacity.
  • the fine organic particles of the cation-exchanging inorganic material are effective for imparting an enhanced bonding or adhesive activity to the wholly aromatic polyamide fiber surface which, per se, has a very poor bonding or adhesive property.
  • a polyalkylene amine compound is usable as a bonding agent for polyester fibers or aramide fibers with a rubber material.
  • the bonding property of the aramide fiber surface to the polyalkylene amine compound can be increased by applying the cation-exchanging fine inorganic particles to the fiber surface. This is true not only for the polyalkylene amine compounds but also for polyamide amine compounds and aminosilane compounds.
  • the cationic organic compounds usable for the present invention include epoxy-containing-amino compounds, for example, tetraepoxy compounds of xylylene diamine and cyclohexylene diamine which are available under trademarks of TETRAD-X® and TETRAD-C®, made by Mitsubishi Gas Chemical Co., Inc.; tetraepoxy compounds of diethylenetriamine; which is available under a trademark of EPO TOHTO Y-H-434, made by Tohto Kasei K.K., and tetraepoxy compounds of aromatic diamines which are available under trademarks of Sumiepoxy ELM-434 and ELM-434HV, made by Sumitomo Chemical.
  • epoxy-containing-amino compounds for example, tetraepoxy compounds of xylylene diamine and cyclohexylene diamine which are available under trademarks of TETRAD-X® and TETRAD-C®, made by Mitsubishi Gas Chemical Co., Inc.
  • the cationic organic compound include tert-cationic onium radical-modified organic compounds and polymers, for example, water soluble, tert-onium radical-containing polyurethane polymers.
  • the above-mentioned cationic organic compounds can be firmly fixed by the cation-exchanging sites of the fine inorganic particles applied to the wholly aromatic polyamide fiber surface to modify the fiber surface to that having a high durable abrasion resistance and an enhanced durable bonding property.
  • the surface of the wholly aromatic polyamide fiber can be imparted a specific property and function of the cationic organic compound in accordance with the present invention.
  • the fine inorganic particle-applied fiber surface is treated with an organic silicone compound having two or more different types of reactive radicals.
  • the organic silicone compound is preferably selected from silane-coupling compounds of the general formula (2): R m - Si - X l (2) where R represents a member selected from the group consisting of epoxy, amino, isocyanate and vinyl radicals X represents a member selected from the group consisting of methoxy, ethoxy and ethylene-glycol monoether radicals, l and m respectively represent an integer of 1, 2 or 3, and the sum of l and m must be 4.
  • the silicone compounds of the formula (2) are, for example, ⁇ -glycidyldoxpropyltrimethoxy silane, ⁇ -amino-propyltriethoxy silane, and vinyltrimethoxy silane.
  • the additive is applied in an amount of 0.1 to 5% based on the weight of the non-surface modified fiber.
  • the additive of the present invention may be applied alone or together with another fiber treating agent or oiling agent.
  • the additive of the present invention is applied in the form of a straight, an aqueous emulsion or an organic solvent solution, and in a usual manner, for example, roller coating, spraying or metalling extrusion.
  • the fine inorganic particle-applied fiber can be treated in the form of a fiber, filament yarn, paper-like sheet, nonwoven fabric, woven fabric or knitted fabric by the additive.
  • the additive-treated fiber or fiber material may be heat-treated at an elevated temperature, for example, 120°C to 150°C, for 30 sec to 180 sec.
  • the surface-modified wholly aromatic polyamide fiber is advantageous in the following points.
  • the resistances of the modified surface of the wholly aromatic polyamide fiber to water-washing and detergent-laundering, the strength of the surface-modifying coating membrane, and the bonding property of the surface-modified fiber are tested as follows.
  • a specimen (surface-modified fibers) in an amount of about 3 g was treated with ultrasonic vibration in a solution of 1% by weight of a non-ionic surface active agent consisting of nonylphenol attached with 10 moles of ethylene oxide par mole of the nonyl phenol, at a liquor ratio of 1:100 and at room temperature for one minute or ten minutes.
  • a non-ionic surface active agent consisting of nonylphenol attached with 10 moles of ethylene oxide par mole of the nonyl phenol
  • a specimen consisting of about 3 g of fibers adhered with cation-exchanging fine inorganic particles was treated with cyclohexane at the boilding temperature thereof for 3 hours.
  • the surface tenacity of the surface-modified fibers was represented by a static friction between the fibers.
  • a fiber 1 was loaded at an end thereof with a weight of 1 kg, the fiber 1 was then wound around a pully 3, twisted on a heating plate 4 at room temperature or 200°C at a twist number n, and then taken up through a taking up roller 5 at a speed of 10 cm/min.
  • a taking up tension T2 created on the fiber 1 was measured by a tension meter 2.
  • the coming-in portion of the fiber 1 intersected the going-out portion thereof at an intersecting angle of 20 degrees.
  • the static friction in kg between the coming-in and going-out portions of fiber 1 was determined from the tension (T2-1).
  • the bonding property of the surface-modified fibers was represented by a retention of tensile strength of the fibers.
  • An adhesive solution was prepared in accordance with the following composition.
  • Composition of adhesive agent Component Concentration (% by wt) Amount (part by wt) Water 100 223.5 Resorcinol 100 17.0 Formaldehyde 37 5.6 Sodium hydroxide 10 1.3
  • Surfactant 20 90.0 Note: Latex (1) Trademark: Nippol 2518FS, made by Nihon Zeon Co. Latex (2) Trademark: Nippol LX-112, made by Nihon Zeon Co. Surfactant Trademark: PEXUL, made by Nihon ICI Co.
  • the solid content of the adhesive solution was adjusted to 16% by weight.
  • a cord consisting of surface-modified fibers was immersed in the adhesive solution, and the cord impregnated with the adhesive solution was dried at 100°C for 2 minutes at a fixed length, heat set at 230°C for one minute while allowing the cord to shrink at a shrinkage of 3%, and then wound around a bobbin.
  • T S1 represents the tensile strength of the non-bonded cord
  • T S2 represents the tensile strength of the bonded cord
  • Example 1 to 3 a wholly aromatic polyamide copolymer produced from terephthalic acid dichloride, p-phenylene diamine and 3,4'-diaminodiphenylether was converted to a non-drawn multifilament bundle having a yarn count of 1100 dtex (1000 denier)/667 filaments by usual spinning method and the multifilament bundle was repeatedly washed with water.
  • the multifilament bundle was immersed in an aqueous dispersion of 3% by weight of bentonite particles having an average size of 1.5 ⁇ m so that 0.42% by dry weight of bentonite particles were adhered to the fiber surfaces.
  • the bentonite particle-adhered multifilament bundle was drawn at a high temperature of 500°C at a draw ratio of 10.
  • the drawn filaments exhibited a tensile strength of 265 mN/1.1 dtex (27 g/d) and an ultimate elongation of 4.9%.
  • the bentonite particle-adhered multifilament bundle was treated by an aqueous emulsion of 10% by weight of an amino-modified polysiloxane having a viscosity of 1300 mPa ⁇ s (cst) at room temperature and an amine equivalent of 1700 in Example 1, a viscosity of 2600 mPa ⁇ s (cst) at room temperature and an amino equivalent of 150000 in Example 2 and a viscosity of 3000 mPa ⁇ s (cst)at room temperature and an amino equivalent of 1700, so that the amino-modified polysiloxane adhered at a dry weight of about 0.7% on the filament surfaces.
  • an amino-modified polysiloxane having a viscosity of 1300 mPa ⁇ s (cst) at room temperature and an amine equivalent of 1700 in Example 1, a viscosity of 2600 mPa ⁇ s (cst) at room temperature and an amino equivalent of 150000 in Example 2
  • the multifilament bundle was further treated with an additional aqueous emulsion containing 15% by weight of an oiling agent consisting of 60 parts by weight of isostearyl stearate, 10 parts by weight of dioleyl adipate, 15 parts by weight of hardened castor oil ether added with 20 moles of ethyleneoxide, 10 parts by weight of nonylphenyl ether added with 5 moles of ethylene oxide, and 5 parts by weight of sodium dioctylsulfosuccinate so that 1.5% by dry weight of the oiling agent adhered to the filament surfaces.
  • an oiling agent consisting of 60 parts by weight of isostearyl stearate, 10 parts by weight of dioleyl adipate, 15 parts by weight of hardened castor oil ether added with 20 moles of ethyleneoxide, 10 parts by weight of nonylphenyl ether added with 5 moles of ethylene oxide, and 5 parts by weight of sodium dioctylsulfosuccinate so that 1.
  • Comparative Example 1 the same procedures as in Example 1 were carried out except that the amino-modified polysiloxane was replaced by dimethyl polysiloxane.
  • Comparative Example 2 the same procedures as in Example 1 were carried out except that the amino-modified polysiloxane treatment was omitted.
  • Comparative Example 3 the same procedures as in Example 2 were carried out except that the bentonite treatment was omitted.
  • Table 1 clearly shows that the surface modified fibers in accordance with the present invention exhibited a remarkably enhanced surface tenacity, i.e., a remarkably reduced static friction between fibers.
  • Example 4 the same procedures as those described in Example 1 were carried out except that in the treatment of the bentonite-adhered and drawn multifilament bundle, the amino-modified polysiloxane was replaced by an aqueous solution of a polyethyleneimine having a molecular weight of 1800 and a viscosity of 8500 to 15000 mPa ⁇ s (cps) at 25°C and available under a trademark of SP-018, made by Nihon Shokubai K.K., in Example 4; a molecular weight of 10,000 and a viscosity of 100,000 or more mPa ⁇ s (cps)at 25°C and available under a trademark of SP-200, made by Nihon Shokubai K.K.
  • Example 5 a molecular weight of 70,000 and a viscosity of a 30% aqueous solution thereof of 400 to 900 mPa ⁇ s (cps) at 25°C and available under a trademark of P-1000, made by Nihon Shokubai K.K., in Example 6.
  • the oiling agent adhered in an amount of 1.5% by dry weight to the fiber surfaces.
  • Comparative Example 4 the same procedures as in Example 4 were carried out except that the polyethyleneimine treatment was omitted.
  • Table 2 clearly shows that the surface-modified fiber cords of the present invention exhibited an excellent peeling strength of about twice that of Comparative Example 4.
  • Example 4 The same procedures as in Example 4 were carried out except that the bentonite treatment was omitted.
  • the multifilament bundle was impregnated with an aqueous dispersion containing 1% by weight of fine inorganic particles consisting of 80 parts by weight of talc (hydrated magnesium silicate) particles and 20 parts by weight of hydrated aluminum silicate and having a particle size of 3 ⁇ m or less, and the impregnated multifilament bundle was dried by blowing hot air at a temperature of 300°C, so that the multifilament bundle was impregnated with about 1% by weight of dry particles.
  • talc hydrated magnesium silicate
  • the dried undrawn multifilament bundle was drawn, before winding, on a heating plate having a length of 200 cm, at a temperature of 360°C and a draw ratio of 2.0, and then on another heating plate having a length of 300 cm, at a temperature of 500°C and a draw ratio of 5.0.
  • the resultant drawn multifilament bundle had a yarn count of 550 dtex (500 denier)/333 filaments.
  • the above-mentioned aqueous dispersion of the fine inorganic particles was prepared by mixing the talc particles having an average size of 3 ⁇ m with hydrated aluminum silicate particles having an average size of 3 ⁇ m and available under a trademark of Osmos N®, made of Shiraishi Kogyo K.K., uniformly dispersing the mixture in an aqueous solution containing 3% of sodium heyametaphosphate based on the total weight of the fine inorganic particle mixture, while stirring the dispersion.
  • the fine inorganic particle-adhered multifilament bundle was further impregnated with an aqueous solution containing 3% by weight of ⁇ -glycidoxypropyltrimethoxysilane, which was available under a trademark of Dianasilane GLYMO, made of Dynamite Nobel Co., and the further impregnated multifilament bundle was dried by blowing hot air at a temperature of 130°C for 120 seconds.
  • the amount of the ⁇ -glycidoxypropyltrimethoxysilane adhered to the multifilament bundle was 0.3 to 1.5% based on the weight of the non-modified multi-filament bundle.
  • a surface-modified multifilament bundle was obtained.
  • the surface-modified multifilament bundle was cut to form short fibers having a length of 2 to 6 mm.
  • the short fibers were converted to a paper-like sheet containing 5% to 20%, based on the total weight of the short fibers, of a binder consisting of 80% to 95% by weight of an water-soluble epoxy resin and 5% to 20% by weight of a water-soluble melamine-formaldehyde resin.
  • the sheet was calendered by a pair of calender rolls.
  • the resultant short fiber paper-like sheet was usable as a substrate for an epoxy resin-impregnated prepreg, a polyimide resin-impregnated pregreg or a cyanurate resin-impregnated pregreg.
  • the base material i.e., the paper-like sheet
  • the base material was subjected to a tensile strength test in a dry condition, a tensile strength test in a DMF-wetted condition, and a bulk density test.
  • the processability of the laminate board was tested in a manner such that a round hole having a diameter of 2 mm was formed in a laminate board having a thickness of 0.4 mm by drilling, and the conditions of the hole were observed. It was found that, in the laminate boards of Examples 7 to 13, the holes were easily formed and the inside faces of the holes were smooth.

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Claims (11)

  1. Oberflächenmodifizierte, vollaromatische Polyamidfaser, umfassend:
    eine Fasermatrix, welche ein vollaromatisches Polyamidmaterial umfaßt;
    feine anorganische Partikel, die auf und in einem Oberflächenbereich der Matrix verteilt sind und mindestens ein anorganisches Kationenaustauschermaterial umfassen; und
    ein Additiv, welches an den feinen anorganischen Partikeln angebracht ist,
    dadurch gekennzeichnet, daß das Additiv, wie es angebracht ist, mindestens ein Element umfaßt, welches aus der Gruppe ausgewählt ist, die besteht aus: kationischen, organischen Verbindungen und organischen Silikonverbindungen mit mindestens zwei verschiedenen Typen von reaktiven Radikalen.
  2. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der das vollaromatische Polyamidmaterial mindestens einen Polymertyp umfaßt, welcher 80 bis 100 Mol-% von wiederkehrenden Haupteinheiten gemäß der Formel (1) aufweist:



            -NH-Ar₁-NHCO-Ar₂-CO-   (1),



    wobei Ar₁ und Ar₂ jeweils und unabhängig voneinander für ein Element stehen, welches ausgewählt ist aus der Gruppe, die aus den Bestandteilen gemäß den (folgenden) Formeln besteht:
    Figure imgb0008
     in denen R¹ und R² jeweils und unabhängig voneinander für ein Element stehen, welches aus der Gruppe ausgewählt ist, die besteht aus Halogenidatomen und niedrigeren Alkylradikalen mit 1 bis 2 Kohlenstoffatomen, und wobei n für Null oder eine ganze Zahl von 1 bis 4 steht.
  3. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 2, in der die wiederkehrenden Haupteinheiten gemäß Formel (1) die Bestandteile gemäß den Formeln (A) und (B) in dem Gesamtgehalt von 80 bis 100 Mol-% und die Bestandteile gemäß der Formel (B) in einem Gehalt von 10 bis 40 Mol-%, bezogen auf den Gesamtgehalt an den Bestandteilen, umfaßt, die durch Ar₁ und Ar₂ dargestellt sind.
  4. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der die feinen anorganischen Partikel eine Größe von 0,01 bis 5 µm haben.
  5. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der die feinen anorganischen Partikel in einer Menge von 0,1 bis 5 %, bezogen auf das Gewicht der Fasermatrix, vorhanden sind.
  6. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der das anorganische Kationenaustauschermaterial mindestens ein Element umfaßt, welches aus der Gruppe ausgewählt ist, die besteht aus Siliziumoxyd-Aluminiumoxyd, Siliziumoxyd-Magnesiumoxyd, Bentonit, Kaolin, Fullersche Erde, aktiviertem Ton, Montmorilonit, Halloysit, Talk und einer Mischung aus einem anorganischen Material, die als Hauptkomponente hydriertes Magnesiumsilikat umfaßt sowie ein hydriertes, gelbildendes anorganisches Material.
  7. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 6, bei der das hydrierte, gelbildende anorganische Material als Hauptkomponente ein Aluminiumsilikat umfaßt.
  8. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der das Additiv in einer Menge von 0,1 bis 5 %, bezogen auf das Gewicht der Fasermatrix, vorhanden ist.
  9. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der die kationische, organische Verbindung ausgewählt ist aus der Gruppe, die besteht aus:
    einer Tetraepoxyverbindung des Xylylendiamins, einer Tetraepoxyverbindung des Cyclohexylendiamins, einer Tetraepoxyverbindung des Diäthylentriamins, Tetraepoxyverbindungen aromatischer Diamine und wasserlöslichem Polyurethan mit quaternären kationischen Radikalen.
  10. Oberflächenmodifizierte, vollaromatische Polyamidfaser nach Anspruch 1, bei der die organische Silikonverbindung ausgewählt ist unter denjenigen gemäß der (folgenden) allgemeinen Formel (2):



            Rm-Si-Xℓ   (2),



    in der R für ein Element steht, welches aus der Gruppe ausgewählt ist, die besteht aus Epoxy-, Amino-, Isocyanat- und Vinylradikalen, in der X für ein Element steht, welches aus der Gruppe ausgewählt ist, die besteht aus Methoxy-, Äthoxy- und
    Äthylenglykolmonoäther-Radikalen und in der ℓ und m jeweils für die ganze Zahl 1, 2 oder 3 stehen, wobei die Summe von ℓ und m 4 ist.
  11. Verfahren zum Herstellen einer oberflächenmodifizierten, vollaromatischen Polyamidfaser, umfassend:
    im Zuge eines Spinnschrittes, mindestens eines Streckschrittes und mindestens eines Wärmebehandlungsschrittes wird ein vollaromatisches Polyamidmaterial in eine Faser umgewandelt; und
    in irgend einer Stufe nach dem Spinnschritt werden an der Oberfläche der Faser feine anorganische Partikel angebracht, welche mindestens ein anorganisches Kationenaustauschermaterial umfassen; und
    die feinen anorganischen Partikel, die an der Oberfläche der Faser haften, werden mit einem Additiv behandelt, um zu bewirken, daß das Additiv an den feinen anorganischen Partikeln angebracht wird,
    dadurch gekennzeichnet, daß das Additiv, so wie es angebracht wird, mindestens ein Element umfaßt, welches aus der Gruppe ausgewählt wird, die besteht aus kationischen, organischen Verbindungen und organischen Silikonverbindungen mit mindestens zwei verschiedenen Typen von reaktiven Radikalen.
EP19890103472 1988-03-02 1989-02-28 Oberflächenmodifizierte, vollaromatische Polyamidfaser und Verfahren zu ihrer Herstellung Expired - Lifetime EP0332919B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP47561/88 1988-03-02
JP4756188A JPH0778309B2 (ja) 1988-03-02 1988-03-02 表面変性全芳香族ポリアミド繊維
JP5494688A JPH01239168A (ja) 1988-03-10 1988-03-10 表面改質芳香族ポリアミド繊維の製造方法
JP54946/88 1988-03-10

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EP0332919A2 EP0332919A2 (de) 1989-09-20
EP0332919A3 EP0332919A3 (de) 1991-11-21
EP0332919B1 true EP0332919B1 (de) 1994-01-19

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US11279794B2 (en) 2017-12-15 2022-03-22 Nanjing Forestry University Aramid-based epoxy resin and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2105091C (en) * 1991-03-01 2002-10-29 Serge Rebouillat Surface treated aramid fibers and a process for making them
US5298028A (en) * 1992-06-17 1994-03-29 E. I. Du Pont De Nemours And Company Method of making a yarn of particulate-impregnated aramid fibers
US5552221A (en) * 1994-12-29 1996-09-03 The Dow Chemical Company Polybenzazole fibers having improved tensile strength retention
KR970027518A (ko) * 1995-11-03 1997-06-24 이웅열 전방향족 폴리아미드 펄프의 제조방법
DE10039671A1 (de) * 2000-08-14 2002-03-07 Henkel Kgaa Haftaktivierte Polymerfaser und Zubereitung zur Herstellung einer solchen
US8575045B1 (en) 2004-06-10 2013-11-05 The United States Of America As Represented By The Secretary Of The Army Fiber modified with particulate through a coupling agent
US7718220B2 (en) * 2007-06-05 2010-05-18 Johns Manville Method and system for forming reinforcing fibers and reinforcing fibers having particulate protuberances directly attached to the surfaces

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SE308500B (de) * 1962-12-31 1969-02-17 Monsanto Chemicals
EP0121132B1 (de) * 1983-03-07 1987-01-21 Teijin Limited Verfahren zum Herstellen von unter Spannung wärmebehandelten, völlig aromatischen Polyamidfäden
US4720398A (en) * 1984-03-19 1988-01-19 Akzo Nv Process for the improvement of the adhesion to rubber or a thermoplastic elastomer of synthetic yarns, cords or fabrics made therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11279794B2 (en) 2017-12-15 2022-03-22 Nanjing Forestry University Aramid-based epoxy resin and preparation method thereof

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DE68912367T2 (de) 1994-09-01
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EP0332919A3 (de) 1991-11-21

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