EP0332919A2 - Oberflächenmodifizierte, vollaromatische Polyamidfaser und Verfahren zu ihrer Herstellung - Google Patents

Oberflächenmodifizierte, vollaromatische Polyamidfaser und Verfahren zu ihrer Herstellung Download PDF

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Publication number
EP0332919A2
EP0332919A2 EP89103472A EP89103472A EP0332919A2 EP 0332919 A2 EP0332919 A2 EP 0332919A2 EP 89103472 A EP89103472 A EP 89103472A EP 89103472 A EP89103472 A EP 89103472A EP 0332919 A2 EP0332919 A2 EP 0332919A2
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EP
European Patent Office
Prior art keywords
fiber
aromatic polyamide
wholly aromatic
modified
polyamide fiber
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Application number
EP89103472A
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English (en)
French (fr)
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EP0332919B1 (de
EP0332919A3 (de
Inventor
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
Application filed by Teijin Ltd filed Critical Teijin Ltd
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Publication of EP0332919A3 publication Critical patent/EP0332919A3/de
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Publication of EP0332919B1 publication Critical patent/EP0332919B1/de
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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 and a method of producing same. More particularly, the present invention relates to a wholly aromatic polyamide fiber surface-modified with a 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.
  • 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
  • Japanese Unexamined Patent Publication (Kokai) No. 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 of hypochlorous acid.
  • Japanese Unexamined Patent Publication (Kokai) No. 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.
  • Japanese Unexamined Patent Publica­tion (Kokai) No. 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 surface-modified wholly aromatic polyamide fiber of the present invention which comprises: 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 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 above-mentioned surface-modified wholly aromatic polyamide fiber can be produced by the method of the present invention which comprises: converting a wholly aromatic polyamide material to a fiber through a spinning (fiber forming) 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-exchainging inorganic material to surface of the fiber; and treating the fine inorganic particles adhered to the surface of the fiber with an additive comprising at least one member selected from the group consisting of cationic organic compounds and organic silicone compounds having at last two different types of reactive radicals to cause the additive to be attached to the fine inorganic particles.
  • 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 lowe 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 in
  • 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)
  • 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, as disclosed by British Patent No. 1,501,948, U.S. Patent No. 3,733,964 or Japanese Unexamined Patent Publication No. 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 conponent, 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 thefine 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 compond 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, ⁇ -glycidyldoxypropyltrimethoxy 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 per mole of the nonyl phenol, at a liquor 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 per 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 boiling 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
  • Latex (1) 40 90.0 Latex (2) 40 22.5
  • 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
  • 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 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 cst at room temperature and an amine equivalent of 1700 in Example 1, a viscosity of 2600 cst at room temperature and an amino equivalent of 150000 in Example 2 and a viscosity of 3000 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.
  • 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 amono-­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 Example No. Resistance to Static Friction between fibers Water washing Organic solvent With oiling agent After removing oiling agent 20°C 200°C 20°C 200°C Example 1 3 3 1260 1900 1250 1900 2 3 3 1200 1760 1210 1850 3 3 3 1230 1800 1200 1810 Comparative Example 1 2 1 1350 2050 Broken Broken 2 1 1 1860 Broken Broken Broken 3 1 1 1300 Broken Broken Broken
  • 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 cps at 25°C and available under a trademark of SP-018, made by Nihon Shokubai K.K., in Example 8; a molecular weight of 10,000 and a viscosity of 100,000 or more 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 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 2 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 tht 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 dired 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 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 hexametaphosphate 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 multi­filament 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 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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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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
JP54946/88 1988-03-10
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

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

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Cited By (7)

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WO1993025748A1 (en) * 1992-06-17 1993-12-23 E.I. Du Pont De Nemours And Company Making a yarn of particulate-impregnated aramid fibers
US5275625A (en) * 1991-03-01 1994-01-04 E. I. Du Pont De Nemours And Company Surface treated aramid fibers and a process for making them
US5552221A (en) * 1994-12-29 1996-09-03 The Dow Chemical Company Polybenzazole fibers having improved tensile strength retention
WO1997016596A1 (en) * 1995-11-03 1997-05-09 Kolon Industries, Inc. Method for preparing wholly aromatic polyamide pulp
WO2002014409A1 (de) * 2000-08-14 2002-02-21 Henkel Kommanditgesellschaft Auf Aktien Haftaktivierte polymerfaser und zubereitung zur herstellung einer solchen
US20100196697A1 (en) * 2007-06-05 2010-08-05 D Silva Sean Charles Method and system for forming reinforcing fibers and reinforcing fibers having particulate protuberances directly attached to the surfaces
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

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Publication number Priority date Publication date Assignee Title
CN108047429B (zh) 2017-12-15 2020-12-25 南京林业大学 一种芳纶基环氧树脂及其制备方法

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CH435529A (fr) * 1962-12-31 1967-05-15 Monsanto Chemicals Procédé de traitement des noeuds de fils de polyamides destiné à empêcher la tendance au glissement de ces noeuds
EP0121132A1 (de) * 1983-03-07 1984-10-10 Teijin Limited Verfahren zum Herstellen von unter Spannung wärmebehandelten, völlig aromatischen Polyamidfäden
EP0168066A1 (de) * 1984-03-19 1986-01-15 Akzo N.V. Verfahren zur Verbesserung der Haftung von synthetischen Fasern, Bindfäden oder daraus hergestellten Geweben an Gummi oder einem thermoplastischen Elastomer

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CH435529A (fr) * 1962-12-31 1967-05-15 Monsanto Chemicals Procédé de traitement des noeuds de fils de polyamides destiné à empêcher la tendance au glissement de ces noeuds
EP0121132A1 (de) * 1983-03-07 1984-10-10 Teijin Limited Verfahren zum Herstellen von unter Spannung wärmebehandelten, völlig aromatischen Polyamidfäden
EP0168066A1 (de) * 1984-03-19 1986-01-15 Akzo N.V. Verfahren zur Verbesserung der Haftung von synthetischen Fasern, Bindfäden oder daraus hergestellten Geweben an Gummi oder einem thermoplastischen Elastomer

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US5275625A (en) * 1991-03-01 1994-01-04 E. I. Du Pont De Nemours And Company Surface treated aramid fibers and a process for making them
US5443896A (en) * 1991-03-01 1995-08-22 E. I. Du Pont De Nemours And Company Surface treated aramid fibers and a process for making them
WO1993025748A1 (en) * 1992-06-17 1993-12-23 E.I. Du Pont De Nemours And Company 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
WO1997016596A1 (en) * 1995-11-03 1997-05-09 Kolon Industries, Inc. Method for preparing wholly aromatic polyamide pulp
WO2002014409A1 (de) * 2000-08-14 2002-02-21 Henkel Kommanditgesellschaft Auf Aktien 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
US20100196697A1 (en) * 2007-06-05 2010-08-05 D Silva Sean Charles Method and system for forming reinforcing fibers and reinforcing fibers having particulate protuberances directly attached to the surfaces

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EP0332919B1 (de) 1994-01-19
EP0332919A3 (de) 1991-11-21
DE68912367T2 (de) 1994-09-01
DE68912367D1 (de) 1994-03-03

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