WO2018037658A1 - 撚糸、開繊糸、炭素繊維被覆撚糸、及びそれらの製造方法 - Google Patents
撚糸、開繊糸、炭素繊維被覆撚糸、及びそれらの製造方法 Download PDFInfo
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- WO2018037658A1 WO2018037658A1 PCT/JP2017/020374 JP2017020374W WO2018037658A1 WO 2018037658 A1 WO2018037658 A1 WO 2018037658A1 JP 2017020374 W JP2017020374 W JP 2017020374W WO 2018037658 A1 WO2018037658 A1 WO 2018037658A1
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- Prior art keywords
- carbon fiber
- yarn
- twisted yarn
- covering
- spread
- Prior art date
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Images
Classifications
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/06—Threads formed from strip material other than paper
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/16—Yarns or threads made from mineral substances
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
- D02G3/28—Doubled, plied, or cabled threads
- D02G3/286—Doubled, plied, or cabled threads with alternatively "S" and "Z" direction of twist, e.g. Self-twist process
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/36—Cored or coated yarns or threads
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/38—Threads in which fibres, filaments, or yarns are wound with other yarns or filaments, e.g. wrap yarns, i.e. strands of filaments or staple fibres are wrapped by a helically wound binder yarn
-
- 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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
-
- 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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
- D02G3/402—Yarns in which fibres are united by adhesives; Impregnated yarns or threads the adhesive being one component of the yarn, i.e. thermoplastic yarn
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
Definitions
- the present invention is a twisted yarn formed by twisting a plurality of carbon fiber resins formed by slitting from a carbon fiber resin tape, a spread yarn in which a covering yarn is wound in S and Z around the outer periphery of the twisted yarn, and a twisted yarn on the outer periphery of the core material
- the present invention relates to a carbon fiber-coated twisted yarn formed by winding and a manufacturing method thereof.
- carbon fibers There are many types of carbon fibers from 1K to 64K, and use is selected depending on the application. For example, if it is 12K, it is composed of 12,000 carbon fiber bundles and is twisted into one bundle by sizing (gluing). It is disclosed in International Publication No. 2016/068210 (PCT / JP2015 / 080450) filed by the present applicant that a fiber tape is opened and a resin tape is manufactured by using a fiber opening device or the like for these carbon fiber bundles. Has been.
- the carbon fiber resin tape Since the carbon fiber resin tape has a high tensile strength, is light and strong, the carbon fiber resin tape is used in various products utilizing a double-sided adhesive tape and the like. I tried to use it.
- the present invention has a twist yarn formed by twisting a plurality of carbon fiber resins obtained by slitting a carbon fiber resin tape, and a twist yarn comprising a carbon fiber resin tape and a cover yarn.
- One embodiment of the present invention is a twisted yarn formed by twisting a carbon fiber resin obtained by slitting a carbon fiber resin tape, and a spread yarn obtained by winding S and Z windings of a covering yarn around the outer periphery of the twisted yarn, more specifically, a twisted yarn and
- the present invention relates to a spread yarn in which a covering yarn is wound in S and Z on a twisted yarn.
- Another embodiment of the present invention relates to a carbon fiber-coated twisted yarn obtained by winding a carbon fiber resin formed by slitting a core material with a carbon fiber resin tape.
- the present invention includes a first step of spreading a carbon fiber bundle flatly by immersing a carbon fiber bundle having a plurality of carbon fibers in reduced water having a negative redox potential; After the first step, the carbon fiber bundle is immersed in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate, or an adhesive solution containing an adhesive, alumina sol, and benzoyl.
- a second step to perform After the second step, a third step of producing a carbon fiber resin tape for drying the carbon fiber bundle,
- a method for producing a twisted yarn comprising a fourth step of slitting a carbon fiber resin tape and applying a twist of 15 to 80 times / m to a plurality of slitted carbon fiber resins to form a twisted yarn,
- the present invention relates to a method for producing a spread yarn including a fifth step of winding a covering yarn with Z winding.
- the present invention includes a first step in which a carbon fiber bundle having a plurality of carbon fibers is immersed in reducing water having a negative oxidation-reduction potential to spread the carbon fiber bundle flatly, After the first step, either the carbon fiber bundle, the carbon fiber bundle, an adhesive solution containing an adhesive, alumina sol, and potassium persulfate, or an adhesive solution containing an adhesive, alumina sol, and benzoyl.
- the present invention relates to a method for producing a carbon fiber-covered twisted yarn comprising a fifth step of winding a twisted yarn comprising a carbon fiber resin tape around the outer periphery of a core material, one covering wire being wound with S and the other being wound with Z.
- the present invention relates to a method for producing a resin-coated yarn comprising a step of cutting a spread fiber or a carbon fiber-covered twisted yarn, and a step of combining and extruding the cut spread fiber or twisted yarn with a resin.
- One embodiment of the present invention is a twisted yarn obtained by twisting a plurality of carbon fiber resins formed by slitting from a carbon fiber resin tape, and a spread yarn in which a covering yarn is wound S and Z around the outer periphery of the twisted yarn. Yes, it is strong in bending and pulling force and can be used for various applications.
- a carbon fiber-covered twisted yarn obtained by winding a twisted yarn obtained by twisting a carbon fiber resin formed by slitting a carbon fiber resin tape around a core material such as a yarn into a light weight and four times as much as stainless steel. A twisted yarn having strength can be obtained.
- the covering yarn may be one or more selected from nylon fiber, polytetrafluoroethylene, aramid fiber, stainless steel material, or Inconel (registered trademark) wire.
- the core yarn around which a plurality of carbon fiber resins formed by slitting from a carbon fiber resin tape is wound uses Kepler (registered trademark), Teflon (registered trademark), aramid fiber, tough crease (registered trademark), or the like. May be.
- the carbon fiber resin tape produced through the first step to the third step comprises an adhesive and an alumina sol dried on the surface and gap of the produced carbon fiber.
- potassium persulfate the adhesive strength of the carbon fiber resin tape is increased when an adhesive is used.
- a plurality of carbon fiber resin tapes are laminated with the adhesive removed to form a three-dimensional shape, there is no need to pressurize with high pressure, and even when heated, high adhesion is achieved by heating at 100 ° C. or less. Power is obtained.
- the carbon fiber resin tape manufactured through the third step is slit-processed in the fourth step, and a twisted yarn is manufactured by applying a twist of 15 to 80 times / m to the slit-processed plural carbon fiber resins.
- This twisted yarn is strong and can be used for various purposes.
- the twisted yarn manufactured in the fourth step of the present invention is further manufactured in the fifth step by winding two covering yarns around the outer periphery of the twisted yarn, one with S winding and the other with Z winding. .
- Covering with two covering yarns in the fifth step yields a spread yarn that has high durability against bending and tension.
- the method for producing a spread yarn of the present invention can produce a yarn having higher bending resistance by winding a covering yarn around a twisted yarn at equal intervals of 4 mm to 6 mm.
- a twisted yarn formed by twisting a carbon fiber resin formed by slitting from a carbon fiber resin tape around a core material such as a yarn can be wound to obtain a carbon fiber-coated twisted yarn having strength compared to a conventional yarn. it can.
- the low melting point thermoplastic resin is coat
- the carbon fiber resin constituting the twisted yarn is obtained by coating the outer peripheral surface of the spread yarn (specifically, the outer peripheral surface of the layer wound with the covering yarn) with the low melting point thermoplastic resin. The bonding force between the twisted yarn and the covering yarn is improved together with the bonding force between the two.
- the low-melting point thermoplastic resin is coated on the outer peripheral surface of the carbon fiber-coated twisted yarn (specifically, the outer peripheral surface of the layer formed by wrapping the carbon fiber resin). Bonding power is improved.
- the low-melting point thermoplastic resin covering them melts and is adjacent to the low-melting point thermoplastic resin. They are bonded to each other. Thereby, it is possible to process into the article
- the step of coating the twisted yarn, the spread yarn, and the carbon fiber-covered twisted yarn with the low-melting point thermoplastic resin pushes the low-melting point thermoplastic resin together with these from the nozzle while contacting the outer peripheral surface. Is possible. Thereby, while being able to improve the intensity
- a twisted yarn comprising a plurality of carbon fiber resins formed by slitting (cutting) from the carbon fiber resin tape according to the first embodiment of the present invention, and a covering yarn is wound in S and Z around the outer periphery of the twisted yarn.
- the carbon fiber resin tape used in the present invention is a carbon fiber resin tape manufactured by the manufacturing method described in International Publication No. 2016/068210 (PCT / JP2015 / 080450) filed separately by the present applicant.
- a twisted yarn formed by twisting a plurality of carbon fiber resins formed by slitting the carbon fiber resin tape is manufactured.
- the covering yarn may be one or more selected from nylon fibers such as nylon 6 and nylon 66, polytetrafluoroethylene, aramid fiber, stainless steel material such as SUS316L, or Inconel (registered trademark) wire.
- Inconel is an alloy mainly composed of nickel and containing components such as chromium, iron and carbon, and is a heat-resistant and corrosion-resistant alloy used in various applications such as processed materials and cast materials. These can be arbitrarily selected according to the use conditions, temperature, chemical resistance, pressure, and repetition frequency of the spread yarn.
- the wire diameter of the cover yarn to be used is preferably 0.03 to 0.12 mm, preferably 0.03 mm for a yarn made of an inorganic material or an organic material, and 0.08 mm for a metal yarn.
- the covering yarn is wound S and Z around a twisted yarn made of carbon fiber resin tape so as to form an X shape, thereby protecting the yarn from bending.
- the S-wrapped cover yarn and the Z-wrapped cover yarn are wound so as to intersect in an X shape at equal intervals, and the interval between the intersections intersecting in the X shape is preferably 4 mm to 6 mm. If it is 4 mm or less, the material is wasted and the weight increases, resulting in a high price. If it is 6 mm or more, it will be broken when it is bent 180 degrees and will not become a yarn, and it will become a knot and become unstable. is there.
- the diameter of the finished spread yarn is preferably 0.15 mm to 2.5 mm.
- Another embodiment of the present invention is a carbon fiber-covered twisted yarn obtained by winding a carbon fiber resin formed by slitting a carbon fiber resin tape around a yarn as a core material.
- the winding method may be single, may be wound with S and Z, or may be biased at an angle of 45 ° or 60 °.
- carbon fiber or resin may be added to the core material to make it strong, or an infrared ray inhibitor or the like may be applied to obtain a thread having various resistances.
- a carbon fiber bundle composed of a plurality of carbon fibers is immersed in reducing water having a negative oxidation-reduction potential to spread the carbon fiber bundle flatly.
- the second step of immersing the carbon fiber bundle in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate and after the second step, the carbon fiber And a third step of drying the bundle.
- the carbon fiber bundle which consists of a plurality of carbon fibers at a 3rd process, it calls a carbon fiber resin tape.
- the carbon fiber resin tape is slitted as a fourth step, and the plurality of slit carbon fiber resins are twisted 15 to 80 times / m to form a twisted yarn.
- the spread yarn is manufactured by winding two covering yarns around the outer periphery of the twisted yarn, one with S winding and the other with Z winding.
- FIG. 1 shows a carbon fiber resin tape manufacturing apparatus used in the method for manufacturing a carbon fiber resin tape of the present invention.
- the carbon fiber resin tape manufacturing apparatus includes a yarn supplying roller 1 for feeding out the carbon fiber bundle F1 and a winding roller 8 for winding up the formed carbon fiber resin tape F2.
- the carbon fiber resin tape manufacturing apparatus includes a first tank 2 and a second tank 6 in which the carbon fiber bundle F1 is sequentially immersed between the yarn supplying roller 1 and the winding roller 8, and the second tank 6 and the winding roller. 8 is provided with a drying device 7 for drying the carbon fiber bundle F1.
- the carbon fiber resin tape manufacturing apparatus appropriately includes a roller for feeding the carbon fiber bundle F1 between the yarn feeding roller 1 and the take-up roller 8.
- the first tank 2 stores reduced water having a negative redox potential.
- the second tank 6 stores an adhesive solution containing an adhesive, alumina sol, and potassium persulfate.
- the carbon fiber bundle F ⁇ b> 1 is continuously drawn out from the yarn feeding roller 1 and immersed in water stored in the first tank 2 for a predetermined time.
- the carbon fiber bundle F1 include 3K of untwisted carbon fibers (that is, 3000 unbundle carbon fibers), 6K (6000 bundles), 12K (12000 bundles), and the like.
- the carbon fiber any of acrylic type and pitch type can be applied.
- the water stored in the first tank 2 is reduced water having a negative oxidation-reduction potential.
- Ordinary water has a positive oxidation-reduction potential (in the case of tap water: about +400 to +600 mV), but reduced water has a negative oxidation-reduction potential, small water molecule clusters, and excellent penetration.
- the carbon fiber bundle F1 is naturally expanded without being subjected to physical external force such as ultrasonic waves by being immersed in such reduced water.
- the reduced water used in the present invention preferably has a redox potential of ⁇ 800 mV or less.
- the carbon fibers constituting the carbon fiber bundle F1 can be surely spread flat in a short time to obtain a belt-like flat fiber bundle. Further, the obtained belt-like flat fiber bundle is difficult to return to its original state.
- the manufacturing method of the reduced water used in this invention is not specifically limited, For example, the following methods can be illustrated.
- Gas bubbling method> By bubbling nitrogen gas, argon gas or hydrogen gas, the oxygen concentration in the water is lowered and the oxidation-reduction potential is lowered.
- Method by adding hydrazine> By adding hydrazine, the oxygen concentration in the water is lowered and the redox potential is lowered.
- Method by electrolysis> (A) Electrolysis of water is performed by applying a high-frequency voltage with asymmetrical positive and negative peak values and / or duty ratio, and the oxidation-reduction potential is lowered.
- the electrode is composed of one ground electrode (cathode electrode) and two specially shaped electrodes (rhombus mesh electrode or hexagonal mesh electrode) made of Pt and Ti whose anode and cathode electrodes are alternately changed. Then, high-frequency voltage is applied to electrolyze water to lower the redox potential.
- the carbon fiber bundle F1 can be naturally expanded (opened) without applying a physical external force by immersing the carbon fiber bundle F1 in the reducing water as described above. Therefore, a configuration as shown in FIG. 2 may be adopted.
- FIG. 2A shows the second roller 31 among the two transport rollers 3 that support and transport the carbon fiber bundle F ⁇ b> 1 in the first tank 2.
- the cross section (cross section along the rotation axis) of the second roller 31 has a shape that swells from both ends toward the center, as indicated by the tip of the arrow drawn in the drawing. As a result, the fibers easily spread along the surface of the roller 31.
- FIG. 2 (b) is configured to convey the carbon fiber bundle F1 while bending it by providing three or more (three in the figure) conveying rollers 3 in the first tank 2, and the second and subsequent rollers.
- the second roller 32 in the figure is provided with an opening action.
- the roller 32 has a cross-sectional shape similar to that in the case of FIG. 2A so that the fibers can easily spread along the surface of the roller 32.
- a flat plate 4 is provided between transport rollers 3 that support and transport the carbon fiber bundle F1 in the first tank 2, and the carbon fiber bundle F1 is transported along the surface of the flat plate 4. In this way, the fibers are easily spread flat.
- the flat belt 5 is wound around a conveying roller 3 that supports and conveys the carbon fiber bundle F1 in the first tank 2, and the carbon fiber bundle F1 is conveyed along the surface of the flat belt 5.
- the fibers are easily spread flat.
- ⁇ Second step> The carbon fibers (flat fiber bundles) spread flatly by being immersed in the reducing water through the first tank 2 are taken out from the first tank 2 and then continuously into the second tank 6. To be introduced. An adhesive solution containing an adhesive, alumina sol, and potassium persulfate is accommodated in the second tank 6, and the flat fiber bundle obtained by being immersed in reducing water is contained in the second tank 6. In the adhesive solution.
- benzoyl may be used in place of potassium persulfate.
- potassium persulfate is used will be described, but the case where benzoyl is used is the same as potassium persulfate.
- Adhesives have hydrophilic groups and are water-soluble glue such as laundry glue, PVA (polyvinyl alcohol), PTFE dispersion, graphite nano-dispersion, glycol, water-soluble clay dispersion, starch paste, urethane type , silicon, RFL, epoxy, imide dispersed solution, OH - organic or inorganic material containing dispersed solution having a group is preferably used.
- concentration of the adhesive is lower than the predetermined range, the flatly spread carbon fiber bundle F1 may be restored.
- concentration of an adhesive agent is higher than a predetermined range, there exists a possibility that an adhesive agent may become difficult to osmose
- the concentration when the adhesive is PVA is preferably 0.5 to 30 wt%.
- the concentration of the alumina sol is preferably 0.5 to 16.7 wt%.
- the concentration ratio of PVA to alumina sol is preferably 3: 1.
- the concentration of potassium persulfate is preferably 0.5 to 10 wt%.
- the alumina shape of the alumina sol may be any of a plate shape, a column shape, a fiber shape, a hexagonal plate shape, and the like.
- the alumina fiber is a fibrous crystal of alumina, specifically, an alumina fiber formed from an anhydrous alumina and an alumina water formed from alumina containing a hydrate. Japanese fiber etc. are mentioned.
- boehmite is a crystal of alumina hydrate represented by a composition formula: Al 2 O 3 .nH 2 O.
- the crystal system of the alumina fiber can be adjusted by, for example, the type of a hydrolyzable aluminum compound described later, its hydrolysis conditions or peptization conditions.
- the crystal system of the alumina fiber can be confirmed using an X-ray diffractometer (for example, “Mac. Sci. MXP-18”, manufactured by Mac Science).
- FIG. 3 is a diagram schematically showing the steps so far.
- a carbon fiber bundle F1 composed of a plurality of carbon fibers is a flat fiber bundle in which the carbon fibers F3 are spread flat by being immersed in reducing water.
- the flat fiber bundle H is immersed in a liquid containing an adhesive, alumina sol, and potassium persulfate, so that the adhesive S, alumina sol A, and potassium persulfate B penetrate between the carbon fibers F3. .
- the above-described reduced water may be used as a solvent for dissolving the adhesive, and in this way, the penetrating power of the adhesive can be increased.
- the liquid containing an adhesive agent is made into a mist form with respect to the carbon fiber (flat fiber bundle) spread flatly by being immersed in reducing water without providing the 2nd tank 6.
- the spraying method may be adopted.
- ⁇ Third step> The spread carbon fiber bundle F1 after being immersed in the liquid containing the adhesive and the alumina sol is taken out from the second tank 6 and then supplied to the drying device 7 to be dried.
- the type of the drying device 7 is not particularly limited, and may be a heater heating device, a warm air heating device, or a heating device using far infrared rays. However, in the method according to the present invention, the drying device 7 is not necessarily provided, and natural drying may be performed.
- the carbon fiber resin tape F2 may be further washed with water, an excess adhesive agent may be removed, and it may be made to dry. Excess impurities are removed and the peel strength is improved by leaving the necessary OH ⁇ .
- the spread fiber, the adhesive that has permeated between the fibers, the alumina sol, and potassium persulfate are solidified.
- the fibers are hardened with an adhesive in a state where the fibers are spread flat, so that the carbon fiber resin tape F2 having high mechanical strength is obtained without returning to the original state even after a lapse of time.
- the carbon fiber resin tape F2 after passing through the drying device 7 and the adhesive is solidified is taken up by the take-up roller 8, thereby completing the production of the carbon fiber resin tape F2.
- the carbon fiber resin tape F2 manufactured through the third step is slitted.
- the slit process is performed once or more using a slitter machine or the like, and the carbon fiber resin tape F2 is slit (cut) to an arbitrary width and length.
- a plurality of carbon fiber resins are twisted by a twisting machine or the like to obtain a twisted yarn P, and the twist is preferably 15 to 80 times / m.
- the covering yarn C is wound at equal intervals with one S winding and the other Z winding so as to form an X shape. (Refer to i in FIG. 4) If it is 4 mm or less at this time, the material is wasted and the weight increases and the price is high, and if it is 6 mm or more, it will be broken when it is bent 180 degrees and will not become a thread, and the thread will become unstable and become unstable.
- the width (w) is wound so as to have an interval of 4 mm to 6 mm.
- the twisted yarn twisted in the fourth step is used as the core material, and the normal yarn is used as the covering yarn, but the normal yarn is used as the core material and the twisted yarn applied in the fourth step is covered.
- a carbon fiber-covered twisted yarn may be produced by forming a yarn.
- Example 1 A first step of spreading the carbon fiber bundle flatly by immersing the carbon fiber bundle having 12K carbon fiber in reducing water having a negative redox potential; After the first step, a second step of immersing the carbon fiber bundle in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate; After the second step, a 12K carbon fiber resin tape is manufactured through a third step of drying the carbon fiber bundle and manufacturing a carbon fiber resin tape.
- a 12K carbon fiber resin tape is slitted, and the 6K carbon fiber resin is twisted at 15 to 80 turns / m to form a twisted yarn. Two covering yarns, one for S and one for Z Wrapped with to produce an open yarn.
- Example 2 A first step of spreading the carbon fiber bundle flatly by immersing the carbon fiber bundle having 12K carbon fiber in reducing water having a negative redox potential; After the first step, a second step of immersing the carbon fiber bundle in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate; After the second step, a 12K carbon fiber resin tape is manufactured through a third step of drying the carbon fiber bundle and manufacturing a carbon fiber resin tape.
- a 12K carbon fiber resin tape is slitted to 6K, and further slitted to give a 3K carbon fiber resin.
- a 3K carbon fiber resin tape is twisted 15 to 80 times / m to form a twisted yarn, and two covering yarns are wound with one S winding and the other with Z winding to produce an open yarn.
- Example 3 A first step of spreading the carbon fiber bundle flatly by immersing the carbon fiber bundle having 12K carbon fiber in reducing water having a negative redox potential; After the first step, a second step of immersing the carbon fiber bundle in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate; After the second step, a 12K carbon fiber resin tape is manufactured through a third step of drying the carbon fiber bundle and manufacturing a carbon fiber resin tape.
- a 12K carbon fiber resin tape is slitted, and the 6K carbon fiber resin is twisted at 15 to 80 turns / m to make a twisted yarn, with aramid fiber as the core material, one with S winding and the other with Z winding Winding to produce a carbon fiber-coated twisted yarn.
- the opened yarns and carbon fiber-coated twisted yarns produced in the above examples were lighter and four times stronger than stainless steel when glass or ceramic was used as the core material.
- the spread yarn covered with the low-melting point thermoplastic resin according to the second embodiment of the present invention will be described with reference to FIG. 5 (a) and 5 (b), the spread yarn is formed by twisting S and Z around the twisted yarn P formed by twisting the carbon fiber resin formed by slitting from the carbon fiber resin tape, and the outer periphery of the twisted yarn P.
- This is a structure provided with a covering yarn C and a low melting point thermoplastic resin R coated on the outer peripheral surface of a layer formed by winding the covering yarn C in S and Z windings.
- first to fifth steps that is, A first step of spreading the carbon fiber bundle flat by immersing the carbon fiber bundle having a plurality of carbon fibers in reducing water having a negative oxidation-reduction potential; After the first step, either the carbon fiber bundle, the carbon fiber bundle, an adhesive solution containing an adhesive, alumina sol, and potassium persulfate, or an adhesive solution containing an adhesive, alumina sol, and benzoyl.
- the twisted yarn P used for the spread yarn is, for example, arbitrary after slitting the opened carbon fiber resin tape (hereinafter referred to as the spread carbon fiber resin tape) in the same manner as the twisted yarn of the first embodiment. Manufactured by twisting tape of width.
- the twisted yarn P is a spread carbon containing 3K (3000 bundles), 6K (6000 bundles), or 12K (12,000 bundles) untwisted carbon fibers without slitting the spread carbon fiber resin tape. Manufactured by twisting fiber resin tape.
- the spread carbon fiber resin tape used for the production of the twisted yarn the same carbon fiber resin tape as in the first embodiment is used.
- a continuous twisted yarn P can be obtained by applying 50 to 60 twists (twist) per 1 m to such a resin tape by a twisting machine.
- a covering (the fifth step described above) is performed on the twisted yarn P by covering the covering yarn C made of nylon 6, 12, 66, etc. having a diameter of 20 to 50 ⁇ m with S winding and Z winding. Thereby, the spread yarn in which the accumulation layer of the covering yarn C is formed on the outer peripheral surface of the twisted yarn P is obtained.
- the covering yarn C is the same as that of the first embodiment described above. For example, nylon 6, 12, 66 yarns having a diameter of 20 to 50 ⁇ m are used as the covering yarn.
- a low-melting-point thermoplastic resin such as a resin (for example, nylon 6, 12, 66, etc.) of the same material as the covering yarn is further provided on the outer peripheral surface of the spread yarn (that is, the outer peripheral surface of the deposited layer of the covering yarn C).
- R is uniformly coated to a thickness of 3 to 10 ⁇ m without unevenness to obtain a continuous resin-coated spread yarn.
- the low melting point thermoplastic resin R refers to a thermoplastic resin that melts at a melting point equal to or lower than the melting point of the covering yarn, for example, a low melting point of about 98 to 290 ° C.
- thermoplastic resin R for example, nylon fibers such as nylon 6, 12, 66, or ABS (Acrylinityl Butadiene Styrene) resin, PET (Polyethylene terephthalate), PP (Polypropylene), RFL resin (resorcin formalin latex treatment). Resin).
- nylon fibers such as nylon 6, 12, 66, or ABS (Acrylinityl Butadiene Styrene) resin
- PET Polyethylene terephthalate
- PP Polypropylene
- RFL resin resorcin formalin latex treatment
- the low-melting point thermoplastic resin R is coated on the outer peripheral surface of the spread yarn (specifically, the outer peripheral surface of the layer around which the covering yarn C is wound), thereby forming the twisted yarn P.
- the bonding strength between the twisted yarn P and the covering yarn C is improved together with the bonding strength between the carbon fiber resins.
- covers the opening yarn will fuse
- the low melting point thermoplastic resin R in the melting state inside the melting furnace E is brought into contact with the outer peripheral surface of the opened yarn A1 together with the opened yarn A1 from the nozzle N. This is done by extruding. Specifically, the unsealed spread yarn A1 wound around the first roll D1 (that is, the spread yarn with the covering yarn C wound around the twisted yarn P in FIG. 5) is fed to the melting furnace E. Sent out. Inside the melting furnace E is stored a low-melting-point thermoplastic resin R that has been heated to about 150 to 300 ° C. by the heater G and melted.
- the spread yarn A1 fed into the melting furnace G from above is continuously covered with the melted low-melting point thermoplastic resin R and pulled out from the nozzle N provided at the lower part of the melting furnace G. It is. Thereafter, the spread yarn A2 covered with the low-melting point thermoplastic resin R is cooled to about 10 to 15 ° C. by the cooling unit J having a cooling fan and a water cooling jacket, and the low-melting point thermoplastic resin R is solidified. Thereafter, the coated spread yarn A2 is wound around the second roll D2.
- the step of covering the spread yarn A1 with the low-melting point thermoplastic resin R pushes the low-melting point thermoplastic resin R from the nozzle N together with the spread yarn A1 while contacting the outer peripheral surface of the spread yarn A1. Is possible. Thereby, while being able to improve the intensity
- the low melting point thermoplastic resin R is coated on the outer peripheral surface of the spread yarn in which the covering yarn C is wound around the outer peripheral surface of the twisted yarn P.
- the present invention is limited to this. is not. That is, in the third embodiment of the present invention, as shown in FIGS. 7A and 7B, a structure in which the low melting point thermoplastic resin R is directly coated on the outer peripheral surface of the twisted yarn P is shown.
- the twisted yarn P is produced by twisting the spread carbon fiber resin tape in the same manner as the twisted yarns of the first and second embodiments.
- the low melting point thermoplastic resin R is a thermoplastic resin that melts at the same low melting point as in the second embodiment.
- first to fourth steps that is, A first step of spreading the carbon fiber bundle flat by immersing the carbon fiber bundle having a plurality of carbon fibers in reducing water having a negative oxidation-reduction potential; After the first step, the carbon fiber bundle is immersed in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate, or an adhesive solution containing an adhesive, alumina sol, and benzoyl.
- a second step to perform After the second step, a third step of drying the carbon fiber bundle to produce a carbon fiber resin tape, The carbon fiber resin tape is slit-processed, and a fourth process is performed in which the plurality of slit-processed carbon fiber resins are twisted 15 to 80 times / m to form the twisted yarn P.
- a coating step of coating the outer peripheral surface of the twisted yarn P with the low melting point thermoplastic resin R is performed.
- the resin coating may be continuously performed using the continuous coating apparatus shown in FIG. Thereby, as shown in FIGS. 7A and 7B, it is possible to produce a twisted yarn covered with the low-melting point thermoplastic resin R.
- the low melting point thermoplastic resin R is coat
- the step of coating the twisted yarn P with the low-melting point thermoplastic resin R is performed by using the low-melting point thermoplastic resin while contacting the outer peripheral surface of the twisted yarn P using a continuous coating apparatus as shown in FIG. It can be performed by extruding the resin R together with the twisted yarn P from the nozzle N. Thereby, while being able to improve the intensity
- the low-melting point thermoplastic resin is coated on the outer peripheral surfaces of the twisted yarn and the spread yarn that do not have a core material, but the present invention is not limited to this.
- the 8A and 8B includes a core material Q, a twisted yarn R wound around the outer periphery of the core material Q, an S-winding around the outer periphery of the twisted yarn R, and This is a structure provided with a covering yarn C wound by Z winding and a low melting point thermoplastic resin R coated on the outer peripheral surface of a layer formed by winding S and Z windings of the covering yarn C.
- the core material Q is preferably at least one selected from organic or inorganic thread materials, stainless steel materials, or Inconel (registered trademark) wires. By selecting these materials, it is possible to easily produce a carbon fiber-coated twisted yarn that is flexible and has a desired tensile strength.
- the same twisted yarn as in the first to third embodiments is used.
- the covering yarn C a covering yarn similar to that in the first to third embodiments is used.
- the low melting point thermoplastic resin R the same low melting point thermoplastic resin as in the first to third embodiments is used.
- first to fifth steps that is, A first step of spreading the carbon fiber bundle flat by immersing the carbon fiber bundle having a plurality of carbon fibers in reducing water having a negative oxidation-reduction potential; After the first step, a second step of immersing the carbon fiber bundle in an adhesive solution containing an adhesive, alumina sol, and potassium persulfate; After the second step, a third step of drying the carbon fiber bundle to produce a carbon fiber resin tape, A fourth step of slitting the carbon fiber resin tape, and twisting the plurality of carbon fiber resins subjected to the slit treatment to 15 to 80 times / m to form a twisted yarn; A fifth step is performed in which a twisted yarn made of a carbon fiber resin tape is wound around the outer periphery of the core material Q, one with S winding and the other with Z winding.
- a covering step of covering the outer peripheral surface of the layer in which the covering yarn C is wound with S and Z with a low-melting point thermoplastic resin R is performed, so that FIGS. Can be produced.
- the low melting point thermoplastic resin R is coated on the outer peripheral surface of the carbon fiber-covered twisted yarn, so that the binding force between the carbon fiber resins constituting the twisted yarn P is as follows. At the same time, the bonding force between the twisted yarn P and the covering yarn C is improved.
- this invention is limited to this.
- the covering yarn C may be omitted, that is, the twisted yarn P may be wound around the outer periphery of the core material Q, and the outer peripheral surface thereof may be covered with the low melting point thermoplastic resin R.
- the low-melting-point thermoplastic resin covering the carbon fiber-covered twisted yarn is melted and adjacent low-melting-point thermoplastic resins are bonded to each other To do. Thereby, it is possible to process into the article
- the step of coating the twisted yarn, the spread yarn, and the carbon fiber-covered twisted yarn with the low-melting point thermoplastic resin pushes the low-melting point thermoplastic resin together with these from the nozzle while contacting the outer peripheral surface.
- the coating by the said low melting-point thermoplastic resin can be performed continuously.
- the step of coating the carbon fiber-covered twisted yarn with the low-melting point thermoplastic resin R uses the continuous coating apparatus as shown in FIG. It is possible to carry out by extruding the thermoplastic resin R from the nozzle N together with the carbon fiber-coated twisted yarn. Thereby, while being able to improve the intensity
- the twisted yarn, spread yarn and carbon fiber-coated twisted yarn of the present invention have high tensile strength and bending resistance, and are used for sewing thread, knitting thread, fish net, fishing line, tamo net, fishing rod reinforcement, tying belt and V belt reinforcement. It can be used widely.
- Carbon fiber bundle F1 Carbon fiber bundle
- Carbon fiber resin tape A Alumina sol B Potassium persulfate S Adhesive P Twist yarn C Covering yarn R Low melting point thermoplastic resin Q Core material
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Abstract
Description
例えば、12Kであれば12000本の炭素繊維束からなりサイジング(糊付け)によって1本の束に撚って構成している。
これらの炭素繊維束に開繊装置等を用いることで、束を開繊し樹脂テープを製造することが本出願人の出願である国際公開2016/068210号公報(PCT/JP2015/080450)に開示されている。
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液または接着剤とアルミナゾルとベンゾイルとを含む接着剤溶液のうちいずれかの接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させる炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする第四工程からなる撚糸の製造方法および、更に前記撚糸にS巻及びZ巻でカバーリング糸を巻き付ける第五工程を含む開繊糸の製造方法に関する。
前記第一工程の後に、前記炭素繊維束を、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液または接着剤とアルミナゾルとベンゾイルとを含む接着剤溶液のうちいずれかの接着剤溶液に浸漬する第二工程と、に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする第四工程と、
炭素繊維樹脂テープからなる撚糸を芯材の外周に2本のカバーリング糸を1本はS巻、もう1本はZ巻で巻き付ける第五工程とからなる炭素繊維被覆撚糸の製造方法に関する。
また他の実施形態では糸などの芯材に炭素繊維樹脂テープからスリットしてなる炭素繊維樹脂をよじってなる撚糸を巻き付けてなる炭素繊維被覆撚糸にすることで、軽量でかつステンレスの4倍もの強度を有する撚糸を得ることができる。
本発明で炭素繊維樹脂テープからスリットしてなる複数本の炭素繊維樹脂を巻き付ける芯材の糸は、ケプラー(登録商標)、テフロン(登録商標)、アラミド繊維、タフクレースト(登録商標)などを用いていてもよい。
第三工程を経て製造された炭素繊維樹脂テープを第四工程でスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけで撚糸を製造する。
この撚糸は丈夫であり様々な用途に用いることができる。
第五工程で2本のカバーリング糸で覆うことで折り曲げ、引張に対する高い耐久性を有する開繊糸ができる。
本発明の開繊糸の製造方法は、撚糸にカバーリング糸を幅4mm~6mmの等間隔で巻き付けることでより屈曲耐性の強い糸を製造することができる。
さらに、本発明では、開繊糸の外周面(具体的には、カバーリング糸が巻かれた層の外周面)に低融点熱可塑性樹脂が被覆されることにより、撚糸を構成する炭素繊維樹脂の間の結合力とともに撚糸とカバーリング糸との間の結合力が向上する。
また、本発明では、炭素繊維被覆撚糸の外周面(具体的には、炭素繊維樹脂を巻き付けてなる層の外周面)に低融点熱可塑性樹脂が被覆されることにより、炭素繊維樹脂の間の結合力が向上する。
さらに、これらの撚糸、開繊糸、および炭素繊維被覆撚糸のいずれかによって編物や織物を製造した後に加熱すれば、これらを被覆する低融点熱可塑性樹脂が溶融して隣接する低融点熱可塑性樹脂同士が互いに結合する。これにより、編物や織物を容易に一体化した物品に加工することが可能である。
また、本発明では、撚糸、開繊糸、および炭素繊維被覆撚糸を低融点熱可塑性樹脂によって被覆する工程は、これらの外周面に接触しながら当該低融点熱可塑性樹脂をこれらとともにノズルから押し出すことによって行うことが可能である。これにより、これら撚糸、開繊糸、および炭素繊維被覆撚糸の強度を向上することができるとともに、当該低融点熱可塑性樹脂によるコーティングを連続的に行うことができる。
以下、本発明の第1実施形態である炭素繊維樹脂テープからスリット(裁断)してなる複数本の炭素繊維樹脂をよってなる撚糸、及び撚糸の外周にカバーリング糸がS巻き及びZ巻きされてなる開繊糸、及びそれらの製造方法及び他の実施形態である 芯材である糸に炭素繊維樹脂テープからスリットしてなる炭素繊維樹脂をよじってなる撚糸を巻き付けてなる炭素繊維被覆撚糸について説明する。
カバーリング糸はナイロン6やナイロン66などのナイロン繊維、ポリテトラフルオロエチレン、アラミド繊維、SUS316Lなどのステンレス鋼材、またはインコネル(登録商標)線材から選択される一種以上を用いてもよい。インコネルは、ニッケルを主体とし、クロム、鉄、炭素などの成分を含む合金であり、加工材料や鋳物材料などの様々な用途で使われる耐熱および耐蝕合金である。
これらは開繊糸の使用条件、温度、耐薬品性、圧力、繰り返し頻度によって任意に選択できる。
使用するカバー糸の線径は直径0.03~0.12mmがよく、好適には無機物または有機物でできた糸の場合は0.03mm、金属製の糸の場合は0.08mmが好ましい。
このときS巻きされたカバー糸と、Z巻きされたカバー糸が等間隔でX字状に交わるように巻き付け、X字状に交わる各交点間の間隔は4mm~6mmが好ましい。
4mm以下だと材料の無駄が生じ重量が重くなり価格が高くなり、6mm以上だと屈曲時180度折り曲げた時に折れてしまい糸にならなくなるばかりかこぶ状になり糸が不安定になるためである。
また出来上がった開繊糸の直径は0.15mm乃至2.5mmが好ましい。
巻き付け方はシングルでも良く、S巻及びZ巻のダブルで巻いてもよく、45°や60°の角度でバイアスにまいてもよい。
また芯材に炭素繊維や樹脂を加えて丈夫にしてもよく、赤外線防止剤等を塗布することで様々な耐性を有する糸としてもよい。
なお、本実施形態では、複数本の炭素繊維からなる炭素繊維束を第三工程で乾燥した後を炭素繊維樹脂テープと呼ぶ。
第三工程の後に、第四工程として炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする。
さらに第五工程として、撚糸の外周に2本のカバーリング糸を1本はS巻、もう1本はZ巻で巻き付けることで開繊糸が製造される。
炭素繊維樹脂テープ製造装置は、給糸ローラ1と巻き取りローラ8との間に炭素繊維束F1を順に浸漬させる第1槽2と第2槽6とを備え、第2槽6と巻き取りローラ8との間に炭素繊維束F1を乾燥させる乾燥装置7を備えている。また、炭素繊維樹脂テープ製造装置は、給糸ローラ1と巻き取りローラ8との間に、炭素繊維束F1を送り出すローラを適宜備えている。
第1槽2には、負の酸化還元電位を有する還元水が貯留されている。第2槽6には、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液が貯留されている。
図1に示すように、炭素繊維束F1は、給糸ローラ1から連続的に繰り出されて、第1槽2内に貯留された水中に所定時間浸漬される。
炭素繊維束F1としては、無撚炭素繊維の3K(すなわち、3000本束の無撚炭素繊維)、6K(6000本束)、12K(12000本束)等を例示することができる。炭素繊維としては、アクリル系、ピッチ系のいずれであっても適用可能である。
普通の水は正の酸化還元電位(水道水の場合:+400~+600mV程度)を有しているが、還元水は負の酸化還元電位を有しており、水分子クラスターが小さく、優れた浸透力を有している。
炭素繊維束F1は、このような還元水中に浸漬されることによって、超音波等の物理的外力を作用させることなく自然に拡がる。
このような酸化還元電位が低い還元水を用いることにより、炭素繊維束F1を構成する炭素繊維を短時間で確実に平らに拡げて帯状の平繊繊維束を得ることが可能となる。また、得られた帯状の平繊繊維束が元に戻りにくいものとなる。
<1.ガスバブリング法>
窒素ガス、アルゴンガス又は水素ガスのバブリングにより、水中の酸素濃度を低下させ、酸化還元電位を低下させる。
<2.ヒドラジンの添加による方法>
ヒドラジンを添加することにより、水中の酸素濃度を低下させ、酸化還元電位を低下させる。
<3.電気分解による方法>
(a)正負の波高値及び/又はデューティー比が非対称な高周波電圧を印加して水の電気分解を行い、酸化還元電位を低下させる。
(b)電極を1枚のグランド電極(カソード極)と、アノード極とカソード極が交互に変化する2枚のPtとTiからなる特殊形状電極(菱形網状電極又は六角形網状電極)から構成し、高周波電圧を印加して水の電気分解を行い、酸化還元電位を低下させる。
これは、「3(b)」の方法によれば、他の方法に比べて、より容易且つ確実に酸化還元電位が低く(-800mV以下)、負の酸化還元電位を長時間にわたって維持できる還元水が得られるためである。
尚、「3(b)」の方法を実施するための装置については、本願出願人が特開2000-239456号公報において開示しており、この開示内容に基づいて実施することが可能である。
具体的には、2番目のローラ31の断面(回転軸に沿った断面)形状を、図中に引き出された矢印の先に示しているように、両端から中央に向けて膨らんだ形状とすることにより、ローラ31の表面に沿って繊維が拡がり易くしたものである。
具体的には、ローラ32を図2(a)の場合と同様の断面形状とすることにより、ローラ32の表面に沿って繊維が拡がり易くしたものである。
第1槽2を通って還元水に浸漬されることにより平らに拡げられた炭素繊維(平繊繊維束)は、第1槽2から取り出された後、引き続いて第2槽6内に連続的に導入される。
第2槽6内には、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液が収容されており、還元水に浸漬されることにより得られた平繊繊維束は、第2槽6内において接着剤溶液に浸漬される。
本発明において過硫酸カリウムに代えてベンゾイルを用いてもよく、以下過硫酸カリウムを用いた場合について記載するがベンゾイルを用いた場合も過硫酸カリウムと同様である。
接着剤としては親水基を有するものであり、洗濯糊のような水溶性の糊、PVA(ポリビニルアルコール)、PTFEディスパージョン、黒鉛ナノディスパージョン、グリコール、水溶性粘土ディスパージョン、でんぷん糊、ウレタン系、シリコン系、RFL系、エポキシ系、イミド系分散溶液、OH-基を有する有機又は無機材含有分散溶液が好適に用いられる。
接着剤の濃度が所定の範囲より低いと、平らに広がった炭素繊維束F1が元に戻るおそれがある。また、接着剤の濃度が所定の範囲より高いと、接着剤が炭素繊維束F1の中に浸透し難くなるおそれがある。
接着剤がPVAの場合の濃度は、0.5~30wt%が好ましい。
アルミナゾルの濃度は、0.5~16.7wt%が好ましい。アルミナゾルの濃度が前記下限より低いと、炭素繊維樹脂テープの接着力が低くなるおそれがある。また、アルミナゾルの濃度が前記上限より高くても、炭素繊維樹脂テープの接着力はそれ以上には増加しにくい。
また、PVAとアルミナゾルとの濃度比は3:1が好ましい。また、過硫酸カリウムの濃度は0.5~10wt%が好ましい。
また、アルミナゾルが繊維状の場合のアルミナファイバーは、アルミナの繊維状結晶であり、具体的には、アルミナの無水和物で形成されたアルミナファイバー、水和物を含むアルミナで形成されたアルミナ水和物ファイバー等が挙げられる。
図3は、これまでの工程を模式的に示す図であり、複数本の炭素繊維からなる炭素繊維束F1は、還元水に浸漬されることによって炭素繊維F3が平らに拡がった平繊繊維束Hとなり、この平繊繊維束Hが接着剤とアルミナゾルと過硫酸カリウムとを含む液内に浸漬されることにより炭素繊維F3の間に接着剤SとアルミナゾルAと過硫酸カリウムBとが浸透する。
また、本発明においては、第2槽6を設けずに、還元水に浸漬されることにより平らに拡げられた炭素繊維(平繊繊維束)に対して、接着剤を含む液を霧状にして吹き付ける方法を採用してもよい。
接着剤とアルミナゾルとを含む液内に浸漬された後の拡がった炭素繊維束F1は、第2槽6から取り出された後、乾燥装置7に供給されて乾燥処理が施される。
乾燥装置7の種類は特に限定されず、ヒーター加熱装置でもよいし、温風加熱装置でもよいし、遠赤外線を利用した加熱装置でもよい。但し、本発明に係る方法においては、必ずしも乾燥装置7を設ける必要はなく、自然乾燥を行ってもよい。
なお、この第三工程の後に、炭素繊維樹脂テープF2をさらに水洗して余分な接着剤を除去し、乾燥させてもよい。余分な不純物が除去され、必要なOH-を残すことによりはく離強度が向上する。
このように、繊維が平らに拡がった状態で接着剤により固められることにより、時間が経過しても元に戻ることがなく、しかも高い機械的強度を有する炭素繊維樹脂テープF2が得られる。
但し、本発明においては、物理的外力を作用させることを完全に排除するものではなく、本発明に係る方法と従来の物理的外力を作用させる方法を組み合わせてもよい。
この場合、還元水の開繊作用によって、超音波の出力を弱くしても充分な開繊が得られるため、繊維の損傷を確実に防ぎつつ、充分に拡がった帯状の平繊繊維束を効率良く製造することができるという効果が奏される。
上記第三工程を経て製造された炭素繊維樹脂テープF2をスリット処理する。
スリット処理はスリッター機などを用いて1回以上行われ、炭素繊維樹脂テープF2を任意の幅や長さにスリット(切断)される。
スリットされた後、複数本の炭素繊維樹脂を撚糸機等によって撚ることにより撚糸Pにし、撚りは15乃至80回/mが好ましい。
上記第四工程で、撚りを掛けられた撚糸Pの外周に2本のカバーリング糸Cを巻き付ける。
この時カバーリング糸CはX字状になるように1本はS巻、もう一本はZ巻で等間隔に巻き付ける。(図4のi参照)
この時4mm以下だと材料の無駄が生じ重量が重くなり価格が高くなり、6mm以上だと180度折り曲げた時に折れてしまい糸にならなくなるばかりかこぶ状になり糸が不安定になるため、幅(w)は4mm~6mmの間隔になるように巻き付ける。
上記第五工程は第四工程で撚りを掛けられた撚糸を芯材、通常の糸をカバーリング糸としているが、通常の糸を芯材とし第四工程で撚りを掛けられた撚糸をカバーリング糸とすることで炭素繊維被覆撚糸を製造してもよい。
12Kの炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、を経て12Kの炭素繊維樹脂テープを製造する。
12Kの炭素繊維樹脂テープをスリット処理し、6Kにした炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にし、2本のカバーリング糸を1本はS巻、もう1本はZ巻で巻き付けて開繊糸を製造する。
12Kの炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、を経て12Kの炭素繊維樹脂テープを製造する。
12Kの炭素繊維樹脂テープを6Kになるようにスリット処理し、さらにスリット処理し3Kの炭素繊維樹脂にする。
3Kの炭素繊維樹脂テープに15乃至80回/mの撚りをかけ撚糸にし、2本のカバーリング糸を1本はS巻、もう1本はZ巻で巻き付けて開繊糸を製造する。
12Kの炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、を経て12Kの炭素繊維樹脂テープを製造する。
12Kの炭素繊維樹脂テープをスリット処理し、6Kにした炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にし、アラミド繊維を芯材とし1本はS巻、もう1本はZ巻で巻き付けて炭素繊維被覆撚糸を製造する。
つぎに、図5を参照しながら、本発明の第2実施形態に係る低融点熱可塑性樹脂で被覆された開繊糸について説明する。
図5(a)、(b)に示される開繊糸は、炭素繊維樹脂テープからスリットしてなる炭素繊維樹脂をよじってなる撚糸Pと、撚糸Pの外周にS巻き及びZ巻きされてなるカバーリング糸Cと、カバーリング糸CがS巻き及びZ巻きされてなる層の外周面に被覆されている低融点熱可塑性樹脂Rとを備えた構造である。
複数本の炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液または接着剤とアルミナゾルとベンゾイルとを含む接着剤溶液のうちいずれかの接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸Pにする第四工程と、
炭素繊維樹脂テープからなる撚糸Pの外周に2本のカバーリング糸Cを1本はS巻、もう1本はZ巻で巻き付ける第五工程と
を行う。
撚糸の製造のために用いられる開繊炭素繊維樹脂テープとしては、上記第1実施形態の炭素繊維樹脂テープと同様のものが用いられ、例えば、3K~24K程度(3000本束~24000本束)のレギュラートウ(R/T)が用いられるが、24Kよりも大きいK値(例えば、48K、64K以上)のラージトウ(L/T)が用いられてもよい。
このような樹脂テープに対して撚糸機によって1m当たり50~60回の撚り(ねじり)を掛けることにより、連続した撚糸Pが得られる。
カバーリング糸Cは、上記の第1実施形態と同様のものが用いられ、例えば、直径20~50μmの太さのナイロン6、12、66の糸がカバーリング糸として用いられる。
低融点熱可塑性樹脂Rは、カバーリング糸の融点と同じかそれ以下の融点、たとえば98~290℃程度の低融点で溶融する熱可塑性樹脂のことを言う。
低融点熱可塑性樹脂Rとしては、例えば、ナイロン6、12、66などのナイロン繊維、または、ABS(Acrylnitrile Butadiene Styrene)樹脂、PET(Polyethyleneterephthalate)、PP(Polypropylene)、RFLレジン(レゾルシンホルマリンラテックス処理された樹脂)などが用いられる。
さらに、上記の開繊糸によって編物や織物を製造した後に加熱すれば、開繊糸を被覆する低融点熱可塑性樹脂が溶融して隣接する低融点熱可塑性樹脂同士が互いに結合する。これにより、編物や織物を容易に一体化した物品に加工することが可能である。
具体的には、第1ロールD1に巻き取られたコーティング前の開繊糸A1(すなわち、図5の撚糸Pにカバーリング糸Cが巻かれた状態の開繊糸)は、溶融炉Eに送り出される。溶融炉Eの内部には、ヒータGによって150~300℃程度に加熱されて溶融された低融点熱可塑性樹脂Rが貯留されている。溶融炉G内部に上方から送り込まれた開繊糸A1は、その外周面が溶融された低融点熱可塑性樹脂Rによって連続的に被覆され、溶融炉Gの下部に設けられたノズルNから引っ張り出される。その後、低融点熱可塑性樹脂Rによって被覆された開繊糸A2は、冷却ファンおよび水冷ジャケットなどを有する冷却部Jによって10~15℃程度まで冷却され、低融点熱可塑性樹脂Rが固化される。その後、被覆された開繊糸A2は、第2ロールD2に巻き取られる。
上記第2実施形態では、カバーリング糸Cが撚糸Pの外周面に巻き付けられた開繊糸の外周面に低融点熱可塑性樹脂Rが被覆されているが、本発明はこれに限定されるものではない。
すなわち、本発明の第3実施形態では、図7(a)、(b)に示されるように、撚糸Pの外周面に低融点熱可塑性樹脂Rが直接被覆された構造が示されている。
この撚糸Pは、上記の第1~2実施形態の撚糸と同様に、開繊炭素繊維樹脂テープをよじることによって製造される。
低融点熱可塑性樹脂Rは、上記第2実施形態と同様の低融点で溶融する熱可塑性樹脂である。
複数本の炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液または接着剤とアルミナゾルとベンゾイルとを含む接着剤溶液のうちいずれかの接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸Pにする第四工程を行う。
これにより、図7(a)、(b)に示されるように、低融点熱可塑性樹脂Rで被覆された撚糸を製造することが可能である。
第3実施形態では、撚糸Pの外周面に低融点熱可塑性樹脂Rが被覆されることにより、撚糸Pを構成する炭素繊維樹脂の間の結合力が向上する。
また、第3実施形態において撚糸Pを低融点熱可塑性樹脂Rによって被覆する工程は、図6に示されるような連続コーティング装置を用いて当該撚糸Pの外周面に接触しながら当該低融点熱可塑性樹脂Rを撚糸PとともにノズルNから押し出すことによって行うことが可能である。これにより、これら撚糸の強度を向上することができるとともに、当該低融点熱可塑性樹脂Rによるコーティングを連続的に行うことができる。
上記第2~3実施形態では、芯材を有しない撚糸および開繊糸の外周面に低融点熱可塑性樹脂が被覆されているが、本発明はこれに限定されるものではない。
本発明の第4実施形態として、図8(a)、(b)に示されるように、芯材Qを有する炭素繊維被覆撚糸が低融点熱可塑性樹脂Rで被覆されたものでもよい。
具体的には、図8(a)、(b)に示される炭素繊維被覆糸は、芯材Qと、当該芯材Qの外周に巻き付けられた撚糸Rと、撚糸Rの外周にS巻およびZ巻により巻き付けられたカバーリング糸Cと、カバーリング糸CがS巻き及びZ巻きされてなる層の外周面に被覆されている低融点熱可塑性樹脂Rとを備えた構造である。
芯材Qは、有機あるいは無機の糸材、ステンレス鋼材、またはインコネル(登録商標)線材から選択される一種以上であるのが好ましい。これらの材料を選択することにより、柔軟でかつ所望の引張強度を備えた炭素繊維被覆撚糸を容易に製造することが可能である。
このような炭素繊維被覆撚糸を製造する場合、まず、上記第1実施形態の炭素繊維被覆撚糸の製造方法と同様に、第一工程~第五工程、すなわち、
複数本の炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする第四工程と、
炭素繊維樹脂テープからなる撚糸を芯材Qの外周に1本はS巻、もう1本はZ巻で巻き付ける第五工程と
を行う。
なお、第4実施形態では、図8(a)、(b)に示されるようにカバーリング糸Cを含む炭素繊維被覆撚糸の例が示されているが、本発明はこれに限定されるものではなく、カバーリング糸Cを省略した構造、すなわち、心材Qの外周に撚糸Pが巻き付けられ、その外周面を低融点熱可塑性樹脂Rによって被覆してもよい。
さらに、第4実施形態の炭素繊維被覆撚糸によって編物や織物を製造した後に加熱すれば、炭素繊維被覆撚糸を被覆する低融点熱可塑性樹脂が溶融して隣接する低融点熱可塑性樹脂同士が互いに結合する。これにより、編物や織物を容易に一体化した物品に加工することが可能である。
また、第4実施形態において炭素繊維被覆撚糸を低融点熱可塑性樹脂Rによって被覆する工程は、図6に示されるような連続コーティング装置を用いて当該撚糸Pの外周面に接触しながら当該低融点熱可塑性樹脂Rを炭素繊維被覆撚糸とともにノズルNから押し出すことによって行うことが可能である。これにより、炭素繊維被覆撚糸の強度を向上することができるとともに、当該低融点熱可塑性樹脂Rによるコーティングを連続的に行うことができる。
F2 炭素繊維樹脂テープ
A アルミナゾル
B 過硫酸カリウム
S 接着剤
P 撚糸
C カバーリング糸
R 低融点熱可塑性樹脂
Q 芯材
Claims (20)
- 炭素繊維樹脂テープからスリットしてなる炭素繊維樹脂をよじってなる撚糸。
- 前記撚糸の外周面に低融点熱可塑性樹脂が被覆されている請求項1に記載の撚糸。
- 前記請求項1に記載の撚糸の外周にカバーリング糸がS巻き及びZ巻きされてなる開繊糸。
- 前記カバーリング糸がS巻き及びZ巻きされてなる層の外周面に低融点熱可塑性樹脂が被覆されている請求項3に記載の開繊糸。
- 前記カバーリング糸はナイロン繊維、ポリテトラフルオロエチレン、アラミド繊維、ステンレス鋼材またはインコネル(登録商標)線材から選択される一種以上であることを特徴とする請求項3または4に記載の開繊糸。
- 前記開繊糸の直径は0.15mm乃至2.5mmであることを特徴とする請求項3乃至5に記載の開繊糸。
- 芯材の外周に前記請求項1に記載の撚糸を巻き付けてなる炭素繊維被覆撚糸。
- 前記炭素繊維樹脂を巻き付けてなる層の外周面に低融点熱可塑性樹脂が被覆されている請求項7に記載の炭素繊維被覆撚糸。
- 前記芯材は、有機あるいは無機の糸材、ステンレス鋼材、またはインコネル(登録商標)線材から選択される一種以上であることを特徴とする7または8に記載の炭素繊維被覆撚糸。
- 複数本の炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液または接着剤とアルミナゾルとベンゾイルとを含む接着剤溶液のうちいずれかの接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする第四工程からなる請求項1に記載の炭素繊維樹脂テープからなる撚糸の製造方法。 - 前記第四工程の後に、前記撚糸の外周面に低融点熱可塑性樹脂を被覆する被覆工程をさらに含む、
請求項10に記載の撚糸の製造方法。 - 前記被覆工程は、溶融状態の前記低融点熱可塑性樹脂を前記外周面に接触しながら前記撚糸とともにノズルから押し出すことによって行われる、
請求項11に記載の撚糸の製造方法。 - 複数本の炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液または接着剤とアルミナゾルとベンゾイルとを含む接着剤溶液のうちいずれかの接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする第四工程と、
炭素繊維樹脂テープからなる撚糸の外周に2本のカバーリング糸を1本はS巻、もう1本はZ巻で巻き付ける第五工程とからなる請求項3に記載の開繊糸の製造方法。 - 前記第五工程の後に、前記カバーリング糸がS巻き及びZ巻きされてなる層の外周面に低融点熱可塑性樹脂を被覆する被覆工程をさらに含む、
請求項13に記載の開繊糸の製造方法。 - 前記被覆工程は、溶融状態の前記低融点熱可塑性樹脂を前記外周面に接触しながら前記開繊糸とともにノズルから押し出すことによって行われる、
請求項14に記載の開繊糸の製造方法。 - 前記第五工程は、撚糸の外周に幅4mm~6mmの等間隔でカバーリング糸を巻き付けることを特徴とする請求項13乃至15のいずれか1項に記載の開繊糸の製造方法。
- 複数本の炭素繊維を有する炭素繊維束を負の酸化還元電位を有する還元水に浸漬して該炭素繊維束を平らに拡げる第一工程と、
前記第一工程の後に、前記炭素繊維束を、接着剤とアルミナゾルと過硫酸カリウムとを含む接着剤溶液に浸漬する第二工程と、
前記第二工程の後に、前記炭素繊維束を乾燥させ炭素繊維樹脂テープを製造する第三工程と、
炭素繊維樹脂テープをスリット処理し、スリット処理した複数本の炭素繊維樹脂に15乃至80回/mの撚りをかけ撚糸にする第四工程と、
炭素繊維樹脂テープからなる撚糸を芯材の外周に1本はS巻、もう1本はZ巻で巻き付ける第五工程とからなる請求項7に記載の炭素繊維被覆撚糸の製造方法。 - 前記第五工程の後に、前記撚糸がS巻き及びZ巻きされてなる層の外周面に低融点熱可塑性樹脂を被覆する被覆工程をさらに含む、
請求項17に記載の炭素繊維被覆撚糸の製造方法。 - 前記被覆工程は、溶融状態の前記低融点熱可塑性樹脂を前記外周面に接触しながら前記炭素繊維被覆撚糸とともにノズルから押し出すことによって行われる、
請求項18に記載の炭素繊維被覆撚糸の製造方法。 - 前記第五工程は、芯材の外周に幅4mm~6mmの等間隔でカバーリング糸を巻き付けることを特徴とする請求項17乃至19のいずれか1項に記載の炭素繊維被覆撚糸の製造方法。
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- 2017-05-31 WO PCT/JP2017/020374 patent/WO2018037658A1/ja active Application Filing
- 2017-05-31 JP JP2017561007A patent/JP6334073B1/ja active Active
- 2017-05-31 CN CN201780005907.9A patent/CN108431312B/zh not_active Expired - Fee Related
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2018
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Cited By (6)
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JP2022097501A (ja) * | 2018-04-23 | 2022-06-30 | 日亜化学工業株式会社 | 樹脂付リードフレームおよびその製造方法 |
JP7425350B2 (ja) | 2018-04-23 | 2024-01-31 | 日亜化学工業株式会社 | 樹脂付リードフレームおよびその製造方法 |
JP2020132782A (ja) * | 2019-02-21 | 2020-08-31 | ジャパンマテックス株式会社 | プリプレグおよびその製造方法 |
US11603439B2 (en) | 2019-02-21 | 2023-03-14 | Japan Matex Co., Ltd. | Prepreg and producing method thereof |
WO2021261491A1 (ja) * | 2020-06-27 | 2021-12-30 | ジャパンマテックス株式会社 | 炭素繊維原糸から開繊炭素繊維糸に撚り加工を施した極細炭素繊維糸及びその製造方法 |
JP2022007809A (ja) * | 2020-06-27 | 2022-01-13 | ジャパンマテックス株式会社 | 炭素繊維原糸から開繊炭素繊維糸に撚り加工を施した極細炭素繊維糸及びその製造方法 |
Also Published As
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US11060211B2 (en) | 2021-07-13 |
CN108431312B (zh) | 2021-12-21 |
JPWO2018037658A1 (ja) | 2018-08-30 |
US20190169770A1 (en) | 2019-06-06 |
EP3505662A4 (en) | 2020-07-01 |
KR20190040930A (ko) | 2019-04-19 |
EP3505662A1 (en) | 2019-07-03 |
CN108431312A (zh) | 2018-08-21 |
JP6334073B1 (ja) | 2018-05-30 |
US20210301427A1 (en) | 2021-09-30 |
HK1254051A1 (zh) | 2019-07-12 |
US20200347526A1 (en) | 2020-11-05 |
US10844523B2 (en) | 2020-11-24 |
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