TW201406842A - Carbon fiber composite material and molded article formed by the same, and manufacturing method of these - Google Patents

Carbon fiber composite material and molded article formed by the same, and manufacturing method of these Download PDF

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Publication number
TW201406842A
TW201406842A TW102120495A TW102120495A TW201406842A TW 201406842 A TW201406842 A TW 201406842A TW 102120495 A TW102120495 A TW 102120495A TW 102120495 A TW102120495 A TW 102120495A TW 201406842 A TW201406842 A TW 201406842A
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Taiwan
Prior art keywords
carbon fiber
fiber composite
composite material
thermoplastic resin
molded article
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TW102120495A
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Chinese (zh)
Inventor
Kazuhiko Tomioka
Kazuyoshi Nakano
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Toyo Plastic Seiko Co Ltd
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Publication of TW201406842A publication Critical patent/TW201406842A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2793/00—Shaping techniques involving a cutting or machining operation
    • B29C2793/0027—Cutting off
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B29C48/2886—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules of fibrous, filamentary or filling materials, e.g. thin fibrous reinforcements or fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/355—Conveyors for extruded articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/387—Plasticisers, homogenisers or feeders comprising two or more stages using a screw extruder and a gear pump
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/76—Venting, drying means; Degassing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

A manufacturing method of a carbon fiber composite material, which melts a second thermoplastic resin and a pellet comprising a core-sheath structure that contains a carbon fiber as a core component and a first thermoplastic resin as a sheath component, and kneads a melted pellet and a second thermoplastic resin at a prescribed temperature. And also, a manufacturing method of producing a molded article, which melts a product of the manufacturing method of a carbon fiber composite material, than molds into a molded article. Furthermore, a carbon fiber composite material is characteristic by comprising a first thermoplastic resin, a second thermoplastic resin, a carbon fiber, and having a structure with a sea phase composed of a second thermoplastic resin and an island phase composed of a first thermoplastic resin dispersed in the sea phase; and a molded article is molded by the carbon fiber composite material. According to these, can provides carbon fiber composite materials which can realize an advancement of strength physical properties, and which are easy for post-processing, optimized carbon fiber composite materials (hybrid alloy carbon fiber composite resin and hybrid nanoalloy carbon fiber composite resin) for producing a high rigidity molded article; and a molded article molded form the carbon fiber composite materials; and manufacturing method of these.

Description

碳纖維複合材料及使用其而成之成形品、以及彼等之製造方法 Carbon fiber composite material, molded article using the same, and manufacturing method thereof

本發明關於謀求力學特性的提升，後加工容易，適合於擠壓成形之碳纖維複合材料，使用該碳纖維複合材料而成之成形品，以及該碳纖維複合材料及該成形品之製造方法。 The present invention relates to a carbon fiber composite material which is suitable for extrusion molding, a molded product obtained by using the carbon fiber composite material, and a carbon fiber composite material and a method for producing the molded article.

於習知技術中，準備於碳纖維浸漬有液狀的熱硬化性樹脂之預浸漬物，藉由將其在高溫高壓化下進行高壓釜處理，而得到碳纖維複合材料。然而，需要將預浸漬物在低溫下保管用之低溫設備，或高壓釜用之高溫設備等的高價設備，具有此等設備係大的負擔。 In the prior art, a prepreg in which a carbon fiber is impregnated with a liquid thermosetting resin is prepared, and the carbon fiber composite material is obtained by subjecting it to autoclave treatment under high temperature and high pressure. However, there is a need for a high-priced equipment such as a low-temperature device for storing a prepreg at a low temperature or a high-temperature device for an autoclave, which has a large burden on such equipment.

因此，作為代替以往的熱硬化性樹脂而使用操作容易的熱塑性樹脂之方法，專利文獻1中揭示在連續的碳纖維束之周圍被覆熱塑性樹脂而成之成形用材料，將成形材料切斷成50mm以下者。於該構成中，為了提高碳纖維與樹脂之密接性，較佳為使用低黏度的熱塑性樹脂。 Therefore, as a method of using a thermoplastic resin which is easy to handle in place of the conventional thermosetting resin, Patent Document 1 discloses a molding material obtained by coating a thermoplastic resin around a continuous carbon fiber bundle, and cutting the molding material to 50 mm or less. By. In this configuration, in order to improve the adhesion between the carbon fibers and the resin, it is preferred to use a thermoplastic resin having a low viscosity.

然而，低黏度樹脂雖然適合於藉由對模具內填充樹脂而進行成形之射出成形，但於藉由使熔融的樹脂自擠壓機流入模頭而進行成形的擠壓成形中，成形品之形狀不安定，具有切削性或力學特性不足的傾向之問題，而摸索併用高黏度的熱塑性樹脂之方法。 However, although the low-viscosity resin is suitable for injection molding in which molding is performed by filling a resin in a mold, the shape of the molded article is formed by extrusion molding in which molten resin is introduced into the die from the extruder. Unstable, having the problem of insufficient machinability or mechanical properties, and exploring and using a high-viscosity thermoplastic resin.

因此，作為使用高黏度的熱塑性樹脂之方 法，專利文獻2中揭示以低黏度的熱塑性樹脂被覆碳纖維之束後，更以高黏度的熱塑性樹脂被覆之顆粒之製造方法。 Therefore, as a side of a thermoplastic resin using high viscosity In the method, Patent Document 2 discloses a method of producing a pellet coated with a high-viscosity thermoplastic resin after coating a bundle of carbon fibers with a low-viscosity thermoplastic resin.

然而，使用此方法所得之顆粒於擠壓成形時，低黏度的熱塑性樹脂與高黏度的熱塑性樹脂係完全分離，由於樹脂內的碳纖維之分散不充分，在成形時或成形後多發生裂紋或空隙，難以作為製品利用。 However, when the granules obtained by this method are extruded, the low-viscosity thermoplastic resin is completely separated from the high-viscosity thermoplastic resin, and since the dispersion of the carbon fibers in the resin is insufficient, cracks or voids often occur during or after the forming. It is difficult to use as a product.

因此，專利文獻3中揭示使經並絲的長纖 維浸漬有合成樹脂而成之長纖維強化合成樹脂線料(strand)或經切斷成任意長度的長纖維強化合成樹脂顆粒(pellet)，其由纖維含有率高之層與纖維含有率低之層所構成。而且，作為藉由該線料或顆粒所得之發明的效果，可舉出由於是長纖維成束且保持並絲的狀態之線料或顆粒，而成形品的耐衝撃強度良好；浸漬纖維束用的樹脂係低黏度者，浸漬速率快；於浸漬纖維束用的樹脂以外，由於為了彌補樹脂的分子量不足等問題，而使用其它樹脂之複合線料或顆粒，可得到高強度．高彈性之成形品等。 Therefore, Patent Document 3 discloses long filaments which are fused by filaments. A long fiber reinforced synthetic resin strand impregnated with a synthetic resin or a long fiber reinforced synthetic resin pellet cut into an arbitrary length, which has a low fiber content and a low fiber content. The layer is composed. Further, as an effect of the invention obtained by the strand or the pellet, a strand or a pellet in a state in which long fibers are bundled and held in a twinned state is obtained, and the stamping strength of the molded article is good; The resin is low in viscosity and has a high impregnation rate. In addition to the resin for impregnating the fiber bundle, high strength can be obtained by using a composite strand or pellet of another resin in order to compensate for the problem of insufficient molecular weight of the resin. Highly elastic molded articles, etc.

然而，使用該線料或顆粒於擠壓成形時，由於長纖維成束而收束，而在經熔融的樹脂內，碳纖維無法開纖，而且於成形為複雜化的形狀時，碳纖維係變成密集之狀態。結果，於擠壓成形之際，因長纖維而樹脂發生彈出彈回，不僅難以得到目的之形狀，而且碳纖維不均勻分散在樹脂全體中，反而有成為成形品的裂紋或空隙的原因之虞。 However, when the strand or granule is used for extrusion, the long fibers are bundled, and the carbon fibers are not opened in the molten resin, and the carbon fibers become dense when formed into a complicated shape. State. As a result, in the case of extrusion molding, the resin is ejected by the long fibers, and it is difficult to obtain the desired shape, and the carbon fibers are unevenly dispersed in the entire resin, and the cracks or voids of the molded article are caused.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1 日本實開昭60-62912號公報 Patent Document 1 Japanese Unexamined 60-62912

專利文獻2 日本特開2009-263482號公報 Patent Document 2 Japanese Patent Laid-Open Publication No. 2009-263482

專利文獻3 日本特開平6-320536號公報 Patent Document 3 Japanese Patent Laid-Open No. Hei 6-320536

本發明係鑒於該習知技術之問題點而完成者，其目的在於提供包含熱塑性樹脂及碳纖維之力學特性及加工容易性優異之適合擠壓成形之碳纖維複合材料，使用該碳纖維複合材料而成之成形品，以及該碳纖維複合材料及該成形品之製造方法。 The present invention has been made in view of the problems of the prior art, and an object thereof is to provide a carbon fiber composite material suitable for extrusion molding which is excellent in mechanical properties and ease of processing of a thermoplastic resin and carbon fibers, and is formed using the carbon fiber composite material. A molded article, and the carbon fiber composite material and a method of producing the molded article.

為了解決上述問題，本發明之碳纖維複合材料及使用其而成之成形品、以及彼等之製造方法，係具有以下之構成。 In order to solve the above problems, the carbon fiber composite material of the present invention, a molded article using the same, and a method for producing the same have the following constitutions.

(1)一種碳纖維複合材料之製造方法，其係 將具有包含碳纖維之芯成分和包含第1熱塑性樹脂之鞘成分之芯鞘構造的顆粒與第2熱塑性樹脂予以熔融，將經熔融的顆粒及第2熱塑性樹脂在指定溫度混煉的碳纖維複合材料之製造方法，其特徵為：第2熱塑性樹脂係在指定溫度之黏度比第1熱塑性樹脂還高。 (1) A method for producing a carbon fiber composite material, A pellet having a core-sheath structure including a carbon fiber core component and a sheath component containing a first thermoplastic resin and a second thermoplastic resin are melted, and the melted pellet and the second thermoplastic resin are kneaded at a predetermined temperature. The manufacturing method is characterized in that the viscosity of the second thermoplastic resin at a predetermined temperature is higher than that of the first thermoplastic resin.

(2)如(1)之碳纖維複合材料之製造方法，其中於指定溫度，第2熱塑性樹脂之黏度係第1熱塑性樹脂之黏度的10~750倍。 (2) The method for producing a carbon fiber composite material according to (1), wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at a predetermined temperature.

(3)如(1)或(2)之碳纖維複合材料之製造方法，其中在指定溫度的第1熱塑性樹脂之黏度為50~500泊，在指定溫度的第2熱塑性樹脂之黏度為1,000~10,000泊。 (3) The method for producing a carbon fiber composite material according to (1) or (2), wherein the viscosity of the first thermoplastic resin at the specified temperature is 50 to 500 poise, and the viscosity of the second thermoplastic resin at the specified temperature is 1,000 to 10,000. Parking.

(4)如(1)~(3)中任一項之碳纖維複合材料之製造方法，其中指定溫度係比第2熱塑性樹脂之熔點還高，指定溫度與第2熱塑性樹脂之熔點之差為30~90℃。 (4) The method for producing a carbon fiber composite material according to any one of (1) to (3) wherein the specified temperature is higher than the melting point of the second thermoplastic resin, and the difference between the specified temperature and the melting point of the second thermoplastic resin is 30. ~90 ° C.

(5)如(1)~(4)中任一項之碳纖維複合材料之製造方法，其中第2熱塑性樹脂之熔點為100~370℃。 (5) The method for producing a carbon fiber composite material according to any one of (1) to (4) wherein the second thermoplastic resin has a melting point of from 100 to 370 °C.

(6)如(1)~(5)中任一項記載之碳纖維複合材料之製造方法，其中於經熔融的顆粒及第2熱塑性樹脂中，更添加碳纖維。 (6) The method for producing a carbon fiber composite material according to any one of (1) to (5), wherein the carbon particles are further added to the molten particles and the second thermoplastic resin.

(7)如(1)~(6)中任一項記載之碳纖維複合材料之製造方法，其中於碳纖維複合材料中，以5~60重量%之比例含有碳纖維。 (7) The method for producing a carbon fiber composite material according to any one of (1) to (6), wherein the carbon fiber composite material contains carbon fibers in a proportion of 5 to 60% by weight.

(8)一種成形品之製造方法，其特徵為將由如(1)~(7)中任一項之碳纖維複合材料之製造方法所製造的碳纖維複合材料予以熔融，然後成形。 (8) A method of producing a molded article, characterized in that the carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of (1) to (7) is melted and then formed.

(9)如(8)之成形品之製造方法，其中藉由熔融擠壓法(melt extrusion molding method)或固化擠壓法(solidification extrusion molding method)將碳纖維複合材料予以成形。 (9) A method of producing a molded article according to (8), wherein the carbon fiber composite material is formed by a melt extrusion molding method or a solidification extrusion molding method.

(10)如(8)之成形品之製造方法，其中於將碳纖維複合材料予以成形而形成成形中間體後，更藉由加壓成型法、真空成型法、吹塑成形法或彎曲加工將該成形中間體予以成形。 (10) The method for producing a molded article according to (8), wherein after the carbon fiber composite material is molded to form a shaped intermediate body, the press molding method, vacuum molding method, blow molding method, or bending process is further employed. The shaped intermediate is shaped.

(11)如(10)之成形品之製造方法，其中成形中間體係在壓力0.2~100MPa及溫度100~370℃之條件下被熱壓。 (11) The method for producing a molded article according to (10), wherein the forming intermediate system is hot pressed under a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 °C.

(12)如(10)之成形品之製造方法，其中成形中間體係在壓力1×10-5~0.05MPa及溫度100~370℃之條件下被真空成型。 (12) The method for producing a molded article according to (10), wherein the forming intermediate system is vacuum-formed under the conditions of a pressure of 1 × 10 -5 to 0.05 MPa and a temperature of 100 to 370 °C.

(13)如(10)之成形品之製造方法，其中成形中間體係在氣壓0.2~10MPa及溫度100~370℃之條件下被吹塑成形。 (13) The method for producing a molded article according to (10), wherein the forming intermediate system is blow molded under the conditions of a gas pressure of 0.2 to 10 MPa and a temperature of 100 to 370 °C.

(14)如(10)~(13)中任一項之成形品之製造方法，其中成形中間體係在與熱塑性樹脂材料、玻璃纖維基布或碳纖維複合材料彼此積層之狀態下被成形。 (14) The method for producing a molded article according to any one of (10) to (13) wherein the forming intermediate system is formed in a state in which a thermoplastic resin material, a glass fiber base fabric or a carbon fiber composite material is laminated to each other.

(15)一種碳纖維複合材料，其特徵為包含第1熱塑性樹脂、第2熱塑性樹脂及碳纖維，具有於由第2熱塑性樹脂所構成的海相內，分散有由第1熱塑性樹脂所構成的島相之構造。 (15) A carbon fiber composite material comprising a first thermoplastic resin, a second thermoplastic resin, and carbon fibers, and having an island phase composed of a first thermoplastic resin dispersed in a marine phase composed of a second thermoplastic resin Construction.

(16)如(15)之碳纖維複合材料，其中第1熱塑性樹脂的折射率係與第2熱塑性樹脂的折射率相異。 (16) The carbon fiber composite material according to (15), wherein the refractive index of the first thermoplastic resin is different from the refractive index of the second thermoplastic resin.

(17)如(15)或(16)之碳纖維複合材料，其中碳纖維複合材料所含有的碳纖維之中50重量%以上存在於島相內。 (17) The carbon fiber composite material according to (15) or (16), wherein 50% by weight or more of the carbon fibers contained in the carbon fiber composite material are present in the island phase.

(18)如(15)~(17)中任一項之碳纖維複合材料，其中以5~60重量%之比例含有碳纖維。 (18) The carbon fiber composite material according to any one of (15) to (17), wherein the carbon fiber is contained in a proportion of 5 to 60% by weight.

(19)如(15)~(18)中任一項之碳纖維複合材料，其中島相的平均直徑為10nm~100μm。 (19) The carbon fiber composite material according to any one of (15) to (18), wherein the island phase has an average diameter of 10 nm to 100 μm.

(20)如(19)之碳纖維複合材料，其中島相的平均直徑為10nm~1μm。 (20) A carbon fiber composite material according to (19), wherein the island phase has an average diameter of 10 nm to 1 μm.

(21)一種成形品，其係將如(15)~(20)中任一項碳纖維複合材料予以成形而成。 (21) A molded article obtained by molding a carbon fiber composite material according to any one of (15) to (20).

(22)如(21)之成形品，其係藉由熔融擠壓法或固化擠壓法所成形。 (22) A molded article according to (21), which is formed by a melt extrusion method or a curing extrusion method.

(23)如(21)之成形品，其中在將碳纖維複合材料予以成形而形成成形中間體後，更藉由加壓成型法、真空成型法、吹塑成形法或彎曲加工將該成形中間體予以成形而成。 (23) The molded article according to (21), wherein after the carbon fiber composite material is molded to form a shaped intermediate, the forming intermediate is further formed by a press molding method, a vacuum forming method, a blow molding method, or a bending process. It is formed.

(24)如(23)之成形品，其中成形中間體係在壓力0.2~100MPa及溫度100~370℃之條件下被熱壓。 (24) A molded article according to (23), wherein the forming intermediate system is hot pressed under a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 °C.

(25)如(23)之成形品，其中成形中間體係在壓力1×10-5~0.05MPa及溫度100~370℃之條件下被真空成型。 (25) The molded article according to (23), wherein the forming intermediate system is vacuum-formed under the conditions of a pressure of 1 × 10 -5 to 0.05 MPa and a temperature of 100 to 370 °C.

(26)如(23)之成形品，其中成形中間體係在氣壓0.2~10MPa及溫度100~370℃之條件下被吹塑成形。 (26) The molded article according to (23), wherein the forming intermediate system is blow molded under the conditions of a gas pressure of 0.2 to 10 MPa and a temperature of 100 to 370 °C.

(27)如(23)~(26)中任一項之成形品，其中成形中間體係在與熱塑性樹脂材料、玻璃纖維基布或碳纖維複合材料彼此積層之狀態下被成形。 (27) The molded article according to any one of (23) to (26) wherein the forming intermediate system is formed in a state in which a thermoplastic resin material, a glass fiber base fabric or a carbon fiber composite material is laminated to each other.

藉由使用本發明的碳纖維複合材料，在擠壓成形中，可抑制在製品中所發生的裂紋或空隙。結果，藉由切削加工或熱處理處理之加壓加工或彎曲加工之後加工係可容易。 By using the carbon fiber composite material of the present invention, cracks or voids occurring in the product can be suppressed in extrusion molding. As a result, the processing system can be easily processed by press working or bending processing by cutting or heat treatment.

又，由於樹脂為熱塑性，可提供容易回收再利用之成形品。 Further, since the resin is thermoplastic, it is possible to provide a molded article which is easy to recycle and reuse.

1‧‧‧包含碳纖維複合材料的顆粒 1‧‧‧Particles containing carbon fiber composites

2‧‧‧碳纖維 2‧‧‧carbon fiber

3‧‧‧第1熱塑性樹脂 3‧‧‧1st thermoplastic resin

4‧‧‧第2熱塑性樹脂 4‧‧‧2nd thermoplastic resin

5‧‧‧具有3層構造的顆粒 5‧‧‧Particles with 3-layer structure

6‧‧‧具有2層構造的顆粒 6‧‧‧Particles with two layers of structure

20‧‧‧馬達 20‧‧‧Motor

21‧‧‧變速機 21‧‧‧Transmission

22‧‧‧擠壓機 22‧‧‧Extrusion machine

23‧‧‧齒輪泵 23‧‧‧ Gear pump

24‧‧‧冷卻部 24‧‧‧The Ministry of Cooling

25‧‧‧側進給器 25‧‧‧ side feeder

26‧‧‧模頭 26‧‧‧Mold

27‧‧‧線料切刀 27‧‧‧Wire cutter

28‧‧‧腸線 28‧‧‧ Gut

29‧‧‧排氣口 29‧‧‧Exhaust port

30‧‧‧供給口 30‧‧‧ supply port

42、43‧‧‧顆粒供給裝置 42, 43‧‧‧Particle supply device

45‧‧‧筒管 45‧‧‧Bob

46‧‧‧碳纖維粗紗 46‧‧‧carbon fiber roving

50‧‧‧開纖裝置 50‧‧‧Finishing device

51‧‧‧模頭 51‧‧‧Mold

52‧‧‧熨平桿 52‧‧‧Screed rod

53‧‧‧收束賦型部 53‧‧‧Contracting and shaping department

54‧‧‧冷卻部 54‧‧‧The cooling department

55‧‧‧底輥 55‧‧‧ bottom roller

56‧‧‧頂輥 56‧‧‧ top roller

57‧‧‧線料切刀 57‧‧‧Wire cutter

58‧‧‧旋轉刀 58‧‧‧Rotary knife

60‧‧‧擠壓機 60‧‧‧Extrusion machine

61‧‧‧第1熱塑性樹脂 61‧‧‧1st thermoplastic resin

62‧‧‧固定刀 62‧‧‧ fixed knife

70‧‧‧模頭 70‧‧‧die

71‧‧‧第2熱塑性樹脂 71‧‧‧2nd thermoplastic resin

72a、72b‧‧‧導入孔 72a, 72b‧‧‧Importing holes

75‧‧‧顆粒 75‧‧‧Particles

111‧‧‧熔融擠壓片之製造裝置 111‧‧‧Manufacturing device for melt extruded sheet

112‧‧‧模頭 112‧‧‧Mold

114‧‧‧碳纖維複合材料 114‧‧‧Carbon fiber composite

116、118、120‧‧‧加熱輥 116,118,120‧‧‧heating roller

122‧‧‧帶用加熱輥 122‧‧‧With heating roller

124‧‧‧不銹鋼帶 124‧‧‧Stainless steel belt

126‧‧‧加熱爐 126‧‧‧heating furnace

128‧‧‧切刀 128‧‧‧Cutter

129、129a、129b‧‧‧片 129, 129a, 129b‧‧‧

130‧‧‧熔融擠壓管之製造裝置 130‧‧‧Manufacturing device for melt extruded pipe

131‧‧‧熔融擠壓管用模頭 131‧‧‧Dry extrusion pipe die

135‧‧‧管用修準模 135‧‧‧Management model

139‧‧‧冷卻部 139‧‧‧The Ministry of Cooling

141‧‧‧溫度調節水入口 141‧‧‧temperature regulating water inlet

145‧‧‧溫度調節水出口 145‧‧‧temperature regulating water outlet

147‧‧‧恒溫水槽 147‧‧‧Constant water tank

149‧‧‧牽引機 149‧‧‧ traction machine

150‧‧‧切刀 150‧‧‧Cutter

151‧‧‧熔融擠壓管 151‧‧‧Molten extruded tube

180‧‧‧熔融擠壓實心成形品之製造裝置 180‧‧‧Manufacturing device for melt-squeezed solid molded products

185‧‧‧熔融擠壓實心成形品用模頭 185‧‧‧Molded die for solid extrusion

187‧‧‧實心成形品用修準模 187‧‧‧Fixed molds for solid molded products

188‧‧‧熔融擠壓實心品 188‧‧‧Molten extrusion solid products

190‧‧‧熔融擠壓異形品之製造裝置 190‧‧‧Manufacturing device for melt extrusion shaped products

191‧‧‧熔融擠壓異形品用模頭 191‧‧‧Molded extrusion die

192‧‧‧異形品用修準模 192‧‧‧Special model

194‧‧‧熔融擠壓異形品 194‧‧‧Molten extrusion shaped products

197‧‧‧I形異形品 197‧‧‧I Shaped Shaped Goods

198‧‧‧H形異形品 198‧‧‧H-shaped shaped goods

199‧‧‧T形異形品 199‧‧‧T-shaped shaped goods

210‧‧‧固化擠壓成形品之製造裝置 210‧‧‧Manufacturing device for cured extruded products

212‧‧‧固化擠壓成形品用模頭 212‧‧‧Clamp for curing extruded products

213‧‧‧加熱部 213‧‧‧ heating department

215‧‧‧加熱器 215‧‧‧heater

217‧‧‧冷卻部 217‧‧‧The Ministry of Cooling

218‧‧‧隔熱材 218‧‧‧Insulation

219‧‧‧水路 219‧‧‧ Waterway

227‧‧‧牽引機 227‧‧‧ traction machine

230‧‧‧固化擠壓成形品 230‧‧‧Cured extruded products

231‧‧‧塊 231‧‧‧

232‧‧‧圓棒 232‧‧‧ round bar

300‧‧‧積層體 300‧‧‧Layer

301‧‧‧凹模 301‧‧‧ concave die

302‧‧‧凸模 302‧‧‧ punch

305‧‧‧加熱器 305‧‧‧heater

306‧‧‧水冷管 306‧‧‧Water-cooled tube

308、308a、308b‧‧‧熱壓成形片 308, 308a, 308b‧‧‧ thermoformed sheets

320‧‧‧盒形狀用凹模 320‧‧‧Box shape die

321‧‧‧盒形狀用凸模 321‧‧‧Box shape punch

324、327、327a、394‧‧‧熱壓成形體 324, 327, 327a, 394‧‧‧ hot formed bodies

325、326、326a、375、379、393‧‧‧熱壓成形品 325, 326, 326a, 375, 379, 393‧‧‧Hot-pressed products

342‧‧‧真空成形模具 342‧‧‧vacuum forming mould

344‧‧‧吸引孔 344‧‧‧ attracting holes

345‧‧‧吸引口 345‧‧‧ attracting mouth

346‧‧‧真空成形體 346‧‧‧ Vacuum formed body

347‧‧‧真空成形品 347‧‧‧Vacuum molded products

351‧‧‧片固定具 351‧‧‧ piece fixture

352‧‧‧片保持體 352‧‧‧ piece holder

353、392‧‧‧下模 353, 392‧‧‧

354、391‧‧‧上模 354, 391‧‧‧上模

355‧‧‧吹口 355‧‧‧Blowing mouth

356‧‧‧吹孔 356‧‧‧Blow holes

357‧‧‧吹塑成形品保持體 357‧‧‧Blow molded product holder

358‧‧‧吹塑成形品 358‧‧‧Blow molded products

371‧‧‧玻璃纖維織物 371‧‧‧glass fabric

372、378‧‧‧積層體 372, 378‧‧‧ laminated body

377‧‧‧熱塑性樹脂片 377‧‧‧ thermoplastic resin sheet

401‧‧‧S字狀彎曲加工品 401‧‧‧S-shaped curved products

402‧‧‧四方形彎曲加工品 402‧‧‧Square curved products

P1、P2、P3‧‧‧顆粒供給路徑 P1, P2, P3‧‧‧ particle supply path

第1圖係顯示本發明的一實施型態之包含碳纖維複合材料的顆粒之示意斜視圖。 Fig. 1 is a schematic perspective view showing particles of a carbon fiber composite material according to an embodiment of the present invention.

第2圖係用於說明第1圖所示的顆粒之構造的部分放大截面圖，(a)係顯示碳纖維複合材料的構造之一例的模型橫截面圖，(b)係顯示用電子顯微鏡觀察碳纖維複合材料的側截面之結果的一例之截面觀察圖。 Fig. 2 is a partially enlarged cross-sectional view for explaining the structure of the pellet shown in Fig. 1, (a) is a model cross-sectional view showing an example of a structure of a carbon fiber composite material, and (b) is a view showing carbon fiber observed by an electron microscope. A cross-sectional view of an example of the result of the side cross section of the composite material.

第3圖係顯示以往之具有3層構造的顆粒之一例的示意斜視圖。 Fig. 3 is a schematic perspective view showing an example of a conventional three-layer structure.

第4圖係顯示以往之具有2層構造的顆粒之一例的示意斜視圖。 Fig. 4 is a schematic perspective view showing an example of a conventional particle having a two-layer structure.

第5圖係顯示第1圖之顆粒的製造方法之一例的製造步驟圖。 Fig. 5 is a view showing a manufacturing step of an example of a method for producing the pellet of Fig. 1.

第6圖係顯示第1圖之顆粒的製造方法之另一例的製造步驟圖。 Fig. 6 is a view showing a manufacturing step of another example of the method for producing the pellet of Fig. 1.

第7圖係顯示第4圖之顆粒的製造方法之一例的製造步驟圖。 Fig. 7 is a view showing a manufacturing step of an example of a method for producing the pellet of Fig. 4.

第8圖係顯示第3圖之顆粒的製造時所用之模頭的一例之示意縱截面圖。 Fig. 8 is a schematic longitudinal cross-sectional view showing an example of a die used in the production of the pellet of Fig. 3.

第9圖係顯示藉由熔融擠壓法的片之製造方法的一例之製造步驟圖。 Fig. 9 is a view showing a manufacturing step of an example of a method for producing a sheet by a melt extrusion method.

第10圖係顯示藉由熔融擠壓法的管之製造方法的一例之製造步驟圖。 Fig. 10 is a view showing a manufacturing step of an example of a method for producing a tube by a melt extrusion method.

第11圖係例示藉由第10圖之製造方法所製造的管之截面形狀的示意截面圖。 Fig. 11 is a schematic cross-sectional view showing a cross-sectional shape of a tube manufactured by the manufacturing method of Fig. 10.

第12圖係顯示藉由熔融擠壓法的圓棒之製造方法的一例之製造步驟圖。 Fig. 12 is a view showing a manufacturing step of an example of a method for producing a round bar by a melt extrusion method.

第13圖係例示藉由第12圖之製造方法所製造的圓棒之截面形狀的示意截面圖。 Fig. 13 is a schematic cross-sectional view showing a cross-sectional shape of a round bar manufactured by the manufacturing method of Fig. 12.

第14圖係顯示藉由熔融擠壓法的異形品之製造方法的一例之製造步驟圖。 Fig. 14 is a view showing a manufacturing step of an example of a method for producing a shaped article by a melt extrusion method.

第15圖係例示藉由第14圖之製造方法所製造的異形品之截面形狀的示意截面圖，(a)表示I形異形品之截面形狀，(b)表示H形異形品之截面形狀，(c)表示T形異形品之截面形狀。 Fig. 15 is a schematic cross-sectional view showing a cross-sectional shape of a profiled article manufactured by the manufacturing method of Fig. 14, wherein (a) shows a cross-sectional shape of an I-shaped profiled product, and (b) shows a sectional shape of an H-shaped profiled article, (c) shows the cross-sectional shape of the T-shaped profiled product.

第16圖係顯示藉由固化擠壓法的成形品之製造方法的一例之製造步驟圖。 Fig. 16 is a view showing a manufacturing step of an example of a method for producing a molded article by a curing extrusion method.

第17圖係例示藉由第16圖之製造方法所製造的成形品之截面形狀的示意截面圖，(a)表示擠出塊的截面形狀，(b)表示圓棒的截面形狀。 Fig. 17 is a schematic cross-sectional view showing a cross-sectional shape of a molded article produced by the manufacturing method of Fig. 16, wherein (a) shows a cross-sectional shape of the extruded block, and (b) shows a cross-sectional shape of the round bar.

第18圖係顯示藉由熱壓成形的成形步驟之第1例的流程圖，(a)表示準備作為材料的碳纖維複合材料片之步 驟，(b)表示在模具內將片予以積層之步驟，(c)表示將片積層而成的積層體投入模具內的指定位置之步驟，(d)表示關閉模具進行熱壓之步驟，(e)表示打開模具取出成形體之步驟，(f)表示進行成形體之修邊而得到成形品之步驟。 Fig. 18 is a flow chart showing a first example of a forming step by hot press forming, and (a) shows a step of preparing a carbon fiber composite sheet as a material. (b) shows a step of laminating the sheet in the mold, (c) shows a step of putting the laminated body formed into a sheet into a predetermined position in the mold, and (d) shows a step of closing the mold for hot pressing, ( e) shows a step of opening the mold to take out the molded body, and (f) shows a step of performing trimming of the formed body to obtain a molded article.

第19圖係顯示藉由熱壓成形的成形步驟之第2例的流程圖，(a)表示準備作為材料的碳纖維複合材料片之步驟，(b)表示將片置入模具內之步驟，(c)表示關閉模具進行熱壓之步驟，(d)表示打開模具取出成形體之步驟，(e)表示進行成形體的修邊而得到成形品之步驟。 Fig. 19 is a flow chart showing a second example of a forming step by hot press forming, wherein (a) shows a step of preparing a carbon fiber composite material sheet as a material, and (b) shows a step of placing a sheet into a mold, ( c) is a step of closing the mold to perform hot pressing, (d) is a step of opening the mold to take out the molded body, and (e) is a step of performing trimming of the formed body to obtain a molded article.

第20圖係顯示藉由熱壓成形的成形步驟之第3例的流程圖，(a)表示準備作為材料的碳纖維複合材料片之步驟，(b)表示將片置入模具內之步驟，(c)表示關閉模具進行熱壓之步驟，(d)表示打開模具取出成形體之步驟，(e)表示進行成形體的修邊而得到成形品之步驟。 Fig. 20 is a flow chart showing a third example of a forming step by hot press forming, wherein (a) shows a step of preparing a carbon fiber composite material sheet as a material, and (b) shows a step of placing a sheet into a mold, ( c) is a step of closing the mold to perform hot pressing, (d) is a step of opening the mold to take out the molded body, and (e) is a step of performing trimming of the formed body to obtain a molded article.

第21圖係顯示藉由熱壓成形的成形步驟之第4例的流程圖，(a)表示加熱碳纖維複合材料片之步驟，(b)表示將經加熱的片置入模具內之步驟，(c)表示關閉模具進行熱壓之步驟，(d)表示打開模具取出成形體之步驟，(e)表示進行成形體的修邊而得到成形品之步驟。 Figure 21 is a flow chart showing a fourth example of a forming step by hot press forming, wherein (a) shows a step of heating a carbon fiber composite sheet, and (b) shows a step of placing a heated sheet into a mold, ( c) is a step of closing the mold to perform hot pressing, (d) is a step of opening the mold to take out the molded body, and (e) is a step of performing trimming of the formed body to obtain a molded article.

第22圖係顯示藉由真空成形的成形步驟之一例的流程圖，(a)表示加熱碳纖維複合材料片之步驟，(b)表示將經加熱的片置入模具內之步驟，(c)表示將片予以賦型而進行真空成形之步驟，(d)表示自模具取出成形體之步驟，(e)表示進行成形體的修邊而得到成形品之步驟。 Figure 22 is a flow chart showing an example of a forming step by vacuum forming, (a) showing the step of heating the carbon fiber composite sheet, (b) showing the step of placing the heated sheet into the mold, and (c) showing The step of vacuum forming the sheet is carried out, (d) shows the step of taking out the molded body from the mold, and (e) shows the step of trimming the formed body to obtain a molded article.

第23圖係顯示藉由吹塑成形的成形步驟之一例的流程圖，(a)表示將使用碳纖維複合材料片所成的片保持體予以加熱之步驟，(b)表示將經加熱的片保持體置入模具內之步驟，(c)表示關閉模具進行吹塑成形之步驟，(d)表示打開模具取出成形品保持體之步驟，(e)表示進行保持體的卸除及成形體的修邊而得到成形品之步驟，(f)表示所得之成形品的截面圖。 Figure 23 is a flow chart showing an example of a forming step by blow molding, in which (a) shows a step of heating a sheet holder formed using a carbon fiber composite sheet, and (b) shows that the heated sheet is held. The step of inserting the body into the mold, (c) showing the step of closing the mold for blow molding, (d) indicating the step of opening the mold to take out the molded article holder, and (e) indicating the removal of the holder and the repair of the formed body. The step of obtaining a molded article is obtained, and (f) is a cross-sectional view of the obtained molded article.

第24圖係顯示藉由熱壓成形的成形步驟之第5例的流程圖，(a)表示準備碳纖維複合材料片及玻璃纖維織物作為材料之步驟，(b)表示將片及織物在模具內積層之步驟，(c)表示將片及織物積層而成的積層體投入模具內的指定位置之步驟，(d)表示關閉模具進行熱壓之步驟，(e)表示打開模具取出成形體之步驟，(f)表示進行成形體的修邊而得到成形品之步驟。 Figure 24 is a flow chart showing a fifth example of a forming step by hot press forming, wherein (a) shows a step of preparing a carbon fiber composite sheet and a glass fiber fabric as a material, and (b) shows that the sheet and the fabric are in a mold. In the step of laminating, (c) is a step of putting a laminate in which the sheet and the fabric are laminated into a predetermined position in the mold, (d) a step of closing the mold for hot pressing, and (e) a step of opening the mold to take out the formed body. (f) shows a step of obtaining a molded article by trimming the molded body.

第25圖係顯示藉由熱壓成形的成形步驟之第6例的流程圖，(a)表示準備碳纖維複合材料片及熱塑性樹脂片作為材料之步驟，(b)表示將片在模具內積層之步驟，(c)表示將片積層而成的積層體投入模具內的指定位置之步驟，(d)表示關閉模具進行熱壓之步驟，(e)表示打開模具取出成形體之步驟，(f)表示進行成形體的修邊而得到成形品之步驟。 Fig. 25 is a flow chart showing a sixth example of a forming step by hot press forming, wherein (a) shows a step of preparing a carbon fiber composite material sheet and a thermoplastic resin sheet as a material, and (b) shows a step of laminating the sheet in a mold. Step (c) shows a step of putting a laminated body of a laminated layer into a predetermined position in the mold, (d) a step of closing the mold for hot pressing, and (e) a step of opening the mold to take out the molded body, (f) The step of obtaining a molded article by trimming the molded body.

第26圖表示藉由熱壓成形的成形步驟之第7例的流程圖，(a)表示將作為材料的碳纖維複合材料片置入模具內之步驟，(b)表示關閉模具進行熱壓之步驟，(c)表示打開模具取出成形體之步驟，(d)表示進行成形體的修邊而得到成形品之步驟。 Fig. 26 is a flow chart showing a seventh example of the forming step by hot press forming, wherein (a) shows a step of placing a carbon fiber composite material sheet as a material into a mold, and (b) shows a step of closing the mold for hot pressing. (c) shows a step of opening the mold to take out the molded body, and (d) shows a step of performing trimming of the formed body to obtain a molded article.

第27圖係顯示成形品的二次加工之一例的示意斜視圖，(a)表示成為二次加工的材料之異形擠壓品，(b)表示將異形擠壓品予以彎曲加工而成的S字彎曲加工品，(c)將異形擠壓品予以彎曲加工而成的四方形彎曲加工品。 Fig. 27 is a schematic perspective view showing an example of secondary processing of a molded article, wherein (a) shows a profiled extrusion which is a material for secondary processing, and (b) shows a profile of a profiled extrusion which is bent. Word bending product, (c) a square curved product obtained by bending a profiled extrusion.

實施發明的形態 Form of implementing the invention

以下，詳細說明本發明。 Hereinafter, the present invention will be described in detail.

本發明中的碳纖維複合材料之製造方法，係將具有包含碳纖維之芯成分和包含第1熱塑性樹脂之鞘成分之芯鞘構造的顆粒與第2熱塑性樹脂予以熔融，將經熔融的顆粒及第2熱塑性樹脂在指定溫度混煉的碳纖維複合材料之製造方法，該方法之特徵為：第2熱塑性樹脂係在指定溫度之黏度比第1熱塑性樹脂還高。 In the method for producing a carbon fiber composite material according to the present invention, the pellet having the core-sheath structure including the core component of the carbon fiber and the sheath component containing the first thermoplastic resin and the second thermoplastic resin are melted, and the molten pellet and the second layer are melted. A method for producing a carbon fiber composite material in which a thermoplastic resin is kneaded at a predetermined temperature, wherein the second thermoplastic resin has a higher viscosity at a predetermined temperature than the first thermoplastic resin.

又，本發明亦提供由上述製造方法所製造之碳纖維複合材料。即，本發明中的碳纖維複合材料係含有特徵為包含第1熱塑性樹脂、第2熱塑性樹脂及碳纖維，具有於由第2熱塑性樹脂所構成的海相內，分散有由第1熱塑性樹脂所構成的島相之構造者。再者，該碳纖維複合材料亦稱為混雜碳纖維複合樹脂或混雜合金(hybrid alloy)碳纖維複合樹脂。特別是島相的平均直徑(後述)為1μm以下者，係具有與Nanoalloy(註冊商標)類似的優異特性，亦稱為混雜奈米合金碳纖維複合樹脂。 Further, the present invention also provides a carbon fiber composite material produced by the above production method. In other words, the carbon fiber composite material according to the present invention is characterized in that the first thermoplastic resin, the second thermoplastic resin, and the carbon fiber are contained, and the first thermoplastic resin is dispersed in the sea phase composed of the second thermoplastic resin. The constructor of the island. Further, the carbon fiber composite material is also referred to as a hybrid carbon fiber composite resin or a hybrid alloy carbon fiber composite resin. In particular, the average diameter (described later) of the island phase is 1 μm or less, and has excellent properties similar to those of Nanoalloy (registered trademark), and is also referred to as a hybrid nano-carbon fiber composite resin.

於作為成形的材料使用之碳纖維複合材料中，碳纖維與樹脂的親和性，即密接性高，係成形時最 重要之點。又，一般於熱塑性樹脂中，黏度愈低則與碳纖維的密接性愈高。因此，例如亦可考慮使用包含碳纖維與低黏度的樹脂之顆粒來製造碳纖維複合材料。然而，作為碳纖維複合材料的樹脂，若僅使用黏度低的樹脂，則由於在成形時樹脂會追隨碳纖維的配向，有發生碳纖維推開彈回樹脂或裂紋、空隙等的不良狀況之虞，難以得到目的之成形品。相對於此，由上述碳纖維複合材料之製造方法所製造的碳纖維複合材料，係可一邊藉由黏度相對低的第1熱塑性樹脂包裹碳纖維而確保碳纖維與樹脂之親和性，一邊藉由黏度相對高的第2熱塑性樹脂覆蓋第1熱塑性樹脂而抑制彈回(springback)或裂紋、空隙等之不良狀況，而可得到目的之成形品。而且，與習知技術的碳纖維複合材料不同，由於碳纖維、第1熱塑性樹脂及第2熱塑性樹脂皆均勻分散，可得到剛性高之成形品。 In the carbon fiber composite material used as the molding material, the affinity between the carbon fiber and the resin, that is, the adhesion is high, and the most is formed. Important point. Further, generally, in the thermoplastic resin, the lower the viscosity, the higher the adhesion to the carbon fibers. Therefore, for example, it is also conceivable to use a pellet comprising carbon fibers and a low-viscosity resin to produce a carbon fiber composite. However, when a resin having a low viscosity is used as the resin of the carbon fiber composite material, since the resin follows the alignment of the carbon fibers during molding, there is a problem that the carbon fibers are pushed back to repel the resin, cracks, voids, and the like, and it is difficult to obtain The molded article of interest. On the other hand, the carbon fiber composite material produced by the method for producing a carbon fiber composite material can ensure the affinity between the carbon fiber and the resin while encapsulating the carbon fiber with the first thermoplastic resin having a relatively low viscosity, and the viscosity is relatively high. The second thermoplastic resin covers the first thermoplastic resin and suppresses defects such as springback, cracks, and voids, and the desired molded article can be obtained. Further, unlike the carbon fiber composite material of the prior art, since the carbon fiber, the first thermoplastic resin, and the second thermoplastic resin are uniformly dispersed, a molded article having high rigidity can be obtained.

上述第1熱塑性樹脂的折射率與第2熱塑性樹脂的折射率相異為較佳。 The refractive index of the first thermoplastic resin is preferably different from the refractive index of the second thermoplastic resin.

從碳纖維與樹脂的親和性之確保的觀點來看，上述碳纖維複合材料所含有的碳纖維之中50重量%以上存在於島相內較佳。又，存在於島相內的碳纖維之比例更佳為70重量%以上，尤佳為90重量%以上。 From the viewpoint of ensuring the affinity of the carbon fiber and the resin, it is preferable that 50% by weight or more of the carbon fibers contained in the carbon fiber composite material are present in the island phase. Further, the proportion of the carbon fibers present in the island phase is more preferably 70% by weight or more, and particularly preferably 90% by weight or more.

本發明中的碳纖維之纖維直徑較佳為0.5~20μm，更佳為5~15μm。纖維直徑若太粗，則在成形品的熱彎曲加工時，回彈變強，有發生扭曲或凹凸之虞。又，纖維直徑若細，則成形品的機械強度有降低之虞。 The fiber diameter of the carbon fiber in the present invention is preferably from 0.5 to 20 μm, more preferably from 5 to 15 μm. If the fiber diameter is too thick, the rebound becomes strong during the hot bending of the molded article, and distortion or unevenness may occur. Further, if the fiber diameter is small, the mechanical strength of the molded article is lowered.

於上述碳纖維複合材料中，含有碳纖維之比例較佳為5~60重量%，更佳為15~50重量%，尤佳為20~40重量%。 The carbon fiber composite material preferably has a ratio of carbon fibers of 5 to 60% by weight, more preferably 15 to 50% by weight, still more preferably 20 to 40% by weight.

上述的指定溫度較第2熱塑性樹脂之熔點(第2熱塑性樹脂為非晶性時係玻璃轉移點)高為較佳。又，指定溫度與第2熱塑性樹脂之熔點之差較佳為30~90℃，更佳為40~90℃。 The above specified temperature is preferably higher than the melting point of the second thermoplastic resin (the glass transition point when the second thermoplastic resin is amorphous). Further, the difference between the specified temperature and the melting point of the second thermoplastic resin is preferably from 30 to 90 ° C, more preferably from 40 to 90 ° C.

再者，第1熱塑性樹脂之熔點較佳為100~370℃。又，第2熱塑性樹脂之熔點較佳為100~370℃。 Further, the melting point of the first thermoplastic resin is preferably from 100 to 370 °C. Further, the melting point of the second thermoplastic resin is preferably from 100 to 370 °C.

第2熱塑性樹脂之黏度係在上述指定溫度時，相對於第1熱塑性樹脂之黏度，較佳為10~750倍，更佳為20~500倍，尤佳為50~200倍。 When the viscosity of the second thermoplastic resin is at the above specified temperature, the viscosity of the first thermoplastic resin is preferably from 10 to 750 times, more preferably from 20 to 500 times, even more preferably from 50 to 200 times.

又，於上述指定溫度時，第1熱塑性樹脂之黏度為50~500泊，第2熱塑性樹脂之黏度為1,000~10,000泊較佳。再者，於上述指定溫度時，第1熱塑性樹脂之黏度為100~300泊，第2熱塑性樹脂之黏度為1,500泊~5000泊更佳。 Further, at the above specified temperature, the viscosity of the first thermoplastic resin is 50 to 500 poise, and the viscosity of the second thermoplastic resin is preferably 1,000 to 10,000 poise. Further, at the above specified temperature, the viscosity of the first thermoplastic resin is 100 to 300 poise, and the viscosity of the second thermoplastic resin is preferably 1,500 to 5,000 poise.

再者，第1熱塑性樹脂與第2熱塑性樹脂係樹脂成分可相同或相異。例如，於成分相同但聚合度及黏度相異的2種類之樹脂之中，可使用黏度相對地低之樹脂作為第1熱塑性樹脂，使用黏度相對地高之樹脂作為第2熱塑性樹脂。 Further, the first thermoplastic resin and the second thermoplastic resin-based resin component may be the same or different. For example, among the two types of resins having the same composition but different polymerization degrees and viscosities, a resin having a relatively low viscosity can be used as the first thermoplastic resin, and a resin having a relatively high viscosity can be used as the second thermoplastic resin.

碳纖維複合材料之製造時可使用的熱塑性樹脂，係可為聚烯烴(例如聚乙烯、聚丙烯(PP)、聚丁烯、 聚苯乙烯)，或聚醯胺(例如尼龍6、尼龍66、尼龍11、尼龍12、尼龍610、芳香族尼龍)，或聚醯亞胺、聚醯胺醯亞胺、或聚碳酸酯、或聚酯(例如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸丙二酯)，或聚苯硫(PPS)、聚亞碸、或聚四氟乙烯、丙烯腈丁二烯苯乙烯共聚物(ABS)、聚縮醛、聚醚、聚醚．醚．酮、聚甲醛。又，亦可為上述熱塑性樹脂之衍生物，或上述熱塑性樹脂之共聚物，以及彼等之混合物。 The thermoplastic resin that can be used in the manufacture of the carbon fiber composite material can be a polyolefin (for example, polyethylene, polypropylene (PP), polybutene, Polystyrene), or polyamine (such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, aromatic nylon), or polyimine, polyamidimide, or polycarbonate, or Polyester (such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate), or polyphenylene sulfide (PPS), polyarylene, or polytetrafluoroethylene, Acrylonitrile butadiene styrene copolymer (ABS), polyacetal, polyether, polyether. ether. Ketone, polyoxymethylene. Further, it may be a derivative of the above thermoplastic resin, or a copolymer of the above thermoplastic resin, and a mixture thereof.

作為上述熱塑性樹脂，較佳為聚醯胺，更 佳為尼龍6、尼龍66、彼等之衍生物或共聚物、或含有上述任一者之混合物，尤佳為尼龍6、尼龍66。 As the above thermoplastic resin, polydecylamine is preferred, Preferably, nylon 6, nylon 66, derivatives or copolymers thereof, or a mixture of any of the above, more preferably nylon 6, nylon 66.

又，作為上述熱塑性樹脂聚烯烴亦較佳，更佳為聚乙烯、聚丙烯、彼等之衍生物或共聚物、或含有上述任一者之混合物，尤佳為聚乙烯、聚丙烯。 Further, as the thermoplastic resin polyolefin, it is more preferably polyethylene, polypropylene, derivatives or copolymers thereof, or a mixture containing any of the above, and particularly preferably polyethylene or polypropylene.

再者，丙烯腈丁二烯苯乙烯共聚物、其衍生物或共聚物、或含有上述任一者之混合物亦較佳。 Further, an acrylonitrile butadiene styrene copolymer, a derivative or copolymer thereof, or a mixture containing any of the above is also preferred.

更且，聚苯硫、其衍生物或共聚物、或含有上述任一者之混合物亦較佳。 Further, polyphenylene sulfide, a derivative or copolymer thereof, or a mixture containing any of the above is also preferred.

上述島相的平均直徑較佳為10nm~500μm。 再者，所謂島相的平均直徑，意指在碳纖維複合材料之截面中，將各島相換算成同一面積的真圓時之直徑的平均值。島相的平均直徑為1μm以上的混雜合金碳纖維複合樹脂時，平均直徑較佳為1μm~500μm，更佳為1μm~100μm。又，島相的平均直徑小於1μm時的混雜奈米合金碳纖維複合樹脂時，平均直徑較佳為10nm~1μm，更佳為50nm~1μm，尤佳為150nm~1μm。 The average diameter of the above island phase is preferably from 10 nm to 500 μm. In addition, the average diameter of the island phase means the average value of the diameter at the time of converting each island phase into the true circle of the same area in the cross section of a carbon fiber composite material. When the average phase diameter of the island phase is 1 μm or more of the hybrid alloy carbon fiber composite resin, the average diameter is preferably from 1 μm to 500 μm, more preferably from 1 μm to 100 μm. Further, in the case of the hybrid nano-carbon fiber composite resin having an average island diameter of less than 1 μm, the average diameter is preferably from 10 nm to 1 μm, more preferably from 50 nm to 1 μm, still more preferably from 150 nm to 1 μm.

再者，於混煉中，較佳為使用一軸或二軸 的擠壓機。又，較佳為在該擠壓機的圓筒後半部設置真空排氣口，更佳為在該擠壓機的前端具備齒輪泵。 Furthermore, in the kneading, it is preferred to use one or two axes. Extruder. Further, it is preferable to provide a vacuum exhaust port in the rear half of the cylinder of the extruder, and it is more preferable to provide a gear pump at the tip end of the extruder.

於上述碳纖維複合材料之製造方法中，亦 可更將碳纖維添加至經熔融的顆粒及第2熱塑性樹脂中。藉此，可提高碳纖維複合材料中的碳纖維之含有率，提高強度。作為添加碳纖維之方法，例如可舉出將由碳纖維粗紗所拉出的碳纖維長絲直接供應給擠壓機之方法，將切割成適度長度的碳纖維供應給擠壓機之方法等，惟不受此等所限定。 In the above method for producing a carbon fiber composite material, Carbon fibers may be further added to the molten particles and the second thermoplastic resin. Thereby, the content rate of the carbon fiber in the carbon fiber composite material can be improved and the strength can be improved. Examples of the method of adding the carbon fiber include a method of directly supplying the carbon fiber filament drawn from the carbon fiber roving to the extruder, and a method of supplying the carbon fiber cut into an appropriate length to the extruder, but not the like. Limited.

上述碳纖維複合材料係適合於成形用途。即，藉由將上述碳纖維複合材料予以熔融，然後成形，可得到力學強度及加工容易性優異之成形品。特別是包含碳纖維及熱塑性樹脂之上述碳纖維複合材料，係適合於習知技術中難以抑制彈回等的不良狀況之擠壓成形，亦可合適地利用於熔融擠壓法、固化擠壓法之任一者。又，上述碳纖維複合材料也可適用於以往的射出成形。 The above carbon fiber composite material is suitable for molding applications. In other words, by molding the carbon fiber composite material and then molding it, a molded article excellent in mechanical strength and ease of processing can be obtained. In particular, the above-mentioned carbon fiber composite material containing a carbon fiber and a thermoplastic resin is suitable for extrusion molding in which it is difficult to suppress a problem such as springback in the prior art, and can be suitably used in a melt extrusion method or a solidification extrusion method. One. Further, the carbon fiber composite material can also be applied to conventional injection molding.

成形方法係沒有特別的限定，例如可使用日本特開平4-152122號公報中記載的心軸之製造方法及樹脂心軸之擠壓成形裝置、日本特開2001-315193號公報中記載的熔融擠壓之合成樹脂的管之製造方法、日本特開2000-313052號公報中記載的固化擠壓成形製法及其製造裝置、日本特開2008-246865號公報中記載的厚度不等樹脂片之製造方法及裝置等眾所周知之手段，得到包含上述碳纖維複合材料之成形品。又，關於成形品 之形狀，例如可藉由在模頭周圍進行加熱、冷卻、減壓(真空減壓)、隔熱等，而調整至目的之形狀。 The molding method is not particularly limited, and for example, the method for producing a mandrel described in Japanese Laid-Open Patent Publication No. Hei-4-152122, and the extrusion molding apparatus for a resin mandrel, and the melt extrusion described in JP-A-2001-315193 The method for producing a resin sheet having a thickness different from that described in JP-A-2008-246865, and the method for producing a resin sheet having different thicknesses as described in JP-A-2008-246865 A molded article comprising the above carbon fiber composite material is obtained by a well-known means such as a device. Also, about molded products The shape can be adjusted to the intended shape by, for example, heating, cooling, decompression (vacuum decompression), heat insulation, or the like around the die.

再者，對上述成型方法所得之由碳纖維複 合材料所構成的成形品，亦可更施予二次加工，再成形為目的之形狀。作為二次加工之方法，例如可舉出異材積層、同材積層、模內加熱、模外加熱、模內冷卻、模外冷卻、模內加壓、模外加壓、模內減壓(真空減壓)、模外減壓、模內熱彎曲加工、模外熱彎曲加工、延伸、隔熱等，亦可組合此等方法而實施。 Furthermore, the carbon fiber fiber obtained by the above molding method is The molded article composed of the composite material may be further subjected to secondary processing and then shaped into a desired shape. Examples of the method of secondary processing include dissimilar material lamination, homogenous lamination, in-mold heating, over-mold heating, in-mold cooling, over-mold cooling, in-mold pressurization, over-mold pressurization, and in-mold decompression (vacuum The pressure reduction, the external pressure reduction, the in-mold thermal bending process, the external heat bending process, the extension, the heat insulation, etc. may be carried out by combining these methods.

再者，於上述成形中，亦可在包含碳纖維複合材料的顆粒中，更混煉其它顆粒後，進行成形。 Further, in the above molding, the particles may be further kneaded in the particles including the carbon fiber composite material and then molded.

於上述碳纖維複合材料中，亦可含有上述的顆粒或樹脂、碳纖維以外者。例如，亦可含有1~10重量%碳纖維之束的收束或表面處理用的熱硬化性樹脂。又，也可含有如胺基矽烷、環氧矽烷、醯胺矽烷、疊氮矽烷、丙烯酸矽烷之矽烷偶合劑，或鈦酸酯系偶合劑，或此等之混合物。 The carbon fiber composite material may contain particles, resins, or carbon fibers as described above. For example, it may contain a bundle of 1 to 10% by weight of carbon fibers, or a thermosetting resin for surface treatment. Further, a decane coupling agent such as an amino decane, an epoxy decane, an amidoxime, an azide or a decane acrylate, or a titanate coupling agent may be contained, or a mixture thereof.

再者，作為具有芯鞘構造的顆粒之製造方法，可使用眾所周知的方法。例如，設置具備有樹脂浸漬用輥的浸漬模頭，將經擠壓機熔融的第1熱塑性樹脂積蓄於浸漬模頭的樹脂槽內。將經開纖的粗紗狀碳纖維導入浸漬模頭的樹脂槽內，一邊以第1熱塑性樹脂被覆碳纖維粗紗之表面，一邊藉由浸漬輥夾住碳纖維粗紗而使碳纖維粗紗浸漬有第1樹脂。此時，碳纖維粗紗的搬送係藉由將位於樹脂槽的下游之進給輥來牽引碳纖維粗 紗而進行。搬送至下游的碳纖維粗紗係在藉由模頭調整樹脂量，調整截面形狀後，送進具有切刀的切斷裝置。 然後，藉由切斷裝置之切刀來切斷該第1熱塑性樹脂所覆蓋的碳纖維粗紗，而可得到包含碳纖維的芯被第1熱塑性樹脂所覆蓋之具有芯鞘構造的顆粒。又，於此方法所得之具有芯鞘構造的顆粒中，添加包含第2熱塑性樹脂的顆粒，藉由二軸的擠壓機來混煉此等的顆粒，藉由模頭調整樹脂量，調整截面形狀後，送入具有切刀的切斷裝置而切斷，而可製造包含上述碳纖維複合材料的顆粒。 Further, as a method of producing particles having a core-sheath structure, a well-known method can be used. For example, an impregnation die provided with a roller for resin impregnation is provided, and the first thermoplastic resin melted by the extruder is stored in a resin bath of the dip die. The opened roving-like carbon fiber is introduced into the resin tank of the impregnation die, and the carbon fiber roving is impregnated with the first resin while the surface of the carbon fiber roving is coated with the first thermoplastic resin while the carbon fiber roving is sandwiched by the dip roller. At this time, the carbon fiber roving is conveyed by pulling the carbon fiber coarsely by the feed roller located downstream of the resin tank. The yarn is carried out. The carbon fiber roving conveyed to the downstream is adjusted by adjusting the amount of the resin by the die, and the cross-sectional shape is adjusted, and then the cutting device having the cutter is fed. Then, the carbon fiber roving covered by the first thermoplastic resin is cut by a cutter of the cutting device, whereby particles having a core-sheath structure in which the core including the carbon fibers is covered with the first thermoplastic resin can be obtained. Further, in the pellet having the core-sheath structure obtained by the method, particles containing the second thermoplastic resin are added, and the particles are kneaded by a two-axis extruder, and the amount of the resin is adjusted by the die to adjust the cross section. After the shape, it is cut into a cutting device having a cutter and cut, and particles containing the above carbon fiber composite material can be produced.

於熱塑性樹脂中，只要不大幅損害其特性， 則亦可添加添加劑。例如，受阻酚類、磷化合物、受阻胺類、硫化合物、銅化合物、鹼金屬的鹵化物或此等的混合物係可作為熱安定劑、抗氧化劑、強化材、顏料、著色防止劑、耐候劑、難燃劑、可塑劑、結晶核劑、脫模劑等添加劑來添加。 In the thermoplastic resin, as long as the properties are not greatly impaired, Additives can also be added. For example, hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides or mixtures thereof can be used as heat stabilizers, antioxidants, reinforcing materials, pigments, coloring inhibitors, weathering agents Additives such as flame retardant, plasticizer, crystal nucleating agent, and release agent are added.

再者，於上述成形中，亦可實施複數次的 成形步驟。例如，作為上述的成形方法，可採用一次將碳纖維複合材料成形而形成成形中間體後，將所得之成形中間體，更藉由加壓成形法、真空成形法或吹塑成形法進行成形而製造成形品之方法。又，於將成形中間體成形時，亦可組合複數的成形方法來實施。 Furthermore, in the above forming, it is also possible to carry out a plurality of times. Forming step. For example, as the above-described molding method, the carbon fiber composite material may be molded once to form a molding intermediate, and the obtained molding intermediate body may be molded by a press molding method, a vacuum molding method, or a blow molding method. The method of forming a product. Further, when the shaped intermediate is molded, it may be carried out by combining a plurality of molding methods.

於成形步驟中，將模具或碳纖維複合材料 加熱之方法係沒有特別的限定，可適宜使用電熱器、煤氣爐、感應線圈、高壓蒸氣等眾所周知的加熱手段。 In the forming step, the mold or carbon fiber composite material The method of heating is not particularly limited, and a well-known heating means such as an electric heater, a gas furnace, an induction coil, or a high-pressure vapor can be suitably used.

對於在成形品周圍所形成的毛邊，可在模 具的嵌合時同時地切除，也可在另一步驟中藉由湯姆森(Tomson)切裁而拔除。又，藉由使用尺寸比模具小的碳纖維複合材料片來完全填充模具內，亦可抑制毛邊的發生本身。 For the burrs formed around the molded article, it can be used in the mold. Simultaneous excision with the chimerism can be removed in another step by cutting with Tomson. Further, by completely filling the inside of the mold by using a carbon fiber composite material sheet having a smaller size than the mold, the occurrence of the burrs itself can be suppressed.

於上述成形中，碳纖維複合材料亦可積層 而使用，亦可與碳纖維複合材料相異的其它材料組合而使用。例如，可使用使複數的碳纖維複合材料彼此積層而成之積層體來進行成形，也可使單獨或複數的碳纖維複合材料與單獨或複數的其它材料積層而構成積層體，進行成形。作為可積層的其它材料，例如可舉出包含金屬、玻璃或PTFE、聚酯、聚醯胺等熱塑性樹脂之纖維，包含聚胺基甲酸酯等的熱硬化性樹脂之基布、不織布或片，以及熱硬化型的CFRP之片或帶等，亦可組合2種類以上的材料而使用。又，該其它材料係可配置於積層體內的任一層，也可積層於積層體的上端及/或下端。 In the above forming, the carbon fiber composite material may also be laminated. For use, it can also be used in combination with other materials that are different from carbon fiber composite materials. For example, the laminate may be formed by laminating a plurality of carbon fiber composite materials, or a single or plural carbon fiber composite material may be laminated with another material or a plurality of other materials to form a laminate. Examples of the other material which can be laminated include a fiber comprising a thermoplastic resin such as metal, glass or PTFE, polyester or polyamide, and a base fabric, a nonwoven fabric or a sheet of a thermosetting resin such as a polyurethane. And a thermosetting type CFRP sheet or tape, or a combination of two or more types of materials. Further, the other material may be disposed in any layer in the laminate or may be laminated on the upper end and/or the lower end of the laminate.

又，亦可預先在碳纖維複合材料中混合光 澤系的金屬粉、礦物、岩石、砂類。 Also, it is also possible to mix light in a carbon fiber composite material in advance. Zefen's metal powder, minerals, rocks, and sands.

再者，使碳纖維複合材料積層而使用時， 較佳為考慮碳纖維的配向狀態，以碳纖維的配向方向成為90°交叉之方式將碳纖維複合材料予以積層。藉由如此地調整碳纖維的配向方向，可提高成形體的物性。 Furthermore, when the carbon fiber composite material is laminated and used, It is preferable to consider the alignment state of the carbon fibers, and laminate the carbon fiber composite material so that the alignment direction of the carbon fibers becomes 90°. By adjusting the alignment direction of the carbon fibers in this manner, the physical properties of the molded body can be improved.

又，積層體的各自層，亦可由單一的大略 片狀之碳纖維複合材料所構成，也可由複數的碳纖維複合材料之組合來構成。例如，亦可將複數之帶狀的碳纖 維複合材料在寬度方向並排而形成一個層，或將複數之帶狀的碳纖維複合材料組合成格子狀而形成層。特別是較佳為將複數之帶狀的碳纖維複合材料在寬度方向並排而成之層，邊使碳纖維複合材料的排列方向成為90°交叉邊積層。藉由採用該構成，可一邊確保更寬廣的面積，一邊在上下方增厚。 Moreover, the respective layers of the laminated body may also be a single general The sheet-like carbon fiber composite material may be composed of a combination of a plurality of carbon fiber composite materials. For example, a plurality of ribbons of carbon fiber can also be used. The composite material is formed side by side in the width direction to form a layer, or a plurality of ribbon-shaped carbon fiber composite materials are combined into a lattice to form a layer. In particular, it is preferable to laminate a plurality of strip-shaped carbon fiber composite materials in a width direction, and to form a carbon fiber composite material in an arrangement direction of 90°. By adopting this configuration, it is possible to thicken the upper and lower sides while securing a wider area.

再者，藉由事先經加熱的上下之平板的模 具來夾住，施加0.2MPa~100MPa之壓力，亦可以片化成為一片具厚度之大面積的片。 Furthermore, the mold of the upper and lower plates by heating beforehand When it is clamped and applied with a pressure of 0.2 MPa to 100 MPa, it can also be sliced into a sheet having a large area of thickness.

使用上述之加壓成形法進行碳纖維複合材 料之成形時，例如於實施熱壓加工時，壓力較佳為0.2~100MPa，更佳為1~50MPa。 Carbon fiber composite material using the above pressure forming method When the material is formed, for example, when hot press processing is performed, the pressure is preferably 0.2 to 100 MPa, more preferably 1 to 50 MPa.

又，熱壓之溫度較佳為100~370℃。更詳 言之，以碳纖維複合材料中所含有的熱塑性樹脂之熔點作為基準，模具溫度較佳在-10~90℃之範圍內，更佳在0~50℃之範圍內。 Further, the temperature of the hot pressing is preferably from 100 to 370 °C. More detailed In other words, the mold temperature is preferably in the range of -10 to 90 ° C, more preferably in the range of 0 to 50 ° C, based on the melting point of the thermoplastic resin contained in the carbon fiber composite material.

熱壓成形之方法係沒有特別的限定，可舉 出以下之方法作為一例。首先，將一個或複數個的碳纖維複合材料以上述溫度加熱而熔融後，將此置入模具內，關閉模具而成為密閉狀態。然後，於模具之溫度為碳纖維複合材料之熔點以下的狀態，以上述壓力進行加壓，打開模具，取出成形品。 The method of hot press forming is not particularly limited, and The following method is taken as an example. First, one or a plurality of carbon fiber composite materials are heated and melted at the above temperature, and then placed in a mold to close the mold to be in a sealed state. Then, in a state where the temperature of the mold is equal to or lower than the melting point of the carbon fiber composite material, the pressure is applied under the above pressure, and the mold is opened to take out the molded article.

作為熱壓成形的另一方法，將一個或複數 個的碳纖維複合材料置入模具溫度經調整至碳纖維複合材料之熔點以下的模具內，關閉模具。接著，將模具之 溫度加熱至上述溫度為止，而使碳纖維複合材料成為熔融狀態，以上述壓力進行加壓。此時，模具係成為密閉狀態。然後，藉由放置冷卻或水冷等而將模具冷卻，於模具內的碳纖維複合材料固化後，打開模具，取出成形品。 As another method of hot press forming, one or plural The carbon fiber composite material is placed in a mold whose mold temperature is adjusted to be below the melting point of the carbon fiber composite material, and the mold is closed. Next, the mold The temperature is heated to the above temperature, and the carbon fiber composite material is brought into a molten state, and pressurized at the above pressure. At this time, the mold is in a sealed state. Then, the mold is cooled by standing cooling or water cooling, and after the carbon fiber composite material in the mold is solidified, the mold is opened and the molded article is taken out.

作為熱壓成形的再另一方法，將一個或複 數個的碳纖維複合材料以上述溫度加熱而成為半熔融狀態，將此置入模具內。此時，較佳為碳纖維複合材料僅表面成為半熔融狀態。接著，關閉模具，但不完全密閉，使模具成為開放狀態。然後，於模具之溫度成為碳纖維複合材料之熔點以下的狀態，以上述壓力進行加壓後，打開模具，取出成形品。 As another method of hot press forming, one or more A plurality of carbon fiber composite materials are heated at the above temperature to be in a semi-molten state, and are placed in a mold. At this time, it is preferred that the carbon fiber composite material only has a surface in a semi-molten state. Next, the mold is closed, but not completely sealed, and the mold is opened. Then, after the temperature of the mold becomes equal to or lower than the melting point of the carbon fiber composite material, the pressure is applied under the above pressure, and then the mold is opened to take out the molded article.

進行該熱壓成形時，碳纖維複合材料之形 狀較佳為片狀。片之厚度較佳為0.1~3mm，更佳為0.5~2mm，尤佳為1.0~1.5mm。 The shape of the carbon fiber composite material during the hot press forming The shape is preferably in the form of a sheet. The thickness of the sheet is preferably from 0.1 to 3 mm, more preferably from 0.5 to 2 mm, and even more preferably from 1.0 to 1.5 mm.

又，當模具係由凸模及對應其之凹模所構 成時，模具之配置係沒有特別的限制。例如，可上模為凸模，下模為對應其之凹模，也可為其之相反。 Also, when the mold is constructed by a punch and a corresponding die At the time of the formation, there is no particular limitation on the configuration of the mold. For example, the upper mold may be a convex mold, and the lower mold may be a concave mold corresponding thereto, or may be opposite thereto.

使用上述之真空成形法進行碳纖維複合材 料之成形時，壓力較佳為1×10-5~0.05MPa，更佳為0.5×10-4~0.05MPa，尤佳為0.5×10-4~1×10-3MPa。 When the carbon fiber composite material is formed by the above vacuum forming method, the pressure is preferably from 1 × 10 -5 to 0.05 MPa, more preferably from 0.5 × 10 -4 to 0.05 MPa, and particularly preferably from 0.5 × 10 -4 to 1 ×. 10 -3 MPa.

又，真空成形時之溫度較佳為100~370℃。 更詳言之，以碳纖維複合材料中所含有的熱塑性樹脂之熔點作為基準，溫度較佳在-10~90℃之範圍內，更佳在0~50℃之範圍內。 Further, the temperature at the time of vacuum forming is preferably from 100 to 370 °C. More specifically, the temperature is preferably in the range of -10 to 90 ° C, more preferably in the range of 0 to 50 ° C, based on the melting point of the thermoplastic resin contained in the carbon fiber composite material.

真空成形之方法係沒有特別的限定，可舉 出以下之方法作為一例。首先，將一個或複數個之碳纖維複合材料以上述溫度加熱而成為熔融狀態，將此置入模具內，關閉模具。然後，於模具之溫度成為碳纖維複合材料之熔點以下之狀態，以上述壓力進行減壓後，打開模具，取出成形品。此時，減壓係可在上模側或下模側的任一側進行，也可在上模側及下模側這兩側同時進行。 The method of vacuum forming is not particularly limited, and The following method is taken as an example. First, one or a plurality of carbon fiber composite materials are heated at the above temperature to be in a molten state, and this is placed in a mold to close the mold. Then, after the temperature of the mold becomes lower than the melting point of the carbon fiber composite material, the pressure is reduced by the above pressure, and then the mold is opened to take out the molded article. In this case, the pressure reduction system may be performed on either the upper mold side or the lower mold side, or may be performed simultaneously on both the upper mold side and the lower mold side.

作為真空成形之另一方法，將一個或複數 個之碳纖維複合材料以上述溫度加熱而成為熔融狀態，將此置入模具內。然後，於使模具的下模上升後，自下模側以上述壓力進行吸引，打開模具，取出成形品。 As another method of vacuum forming, one or plural The carbon fiber composite material is heated at the above temperature to be in a molten state, and this is placed in a mold. Then, after raising the lower mold of the mold, suction is performed from the lower mold side under the above pressure, and the mold is opened to take out the molded product.

作為真空成形之再另一方法，將一個或複 數個之碳纖維複合材料以上述溫度加熱而成熔融狀態，將此置入模具內。然後，於使模具的上模上升後，自上模側以上述壓力進行吸引，打開模具，取出成形品。 As another method of vacuum forming, one or more A plurality of carbon fiber composite materials are heated to a molten state at the above temperature, and placed in a mold. Then, after raising the upper mold of the mold, suction is performed from the upper mold side under the above pressure, and the mold is opened to take out the molded product.

於進行該真空成形時，在加熱碳纖維複合 材料後，於藉由模具進行成形之前，自下方噴吹空氣，或使用壓縮空氣，亦可謀求成形的均一化。此時，碳纖維複合材料之形狀較佳為片狀。再者，使用壓縮空氣時，壓力較佳為0.1~10MPa，較佳為以碳纖維複合材料不破損之方式，調整壓力。 In the vacuum forming, heating carbon fiber composite After the material is formed, it is also possible to form a uniform shape by blowing air from below or using compressed air before molding by a mold. At this time, the shape of the carbon fiber composite material is preferably a sheet shape. Further, when compressed air is used, the pressure is preferably 0.1 to 10 MPa, and it is preferred to adjust the pressure so that the carbon fiber composite material is not damaged.

使用上述之吹塑成形法進行碳纖維複合材 料之成形時，吹塑壓力較佳為0.2~10MPa，更佳為0.5~2MPa。 Carbon fiber composite material using the above blow molding method When the material is formed, the blowing pressure is preferably 0.2 to 10 MPa, more preferably 0.5 to 2 MPa.

又，吹塑成形時之溫度較佳為100~370℃。 更詳言之，以碳纖維複合材料中所含有的熱塑性樹脂之熔點作為基準，溫度較佳在-10~90℃之範圍內，更佳在0~50℃之範圍內。 Further, the temperature at the time of blow molding is preferably from 100 to 370 °C. More specifically, the temperature is preferably in the range of -10 to 90 ° C, more preferably in the range of 0 to 50 ° C, based on the melting point of the thermoplastic resin contained in the carbon fiber composite material.

真空成形之方法係沒有特別的限定，可舉 出以下之方法作為一例。首先，以上述溫度加熱包含碳纖維複合材料之一張或複數張之片，成為半熔融狀態後，進行吹塑而將片擴展。此時，較佳為片僅表面成為半熔融狀態。接著，將半熔融狀態之片置入模具內，關閉模具，進行吹塑。此時，模具係密閉狀態。然後，於模具之溫度為碳纖維複合材料的熔點以下之狀態，以上述壓力進行加壓後，打開模具，取出成形品。 The method of vacuum forming is not particularly limited, and The following method is taken as an example. First, one or a plurality of sheets including the carbon fiber composite material are heated at the above temperature to be in a semi-molten state, and then blown to expand the sheet. At this time, it is preferred that only the surface of the sheet is in a semi-molten state. Next, the sheet in a semi-molten state was placed in a mold, and the mold was closed to perform blow molding. At this time, the mold is in a sealed state. Then, after the temperature of the mold is equal to or lower than the melting point of the carbon fiber composite material, the pressure is applied under the above pressure, and then the mold is opened to take out the molded article.

彎曲加工之方法係沒有特別的限定，可舉 出以下之方法作為一例。首先，以100~370℃加熱包含一個或複數個之碳纖維複合材料之I形異形擠壓品，成為半熔融狀態後，沿著模具固定，於烘箱內更以100~370℃加熱。然後，冷卻至室溫為止後，自模具卸下，取出成形品。 The method of bending processing is not particularly limited, and The following method is taken as an example. First, an I-shaped extruded product comprising one or a plurality of carbon fiber composite materials is heated at 100 to 370 ° C to be in a semi-molten state, fixed along a mold, and heated at 100 to 370 ° C in an oven. Then, after cooling to room temperature, it was removed from the mold, and the molded article was taken out.

再者，難以彎曲時，亦可局部地使用有機溶劑等使彎曲部分等柔軟後，加熱，進行彎曲加工。 Further, when it is difficult to bend, the bent portion or the like may be softened by using an organic solvent or the like locally, and then heated to perform bending.

其次，藉由實施例來更具體說明本發明。 惟，各實施例及比較例中，所使用的材料及破壞強度之測定方法係如以下。 Next, the present invention will be more specifically described by way of examples. However, in each of the examples and comparative examples, the materials used and the method for measuring the breaking strength are as follows.

(1)所使用的材料 (1) Materials used

(A)碳纖維粗紗(roving)/長絲(filament) (A) carbon fiber roving / filament

準備纖維直徑7um、支數200tex、捲長30,000m之碳纖維長絲。將此長絲5條合絲，給予2重量%的聚胺基甲酸酯之收束劑，準備平坦帶狀之碳纖維粗紗。 Carbon fiber filaments having a fiber diameter of 7 μm, a count of 200 tex, and a roll length of 30,000 m were prepared. The 5 filaments of the filaments were subjected to a 2% by weight polyurethane bunching agent to prepare a flat ribbon-shaped carbon fiber roving.

(B)第1熱塑性樹脂 (B) First thermoplastic resin

B1：尼龍6(熔點：在225℃、275℃的黏度：100泊) B1: Nylon 6 (melting point: viscosity at 225 ° C, 275 ° C: 100 poise)

B2：尼龍66(熔點：在255℃、305℃的黏度：250泊) B2: Nylon 66 (melting point: viscosity at 255 ° C, 305 ° C: 250 poise)

B3：PP(熔點：在170℃、220℃的黏度：70泊) B3: PP (melting point: viscosity at 170 ° C, 220 ° C: 70 poise)

B4：ABS(玻璃轉移點(軟化點)：在190℃、240℃的黏度：120泊) B4: ABS (glass transition point (softening point): viscosity at 190 ° C, 240 ° C: 120 poise)

B5：PPS(熔點：在285℃、335℃的黏度：260泊) B5: PPS (melting point: viscosity at 285 ° C, 335 ° C: 260 poise)

(C)第2熱塑性樹脂 (C) second thermoplastic resin

C1：尼龍6(熔點：在225℃、275℃的黏度：1,100泊) C1: Nylon 6 (melting point: viscosity at 225 ° C, 275 ° C: 1,100 poise)

C2：尼龍66(熔點：在255℃、305℃的黏度：5,500泊) C2: Nylon 66 (melting point: viscosity at 255 ° C, 305 ° C: 5,500 poise)

C3：PP(熔點：在170℃、220℃的黏度：1,770泊) C3: PP (melting point: viscosity at 170 ° C, 220 ° C: 1,770 poise)

C4：ABS(軟化點：在190℃、240℃的黏度：2,520泊) C4: ABS (softening point: viscosity at 190 ° C, 240 ° C: 2,520 poise)

C5：PPS(熔點：在255℃、335℃的黏度：8,060泊) C5: PPS (melting point: viscosity at 255 ° C, 335 ° C: 8,060 poise)

(2)破壞強度之測定方法 (2) Method for determining the breaking strength

於破壞強度(彎曲強度及彎曲彈性模數(flexural modulus))之測定時，依照JIS規格K7161，使用Tensilon 拉伸試驗機(RTF-1360)。 For the measurement of the breaking strength (bending strength and flexural modulus), a Tensilon tensile tester (RTF-1360) was used in accordance with JIS Standard K7161.

[實施例1] [Example 1]

以下，各實施例及比較例中的試驗條件，只要沒有特別的記載，則基本上以實施例1為準。 Hereinafter, the test conditions in the respective examples and comparative examples are basically as in the first embodiment unless otherwise specified.

第7圖顯示包含碳纖維的芯經由熱塑性樹脂覆蓋之具有芯鞘構造的顆粒之習知技術的製造方法。於第7圖的製造方法中，藉由使平坦帶狀的碳纖維粗紗46通過開纖裝置50送出至擠壓機60，同時將包含尼龍6的第1熱塑性樹脂B1投入擠壓機60中，使經熔融的第1熱塑性樹脂61(B1)通過模頭51以溫度275℃吐出至碳纖維粗紗，而以樹脂B1被覆碳纖維粗紗46之表面。自模頭51所拉出的碳纖維粗紗46，係在通過熨平桿52提高樹脂B1對碳纖維的浸漬度後，在收束賦型部53調整形狀，在冷卻部54被冷卻。然後，一邊藉由頂輥55及底輥56牽引表面經樹脂B1被覆的碳纖維粗紗46，一邊藉由具備旋轉刀58與固定刀62的線料切刀57進行切割，而得到如第4圖所示包含碳纖維的芯經由尼龍6覆蓋之具有芯鞘構造的顆粒6(第7圖中的顆粒59)。再者，所得之顆粒6中的碳纖維之含有率為30%。 Fig. 7 shows a manufacturing method of a conventional technique including a core having a core-sheath structure in which a core of carbon fibers is covered with a thermoplastic resin. In the manufacturing method of Fig. 7, the flat ribbon-shaped carbon fiber rovings 46 are sent to the extruder 60 through the fiber opening device 50, and the first thermoplastic resin B1 containing the nylon 6 is introduced into the extruder 60. The molten first thermoplastic resin 61 (B1) is discharged through a die 51 to a carbon fiber roving at a temperature of 275 ° C, and the surface of the carbon fiber roving 46 is covered with a resin B1. The carbon fiber rovings 46 pulled out from the die 51 are adjusted in the shape of the bundle B, and then cooled in the cooling unit 54 after the degree of impregnation of the carbon fibers by the resin B1 is increased by the ironing rod 52. Then, the carbon fiber roving 46 coated with the resin B1 is pulled by the top roller 55 and the bottom roller 56, and is cut by the wire cutter 57 including the rotary blade 58 and the fixed blade 62, thereby obtaining the image as shown in Fig. 4. The core 6 (particle 59 in Fig. 7) having a core sheath structure covered with a core comprising carbon fibers is covered with nylon 6. Further, the content of the carbon fibers in the obtained pellets 6 was 30%.

將此芯鞘型之含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，自顆粒供給路徑P1通過供給口30，對擠壓機22內供給該顆粒。又，將包含第2熱塑性樹脂C1的顆粒投入顆粒供給裝置43中，自顆粒供給路徑P2通過供給口30，對擠壓機22內供給該顆粒。此第2熱塑性樹脂C1係包含尼龍6，黏度比上述B1高。 藉由將此等顆粒在具備馬達20及變速機21的擠壓機22內，以溫度275℃進行混煉，在排氣口29脫氣，邊以齒輪泵23計量邊流入模頭26，而得到腸線(gut)28。然後，將所得之腸線28在冷卻部24冷卻後，用線料切刀27進行切割，得到包含尼龍6之混雜顆粒1(包含碳纖維複合材料之顆粒)。此包含尼龍6的混雜顆粒1中之碳纖維的含有率為15重量%。 The core-sheath type carbon fiber-containing resin particles 6 are introduced into the pellet supply device 42 shown in Fig. 5, and the pellets are supplied from the pellet supply path P1 through the supply port 30 to the inside of the extruder 22. Moreover, the pellet containing the second thermoplastic resin C1 is introduced into the pellet supply device 43, and the pellet is supplied from the pellet supply path P2 through the supply port 30 to the inside of the extruder 22. The second thermoplastic resin C1 contains nylon 6, and has a higher viscosity than the above B1. These particles are kneaded at a temperature of 275 ° C in the extruder 22 including the motor 20 and the speed change machine 21, degassed at the exhaust port 29, and flowed into the die 26 while being metered by the gear pump 23. A gut 28 is obtained. Then, the obtained gut 28 is cooled by the cooling portion 24, and then cut with a strand cutter 27 to obtain hybrid particles 1 containing nylon 6 (particles comprising a carbon fiber composite). The content of the carbon fibers in the hybrid particles 1 containing nylon 6 was 15% by weight.

使用此混雜顆粒進行射出成形，製作測定寬度10±0.5mm、測定長度80±2mm之啞鈴片。所得之啞鈴片的彎曲強度為250MPa，彎曲彈性模數為10.2GPa。 This hybrid particle was subjected to injection molding to prepare a dumbbell piece having a measurement width of 10 ± 0.5 mm and a measurement length of 80 ± 2 mm. The obtained dumbbell piece had a bending strength of 250 MPa and a bending elastic modulus of 10.2 GPa.

第1圖及第2圖中顯示藉由實施例1記載之方法所製造的由碳纖維複合材料所構成的顆粒1之構造。第1圖係顯示本發明的一實施型態之混雜顆粒1(包含碳纖維複合材料的顆粒)之示意斜視圖。又，第2圖係用於說明混雜顆粒1之構造用的部分放大截面圖，(a)係顯示混雜顆粒1的截面1a狀態之模型橫截面圖，(b)係顯示用電子顯微鏡觀察藉由實施例1之方法所製造的混雜顆粒1之側截面1b的結果之截面觀察圖。再者，於第2圖(b)中，為了使碳纖維2及島相3之識別成為容易化，將黑色表示的碳纖維2之周圍以細白線鑲邊，同時將由第1熱塑性樹脂所構成的島相3以粗白線來包圍而表示。如第2圖所示，混雜顆粒1係具有在包含第2熱塑性樹脂的海相4內，分散有包含第1熱塑性樹脂的島相3之構造、碳纖維2及島相3係均勻分散在混雜顆粒1內。藉由該碳纖維複合材料，由於可將起因於碳纖維或 熱塑性樹脂的偏向存在所造成的不良狀況(例如彈回或空隙)防患於未然，不僅在射出成形中，即使在擠壓成形中，也可得到表面狀態良好之剛性優異的成形品。 The structure of the pellet 1 composed of the carbon fiber composite material produced by the method described in Example 1 is shown in Figs. 1 and 2 . Fig. 1 is a schematic perspective view showing a hybrid particle 1 (particles comprising a carbon fiber composite material) of an embodiment of the present invention. Further, Fig. 2 is a partially enlarged cross-sectional view for explaining the structure of the hybrid particle 1, (a) showing a cross-sectional view of the cross section 1a of the hybrid particle 1, and (b) showing the observation by an electron microscope. A cross-sectional observation of the result of the side section 1b of the hybrid particle 1 produced by the method of Example 1. In addition, in the second drawing (b), in order to facilitate the identification of the carbon fiber 2 and the island phase 3, the periphery of the carbon fiber 2 indicated by black is rimmed with a fine white line, and the island made of the first thermoplastic resin is used. Phase 3 is represented by a thick white line. As shown in Fig. 2, the hybrid particles 1 have a structure in which the island phase 3 containing the first thermoplastic resin is dispersed in the sea phase 4 including the second thermoplastic resin, and the carbon fibers 2 and the island phase 3 are uniformly dispersed in the mixed particles. 1 inside. With the carbon fiber composite, it can be caused by carbon fiber or The defective state (for example, springback or void) caused by the deflection of the thermoplastic resin is prevented, and a molded article excellent in rigidity in a good surface state can be obtained not only in the injection molding but also in extrusion molding.

第4圖顯示實施例1記載之方法中使用的顆粒6之構造。於第4圖中，包含含有碳纖維的樹脂之顆粒6係具有包含碳纖維2的芯經由熱塑性樹脂3(實施例1中，包含尼龍6的第1熱塑性樹脂B1)覆蓋之芯鞘構造。再者，具有芯鞘構造的顆粒之構成係不僅限定於上述，而可適宜利用各種的顆粒。例如，如第3圖所示，包含碳纖維2的芯被熱塑性樹脂3所覆蓋，更且在其外側被黏度比熱塑性樹脂3高之熱塑性樹脂4(例如包含尼龍6的第2熱塑性樹脂B2)所覆蓋之顆粒5，亦可使用作為碳纖維複合材料之原料。 Fig. 4 shows the structure of the particles 6 used in the method described in the first embodiment. In Fig. 4, the pellet 6 containing the carbon fiber-containing resin has a core-sheath structure in which the core including the carbon fiber 2 is covered with the thermoplastic resin 3 (the first thermoplastic resin B1 containing the nylon 6 in the first embodiment). Further, the constitution of the particles having the core-sheath structure is not limited to the above, and various particles can be suitably used. For example, as shown in Fig. 3, the core including the carbon fiber 2 is covered with the thermoplastic resin 3, and the thermoplastic resin 4 having a higher viscosity than the thermoplastic resin 3 (for example, the second thermoplastic resin B2 containing nylon 6) is provided on the outer side thereof. The coated particles 5 can also be used as a raw material for the carbon fiber composite material.

[實施例2] [Embodiment 2]

於第7圖所示的製造方法中，將包含尼龍66的第1熱塑性樹脂B2自擠壓機60以溫度305℃吐出至平坦帶狀的碳纖維粗紗，而得到包含碳纖維的芯經由尼龍66覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為40重量%。 In the manufacturing method shown in Fig. 7, the first thermoplastic resin B2 containing nylon 66 is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 305 ° C to obtain a core containing carbon fibers covered with nylon 66. A core-sheath type resin particle 6 containing a carbon fiber structure having a core-sheath structure. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 40% by weight.

將此包含尼龍66之芯鞘型含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，同時將包含第2熱塑性樹脂C2的顆粒投入顆粒供給裝置43中。此第2熱塑性樹脂C2係包含尼龍66，黏度比上述B2高。將此 等顆粒在溫度305℃混煉，藉由第5圖所示之製造方法，得到包含尼龍66的混雜顆粒1。此包含尼龍66的混雜顆粒1中之碳纖維的含有率為20重量%。 The core-sheath type carbon fiber-containing resin particles 6 containing nylon 66 are put into the pellet supply device 42 shown in Fig. 5, and the particles containing the second thermoplastic resin C2 are put into the pellet supply device 43. The second thermoplastic resin C2 contains nylon 66 and has a higher viscosity than the above B2. Do this The particles were kneaded at a temperature of 305 ° C, and the hybrid particles 1 containing nylon 66 were obtained by the production method shown in Fig. 5. The content of the carbon fibers in the hybrid particles 1 containing nylon 66 was 20% by weight.

[實施例3] [Example 3]

於第7圖所示之製造方法中，將包含PP的第1熱塑性樹脂B3自擠壓機60以溫度220℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由PP覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中之碳纖維的含有率為20重量%。 In the production method shown in Fig. 7, the first thermoplastic resin B3 containing PP is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 220 ° C to obtain a core comprising a carbon fiber core covered with PP. A core-sheath type resin particle 6 containing carbon fibers is constructed. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 20% by weight.

將此包含PP之芯鞘型含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，同時將包含第2熱塑性樹脂C3的顆粒投入顆粒供給裝置43中。此第2熱塑性樹脂C3係包含PP，黏度比上述B3高。將此等顆粒在溫度220℃混煉，藉由第5圖所示之製造方法，得到包含PP的混雜顆粒1。此包含PP的混雜顆粒1中之碳纖維的含有率為15重量%。 The core-sheath type carbon fiber-containing resin particles 6 containing PP are put into the pellet supply device 42 shown in Fig. 5, and the particles containing the second thermoplastic resin C3 are put into the pellet supply device 43. The second thermoplastic resin C3 contains PP and has a higher viscosity than the above B3. These particles were kneaded at a temperature of 220 ° C, and the hybrid particles 1 containing PP were obtained by the production method shown in Fig. 5 . The content of the carbon fibers in the hybrid particles 1 containing PP was 15% by weight.

[實施例4] [Example 4]

於第7圖所示之製造方法中，將包含ABS的第1熱塑性樹脂B4自擠壓機60以溫度240℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由ABS覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為25重量%。 In the manufacturing method shown in Fig. 7, the first thermoplastic resin B4 containing ABS is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 240 ° C to obtain a core sheath containing a carbon fiber core covered with ABS. A core-sheath type resin particle 6 containing carbon fibers is constructed. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 25% by weight.

將此包含ABS之芯鞘型含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，同時將包含第2熱塑性樹脂C4的顆粒投入顆粒供給裝置43中。此第2熱塑性樹脂C4係包含ABS，黏度比上述B4高。將此等以溫度240℃混煉，藉由第5圖所示之製造方法，得到包含ABS的混雜顆粒1。此包含ABS所的混雜顆粒1中之碳纖維的含有率為15重量%。 The core-sheath type carbon fiber-containing resin particles 6 containing ABS are introduced into the pellet supply device 42 shown in Fig. 5, and the particles containing the second thermoplastic resin C4 are introduced into the pellet supply device 43. The second thermoplastic resin C4 contains ABS and has a higher viscosity than the above B4. These were kneaded at a temperature of 240 ° C, and the hybrid particles 1 containing ABS were obtained by the production method shown in Fig. 5 . The content of the carbon fibers in the hybrid particles 1 containing ABS was 15% by weight.

[實施例5] [Example 5]

於第7圖所示之製造方法中，將包含PPS的第1熱塑性樹脂B5自擠壓機60以溫度335℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由PPS覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為30重量%。 In the production method shown in Fig. 7, the first thermoplastic resin B5 containing PPS is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 335 ° C to obtain a core sheath containing a carbon fiber core covered with PPS. A core-sheath type resin particle 6 containing carbon fibers is constructed. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 30% by weight.

將此包含PPS之芯鞘型含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，同時將包含第2熱塑性樹脂C5的顆粒投入顆粒供給裝置43中。此第2熱塑性樹脂C5係包含PPS，黏度比上述B5高。將此等顆粒在溫度335℃混煉，藉由第5圖所示之製造方法，得到包含PPS的混雜顆粒1。此包含PPS的混雜顆粒1之碳纖維的含有率為20重量%。 The core-sheath type carbon fiber-containing resin particles 6 containing PPS are placed in the pellet supply device 42 shown in Fig. 5, and the particles containing the second thermoplastic resin C5 are introduced into the pellet supply device 43. The second thermoplastic resin C5 contains PPS and has a higher viscosity than the above B5. These particles were kneaded at a temperature of 335 ° C, and the hybrid particles 1 containing PPS were obtained by the production method shown in Fig. 5 . The content of the carbon fibers of the hybrid particles 1 containing PPS was 20% by weight.

[實施例6] [Embodiment 6]

於第7圖所示之製造方法中，將包含尼龍6的第1熱塑性樹脂B1自擠壓機60以溫度275℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由尼龍6覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為30重量%。 In the manufacturing method shown in Fig. 7, the first thermoplastic resin B1 containing nylon 6 is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 275 ° C to obtain a core containing carbon fibers covered with nylon 6 A core-sheath type core-sheath type resin particle containing carbon fibers. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 30% by weight.

將此包含尼龍6之芯鞘型含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，自顆粒供給路徑P1通過供給口30，對擠壓機22供給該顆粒。又，將包含第2熱塑性樹脂C1的顆粒投入顆粒供給裝置43中，代替顆粒供給路徑P2，自顆粒供給路徑P3通過側進給器25，對擠壓機22供給該顆粒。將此等顆粒在溫度270℃混煉，藉由第5圖所示之製造方法，得到包含尼龍6的混雜顆粒1。此包含尼龍6的混雜顆粒1中之碳纖維的含有率為20重量%。 The resin particles 6 containing the nylon 6 core-sheath type carbon fiber are introduced into the pellet supply device 42 shown in Fig. 5, and the pellets 22 are supplied from the pellet supply path P1 through the supply port 30 to the extruder 22. Moreover, the pellet containing the second thermoplastic resin C1 is put into the pellet supply device 43, and the pellet is supplied to the extruder 22 from the pellet supply path P3 through the side feeder 25 instead of the pellet supply path P2. These particles were kneaded at a temperature of 270 ° C, and the hybrid particles 1 containing nylon 6 were obtained by the production method shown in Fig. 5 . The content of the carbon fibers in the hybrid particles 1 containing nylon 6 was 20% by weight.

[實施例7] [Embodiment 7]

於第7圖所示之製造方法中，將包含尼龍6的第1熱塑性樹脂B1自擠壓機60以溫度275℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由尼龍6覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為30重量%。 In the manufacturing method shown in Fig. 7, the first thermoplastic resin B1 containing nylon 6 is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 275 ° C to obtain a core containing carbon fibers covered with nylon 6 The core-sheath type core-sheath type resin particles 6 containing carbon fibers. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 30% by weight.

將此尼龍6的芯鞘型碳纖維樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，自顆粒供給路徑P1通過供給口30，對擠壓機22內供給該顆粒。又，將包含第2熱塑性樹脂C1的顆粒投入顆粒供給裝置43中，代替顆粒供給路徑P2，自顆粒供給路徑P3通過側進給器25，對擠壓機22內供給該顆粒。然後，將此等顆粒在溫度275℃混煉，藉由第5圖所示之製造方法，得到包含尼龍6的混雜顆粒1。此包含尼龍6的混雜顆粒1中之碳纖維的含有率為20重量%。 The core-sheath type carbon fiber resin pellets 6 of the nylon 6 are put into the pellet supply device 42 shown in Fig. 5, and the pellets are supplied into the extruder 22 through the supply port 30 from the pellet supply path P1. Moreover, the pellet containing the second thermoplastic resin C1 is put into the pellet supply device 43, and the pellet is supplied from the pellet supply path P3 to the extruder 22 through the side feeder 25 instead of the pellet supply path P2. Then, these particles were kneaded at a temperature of 275 ° C, and the hybrid particles 1 containing nylon 6 were obtained by the production method shown in Fig. 5 . The content of the carbon fibers in the hybrid particles 1 containing nylon 6 was 20% by weight.

[實施例8] [Embodiment 8]

於第7圖所示之製造方法中，將包含尼龍6的第1熱塑性樹脂B1自擠壓機60以溫度275℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由尼龍6覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為30重量%。 In the manufacturing method shown in Fig. 7, the first thermoplastic resin B1 containing nylon 6 is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 275 ° C to obtain a core containing carbon fibers covered with nylon 6 The core-sheath type core-sheath type resin particles 6 containing carbon fibers. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 30% by weight.

將此包含尼龍6之芯鞘型含有碳纖維的樹脂顆粒6投入第5圖所示的顆粒供給裝置42中，自顆粒供給路徑P1通過供給口30，對擠壓機22供給該顆粒。又，將包含第2熱塑性樹脂C2的顆粒投入顆粒供給裝置43中，代替顆粒供給路徑P2，自顆粒供給路徑P3通過側進給器25，對擠壓機22內供應該顆粒。然後，將此等顆粒在溫度305℃混煉，藉由第5圖所示之製造方法，得到包含尼龍6及尼龍66的混雜顆粒1。此混雜顆粒1中之碳纖維的含有率為15重量%。 The resin particles 6 containing the nylon 6 core-sheath type carbon fiber are introduced into the pellet supply device 42 shown in Fig. 5, and the pellets 22 are supplied from the pellet supply path P1 through the supply port 30 to the extruder 22. Moreover, the pellet containing the second thermoplastic resin C2 is put into the pellet supply device 43, and the pellet is supplied from the pellet supply path P3 to the extruder 22 through the side feeder 25 instead of the pellet supply path P2. Then, the particles were kneaded at a temperature of 305 ° C, and the hybrid particles 1 containing nylon 6 and nylon 66 were obtained by the production method shown in Fig. 5 . The content of the carbon fibers in the hybrid particles 1 was 15% by weight.

[實施例9] [Embodiment 9]

於第7圖所示之製造方法中，將包含尼龍6的第1熱塑性樹脂B1自擠壓機60以溫度275℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由尼龍6覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。芯鞘型含有碳纖維的樹脂顆粒6中之碳纖維的含有率為35重量%。 In the manufacturing method shown in Fig. 7, the first thermoplastic resin B1 containing nylon 6 is discharged from the extruder 60 to a flat ribbon-shaped carbon fiber roving at a temperature of 275 ° C to obtain a core containing carbon fibers covered with nylon 6 The core-sheath type core-sheath type resin particles 6 containing carbon fibers. The content of the carbon fibers in the core-sheath type resin particles 6 containing carbon fibers was 35% by weight.

將此包含尼龍6之芯鞘型含有碳纖維的樹脂顆粒6投入第6圖所示的顆粒供給裝置42中，自顆粒供給路徑P1通過供給口30，對擠壓機22內供給該顆粒。又，將包含第2熱塑性樹脂的顆粒投入顆粒供給裝置43中，自顆粒供給路徑P2通過供給口30，對擠壓機22內供給該顆粒。再者，如第6圖所示，通過側進給器25的開口部，將平坦帶狀的碳纖維粗紗供應到擠壓機22內。將此等顆粒及碳纖維粗紗在溫度275℃混煉，藉由第6圖所示之製造方法，得到包含尼龍6的混雜顆粒1。此包含尼龍6的混雜顆粒1中之碳纖維的含有率為47重量%。 The resin particles 6 containing the nylon 6 core-sheath type carbon fibers are introduced into the pellet supply device 42 shown in Fig. 6, and the pellets are supplied from the pellet supply path P1 through the supply port 30 to the inside of the extruder 22. Moreover, the pellet containing the second thermoplastic resin is introduced into the pellet supply device 43, and the pellet is supplied from the pellet supply path P2 through the supply port 30 to the inside of the extruder 22. Further, as shown in Fig. 6, the flat strip-shaped carbon fiber roving is supplied into the extruder 22 through the opening of the side feeder 25. These particles and the carbon fiber roving were kneaded at a temperature of 275 ° C, and the hybrid particles 1 containing nylon 6 were obtained by the production method shown in Fig. 6 . The content of the carbon fibers in the hybrid particles 1 containing nylon 6 was 47% by weight.

[實施例10] [Embodiment 10]

使用上述實施例1中記載的混雜顆粒1，藉由第9圖所示的熔融擠壓片之製造裝置111，以吐出量200g/min進行擠壓成形，製作寬度300mm、厚度0.3mm之片。 Using the hybrid particles 1 described in the above-described first embodiment, the melt-extruded sheet manufacturing apparatus 111 shown in Fig. 9 was subjected to extrusion molding at a discharge amount of 200 g/min to prepare a sheet having a width of 300 mm and a thickness of 0.3 mm.

具體而言，於第9圖所示的熔融擠壓片之製造裝置111中，自模頭112擠出成片狀的熔融狀態之樹脂材料 114，係在通過加熱輥116、118、120之間後，藉由具備不銹鋼帶124及帶用加熱輥122之加熱爐126來調節溫度。然後，藉由切刀128來切斷經溫度調節的片狀樹脂材料114，得到作為熔融擠壓成形品之片129。 Specifically, in the apparatus for manufacturing a melt-squeezed sheet 111 shown in Fig. 9, a molten resin material is extruded from a die 112 into a sheet shape. 114, after passing between the heating rolls 116, 118, 120, the temperature is adjusted by a heating furnace 126 having a stainless steel belt 124 and a heating roller 122. Then, the temperature-adjusted sheet-like resin material 114 is cut by a cutter 128 to obtain a sheet 129 as a melt-extruded product.

於本實施例中，測定所得之片129的破壞強度，結果縱向(長度方向)的彎曲強度為231MPa，彎曲彈性模數為9.8GPa。又，橫向(寬度方向)的彎曲強度為212MPa，彎曲彈性模數為9.2GPa。 In the present example, the breaking strength of the obtained sheet 129 was measured, and as a result, the bending strength in the longitudinal direction (longitudinal direction) was 231 MPa, and the bending elastic modulus was 9.8 GPa. Further, the bending strength in the transverse direction (width direction) was 212 MPa, and the bending elastic modulus was 9.2 GPa.

[實施例11] [Example 11]

使用上述實施例1之混雜顆粒1，藉由第10圖所示的熔融擠壓管之製造裝置130，以吐出量50g/min進行擠壓成形，製作內徑20mm、外徑25mm之管。 Using the hybrid particles 1 of the above-described first embodiment, the apparatus for manufacturing the melt-squeezed tube shown in Fig. 10 was subjected to extrusion molding at a discharge amount of 50 g/min to prepare a tube having an inner diameter of 20 mm and an outer diameter of 25 mm.

具體而言，於第10圖所示的熔融擠壓管之製造裝置130中，自熔融擠壓管用模頭131以熔融狀態擠出的樹脂材料114，係藉由具有溫度調節水入口141及溫度調節水出口145連通之冷卻部139的管用修準模(sizing die)135來調整形狀，在恒溫水槽147被冷卻。然後，藉由一邊用牽引機149連續地牽引經冷卻的樹脂材料114，一邊用切刀150來切斷，而得到熔融擠壓管151。 Specifically, in the apparatus for manufacturing a molten extruded tube shown in Fig. 10, the resin material 114 extruded from the molten extrusion tube die 131 in a molten state is provided with a temperature-regulating water inlet 141 and a temperature. The tube of the cooling portion 139 that regulates the connection of the water outlet 145 is adjusted in shape by a sizing die 135, and is cooled in the constant temperature water tank 147. Then, the cooled resin material 114 is continuously pulled by the tractor 149 while being cut by the cutter 150 to obtain a molten extruded tube 151.

於本實施例中，所得之管151的彎曲強度為236MPa，彎曲彈性模數為9.6GPa。又，第11圖中顯示此管151之截面形狀。 In the present embodiment, the obtained tube 151 had a bending strength of 236 MPa and a bending elastic modulus of 9.6 GPa. Further, the cross-sectional shape of this tube 151 is shown in Fig. 11.

[實施例12] [Embodiment 12]

使用上述實施例1之混雜顆粒1，藉由第12圖所示之熔融擠壓實心成形品之製造裝置180，以吐出量70g/min進行擠壓成形，製作外徑15mm之圓棒。 Using the hybrid particles 1 of the above-described first embodiment, the apparatus for producing a melt-squeezed solid molded product shown in Fig. 12 was extrusion-molded at a discharge amount of 70 g/min to prepare a round bar having an outer diameter of 15 mm.

具體而言，於第12圖所示的熔融擠壓實心品的製造裝置180中，自熔融擠壓實心品用模頭185以熔融狀態擠出的樹脂材料114，係藉由實心成形品用修準模187來調整形狀，藉由恒溫水槽147冷卻。然後，藉由一邊用牽引機149連續地牽引經冷卻的樹脂材料114，一邊用切刀150來切斷，而得到熔融擠壓實心品188(本實施例中為圓棒)。再者，由於製造裝置180之其它構成係與第10圖所示之製造裝置130同樣，藉由附有與第10圖相同之符號而省略說明。 Specifically, in the apparatus for manufacturing a melt-extruded solid product shown in Fig. 12, the resin material 114 extruded from the melt-pressed solid product die 185 in a molten state is repaired by a solid molded product. The quasi-mode 187 adjusts the shape and is cooled by the constant temperature water tank 147. Then, by continuously pulling the cooled resin material 114 by the tractor 149 while cutting with a cutter 150, a melt-pressed solid product 188 (in the present embodiment, a round bar) is obtained. In addition, the other configuration of the manufacturing apparatus 180 is the same as that of the manufacturing apparatus 130 shown in FIG. 10, and the same reference numerals as in FIG. 10 are attached, and the description thereof is omitted.

於本實施例中，所得之圓棒188的彎曲強度為241MPa，彎曲彈性模數為9.9GPa。又，第13圖中顯示此圓棒188之截面形狀。 In the present embodiment, the obtained round bar 188 had a bending strength of 241 MPa and a bending elastic modulus of 9.9 GPa. Further, the cross-sectional shape of this round bar 188 is shown in Fig. 13.

[實施例13] [Example 13]

使用上述實施例1之混雜顆粒1，藉由第14圖所示的熔融擠壓異形品之製造裝置190，以吐出量70g/min進行擠壓成形，製作I型、H型、T型之異形擠壓成形品。 Using the hybrid particles 1 of the above-described first embodiment, the apparatus for producing a melt-extruded profiled product shown in Fig. 14 was extrusion-molded at a discharge amount of 70 g/min to produce I-shaped, H-shaped, and T-shaped irregularities. Extruded products.

具體而言，於第14圖所示的熔融擠壓實心品之製造裝置190中，自熔融擠壓異形品用模頭191以熔融狀態擠出的樹脂材料114，係藉由熔融擠壓異形品用修準模192來調整形狀，藉由恒溫水槽147冷卻。然後，藉由 一邊用牽引機149連續地牽引經冷卻的樹脂材料114，一邊用切刀150來切斷，而得到熔融擠壓異形品194。再者，由於製造裝置190之其它構成係與第10圖所示之製造裝置130同樣，藉由附有與第10圖相同之符號而省略說明。 Specifically, in the manufacturing apparatus 190 of the melt-squeezed solid product shown in Fig. 14, the resin material 114 extruded from the melt-extruded die 191 in a molten state is melt-squeezed by a profiled product. The shape is adjusted by the trimming die 192 and cooled by the constant temperature water tank 147. Then, by While the cooled resin material 114 is continuously pulled by the tractor 149, it is cut by a cutter 150 to obtain a melt-extruded profiled article 194. In addition, the other components of the manufacturing apparatus 190 are the same as those of the manufacturing apparatus 130 shown in FIG. 10, and the same reference numerals as in FIG. 10 are attached, and the description thereof is omitted.

於本實施例中，所得之異形擠壓成形品194的彎曲強度為238MPa，彎曲彈性模數為10.1GPa。又，第15圖中顯示I型異形品197、H型異形品198、T型異形品199之截面形狀。 In the present embodiment, the obtained deformed extruded article 194 had a flexural strength of 238 MPa and a flexural modulus of elasticity of 10.1 GPa. Further, Fig. 15 shows the cross-sectional shape of the I-shaped profiled article 197, the H-shaped profiled article 198, and the T-shaped profiled article 199.

[實施例14] [Embodiment 14]

使用上述實施例1之混雜顆粒1，藉由第16圖所示的固化擠壓成形品之製造裝置210，以吐出量30g/min進行擠壓成形，製作寬度300mm、厚度100mm之擠出塊。 Using the hybrid particles 1 of the above-described first embodiment, the apparatus for manufacturing a cured extruded product shown in Fig. 16 was extrusion-molded at a discharge amount of 30 g/min to prepare an extruded block having a width of 300 mm and a thickness of 100 mm.

具體而言，於第16圖所示的固化擠壓成形品之製造裝置210中，自固化擠出用模頭212以熔融狀態擠出的樹脂材料114，係藉由具備加熱器215的加熱部213來加熱後，藉由具備水路219的冷卻部217來冷卻，藉由牽引機227連續地牽引，成為固化擠壓成形品230。再者，於加熱部213與冷卻部217之間設置隔熱材218。 Specifically, in the manufacturing apparatus 210 of the cured extruded product shown in FIG. 16, the resin material 114 extruded from the solidification extrusion die 212 in a molten state is provided by the heating unit including the heater 215. After heating by 213, it is cooled by the cooling unit 217 having the water path 219, and is continuously pulled by the tractor 227 to form the cured extruded product 230. Further, a heat insulating material 218 is provided between the heating portion 213 and the cooling portion 217.

將藉由此製造裝置210所得之擠出塊231予以切削加工，製作測定寬度10±0.5mm、測定長度80±2mm的啞鈴片。所得之啞鈴片的彎曲強度為275MPa，彎曲彈性模數為11.5GPa。又，第17圖(a)中顯示擠出塊231之截面形狀。 The extrusion block 231 obtained by the manufacturing apparatus 210 was subjected to cutting processing to prepare a dumbbell piece having a measurement width of 10 ± 0.5 mm and a measurement length of 80 ± 2 mm. The obtained dumbbell piece had a bending strength of 275 MPa and a bending elastic modulus of 11.5 GPa. Further, the cross-sectional shape of the extrusion block 231 is shown in Fig. 17 (a).

[實施例15] [Example 15]

使用上述實施例1之混雜顆粒1，藉由第16圖所示的固化擠壓成形品之製造裝置210，使用圓棒用模頭，以吐出量30g/min進行擠壓成形，製作Φ150mm的圓棒。 Using the hybrid particles 1 of the above-described first embodiment, the manufacturing apparatus 210 for a cured extruded product shown in Fig. 16 was subjected to extrusion molding using a die for a round bar at a discharge amount of 30 g/min to prepare a circle of Φ 150 mm. Baton.

所得之圓棒232的彎曲強度為265MPa，彎曲彈性模數為10.8GPa。又，第17圖(b)中顯示圓棒232之截面形狀。 The obtained round bar 232 had a bending strength of 265 MPa and a bending elastic modulus of 10.8 GPa. Further, the cross-sectional shape of the round bar 232 is shown in Fig. 17(b).

[實施例16] [Example 16]

使用實施例2中記載之包含尼龍66及碳纖維的混雜顆粒1，與實施例10同樣地，藉由第9圖所示的熔融擠壓片之製造裝置111以吐出量200g/min進行擠壓成形，製作寬度300mm、厚度0.6mm之片。所得之片沒有發生彈回或空隙(void)，形狀及表面狀態亦良好。 In the same manner as in the tenth embodiment, the hybrid pellet 1 containing the nylon 66 and the carbon fiber described in the second embodiment was extruded at a discharge amount of 200 g/min by the apparatus for producing a melt extruded sheet shown in Fig. 9. A sheet having a width of 300 mm and a thickness of 0.6 mm was produced. The resulting sheet did not rebound or void, and the shape and surface condition were also good.

[實施例17] [Example 17]

使用實施例3記載之包含PP及碳纖維的混雜顆粒1，與實施例13同樣地，藉由第14圖所示的熔融擠壓異形品之製造裝置190以吐出量70g/min進行擠壓成形，製作I型、H型、T型之異形擠壓成形品。所得之異形擠壓成形品沒有發生彈回或空隙，形狀及表面狀態亦良好。 In the same manner as in the thirteenth embodiment, the hybrid granules 1 containing the PP and the carbon fibers described in the third embodiment were extruded at a discharge amount of 70 g/min by the apparatus for producing a melt-extruded profiled product shown in Fig. 14 . Shaped extruded products of type I, H type, and T type are produced. The obtained shaped extrusion molded article did not rebound or void, and the shape and surface condition were also good.

[實施例18] [Embodiment 18]

使用實施例4記載之包含ABS及碳纖維的混雜顆粒1，與實施例11同樣地，藉由第10圖所示的熔融擠壓管之製造裝置130以吐出量50g/min進行擠壓成形，製作內徑21mm、外徑25mm之管。所得之管沒有發生彈回或空隙，形狀及表面狀態亦良好。 In the same manner as in the eleventh embodiment, the mixed pellets 1 containing the ABS and the carbon fibers described in the fourth embodiment were extruded at a discharge amount of 50 g/min by the apparatus for manufacturing the melt-squeezed tube shown in Fig. 10 . A tube having an inner diameter of 21 mm and an outer diameter of 25 mm. The resulting tube did not rebound or void, and the shape and surface condition were also good.

[實施例19] [Embodiment 19]

使用實施例5記載之包含PPS及碳纖維的混雜顆粒1，與實施例10同樣地，藉由第9圖所示的熔融擠壓片之製造裝置111以吐出量200g/min進行擠壓成形，製作寬度300mm、厚度0.5mm之片。所得之片沒有發生彈回或空隙，形狀及表面狀態亦良好。 In the same manner as in the tenth embodiment, the hybrid pellet 1 containing the PPS and the carbon fiber described in the fifth embodiment was extruded at a discharge amount of 200 g/min by the apparatus for producing a melt extruded sheet shown in Fig. 9 . A sheet having a width of 300 mm and a thickness of 0.5 mm. The resulting sheet did not rebound or void, and the shape and surface condition were also good.

[實施例20] [Example 20]

使用實施例10之熔融擠壓成形片作為成形中間體，如第18圖所示，藉由熱壓成形法來作成片。具體的地，首先以寬度300mm、長度1200mm來切割實施例10所得之熔融擠壓成形片129，作成片129a。然後，如第18圖(a)所示，將合計16張之片129a各4張積層為4層，以各層之片與鄰接的其它層之片成90度交叉之方式，將片排列，作為第18圖(b)所示之4層的積層體300。將此積層體300，如第18圖(c)所示，置入具備包含凹模301及凸模302的加熱器305及水冷管306之模具內，如第18圖(d)所示地關閉模具後，於模具溫度250℃、壓力20MPa之條件下加壓5分鐘。然後，藉由水冷管306來 冷卻模具後，如第18圖(e)所示地打開模具，得到第18圖(f)所示之熱壓成形片308。 Using the melt-extruded sheet of Example 10 as a forming intermediate, as shown in Fig. 18, a sheet was formed by a hot press forming method. Specifically, the melt-extruded sheet 129 obtained in Example 10 was first cut to have a width of 300 mm and a length of 1200 mm to prepare a sheet 129a. Then, as shown in Fig. 18(a), four sheets of the total of 16 sheets 129a are laminated into four layers, and the sheets of each layer are arranged at 90 degrees with the adjacent sheets of the other layers, and the sheets are arranged as The four-layered laminate 300 shown in Fig. 18(b). The laminated body 300 is placed in a mold having a heater 305 including a concave mold 301 and a punch 302 and a water-cooling tube 306 as shown in Fig. 18(c), and is closed as shown in Fig. 18(d). After the mold, it was pressurized at a mold temperature of 250 ° C and a pressure of 20 MPa for 5 minutes. Then, by the water cooling tube 306 After the mold was cooled, the mold was opened as shown in Fig. 18 (e) to obtain a hot press formed sheet 308 shown in Fig. 18 (f).

所得之熱壓成形片308的尺寸係縱、橫皆1200mm，厚度為1.19mm。 The obtained hot press formed sheet 308 has a size of 1200 mm in both vertical and horizontal directions and a thickness of 1.19 mm.

[實施例21] [Example 21]

使用實施例10之熔融擠壓成形片作為成形中間體，如第19圖所示，藉由熱壓成形法來製作成形品。具體而言，首先以寬度300mm、長度300mm來切割實施例10所得之熔融擠壓成形片129，作成第19圖(a)所示之片129b後，如第19圖(b)所示，將此片129b置入具備加熱器305及水冷管306的單腔模具內。此模具係包含盒狀凹模320及對應其之形狀的凸模321，賦型部的尺寸為高度10mm、寬度150mm、長度170mm。接著，如第19圖(c)所示地關閉模具，於模具溫度250℃、壓力15MPa之條件下加壓5分鐘。然後，藉由水冷管306來冷卻模具，如第19圖(d)所示地打開模具後，進行所取出的熱壓成形體324之修邊，得到第19圖(e)所示之盒狀的熱壓成形品325。 Using the melt-extruded sheet of Example 10 as a forming intermediate, as shown in Fig. 19, a molded article was produced by a hot press forming method. Specifically, first, the melt-extruded sheet 129 obtained in Example 10 was cut to have a width of 300 mm and a length of 300 mm to form a sheet 129b shown in Fig. 19(a), and as shown in Fig. 19(b), This piece 129b is placed in a single-cavity mold having a heater 305 and a water-cooled tube 306. The mold includes a box-shaped die 320 and a punch 321 corresponding to the shape thereof. The size of the shaped portion is 10 mm in height, 150 mm in width, and 170 mm in length. Next, the mold was closed as shown in Fig. 19 (c), and pressurized at a mold temperature of 250 ° C and a pressure of 15 MPa for 5 minutes. Then, the mold is cooled by the water-cooling tube 306, and after the mold is opened as shown in Fig. 19(d), the removed hot-pressed molded body 324 is trimmed to obtain a box shape as shown in Fig. 19(e). Hot pressed product 325.

所得之熱壓成形品325的尺寸係高度10mm、寬度150mm、長度170mm，厚度為0.25mm。 The obtained hot-pressed product 325 has a height of 10 mm, a width of 150 mm, a length of 170 mm, and a thickness of 0.25 mm.

[實施例22] [Example 22]

使用實施例20之熱壓成形片作為成形中間體，如第20圖所示，藉由熱壓成形法來製作成形品。具體而言， 首先以寬度300mm、長度300mm來切割實施例20所得之熱壓成形片308，作成第20圖(a)所示之片308a後，如第20圖(b)所示，將此片308a置入具備加熱器305及水冷管306的單腔模具內。此模具係包含盒狀凹模320及對應其之形狀的凸模321，賦型部的尺寸為高度10mm、寬度150mm、長度170mm。接著，如第20圖(c)所示地關閉模具，於模具溫度250℃、壓力15MPa之條件下加壓5分鐘。然後，藉由水冷管306來冷卻模具，如第20圖(d)所示地打開模具後，進行所取出的熱壓成形體327之修邊，得到第20圖(e)所示之盒狀的熱壓成形品326。 Using the hot press formed sheet of Example 20 as a forming intermediate, as shown in Fig. 20, a molded article was produced by a hot press forming method. in particular, First, the hot-pressed sheet 308 obtained in Example 20 was cut to have a width of 300 mm and a length of 300 mm to form a sheet 308a shown in Fig. 20(a). Then, as shown in Fig. 20(b), the sheet 308a was placed. The heater 305 and the water-cooled tube 306 are provided in a single-cavity mold. The mold includes a box-shaped die 320 and a punch 321 corresponding to the shape thereof. The size of the shaped portion is 10 mm in height, 150 mm in width, and 170 mm in length. Next, the mold was closed as shown in Fig. 20 (c), and pressurized at a mold temperature of 250 ° C and a pressure of 15 MPa for 5 minutes. Then, the mold is cooled by the water-cooling tube 306, and after the mold is opened as shown in Fig. 20(d), the removed hot-pressed molded body 327 is trimmed to obtain a box shape as shown in Fig. 20(e). Hot pressed molded article 326.

所得之熱壓成形品326的尺寸係高度10mm、寬度150mm、長度170mm，厚度為1.04mm。 The obtained hot-pressed product 326 had a height of 10 mm, a width of 150 mm, a length of 170 mm, and a thickness of 1.04 mm.

[實施例23] [Example 23]

使用實施例20之熱壓成形片作為成形中間體，如第21圖所示，藉由熱壓成形法來製作成形品。具體而言，首先以寬度300mm、長度300mm來切割實施例20所得之熱壓成形片308，作成第21圖(a)所示之片308a。然後，藉由瓦斯加熱烘箱將此片308a以245℃加熱5分鐘後，如第21圖(b)所示，置入包含盒狀凹模320與對應其之凸模321的單腔模具內。此模具係預先經加熱器305加熱至130℃，賦型部的尺寸為高度10mm、寬度150mm、長度170mm。接著，如第21圖(c)所示地關閉模具，以壓力20MPa進行2分鐘加壓。然後，如第21圖(d)所示地打開模具後，進行所取出的熱壓成形體327a 之修邊，得到第21圖(e)所示之箱形狀的熱壓成形品326a。 Using the hot press formed sheet of Example 20 as a forming intermediate, as shown in Fig. 21, a molded article was produced by a hot press forming method. Specifically, first, the hot press formed sheet 308 obtained in Example 20 was cut to have a width of 300 mm and a length of 300 mm to form a sheet 308a shown in Fig. 21 (a). Then, the sheet 308a was heated at 245 ° C for 5 minutes by a gas heating oven, and as shown in Fig. 21 (b), placed in a single-cavity mold including a box-shaped concave die 320 and a punch 321 corresponding thereto. This mold was previously heated to 130 ° C by a heater 305, and the size of the shaped portion was 10 mm in height, 150 mm in width, and 170 mm in length. Next, the mold was closed as shown in Fig. 21 (c), and pressurized at a pressure of 20 MPa for 2 minutes. Then, after the mold is opened as shown in Fig. 21 (d), the taken-out hot-pressed molded body 327a is taken out. The trimming was carried out to obtain a box-shaped hot-pressed product 326a shown in Fig. 21(e).

所得之熱壓成形品326a的尺寸係高度10mm、寬度150mm、長度170mm，厚度為1.09mm。 The obtained hot-pressed product 326a had a height of 10 mm, a width of 150 mm, a length of 170 mm, and a thickness of 1.09 mm.

[實施例24] [Example 24]

使用實施例20之熱壓成形片作為成形中間體，如第22圖所示，藉由真空成形法來製作成形品。具體而言，首先以寬度300mm、長度300mm來切割實施例20所得之熱壓成形片308，作成第22圖(a)所示之片308a，藉由上下2片的電氣紅外線加熱器以245℃將此片308a加熱5分鐘。接著，如第22圖(b)所示，於具備吸引孔334、吸引口335及加熱器305之單腔的真空成形模具342中置入片308a，在模具溫度80℃，如第22圖(c)所示地將片308a賦型後，於壓力1.0×10-4MPa之條件下2分鐘，藉由吸引孔334進行減壓吸引。此模具的賦型部之尺寸係高度8mm、寬度140mm、長度170mm。然後，如第22圖(d)所示地打開模具後，進行所取出的真空成形體346之修邊，得到第22圖(e)所示的盒狀之真空成形品347。 Using the hot press formed sheet of Example 20 as a forming intermediate, as shown in Fig. 22, a molded article was produced by a vacuum forming method. Specifically, first, the hot-pressed sheet 308 obtained in Example 20 was cut to have a width of 300 mm and a length of 300 mm to form a sheet 308a shown in Fig. 22 (a), which was 245 ° C by two electric and infrared heaters. This piece 308a was heated for 5 minutes. Next, as shown in Fig. 22(b), a sheet 308a is placed in a vacuum forming mold 342 having a single cavity of a suction hole 334, a suction port 335, and a heater 305 at a mold temperature of 80 ° C as shown in Fig. 22 ( c) After the sheet 308a was shaped as shown, it was subjected to vacuum suction by the suction holes 334 for 2 minutes under the conditions of a pressure of 1.0 × 10 -4 MPa. The dimensions of the shaped portion of the mold are 8 mm in height, 140 mm in width, and 170 mm in length. Then, after the mold is opened as shown in Fig. 22 (d), the vacuum-molded body 346 to be taken out is trimmed to obtain a box-shaped vacuum-molded article 347 shown in Fig. 22(e).

所得之真空成形品347的尺寸係高度10mm、寬度150mm、長度170mm，厚度為0.67mm。 The obtained vacuum molded product 347 had a height of 10 mm, a width of 150 mm, a length of 170 mm, and a thickness of 0.67 mm.

[實施例25] [Example 25]

使用實施例20之熱壓成形片作為成形中間體，如第23圖所示，藉由吹塑成形法來製作成形品。具體而言，首先以寬度300mm、長度500mm來切割實施例20所得之熱壓成形片308，而作成片308b。接著，如第23圖(a)所示，將2張之片308b固定在片固定具351而作成片保持體352，藉由紅外線加熱器將此片保持體352以245℃加熱5分鐘後，置入經加熱至155℃的模具內。此模具係如第23圖(b)所示，包含凹型的上模354及凸型的下模353，具備吹口355、吹孔356及加熱器305。又，上模354之賦型部的尺寸係高度30mm、寬度110mm、長度160mm，下模353之賦型部的尺寸係高度10mm、寬度110mm、長度160mm。如第23圖(c)所示地關閉模具後，於氣壓1.5MPa使壓縮空氣自吹孔356流入2分鐘，進行成形。然後，如第23圖(d)所示地打開模具後，對於所取出的吹塑成形品保持體357，進行片固定具351的卸除及修邊，得到第23圖(e)及第23圖(f)所示之盒狀的吹塑成形品358。 Using the hot press formed sheet of Example 20 as a forming intermediate, as shown in Fig. 23, a molded article was produced by a blow molding method. Specifically, first, the hot press formed sheet 308 obtained in Example 20 was cut to have a width of 300 mm and a length of 500 mm to form a sheet 308b. Next, as shown in Fig. 23(a), two sheets 308b are fixed to the sheet holder 351 to form a sheet holding body 352, and the sheet holding member 352 is heated at 245 ° C for 5 minutes by an infrared heater. Place in a mold heated to 155 °C. As shown in Fig. 23(b), the mold includes a concave upper mold 354 and a convex lower mold 353, and includes a mouthpiece 355, a blow hole 356, and a heater 305. Further, the dimension of the upper mold 354 is 30 mm in height, 110 mm in width, and 160 mm in length, and the dimension of the forming portion of the lower mold 353 is 10 mm in height, 110 mm in width, and 160 mm in length. After the mold was closed as shown in Fig. 23 (c), the compressed air was allowed to flow from the blow hole 356 at a pressure of 1.5 MPa for 2 minutes to carry out molding. Then, after the mold is opened as shown in Fig. 23(d), the sheet-form fixture 351 is removed and trimmed with respect to the blow-molded article holder 357 taken out, and the figure 23 (e) and the 23rd are obtained. The box-shaped blow molded article 358 shown in Fig. (f).

所得之吹塑成形品358的尺寸係高度20mm、寬度110mm、長度160mm，厚度為0.51mm。又，如由第23圖(f)所示之吹塑成形品358的截面圖可知，吹塑成形品358的內部係中空。 The obtained blow molded article 358 has a height of 20 mm, a width of 110 mm, a length of 160 mm, and a thickness of 0.51 mm. Further, as is clear from the cross-sectional view of the blow molded article 358 shown in Fig. 23(f), the inside of the blow molded article 358 is hollow.

[實施例26] [Example 26]

使用實施例10之熔融擠壓成形片作為成形中間體，如第24圖所示，藉由熱壓成形法來製作成形品。具 體而言，首先以寬度300mm、長度1200mm來切割實施例10所得之熔融擠壓成形片129，而作成片129a。然後，如第24圖(a)所示，將合計8張之片129a各4張積層為2層，以上層之片相對於下層之片呈90度交叉之方式，將各層之片排列，同時將單位面積重量110g/m2、厚度0.15mm之玻璃纖維織物371載置於最上面，作成3層之積層體372。將此積層體372，如第24圖(b)及第24圖(c)所示地，置入包含凹模301及凸模302之具備加熱器305及水冷管306之模具內，如第24圖(d)所示地關閉模具後，於模具溫度250℃、壓力15MPa之條件下加壓5分鐘。然後，藉由水冷管306來冷卻模具後，如第24圖(e)所示地打開模具，如第24圖(f)所示地，得到包含碳纖維複合材料及玻璃纖維織物之熱壓成形片375。 Using the melt-extruded sheet of Example 10 as a molding intermediate, as shown in Fig. 24, a molded article was produced by a hot press forming method. Specifically, the melt-extruded sheet 129 obtained in Example 10 was first cut to have a width of 300 mm and a length of 1200 mm to form a sheet 129a. Then, as shown in Fig. 24(a), four sheets of a total of eight sheets 129a are laminated into two layers, and the sheets of the upper layer are arranged at 90 degrees with respect to the lower layer sheets, and the sheets of the respective layers are arranged while A glass fiber woven fabric 371 having a basis weight of 110 g/m 2 and a thickness of 0.15 mm was placed on the uppermost side to form a three-layered laminated body 372. The laminated body 372 is placed in a mold including the heater 305 and the water-cooling tube 306 including the female mold 301 and the male mold 302 as shown in FIGS. 24(b) and 24(c), as shown in FIG. After the mold was closed as shown in Fig. (d), it was pressurized at a mold temperature of 250 ° C and a pressure of 15 MPa for 5 minutes. Then, after the mold is cooled by the water-cooling tube 306, the mold is opened as shown in Fig. 24(e), and as shown in Fig. 24(f), a thermoformed sheet comprising a carbon fiber composite material and a glass fiber fabric is obtained. 375.

所得之熱壓成形片375的尺寸係縱、橫皆1200mm，厚度為0.72mm。 The obtained hot press formed sheet 375 has a size of 1200 mm in both vertical and horizontal directions and a thickness of 0.72 mm.

[實施例27] [Example 27]

使用實施例10之熔融擠壓片作為成形中間體，如第25圖所示，藉由熱壓成形法來製作成形品。具體而言，首先以寬度300mm、長度1200mm來切割實施例10所得之熔融擠壓成形片129，而作成片129a。然後，如第25圖(a)所示，將合計8張之片材129a各4張積層為2層，以上層之片相對於下層之片呈90度交叉之方式，將各層之片材排列，同時於此2層之間配置包含聚丙烯之厚度0.50mm的熱塑性樹脂片377，作成3層之積層體378。 將此積層體372，如第25圖(b)及第25圖(c)所示地，置入包含凹模301及凸模302之具備加熱器305及水冷管306之模具內，如第25圖(d)所示地關閉模具後，於模具溫度250℃、壓力10MPa之條件下加壓5分鐘。然後，藉由水冷管306來冷卻模具後，如第25圖(e)所示地打開模具，如第25圖(f)所示地，得到包含碳纖維複合材料及聚丙烯之熱壓成形片379。 Using the melt extruded sheet of Example 10 as a forming intermediate, as shown in Fig. 25, a molded article was produced by a hot press forming method. Specifically, the melt-extruded sheet 129 obtained in Example 10 was first cut to have a width of 300 mm and a length of 1200 mm to form a sheet 129a. Then, as shown in Fig. 25(a), four sheets of the total of eight sheets 129a are laminated into two layers, and the sheets of the upper layer are arranged at 90 degrees with respect to the sheets of the lower layer, and the sheets of the respective layers are arranged. At the same time, a thermoplastic resin sheet 377 having a thickness of 0.50 mm of polypropylene was placed between the two layers to form a three-layered laminated body 378. The laminated body 372 is placed in a mold including a heater 305 and a water-cooling tube 306 including a female mold 301 and a male mold 302 as shown in Figs. 25(b) and 25(c), as in the 25th. After the mold was closed as shown in Fig. (d), it was pressurized at a mold temperature of 250 ° C and a pressure of 10 MPa for 5 minutes. Then, after the mold is cooled by the water-cooling tube 306, the mold is opened as shown in Fig. 25(e), and as shown in Fig. 25(f), a thermoformed sheet 379 comprising a carbon fiber composite material and polypropylene is obtained. .

所得之熱壓成形片379的尺寸係縱、橫皆1200mm，厚度為1.05mm。 The obtained thermoformed sheet 379 was 1200 mm in both vertical and horizontal directions and had a thickness of 1.05 mm.

[實施例28] [Example 28]

使用實施例26之熱壓成形片作為成形中間體，如第26圖所示，藉由熱壓成形法來製作成形品。具體而言，首先將實施例26所得之熱壓成形片375，如第26圖(a)所示地，置入具備加熱器305及水冷管306的三腔模具內。此模具係包含上模391及對應其之下模392，賦型部的尺寸皆為高度5mm、寬度140mm、長度200mm。接著，如第26圖(b)所示地關閉模具，於模具溫度250℃、壓力12MPa之條件下加壓7分鐘。然後，藉由水冷管306來冷卻模具，如第26圖(c)所示地打開模具後，進行所取出的熱壓成形體394之修邊，得到第26圖(d)所示之3個盒狀的熱壓成形品393。 Using the hot press formed sheet of Example 26 as a forming intermediate, as shown in Fig. 26, a molded article was produced by a hot press forming method. Specifically, first, the hot press formed sheet 375 obtained in Example 26 is placed in a three-cavity mold including a heater 305 and a water-cooled tube 306 as shown in Fig. 26(a). The mold comprises an upper die 391 and a lower die 392. The dimensions of the shaped portions are 5 mm in height, 140 mm in width, and 200 mm in length. Next, the mold was closed as shown in Fig. 26(b), and pressurized at a mold temperature of 250 ° C and a pressure of 12 MPa for 7 minutes. Then, the mold is cooled by the water-cooling tube 306, and after the mold is opened as shown in Fig. 26(c), the trimmed hot-pressed molded body 394 is trimmed to obtain three sheets as shown in Fig. 26(d). Box-shaped thermoformed product 393.

所得之熱壓成形品393的尺寸係高度5mm、寬度140mm、長度250mm，厚度為0.89mm。 The obtained hot-pressed product 393 has a height of 5 mm, a width of 140 mm, a length of 250 mm, and a thickness of 0.89 mm.

[實施例29] [Example 29]

使用實施例10之熔融擠壓片作為成形中間體，藉由與實施例27大致同樣之方法，將成形品成形。具體而言，首先以寬度300mm、長度1200mm來切割實施例10所得之熔融擠壓片129，而作成片。然後，將合計8張之片各4張積層為2層，以上層之片相對於下層之片呈90度交叉之方式，將各層之片排列，同時於此2層之間配置單位面積重量90g/m2且厚度0.15mm之碳纖維織物，作成3層之積層體。將此積層體置入包含凹模及凸模之模具內，關閉模具後，於模具溫度250℃、壓力20MPa之條件下加壓5分鐘。然而，藉由水冷管306來冷卻模具後，打開模具，得到包含碳纖維複合材料及碳纖維織物之熱壓成形片。 Using the melt extruded sheet of Example 10 as a molding intermediate, a molded article was molded in substantially the same manner as in Example 27. Specifically, the melt extruded sheet 129 obtained in Example 10 was first cut to have a width of 300 mm and a length of 1200 mm to prepare a sheet. Then, a total of 8 sheets of 4 sheets are laminated into 2 layers, and the sheets of the upper layer are arranged at 90 degrees with respect to the sheets of the lower layer, and the sheets of the respective layers are arranged, and the weight per unit area is 90 g between the two layers. A carbon fiber fabric having a thickness of /m 2 and a thickness of 0.15 mm was formed into a laminate of three layers. This laminated body was placed in a mold including a female mold and a male mold, and the mold was closed, and then pressurized at a mold temperature of 250 ° C and a pressure of 20 MPa for 5 minutes. However, after the mold is cooled by the water-cooling tube 306, the mold is opened to obtain a thermoformed sheet comprising a carbon fiber composite material and a carbon fiber fabric.

所得之熱壓成形片的尺寸係縱、橫皆1200mm，厚度為0.71mm。 The obtained thermoformed sheet was 1200 mm in both vertical and horizontal directions and had a thickness of 0.71 mm.

[實施例30] [Example 30]

使用實施例29之熱壓成形片作為成形中間體，藉由與實施例24大致同樣之方法，將成形品成形。具體而言，首先以寬度300mm、長度300mm來切割實施例29所得之熱壓成形片，而作成片，藉由上下2片的電氣紅外線加熱器以245℃將此片加熱5分鐘。接著，將此片置入單腔的的真空成形模具內，於模具溫度80℃將片賦型後，於壓力1.0×10-4MPa之條件下，進行2分鐘減壓 吸引。模具的賦型部之尺寸係高度8mm、寬度140mm、長度170mm。然後，打開模具後，進行所取出的真空成形體之修邊，得到盒狀的真空成形品。 Using the hot press formed sheet of Example 29 as a molding intermediate, the molded article was molded in the same manner as in Example 24. Specifically, the hot-pressed sheet obtained in Example 29 was first cut at a width of 300 mm and a length of 300 mm to prepare a sheet, which was heated at 245 ° C for 5 minutes by means of two upper and lower electric infrared heaters. Next, the sheet was placed in a single-cavity vacuum forming mold, and the sheet was shaped at a mold temperature of 80 ° C, and then subjected to vacuum suction at a pressure of 1.0 × 10 -4 MPa for 2 minutes. The dimensions of the shaped portion of the mold are 8 mm in height, 140 mm in width, and 170 mm in length. Then, after the mold was opened, the removed vacuum molded body was trimmed to obtain a box-shaped vacuum molded product.

所得之真空成形品的尺寸係高度8mm、寬度140mm、長度170mm，厚度為0.61mm。 The obtained vacuum molded article had a height of 8 mm, a width of 140 mm, a length of 170 mm, and a thickness of 0.61 mm.

[實施例31] [Example 31]

使用實施例27之熱壓成形片作為成形中間體，藉由與實施例25大致同樣之方法，將成形品成形。具體而言，首先以寬度300mm、長度500mm來切割實施例20所得之熱壓成形片，而作成片，將此2張之片固定於片固定具而作成片保持體。藉由紅外線加熱器將此片保持體以245℃加熱5分鐘後，置入模具內，關閉模具。接著，於模具溫度80℃之條件下，以壓力1.5MPa使空氣流入2分鐘，進行成形。然後，打開模具後，進行所取出的吹塑成形體之修邊，得到中空且盒狀之吹塑成形品。 Using the hot press formed sheet of Example 27 as a forming intermediate, the molded article was molded in substantially the same manner as in Example 25. Specifically, the hot-pressed sheet obtained in Example 20 was cut at a width of 300 mm and a length of 500 mm to prepare a sheet, and the two sheets were fixed to a sheet holder to form a sheet holder. The sheet holder was heated at 245 ° C for 5 minutes by an infrared heater, placed in a mold, and the mold was closed. Next, air was allowed to flow at a pressure of 1.5 MPa for 2 minutes under the conditions of a mold temperature of 80 ° C to carry out molding. Then, after the mold was opened, the blow-molded body to be taken out was trimmed to obtain a blow molded article having a hollow shape and a box shape.

所得之吹塑成形品的尺寸係高度20mm、寬度110mm、長度160mm，厚度為0.50mm。又，所得之吹塑成形品的內部為中空。 The obtained blow molded article had a height of 20 mm, a width of 110 mm, a length of 160 mm, and a thickness of 0.50 mm. Further, the inside of the obtained blow molded article was hollow.

[實施例32] [Example 32]

將實施例17所得之異形擠壓品I型197在烘箱中加熱至200℃，進行彎曲加工。如第27圖所示，可得到S字狀的彎曲加工品401或四方形的彎曲加工品402。 The profiled extrusion type I 197 obtained in Example 17 was heated to 200 ° C in an oven to carry out a bending process. As shown in Fig. 27, an S-shaped bent product 401 or a square curved product 402 can be obtained.

[比較例1] [Comparative Example 1]

以下，各比較例的試驗條件只要沒有特別的記載，則基本上以實施例1為準。 Hereinafter, the test conditions of the respective comparative examples are basically the same as in the first embodiment unless otherwise specified.

於具有芯鞘構造的顆粒之習知技術的製造方法之第7圖的製造方法中，將包含尼龍6的第1熱塑性樹脂B1自擠壓機60以溫度275℃吐出至平坦帶狀的碳纖維粗紗，得到包含碳纖維的芯經由尼龍6覆蓋之具有芯鞘構造的芯鞘型含有碳纖維的樹脂顆粒6。所得之芯鞘型含有碳纖維的樹脂顆粒6中的碳纖維之含有率為15%。 In the manufacturing method of Fig. 7 of the prior art manufacturing method of the core-sheath structure, the first thermoplastic resin B1 containing nylon 6 is discharged from the extruder 60 at a temperature of 275 ° C to a flat ribbon-shaped carbon fiber roving. A core-sheath type carbon fiber-containing resin particle 6 having a core-sheath structure covered with a core comprising carbon fibers is obtained. The content of the carbon fibers in the obtained core-sheath type carbon fiber-containing resin particles 6 was 15%.

使用此顆粒進行射出成形，作成與實施例1同樣之啞鈴片。所得之啞鈴片的彎曲強度為188MPa，彎曲彈性模數為8.0GPa。 This pellet was used for injection molding to prepare a dumbbell sheet similar to that of Example 1. The obtained dumbbell piece had a bending strength of 188 MPa and a flexural modulus of elasticity of 8.0 GPa.

[比較例2] [Comparative Example 2]

於具有芯鞘構造的顆粒之習知技術的製造方法之第7圖的製造方法中，藉由使用第8圖之模頭70代替模頭51，而製造第3圖所示之具有3層構造的顆粒5。具體而言，於模頭70內，使經熔融的第1熱塑性樹脂61通過導入孔72a而吐出至碳纖維粗紗46，以第1熱塑性樹脂61被覆碳纖維粗紗46之表面。接著，使經熔融的第2熱塑性樹脂71通過導入孔72b而吐出至碳纖維粗紗46，以第2熱塑性樹脂71被覆第1熱塑性樹脂61之表面。其它程序係與第7圖所示的製造方法同樣。於本比較例中，藉由使用包含尼龍6的樹脂B1作為第1熱塑性 樹脂，使用包含尼龍6的樹脂B2作為第2熱塑性樹脂，使模頭70內之溫度成為275℃，而得第3圖記載之具有3層構造的顆粒5。所得之芯鞘型碳纖維樹脂顆粒5中之碳纖維的含有率為15%。 In the manufacturing method of the seventh embodiment of the manufacturing method of the prior art having the core-sheath structure, the three-layer structure shown in Fig. 3 is produced by using the die 70 of Fig. 8 instead of the die 51. Particles 5. Specifically, in the die 70, the molten first thermoplastic resin 61 is discharged to the carbon fiber rovings 46 through the introduction holes 72a, and the surface of the carbon fiber rovings 46 is covered with the first thermoplastic resin 61. Then, the molten second thermoplastic resin 71 is discharged to the carbon fiber rovings 46 through the introduction holes 72b, and the surface of the first thermoplastic resin 61 is coated with the second thermoplastic resin 71. The other procedures are the same as those shown in Fig. 7. In this comparative example, by using the resin B1 containing nylon 6 as the first thermoplastic In the resin, the resin B2 containing nylon 6 was used as the second thermoplastic resin, and the temperature in the die 70 was 275 ° C to obtain the particles 5 having the three-layer structure described in Fig. 3 . The content of the carbon fibers in the obtained core-sheath type carbon fiber resin particles 5 was 15%.

使用此顆粒進行射出成形，作成與實施例1同樣之啞鈴片。所得之啞鈴片的彎曲強度為210MPa，彎曲彈性模數為9.3GPa。 This pellet was used for injection molding to prepare a dumbbell sheet similar to that of Example 1. The obtained dumbbell piece had a bending strength of 210 MPa and a bending elastic modulus of 9.3 GPa.

[比較例3] [Comparative Example 3]

又，使用上述比較例1記載之芯鞘型含有碳纖維的樹脂顆粒6，嘗試藉由日本特開平4-152122號公報記載之心軸的製造方法及擠壓成形裝置、日本特開2001-315193號公報記載之熔融擠壓的合成樹脂之管的製造方法、日本特開2000-313052號公報記載之固化擠壓成形製法及其製造裝置、以及日本特開2008-246865號公報記載之厚度不等樹脂片之製造方法及裝置等眾所周知之手段來製作成形品，但碳纖維推開低黏度的樹脂，得不到能滿足作為製品的品質基準之成形品。又，由於碳纖維的分散不充分，所得之成形品係碳纖維出現在表面，形狀亦顯著地差。 In addition, the core-sheath type carbon fiber-containing resin particles 6 described in the above-mentioned Comparative Example 1 are used, and the mandrel manufacturing method and extrusion molding apparatus described in JP-A-4-152122, No. 2001-315193 The method for producing a tube of a melt-squeezed synthetic resin according to the above-mentioned publication, the method for producing a press-molding method described in JP-A-2000-313052, the production device thereof, and the resin of the thickness described in JP-A-2008-246865 A molded article is produced by a well-known method such as a method and a device for producing a sheet. However, the carbon fiber is opened to a resin having a low viscosity, and a molded article which satisfies the quality standard of the product cannot be obtained. Further, since the dispersion of the carbon fibers is insufficient, the obtained molded product carbon fibers appear on the surface and the shape is remarkably inferior.

[比較例4] [Comparative Example 4]

又，使用上述比較例2記載之包含尼龍6之含有碳纖維的樹脂顆粒5，嘗試藉由日本特開平4-152122號公報記載之心軸的製造方法及擠壓成形裝置、日本特開 2001-315193號公報記載之熔融擠壓的合成樹脂之管的製造方法、日本特開2000-313052號公報記載之固化擠壓成形製法及其製造裝置、以及日本特開2008-246865號公報記載之厚度不等樹脂片之製造方法及裝置等眾所周知之手段來製作成形品，但碳纖維、樹脂B1及比該B1還黏度高之樹脂B2的分散係皆不充分，得不到能滿足作為製品的品質基準之成形品。又，由於碳纖維的分散不充分，所得之成形品係碳纖維出現在表面，形狀亦顯著地差。 In addition, the method of producing a mandrel described in JP-A-4-152122, an extrusion molding apparatus, and the Japanese special opening are used. A method for producing a tube of a melt-squeezed synthetic resin according to JP-A-2000-313052, and a method for producing the same, and a method for producing the same, and a method described in JP-A-2008-246865 The molded article is produced by a well-known method such as a method and a device for producing a resin sheet having a thickness different from that of the resin sheet, but the carbon fiber, the resin B1, and the resin B2 having a higher viscosity than the B1 are not sufficiently dispersed, and the quality of the product can not be satisfied. The molded product of the standard. Further, since the dispersion of the carbon fibers is insufficient, the obtained molded product carbon fibers appear on the surface and the shape is remarkably inferior.

[比較例5] [Comparative Example 5]

使用上述比較例1記載之顆粒6，藉由第9圖所示的熔融擠壓片之製造裝置111，以吐出量200g/min進行擠壓成形，嘗試製作寬度300mm、厚度0.3mm之片，但無法得到目的厚度之片，0.7mm的厚度為極限。又，雖然可製作0.7mm厚之片，但所得之片係開纖性低，表面品質亦差。 Using the pellets 6 described in the first comparative example, the melt-extruded sheet manufacturing apparatus 111 shown in Fig. 9 was subjected to extrusion molding at a discharge amount of 200 g/min, and a sheet having a width of 300 mm and a thickness of 0.3 mm was produced. The sheet of the desired thickness could not be obtained, and the thickness of 0.7 mm was the limit. Further, although a sheet having a thickness of 0.7 mm can be produced, the obtained sheet has low openability and poor surface quality.

[比較例6] [Comparative Example 6]

使用上述比較例1記載之顆粒6，藉由第10圖所示的熔融擠壓管之製造裝置130，以吐出量50g/min進行擠壓成形，嘗試製作內徑20mm、外徑25mm之管，但發生因碳纖維所造成的彈回，無法製作所欲的管。 Using the pellets 6 described in Comparative Example 1, the apparatus for manufacturing the melt-squeezed tube shown in Fig. 10 was extruded at a discharge amount of 50 g/min, and a tube having an inner diameter of 20 mm and an outer diameter of 25 mm was produced. However, due to the rebound caused by carbon fiber, it is impossible to make the desired tube.

[比較例7] [Comparative Example 7]

使用上述比較例1記載之顆粒6，藉由第12圖所示的熔融擠壓實心成形品之製造裝置180，以吐出量70g/min進行擠壓成形，嘗試製作外徑15mm之圓棒，但發生因碳纖維所造成的彈回，無法製作所欲的圓棒。 Using the pellets 6 described in the above-mentioned Comparative Example 1, the apparatus for manufacturing a melt-squeezed solid molded product shown in Fig. 12 was subjected to extrusion molding at a discharge amount of 70 g/min, and a round bar having an outer diameter of 15 mm was attempted. The rebound caused by the carbon fiber occurred, and the desired round bar could not be produced.

[比較例8] [Comparative Example 8]

使用上述比較例1記載之顆粒6，藉由第14圖所示的熔融擠壓異形品之製造裝置190，以吐出量70g/min進行擠壓成形，嘗試製作I型、H型、T型之異形擠壓成形品，但發生碳纖維的彈回，無法製作所欲的成形品。 Using the pellets 6 described in the above Comparative Example 1, the apparatus for producing a melt-extruded profiled product shown in Fig. 14 was extruded at a discharge amount of 70 g/min, and an attempt was made to produce type I, type H, and type T. When the molded article is deformed, the carbon fiber is bounced back, and the desired molded article cannot be produced.

[比較例9] [Comparative Example 9]

使用上述比較例1記載之顆粒6，藉由第16圖所示的固化擠壓成形品之製造裝置210，以吐出量30g/min進行擠壓成形，作成寬度300mm、厚度100mm之擠出塊。 Using the pellets 6 described in Comparative Example 1, the apparatus for manufacturing a cured extruded product shown in Fig. 16 was extrusion-molded at a discharge amount of 30 g/min to prepare an extruded block having a width of 300 mm and a thickness of 100 mm.

將此擠出塊予以切削加工，欲製作測定寬度10±0.5mm、測定長度80±2mm之啞鈴片，但塊內有空隙，無法製作所欲的啞鈴片。 The extruded block was subjected to cutting, and a dumbbell piece having a width of 10 ± 0.5 mm and a length of 80 ± 2 mm was prepared, but there was a gap in the block, and the desired dumbbell piece could not be produced.

[比較例10] [Comparative Example 10]

使用上述比較例1記載之顆粒6，藉由第16圖所示的固化擠壓成形品之製造裝置210，以吐出量30g/min進行擠壓成形，嘗試製作Φ150mm之圓棒，但在截面有許多空隙，無法製作所欲的圓棒。 Using the pellets 6 described in Comparative Example 1, the apparatus for manufacturing a cured extruded product shown in Fig. 16 was subjected to extrusion molding at a discharge amount of 30 g/min, and an attempt was made to produce a round rod having a diameter of 150 mm. Many gaps make it impossible to make a desired round bar.

[比較例11] [Comparative Example 11]

使用含有20重量%的玻璃纖維之尼龍6的顆粒110，藉由第9圖所示的熔融擠壓片之製造裝置111，以吐出量200g/min進行擠壓成形，嘗試製作寬度300mm、厚度0.7mm之片，但發生堵塞，無法製作所欲之片。 The pellets 110 of the nylon 6 containing 20% by weight of glass fibers were extruded by a production apparatus 111 of the melt-extruded sheet shown in Fig. 9 at a discharge amount of 200 g/min, and a width of 300 mm and a thickness of 0.7 were attempted. The piece of mm, but blocked, can not make the desired piece.

因此，使用此顆粒進行射出成形，製作與實施例1同樣之啞鈴片。所得之啞鈴片的彎曲強度為171MPa，彎曲彈性模數為5.8GPa。 Therefore, this pellet was used for injection molding, and the same dumbbell piece as in Example 1 was produced. The obtained dumbbell piece had a bending strength of 171 MPa and a bending elastic modulus of 5.8 GPa.

[比較例12] [Comparative Example 12]

使用比較例2記載之顆粒5，藉由第10圖所示的熔融擠壓管之製造裝置130，以吐出量50g/min進行擠壓成形，嘗試製作內徑20mm、外徑25mm之管，但發生堵塞，無法製作所欲之成形品。 Using the pellets 5 described in Comparative Example 2, extrusion molding was carried out at a discharge amount of 50 g/min by the apparatus for manufacturing a melt-squeezed tube shown in Fig. 10, and a tube having an inner diameter of 20 mm and an outer diameter of 25 mm was produced. The blockage occurred and the desired molded product could not be produced.

[比較例13] [Comparative Example 13]

使用比較例2記載之顆粒5，藉由第12圖所示的熔融擠壓實心成形品之製造裝置180，以吐出量70g/min進行擠壓成形，嘗試製作外徑15mm之圓棒，但所得之圓棒係在截面有許多的空隙，無法安定連續地成形。 Using the pellets 5 described in Comparative Example 2, the apparatus for manufacturing a melt-squeezed solid molded product shown in Fig. 12 was extruded at a discharge amount of 70 g/min, and a round bar having an outer diameter of 15 mm was produced, but the obtained was obtained. The round bar has a large number of voids in the cross section and cannot be stably formed continuously.

[比較例14] [Comparative Example 14]

使用比較例2記載之顆粒5，藉由第14圖所示的熔融擠壓異形品之製造裝置190，以吐出量70g/min進行擠 壓成形，嘗試製作I型、H型、T型之異形擠壓成形品，但所得之成形品係在截面有許多的空隙，無法安定連續地成形。 Using the pellets 5 described in Comparative Example 2, the apparatus for melting and extruding the shaped article 190 shown in Fig. 14 was extruded at a discharge amount of 70 g/min. In the press forming, it is attempted to produce a profiled extruded article of type I, type H, or type T. However, the obtained molded article has a large number of voids in the cross section, and cannot be continuously formed in a stable manner.

[比較例15] [Comparative Example 15]

使用比較例2記載之顆粒5，藉由第16圖所示的固化擠壓成形品之製造裝置210，以吐出量30g/min進行擠壓成形，製作寬度300mm、厚度100mm之擠出塊。 Using the pellets 5 described in Comparative Example 2, the apparatus for manufacturing a cured extruded product shown in Fig. 16 was extrusion-molded at a discharge amount of 30 g/min to prepare an extruded block having a width of 300 mm and a thickness of 100 mm.

將此擠出塊予以切削加工，嘗試製作測定寬度10±0.5mm、測定長度80±2mm之啞鈴片，但塊內有空隙，無法製作所欲之啞鈴片。 The extruded block was subjected to cutting, and a dumbbell piece having a width of 10 ± 0.5 mm and a length of 80 ± 2 mm was produced, but there was a gap in the block, and the desired dumbbell piece could not be produced.

[比較例16] [Comparative Example 16]

使用比較例2記載之顆粒5，藉由第16圖所示的固化擠壓成形品之製造裝置210，以吐出量30g/min進行擠壓成形，嘗試製作Φ150mm之圓棒。調查所得之圓棒，結果在截面發生空隙。 Using the pellets 5 described in Comparative Example 2, the apparatus for manufacturing a cured extruded product shown in Fig. 16 was subjected to extrusion molding at a discharge amount of 30 g/min, and an attempt was made to produce a round bar having a diameter of 150 mm. The round rod obtained was investigated, and as a result, a void occurred in the cross section.

[比較例17] [Comparative Example 17]

使用包含尼龍6之沒有添加強化纖維的非強化顆粒，藉由第16圖所示的固化擠壓成形品之製造裝置210，以吐出量30g/min進行擠壓成形，製作寬度300mm、厚度100mm之擠出塊。然後，將上述擠出塊予以切削加工以製作啞鈴片，進行強度之測定，結果彎曲強度為106MPa，彎曲彈性模數為2.7GPa。 By using the non-reinforced particles containing the reinforcing fibers of the nylon 6 and the manufacturing apparatus 210 of the cured extruded product shown in Fig. 16, extrusion molding was carried out at a discharge amount of 30 g/min to prepare a width of 300 mm and a thickness of 100 mm. Extruded the block. Then, the above-mentioned extruded block was cut to prepare a dumbbell piece, and the strength was measured. As a result, the bending strength was 106 MPa, and the bending elastic modulus was 2.7 GPa.

產業上之利用可能性 Industrial use possibility

本發明之碳纖維複合材料及其成形品，係適合要求高強度與優異加工性的一切用途，不僅在作為緩衝材、隔熱材、補強材、片帶、管等之量產品的用途，而且在作為模具製造前之樣品或針對半導體產業的製品等之要求高精度的多品種少量生產品之用途亦合適。 The carbon fiber composite material and the molded article thereof of the present invention are suitable for all applications requiring high strength and excellent processability, and are not only used as a cushioning material, a heat insulating material, a reinforcing material, a sheet, a tube, etc., but also in It is also suitable for use as a sample before mold production or as a product of the semiconductor industry, which requires high-precision multi-species small-sized raw products.

1‧‧‧由包含碳纖維複合材料所構成的顆粒 1‧‧‧Parts consisting of carbon fiber composites

20‧‧‧馬達 20‧‧‧Motor

21‧‧‧變速機 21‧‧‧Transmission

22‧‧‧擠壓機 22‧‧‧Extrusion machine

23‧‧‧齒輪泵 23‧‧‧ Gear pump

24‧‧‧冷卻部 24‧‧‧The Ministry of Cooling

25‧‧‧側進給器 25‧‧‧ side feeder

26‧‧‧模頭 26‧‧‧Mold

27‧‧‧線料切刀 27‧‧‧Wire cutter

28‧‧‧腸線 28‧‧‧ Gut

29‧‧‧排氣口 29‧‧‧Exhaust port

30‧‧‧供給口 30‧‧‧ supply port

42、43‧‧‧顆粒供給裝置 42, 43‧‧‧Particle supply device

P1、P2、P3‧‧‧顆粒供給路徑 P1, P2, P3‧‧‧ particle supply path

Claims (27)

一種碳纖維複合材料之製造方法，其係將具有包含碳纖維之芯成分和包含第1熱塑性樹脂之鞘成分之芯鞘構造的顆粒與第2熱塑性樹脂予以熔融，將經熔融的該顆粒及第2熱塑性樹脂在指定溫度混煉的碳纖維複合材料之製造方法，其特徵為：該第2熱塑性樹脂係在該指定溫度之黏度比該第1熱塑性樹脂還高。 A method for producing a carbon fiber composite material, which comprises melting a pellet having a core material comprising a core component of a carbon fiber and a sheath component comprising a first thermoplastic resin, and a second thermoplastic resin, and melting the pellet and the second thermoplastic A method for producing a carbon fiber composite material in which a resin is kneaded at a predetermined temperature, characterized in that the viscosity of the second thermoplastic resin at the specified temperature is higher than that of the first thermoplastic resin. 如請求項1之碳纖維複合材料之製造方法，其中在該指定溫度，該第2熱塑性樹脂之黏度係該第1熱塑性樹脂之黏度的10~750倍。 The method for producing a carbon fiber composite material according to claim 1, wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at the specified temperature. 如請求項1或2之碳纖維複合材料之製造方法，其中在該指定溫度的該第1熱塑性樹脂之黏度為50~500泊，在該指定溫度的該第2熱塑性樹脂之黏度為1,000~10,000泊。 The method for producing a carbon fiber composite material according to claim 1 or 2, wherein the viscosity of the first thermoplastic resin at the specified temperature is 50 to 500 poise, and the viscosity of the second thermoplastic resin at the specified temperature is 1,000 to 10,000 poise. . 如請求項1至3中任一項之碳纖維複合材料之製造方法，其中該指定溫度係比該第2熱塑性樹脂之熔點還高，該指定溫度與該第2熱塑性樹脂之熔點之差為30~90℃。 The method for producing a carbon fiber composite material according to any one of claims 1 to 3, wherein the specified temperature is higher than a melting point of the second thermoplastic resin, and a difference between the specified temperature and a melting point of the second thermoplastic resin is 30~ 90 ° C. 如請求項1至4中任一項之碳纖維複合材料之製造方法，其中該第2熱塑性樹脂之熔點為100~370℃。 The method for producing a carbon fiber composite material according to any one of claims 1 to 4, wherein the second thermoplastic resin has a melting point of 100 to 370 °C. 如請求項1至5中任一項之碳纖維複合材料之製造方法，其中於經熔融的該顆粒及該第2熱塑性樹脂中，更添加碳纖維。 The method for producing a carbon fiber composite material according to any one of claims 1 to 5, wherein a carbon fiber is further added to the melted particles and the second thermoplastic resin. 如請求項1至6中任一項之碳纖維複合材料之製造方法，其中於該碳纖維複合材料中，以5~60重量%之比例含有碳纖維。 The method for producing a carbon fiber composite material according to any one of claims 1 to 6, wherein the carbon fiber composite material contains carbon fibers in a proportion of 5 to 60% by weight. 一種成形品之製造方法，其特徵為將由如請求項1至7中任一項之碳纖維複合材料之製造方法所製造的碳纖維複合材料予以熔融，然後成形。 A method of producing a molded article, characterized in that the carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of claims 1 to 7 is melted and then formed. 如請求項8之成形品之製造方法，其中藉由熔融擠壓法(melt extrusion molding method)或固化擠壓法(solidification extrusion molding method)將該碳纖維複合材料予以成形。 The method of producing a molded article according to claim 8, wherein the carbon fiber composite material is formed by a melt extrusion molding method or a solidification extrusion molding method. 如請求項8之成形品之製造方法，其中於將該碳纖維複合材料予以成形而形成成形中間體後，更藉由加壓成型法、真空成型法、吹塑成形法或彎曲加工將該成形中間體予以成形。 The method for producing a molded article according to claim 8, wherein the carbon fiber composite material is formed into a shaped intermediate body, and further formed by a press molding method, a vacuum molding method, a blow molding method, or a bending process. The body is shaped. 如請求項10之成形品之製造方法，其中該成形中間體係在壓力0.2~100MPa及溫度100~370℃之條件下被熱壓。 The method for producing a molded article according to claim 10, wherein the forming intermediate system is hot pressed under a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 °C. 如請求項10之成形品之製造方法，其中該成形中間體係在壓力1×10-5~0.05MPa及溫度100~370℃之條件下被真空成型。 The method for producing a molded article according to claim 10, wherein the forming intermediate system is vacuum-formed under the conditions of a pressure of 1 × 10 -5 to 0.05 MPa and a temperature of 100 to 370 °C. 如請求項10之成形品之製造方法，其中該成形中間體係在氣壓0.2~10MPa及溫度100~370℃之條件下被吹塑成形。 The method for producing a molded article according to claim 10, wherein the forming intermediate system is blow molded under the conditions of a gas pressure of 0.2 to 10 MPa and a temperature of 100 to 370 °C. 如請求項10至13中任一項之成形品之製造方法，其中該成形中間體係在與熱塑性樹脂材料、玻璃纖維基布或該碳纖維複合材料彼此積層之狀態下被成形。 The method of producing a molded article according to any one of claims 10 to 13, wherein the forming intermediate system is formed in a state in which a thermoplastic resin material, a glass fiber base fabric or the carbon fiber composite material is laminated to each other. 一種碳纖維複合材料，其特徵為包含第1熱塑性樹脂、第2熱塑性樹脂及碳纖維，且具有於由該第2熱 塑性樹脂所構成的海相內，分散有由該第1熱塑性樹脂所構成的島相之構造。 A carbon fiber composite material comprising a first thermoplastic resin, a second thermoplastic resin, and carbon fibers, and having the second heat In the sea phase composed of the plastic resin, the structure of the island phase composed of the first thermoplastic resin is dispersed. 如請求項15之碳纖維複合材料，其中該第1熱塑性樹脂的折射率係與該第2熱塑性樹脂的折射率相異。 The carbon fiber composite material according to claim 15, wherein the refractive index of the first thermoplastic resin is different from the refractive index of the second thermoplastic resin. 如請求項15或16之碳纖維複合材料，其中該碳纖維複合材料所含有的碳纖維之中50重量%以上存在於該島相內。 The carbon fiber composite material according to claim 15 or 16, wherein more than 50% by weight of the carbon fibers contained in the carbon fiber composite material are present in the island phase. 如請求項15至17中任一項之碳纖維複合材料，其中以5~60重量%之比例含有該碳纖維。 The carbon fiber composite material according to any one of claims 15 to 17, wherein the carbon fiber is contained in a proportion of 5 to 60% by weight. 如請求項15至18中任一項之碳纖維複合材料，其中該島相的平均直徑為10nm~100μm。 The carbon fiber composite material according to any one of claims 15 to 18, wherein the island phase has an average diameter of 10 nm to 100 μm. 如請求項19之碳纖維複合材料，其中該島相的平均直徑為10nm~1μm。 The carbon fiber composite material of claim 19, wherein the island phase has an average diameter of 10 nm to 1 μm. 一種成形品，其係將如請求項15至20中任一項碳纖維複合材料予以成形而成。 A molded article obtained by molding a carbon fiber composite material according to any one of claims 15 to 20. 如請求項21之成形品，其係藉由熔融擠壓法或固化擠壓法所成形。 The molded article of claim 21 which is formed by melt extrusion or solidification extrusion. 如請求項21之成形品，其中在將該碳纖維複合材料予以成形而形成成形中間體後，更藉由加壓成型法、真空成型法、吹塑成形法或彎曲加工將該成形中間體予以成形而成。 The molded article of claim 21, wherein after the carbon fiber composite material is molded to form a shaped intermediate body, the shaped intermediate body is further formed by a press molding method, a vacuum forming method, a blow molding method, or a bending process. Made. 如請求項23之成形品，其中該成形中間體係在壓力0.2~100MPa及溫度100~370℃之條件下被熱壓。 The molded article of claim 23, wherein the forming intermediate system is hot pressed under a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 °C. 如請求項23之成形品，其中該成形中間體係在壓力1×10-5~0.05MPa及溫度100~370℃之條件下被真空成型。 The molded article of claim 23, wherein the forming intermediate system is vacuum formed under the conditions of a pressure of 1 × 10 -5 to 0.05 MPa and a temperature of 100 to 370 °C. 如請求項23之成形品，其中該成形中間體係在氣壓0.2~10MPa及溫度100~370℃之條件下被吹塑成形。 The molded article of claim 23, wherein the forming intermediate system is blow molded under the conditions of a gas pressure of 0.2 to 10 MPa and a temperature of 100 to 370 °C. 如請求項23至26中任一項之成形品，其中該成形中間體係在與熱塑性樹脂材料、玻璃纖維基布或該碳纖維複合材料彼此積層之狀態下被成形。 The molded article according to any one of claims 23 to 26, wherein the shaped intermediate system is formed in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric or the carbon fiber composite material.
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