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WO2025169663A1 - Matériau de moulage à base de résine renforcée par des fibres et article moulé - Google Patents

Matériau de moulage à base de résine renforcée par des fibres et article moulé

Info

Publication number
WO2025169663A1
WO2025169663A1 PCT/JP2025/000614 JP2025000614W WO2025169663A1 WO 2025169663 A1 WO2025169663 A1 WO 2025169663A1 JP 2025000614 W JP2025000614 W JP 2025000614W WO 2025169663 A1 WO2025169663 A1 WO 2025169663A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
molding material
resin
reinforced resin
resin molding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/000614
Other languages
English (en)
Japanese (ja)
Inventor
仙頭裕一朗
濱口美都繁
二井内哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Publication of WO2025169663A1 publication Critical patent/WO2025169663A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a molding material containing carbon fiber as a reinforcing fiber and a thermoplastic resin, and a molded article containing carbon fiber and a thermoplastic resin.
  • Fiber-reinforced resins which are made from reinforcing fibers and thermoplastic resins, are lightweight and have excellent mechanical properties, making them widely used in a variety of industrial applications.
  • molded products made from pelletized molding materials using economical and productive molding methods such as injection molding and stamping molding are frequently used in automotive parts and components and housings for electrical and electronic devices such as personal computers, OA (Office Automation) equipment, AV (Audio Visual) equipment, mobile phones, telephones, home appliances, and toys.
  • fiber-reinforced resins that use carbon fiber as the reinforcing fiber are frequently used when high levels of lightness and mechanical properties are required, as the excellent specific strength of carbon fiber allows them to exhibit high tensile strength and elastic modulus despite their light weight.
  • Patent Document 1 discloses that a molded article with excellent mechanical properties can be obtained by injection molding a molding material consisting of reinforcing fibers and a thermoplastic resin.
  • Patent Document 2 also discloses that a molded article with improved mechanical properties and appearance quality can be obtained by injection molding thermoplastic resin pellets that combine two types of reinforcing fibers, one with a long fiber length and one with a short fiber length, with a thermoplastic resin.
  • Patent Document 3 further discloses that a molded article with excellent mechanical properties can be obtained by injection molding a molding material that combines carbon fiber as the reinforcing fiber with recycled resin.
  • the objective of the present invention is to provide a fiber-reinforced resin molding material that contains recycled resin and has excellent moldability and mechanical properties.
  • the present invention has the following configuration.
  • the carbon fiber (A) has a fiber length of 3 mm or more and 10 mm or less, and contains carbon fibers oriented in the longitudinal direction of the molding material.
  • the fiber-reinforced resin molding material contains a compound (C) present in a state where it fills the spaces between the carbon fibers, and the thermoplastic resin (B) contains a recycled resin.
  • the carbon fiber (A) comprises carbon fiber (A-1) and carbon fiber (A-2), and the carbon fiber (A-1) has a fiber length of 3 mm or more and 10 mm or less and is oriented in the longitudinal direction of the molding material, and the carbon fiber (A-2) has a fiber length of 0.1 mm or more and 0.4 mm or less.
  • the fiber reinforced resin molding material comprises a long fiber reinforced resin molding material (X) and a short fiber reinforced resin molding material (Y), and the long fiber reinforced resin molding material (X) comprises the carbon fiber (A-1), a thermoplastic resin (B-1) and a flame retardant (D), and contains a compound (C) that exists in a state of filling the spaces between each carbon fiber (A-1), and the short fiber reinforced resin molding material (Y) comprises the carbon fiber (A-2), a thermoplastic resin (B-2) and a flame retardant (D), and the thermoplastic resin (B-2) comprises a recycled resin.
  • the fiber reinforced resin molding material according to the present invention is a long fiber reinforced resin molding material (X) and a short fiber reinforced resin molding material (Y)
  • the long fiber reinforced resin molding material (X) comprises the carbon fiber (A-1), a thermoplastic resin (B-1) and a flame retardant (D), and contains a compound (C) that exists in a state of filling the spaces between each carbon fiber (A-1)
  • the fiber-reinforced resin molding material according to (3) characterized in that the short fiber-reinforced resin molding material (Y) contains polytetrafluoroethylene resin.
  • thermoplastic resin (B) contains a polyamide resin.
  • compound (C) has a lower melt viscosity than the thermoplastic resin (B).
  • the polycarbonate resin is a recycled polycarbonate resin.
  • the molding material of the present invention while containing recycled resin, has excellent fluidity during molding processing, making it easy to produce molded products with excellent mechanical properties. As a result, it can be applied to a wide range of molding methods, including not only injection molding, transfer molding, blow molding, and insert molding, but also plunger molding, press molding, and stamping molding.
  • the molded articles of the present invention have excellent flowability during molding and maintain their mechanical properties despite containing recycled resins. They can be used in automotive parts such as thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, and pedals; semiconductor and liquid crystal manufacturing equipment parts such as silicon wafer carriers, IC chip trays, electrolytic capacitor trays, and insulating films; industrial machinery parts such as compressor parts (pumps, valves, and seals) and aircraft cabin interior parts; medical equipment parts such as sterilization instruments, columns, and piping; food and beverage manufacturing equipment parts; and electrical and electronic equipment parts and housings for personal computers, office equipment, audiovisual equipment, mobile phones, telephones, home appliances, and toys.
  • the conductive carbon fibers used as reinforcing fibers provide electromagnetic shielding properties, making them ideal for electrical and electronic equipment parts and housings.
  • the fiber-reinforced resin molding material of the present invention (hereinafter, sometimes simply referred to as "molding material”) is a molding material that satisfies the following requirements.
  • the molding material of the present invention is a molding material containing at least carbon fiber (A) and thermoplastic resin (B), and contains 10 to 40 parts by weight of carbon fiber (A) and 60 to 90 parts by weight of thermoplastic resin (B) relative to a total of 100 parts by weight of carbon fiber (A) and thermoplastic resin (B),
  • the carbon fiber (A) has a fiber length of 3 mm or more and 10 mm or less and contains carbon fibers oriented in the longitudinal direction of the molding material
  • the fiber-reinforced resin molding material contains compound (C) present in a state filling the spaces between the carbon fibers
  • the thermoplastic resin (B) contains recycled resin.
  • the fiber length of the carbon fiber can be maintained while maintaining fluidity, making it possible to obtain molded articles that exhibit mechanical properties equivalent to those of virgin resin.
  • Carbon fiber (A) The carbon fiber (A) in the present invention will be described.
  • the type of carbon fiber (A) used in the present invention is not particularly limited, and carbon fibers such as PAN (polyacrylonitrile), pitch, and rayon are preferably used.
  • carbon fibers having a tensile strength of 3,000 MPa or more are preferred, more preferably 4,000 MPa or more.
  • carbon fibers having a tensile modulus of 200 GPa or more are preferred, more preferably 300 GPa or more.
  • the fiber diameter of carbon fiber (A) is preferably 3 to 20 ⁇ m, more preferably 4 to 15 ⁇ m, and even more preferably 4.2 to 13 ⁇ m.
  • recycled carbon fibers refer to carbon fibers recovered and reused from molded articles containing used carbon fiber, or from process scraps of resin compositions or molded articles containing carbon fiber.
  • a sizing agent be attached to the carbon fiber (A).
  • a sizing agent By attaching a sizing agent to the carbon fiber (A), it is possible to improve the handleability of the carbon fiber during transportation, the processability during the manufacturing process of the molding material, and the mechanical properties and appearance properties of the molded product.
  • sizing agent there are no particular restrictions on the type of sizing agent, but it is possible to use one or more types of sizing agents such as epoxy resins, urethane resins, acrylic resins, and various thermoplastic resins in combination.
  • the amount of carbon fiber (A) is 10 to 40 parts by weight per 100 parts by weight of the total of carbon fiber (A) and thermoplastic resin (B). It is more preferably 10 to 35 parts by weight, and even more preferably 10 to 30 parts by weight. If it is less than 10 parts by weight, the mechanical properties may be insufficient, and if it exceeds 40 parts by weight, the fluidity during molding may be insufficient and the carbon fiber (A) may fall off during cutting, resulting in a poor surface appearance.
  • the carbon fibers (A) in the molding material preferably have a fiber length of 3 mm or more and 10 mm or less, and contain carbon fibers oriented in the longitudinal direction of the molding material. It is more preferable that the carbon fibers (A) contain fibers with a length of 5 to 9 mm.
  • Carbon fiber (A) may include two types of carbon fiber: carbon fiber (A-1) and carbon fiber (A-2).
  • Examples of the types of carbon fiber (A-1) and carbon fiber (A-2) include the carbon fibers described in the description of carbon fiber (A).
  • the carbon fibers (A-1) are preferably aligned in the longitudinal direction of the molding material, and have a length of 3 mm or more and 10 mm or less.
  • the length of the carbon fibers (A-1) is preferably substantially the same as the length of the molding material.
  • “Aligned in the longitudinal direction of the molding material” here refers to a state in which the longitudinal axis of the carbon fibers (A-1) and the longitudinal axis of the molding material are oriented in the same direction, with the angular deviation between the axes being preferably 20° or less, more preferably 10° or less, and even more preferably 5° or less.
  • substantially the same length means, for example, that in pellet-shaped molding material, the carbon fibers (A-1) are not cut midway through the pellet, and carbon fibers (A-1) significantly shorter than the entire length of the pellet are not substantially contained.
  • the entire length of the pellet refers to the length in the orientation direction of the carbon fibers (A-1) in the pellet.
  • the carbon fiber (A-2) preferably has a fiber length of 0.1 mm or more and 0.4 mm or less, more preferably 0.2 to 0.4 mm. If the fiber length of the carbon fiber (A-2) is less than 0.1 mm, the mechanical properties of the molded product may be insufficient. On the other hand, if the fiber length of the carbon fiber (A-2) is 0.4 mm or more, the fluidity during molding may be insufficient.
  • Fiber length of carbon fibers refers to the number average fiber length calculated from the following formula 1.
  • Fiber length of carbon fiber ⁇ (Li)/1,000 (Equation 1)
  • the fiber length of the carbon fibers can be measured using the following method. Using an optical microscope equipped with a hot stage, appropriate test pieces are extracted from the molding material, and heated between glass plates on a hot stage set at 150 to 500°C, matching the melting temperature of the thermoplastic resin (B) used. The pieces are then formed into a film, uniformly dispersing the carbon fibers (A). The film is then observed under an optical microscope (50 to 200 magnification) while the thermoplastic resin (B) is molten. The fiber lengths of 1,000 randomly selected carbon fibers are measured, and the fiber length is calculated using Equation 1 above.
  • test pieces extracted from the molding material are placed in a solvent that dissolves the thermoplastic resin (B), and heated as needed to create a solution in which the carbon fibers are uniformly dispersed.
  • the solution is then filtered, and the carbon fibers dispersed on the filter paper are observed under an optical microscope (50 to 200 magnification).
  • the fiber lengths of 1,000 randomly selected carbon fibers are measured, and the fiber length is calculated using Equation 1 above.
  • the filter paper used here may be quantitative filter paper (model number: No. 5C) manufactured by Advantec Co., Ltd.
  • recycled carbon fiber As the recycled carbon fiber, a fiber produced by a known production method can be used, and an example of the recycled carbon fiber is a method of obtaining recycled carbon fiber by carrying out the following steps (a) to (c): (a) a crushing step in which fiber-reinforced resin waste is crushed to produce crushed pieces having a predetermined fiber length; (b) a pyrolysis treatment step in which the crushed pieces are heated while being supplied in a fixed quantity to a pyrolysis furnace, and the matrix resin component is removed to obtain a pyrolyzed product; and (c) a classification step in which the pyrolyzed product is classified by fiber length to obtain recycled carbon fiber.
  • a sizing agent may be added to the recycled carbon fiber after the classification process.
  • the recycled carbon fiber is preferably contained in an amount of 10 to 80 parts by weight, and more preferably 15 to 70 parts by weight, per 100 parts by weight of carbon fiber (A).
  • the carbon fiber (A-2) may be in a dispersed state of single filaments, or may contain some bundled fibers.
  • the inclusion of bundled fibers increases the impact strength of the molded article compared to dispersed single filaments, but the carbon fibers may fall off during cutting, resulting in a poor surface appearance.
  • Dispersed single filaments are preferred, which, compared to the inclusion of bundled fibers, results in slightly lower impact strength, but superior surface appearance and mechanical properties for the molded article.
  • the carbon fiber (A-1) is the carbon fiber contained in the molding material (X) described below, and the carbon fiber (A-2) is the carbon fiber contained in the molding material (Y) described below.
  • the thermoplastic resin (B) preferably has a molding temperature (melting temperature) of 200 to 450°C, and examples thereof include polyolefin resins, polystyrene resins, polyamide resins, halogenated vinyl resins, polyacetal resins, saturated polyester resins, polycarbonate resins, polyarylsulfone resins, polyarylketone resins, polyphenylene ether resins, polyphenylene sulfide resins, polyaryletherketone resins, polyethersulfone resins, polyphenylene sulfide sulfone resins, and polyarylate resins, and two or more of these can also be used.
  • the thermoplastic resins polyolefin resins, polyamide resins, polycarbonate resins, and polyarylene sulfide resins are more preferred because they are lightweight and have an excellent balance of mechanical properties and moldability.
  • thermoplastic resin (B) preferably contains recycled resin obtained through material recycling or chemical recycling, and from the perspective of environmental impact, it is more preferable that it contains recycled resin obtained through material recycling.
  • polyolefin resin as used here includes both unmodified and modified resins.
  • unmodified polypropylene resin is specifically a propylene homopolymer or a copolymer of propylene with at least one ⁇ -olefin, conjugated diene, non-conjugated diene, etc.
  • ⁇ -olefins examples include ⁇ -olefins (excluding propylene) having 2 to 12 carbon atoms, such as ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene, and 1-dodecene.
  • conjugated and non-conjugated dienes examples include butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene.
  • Examples of the skeletal structure of unmodified polypropylene resin include propylene homopolymers, random or block copolymers of propylene and the other monomers mentioned above, and random or block copolymers of propylene and other thermoplastic monomers. Suitable examples include polypropylene, ethylene-propylene copolymers, propylene-1-butene copolymers, and ethylene-propylene-1-butene copolymers. Propylene homopolymers are preferred from the perspective of further improving the rigidity of molded articles, while random or block copolymers of propylene and the other monomers mentioned above are preferred from the perspective of further improving the impact strength of molded articles.
  • acid-modified polypropylene resins are preferred as modified polypropylene resins, and polypropylene resins having carboxylic acid and/or salt groups thereof bound to the polymer chain are more preferred.
  • the acid-modified polypropylene resins can be obtained by various methods, for example, by graft polymerizing a monomer having a neutralized or unneutralized carboxylic acid group and/or a monomer having a saponified or unsaponified carboxylic acid ester onto a polypropylene resin.
  • Examples of monomers having a neutralized or unneutralized carboxylic acid group or a monomer having a saponified or unsaponified carboxylic acid ester group include ethylenically unsaturated carboxylic acids, their anhydrides, and esters thereof. Furthermore, compounds having unsaturated vinyl groups other than olefins can also be used.
  • ethylenically unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid, and examples of their anhydrides include Nadic acidTM (endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, and citraconic anhydride.
  • Esters of ethylenically unsaturated carboxylic acids include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and decyl (meth)acrylate.
  • Monomers containing an unsaturated vinyl group other than olefins include isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate; aromatic vinyls such as styrene, ⁇ -methylstyrene, vinyltoluene, and t-butylstyrene; amide group-containing vinyls such as acrylamide, methacrylamide, N-methylol methacrylamide, N-methylol acrylamide, diacetone acrylamide, and maleic acid amide; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated sulfonic acids such as styrene sulfonic acid, sodium styrene sulfonate, and 2-acrylamido-2-methylpropanesulfonic acid; and unsaturated phosphoric acids such as mono(2-methacryloyloxyethyl) acid phosphate and mono(2-acryloyloxyethyl) acid
  • ethylenically unsaturated carboxylic acid anhydrides are preferred, with maleic anhydride being more preferred.
  • unmodified polypropylene resin to modified polypropylene resin in a weight ratio of 95/5 to 75/25.
  • a ratio of 95/5 to 80/20 is more preferable, and 90/10 to 80/20 is even more preferable.
  • the polyolefin resin used in the present invention may be one obtained by polymerization as described above, but it is preferable to use a polyolefin resin obtained through material recycling.
  • the source of polyolefin resin for material recycling is sorted and used from process offcuts, containers and packaging, electrical and electronic components, and other polyolefin-based materials.
  • Material recycling can involve further separating the collected and sorted raw materials into polyolefin resin and other materials (metals, lint, paper scraps, film scraps, other resin scraps, etc.) using vibration or wind sorting, water gravity difference sorting in a water tank (floating/sedimentation), electrostatic sorting, or near-infrared sorting.
  • Polyamide resins are resins whose main raw materials are amino acids, lactams, or diamines and dicarboxylic acids. Typical examples of these main raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid; lactams such as ⁇ -caprolactam and ⁇ -laurolactam; aliphatic diamines such as tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, and 5-methylnonamethylenediamine; aromatic diamines such as metaxylylenediamine and paraxylylenediamine; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cycl
  • suitable dicarboxylic acids include alicyclic diamines such as hexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine; aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; and alicyclic dicarboxylic acids such as 1,4
  • polyamide resins with a melting point of 170°C or higher are particularly useful because of their excellent heat resistance and strength.
  • Specific examples thereof include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polycaproamide/polyhexamethylene adipamide copolymer (nylon 6/66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene decamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polydodecamethylene dodecamide (nylon 1212), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene terephthalamide/polycaproamide copolymer (nylon 6T/6), polyhexamethylene adipamide/polyhexamethylene terephthalamide copolymer (nylon 6T/6), polyhe
  • the polyamide resin used in the present invention may be one obtained by polymerization as described above, but it is preferable to use recycled resin obtained through material recycling or chemical recycling, and from the perspective of environmental impact, it is even more preferable to use polyamide resin obtained through material recycling.
  • the polyamide resin used in material recycling is selected and used from polyamide-based components such as automobile parts and electrical and electronic components, as well as process offcuts generated during the manufacturing process of each component.
  • Material recycling can involve further separating the collected and selected raw materials into polyamide resin and other materials (metals, lint, paper scraps, film scraps, other resin scraps, etc.) using vibration or wind sorting, water gravity separation in a water tank (floating/sedimentation), electrostatic sorting, or near-infrared sorting.
  • Polycarbonate resins are obtained by reacting a dihydric phenol with a carbonate precursor. They may also be copolymers obtained using two or more dihydric phenols or two or more carbonate precursors. Examples of reaction methods include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. Such polycarbonate resins are known per se; for example, the polycarbonate resins described in JP 2002-129027 A can be used.
  • dihydric phenols examples include 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)alkanes (such as bisphenol A), 2,2-bis ⁇ (4-hydroxy-3-methyl)phenyl ⁇ propane, ⁇ , ⁇ '-bis(4-hydroxyphenyl)-m-diisopropylbenzene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Two or more of these may be used. Among these, bisphenol A is preferred, as it allows the production of polycarbonate resins with superior impact resistance. On the other hand, copolymers obtained using bisphenol A and other dihydric phenols are excellent in terms of high heat resistance and low water absorption.
  • the carbonate precursor may be, for example, a carbonyl halide, a carbonic acid diester, or a haloformate, and specific examples include phosgene, diphenyl carbonate, or a dihaloformate of a dihydric phenol.
  • catalysts When producing polycarbonate resin from the above dihydric phenol and carbonate precursor, catalysts, end-capping agents, antioxidants to prevent oxidation of the dihydric phenol, etc. may be used as needed.
  • the polycarbonate resins used in the present invention also include branched polycarbonate resins copolymerized with trifunctional or higher polyfunctional aromatic compounds, polyester carbonate resins copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids, copolymer polycarbonate resins copolymerized with bifunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and bifunctional alcohols. These polycarbonate resins are also known. Two or more of these polycarbonate resins may also be used.
  • the polycarbonate resin is preferably a resin obtained by mixing a polycarbonate resin having a weight-average molecular weight of 28,000 to 45,000 with a polycarbonate resin having a weight-average molecular weight of 50,000 to 60,000 in a weight ratio of 5/95 to 40/60.
  • a weight ratio of 5/95 to 45/65 is more preferable.
  • the polycarbonate resin used in the present invention may be one obtained by polymerization as described above, but it is preferable to use a polycarbonate resin obtained through material recycling.
  • Sources of polycarbonate resin for material recycling include information media discs such as CDs and DVDs, materials sorted and used in gallon bottles and other water bottles, semiconductor trays, headlights, and process offcuts generated during various manufacturing processes.
  • Material recycling can involve further separating the collected and sorted raw materials into polycarbonate resin and other materials (metals, lint, paper scraps, film scraps, other resin scraps, etc.) using vibration or wind sorting, water gravity difference sorting in a water tank (floating/sedimentation), electrostatic sorting, or near-infrared sorting.
  • Polycarbonate resin with a weight-average molecular weight of 28,000 to 45,000 is easily obtained from information media discs such as CDs and DVDs, while polycarbonate resin with a weight-average molecular weight of 50,000 to 60,000 is easily obtained from water bottles such as gallon bottles.
  • the weight average molecular weight refers to the value determined for components with a polystyrene-equivalent molecular weight of 3,000 or more (however, if an alkyl ester monomer is used for the unsaturated carboxylic acid, the molecular weight is calculated as a polymethyl methacrylate-equivalent molecular weight).
  • examples of polyarylene sulfide resins include polyphenylene sulfide (PPS) resin, polyphenylene sulfide sulfone resin, polyphenylene sulfide ketone resin, and random or block copolymers thereof. Two or more of these may be used. Of these, polyphenylene sulfide resin is particularly preferred.
  • Polyarylene sulfide resins can be produced by any method, such as the method for obtaining polymers with relatively low molecular weights described in Japanese Patent Publication No. 45-3368, or the methods for obtaining polymers with relatively high molecular weights described in Japanese Patent Publication No. 52-12240 and Japanese Patent Laid-Open Publication No. 61-7332.
  • the resulting polyarylene sulfide resin may be subjected to various treatments, such as crosslinking/polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvents, hot water, acid aqueous solutions, etc., or activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, and functional group-containing disulfide compounds.
  • treatments such as crosslinking/polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvents, hot water, acid aqueous solutions, etc., or activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, and functional group-containing disulfide compounds.
  • the polyarylene sulfide resin used in the present invention may be one obtained by polymerization as described above, but it is preferable to use a polyarylene sulfide resin obtained through material recycling.
  • the polyarylene sulfide resin used in material recycling is selected and used from automobile parts, electrical and electronic parts, plumbing components, and other components that use polyarylene sulfide, as well as process scraps generated during each manufacturing process.
  • Material recycling can involve further separating the recovered and sorted raw materials into polyarylene sulfide resin and other materials (metals, lint, paper, film, and other resin waste, etc.) using vibration or wind sorting, water gravity separation in a water tank (floating/sedimentation), electrostatic sorting, or near-infrared sorting.
  • the molding material contains, in addition to carbon fibers (A) and a thermoplastic resin (B), a compound (C) different from the thermoplastic resin (B) that is present and fills the spaces between the carbon fibers (A). It is preferable that the compound (C) is present and fills the spaces between the carbon fibers (A-1).
  • the presence of the compound (C) in a state where it fills the spaces between the carbon fibers can improve the dispersion of the fibers during molding and can also suppress fiber breakage during molding.
  • the compound (C) preferably has a lower melt viscosity than the thermoplastic resin (B). Because the melt viscosity of the compound (C) is lower than that of the thermoplastic resin (B), the fluidity of the compound (C) is high when molding the molding material, which can further improve the dispersion effect of the carbon fiber (A) in the thermoplastic resin (B), and can suppress fiber breakage. Furthermore, the compound (C) preferably has a high affinity with the thermoplastic resin (B). By selecting a compound with a high affinity with the thermoplastic resin (B), it is efficiently compatible with the thermoplastic resin (B) during molding, thereby further improving the dispersibility of the carbon fiber.
  • the compound (C) is preferably a resin selected from the group consisting of epoxy resins, phenolic resins, terpene resins, and rosin resins, and examples thereof include homopolymers and reaction products with other components.
  • the number average molecular weight of compound (C) is preferably 200 to 5,000.
  • a number average molecular weight of 200 or more can further improve the bending strength and tensile strength of the molded article.
  • a number average molecular weight of 1,000 or more is more preferable.
  • a number average molecular weight of 5,000 or less will result in a compound with a suitably low viscosity, resulting in excellent impregnation into carbon fiber (A-1) and further improved dispersibility of the carbon fiber in the molded article.
  • a number average molecular weight of 3,000 or less is more preferable.
  • the number average molecular weight of such a compound can be measured using gel permeation chromatography (GPC).
  • the amount of compound (C) is preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, per 100 parts by weight of molding material (X). By using this range, a molding material with excellent moldability and handleability can be obtained.
  • the molding material preferably contains a flame retardant (D) in addition to the carbon fiber (A), the thermoplastic resin (B), and the compound (C).
  • the flame retardant (D) preferably has a heat loss of 5% or less when heated at 300°C for 10 minutes under nitrogen. A heat loss of 5% or less is preferable because it reduces the amount of gas generated when the resin melts during molding, thereby suppressing gas burning.
  • the type of flame retardant (D) is not particularly limited, and known flame retardants can be used. Examples include halogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide-based flame retardants such as aluminum hydroxide and magnesium hydroxide, organic sulfonic acid-based flame retardants such as sodium styrene sulfonate, potassium styrene sulfonate, and calcium styrene sulfonate, zinc borate, antimony trioxide, antimony pentoxide, melamine, melamine cyanurate, and silicone-based flame retardants.
  • halogen-based flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide-based flame retardants such as aluminum hydroxide and magnesium hydroxide, organic sulfonic acid-based flame retardants such as sodium styrene sulfonate, potassium styrene sulfonate, and calcium s
  • halogen-based flame retardants include decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, 1,2-bis(2',3',4',5',6'-pentabromophenyl)ethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, 2,6-(or 2,4-)dibromophenol, brominated polystyrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromobenzyl acrylate, and the like.
  • brominated flame retardants containing bromine-containing compounds such as bis(3,5-dibromo-2,4-dibromopropoxyphenyl)sulfone, 2,2-bis[4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl]-propane, bis(3,5-dibromo-2,4-dibromopropoxyphenyl)sulfone, and tris(2,3-dibromopropyl)isocyanurate; and chlorinated flame retardants containing chlorine-containing compounds such as chlorinated paraffin, chlorinated polyethylene, chlorinated polypropylene, perchloropentacyclodecane, dodecachlorododecahydrodimethanodibenzocyclooctene, and dodecachlorooctahydrodimethanodibenzofuran.
  • bromine-containing compounds such as bis(3,5-dibrom
  • phosphorus-based flame retardants include phosphate ester-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trimethyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and other aromatic phosphate esters; halogen-containing phosphate ester-based flame retardants such as trisdichloropropyl phosphate, trischloroethyl phosphate, and trischloropropyl phosphate; condensed phosphate ester-based flame retardants such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and biphenyl bisdiphenyl phosphate; phosphate flame retardants such as ammonium polyphosphate
  • Phosphorus-based flame retardants and red phosphorus-based flame retardants are preferably used because they accelerate dehydration and carbonization, forming dense char on the surface of molded articles, blocking heat and oxygen and preventing flame propagation. They also exhibit flame retardancy by stabilizing active H and OH radicals in the combustion field through their radical trapping effect against the radical chain reaction during thermal decomposition.
  • the phosphorus concentration of phosphorus-based flame retardants is preferably 5 to 50%.
  • the phosphorus concentration refers to the weight of phosphorus in the phosphorus-based flame retardant; if it is 5% or higher, dense char is more likely to form, improving flame retardancy. 7% or higher is preferable, and 9% or higher is even more preferable.
  • a phosphorus concentration of 50% or less is preferable, as it improves compatibility with thermoplastic resins and therefore increases flame retardancy.
  • Halogen-based flame retardants, phosphorus-based flame retardants, and organic sulfonic acid-based flame retardants are preferred due to their high flame retardancy, and among these, flame retardants selected from red phosphorus-based flame retardants, phosphate ester-based flame retardants, condensed phosphate ester-based flame retardants, metal phosphinate-based flame retardants, and phosphazene-based flame retardants are more preferred due to their safety and environmental impact.
  • thermoplastic resin (B) is a polycarbonate resin
  • metal phosphinate-based flame retardant when the thermoplastic resin (B) is a polyamide resin
  • Such flame retardants may be used alone or in combination of two or more types.
  • the long-fiber-reinforced resin molding material includes carbon fibers (A-1) having a fiber length of 3 mm or more and 10 mm or less and oriented in the longitudinal direction of the molding material, a thermoplastic resin (B-1), and a flame retardant (D), and also includes a compound (C) present in a state of filling the spaces between the carbon fibers (A-1).
  • the type of thermoplastic resin (B-1) is not particularly limited, and examples thereof include the thermoplastic resins described above in the description of the thermoplastic resin (B).
  • the flame retardant (D) is highly compatible with thermoplastic resins, and the mixture exhibits excellent flame retardancy and fluidity. It is preferable that the flame retardant (D) is compatible with the thermoplastic resin (B). Higher compatibility is preferable, as it results in higher flame retardancy. Compatibility can be confirmed by changes in the glass transition temperature of the thermoplastic resin (B).
  • the glass transition temperature of the mixture can be measured using a differential scanning calorimeter (DSC) at a heating rate of 20°C/minute in accordance with JIS K7121.
  • the flame retardant (D) may be contained in any of the raw materials used as the molding material (X) during molding.
  • Specific examples of preferred raw materials in the present invention include a resin composition prepared by melt-kneading a thermoplastic resin and a flame retardant, which is contained in the resin that coats the reinforcing fibers, or the flame retardant may be pre-impregnated into the reinforcing fiber bundles during the process of obtaining the reinforcing fibers.
  • the molding material (X) of the present invention preferably contains an antioxidant, and the antioxidant preferably used is a hindered phenol, hydroquinone, phosphorus, phosphite, amine, sulfur, or substituted derivative thereof.
  • phosphorus and phosphite antioxidants include tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphonite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, cyclic Examples include neopentanetetrayl
  • Hindered phenol antioxidants include, for example, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl
  • amine-based antioxidant examples include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ ], 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis(2,2,6,6-tetramethyl-4-piperidyl), bis(1,2,3,4-pentamethyl-4-piperidyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4
  • sulfur-based antioxidants examples include 4,4'-thiobis(6-t-butyl-3-methylphenol), dialkyl (C12-18) 3,3'-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiopropionate), and mixtures thereof. It is preferable to use antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphorus compounds, phosphites, amines, sulfur compounds, and their substituted derivatives, etc.).
  • sulfur-based antioxidants hindered phenol-based antioxidants, or mixtures thereof are preferably used.
  • the antioxidant content is preferably 1 part by weight or more per 100 parts by weight of molding material (X). If 1 part by weight or more is included, decomposition of the molding material components during molding and heating is suppressed, resulting in excellent surface appearance.
  • the upper limit is preferably 2 parts by weight or less. If it is 2 parts by weight or less, gas burning due to decomposition of the antioxidant itself is suppressed, resulting in excellent surface appearance.
  • thermoplastic resin (B-1) is not particularly limited, and examples thereof include the thermoplastic resins described in the description of the thermoplastic resin (B).
  • the molding material (Y) preferably contains polytetrafluoroethylene.
  • polytetrafluoroethylene may be referred to as PTFE.
  • Fibril-forming PTFE is more preferred. Fibril-forming PTFE has an extremely high molecular weight and tends to bond together to form fibers when subjected to external forces such as shear. Its molecular weight, calculated based on the standard specific gravity, is 1 million to 10 million, more preferably 2 million to 9 million, in number average molecular weight.
  • Such fibril-forming PTFE can also be used in a mixed form with other resins to improve dispersibility in resins and achieve even better flame retardancy and impact resistance.
  • Acrylic resin-tetrafluoroethylene polymers are particularly preferred because of their excellent dispersibility in thermoplastic resin (B).
  • the molding material was injection molded using an injection molding machine (J110AD manufactured by The Japan Steel Works, Ltd.) using a mold having a width of 10 mm, a length of 125 mm, and a thickness of 1 mm under the following conditions: injection speed 30 mm/s, back pressure 10 MPa, dwell pressure 60 MPa, cylinder temperature 280°C, and mold temperature 80°C.
  • the cylinder peak pressure when producing a molded product was used as an index of fluidity.
  • the cylinder pressure was the average value of 20 shots, and this average value was used for evaluation of each example and comparative example.
  • V Test Method The flame of a gas burner is applied to the lower end of the test piece held vertically for 10 seconds. If the burning stops within 30 seconds, the flame is applied for another 10 seconds. This test is carried out on five test pieces. The evaluation criteria are as follows:
  • V-0 After any flame application, no specimen continues to burn for more than 10 seconds. The total burning time for 10 flame applications on 5 test specimens does not exceed 50 seconds. No test specimen burns up to the fixing clamp position. No test specimen will drop burning particles that will ignite the cotton wool placed underneath. After the second exposure to flame, none of the specimens remained red hot for more than 30 seconds.
  • V-1 After any flame application, no specimen continues to burn for more than 30 seconds. The total burning time for 10 flame applications on 5 test specimens does not exceed 250 seconds. No test specimen burns up to the fixing clamp position. No test specimen will drop burning particles that will ignite the cotton wool placed underneath. After the second exposure to flame, none of the specimens remained red hot for more than 60 seconds.
  • V-2 After any flame application, no specimen continues to burn for more than 30 seconds. The total burning time for 10 flame applications on 5 test specimens does not exceed 250 seconds. No test specimen burns up to the fixing clamp position. The specimen is allowed to fall, causing burning particles to ignite absorbent cotton placed underneath. After the second exposure to flame, none of the specimens remained red hot for more than 30 seconds.
  • Reference Example 1 [Preparation of carbon fiber (A-1)]
  • a sizing agent mother solution was prepared by dissolving glycerol polyglycidyl ether as a polyfunctional compound in water to 2% by weight for Torayca (registered trademark) carbon fiber T700S-24000 (total number of single fibers: 24,000, single fiber diameter: 7 ⁇ m), manufactured by Toray Industries, Inc.
  • the sizing agent was applied to the carbon fiber by a dipping method, and the carbon fiber was dried at 230° C.
  • the amount of sizing agent attached to the carbon fiber thus obtained was 1.0% by weight.
  • the extruder cylinder temperature was set to 280 ° C.
  • the thermoplastic resin (B), flame retardant (D), and antioxidant (E) shown above were fed from the main hopper and melt-kneaded at a screw rotation speed of 200 rpm.
  • the compound (C) was heated and melted at 250 ° C.
  • the discharge rate was adjusted so that the ratios shown in Tables 1 to 3 were obtained relative to a total of 100 parts by weight of carbon fiber (A-1), thermoplastic resin (B), flame retardant (D), and antioxidant (E). Thereafter, the compound (C) was discharged and impregnated into a fiber bundle made of carbon fiber (A-1).
  • the fiber bundle of carbon fiber (A-1) to which the compound (C) had been applied was then supplied to a die hole (diameter 3 mm) through which the molten thermoplastic resin (B) was discharged.
  • the fiber bundle was continuously arranged so that the thermoplastic resin (B) covered the periphery of the carbon fiber (A-1).
  • the internal cross section of the fiber bundle showed that at least a portion of the carbon fiber (A-1) was in contact with the thermoplastic resin (B).
  • the resulting strand was cooled and then cut into pellets 7 mm long with a cutter to obtain a long fiber reinforced resin molding material (X).
  • the take-up speed was adjusted so that the proportion of carbon fiber (A-1) relative to a total of 100 parts by weight of the long fiber reinforced resin molding material was as shown in Tables 1 to 3.
  • the length of the carbon fiber (A-1) in the obtained fiber reinforced resin molding material (X) was substantially the same as the pellet length, and the carbon fiber bundles were aligned parallel to the axial direction of the molding material.
  • Molding materials and molded articles were obtained using the method for producing the long fiber reinforced resin molding material (X), the method for producing the short fiber reinforced resin molding material (Y), and the method for producing the fiber reinforced resin molding material, so as to obtain the ratios of components shown in Tables 1 to 3.
  • the evaluation results of the molded articles are shown in Tables 1 to 3.
  • Examples 1-4, 7, 10, and 11 all had excellent fluidity, mechanical properties, surface appearance, and flame retardancy, and also had a high recycling rate.
  • Examples 5-6 had a different proportion of recycled polycarbonate resin compared to Examples 1-2, and although they were slightly inferior in various properties, they still exhibited excellent properties.
  • Examples 8-9 did not contain short fiber reinforced resin molding material, and therefore were inferior in fluidity and surface appearance, but they exhibited excellent mechanical properties.
  • Example 12 had a different type of recycled polycarbonate resin compared to Example 1, and although they were slightly inferior in various properties, they still exhibited excellent properties.
  • Comparative Examples 1 and 2 were excellent in fluidity, mechanical properties, surface appearance, and flame retardancy, but did not contain recycled materials, resulting in a high environmental impact.
  • Comparative Example 3 did not contain compound (C) compared to Example 1, resulting in insufficient fiber dispersion and inferior surface appearance and flame retardancy.
  • Comparative Examples 4 to 8 did not use carbon fibers with a fiber length of 3 mm or more and 10 mm or less, resulting in inferior mechanical properties.
  • Examples 13 and 14 were excellent in fluidity, mechanical properties, and surface appearance, and also had a high recycling rate.
  • Comparative Examples 9 and 10 did not use carbon fibers with a fiber length of 3 mm or more and 10 mm or less, resulting in inferior mechanical properties.

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Abstract

La présente invention concerne un matériau de moulage à base de résine renforcée par des fibres contenant une fibre de carbone (A) et une résine thermoplastique (B). Le matériau de moulage à base de résine renforcée par des fibres contient 10 à 40 parties en poids de fibre de carbone (A) et 60 à 90 parties en poids de résine thermoplastique (B) par rapport à 100 parties en poids au total de fibre de carbone (A) et de résine thermoplastique (B). La fibre de carbone (A) contient des fibres de carbone présentant une longueur de fibre de 3 à 10 mm et orientées dans la direction longitudinale d'un matériau de moulage. Le matériau de moulage à base de résine renforcée par des fibres contient un composé (C) comblant les espaces entre les fibres de carbone. La résine thermoplastique (B) contient une résine recyclée. Le matériau de moulage de la présente invention présente une excellente fluidité pendant le moulage tout en comprenant une résine recyclée et peut facilement produire un article moulé présentant d'excellentes propriétés mécaniques, et peut donc être appliqué à une large gamme de procédés de moulage.
PCT/JP2025/000614 2024-02-07 2025-01-10 Matériau de moulage à base de résine renforcée par des fibres et article moulé Pending WO2025169663A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11166054A (ja) * 1997-10-02 1999-06-22 Daicel Chem Ind Ltd リサイクル樹脂組成物及びその成形方法
JP2001113528A (ja) * 1999-10-21 2001-04-24 Daicel Chem Ind Ltd リサイクル樹脂組成物、リサイクル樹脂組成物の成形方法及び成形品
JP2012116917A (ja) * 2010-11-30 2012-06-21 Toray Ind Inc 繊維強化樹脂ペレット
WO2012086682A1 (fr) * 2010-12-24 2012-06-28 東レ株式会社 Procédé de production d'un agrégat de fibres de carbone et procédé de production d'un plastique renforcé par des fibres de carbone
JP2013209629A (ja) * 2012-02-29 2013-10-10 Toray Ind Inc ポリカーボネート樹脂成形材料、および成形品
JP2014159560A (ja) * 2013-01-25 2014-09-04 Toray Ind Inc 成形材料および成形品
WO2021124726A1 (fr) * 2019-12-20 2021-06-24 東レ株式会社 Matériau de moulage en résine renforcé de fibres, article moulé en résine renforcé de fibres et procédé de fabrication d'un article moulé en résine renforcé de fibres

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11166054A (ja) * 1997-10-02 1999-06-22 Daicel Chem Ind Ltd リサイクル樹脂組成物及びその成形方法
JP2001113528A (ja) * 1999-10-21 2001-04-24 Daicel Chem Ind Ltd リサイクル樹脂組成物、リサイクル樹脂組成物の成形方法及び成形品
JP2012116917A (ja) * 2010-11-30 2012-06-21 Toray Ind Inc 繊維強化樹脂ペレット
WO2012086682A1 (fr) * 2010-12-24 2012-06-28 東レ株式会社 Procédé de production d'un agrégat de fibres de carbone et procédé de production d'un plastique renforcé par des fibres de carbone
JP2013209629A (ja) * 2012-02-29 2013-10-10 Toray Ind Inc ポリカーボネート樹脂成形材料、および成形品
JP2014159560A (ja) * 2013-01-25 2014-09-04 Toray Ind Inc 成形材料および成形品
WO2021124726A1 (fr) * 2019-12-20 2021-06-24 東レ株式会社 Matériau de moulage en résine renforcé de fibres, article moulé en résine renforcé de fibres et procédé de fabrication d'un article moulé en résine renforcé de fibres

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