WO2013129540A1 - 繊維強化プラスチック成形用複合材及び繊維強化プラスチック成形体 - Google Patents

繊維強化プラスチック成形用複合材及び繊維強化プラスチック成形体 Download PDF

Info

Publication number
WO2013129540A1
WO2013129540A1 PCT/JP2013/055280 JP2013055280W WO2013129540A1 WO 2013129540 A1 WO2013129540 A1 WO 2013129540A1 JP 2013055280 W JP2013055280 W JP 2013055280W WO 2013129540 A1 WO2013129540 A1 WO 2013129540A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
reinforced plastic
composite material
binder
component
Prior art date
Application number
PCT/JP2013/055280
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
浩義 上野
鈴木　茂
立花　宏泰
Original Assignee
王子ホールディングス株式会社
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=49082733&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2013129540(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to JP2014502347A priority Critical patent/JP5949895B2/ja
Publication of WO2013129540A1 publication Critical patent/WO2013129540A1/ja

Links

Images

Classifications

    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
    • B29C70/506—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, 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
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions

Definitions

  • the present invention relates to a fiber reinforced plastic molding composite material, which is a precursor of a fiber reinforced plastic molding using thermoplastic fibers as a matrix resin, and a fiber reinforced plastic molding obtained by heating and pressing the composite material.
  • the matrix resin uses thermoplastic resin fibers called heat engineering and high flame retardancy, so-called super engineering plastics, and the molded product has high flame retardancy and strength and can be molded in a short time.
  • the present invention relates to a fiber reinforced plastic molding composite material and a fiber reinforced plastic molded body obtained by heating and pressing the composite material.
  • fiber reinforced plastic molding composite material that uses polyetherimide resin fibers as a matrix resin, is heat resistant and flame retardant and can be molded in a short time, and heat-press molding it,
  • the present invention relates to a fiber reinforced plastic molded article having high flame retardancy and strength and generating little smoke even when burned.
  • thermosetting resins such as phenol resins
  • thermosetting resin needs to be cured by a polymerization reaction in a heated state, but since the polymerization reaction takes time, there is a problem that the heat molding time becomes long and the productivity is low.
  • thermoplastic resin when used as a matrix resin, the impact resistance of the fiber reinforced resin molded article is excellent, and the storage management of the resin and the fiber reinforced resin composite material in a state before molding processing is easy, and the molding time is short. Therefore, for example, a development study of a fiber reinforced resin molded body made of a fiber reinforced resin composite material using a thermoplastic resin as a matrix resin, such as a polycarbonate resin, a polyester resin, or a polypropylene resin, has been conducted.
  • a thermoplastic resin as a matrix resin such as a polycarbonate resin, a polyester resin, or a polypropylene resin
  • Non-Patent Document 1 when a fiber reinforced plastic molded body is prepared from these resins, the composite material that is a precursor thereof is manufactured by a melting method (hot melt method), a solvent, depending on the type of resin impregnation method for the fiber.
  • a melting method hot melt method
  • a solvent depending on the type of resin impregnation method for the fiber.
  • Methods, dry powder coating methods, powder suspension methods, resin film impregnation methods (film stacking methods), mixed weaving methods (Commingle), and the like have been proposed (Non-Patent Document 1).
  • the melting method is a manufacturing method in which a thermoplastic resin is melted by an extruder, continuous fibers are passed through a melting bath, and the resin is impregnated into the inside of the fiber.
  • the solvent method is a resin (mainly amorphous resin) that is a solvent. This is a production method in which a reinforcing fiber is impregnated using a solution dissolved in (1).
  • the dry powder coating method is a method in which dry powder is adhered to reinforcing fibers and heated in the next step to melt and impregnate the powder.
  • the powder suspension method is a method in which reinforcing fibers are passed through a tank in which resin powder is uniformly dispersed in water or a solvent, the powder is adhered to the reinforcing fibers, and heated in the next step to melt and impregnate the powder.
  • the resin film impregnation method is a manufacturing method in which a resin film and reinforcing fibers are overlapped and the resin is melted and impregnated by a double belt press or an intermittent press method.
  • the mixed weaving method is a technique for producing a composite yarn by combining a reinforcing fiber and a thermoplastic resin fiber.
  • the composite yarn is woven (unidirectional, plain weave, braided, multiaxial woven fabric, etc.) to obtain an intermediate material, which is directly passed through a thermoforming process, and a thermoplastic resin fiber is impregnated into the reinforcing fiber to obtain a product.
  • Patent Document 1 a technique has been proposed in which a short fiber of a thermoplastic resin and a reinforcing fiber are mixed and dispersed in air or water to form a sheet, and the thermoplastic resin short fiber and the reinforcing fiber are combined (Patent Document 1,).
  • Patent Document 2 a technique has been proposed in which a short fiber of a thermoplastic resin and a reinforcing fiber are mixed and dispersed in air or water to form a sheet, and the thermoplastic resin short fiber and the reinforcing fiber are combined.
  • Patent Document 1 a proposal is made to heat and press-mold a web obtained by uniformly mixing carbon fibers as reinforcing fibers and a thermoplastic fibrous matrix resin in air or water and capturing them on a net.
  • Patent Document 2 discloses a technique for heat-pressing a paper-making substrate obtained by dispersing reinforcing fibers and matrix resin fibers in a dispersion medium, mixing them, and then removing the dispersion medium. ing.
  • a fiber reinforced resin molded article using a thermoplastic resin such as polycarbonate resin, polyester resin, or polypropylene resin as a matrix resin as described above has a thermosetting resin as a matrix resin in terms of heat resistance and flame retardancy. There is a disadvantage that it is inferior to the fiber reinforced resin molded product.
  • thermoplastic resins with excellent heat resistance and chemical resistance have been actively developed, and the above-mentioned drawbacks that have been common knowledge about thermoplastic resins have been remarkably improved. It is coming.
  • thermoplastic resins are so-called “super engineering plastics”, which are polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyamide imide (PAI), polyether imide (PEI).
  • PPS polyphenylene sulfide
  • PEEK polyether ether ketone
  • PAI polyamide imide
  • PEI polyether imide
  • thermoplastic resin called “super engineering plastic” is not only excellent in strength but also has a very high flame retardancy, and has a critical oxygen index of 30 or more in a resin block state.
  • PEI polyetherimide
  • PEI polyetherimide
  • thermosetting prepregs manufactured by the melt method hot melt method
  • solvent method dry powder coating method
  • powder suspension method dry powder coating method
  • resin film impregnation method film stacking method
  • mixed weaving method Single method
  • prepregs using super engineering plastics are characterized by a shorter molding time than thermosetting prepregs.
  • the melting method hot melt method
  • solvent method dry powder coating method
  • powder suspension method resin
  • the prepreg produced by the film impregnation method has poor air permeability. Therefore, if molding is attempted in a short period of time, bubbles existing between the hot plate for pressing and the sheet cannot be completely removed, and the molten resin is contained in the molten resin. Intrusion tends to cause defects such as poor appearance and defects in strength.
  • the woven fabric obtained by the mixed weaving method can give flexibility before forming, but generally has a lower productivity than the method in which short fibers are dispersed in air or water to form a sheet. It has the disadvantage of high cost.
  • Patent Document 1 and Patent Document 2 carbon fibers that are reinforcing fibers and thermoplastic fibrous matrix resin are uniformly mixed in air or water and captured on a net.
  • a proposal has been made to heat-press the obtained web, and Patent Document 2 obtained by dispersing reinforcing fibers and matrix resin fibers in a dispersion medium, mixing them, and then removing the dispersion medium.
  • a technique for heat-pressing a papermaking substrate has been disclosed, such a web or papermaking substrate has a binder as an essential component in order to obtain process strength when moving to a pressing process after mat formation. .
  • a prepreg made of a thermoplastic resin which is a super engineering plastic with high heat resistance and flame retardancy, is exposed to a high temperature of 300 ° C. or higher during heat and pressure molding, and therefore it is thermally decomposed and vaporized in the molded product.
  • Voids (hereinafter referred to as “voids”) are generated due to the binder, and both appearance and strength are likely to decrease. None of the above-mentioned prior art documents disclose a technique relating to a binder that can withstand the heating and pressing process at a high temperature as described above.
  • the binder component that can be generally used in the process of producing a normal web or papermaking substrate has lower flame retardancy than PEI fiber, and does not emit smoke during combustion. Many. Therefore, when a prepreg using such a binder component is subjected to heat and pressure molding, the characteristics of the PEI resin such as heat resistance, flame retardancy, and low heat generation are impaired. Furthermore, at the molding temperature of the PEI resin of 300 ° C. or higher, the binder as described above starts thermal decomposition and emits an odor, which causes a problem that the working environment is deteriorated.
  • Patent Document 3 introduces that a web is made by entwining carbon fibers by a papermaking method, but this method is weak and cannot be industrially produced. Further, Patent Document 4 discloses a method for fixing a fiber or a papermaking substrate between fibers with PEI resin itself.
  • a fiber from which a fiber-reinforced resin molded article having high strength, high heat resistance, and excellent flame retardancy using a thermoplastic resin having high heat resistance and flame retardancy as a matrix resin is obtained.
  • composite materials for reinforced plastic molding sufficient strength can be obtained without generating voids even in a very short heating and pressure molding time, the composite material itself is highly productive, and it is easy to handle in the processing process.
  • An object is to provide an excellent fiber-reinforced plastic molding composite material at low cost.
  • the present invention is also a fiber reinforced plastic molding composite material using PEI fibers as a matrix resin, and can be continuously produced with high production efficiency, has a low odor when processed into a molded body, and is heated and pressed. It is an object of the present invention to provide a composite material for molding fiber-reinforced plastics having features of high heat resistance, flame retardancy, and low smoke generation.
  • thermoplastic resin fibers with a diameter as the matrix resin the heat and pressure molding time is shorter than the conventional fiber reinforced plastic molding composite material using a high heat resistant thermoplastic resin.
  • the fibers are sufficiently melted and sufficient strength can be obtained.
  • the chopped strands (short fibers) of the thermoplastic fibers and reinforcing fibers are formed into a sheet shape.
  • a binder As a method for binding the intersections of the short fibers, it is necessary to provide a binder.
  • the binder type / mixing ratio / distribution in the composite material has specific conditions, the handling property as a fiber-reinforced plastic molding composite material is good, and the fiber after heat-pressure molding It has been found that the reinforced plastic has no voids and has a good appearance and high strength.
  • the flame retardancy and low smoke generation characteristics of PEI are achieved by effectively using a binder that is inferior in flame retardance to PEI resin, generates a lot of smoke, and generates odor at the molding temperature of PEI resin. It can be continuously produced with good manufacturing efficiency without loss, has low odor when processed into a molded product, and has high heat resistance, flame retardancy, and low smoke generation after being heated and pressed. It has been found that a fiber-reinforced plastic molding composite material having characteristics can be obtained.
  • the present invention includes the following.
  • Reinforcing fiber component composed of at least one kind of inorganic fiber selected from glass fiber and carbon fiber, a limiting oxygen index of 25 or more, a fiber diameter of 30 ⁇ m or less, and 4 times or less of the fiber diameter of the reinforcing fiber
  • a fiber-reinforced plastic molding composite material stampable sheet comprising a matrix resin component comprising super engineering plastic fibers.
  • the binder component in the fiber reinforced plastic molding composite material (stampable sheet) is unevenly distributed so that many portions thereof are present on the surface layer portion of the fiber reinforced plastic molding composite material (stampable sheet).
  • the fiber-reinforced plastic molding composite material (stampable sheet) according to (4).
  • binder component according to any one of (4) to (6), wherein the binder component is applied to the nonwoven fabric sheet by a coating method or an impregnation method as a solution or emulsion containing the binder component.
  • Fiber reinforced plastic molding composite material stampable sheet.
  • a method for producing a fiber-reinforced plastic molding composite material (stampable sheet) comprising a step of mixing a matrix resin component made of engineering plastic fibers to form a nonwoven fabric sheet.
  • the process of forming the said nonwoven fabric sheet forms the nonwoven fabric sheet in which many parts of the binder amount contained in all the nonwoven fabric sheets are unevenly distributed in the surface layer part of the front and back of a nonwoven fabric sheet using a binder containing liquid.
  • the step of forming the nonwoven fabric sheet includes a step of heat-treating the nonwoven fabric sheet having a matrix resin component composed of the reinforcing fiber component and the super engineering plastic fiber under conditions in which the super engineering plastic fiber is partially melted.
  • a reinforcing fiber component made of inorganic fiber, a matrix resin fiber component made of polyetherimide fiber, and a non-woven sheet containing at least one binder component, and the fiber components in the surface layer portion of the non-woven sheet are A fiber-reinforced plastic molding composite material (stampable sheet) characterized in that it is bonded mainly at the intersection of the fiber components by the binder component localized in the form of a drainage film.
  • the binder component that is localized in the form of a scraping film at the intersection of the fiber components in the surface layer portion contains at least one selected from methyl methacrylate and ethyl methacrylate as the monomer component (13)
  • the at least one binder component contains a particulate or fibrous thermoplastic resin that is compatible with the polyetherimide fiber component in a heat-melted state, (13) or (13) 14) Fiber-reinforced plastic molding composite material (stampable sheet).
  • the content of the copolymer with respect to the fiber-reinforced plastic molding composite material (stampable sheet) is 0.7 to 4.0% by mass, and the fiber-reinforced composite material for fiber-reinforced plastic molding ( The fiber-reinforced plastic molding composite material (stampable sheet) according to (17), wherein the content is 1.5% by mass to 6% by mass relative to the stampable sheet) and the total content of the binder component is 8% by mass or less ).
  • the fiber component in the intermediate layer between the surface layers is bonded (melt-bonded) by a particulate or fibrous thermoplastic resin that is compatible with the polyetherimide fiber component in a heated and melted state.
  • the composite material (stampable sheet) for fiber-reinforced plastic molding according to any one of (13) to (18).
  • a non-woven fabric having a matrix resin fiber component is applied with a solution-type or emulsion-type binder solution, and then the non-woven fabric is dried while the non-woven fabric is rapidly heated to transfer the main part of the binder solution to the non-woven fabric surface layer portion.
  • a method for producing a fiber-reinforced plastic molding composite material characterized in that the intersections of the fiber components of the surface layer portion of the nonwoven fabric are bonded with a binder localized in the form of a water-scrip film.
  • the fiber-reinforced plastic molding composite material (stampable sheet) according to any one of (13) to (19) is formed by heating and pressing at a temperature of 250 ° C. or higher and 430 ° C. or lower. , Fiber reinforced plastic molding.
  • a stampable sheet is a member before molding of a fiber-reinforced plastic molded body using a thermoplastic resin as a matrix resin.
  • a member before molding fiber-reinforced plastic with a so-called thermosetting resin is usually called a “prepreg”, and a stampable sheet corresponds to this “prepreg”.
  • the “prepreg” includes a member before molding a fiber reinforced plastic with a thermoplastic resin.
  • the composite material for molding a fiber-reinforced plastic of the present invention is molded into a fiber-reinforced plastic body that is free from voids and good in strength and appearance by being heated and pressed.
  • a sheet of a nonwoven fabric-like structure containing a thermoplastic matrix resin fiber component made of flame retardant PEI fiber and a reinforcing fiber component made of inorganic fiber which can be industrially continuously produced. It is possible, composite material for fiber-reinforced plastic molding with excellent handling properties that has sufficient interlayer strength even in the process of processing into molded bodies by lamination, heat press, etc., and excellent flame retardancy and low smoke generation A fiber-reinforced plastic molded article is provided.
  • General reinforcing fibers such as metal fibers, ceramic fibers, glass fibers, and carbon fibers can be widely used as the reinforcing fibers used in the fiber-reinforced plastic molding composite material of the present invention.
  • These inorganic fibers are all preferable in terms of flame retardancy and low smoke generation, and one of them can be used, or a plurality of them can be used in combination.
  • carbon fiber and glass fiber are preferable from the viewpoints of fiber strength and weight, adhesiveness with a thermoplastic resin, and the like.
  • the thickness of the reinforcing fiber is not particularly limited, but is preferably 3 ⁇ m to 18 ⁇ m. If the fiber diameter of the reinforcing fiber is smaller than this, it may be carcinogenic when taken into the human body during the manufacturing process or use, which is not preferable. Further, if the fiber diameter of the reinforcing fiber is larger than this, the uniformity of the mixture with the super engineering plastic fiber is deteriorated, which is not preferable in terms of strength.
  • the fiber length of the reinforcing fiber is preferably about 3 mm to 30 mm. When longer than this, a fiber will not disperse
  • the fiber diameter and fiber length may be single, or those having different fiber diameters and fiber lengths may be blended and used.
  • thermoplastic resin fiber used in the composite material for molding a fiber-reinforced plastic of the present invention is a fiber made from a heat-resistant and flame-retardant thermoplastic resin called a so-called super engineering plastic.
  • thermoplastic resins include polyetheretherketone (PEEK), polyamideimide (PAI), polyphenylene sulfide (PPS), polyetherimide (PEI), polyetherketoneketone (PEKK), etc. It is not limited to this.
  • the super engineering plastic fiber obtained by fiberizing a resin which is a super engineering plastic used for the fiber-reinforced plastic molding composite of the present invention has a critical oxygen index of 25 or more and a glass transition temperature of 140 ° C. or more in the fiber state. Further, even if the glass transition temperature is lower than this, it is preferable that the resin has a deflection temperature under load of 190 ° C. or higher.
  • Such a super engineering plastic fiber has a very high flame retardance with a critical oxygen index of 30 or more in a state of being melted by heating and pressurizing to form a resin block.
  • the thermoplastic resin fiber used in the fiber-reinforced plastic molding composite of the present invention is a PEI fiber obtained by fiberizing a PEI resin.
  • the PEI resin used in this fiber has a critical oxygen index of 40 or more after being melted and processed, and a smoke generation amount of about 30 ds when burned for 20 minutes as measured by the method described in ASTM E-662. It is characterized by low smoke generation.
  • the “limit oxygen index” represents an oxygen concentration necessary to continue combustion, and is a numerical value measured by a method described in JIS K7201. That is, a critical oxygen index of 20 or less is a numerical value indicating that combustion is performed in normal air.
  • the composite material for molding fiber reinforced plastics of the present invention is a mixed weaving method in which super engineering plastic fibers that form a matrix by reinforcing fibers and thermoforming are alternately knitted, or super engineering plastic fibers that form a matrix by reinforcing fibers and thermoforming.
  • a method of forming a web by dispersing chopped strands cut to a length in air and trapping them in a net (dry nonwoven fabric method), or dispersing both the chopped strands in a solvent, and then removing the solvent to remove the web Although it can manufacture by methods, such as the method of forming (wet nonwoven fabric method), it is not limited to these.
  • thermoplastic resin forming the matrix by thermoforming is in fiber form. Therefore, unlike composite materials in which the resin is completely buried between the fibers, such as melting method (hot melt method), solvent method, dry powder coating method, powder suspension method, resin film impregnation method (film stacking method), etc.
  • the sheet itself is flexible and draped, and can be stored and transported in the form of winding, and can be heat-pressed after being placed along a curved mold. It is characterized by superiority.
  • the super engineering plastic fiber used for the fiber-reinforced plastic molding composite material of the present invention is sufficiently fluid under temperature conditions of 300 ° C. to 400 ° C. when the fiber-reinforced plastic molding composite material is heated and pressed. It is required to be. Further, the glass transition temperature of the fiberized super engineering plastic fiber should be 140 ° C. or higher so that the fiber state can be sufficiently maintained under the heating conditions applied in the production stage of the fiber reinforced plastic molding composite material. preferable. Further, even if the glass transition temperature is lower than this, it is preferable that the resin has a deflection temperature under load of 190 ° C. or higher.
  • Fiber reinforced plastic molding composites in which the resin that forms the matrix during heat and pressure molding is super engineering plastic fibers is heated when processed into fiber reinforced plastics rather than fiber reinforced plastic molding composites that use thermosetting resins.
  • the original characteristic is that the pressure molding time is short and the productivity is excellent.
  • the super engineering plastic fiber in order to heat and pressure-mold a fiber reinforced plastic molding composite material in a short time, it is necessary for the super engineering plastic fiber to be used to quickly melt at a high temperature. Thinner fiber diameters are preferred. This is necessary for melting because the number of contact points between fibers increases when the fiber diameter is small, the contact area between the fibers increases, heat conduction becomes better, and the heat capacity of the fibers decreases. This is because the amount of heat is reduced.
  • the fiber diameter is preferably 30 ⁇ m or less, and more preferably 1 to 20 ⁇ m or less.
  • the fiber length of the super engineering plastic fiber is not particularly limited, but is preferably about 3 mm to 30 mm when manufactured by a wet or dry nonwoven fabric method. When longer than this, a fiber will not disperse
  • the fiber diameter and fiber length may be single, or those having different fiber diameters and fiber lengths may be blended and used.
  • the fiber diameters of the reinforcing fiber and the matrix resin fiber are close.
  • the fiber diameter of the super engineering plastic fiber is preferably 4 times or less of the fiber diameter of the reinforcing fiber, more preferably 3 times or less, and most preferably the fiber diameter of the super engineering plastic fiber and the reinforcing fiber. The fiber diameter is almost the same.
  • the matrix resin has a high melt viscosity, it is difficult to uniformly disperse the reinforcing fibers when a large amount of the reinforcing fibers are blended by a method such as injection molding, so that the blending ratio of the reinforcing fibers is limited.
  • the ratio of the reinforcing fiber to the matrix resin fiber can be set relatively freely according to the required strength.
  • the fiber diameter of the super engineering plastic fiber it is preferable to select a fiber having a fiber diameter of 30 ⁇ m or less and 4 times or less of the fiber diameter of the reinforcing fiber. Thereby, shortening of the heating and pressing time and the strength of the fiber reinforced plastic after the heating and pressing can be made compatible.
  • the fiber reinforced plastic molding composite material of the present invention has a fibrous matrix and is highly air permeable, the air content existing between the press plate and the composite material and the volatile gas content generated from the composite material are , It is easy to slip out of the sheet during pressing, and has the characteristics that voids and the like are unlikely to occur even in a short time heating and pressing treatment.
  • the air permeability of the fiber reinforced plastic molding composite material is 200 seconds or less as measured by a method based on the JAPAN TAPPI paper pulp test method. This numerical value indicates that the smaller the number, the easier air can pass through (the better the air permeability).
  • the composite material for molding a fiber-reinforced plastic in the present invention can be manufactured using chopped strands in which matrix resin fibers and reinforcing fibers are cut into a predetermined length to shorten the length.
  • the matrix resin and the reinforced fiber chopped strands are dispersed and mixed in the air, captured in a net and formed into a sheet, a so-called dry nonwoven fabric method, the matrix resin fibers and the reinforced fiber chopped strands in a solvent.
  • the composite material for molding a fiber reinforced plastic can be produced by a so-called wet non-woven method or the like, which is then dispersed into a sheet and then formed into a sheet by removing the solvent.
  • the strength as a sheet that can be handled may be insufficient only by physical entanglement between fibers.
  • the super engineering plastic fibers may be partially melted by heating the sheet, and the fibers may be fused.
  • a binder may be added to bind the fibers.
  • thermosetting resins such as acrylic resin, styrene / acrylic resin, epoxy resin, phenol resin, thermoplastic resin such as urethane resin, polyester resin, polypropylene resin, polyethylene resin, ethylene / vinyl acetate resin, or polyvinyl What is used for general nonwoven fabric manufacture, such as resin which melts hot water like alcohol etc., can be used.
  • the binder content is preferably 10% by mass or less in the fiber-reinforced plastic molding composite.
  • a binder component may start pyrolysis at the heating and pressing temperature of the fiber reinforced plastic molding composite material to generate gas. For this reason, if the binder content is higher than this, a large amount of gas is generated. Therefore, even if the fiber-reinforced plastic molding composite has the above-described air permeability, voids are formed in the fiber-reinforced plastic after heat and pressure molding. In addition, since the binder itself is discolored, the appearance and strength are often inferior.
  • the content of the binder component is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% with respect to the fiber reinforced plastic molding composite material. It is below mass%. If the amount of the binder is too small, the strength of the sheet is too weak to be broken during the operation, or fibers on the surface of the fiber-reinforced plastic molding composite material are easily dropped and scattered in the processing step, which is not preferable.
  • the super engineering plastic fiber component used in the fiber-reinforced plastic molding composite material according to the present invention has a flame resistance because it has a critical oxygen index of 25 or more.
  • the limiting oxygen index of the binder component is generally lower than that of the super engineering plastic fiber component used in the fiber-reinforced plastic molding composite material of the present invention, the flame retardance is impaired when the binder content is large.
  • the content of the binder is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less with respect to the fiber-reinforced plastic molding composite material.
  • the PPS resin has high chemical resistance and high heat resistance.
  • a fiber reinforced plastic having excellent strength can be obtained.
  • PEI resin has excellent adhesion to carbon fiber and glass fiber, and has a critical oxygen index of resin. Since it is very high at 47 in the block state, a fiber reinforced plastic excellent in strength and flame retardancy can be obtained.
  • PEEK polyether ether ketone
  • the binder component used for the fiber-reinforced plastic molding composite material in the present invention is preferably unevenly distributed in the surface layer portion of the fiber-reinforced plastic molding composite material.
  • the inner layer has relatively less binder component.
  • the binder component As a method for making the binder component relatively present in the surface layer of the fiber reinforced plastic molding composite, after forming a web by a wet nonwoven fabric method or a dry nonwoven fabric method, a liquid material in which the binder component is dissolved in a solvent, or a binder
  • a liquid material in which the binder component is dissolved in a solvent, or a binder The manufacturing method of giving the emulsion (emulsion) of a component by dipping or a spray method etc., and heat-drying is mentioned. According to this method, since the moisture inside the web moves to the surface layers on both sides and evaporates during heating and drying, a relatively large amount of the binder component concentrates on the surface layer as the moisture moves.
  • a manufacturing method in which a liquid binder component such as a solution or emulsion of the binder component is used and dried by heating is employed. Can do. In this case, it is preferable that the solvent move more because the uneven distribution of the binder component becomes stronger.
  • the web moisture can be adjusted by adjusting the concentration of the binder solution in the aqueous solution or emulsion, or the moisture suction force by wet suction or dry suction in the wet nonwoven fabric manufacturing process.
  • the preferred web moisture for making the binder component unevenly distributed is 50% or more. However, if there is too much moisture, the drying load increases and the production cost increases. Therefore, it is preferable to appropriately adjust the moisture in consideration of both.
  • the degree of uneven distribution of the binder component can be grasped by dividing the sheet into approximately 3 to 5 parts in the thickness direction (Z-axis direction) and measuring the amount of each binder.
  • the degree of uneven distribution of the binder component is preferably about 1/2 to 1/10 of the amount of binder in the inner layer with respect to the surface layer when divided into approximately three equal parts.
  • the binder component in the fiber-reinforced plastic molding composite material of the present invention is a resin component that is compatible with the resin when the super engineering plastic fiber that becomes the matrix after heat-pressure molding is melted by heat-pressure molding. Particularly preferred.
  • a resin component is used as a binder, after heat and pressure molding, the matrix resin and the binder resin are integrated without any interface, and the strength is good. Further, the glass of the matrix resin caused by the binder resin It has the feature that there is little decrease in the transition temperature.
  • PET or modified PET is used as a preferable binder component in terms of being compatible with the resin when melted by heat and pressure molding. It is preferable.
  • the shape is powder, fibrous, or ordinary PET placed on the core, and the periphery is covered with modified PET having a melting point lower than that of the core.
  • a sheath-structured PET fiber or the like is preferably used.
  • the melting point of the modified PET is preferably 140 ° C. or less, more preferably 120 ° C. or less.
  • the present invention comprises a non-woven sheet comprising a reinforcing fiber component composed of inorganic fibers, a matrix resin fiber component composed of polyetherimide fibers (PEI fibers), and at least one binder component.
  • seat is related with the composite material for fiber-reinforced plastics shaping
  • this embodiment will be particularly described.
  • the fiber-reinforced plastic molding composite material of the above embodiment includes a method of dispersing reinforcing fibers and PEI fibers in the air and capturing them in a net to form a web (dry nonwoven fabric method), and reinforcing fibers and PEI fibers in a solvent. And a method of forming a web after removing the solvent (wet nonwoven fabric method).
  • a liquid binder that is, a binder component solution or an emulsion liquid
  • the liquid binder is concentrated on the fiber intersection by the surface tension of the binder liquid during the drying process after applying the binder to the web by the production process, that is, the coating method or the impregnation method, and then shrinks by drying. Therefore, after drying, as shown in FIG. Due to such a property, it is excellent in strength for bonding fibers even in a very small amount.
  • the binder component is as described above.
  • the moisture in the web containing the binder liquid evaporates from both surface layers of the fiber-reinforced plastic molding composite material. concentrate. Therefore, even if a small amount of the binder is used, the falling and scattering of the surface fibers of the composite material are suppressed, and a composite material for molding a fiber-reinforced plastic that has excellent handling properties in a heat molding process or the like can be obtained.
  • the flame retardancy and low smoke generation can be made excellent. The reason is considered as follows.
  • the method for unevenly distributing the binder component on the surface layer (both surface layers) of the fiber reinforced plastic molding composite is as described above.
  • the molding temperature is as high as 250 ° C. to 400 ° C. because polyetherimide having high heat resistance is used as the matrix resin.
  • a temperature range exceeds the thermal decomposition temperature of an acrylic resin or the like normally used as a binder component. Therefore, it is considered that the binder component is thermally decomposed and volatilized at the time of thermoforming, so that the binder component does not remain in the thermoformed product, and thus the binder component does not hinder the flame retardancy and low smoke generation of the thermoformed product.
  • fiber reinforced plastic molding composites manufactured by the usual binder addition method if the processing is carried out by heating and pressing for a short time, the molding process is completed before the binder components are sufficiently decomposed and volatilized. The remaining binder component inhibits the flame retardancy and low smoke generation of the thermoformed product.
  • the binder component By concentrating the binder component in the vicinity of the surface of the fiber reinforced plastic molding composite, the binder component is effectively heated during hot-press molding by a high-temperature mold or press plate. -It is considered that the binder component that volatilizes and remains in the thermoformed product becomes a very small amount.
  • the binder component used for the fiber-reinforced plastic molding composite material preferably contains a copolymer of methyl methacrylate, ethyl methacrylate, ethyl acrylate, and / or methyl acrylate, and particularly glass fiber or the like as the reinforcing fiber.
  • the binder component preferably contains a copolymer containing at least one selected from methyl methacrylate and ethyl methacrylate as a monomer component.
  • Granular or fibrous binders can also be included in the fiber reinforced plastic molding composite. As a result, the interlayer strength of the fiber-reinforced plastic molding composite material is increased, and the handling property during the heat molding process is further improved.
  • a granular or fibrous binder can be dispersed in the air together with reinforcing fibers and PEI fibers and captured on a net to form a web (dry nonwoven fabric method), or dispersed in a solvent, and then the solvent is removed to remove the web.
  • the binder component When supplied as a liquid binder or when supplied as a granular or fibrous binder, the binder component is preferably a binder component that is compatible with PEI fibers when heated and melted. According to the study by the present inventors, it has been found that when such a component is selected, the flame retardancy and low smoke generation of the PEI resin are hardly impaired after the heat and pressure molding.
  • a polyester resin or a modified polyester resin may be mentioned. These resins can be used as an emulsion liquid or can be contained in the layer of the fiber-reinforced plastic molding composite material in a granular or fibrous form. In any case, the flame retardancy and low smoke generation properties of the PEI resin are not impaired, but a modified polyester resin is particularly preferable because the fusing temperature can be set so as to be suitable for the production process of the fiber-reinforced plastic molding composite.
  • the binder component used is a fiber reinforced plastic in which the total amount of the binder component supplied in the state of a solution or an emulsion and the binder component supplied in a granular or fibrous form, if necessary, It is preferable that it is 0.3 mass% or more and 10 mass% or less with respect to the shaping
  • the ratio of the two can be arbitrarily set so as to be suitable for the manufacturing process.
  • the amount of the binder component is less than 0.3% by mass, the strength during the manufacturing process is insufficient and the handling property is lowered.
  • the above-mentioned binder component does not inhibit the flame retardancy and low smoke generation, but if the amount is too large, the flame retardancy and low smoke generation are likely to be impaired. It is 10% by mass or less, and sufficient process strength and handling properties can be obtained with this addition amount.
  • the liquid binder composed of methyl methacrylate, ethyl ethacrylate, ethyl acrylate, and / or methyl acrylate copolymer is concentrated on both surface layers of the fiber reinforced plastic molding composite, and the fiber components of both surface layers. Because it is localized in the form of a draining film at the intersection of each other, even if the binder component is small, it is suitable for the fiber reinforced plastic molding composite material because there is little loss of fibers on both surface layers even in the use process, and there is little discoloration. Immediately after papermaking, it can be suitably used in a process of cutting, laminating and pressing a flat plate.
  • winding is once manufactured with a paper machine or the like, and is further cut into a predetermined width while being wound with a winder or the like in order to obtain a predetermined width.
  • the problem becomes more serious because the number of times the sheet is rolled is increased.
  • the interlaminar strength can be improved by using a fibrous or granular binder.
  • a fibrous or granular binder can be used for both fiber-reinforced plastic molding composites such as a liquid binder. Since it is not localized in the surface layer, most of the binder remains in the composite material even after the hot pressing. Therefore, the fibrous or granular binder is particularly preferably a binder that is compatible with the PEI resin, and is preferably a polyester resin or a modified polyester resin.
  • the fibrous binder is mixed with PEI fibers and reinforcing fibers and dispersed in water, and when the paper is made by a wet papermaking method, the yield drops by dropping from the eyes of the papermaking wire like a granular binder, It is particularly preferable because it is not unevenly distributed on the wire side.
  • a fibrous modified polyester resin binder is particularly suitable for producing a winding.
  • a binder fiber having a core-sheath structure in which a polyester resin is disposed in the core part and a modified polyester resin is disposed in the sheath part, and the melting point of the sheath part is lower than that of the core part can be suitably used.
  • Polyester resin is preferably polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the modified polyester resin is not particularly limited as long as the melting point is lowered by modifying the polyester resin, but modified polyethylene terephthalate is preferable.
  • modified polyethylene terephthalate copolymerized polyethylene terephthalate (CoPET) is preferable, and examples thereof include urethane-modified copolymerized polyethylene terephthalate.
  • the copolymerized polyethylene terephthalate preferably has a melting point of 140 ° C. or lower, more preferably 120 ° C. or lower.
  • a modified polyester resin as described in JP-B-1-30926 may be used.
  • melty 4000 (a fiber in which all fibers are copolymerized polyethylene terephthalate) manufactured by Unitika is preferably exemplified.
  • core-sheath-structured binder fiber Melty 4080 manufactured by Unitika, N-720 manufactured by Kuraray, or the like can be suitably used.
  • the emulsion binder is 0.7 to 4.0% by mass
  • the binder selected from the polyester resin and the modified polyester resin is 1.5 to 6.0% by mass
  • the total amount of the binder components is When the content is 8% by mass or less, sufficient surface strength and interlayer strength can be obtained even when winding and repeated cutting.
  • the blending amount of the liquid binder containing a copolymer of methyl methacrylate, ethyl ethacrylate, ethyl acrylate, and methyl acrylate as a component is smaller than that of the polyester resin or the modified polyester resin, and the odor is related. From these results, favorable results are obtained. Since the polyester binder is compatible with the matrix resin, it is difficult to generate odor even if the addition amount is relatively large, and since the liquid binder tends to be concentrated and concentrated at the intersection of the fibers, such a result is obtained. Estimated.
  • the fiber-reinforced plastic molding composite material of the present invention is a single sheet or laminated to have a desired thickness and heat-pressed by hot pressing, pre-heated with an infrared heater or the like in advance, )
  • a fiber reinforced plastic excellent in strength and flame retardancy can be obtained by processing using a general method for heating and pressing a fiber reinforced plastic molding composite material such as pressure molding.
  • the basis weight of the fiber-reinforced plastic molding composite material of the present invention is not particularly limited, but it is preferable to reduce the number of laminated layers because it is necessary to thermally decompose and volatilize the binder component on the surface of the fiber-reinforced plastic molding composite material during heat molding. Therefore, a higher basis weight is preferable. From such a viewpoint, the preferred basis weight is 400 g / m 2 or more, more preferably 550 g / m 2 or more. In addition, the upper limit of a fabric weight can be suitably set according to the thickness of the target fiber reinforced plastic molding composite material.
  • the smoke concentration after 20 minutes in the flame test measured by the method according to ASTM-662 is 43DS or less, It is possible to obtain a fiber-reinforced plastic molded article having a very low fuming property of 37 DS or less.
  • Production examples 1 to 4 A PAN-based carbon fiber having a fiber diameter of 7 ⁇ m and a fiber length of 13 mm and a PPS resin fiber having a fiber diameter shown in Table 1 (manufactured by Fiber Innovation Technology, fiber length of 13 mm, critical oxygen index of 41) and a mass ratio of polyacrylonitrile (PAN) ) It measured so that it might become the polyphenylene sulfide (PPS) resin fiber 60 with respect to the system carbon fiber 40, and it injected
  • PPS polyphenylene sulfide
  • Particulate polyvinyl alcohol (Unitika Ltd., trade name “OV-N”) was added to water so as to have a concentration of 10%, and stirred to prepare a binder slurry.
  • the granular PVA slurry was put into a fiber slurry, a wet web was formed by wet papermaking, and heat drying was performed at 180 ° C. to obtain a nonwoven fabric having a basis weight of 250 g / m 2 .
  • This nonwoven fabric was heated and pressurized with a 220 ° C. hot press to obtain a fiber reinforced plastic molding composite material having air permeability shown in Table 1.
  • the air pressure is adjusted as shown in Table 1 by shortening the heating and pressing time and lowering the density as compared with Production Example 1, and in Production Example 4 the heating and pressurization is more than in Production Example 1.
  • the air permeability was adjusted as shown in Table 1 by extending the time and increasing the density.
  • concentration was adjusted suitably so that the compounding rate with respect to the composite material for fiber reinforced plastics shaping
  • Production Example 5 Except for changing the PPS resin fiber to the PPS fiber having the fiber diameter shown in Table 1 (manufactured by KB Selen Co., Ltd., glass transition temperature 92 ° C., fiber length 13 mm, critical oxygen index 41), the same as in Production Example 1 Thus, a composite material for molding fiber reinforced plastic was prepared.
  • Production Examples 6-9 The PAN-based carbon fiber having a fiber diameter of 7 ⁇ m and a fiber length of 13 mm in Production Example 1 was changed to a glass fiber having a fiber diameter of 9 ⁇ m and a fiber length of 18 mm, and the PPS resin fiber (manufactured by Fiber Innovation Technology Co., Ltd.) was produced. , Glass transition temperature 92 ° C., limiting oxygen index 41) to polyetherimide (PEI) resin fibers (Fiber Innovation Technology, glass transition temperature 220 ° C., fiber length 13 mm, limiting oxygen index 47) shown in Table 2. Except having changed, it carried out similarly to manufacture example 1, and obtained the nonwoven fabric whose fabric weight is 250 g / m ⁇ 2 >.
  • PEI polyetherimide
  • the obtained sheet was heated and pressed by a heat press at 220 ° C. to appropriately adjust the air permeability as shown in Table 2, and the fiber-reinforced plastic molding composite materials of Production Examples 6 and 7 were produced.
  • the air permeability was adjusted as shown in Table 2 by shortening the heating and pressing time by 220 ° C. hot pressing and lowering the density as compared with Production Example 6.
  • glass fiber in Production Example 6 was changed to glass fiber having a fiber diameter of 6 ⁇ m and a fiber length of 18 mm, and a fiber-reinforced plastic molding composite material of Production Example 9 was produced in the same manner as Production Example 6.
  • Production Examples 10-15 The PPS resin fiber in Production Example 1 was replaced with a PPS resin fiber having a fiber diameter of 16 ⁇ m (manufactured by Fiber Innovation Technology, glass transition temperature 92 ° C., fiber length 13 mm, critical oxygen index 41), and instead of granular PVA, a wet web was used.
  • the composite material for molding fiber reinforced plastics of Production Examples 10 to 15 was the same as Production Example 1 except that the binder liquid shown in Table 3 was added in the amount shown in Table 3 by spraying after the formation, and was heated and dried. Was made.
  • Production Examples 16-21 Production Examples 10 to 15 except that the PPS resin fibers in Production Examples 10 to 15 are replaced with PEI resin fibers having a fiber diameter of 15 ⁇ m (manufactured by Fiber Innovation Technology, glass transition temperature 220 ° C., fiber length 13 mm, critical oxygen index 41). Fiber reinforced plastic molding composite materials of Production Examples 16 to 21 corresponding to the above were produced.
  • a PVA aqueous solution in which “PVA117” manufactured by Kuraray was dissolved in hot water was used as the PVA aqueous solution.
  • the styrene acrylic emulsion used was “GM-1000” manufactured by DIC, and the urethane emulsion used was “AP-X101” manufactured by DIC.
  • Tables 1 to 4 show the appearance of the obtained fiber reinforced plastic and the bending strength measured by a method based on JIS K7074. Appearance is good with no voids, etc. ⁇ , slightly voids can only be confirmed ⁇ , voids are generated but there is no practical problem, ⁇ , apparently due to voids Was bad and could not be used as a product.
  • the fiber reinforced plastic bodies obtained by heating and pressing the fiber reinforced plastic molding composites of Production Examples 1 and 2, Production Examples 6 to 8, and Production Examples 10 to 21 are as follows. It is manufactured by heat and pressure molding a gas-permeable fiber reinforced plastic molding composite material having a thermoplastic fiber called a super engineering plastic having a specific fiber diameter and a reinforcing fiber made of carbon fiber or glass fiber. As a result, the fiber-reinforced plastic body has high strength and good appearance.
  • the fiber reinforced plastic molded from the fiber reinforced plastic molding composite material of Production Example 4 having an air permeability of 210 and slightly less permeable than those of each of the above production examples is somewhat inferior in appearance.
  • the strength is slightly lower than those of Production Examples 1 and 2.
  • the fiber diameter of the super engineering plastic fiber exceeds 30 ⁇ m, so that the appearance after heating and pressing is that of Production Examples 1 to 4. It is clearly inferior to a fiber reinforced plastic body molded from a fiber reinforced plastic molding composite.
  • the fiber reinforcement is carried out by using the super engineering plastic fiber which has a fiber diameter exceeding 4 times the fiber diameter of a reinforcement fiber Fiber reinforcement in which the mixed state of the reinforcing fiber and matrix fiber in the plastic molding composite material is deteriorated, and the appearance of the laminate after the heat and pressure molding is molded from the fiber reinforced plastic molding composite material of Production Examples 1 to 4 It is clearly inferior to the plastic body.
  • molded from the composite material for fiber reinforced plastic molding of the manufacture example 3 is fiber because the amount of binders in the composite material for fiber reinforced plastic molding is larger than that of the manufacture examples 1 and 2.
  • the content of the binder used is also the fiber reinforced plastic after molding so that the appearance of the reinforced plastic body is slightly inferior to those of Production Examples 1 and 2. It can be seen that this affects the appearance and strength.
  • Example 1 A PAN-based carbon fiber having a fiber diameter of 7 ⁇ m and a fiber length of 13 mm and a PEI resin fiber having a fiber diameter of 15 ⁇ m (fiber length of 13 mm) are set to have a PEI resin fiber 60 with respect to the polyacrylonitrile (PAN) -based carbon fiber 40. Weighed and put into water. The amount of water added was 200 times the total mass of the PAN-based carbon fiber and the PEI resin fiber (that is, the fiber slurry concentration was 0.5%).
  • PAN polyacrylonitrile
  • a wet web is formed from this fiber slurry by a wet papermaking method, and an emulsion liquid binder (methyl methacrylate copolymer, EMN-188E manufactured by Nippon Shokubai Co., Ltd.) having a concentration of 5% is applied by a spray method.
  • an emulsion liquid binder methyl methacrylate copolymer, EMN-188E manufactured by Nippon Shokubai Co., Ltd.
  • the web moisture was appropriately dehydrated by suction, and heated and dried at 180 ° C. to obtain a fiber-reinforced plastic molding composite material having a basis weight of 550 g / m 2 .
  • Example 2 A binder slurry liquid in which a modified polyester granular binder (powder resin G-120, manufactured by Tokyo Ink Co., Ltd.) having a melting point of 110 ° C. was dispersed in water so as to have a solid content mass concentration of 10% was prepared. Except for adding this binder slurry liquid to the fiber slurry prepared in Example 1, a wet web is formed by the wet papermaking method in the same manner as in Example 1, and an emulsion liquid binder is added to heat and dry the fabric. A fiber-reinforced plastic molding composite material having a weight of 550 g / m 2 was obtained. In addition, the addition amount of the binder slurry liquid was adjusted so that the solid content mass addition amount of the modified polyester granular binder was as shown in Table 5.
  • a modified polyester granular binder binder resin G-120, manufactured by Tokyo Ink Co., Ltd.
  • Example 3 a fiber reinforced plastic molding composite was obtained in the same manner as in Example 2 except that the modified polyester granular binder having a melting point of 110 ° C. was changed to a modified polyester fibrous binder (Melty 4000 manufactured by Unitika).
  • Example 4 In Example 1, the emulsion liquid binder was changed to a 2% concentration PVA solution binder (Kuraray PVA117 dissolved in warm water and cooled), and the solid mass addition amount of the binder to the fiber-reinforced plastic molding composite was changed to A fiber-reinforced plastic molding composite material was obtained in the same manner as in Example 1 except that it was as shown in Table 5.
  • Example 5 A fiber-reinforced plastic molding composite was produced in the same manner as in Example 2 except that the modified polyester granular binder in Example 2 was changed to PVA granular binder (OV-N manufactured by Unitika Ltd.).
  • Example 5 a fiber reinforced plastic molding composite was produced in the same manner as in Example 5 except that the emulsion liquid binder was not applied and the addition amount of the granular PVA binder was changed as shown in Table 5.
  • Comparative Example 2 A fiber reinforced plastic molding composite was produced in the same manner as in Comparative Example 1, except that the amount of the granular PVA binder added was changed as shown in Table 5.
  • Comparative Examples 3-4 In Comparative Examples 1 and 2, the reinforcing fiber was changed to a glass fiber having a fiber diameter of 9 ⁇ m and a fiber length of 18 mm, and the ratio of the reinforcing fiber to the polyetherimide fiber was changed as shown in Table 6. Comparative Example 1 A composite material for molding a fiber-reinforced plastic was produced in the same manner as in (2).
  • Examples 11 to 26 The solid content of the methyl methacrylate copolymer (EMC-188E manufactured by Nippon Shokubai Co., Ltd.) is as shown in Table 5, and the solid content of the modified polyester fibrous binder (Melty 4000 manufactured by Unitika) is also shown. A composite material for molding a fiber-reinforced plastic was obtained in the same manner as in Example 3 except that it was as shown in FIG. The solid content of the binder (EMN-188E manufactured by Nippon Shokubai Co., Ltd.), which is a methyl methacrylate copolymer, was adjusted to a predetermined level by appropriately adjusting the spray liquid concentration at the time of adding the binder.
  • Example 27 A fiber reinforced plastic molding composite was prepared in the same manner as in Example 1 except that the solid content of the emulsion liquid binder (methyl methacrylate copolymer, EMN-188E manufactured by Nippon Shokubai Co., Ltd.) was as shown in Table 6. Manufactured. The solid content of the binder (EMN-188E manufactured by Nippon Shokubai Co., Ltd.), which is a methyl methacrylate copolymer, was adjusted to a predetermined level by appropriately adjusting the spray liquid concentration at the time of adding the binder.
  • the solid content of the emulsion liquid binder methyl methacrylate copolymer, EMN-188E manufactured by Nippon Shokubai Co., Ltd.
  • Example 11 was changed except that the reinforcing fiber was changed to a glass fiber having a fiber diameter of 9 ⁇ m and a fiber length of 18 mm, and the ratio of the reinforcing fiber to the polyetherimide fiber was changed as shown in Table 6.
  • fiber reinforced plastic molding composite materials of Examples 23 ⁇ 44 were produced.
  • each fiber reinforced plastic molding composite material having a width of 2.3 m was manufactured, and (1) cut with a two-drum winder so as to have a width of 1100 mm. A winding was obtained.
  • the winding obtained in the previous period (1) was further cut with a two-drum winder so as to have a width of 500 mm to obtain a winding of 300 m. Then, the dropping and scattering of the surface fibers of the fiber reinforced plastic molding composite material during the operations (1) and (2) were evaluated as follows.
  • the composite material for fiber-reinforced plastic molding after the steps (1) and (2) were evaluated as follows.
  • Table 5 and Table 6 show the smoke concentration (according to ASTM E-662, after heating for 20 minutes) and the limiting oxygen index of the obtained fiber reinforced plastic by the flame method.
  • granular polyester represents a modified polyester granular binder (powder resin G-120, manufactured by Tokyo Ink Co., Ltd.), and “fibrous polyester” represents a modified polyester fibrous binder (manufactured by Unitika). 4000).
  • the fiber-reinforced plastic molding composites according to the present invention are less likely to lose surface fibers, have sufficient sheet strength, and have good handling properties in the work process.
  • the fiber reinforced plastic body showed excellent flame retardancy, that is, low smoke concentration and high limit oxygen index.
  • Examples 2, 3, 7 and 8 using granular polyester and fibrous polyester, which are binders compatible with polyetherimide, are particularly difficult to handle, in addition to excellent handling properties. It showed flammability, that is, low smoke concentration and high critical oxygen index.
  • the surface fibers often fall off, the sheet is not easily handled, and the flame retardant plastic body is inferior in flame retardancy.
  • Increasing the amount of binder to improve surface fiber shedding and sheet handling results in further inferior flame retardancy of the fiber reinforced plastic body.
  • the fiber-reinforced plastic molding composite material of the present invention contains a thermoplastic super engineering plastic fiber having high heat resistance and high flame retardancy as a matrix resin component, so that the productivity of the fiber-reinforced plastic molding composite material itself is high. Excellent handling in processing.
  • the composite material for molding fiber reinforced plastics which is a nonwoven fabric structure containing thermoplastic polyetherimide fibers with excellent heat resistance and flame retardancy as matrix resin components and inorganic fibers as reinforcing fiber components, is a surface layer. Since the fiber components of the parts are mainly bonded and fixed with a small amount of binder, the handleability in the processing process is also excellent.
  • the fiber-reinforced plastic molding composite material of the present invention can be molded into a fiber-reinforced resin molded article having high strength, high heat resistance and excellent flame retardancy, a lightweight and high-strength composite material is required. It is useful as sports equipment, leisure equipment, aircraft materials, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
PCT/JP2013/055280 2012-02-29 2013-02-28 繊維強化プラスチック成形用複合材及び繊維強化プラスチック成形体 WO2013129540A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014502347A JP5949895B2 (ja) 2012-02-29 2013-02-28 繊維強化プラスチック成形用複合材及び繊維強化プラスチック成形体

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2012044141 2012-02-29
JP2012-044141 2012-02-29
JP2012093479 2012-04-17
JP2012-093479 2012-04-17
JP2012155590 2012-07-11
JP2012-155590 2012-07-11
JP2012-280652 2012-12-25
JP2012280652 2012-12-25

Publications (1)

Publication Number Publication Date
WO2013129540A1 true WO2013129540A1 (ja) 2013-09-06

Family

ID=49082733

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2013/055281 WO2013129541A1 (ja) 2012-02-29 2013-02-28 繊維強化プラスチック成形体用シート及びその成形体
PCT/JP2013/055280 WO2013129540A1 (ja) 2012-02-29 2013-02-28 繊維強化プラスチック成形用複合材及び繊維強化プラスチック成形体

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/055281 WO2013129541A1 (ja) 2012-02-29 2013-02-28 繊維強化プラスチック成形体用シート及びその成形体

Country Status (3)

Country Link
JP (5) JP5949896B2 (ru)
TW (2) TW201343407A (ru)
WO (2) WO2013129541A1 (ru)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014021084A1 (ja) * 2012-07-30 2014-02-06 株式会社クラレ 耐熱性樹脂複合体およびその製造方法、ならびに耐熱性樹脂複合体用不織布
JP2014062143A (ja) * 2012-09-19 2014-04-10 Teijin Ltd 繊維強化プラスチック
JP2016020421A (ja) * 2014-07-14 2016-02-04 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
JP2016079401A (ja) * 2014-10-17 2016-05-16 王子ホールディングス株式会社 繊維強化プラスチック成形体及び繊維強化プラスチック成形体用基材
WO2016121136A1 (ja) * 2015-01-29 2016-08-04 王子ホールディングス株式会社 繊維強化プラスチック成形体用シート
JP2016150981A (ja) * 2015-02-18 2016-08-22 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
CN106003937A (zh) * 2016-05-04 2016-10-12 江苏宝光新型材料科技有限公司 板材生产设备及方法
WO2018117188A1 (ja) * 2016-12-22 2018-06-28 東レ株式会社 構造体
CN109996914A (zh) * 2016-11-18 2019-07-09 株式会社可乐丽 吸声绝热材料
WO2022211116A1 (ja) 2021-03-31 2022-10-06 Ｋｂセーレン株式会社 ポリフェニレンスルフィドモノフィラメントとその製造方法及び繊維パッケージ

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201343407A (zh) * 2012-02-29 2013-11-01 Oji Holdings Corp 纖維強化塑膠成形體用片材及其成形體
WO2014203734A1 (ja) * 2013-06-21 2014-12-24 三菱電機株式会社 繊維強化プラスチック、エレベータ用整風カバーおよび繊維強化プラスチックの製造方法
JP6142737B2 (ja) * 2013-08-27 2017-06-07 王子ホールディングス株式会社 熱可塑性プリプレグ及び熱可塑性プリプレグの製造方法
JP6131779B2 (ja) * 2013-08-27 2017-05-24 王子ホールディングス株式会社 熱可塑性プリプレグ及び熱可塑性プリプレグの製造方法
JP6163970B2 (ja) * 2013-08-27 2017-07-19 王子ホールディングス株式会社 加飾成形品及び加飾成形品の製造方法
JP6369287B2 (ja) * 2013-10-28 2018-08-08 王子ホールディングス株式会社 繊維強化プラスチック成形体用シート
JP6235308B2 (ja) * 2013-11-14 2017-11-22 株式会社クラレ 繊維強化樹脂複合体用強化繊維基材、及びその成形体
JP6664869B2 (ja) * 2014-05-19 2020-03-13 王子ホールディングス株式会社 多層成形品の製造方法
JP6493147B2 (ja) * 2014-10-20 2019-04-03 王子ホールディングス株式会社 不織布、不織布の製造方法および繊維強化プラスチック成形体
JP6413851B2 (ja) * 2015-03-06 2018-10-31 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
JP6547982B2 (ja) * 2015-03-06 2019-07-24 国立大学法人 東京大学 チョップドテープ繊維強化熱可塑性樹脂シート材及びその製造方法
JP6413945B2 (ja) * 2015-06-16 2018-10-31 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材、繊維強化プラスチック成形体用基材の製造方法及び繊維強化プラスチック成形体
JP6788340B2 (ja) * 2015-11-27 2020-11-25 株式会社ユウホウ プリプレグシート
JP6511674B2 (ja) * 2016-02-01 2019-05-15 株式会社日本製鋼所 プリプレグ製造方法
CN116791276A (zh) * 2016-06-10 2023-09-22 乐金华奥斯株式会社 模制体及制造该模制体的方法
WO2017213481A1 (ko) * 2016-06-10 2017-12-14 (주)엘지하우시스 성형체 및 그의 제조방법
US11001035B2 (en) 2016-06-10 2021-05-11 Lg Hausys, Ltd. Sandwich panel and a manufacturing method thereof
WO2017213477A1 (ko) * 2016-06-10 2017-12-14 (주)엘지하우시스 성형체 및 그의 제조방법
KR102243568B1 (ko) * 2016-06-10 2021-04-23 (주)엘지하우시스 성형체 및 그의 제조방법
US11198273B2 (en) 2016-06-10 2021-12-14 Lg Hausys, Ltd. Sandwich panel and a manufacturing method thereof
WO2018021336A1 (ja) * 2016-07-28 2018-02-01 住友ベークライト株式会社 複合成形体、複合成形体用中間体、複合成形体の製造方法および輸送機器用内装材
JP6906937B2 (ja) * 2016-12-12 2021-07-21 株式会社ユウホウ プリプレグシート
JP2018145222A (ja) * 2017-03-01 2018-09-20 住友ベークライト株式会社 強化繊維複合材および強化繊維複合材の製造方法
EP3385069A1 (de) * 2017-04-03 2018-10-10 Quadrant Plastic Composites AG Verfahren zur herstellung eines flächigen verbundbauteils und damit hergestelltes verbundbauteil
JP6394732B2 (ja) * 2017-05-09 2018-09-26 王子ホールディングス株式会社 熱可塑性プリプレグ及び熱可塑性プリプレグの製造方法
JP7368929B2 (ja) * 2017-08-08 2023-10-25 株式会社日本製鋼所 繊維強化樹指中間材の製造方法
DE102018121012A1 (de) * 2018-08-28 2020-03-05 Alzchem Trostberg Gmbh Verfahren zur Herstellung eines Druckgasbehälters
JP6652171B2 (ja) * 2018-09-27 2020-02-19 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
JP6691988B2 (ja) * 2019-03-18 2020-05-13 株式会社日本製鋼所 プリプレグ製造方法
JP7275962B2 (ja) * 2019-07-25 2023-05-18 三菱瓦斯化学株式会社 長尺平板状材料
JP2023029174A (ja) * 2021-08-20 2023-03-03 イビデン株式会社 熱伝達抑制シート及びその製造方法、並びに組電池
JP2023092373A (ja) * 2021-12-21 2023-07-03 イビデン株式会社 熱伝達抑制シート及び組電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03275763A (ja) * 1990-03-26 1991-12-06 Dainippon Ink & Chem Inc 複合成形材料及びその製法
WO2003091015A1 (fr) * 2002-04-23 2003-11-06 Toray Industries, Inc. Pre-impregne, procede de fabrication et article moule
JP2007269308A (ja) * 2006-03-07 2007-10-18 Toray Ind Inc 航空機用内装材
JP2008231290A (ja) * 2007-03-22 2008-10-02 Toray Ind Inc 移動体内装材
JP4708330B2 (ja) * 2003-04-25 2011-06-22 フレンツェリート−ヴェルケ ゲーエムベーハー ウントゥ コー．カーゲー 不織マット、該不織マットの製造方法、及びファイバ複合材料

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02251651A (ja) * 1989-03-20 1990-10-09 Nitto Boseki Co Ltd Ｆｒｐ用繊維質シート状物及びその製造方法
JPH02255735A (ja) * 1989-03-29 1990-10-16 Asahi Chem Ind Co Ltd シート状強化繊維複合体
JP2705202B2 (ja) * 1989-03-31 1998-01-28 日東紡績株式会社 アミン系化合物で処理された織物およびその製造方法
JPH11100767A (ja) * 1997-09-29 1999-04-13 Shin Kobe Electric Mach Co Ltd 積層板用基材及びその製造法ならびにプリプレグ及び積層板
JP2001146637A (ja) * 1999-11-17 2001-05-29 Unitika Ltd バインダー用ポリイミド繊維及びその製造方法
JP4324649B2 (ja) * 2001-11-28 2009-09-02 福井県 繊維強化熱可塑性樹脂シート及びそれを用いた構造材並びに繊維強化熱可塑性樹脂シートの製造方法
JP4613298B2 (ja) * 2004-12-01 2011-01-12 東邦テナックス株式会社 複合シートとそれを用いた平滑な表面を有する複合材料
JP2008307818A (ja) * 2007-06-15 2008-12-25 Kurabo Ind Ltd 繊維強化熱可塑性プラスチック用多軸基材および成形体
JP2010037358A (ja) * 2008-07-31 2010-02-18 Toray Ind Inc 繊維強化成形基材の製造方法
JP5499548B2 (ja) * 2009-07-17 2014-05-21 三菱樹脂株式会社 炭素繊維不織布、炭素繊維強化樹脂シートおよび炭素繊維強化樹脂成形体
JP5571943B2 (ja) * 2009-12-18 2014-08-13 株式会社クラレ 耐熱性難燃紙
JP2011157637A (ja) * 2010-01-29 2011-08-18 Toray Ind Inc 抄紙基材および繊維強化成形基材の製造方法
JP5819939B2 (ja) * 2010-04-22 2015-11-24 スリーエム イノベイティブ プロパティズ カンパニー 化学的に活性な微粒子を含有する不織布ナノ繊維ウェブ並びにそれを作製及び使用する方法
JP5737870B2 (ja) * 2010-06-29 2015-06-17 三菱重工業株式会社 繊維強化複合材用の不織布素材
KR20130091734A (ko) * 2010-07-07 2013-08-19 쓰리엠 이노베이티브 프로퍼티즈 컴파니 패턴화된 에어 레이드 부직포 일렉트릿 섬유질 웨브 및 그 제조 및 사용 방법
CN103025934B (zh) * 2010-07-29 2014-09-10 株式会社可乐丽 非晶性热熔接性纤维、纤维构造体及耐热性成形体
CN103210132B (zh) * 2010-09-14 2016-06-29 沙特基础全球技术有限公司 增强的热塑性制品和用于制造所述制品的复合材料
TW201343407A (zh) * 2012-02-29 2013-11-01 Oji Holdings Corp 纖維強化塑膠成形體用片材及其成形體

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03275763A (ja) * 1990-03-26 1991-12-06 Dainippon Ink & Chem Inc 複合成形材料及びその製法
WO2003091015A1 (fr) * 2002-04-23 2003-11-06 Toray Industries, Inc. Pre-impregne, procede de fabrication et article moule
JP4708330B2 (ja) * 2003-04-25 2011-06-22 フレンツェリート−ヴェルケ ゲーエムベーハー ウントゥ コー．カーゲー 不織マット、該不織マットの製造方法、及びファイバ複合材料
JP2007269308A (ja) * 2006-03-07 2007-10-18 Toray Ind Inc 航空機用内装材
JP2008231290A (ja) * 2007-03-22 2008-10-02 Toray Ind Inc 移動体内装材

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014021084A1 (ja) * 2012-07-30 2016-07-21 株式会社クラレ 耐熱性樹脂複合体およびその製造方法、ならびに耐熱性樹脂複合体用不織布
WO2014021084A1 (ja) * 2012-07-30 2014-02-06 株式会社クラレ 耐熱性樹脂複合体およびその製造方法、ならびに耐熱性樹脂複合体用不織布
JP2018111914A (ja) * 2012-07-30 2018-07-19 株式会社クラレ 耐熱性樹脂複合体
JP2014062143A (ja) * 2012-09-19 2014-04-10 Teijin Ltd 繊維強化プラスチック
JP2016020421A (ja) * 2014-07-14 2016-02-04 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
JP2019130910A (ja) * 2014-10-17 2019-08-08 王子ホールディングス株式会社 繊維強化プラスチック成形体及び繊維強化プラスチック成形体用基材
JP2016079401A (ja) * 2014-10-17 2016-05-16 王子ホールディングス株式会社 繊維強化プラスチック成形体及び繊維強化プラスチック成形体用基材
WO2016121136A1 (ja) * 2015-01-29 2016-08-04 王子ホールディングス株式会社 繊維強化プラスチック成形体用シート
JP2016150981A (ja) * 2015-02-18 2016-08-22 王子ホールディングス株式会社 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
CN106003937A (zh) * 2016-05-04 2016-10-12 江苏宝光新型材料科技有限公司 板材生产设备及方法
JPWO2018092888A1 (ja) * 2016-11-18 2019-10-17 株式会社クラレ 吸音断熱材
CN109996914A (zh) * 2016-11-18 2019-07-09 株式会社可乐丽 吸声绝热材料
EP3540109A4 (en) * 2016-11-18 2019-11-06 Kuraray Co., Ltd. SOUND AND HEAT INSULATION
WO2018117188A1 (ja) * 2016-12-22 2018-06-28 東レ株式会社 構造体
JPWO2018117188A1 (ja) * 2016-12-22 2019-10-31 東レ株式会社 構造体
US11312825B2 (en) 2016-12-22 2022-04-26 Toray Industries, Inc. Structure
WO2022211116A1 (ja) 2021-03-31 2022-10-06 Ｋｂセーレン株式会社 ポリフェニレンスルフィドモノフィラメントとその製造方法及び繊維パッケージ

Also Published As

Publication number Publication date
JP6432615B2 (ja) 2018-12-05
TW201343733A (zh) 2013-11-01
JP2015110791A (ja) 2015-06-18
WO2013129541A1 (ja) 2013-09-06
JP2017125192A (ja) 2017-07-20
TW201343407A (zh) 2013-11-01
JPWO2013129540A1 (ja) 2015-07-30
JP5949896B2 (ja) 2016-07-13
JPWO2013129541A1 (ja) 2015-07-30
JP2015071794A (ja) 2015-04-16
JP5949895B2 (ja) 2016-07-13
JP6090342B2 (ja) 2017-03-08
JP6020612B2 (ja) 2016-11-02

Similar Documents

Publication Publication Date Title
JP6432615B2 (ja) 繊維強化プラスチック成形用複合材及び繊維強化プラスチック成形体
US10889070B2 (en) Composite material including unidirectional continuous fibers and thermoplastic resin
EP1338406B1 (en) Moulding materials and method of forming such materials
JP6087545B2 (ja) 繊維強化プラスチック成形用基材
JP6142737B2 (ja) 熱可塑性プリプレグ及び熱可塑性プリプレグの製造方法
JP2016210080A (ja) 成形体およびその製造方法
JP6225558B2 (ja) 繊維強化プラスチック成形体用シート及び繊維強化プラスチック成形体
JP6311507B2 (ja) 繊維強化プラスチック成形体用基材及び繊維強化プラスチック成形体
JP6225556B2 (ja) 繊維強化プラスチック成形体用シート及び繊維強化プラスチック成形体
JP6131779B2 (ja) 熱可塑性プリプレグ及び熱可塑性プリプレグの製造方法
JP6326739B2 (ja) ハニカムサンドイッチ構造体及びハニカムサンドイッチ構造体の製造方法
JP6681041B2 (ja) 強化繊維複合材料
JP6213347B2 (ja) 繊維強化プラスチック成形体用シート
JP2015044316A (ja) ハニカムサンドイッチ構造体及びハニカムサンドイッチ構造体の製造方法
JP6394732B2 (ja) 熱可塑性プリプレグ及び熱可塑性プリプレグの製造方法
TWI851852B (zh) 預浸漬物、預形體、纖維強化複合材料、及彼等之製造方法
JP6528824B2 (ja) 繊維強化プラスチック成形体用シート及び繊維強化プラスチック成形体
JP6225557B2 (ja) 繊維強化プラスチック成形体用シート及び繊維強化プラスチック成形体
JP2005213704A (ja) Ｆｒｐ用湿式アラミド繊維不織布
JP2017113956A (ja) 繊維強化熱可塑性樹脂の成形方法、及び成形品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13755259

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014502347

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13755259

Country of ref document: EP

Kind code of ref document: A1