WO2014204053A1 - 폴리프로필렌계 수지 및 탄소 장섬유를 포함하는 수송 수단용 복합 재료 - Google Patents

폴리프로필렌계 수지 및 탄소 장섬유를 포함하는 수송 수단용 복합 재료 Download PDF

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WO2014204053A1
WO2014204053A1 PCT/KR2013/008249 KR2013008249W WO2014204053A1 WO 2014204053 A1 WO2014204053 A1 WO 2014204053A1 KR 2013008249 W KR2013008249 W KR 2013008249W WO 2014204053 A1 WO2014204053 A1 WO 2014204053A1
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ionomer
fiber
composite material
acid
propylene
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English (en)
French (fr)
Korean (ko)
Inventor
김동현
임대영
김기영
박노형
안효진
김정수
이은수
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Korea Institute of Industrial Technology KITECH
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Korea Institute of Industrial Technology KITECH
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Priority to JP2016519425A priority Critical patent/JP6116759B2/ja
Priority to US14/897,254 priority patent/US9518177B2/en
Publication of WO2014204053A1 publication Critical patent/WO2014204053A1/ko
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a composite material composition which can be applied to various transportation means as it has improved physical properties including polypropylene-based resin and carbon long fibers.
  • the composite material refers to a material having an effective function by combining two or more kinds of materials having different components or shapes so as to have an interface that is macroscopically separated from each other as a reinforcement and a matrix.
  • the composite material can secure a variety of physical properties by the efficient combination of each material, has been applied to a variety of applications ranging from aviation, space, automobiles, sports, industrial machinery, medical equipment, military supplies, construction and civil engineering materials.
  • the fiber-reinforced composite material is manufactured using fibers such as glass fiber, carbon fiber, aramid fiber, and silicon carbide fiber as reinforcing material, and has been spotlighted among composite materials due to its advantages of high strength, light weight, and excellent formability. Is the material being received.
  • the fiber-reinforced composite material is used in various applications by changing the material of the reinforcing material, the length of the fiber, and the like.
  • Korean Patent Laid-Open Publication No. 2006-7004105 mixes a polypropylene copolymer and glass fiber to car seat, head restraint, knee protector, glove box door, instrument panel. , Bumper Persia, Bumper Beam, etc., and disclosed in the automotive article, Japanese Patent Laid-Open No. 2008-202013 is that it can be applied to exterior panels of automobiles using glass long fibers in polycarbonate / styrene resin It is mentioned.
  • Japanese Patent Laid-Open No. 2011-137077 discloses a fiber reinforced composite material comprising organic long fibers such as polyester or polyamide fibers in a polypropylene resin for use in instrument panels of automobiles.
  • Patent Publication No. 2006-0075902 discloses a fiber-reinforced composite material in which glass fiber, carbon fiber, graphite fiber, metal fiber, and the like are added to a low-brittle propylene resin.
  • Carbon fiber reinforced composite material using carbon fiber as a reinforcing material among the fiber reinforced composite materials has lightness and physical properties such as stiffness, impact resistance, heat resistance, chemical stability, dimensional stability, abrasion resistance, and flexibility than other reinforcing materials. Such physical properties are further improved by using long fibers having a long length of carbon fibers.
  • the fiber reinforced composite material is manufactured by mixing and melting a thermoplastic resin and a fiber reinforcing material used as a matrix, followed by a molding process such as extrusion.
  • a molding process such as extrusion.
  • fibers penetrate between the microstructures of the resin and are uniformly dispersed as a reinforcing material in the matrix.
  • the incompatibility between the microstructures of the resins is not easy due to low compatibility with the resin. There is a problem of deterioration of physical properties.
  • compatibilizer a modified polyolefin (PO) (PP-g-MA) prepared by grafting a polypropylene resin and maleic anhydride (MAH) at 9: 1 is most widely used.
  • PO polyolefin
  • MAH maleic anhydride
  • the type or content of the resin used as a matrix varies depending on the application, and at this time, the selection of glass fiber, carbon fiber, aramid fiber, metal fiber, etc. as a reinforcing material is different.
  • the interfacial properties between these resins and the reinforcing material according to the type of the matrix resin and the reinforcing material it is difficult to secure sufficient physical properties by simply applying PP-g-MA known as a compatibilizer.
  • these interfacial properties are greatly influenced by the parameters of the molding process.
  • the present inventors conducted various studies to select a polypropylene resin as a matrix resin and a carbon long fiber as a reinforcing material, and to select a compatibilizer capable of improving the interfacial properties therebetween.
  • a compatibilizer capable of improving the interfacial properties therebetween.
  • the compatibilizer provides a fiber-reinforced composite material composition for transport means, characterized in that it comprises one selected from the group consisting of ionomers, propylene-polar monomer copolymers, modified water additive polymers, and combinations thereof.
  • the fiber-reinforced composite material proposed by the present invention has improved rigidity, impact resistance, and heat resistance compared to conventional glass fibers or short carbon fibers due to the use of long carbon fibers, and various fields requiring composite materials as well as vehicles, including automobiles. Applicable to
  • Example 1 is a scanning electron microscope image showing the fracture surface of the composite material prepared in Example 1
  • the present invention proposes a suitable compatibilizer to increase the miscibility of polypropylene resin and carbon long fiber, and due to the use of the compatibilizer, the polypropylene resin and carbon long fiber are properly blended in the molding process, and these The interfacial properties of the liver are improved to ensure sufficient physical properties due to reinforcement of carbon long fibers.
  • the fiber-reinforced composite material according to the present invention is 40 to 90% by weight of polypropylene resin, 5 to 60% by weight of carbon long fiber having a fiber diameter of 1 to 50 ⁇ m, and a weight average fiber length of 20 to 150 mm, 0.3 to 15% by weight of compatibilizer.
  • the polypropylene-based resin is not particularly limited in the present invention, and polypropylene homopolymer or copolymer is possible, and includes all isotactic, syndiotactic, and atactic structures.
  • the polypropylene copolymer means a copolymer in which a propylene monomer and an alpha olefin monomer are copolymerized.
  • alpha olefins are hydrocarbons having 3 to 12 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, One species selected from the group consisting of 1-undecene and 1-dodecene, and combinations thereof is possible.
  • the polypropylene copolymer may be a propylene-ethylene copolymer, a propylene-ethylene-alpha olefin copolymer, or the like.
  • the polypropylene copolymer may be in the form of a random copolymer, a block copolymer or a graft copolymer, and may be appropriately selected and used according to the purpose of use.
  • the polypropylene resin is used at 40 to 90% by weight within 100% by weight of the total composite material composition. If the content of the polypropylene resin is less than the above range can not serve as a matrix of the composite material, on the contrary, if the content exceeds the above range, the content of carbon long fibers or compatibilizer is reduced relatively to obtain the desired physical properties. Use suitably within the range.
  • the carbon long fibers used as reinforcing fibers influence the expected effects as reinforcing fibers depending on the diameter, weight average fiber length, and their use content.
  • carbon long fibers should penetrate into the microstructure of molten polypropylene resin and be uniformly dispersed.
  • the carbon long fibers should have an appropriate range of diameter and weight average fiber length to exhibit excellent mechanical and thermal properties.
  • the carbon long fibers of the present invention are those having a fiber diameter of 1 to 50 ⁇ m and a weight average fiber length of 20 to 150 mm at 5 to 60 weight percent within 100 weight percent of the total composition.
  • the diameter of the carbon long fiber is less than the above range, too thin to be used as a reinforcing fiber may not be sufficient to reinforce the physical properties, and the fiber may be entangled. Since it cannot fully penetrate into the fine structure of the polypropylene resin thus obtained, and sufficient desired physical properties cannot be secured, it is suitably used within the above range.
  • the weight average fiber length of the carbon long fibers is less than the above range, it is not possible to sufficiently secure the physical properties (ie, rigidity, impact resistance, heat resistance) to be obtained by using the long fibers as short fibers rather than long fibers, On the contrary, when the fiber length exceeds the above range, entanglement in the molding process occurs due to excessively long length, or the interfacial properties in the microstructure of the polypropylene resin are deteriorated, so that the desired physical properties cannot be sufficiently secured. do.
  • the carbon long fiber proposed in the present invention is used in the content of the above range to ensure sufficient physical properties as a reinforcing material. If the content is less than the above range, the physical properties due to the use of the carbon long fiber can not be sufficiently secured, on the contrary, if the content exceeds the above range, it is difficult to manufacture and the carbon long fiber is agglomerated and dispersed uniformly in the polypropylene resin matrix in the molding process. This may also cause a decrease in physical properties of the composite material, so it is suitably used within the above range.
  • a specific compatibilizer is used in a predetermined range for the miscibility of the polypropylene resin and carbon long fiber as described above.
  • a compatibilizer one type selected from the group consisting of ionomers, propylene-polar monomer copolymers, modified water additive polymers, and combinations thereof is used in an amount of 0.3 to 15% by weight within 100% by weight of the total composition.
  • the compatibilizer may improve the interfacial properties between the propylene-based resin and the long carbon fiber through a chemical bond or a physical bond.
  • the content of such compatibilizers is important not only in their kind but also in content control in the overall composition. That is, only when the compatibilizer is properly used, the miscibility between the polypropylene resin and the long carbon fiber may be improved in the molding process. If the content is less than the above range, the carbon long fibers may not be uniformly dispersed in the polypropylene resin matrix, and thus the physical properties may not be improved due to the use of the long carbon fibers. Since the burden of manufacturing cost rises and this is also not preferable, it uses suitably within the said range.
  • the ionomer is a polymer in which metal ions are bonded to the main chain or the side chain, and the type of the ionomer is not particularly limited.
  • ionomer resins may be used independently, and may mix and use 2 or more types as needed.
  • ionomer resins propylene-methacrylic acid copolymer ionomers and propylene-acrylic acid copolymer ionomers are preferable, and anions of these ionomers include halide ions, particularly anions such as Cl ⁇ , Br ⁇ , I ⁇ , and the like.
  • the metal ions include alkali metal ions such as Li + , Na + , K + , alkaline rare earth metal ions such as Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , and Mn. Transition metal ions such as 2+ , Ni 2+ , Co 2+ , Co 3+ , Fe 3+ and Cr 3+ are possible.
  • the propylene-polar monomer copolymer is a copolymer obtained by copolymerizing a propylene monomer with a monomer containing a polar group such as an acid anhydride group, an epoxy group, a carboxyl group, and a carboxylic acid ester.
  • the copolymerizable monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and anhydrides thereof; Esters of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconate, and dimethyl tetrahydrophthalic anhydride; Glycidyl esters of unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, and p-styryl carboxylic acid glycidyl; Monoglycidyl esters or polyglycidyl esters of unsaturated polycarboxylic acids such as maleic acid, itaconic acid, citraconic acid and butene tricarboxylic acid; Unsaturated glycidyl ethers such as
  • the modified water-added polymer component is not particularly limited, but for example, a water-added styrene-butadiene rubber and a styrene-ethylene butylene-polyethylene-block copolymer modified with an acid anhydride, an epoxy group, a carboxyl group, and a carboxylic acid ester.
  • styrene-ethylene-propylene-styrene-block copolymers are preferred.
  • the ionomer and propylene-polar monomer copolymers of the above-mentioned compatibilizers are capable of chemically bonding to polypropylene-based resins due to functional groups as reactive compatibilizers, thereby further improving the interfacial properties between the resin and the long carbon fiber due to the compatibilizer.
  • the modified water-added polymer it is a non-reactive compatibilizer, but it may also improve the interfacial properties between the resin and the carbon long fiber due to physical mixing with the polypropylene resin.
  • the fiber-reinforced composite material according to the present invention may further include an additive used in the molding process of a conventional thermoplastic resin in order to secure desired physical properties or to facilitate molding according to the purpose.
  • an additive used in the molding process of a conventional thermoplastic resin for example, antioxidants, process stabilizers, light stabilizers, elastomers, flame retardants, inorganic fillers, carbon black, nucleating agents, UV absorbers, vibration dampers, antibacterial agents, insect repellents, deodorants, colorants, softeners, lubricants, pigments, dyes, heat stabilizers , A release agent, an antistatic agent, a plasticizer, a lubricant, a blowing agent, a defoamer, a preservative and a coupling agent, and a mixture thereof.
  • the additive may be added before the molding process of the composite material, for example, before kneading or during kneading, or after kneading separately, and may be added by an impregnation process if necessary.
  • the additive is used in 5% by weight or less in the total composition, it is possible to control the selection and content of additives required by those skilled in the art.
  • the preparation of the fiber-reinforced composite material as described above is not particularly limited in the present invention, and can be produced by various methods known in the art. For example, extrusion, injection molding, pultrusion molding, compression molding, Resin Transfer Molding (RTM) molding, Hand Lay-up molding, Various methods are available, such as autoclave molding and filament winding molding.
  • the polypropylene-based resin may be prepared by heating the polypropylene resin to a melting temperature or higher, followed by adding carbon long fibers thereto, kneading for a predetermined time and then drying. At this time, the compatibilizer is added to the polypropylene resin, the carbon long fiber is purchased in the roving (roving) state and put into the extruder.
  • the kneading conditions other than the above are not specifically limited, For example, what is necessary is just to set suitably so that melting and kneading of a polypropylene resin may be performed smoothly. It is preferable to make internal temperature, such as the cylinder of a kneading
  • the fiber-reinforced composite material obtained by kneading is subjected to a further molding process for each purpose.
  • the molding step is not particularly limited in the present invention, and a known method can be used.
  • the molding step may be performed using a thermocompressor.
  • the fiber-reinforced composite material thus produced has physical properties of 50 MPa or more in breaking strength, 6 GPa or more in tensile modulus, 180 MPa or more in flexural strength, 30 KJ / m 2 or more in impact resistance, and 400 ° C or more in pyrolysis temperature. Can be applied to
  • vehicle materials such as automobiles, aerospace materials, defense component materials, electrical and electronic materials, civil building materials, biomedical materials and various sports materials, and preferably used in automobiles. have.
  • the carbon long fiber reinforced composite material according to the present invention can be applied to a vehicle.
  • the vehicle may be a car, a train, an airplane, a helicopter, a truck, a motorcycle, a bicycle, a boat, a yacht, or the like.
  • the carbon long-fiber composite material is light, so that it can be applied to automobiles, especially automobile exterior materials (eg, bonnets), compared to iron or aluminum, which is currently used as a component, to achieve light weight, and thus has high rigidity, impact resistance, and heat resistance. Some or all of the materials used in the process can be replaced, thereby preoccupying the market.
  • Fiber reinforced composite materials were prepared using the compositions of Tables 1 to 3 below. Specifically, after adding a polypropylene resin (manufacturer: PolyMirae, MI: 12g / 10 min, 230 ° C) and a compatibilizer to the extruder, and kneading sufficiently using a one-stage extruder, carbon long fibers or carbon in the two-stage extruder Short fibers were added to prepare a carbon fiber reinforced polypropylene composite material. At this time, the processing temperature was 250 °C, the screw speed was 100 rpm.
  • a polypropylene resin manufactured by adding a polypropylene resin (manufacturer: PolyMirae, MI: 12g / 10 min, 230 ° C) and a compatibilizer
  • carbon long fibers or carbon in the two-stage extruder Short fibers were added to prepare a carbon fiber reinforced polypropylene composite material.
  • the processing temperature was 250 °C
  • the screw speed was 100 rpm.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Thermoplastic resin PP 89 89 89 89 82 75 Carbon fiber Long carbon fiber (length: 20 mm, diameter 50) 10 10 10 - - - Long carbon fiber (length: 30 mm, diameter 50) - - - 10.7 - - Long carbon fiber (length: 50 mm, diameter 50) - - - - 10 - Long carbon fiber (length: 100 mm, diameter 50) - - - - - 10
  • Compatibilizer Ionomer (1) One - - - - - - Propylene unsaturated copolymers (2006.01) - One - 0.3 8.0 15.0 Modified Water Additive Polymer (3) - - One - - - - -
  • SEBS styrene-ethylene-butylene-styrene-block copolymer
  • SEBS styrene-ethylene-butylene-styrene-block copolymer
  • 1 and 2 are scanning electron microscope images showing the fracture surface of the composite material specimen made of polypropylene and carbon long fiber prepared in Example 1 and Comparative Example 2, respectively.
  • the composite material produced by the present invention is mixed without an empty space at the interface between the polypropylene resin, which is a matrix, and the carbon long fibers. It can be seen that due to the propylene methacrylic acid copolymer as a compatibilizer, chemical bonding between the polypropylene resin and the carbon long fiber occurs, resulting in a composite material having a structure in which carbon long fiber penetrates well between the resins. .
  • the evaluation items for applicability as automobile bonnets include break strength and tensile modulus to evaluate stiffness of molded products for evaluating good moldability, yield elongation to evaluate impact absorption rate, flexural strength test and impact strength test, and thermal decomposition temperature evaluation.
  • the specific evaluation method is as follows.
  • Break strength, tensile modulus, yield elongation Break strength and tensile modulus are one of the typical measurement methods for evaluating stiffness, and yield elongation is one of the methods for evaluating impact absorption in elastic and plastic regions.
  • the test method was measured by ASTM D-638 method, the specimen size was ASTM D-638 No. 1 and the crosshead speed was tested at 5mm / min.
  • Flexural Strength This is a representative measurement method for evaluating rigidity. The higher the flexural strength, the better the mechanical strength and the smaller the final molded product's thickness or the higher the load. Flexural strength was measured by ASTM D-790 method, the specimen size is 12.7 ⁇ 127 ⁇ 6.4mm, the crosshead speed is 10mm / min.
  • Impact strength is a representative test method for evaluating the ability to absorb shock, measured by ASTM D-256 method and conducted at room temperature (23 ° C). Specimen size is 63.5 ⁇ 12.7 ⁇ 3mm.
  • the pyrolysis temperature was measured by TGA (thermogravimetric analysis) by the ASTM E-474 method. The temperature when the weight change of 10% was shown while raising the temperature of TGA uniformly at the speed of 120 degree-C / hr.
  • the longer the length of the applied carbon fiber can be confirmed through the Examples and Comparative Examples that the excellent mechanical and thermal properties of the composite material consisting of polypropylene and carbon long fibers.
  • the physical properties of the composite materials of Comparative Examples 1 to 3 were better than those of the composite materials using the short carbon fibers of Comparative Examples 4 to 6, and the carbons of the compatibilizers of Examples 1 to 6 according to the present invention were used. Longer fibers showed better physical properties. However, if a small amount of compatibilizer is used (Comparative Example 8) or if an excessive amount is used (Comparative Example 9), the physical properties are deteriorated, so that the improvement of physical properties can be expected only when the compatibilizer is used in an optimally controlled content.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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PCT/KR2013/008249 2013-06-21 2013-09-12 폴리프로필렌계 수지 및 탄소 장섬유를 포함하는 수송 수단용 복합 재료 Ceased WO2014204053A1 (ko)

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JP2016519425A JP6116759B2 (ja) 2013-06-21 2013-09-12 ポリプロピレン系樹脂及び炭素長繊維を含む輸送手段用複合材料
US14/897,254 US9518177B2 (en) 2013-06-21 2013-09-12 Composite material for means of transport including polypropylene resin and long carbon fiber

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KR10-2013-0071489 2013-06-21
KR1020130071489A KR101415014B1 (ko) 2013-06-21 2013-06-21 폴리프로필렌계 수지 및 탄소 장섬유를 포함하는 수송 수단용 복합 재료

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EP3095818A1 (en) * 2015-05-22 2016-11-23 Borealis AG Polypropylene - carbon fiber composite
CN113150442A (zh) * 2021-04-16 2021-07-23 重庆理工大学 高模量低密度聚丙烯复合材料及其制备方法

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KR101702998B1 (ko) * 2014-10-31 2017-02-08 한국생산기술연구원 장섬유 강화 열가소성 복합재료의 성형 장치 및 이를 이용한 제조방법
EP3545037B1 (en) * 2016-11-23 2020-08-19 Basell Poliolefine Italia S.r.l. Filled polyolefin composition
JP6910041B2 (ja) * 2017-03-02 2021-07-28 株式会社三栄興業 炭素繊維複合材料
EP3619265B1 (en) 2017-05-03 2022-04-20 Equistar Chemicals, LP Carbon fiber reinforced polyolefin compositons and methods
JPWO2019208826A1 (ja) * 2018-04-27 2021-05-20 株式会社ブリヂストン 強化繊維複合樹脂、コンポジットプリプレグおよび積層体
JPWO2019208823A1 (ja) * 2018-04-27 2021-04-30 株式会社ブリヂストン 強化繊維複合樹脂、コンポジットプリプレグおよび積層体
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