WO2016076411A1 - 炭素繊維強化樹脂組成物及びそれから得られる成形品 - Google Patents
炭素繊維強化樹脂組成物及びそれから得られる成形品 Download PDFInfo
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Definitions
- the present invention relates to a carbon fiber reinforced resin composition having excellent properties such as strength and elastic modulus and a molded product obtained therefrom.
- the cause is that the polyolefin resin is nonpolar, so the interfacial adhesion with the carbon fiber is poor, and the carbon fiber cannot exhibit a sufficient reinforcing effect, or the carbon fiber itself is manufactured through a large amount of energy and complicated manufacturing process This is because it is still expensive.
- a method of adding an acid-modified polyolefin resin to the matrix resin for example, Patent Document 1
- a method of adding a polyamide resin in addition to the acid-modified polyolefin resin for example, Patent Document 2
- a method of adding an acid-modified polyolefin resin and an amino group-containing modified polyolefin resin for example, Patent Documents 3 and 4
- Patent Documents 3 and 4 are disclosed.
- the content of expensive carbon fibers in the entire composition is high, or in the case of using a polyamide resin together, it is at a technical level that a large amount must be used for strength development. There is a need to reduce usage. Further, in terms of strength, further improvements are demanded in the field of automobiles and aircraft parts.
- the present invention has been made in view of the above-described problems of the prior art, and a carbon fiber reinforced resin composition having excellent properties such as strength and elastic modulus even when a large amount of carbon fiber is not used or even when the polyamide content is small.
- An object is to provide a product and a molded product obtained therefrom.
- the gist of the present invention is as follows.
- propylene polymers selected from propylene / ethylene block copolymers, propylene homopolymers, and propylene / ethylene random copolymers having an ethylene content of 5% by mass or less (p) 25 to 95% by mass , Acid-modified polyolefin resin (m) 1 to 60% by mass, Ethylene polymer (e) 0 to 40% by mass, and polyamide (n) 0 to 50% by mass [The total of component (p), component (m), component (e) and component (n) is 100% by mass here]
- a carbon fiber reinforced resin composition comprising 100 parts by mass of a polymer alloy (A) containing 1 to 200 parts by mass of a carbon fiber (B).
- W n mass% the content of (n) is W n mass%
- the sum of W p and W m is 50 to 100 mass%
- W n is 0 to 50 mass% (where W p , W m , The total of W e and W n is 100% by mass)
- the ratio of W p to W m (W p / W m ) is 70/30 to 98/2. .
- the acid-modified polyolefin resin (m) contains a maleic acid-modified propylene polymer (m1), and conforms to ASTM D1238 of the maleic acid-modified propylene polymer (m1) at 230 ° C. under a 2.16 kg load.
- the carbon fiber reinforced resin composition according to [5] wherein the measured melt flow rate (MFR) exceeds 150 g / 10 minutes.
- the content of the component (p) in the polymer alloy (A) is W p mass%
- the content of the component (m1) is W m1 mass% (however, the total content of the component (m) is W m mass%).
- W e mass% content of the component (e) if the content of component (n) was W n mass%, the sum of 50 to 98 mass% of W p and W m1, the W n 2 to 50 mass% (where W p, W m, total 100% by weight of W e and W n), is further compliant 230 ° C.
- the adhesion / affinity between the carbon fiber (B) and the polymer alloy (A) made of a polypropylene resin is improved. Therefore, even if a large amount of carbon fiber is not used or the polyamide content is low.
- the physical properties (especially elastic modulus and impact resistance) of the resin composition can be improved.
- the molded product obtained from the carbon fiber reinforced resin composition of the present invention is suitable as a structural composite material for parts such as automobile parts and aircraft parts that require particularly rigidity and durability.
- the carbon fiber reinforced resin composition of the present invention is one or more propylene polymers selected from propylene / ethylene block copolymers, propylene homopolymers, and propylene / ethylene random copolymers having an ethylene content of 5% by mass or less.
- P 25 to 95% by mass, acid-modified polyolefin resin (m) 1 to 60% by mass, ethylene polymer (e) 0 to 40% by mass, and polyamide (n) 0 to 50% by mass [where component ( p), polymer alloy (A) containing 100% by mass of component (m), component (e) and component (n)], and 1 to 200 parts by mass of carbon fiber (B). It is a carbon fiber reinforced resin composition.
- the content of the carbon fiber (B) per 100 parts by mass of the polymer alloy (A) is appropriately determined depending on the use of the carbon fiber reinforced resin composition in the range of 1 to 200 parts by mass (preferably 1 to 150 parts by mass).
- the carbon fiber (B) content is 100 parts by mass of polymer alloy (A).
- the amount is usually 1 to 100 parts by weight, preferably 1 to 90 parts by weight, and more preferably 1 to 80 parts by weight.
- the content of the carbon fiber (B) is 50 to 150 parts by mass, preferably 60 to 140 parts by mass, per 100 parts by mass of the polymer alloy (A).
- the carbon fiber (B) content is general although it depends on the amount of neat resin blended in the subsequent process. Is 50 to 150 parts by mass per 100 parts by mass of the polymer alloy (A).
- the polymer alloy (A) constituting the carbon fiber reinforced resin composition of the present invention preferably has a melt flow rate (MFR) measured at 230 ° C. under a 2.16 kg load in accordance with ASTM D1238, preferably 30 to 500 g / 10. Minutes.
- MFR melt flow rate
- the preferred MFR of the polymer alloy (A) measured at 230 ° C. under a 2.16 kg load is the content of the polyamide (n) contained in the polymer alloy (A) and the content of the ethylene polymer (e) ( It depends on e).
- the preferred MFR is 40 to 200 g / 10 minutes, and the more preferred MFR is 50 to 150 g / 10 minutes.
- the preferred MFR is 80 to 500 g / 10 minutes, and the more preferred MFR is 100 to 350 g / 10 minutes.
- the carbon fiber reinforced resin composition of the present invention is usually obtained by melt-kneading polymer alloy (A) and carbon fiber (B) as described later, but is not limited to this method.
- a preferred embodiment in the component amount or component ratio of the polymer alloy (A) constituting the carbon fiber reinforced resin composition of the present invention satisfies the following two requirements.
- (Requirement 1) W p mass% content of the component in the polymer alloy (A) (p), W m mass% content of the component (m), W e mass% content of the component (e), When the content of the component (n) is W n mass%, the total of W p and W m is 50 to 100 mass%, and W n is 0 to 50 mass% (where W p , W m m, total 100% by weight of W e and W n).
- (Requirement 2) The ratio of W p to W m (W p / W m ) is 70/30 to 98/2.
- the polymer alloy (A) is classified into the following more preferable embodiments.
- W n mass% the sum of W p and W m is 100 mass%
- W e is 0 mass%
- W n is 0 mass% (where W p , W m , W e And the total of W n is 100% by mass) of the polymer alloy (A).
- the total of W p and W m is 50 to 98% by mass, preferably 60 to 98% by mass, more preferably 70 to 95% by mass
- W n is 2 to 50% by mass, preferably It is 2 to 40% by mass, more preferably 5 to 30% by mass (here, the sum of W p , W e , W m and W n is 100% by mass).
- One preferred embodiment uses, as the acid-modified polyolefin resin (m), one or more resins selected from acid-modified propylene polymers and acid-modified ethylene polymers, and more preferably maleic acid-modified propylene polymers ( m1) and one or more resins selected from the maleic acid-modified ethylene polymer (m2), more preferably, the acid-modified polyolefin resin (m) contains a maleic acid-modified propylene polymer (m1), and
- the melt flow rate (MFR m1 ) measured at 230 ° C. under a 2.16 kg load in accordance with ASTM D1238 of the component (m1) exceeds 150 g / 10 minutes.
- the melt flow rate (MFR) measured at 230 ° C. under a 2.16 kg load according to ASTM D1238 of component (p) is MFR p (g / 10 min), and ASTM D1238 of component (m1) is measured.
- MFR p g / 10 min
- ASTM D1238 of component (m1) is measured.
- the melt flow rate (MFR) measured at 230 ° C. and 2.16 kg load is MFR m1 (g / 10 min)
- the following relational expression (1) preferably the following relational expression (1 ′)
- it is a polymer alloy (A) satisfying the following relational expression (1 ′′), particularly preferably the following relational expression (1 ′ ′′).
- the propylene polymer (p) is one or more polymers selected from a propylene / ethylene block copolymer, a propylene homopolymer, and a propylene / ethylene random copolymer having an ethylene content of 5% by mass or less. .
- a propylene homopolymer or a propylene / ethylene random copolymer is obtained by copolymerizing propylene alone or propylene and ethylene.
- a propylene homopolymer is preferably used as the propylene polymer (p) in the case where importance is placed on the rigidity among the mechanical properties of the molded product obtained from the carbon fiber reinforced resin composition, while the impact resistance is high.
- propylene / ethylene random copolymer is preferably employed as the propylene polymer (p).
- a propylene homopolymer and a propylene / ethylene random copolymer may be used in combination. Specific conditions such as the charging ratio at that time are arbitrarily determined based on the balance between the target rigidity and impact resistance.
- the content ratio of the structural unit derived from ethylene with respect to all the structural units of the random copolymer exceeds 0, and is 5% by mass or less, preferably 1 to 5% by mass, more preferably 1 to 4% by mass.
- this content ratio exceeds 5 mass%, the resin composition becomes too soft, and the strength of the molded product may be lowered.
- This content ratio can be measured by infrared spectroscopy (IR) or NMR.
- the propylene / ethylene block copolymer is preferably composed of a propylene homopolymer portion and a propylene / ethylene random copolymer portion.
- the content of the propylene / ethylene random copolymer part is usually 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 8 to 18% by mass, and the content of the propylene homopolymer part is Usually, it is 70 to 95% by mass, preferably 75 to 95% by mass, more preferably 82 to 92% by mass. These contents are based on a total amount of 100% by mass of the propylene / ethylene random copolymer portion and the propylene homopolymer portion.
- the skeleton content due to ethylene is preferably 1 to 10% by mass, more preferably 3 to 8% by mass.
- the propylene / ethylene block copolymer can be used alone or in combination of two or more.
- the MFR (230 ° C., load 2.16 kg) of the propylene homopolymer portion is usually 2 to 1000 g / 10 minutes, preferably 50 to 500 g / 10 minutes, more preferably 150 to 350 g / 10 min.
- the intrinsic viscosity [ ⁇ ] of propylene / ethylene random copolymer portion measured in decahydronaphthalene at 135 ° C. is usually 4 to 10 dl / g, preferably 5 to 9 dl / g.
- the content of ethylene-derived structural units in the propylene / ethylene random copolymer portion is usually 20 to 60 mol%, preferably 30 to 50 mol%.
- MFR of propylene / ethylene block copolymer, propylene homopolymer or propylene / ethylene random copolymer measured at 230 ° C. and 2.16 kg load measured in accordance with ASTM D1238 is 30 for MFR of polymer alloy (A).
- the component (p) having a wide range of MFR values can be used without limitation.
- the MFR of component (p) is 1 to 400 g / 10 min, preferably 5 to 300 g / 10 min, more preferably 10 to 250 g / 10 min.
- the MFR is less than 1 g / 10 min, the resin fluidity during molding is poor, and the polymer alloy (A) may not be impregnated with resin up to the carbon fiber details. Moreover, when MFR is larger than 400 g / 10 minutes, since sufficient mechanical strength may not be expressed in a molded product, it is not preferable.
- a propylene / ethylene block copolymer, a propylene homopolymer or a propylene / ethylene random copolymer can be prepared by carrying out copolymerization in the presence of a known catalyst for olefin polymerization.
- a known catalyst for olefin polymerization for example, a so-called Ziegler-Natta catalyst including a solid titanium catalyst component and an organometallic compound catalyst component or a metallocene catalyst can be used.
- the ethylene-based polymer (e) is added in order to further improve the mechanical properties including the impact resistance of the molded product obtained from the carbon fiber reinforced resin composition of the present invention.
- the ethylene polymer (e) may be abbreviated as a rubber component.
- the ethylene-based copolymer (e) has a skeleton content derived from ethylene (including the skeleton content when homopolyethylene coexists) of 50 mol% or more, preferably 60 mol% or more. Preferably it is 70 mol% or more of an ethylene-based copolymer.
- an ethylene / ⁇ -olefin copolymer is preferable, and a copolymer of ethylene and an ⁇ -olefin having 3 to 10 carbon atoms is more preferable.
- Examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene is mentioned. These can use 1 type (s) or 2 or more types. Of these, 1-butene and 1-octene are particularly preferable.
- the MFR of the ethylene copolymer (e) measured at 230 ° C. under a 2.16 kg load by ASTM D-1238 is preferably 1 to 100 g / 10 min, more preferably 3 to 80 g / 10 min, and the density is preferably 0.86 to 0.92 g / cm 3 .
- Specific conditions such as the selection of the optimum species from these rubber components and the addition amount thereof are matters that are arbitrarily determined based on the balance between the desired rigidity and impact resistance.
- polyamide (n) The kind of polyamide (n) is not particularly limited.
- amino acids lactam or all melt-moldable polymers obtained by melt polycondensation reaction of diamine and dicarboxylic acid can be used without limitation.
- the following various resins are mentioned.
- a polycondensate of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms for example, polyhexamethylene adipamide which is a polycondensate of hexamethylenediamine and adipic acid [6,6 nylon], polyhexamethylene azelamide [6,9 nylon] which is a polycondensate of hexamethylene diamine and azelaic acid, polyhexamethylene sebaca which is a polycondensate of hexamethylene diamine and sebacic acid [6,10 nylon], polyhexamethylene dodecanoamide [6,12 nylon] which is a polycondensate of hexamethylenediamine and dodecanedioic acid, polycondensate of aromatic dicarboxylic acid and aliphatic diamine Semi-aromatic polyamide (PA6T, PA9T, PA10T, PA11T), bis-p-aminocyclohexylme
- organic dicarboxylic acids include adipic acid, pimelic acid, suberic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phenylenedioxydiacetic acid, oxydibenzoic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, Biphenyl dicarboxylic acid, sebacic acid, dodecanedioic acid may be mentioned.
- organic diamine examples include hexamethylene diamine, octamethylene diamine, nonane diamine, octane diamine, decane diamine, undecane diamine, undecane diamine, and dodecane diamine.
- polycondensate of ⁇ -amino acid for example, polyundecanamide [11 nylon] which is a polycondensate of ⁇ -aminoundecanoic acid.
- Ring-opening polymer of lactam for example, polycapramide [6 nylon] which is a ring-opening polymer of ⁇ -aminocaprolactam, and polylauric lactam [12 nylon] which is a ring-opening polymer of ⁇ -aminolaurolactam.
- polyhexamethylene adipamide (6,6 nylon), polyhexamethylene azelamide (6,9 nylon), and polycaproamide (6 nylon) are preferable.
- a polyamide produced from adipic acid, isophthalic acid and hexamethylenediamine can be used, and a blend containing two or more polyamide resins such as a mixture of 6 nylon and 6,6 nylon can also be used. It can be used.
- the melt flow rate (MFR) at 190 ° C. and 1 kg load according to ASTM D1238 of polyamide (n) is preferably 5 g / 10 min or more, more preferably 10 g / 10 min or more, particularly preferably 12 g / 10 min or more. is there.
- the acid-modified polyolefin resin (m) is a polyolefin resin modified with an acid such as an unsaturated carboxylic acid or a derivative thereof.
- the acid-modified polyolefin resin (m) improves the interfacial strength between the carbon fiber (B) and the polymer alloy (A), and greatly improves strength properties such as fracture stress and bending strength.
- Examples of the acid used for modification include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Also, derivatives of these unsaturated carboxylic acids can be used. Examples of the derivatives include acid anhydrides, esters, amides, imides, and metal salts. Specific examples include maleic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, acrylic acid. Examples include propyl, butyl acrylate, ethyl maleate, acrylamide, maleic amide, sodium acrylate, and sodium methacrylate.
- unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid,
- unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic acid and maleic anhydride are more preferable.
- Unsaturated carboxylic acid or its derivative (s) may be used alone or in combination of two or more. There is no particular limitation on the modification method, and a known method may be used. For example, there are a method in which a polyolefin resin is dissolved in a solvent, an unsaturated carboxylic acid or a derivative thereof and a radical generator are added and heated and stirred, and a method in which the above components are supplied to an extruder and graft copolymerized.
- the acid content in the acid-modified polyolefin resin (m) is preferably 0.1 to 10% by mass, more preferably 0.8 to 8% by mass. Acid content, and IR spectrum of the resin, as determined from the calibration curve prepared separately based on the peak area of 1670cm -1 ⁇ 1810cm -1.
- the intrinsic viscosity [ ⁇ ] of the acid-modified polyolefin resin (m) measured in tetralin at 135 ° C. is preferably 0.1 to 3.0 dL / g. If the intrinsic viscosity [ ⁇ ] is 0.1 dL / g or more, the physical properties such as the strength characteristics of the molded article are hardly lowered, and if it is 3.0 dL / g or less, the fluidity of the composition is hardly lowered and is good. Formability is maintained.
- At least one resin selected from an acid-modified propylene polymer and an acid-modified ethylene polymer as the acid-modified polyolefin resin (m).
- the maleic acid-modified propylene polymer (m1) and the maleic acid are preferably used. It is more preferable to use one or more resins selected from acid-modified ethylene polymers (m2).
- the MFR of the acid-modified polyolefin resin (m) at 230 ° C. and 2.16 kg load according to ASTM D1238 is not particularly limited, but it does not prevent the MFR of the polymer alloy (A) from becoming 30 to 500 g / 10 min. It is preferably a value.
- the MFR of the component (m1) usually exceeds 150 g / 10 minutes, preferably 200 g / 10 minutes or more, more preferably Is 300 g / 10 min or more, particularly preferably 500 g / 10 min or more, and most preferably 600 g / 10 min or more.
- an acid-modified propylene polymer is used as the acid-modified polyolefin resin (m)
- Carbon fiber (B) As the carbon fiber (B) used in the present invention, various known carbon fibers can be used. Specific examples include carbon fibers such as polyacrylonitrile-based, rayon-based, pitch-based, polyvinyl alcohol-based, regenerated cellulose, and pitch-based carbon fibers produced from mesophase pitch.
- the fiber diameter of the carbon fiber (B) is preferably 3 to 30 ⁇ m, more preferably 4 to 10 ⁇ m.
- Each lower limit value of the above range of the fiber diameter is significant in terms of prevention of fiber breakage and fiber bundle productivity. For example, in the case of continuously producing pellets, if the fiber diameter is appropriately increased, the number of fibers to be bundled does not increase, and the troublesome work of connecting the fiber bundles becomes unnecessary, thereby improving the productivity.
- each upper limit value is significant in that the reduction of the fiber aspect ratio is suppressed and the reinforcing effect is maintained when the pellet length is determined.
- the aspect ratio of the carbon fiber (B) is preferably 5 to 6000. This lower limit value is significant in terms of suppressing strength reduction, and the upper limit value is significant in terms of formability.
- the aspect ratio of the carbon fiber (B) is obtained from the average fiber diameter and the average fiber length by the formula of (average fiber length) / (average fiber diameter).
- the carbon fiber (B) may be a long fiber, a short fiber, or a chopped fiber.
- a continuous fiber bundle can be used as a raw material for long fibers, which is commercially available as tow.
- the average fiber diameter is 3 to 30 ⁇ m, and the number of filaments is 500 to 80,000.
- the average fiber diameter is 4 to 10 ⁇ m, and the number of bundles is 12,000 to 50,000.
- the length of the chopped strand is usually 1 to 20 mm, and the fiber diameter is usually 3 to 30 ⁇ m, preferably 4 to 10 ⁇ m.
- the carbon fiber (B) is preferably a carbon fiber bundle bundled using a sizing agent (size agent). Specifically, it is preferable to use a plurality of carbon fibers in a state of being bundled together with a sizing agent.
- the sizing agent constituting the carbon fiber bundle is preferably a urethane emulsion, an epoxy emulsion, or a nylon emulsion from the viewpoint of increasing mechanical strength. More preferred are emulsion adhesives such as urethane emulsions and epoxy emulsions, and epoxy emulsions are most preferred from the viewpoint of further improving mechanical strength.
- the number of carbon fibers constituting the carbon fiber bundle is not particularly limited, but can be, for example, 6000 to 48000.
- the surface of the carbon fiber (B) is preferably subjected to surface treatment by oxidation etching or coating.
- the oxidation etching treatment include air oxidation treatment, oxygen treatment, treatment with oxidizing gas, treatment with ozone, corona treatment, flame treatment, (atmospheric pressure) plasma treatment, oxidizing liquid (nitric acid, alkali metal hypochlorite) Salt aqueous solution, potassium dichromate-sulfuric acid, potassium permanganate-sulfuric acid).
- the substance that covers the carbon fiber include carbon, silicon carbide, silicon dioxide, silicon, plasma monomer, ferrocene, and iron trichloride.
- a sizing agent such as urethane, olefin, acrylic, nylon, butadiene, and epoxy may be used as necessary.
- the carbon fiber (B) has a tensile strength of preferably 2500 to 6000 MPa, more preferably 3500 to 6000 MPa, and particularly preferably 4500 to 6000 MPa from the viewpoint of increasing mechanical strength.
- the carbon fiber reinforced resin composition of the present invention may be a short fiber reinforced resin pellet or a long fiber reinforced resin pellet.
- the above-described component (p), component (m), component (e), component (n) and other optional components, and carbon fiber component (B ) In a roll mill, Banbury mixer, kneader or the like. It may be dry blended with a tumbler blender, Henschel mixer, ribbon mixer or the like, and melt-kneaded with a single screw extruder, twin screw extruder or the like to form a pellet-shaped molding material. In this method, the carbon fiber (B) may be input from either the top or side of the extruder. In this method, all or a part of each component of the polymer alloy (A) may be separately melt-kneaded and then melt-kneaded with the carbon fiber (B).
- the carbon fiber reinforced resin composition of the present invention is a long fiber reinforced resin pellet
- it can be produced by a known method such as a drawing method. You may melt-knead, after melt-kneading a part of above-mentioned component separately.
- carbon fiber roving can be guided to an impregnation die, and the molten resin can be uniformly impregnated between the filaments, and then pelletized by cutting to a required length (2 to 200 mm).
- the carbon fiber reinforced resin composition of the present invention has various additives, such as dispersants, lubricants, plasticizers, flame retardants, antioxidants (phenolic antioxidants, phosphoric antioxidants, sulfurs) depending on the application.
- Colorants Carbon black, titanium oxide, bengara, azo pigment, anthraquinone pigment, phthalocyanine, talc, calcium carbonate, mica, clay, etc .; short fiber filler such as wollastonite; potassium titanate, etc. Of whiskers may be added.
- the molded product of the present invention is formed by molding the above-described fiber-reinforced resin composition of the present invention.
- known molding methods such as an injection molding method, an extrusion molding method, a hollow molding method, a compression molding method, an injection compression molding method, a gas injection injection molding method, and a foam injection molding method can be applied without any limitation.
- an injection molding method, a compression molding method, and an injection compression molding method are preferable.
- Carbon fiber (B) The following three types of short fibers “TENAX (registered trademark) Hopped Fiber” (CF-1 to CF-3) manufactured by Toho Tenax Co., Ltd. and the following filament “TENAX (registered trademark) Filament Yarn” (CF-4) were used.
- CF-1 to CF-3 the following three types of short fibers “TENAX (registered trademark) Hopped Fiber”
- TENAX (registered trademark) Filament Yarn” CF-4
- Comparative Example 1-2 the following glass fiber (GF-1) manufactured by Central Glass Fiber Co., Ltd. was used.
- Polyamide (n) The following three types of polyamide 12 “UBESTA (registered trademark)” (PA-1 to PA-3) manufactured by Ube Industries, Ltd. were used.
- This mixture was supplied to a 30 mm ⁇ twin screw extruder whose temperature was adjusted to 190 ° C., and the strand obtained by melt-kneading at 200 rpm was cooled in a water bath to obtain maleic anhydride-modified polypropylene.
- this maleic anhydride-modified polypropylene was vacuum-dried at 40 ° C. for 2 hours.
- Example 1-1 ⁇ Evaluation method 1 (DSM method)>
- the kneading apparatus Toyo Seiki Seisakusho, Labo Plast Mill (registered trademark) 75C100
- the kneading apparatus has a roller rotation speed of 5 rpm, a set temperature of 180 ° C., and a kneading part with a capacity of 100 cc, the amount of component (n) and component shown in Table 1 (M1), component (m2), component (p), component (e), and component (B) were charged in this order, and the set temperature was raised to 190 ° C. after the charging was completed.
- the above sheet-like carbon fiber reinforced resin composition is made into small pieces with a cutter and charged into a hopper part of a small kneader (DSM Xplore MC15M) of a resin kneading and molding evaluation apparatus (manufactured by Xplore Instruments) and kneaded at 180 ° C for 3 minutes. did. Immediately after that, it is put into a pot part (220 ° C.) of an injection molding machine for producing a test piece (DSM Xplore IM12M), and injection molded at a pressure of 9 MPa (primary) and 12 MPa (secondary) into a mold of 30 to 40 ° C.
- DSM Xplore MC15M small kneader
- a resin kneading and molding evaluation apparatus manufactured by Xplore Instruments
- ⁇ Evaluation Method 2 (Plate Cutting Method)> Screw type extruder in which component (n), component (m1), component (m2), component (p), component (e), and component (B) in the amounts shown in Table 1 were adjusted to 250 ° C. in this order. was put into the hopper.
- the component (B) is expanded and opened at a speed of 100 parts by mass, supplied to the die head of the extruder, converted into a strand, cooled and solidified, and pelletized with a strand cutter to obtain a pellet-like carbon fiber reinforced resin composition. It was.
- the pellet-like carbon fiber reinforced resin composition was put into an injection molding machine having a cylinder temperature of 250 ° C. and a clamping pressure of 100 t, and a plate-like molded product was obtained using a 120 mm ⁇ 120 mm ⁇ 3 mmt mold.
- a cut-out test piece was produced from this plate-shaped molded product in accordance with JIS K 7162 IBA (ISO527-2).
- the cut specimen was subjected to a bending test in accordance with ISO178, and the bending elastic modulus (GPa) and bending strength (MPa) in the stress-strain curve were obtained.
- melt flow rate (MFR) of component (A) was measured at 230 ° C. and a 2.16 kg load. The results are shown in Table 1.
- Example 1-2 Evaluation was conducted in the same manner as in Example 1-1 except that CF-1 as the component (B) was changed to CF-2. The results are shown in Table 1.
- Example 1-3 Evaluation was conducted in the same manner as in Example 1-1 except that CF-1 as the component (B) was changed to CF-3. The results are shown in Table 1.
- Example 1-2 Evaluation was performed in the same manner as in Example 1-1 except that CF-1 as the component (B) was changed to GF-1. The results are shown in Table 1. In this comparative example, the tensile yield stress and the tensile elastic modulus were somewhat larger than those in Comparative Example 1-1 using no fibers, but compared with Examples 1-1 to 1-3 using carbon fibers. And mechanical properties were inferior.
- Example 2-1 The same as Evaluation Method 1 of Example 1-1, except that Lab Plastmill (registered trademark) was charged with the components (p), (m) and (B) in the amounts shown in Table 2 in this order. A test piece was prepared, a tensile test was performed, and a tensile elastic modulus (GPa) and a tensile strength (MPa) in a stress-strain curve were obtained. In addition, MFR (230 ° C., 2.16 kg) of component (A) was also measured. The results are shown in Table 2.
- Example 2-1 A test piece was tried to be molded in the same manner as in Example 2-1, except that the component (m) was not used and the amount of each component was changed as shown in Table 2. However, since the carbon fibers were not melted and kneaded uniformly, they could not be molded.
- Example 2-2 A test piece was prepared in the same manner as in Example 2-1, except that h-PP (4) was used as component (p), component (n) was used in combination, and the amount of each component was changed as shown in Table 2. Were prepared and evaluated. The results are shown in Table 2. In this example, higher tensile properties were exhibited for a lower carbon fiber (component (B)) content than in Example 2-1. Furthermore, the MFR of the polymer alloy (A) of this example showed a high value of 250 g / 10 min. From this, it was found that the melt kneading is easy (the carbon fiber is sufficiently impregnated with a low feed energy amount).
- Example 2-3 A test piece was prepared and evaluated in the same manner as in Example 2-2 except that h-PP (3) was used as the component (p). The results are shown in Table 2. In this example, the MFR of the component (p) was slightly lower than in Example 2-2, and it was found that the tensile properties also tend to be lowered. However, there is no problem in practical use.
- Example 2-1 A test piece was prepared and evaluated in the same manner as in Example 2-2 except that h-PP (1) was used as the component (p). The results are shown in Table 2. In this reference example, since the MFR of the component (p) was considerably lower than that of Example 2-2, the MFR of the polymer alloy (A) was also considerably low, and the tensile properties were lowered to such an extent that improvement was desirable in practice.
- Example 2-4 Evaluation method in the same manner as in Example 2-1, except that h-PP (4), component (m), component (n) and component (B) as component (p) were used in the amounts shown in Table 2.
- the same test piece as 1 was prepared and evaluated.
- the same test piece as in Evaluation Method 2 of Example 1-1 was also produced, and similarly, bending elastic modulus (GPa), bending strength (MPa), and Charpy impact strength (kJ / m 2 ) were obtained.
- GPa bending elastic modulus
- MPa bending strength
- Charpy impact strength kJ / m 2
- test piece of Evaluation Method 2 was subjected to a tensile test at a tensile speed of 5 mm / min, and the tensile elastic modulus (GPa) and tensile strength (MPa) in the stress-strain curve were also obtained.
- GPa tensile elastic modulus
- MPa tensile strength
- Example 2-5 A test piece was prepared and evaluated in the same manner as in Example 2-4 except that h-PP (3) was used as the component (p) and the amount of each component was changed as shown in Table 2. The results are shown in Table 2. In this example, since the MFR of the component (p) was slightly lower than that in Example 2-4, it was found that the tensile properties and bending properties tend to deteriorate. However, there is no problem in practical use.
- Example 2-2 A test piece of Evaluation Method 2 was prepared and evaluated in the same manner as Example 2-4 except that h-PP (1) was used as component (p) (except for Charpy impact strength). The results are shown in Table 2. In this reference example, since the MFR of the component (p) was considerably lower than that of Example 2-4, the MFR of the polymer alloy (A) was also considerably low, and the tensile properties were lowered to such an extent that improvement was desirable in practice.
- Example 3-1 Example 2-4 was repeated except that b-PP, component (e), component (m), component (n), and component (B) as component (p) were used in the amounts shown in Table 2. Thus, a test piece of Evaluation Method 2 was prepared and evaluated. The results are shown in Table 2. In this example, the tensile properties and bending properties were lower than those of Examples 2-4 and 2-5 using h-PP, but the Charpy impact strength was greatly improved.
- Example 3-2 A test piece of Evaluation Method 2 was prepared and evaluated in the same manner as in Example 3-1, except that the amount of component (B) was increased as shown in Table 2. The results are shown in Table 2. In this example, since the amount of carbon fiber (component (B)) is also large in Example 3-1, not only the tensile properties and bending properties are improved, but also the impact resistance (Charpy impact strength) is improved by 30 to 40%. did.
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Abstract
Description
酸変性ポリオレフィン樹脂(m)1~60質量%、
エチレン系重合体(e)0~40質量%、及び
ポリアミド(n)0~50質量%
[ここで成分(p)、成分(m)、成分(e)及び成分(n)の合計は100質量%]
を含むポリマーアロイ(A)100質量部、並びに
炭素繊維(B)1~200質量部
を含んでなる炭素繊維強化樹脂組成物。
[3]ポリマーアロイ(A)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)が30~500g/10分である前記[1]記載の炭素繊維強化樹脂組成物。
[4]ポリマーアロイ(A)中の成分(p)の含有量をWp質量%、成分(m)の含有量をWm質量%、成分(e)の含有量をWe質量%、成分(n)の含有量をWn質量%とした場合、WpとWmの合計が50~100質量%であり、Wnが0~50質量%であり(ここでWp、Wm、We及びWnの合計は100質量%)、且つWpとWmの比率(Wp/Wm)が70/30~98/2である前記[1]記載の炭素繊維強化樹脂組成物。
[5]酸変性ポリオレフィン樹脂(m)が、マレイン酸変性プロピレン系重合体(m1)及びマレイン酸変性エチレン系重合体(m2)から選ばれる一種以上である前記[1]記載の炭素繊維強化樹脂組成物。
[6]酸変性ポリオレフィン樹脂(m)がマレイン酸変性プロピレン系重合体(m1)を含み、且つ該マレイン酸変性プロピレン系重合体(m1)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)が150g/10分を超える前記[5]記載の炭素繊維強化樹脂組成物。
[7]ポリマーアロイ(A)中の成分(p)の含有量をWp質量%、成分(m1)の含有量をWm1質量%(ただし成分(m)全体の含有量はWm質量%)、成分(e)の含有量をWe質量%、成分(n)の含有量をWn質量%とした場合、WpとWm1の合計が50~98質量%であり、Wnが2~50質量%であり(ここでWp、Wm、We及びWnの合計は100質量%)、さらに
成分(p)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)をMFRp(g/10分)、成分(m1)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)をMFRm1(g/10分)とした場合、下記式(1)を満たす前記[5]記載の炭素繊維強化樹脂組成物。
[9]前記[1]記載の炭素繊維強化樹脂組成物を成形してなる成形品。
(要件1)ポリマーアロイ(A)中の成分(p)の含有量をWp質量%、成分(m)の含有量をWm質量%、成分(e)の含有量をWe質量%、成分(n)の含有量をWn質量%とした場合、WpとWmの合計が50~100質量%であり、Wnが0~50質量%である(ここで、Wp、Wm、We及びWnの合計は100質量%)。
(要件2)WpとWmの比率(Wp/Wm)が、70/30~98/2である。
本発明においてプロピレン系重合体(p)は、プロピレン・エチレンブロック共重合体、プロピレン単独重合体及びエチレン含量が5質量%以下のプロピレン・エチレンランダム共重合体から選ばれる一種以上の重合体である。
エチレン系重合体(e)は、本発明の炭素繊維強化樹脂組成物から得られる成形体の耐衝撃性を始めとする力学特性を更に向上させるために添加される。なお以下の説明では、エチレン系重合体(e)のことをゴム成分と略記する場合がある。
ポリアミド(n)の種類は特に限定されない。例えば、アミノ酸ラクタム、あるいはジアミンとジカルボン酸との溶融重縮合反応により得られる溶融成形可能なポリマー全般を制限無く使用できる。具体的には、以下の各種の樹脂が挙げられる。
酸変性ポリオレフィン樹脂(m)は、不飽和カルボン酸又はその誘導体等の酸で変性されたポリオレフィン樹脂である。酸変性ポリオレフィン樹脂(m)は、炭素繊維(B)とポリマーアロイ(A)との界面強度を向上させ、破壊応力や曲げ強さ等の強度特性を大幅に向上させる。
は、マレイン酸変性プロピレン系重合体(m1)を用いることが好ましい。
本発明に用いる炭素繊維(B)としては、公知の種々の炭素繊維を使用することができる。具体例としては、ポリアクリルニトリル系、レーヨン系、ピッチ系、ポリビニルアルコール系、再生セルロース、メゾフェーズピッチから製造されたピッチ系等の炭素繊維が挙げられる。
エポキシ系等の収束剤を使用しても良い。
東邦テナックス社製の下記3種類の短繊維「TENAX(登録商標) Chopped Fiber」(CF-1~CF-3)及び下記フィラメント「TENAX(登録商標) Filament Yarn」(CF-4)を用いた。また比較例1-2では、セントラルグラスファイバー社製の下記ガラス繊維(GF-1)を用いた。
・「CF-1」:HT C251;繊維長=6mm、エポキシ含有率=1.3質量%
・「CF-2」:HT C227;繊維長=6mm、エポキシ含有率=7.0質量%
・「CF-3」:HT C261;繊維長=3mm、エポキシ含有率=1.3質量%
・「CF-4」:HTS40 12K;フィラメント数=12000本、エポキシ含有率=1.3質量%)
・GF-1:繊維長=3mm
プライムポリマー社製の下記プロピレン・エチレンブロック共重合体(b-PP)及び下記4種類のプロピレン単独重合体(h-PP(1)~h-PP(4))を用いた。
・「b-PP」:X855;ASTM D1238に準拠したMFR(以下同じ)(230℃、2.16kg)=15g/10分、25℃キシレン可溶部量=23質量%、25℃キシレン可溶部の極限粘度[η]=7.4dl/g、25℃キシレン可溶部のエチレン含有量=39mol%
・「h-PP(1)」:MFR(230℃、2.16kg)=15g/10分
・「h-PP(2)」:MFR(230℃、2.16kg)=50g/10分
・「h-PP(3)」:MFR(230℃、2.16kg)=63g/10分
・「h-PP(4)」:MFR(230℃、2.16kg)=220g/10分
三井化学社製の下記2種類のエチレン・1-ブテン共重合体「タフマー(登録商標)」(e-1~e-2)を用いた。
・「e-1」:DF940;エチレン含有量=90モル%、MFR(230℃、2.16kg)=6.7g/10分
・「e-2」:DF7350;密度=870kg/m3、MFR(230℃、2.16kg)=65g/10分、融点=55℃
宇部興産社製の下記3種類のポリアミド12「UBESTA(登録商標)」(PA-1~PA-3)を用いた。
・「PA-1」:3012U;ISO11357-3に準拠したる融点(以下同じ)=180℃、ISO11357-3に準拠したMFR(以下同じ)(190℃、1.0kg)=17g/10分)
・「PA-2」:3014U;融点=179℃、MFR(190℃、1.0kg)=9g/10分
・「PA-3」:3020U;融点=178℃、MFR(235℃、2.16kg)=20g/10分)
三井化学社製の下記マレイン酸変性ランダムポリプロピレン「アドマー(登録商標)QE800」(m1-1)、下記方法で調製した無水マレイン酸変性ポリプロピレン(m1-2)、及び三井化学社製の下記マレイン酸変性エチレン系重合体「タフマー(登録商標)MH5020」(m2)を用いた。
・「m1-1」:ASTM D1238に準拠したMFR(以下同じ)(230℃、2.16kg)=9.0g/10分
・「m1-2」:ポリプロピレン(プライムポリマー社製、商品名J106G、MFR(230℃、2.16kg)=15g/10分)100質量部に対して、ジアルキルパーオキサイド(日油社製、パーヘキサ(登録商標)25B)1質量部、粉末化した無水マレイン酸(日油社製、CRYSTAL MAN(登録商標))3質量部を予備混合した。この混合物を190℃に温度調節した30mmφの二軸押出機に供給して、200rpmにて溶融混練して得たストランドを水槽で冷却して無水マレイン酸変性ポリプロピレン得た。未変性の残留無水マレイン酸を除去するために、この無水マレイン酸変性ポリプロピレンを40℃で2時間真空乾燥した。得られた無水マレイン酸変性ポリプロピレン(m1-2)のマレイン酸含量は2.5質量%、MFR(230℃、2.16Kg)は800g/10分であった。
・「m2」:MFR(230℃、2.16Kg)=1.2g/10分
<評価法1(DSM法))>
混練装置(東洋精機製作所製、ラボプラストミル(登録商標)75C100)のローラ回転数を5rpm、設定温度を180℃とし、容量100ccの混練部に、表1に示す量の成分(n)、成分(m1)、成分(m2)、成分(p)、成分(e)、成分(B)をこの順に投入し、投入終了後に設定温度を190℃まで昇温させた。次いで、ローラ回転数を10秒間隔で10→30→50→70→90rpmまで上げる操作を3回繰り返した。その後、30rpmで10分間混練を行った後に混練物をミルから取り出し、塊り状混練物を簡易プレス機でプレスして厚み2mm程度のシート状炭素繊維強化樹脂組成物を得た。
表1に示す量の成分(n)、成分(m1)、成分(m2)、成分(p)、成分(e)、成分(B)をこの順に、250℃に温度調節されたスクリュー式押し出し機のホッパーに投入した。また成分(B)を100質量部になる速度で拡張開繊して押出機のダイヘッドに供給し、ストランド化、冷却固化し、ストランドカッターによってペレット化し、ペレット状の炭素繊維強化樹脂組成物を得た。
ASTM D1238に準拠し、230℃、2.16kg荷重で成分(A)のメルトフローレート(MFR)を測定した。結果を表1に示す。
成分(B)としてのCF-1をCF-2に変更したこと以外は、実施例1-1と同様にして評価した。結果を表1に示す。
成分(B)としてのCF-1をCF-3に変更したこと以外は、実施例1-1と同様にして評価した。結果を表1に示す。
成分(B)を用いなかったこと以外は、実施例1-1と同様にして評価した。結果を表1に示す。
成分(B)としてのCF-1をGF-1に変更したこと以外は、実施例1-1と同様にして評価した。結果を表1に示す。本比較例では、繊維を全く用いた比較例1-1と比べると引張降伏応力及び引張弾性率は多少大きな値を示したが、炭素繊維を用いた実施例1-1~1-3と比べると機械特性が劣っていた。
ラボプラストミル(登録商標)に、表2に示す量の成分(p)、成分(m)及び、成分(B)をこの順に投入したこと以外は、実施例1-1の評価法1と同じ試験片を作製し、引張試験を実施し、応力-歪曲線における引張弾性率(GPa)と引張強度(MPa)を求めた。また、成分(A)のMFR(230℃、2.16kg)も測定した。結果を表2に示す。
成分(m)を用いず、各成分の量を表2に示すように変更したこと以外は、実施例2-1と同様にして試験片を成形しようとした。しかし、炭素繊維が均一に溶融混練しないので成形できなかった。
成分(p)としてh-PP(4)を用い、成分(n)を併用し、各成分の量を表2に示すように変更したこと以外は、実施例2-1と同様にして試験片を作製し評価した。結果を表2に示す。本実施例では、実施例2-1よりも炭素繊維(成分(B))の含量が低い割には高めの引張特性を示した。さらに、本実施例のポリマーアロイ(A)のMFRは250g/10分と高い値を示し、このことから溶融混練し易い(低フィードエネルギー量で炭素繊維が十分に含浸する)ことが分かった。
成分(p)としてh-PP(3)を用いたこと以外は、実施例2-2と同様にして試験片を作製し評価した。結果を表2に示す。本実施例では、実施例2-2に比べて成分(p)のMFRが若干低いので、引張特性も低下する傾向にあることが分かった。ただし、実用上は問題無いレベルである。
成分(p)としてh-PP(1)を用いたこと以外は、実施例2-2と同様にして試験片を作製し評価した。結果を表2に示す。本参考例では、実施例2-2に比べて成分(p)のMFRがかなり低いのでポリマーアロイ(A)のMFRもかなり低くなり、実用上は改善が望ましい程度に引張特性が低下した。
成分(p)としてのh-PP(4)、成分(m)、成分(n)及び成分(B)を表2に示す量用いたこと以外は、実施例2-1と同様にして評価法1と同じ試験片を作製し評価した。また実施例1-1の評価法2と同じ試験片も作製し、同様にして曲げ弾性率(GPa)、曲げ強度(MPa)、シャルピー衝撃強度(kJ/m2)を求めた。さらに、評価法2の試験片について、引張速度5mm/分で引張試験を実施し、応力-歪曲線における引張弾性率(GPa)と引張強度(MPa)も求めた。結果を表2に示す。
成分(p)としてh-PP(3)を用い、各成分の量を表2に示すように変更したこと以外は、実施例2-4と同様にして試験片を作製し評価した。結果を表2に示す。本実施例では、実施例2-4に比べて成分(p)のMFRが若干低いので、引張特性と曲げ特性が低下する傾向にあることが分かった。ただし、実用上は問題無いレベルである。
成分(p)としてh-PP(1)を用いたこと以外は、実施例2-4と同様にして評価法2の試験片を作製し評価した(ただしシャルピー衝撃強度は除く)。結果を表2に示す。本参考例では、実施例2-4に比べて成分(p)のMFRがかなり低いのでポリマーアロイ(A)のMFRもかなり低くなり、実用上は改善が望ましい程度に引張特性が低下した。
成分(p)としてのb-PP、成分(e)、成分(m)、成分(n)、及び成分(B)を表2に示す量用いたこと以外は、実施例2-4と同様にして評価法2の試験片を作製し評価した。結果を表2に示す。本実施例では、引張特性や曲げ特性はh-PPを用いた実施例2-4及び2-5よりも低いが、シャルピー衝撃強度が大きく向上した。
成分(B)の量を表2に示すように増量したこと以外は、実施例3-1と同様にして評価法2の試験片を作製し評価した。結果を表2に示す。本実施例では、炭素繊維(成分(B))の量が実施例3-1も多いので、引張特性と曲げ特性の向上のみならず、耐衝撃性(シャルピー衝撃強度)も30~40%向上した。
Claims (9)
- プロピレン・エチレンブロック共重合体、プロピレン単独重合体、及びエチレン含量が5質量%以下のプロピレン・エチレンランダム共重合体から選ばれる一種以上のプロピレン系重合体(p)25~95質量%、
酸変性ポリオレフィン樹脂(m)1~60質量%、
エチレン系重合体(e)0~40質量%、及び
ポリアミド(n)0~50質量%
[ここで成分(p)、成分(m)、成分(e)及び成分(n)の合計は100質量%]
を含むポリマーアロイ(A)100質量部、並びに
炭素繊維(B)1~200質量部
を含んでなる炭素繊維強化樹脂組成物。 - ポリマーアロイ(A)100質量部と炭素繊維(B)1~80質量部を含んでなる請求項1記載の炭素繊維強化樹脂組成物。
- ポリマーアロイ(A)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)が30~500g/10分である請求項1記載の炭素繊維強化樹脂組成物。
- ポリマーアロイ(A)中の成分(p)の含有量をWp質量%、成分(m)の含有量をWm質量%、成分(e)の含有量をWe質量%、成分(n)の含有量をWn質量%とした場合、WpとWmの合計が50~100質量%であり、Wnが0~50質量%であり(ここでWp、Wm、We及びWnの合計は100質量%)、且つWpとWmの比率(Wp/Wm)が70/30~98/2である請求項1記載の炭素繊維強化樹脂組成物。
- 酸変性ポリオレフィン樹脂(m)が、マレイン酸変性プロピレン系重合体(m1)及びマレイン酸変性エチレン系重合体(m2)から選ばれる一種以上である請求項1記載の炭素繊維強化樹脂組成物。
- 酸変性ポリオレフィン樹脂(m)がマレイン酸変性プロピレン系重合体(m1)を含み、且つ該マレイン酸変性プロピレン系重合体(m1)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)が150g/10分を超える請求項5記載の炭素繊維強化樹脂組成物。
- ポリマーアロイ(A)中の成分(p)の含有量をWp質量%、成分(m1)の含有量をWm1質量%(ただし成分(m)全体の含有量はWm質量%)、成分(e)の含有量をWe質量%、成分(n)の含有量をWn質量%とした場合、WpとWm1の合計が50~98質量%であり、Wnが2~50質量%であり(ここでWp、Wm、We及びWnの合計は100質量%)、さらに
成分(p)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)をMFRp(g/10分)、成分(m1)のASTM D1238に準拠し230℃、2.16kg荷重で測定されるメルトフローレート(MFR)をMFRm1(g/10分)とした場合、下記式(1)を満たす請求項5記載の炭素繊維強化樹脂組成物。
- 炭素繊維(B)が、集束剤を用いて束ねられた炭素繊維束であり、該集束剤がエポキシ系エマルジョンである請求項1記載の炭素繊維強化樹脂組成物。
- 請求項1記載の炭素繊維強化樹脂組成物を成形してなる成形品。
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US10336869B2 (en) | 2019-07-02 |
EP3081591A1 (en) | 2016-10-19 |
JPWO2016076411A1 (ja) | 2017-04-27 |
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EP3081591A4 (en) | 2017-06-28 |
JP2017008332A (ja) | 2017-01-12 |
JP6012914B1 (ja) | 2016-10-25 |
CN107148445A (zh) | 2017-09-08 |
EP3081591B1 (en) | 2019-10-16 |
US20170321019A1 (en) | 2017-11-09 |
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