WO2014156760A1 - Non-tissé de fibres de carbone - Google Patents

Non-tissé de fibres de carbone Download PDF

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Publication number
WO2014156760A1
WO2014156760A1 PCT/JP2014/057105 JP2014057105W WO2014156760A1 WO 2014156760 A1 WO2014156760 A1 WO 2014156760A1 JP 2014057105 W JP2014057105 W JP 2014057105W WO 2014156760 A1 WO2014156760 A1 WO 2014156760A1
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Prior art keywords
carbon fiber
nonwoven fabric
carbon
bundle
fiber nonwoven
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PCT/JP2014/057105
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English (en)
Japanese (ja)
Inventor
三好且洋
橋本貴史
成瀬恵寛
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東レ株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=51623741&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014156760(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to US14/779,437 priority Critical patent/US20160053432A1/en
Priority to CN201480012664.8A priority patent/CN105074082B/zh
Priority to JP2014512995A priority patent/JP6108240B2/ja
Priority to EP14774131.8A priority patent/EP2980309A4/fr
Priority to KR1020157028559A priority patent/KR20150135778A/ko
Publication of WO2014156760A1 publication Critical patent/WO2014156760A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • 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
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Definitions

  • the present invention relates to a carbon fiber nonwoven fabric, and more particularly, to a carbon fiber nonwoven fabric that can achieve both high fluidity and mechanical properties when a molded product of a carbon fiber composite material is produced using the carbon fiber nonwoven fabric.
  • Carbon fiber composite materials made of carbon fiber and thermoplastic resin have been used in the manufacture of various molded products. Conventionally, high mechanical properties of the manufactured molded products and good fluidity during production have been aimed at.
  • Various proposals have been made. Among these, by making the carbon fiber in the carbon fiber composite material into the form of a nonwoven fabric, for example, in Patent Document 1, the ratio of the specific carbon fiber bundle in the carbon fiber nonwoven fabric to the total amount of fibers is kept low, and the specific carbon fiber Carbon fiber nonwoven fabrics have been proposed in which the average number of fibers in the bundle is in a specific range.
  • a carbon fiber nonwoven fabric in which carbon fiber bundles in the carbon fiber nonwoven fabric are thin and the proportion of the bundle is small and the carbon fibers are opened is a carbon fiber composite produced using the carbon fiber nonwoven fabric.
  • the mechanical properties of the molded material are excellent, but the fluidity during molding is low and the moldability is poor. This is because the carbon fibers, which are reinforcing fibers, are sufficiently dispersed, making it difficult for stress to concentrate, and while the carbon fiber reinforcement effect is sufficiently exerted, the carbon fibers cross each other and restrict each other's movement. This is because it becomes difficult to move.
  • Patent Document 2 the ratio of the same specific carbon fiber bundle in the carbon fiber nonwoven fabric to the total amount of fibers is set higher, and the average number of fibers in the specific carbon fiber bundle is set to another specific range.
  • Composite materials have been proposed.
  • the carbon fiber nonwoven fabric having a thick carbon fiber bundle and a large proportion of the bundle as described in Patent Document 2 has a high fluidity when it is used to produce a carbon fiber composite material molded product. Excellent mechanical properties but low mechanical properties and large variation. This is because the carbon fiber bundle is thick, so that the resin impregnation into the bundle is poor, and stress tends to concentrate on the end of the carbon fiber, but the carbon fiber does not form a network and is easy to move.
  • the object of the present invention is to achieve both high fluidity and mechanical properties when molding a carbon fiber composite material, which could not be achieved by the conventional carbon fiber nonwoven fabric as described above, and there is little variation in mechanical properties, and the carbon fiber mat.
  • An object of the present invention is to provide a carbon fiber non-woven fabric having excellent shapeability.
  • the carbon fiber nonwoven fabric according to the present invention has the following configuration.
  • the number average of carbon fibers constituting the carbon fiber bundle (1) having 90 or more fibers is in the range of 90 to 1000 / bundle, and the number of carbon fibers constituting the carbon fiber bundle (1).
  • the carbon fiber nonwoven fabric is characterized in that the standard deviation ⁇ is in the range of 50 to 500.
  • the number average x of the number of carbon fibers constituting the carbon fiber bundle (1) having 90 or more carbon fibers constituting the carbon fiber bundle is in the range of 90 to 1000 / bundle.
  • the carbon fiber nonwoven fabric according to (3), wherein the compound having a plurality of epoxy groups is a compound having an epoxy group only at both ends of the longest atomic chain.
  • the carbon fiber nonwoven fabric according to (1) or (3), wherein the aliphatic compound having a plurality of epoxy groups has 20 to 200 atoms in the longest atomic chain.
  • the aliphatic compound having a plurality of epoxy groups is at least one compound selected from glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol diglycidyl ethers, and polypropylene glycol diglycidyl ethers.
  • (11) A carbon fiber nonwoven fabric containing carbon fiber, wherein the carbon fiber contains at least one compound selected from chemical formulas (III), (IV) and (V) represented by the following chemical formulas (3) to (5): A carbon fiber bundle in which the number of carbon fibers constituting the carbon fiber bundle is 90 or more out of the carbon fiber bundles in the carbon fiber non-woven fabric.
  • the number average x of the number of carbon fibers constituting (1) is in the range of 90 to 1000 / bundle, and the standard deviation ⁇ of the number of carbon fibers constituting the carbon fiber bundle (1) is in the range of 50 to 500.
  • R 1 is H, OH, the following chemical formula 6 or the following chemical formula 7,
  • R 2 is H or OH, m and n are 1 to 49, and m + n is 10 to 50.
  • the carbon fiber non-woven fabric has a drape value (cm) at 25 ° C./single yarn bending rigidity (Pa ⁇ cm 4 ) of 1.4 ⁇ 10 3 to 4.0 ⁇ 10 3 (cm / (Pa ⁇ cm 4 ))
  • the single fiber bending rigidity of the carbon fibers constituting the carbon fiber nonwoven fabric is in the range of 1.0 ⁇ 10 ⁇ 11 to 2.8 ⁇ 10 ⁇ 11 (Pa ⁇ m 4 ), (1) to (14)
  • the carbon fiber nonwoven fabric in any one of.
  • the fiber length Ln (quantity average fiber length) of the carbon fibers constituting the carbon fiber nonwoven fabric is in the range of 3 to 50 mm,
  • the carbon fiber nonwoven fabric according to the present invention when a carbon fiber composite material is molded using the nonwoven fabric, high fluidity and high mechanical properties can be achieved at the same time. It is possible to provide a carbon fiber nonwoven fabric excellent in carbon fiber followability.
  • the carbon fiber used in the present invention is not particularly limited, but high-strength, high-modulus carbon fibers can be used, and these may be used alone or in combination of two or more.
  • PAN-based, pitch-based, rayon-based carbon fibers and the like can be mentioned.
  • PAN-based carbon fibers are more preferable.
  • the density of the carbon fiber is preferably one having 1.65 ⁇ 1.95g / cm 3, further more preferably from 1.70 ⁇ 1.85g / cm 3. When the density is too high, the resulting carbon fiber reinforced plastic is inferior in light weight performance, and when the density is too low, the resulting carbon fiber reinforced plastic may have low mechanical properties.
  • the carbon fiber is preferably a bundle from the viewpoint of productivity, and a fiber having a large number of single yarns in the bundle is preferable.
  • the number of single yarns can be used within the range of 1000 to 350,000, and it is particularly preferable to use within the range of 10,000 to 100,000.
  • the single fiber bending stiffness of the carbon fiber is preferably in the range of 1.0 ⁇ 10 ⁇ 11 to 2.8 ⁇ 10 ⁇ 11 Pa ⁇ m 4 , more preferably 1.0 ⁇ 10 ⁇ 11 to 1.5. X10 ⁇ 11 Pa ⁇ m 4 is preferable.
  • the quality of the obtained carbon fiber nonwoven fabric can be stabilized in the step of producing the carbon fiber nonwoven fabric described later.
  • the carbon fiber is preferably surface-treated for the purpose of improving the adhesion between the carbon fiber and the matrix resin when forming the carbon fiber composite material.
  • surface treatment methods include electrolytic treatment, ozone treatment, and ultraviolet treatment.
  • carbon fiber is sized with the aliphatic compound which has several epoxy groups.
  • the aliphatic compound means an acyclic linear saturated hydrocarbon, a branched saturated hydrocarbon, an acyclic linear unsaturated hydrocarbon, a branched unsaturated hydrocarbon, or carbon of the hydrocarbon.
  • a chain structure in which atoms (CH 3 , CH 2 , CH, C) are replaced with oxygen atoms (O), nitrogen atoms (NH, N), sulfur atoms (SO 3 H, SH), and carbonyl groups (CO). refers to a compound.
  • the aliphatic compound having a plurality of epoxy groups is preferably a compound having an epoxy group at both ends of the longest atomic chain, and particularly a compound having an epoxy group only at both ends of the longest atomic chain.
  • the largest atomic chain among the total number of carbon atoms and hetero atoms (oxygen atoms, nitrogen atoms, etc.) constituting a chain structure connecting two epoxy groups Is called the longest atomic chain
  • the total number of atoms constituting the longest atomic chain is called the number of atoms in the longest atomic chain.
  • the number of atoms such as hydrogen bonded to the atoms constituting the longest atomic chain is not included in the total number.
  • the structure of the side chain is not particularly limited, but a structure that does not easily become a crosslinking point is preferable in order to prevent the density of intermolecular crosslinking of the sizing agent compound from becoming too large.
  • the sizing agent compound has less than two epoxy groups, the bridging between the carbon fiber and the matrix resin cannot be performed effectively. Therefore, the number of epoxy groups needs to be two or more in order to effectively bridge the carbon fiber and the matrix resin.
  • the density of intermolecular crosslinking of the sizing agent compound is increased, resulting in a brittle sizing layer, resulting in a decrease in the tensile strength of the composite.
  • the two epoxy groups are at both ends of the longest atomic chain. That is, the presence of epoxy groups at both ends of the longest atomic chain prevents the local crosslink density from increasing, which is preferable for the composite tensile strength.
  • the structure of the epoxy group is preferably a highly reactive glycidyl group.
  • the molecular weight of the aliphatic compound is preferably 80 or more and 3200 or less, more preferably 100 or more and 1500 or less, from the viewpoint of preventing the handling property as a sizing agent from being deteriorated due to the resin viscosity being too low or too high. More preferably, it is 200 or more and 1000 or less.
  • aliphatic compound having a plurality of epoxy groups in the present invention include, for example, diglycidyl ether compounds, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether. 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether, and the like.
  • polyglycidyl ether compound glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol poly Examples thereof include glycidyl ethers and polyglycidyl ethers of aliphatic polyhydric alcohols.
  • it is an aliphatic polyglycidyl ether compound having a highly reactive glycidyl group. More preferably, polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, alkanediol diglycidyl ethers and those having the structures shown below are preferred.
  • G is a glycidyl group
  • R 1 is -CH 2 CH 2- , -CH 2 CH 2 CH 2- , -CH (CH 3 ) CH 2-
  • R 2 is -CH 2-
  • R 3 , R 4 , R 5 are at least 2 are -G, the others are -H or -G
  • m is an integer of 1 to 25
  • n is an integer of 2 to 75
  • x, y and z are 0 or a positive integer X + y + z is preferably 0-25.
  • the number of atoms of the longest atomic chain is preferably 20 or more. That is, when the number of atoms is less than 20, the crosslink density in the sizing layer is increased, so that a structure with low toughness is likely to be formed, and as a result, composite tensile strength may not be easily exhibited.
  • the number of atoms in the longest atomic chain is large, the sizing layer tends to be flexible and highly tough, and as a result, the composite tensile strength is likely to be improved, and the tensile strength of brittle resin is particularly high. More preferably, the number of atoms of the longest atomic chain is 25 or more, and more preferably 30 or more.
  • the number of atoms in the longest atomic chain the more flexible the structure will be, but if it is too long, it will bend and seal the functional group, resulting in a decrease in the adhesion between the carbon fiber and the resin.
  • the number of atoms is 200 or less, more preferably 100 or less.
  • the aliphatic compound contains a cycloaliphatic skeleton
  • it can be used as long as the epoxy group is sufficiently away from the cyclic skeleton, specifically, if the number of atoms is 6 or more.
  • an aromatic compound having a plurality of epoxy groups having 6 or more atoms between the epoxy group and the aromatic ring is used as a sizing agent.
  • the number of atoms between the epoxy group and the aromatic ring refers to the total number of carbon atoms, heteroatoms (oxygen atoms, nitrogen atoms, etc.), and carbonyl atomic groups constituting the chain structure connecting the epoxy group and the aromatic ring.
  • the number of atoms between the epoxy group and the aromatic ring is less than 6 as a sizing agent, a rigid and sterically large compound is interposed at the interface between the carbon fiber and the matrix resin.
  • the reactivity with the surface functional groups present in the substrate is not improved, and as a result, the improvement of the lateral characteristics of the composite material cannot be expected.
  • R 1 is the following chemical formula 10;
  • R 2 is an alkylene group having 2 to 30 carbon atoms
  • R 3 is —H or —CH 3
  • m and n are integers of 2 to 48
  • m + n is 4 to 50.
  • m and n in the formula [I] are each 2 or more, preferably 3 or more, more preferably 5 or more, and m + n is 4 or more, preferably 6 or more, more preferably 10 or more. In the case where m and n are each less than 2 or m + n is less than 4, the adhesion between the matrix resin and the carbon fiber, which is the object of the present invention, may be lowered.
  • R 2 is preferably —CH 2 CH 2 — or —CH (CH 3 ) CH 2 —.
  • the bisphenol A part or F part in the above formula [I] has the effect of improving the compatibility with the matrix resin and the effect of improving the fluff resistance.
  • the skeleton of the aromatic compound having a plurality of epoxy groups having 6 or more atoms between the epoxy group and the aromatic ring may be a condensed polycyclic aromatic compound.
  • the skeleton of the condensed polycyclic aromatic compound include naphthalene, anthracene, phenanthrene, chrysene, pyrene, naphthacene, triphenylene, 1,2-benzanthracene, benzopyrene, and the like. Naphthalene, anthracene, phenanthrene, and pyrene having a small skeleton are preferable.
  • the epoxy equivalent of the condensed polycyclic aromatic compound having a plurality of epoxy groups is preferably in the range of 150 to 350, more preferably 200 to 300, from the viewpoint of sufficient adhesive improvement effect.
  • the molecular weight of the condensed polycyclic aromatic compound having a plurality of epoxy groups is in the range of 400 to 800, more preferably 400 to 600, from the viewpoint of preventing the resin viscosity from increasing and handling properties as a sizing agent from deteriorating. It is preferable.
  • the sizing agents as described above include “Epicoat” 828, “Epicoat” 834 and other low molecular weight bisphenol type epoxy compounds, linear low molecular weight epoxy compounds, polyethylene glycol, polyurethane, polyester, emulsifiers, surfactants, etc. These components may be added for the purpose of adjusting viscosity, improving scratch resistance, improving fuzz resistance, improving convergence, improving higher-order workability, and the like.
  • the amount of the sizing agent attached to the carbon fiber is 0.01% by weight or more per unit weight of the carbon fiber from the viewpoint of increasing the range of improvement in adhesion to the resin, while preventing the consumption of the sizing agent from becoming excessive. % By weight or less is preferable, 0.05% by weight or more and 5% by weight or less is more preferable, and 0.1% by weight or more and 2% by weight or less is more preferable.
  • the sizing agent is preferably uniformly coated and coated. That is, it is preferable that the thickness of the sizing agent layer is 20 to 200 ⁇ , and the maximum value of the thickness does not exceed twice the minimum value. By such a uniform sizing agent layer, the coupling effect can be expressed more effectively.
  • the carbon fiber nonwoven fabric according to the third aspect of the present invention, at least one selected from the chemical formulas (III), (IV) and (V) shown in the chemical formulas (3) to (5) described above for the carbon fibers of the carbon fiber nonwoven fabric.
  • a certain specific compound (hereinafter sometimes simply referred to as a sizing agent) is deposited in an amount of 0.1 to 5.0% by weight based on 100% by weight of the carbon fiber.
  • the polyethylene oxide or / and polypropylene oxide part in such a compound has the effect of imparting smoothness to the carbon fiber and lowering the friction coefficient, and when the carbon fiber nonwoven fabric described later is used, the frictional force due to the entanglement of the carbon fibers. Can be reduced, and fluidity and shaping can be improved.
  • the bisphenol A part has the effect of improving the compatibility with the matrix resin.
  • a compound having m + n of less than 10 in the chemical formula is not preferable because the effect of reducing the friction coefficient is small. Further, if m + n exceeds 50, the compatibility with the matrix resin is lowered, and the adhesiveness between the matrix resin and the carbon fiber is lowered, which is not preferable.
  • the sizing agent treatment as described above generally includes a sizing agent after drying a water-wet carbon fiber bundle having a moisture content of about 20 to 80% by weight wetted by water in a known surface treatment process and water washing process.
  • a processing method for adhering a liquid (sizing liquid) to be applied can be applied.
  • the means for applying the sizing agent there are no particular restrictions on the means for applying the sizing agent, but there are, for example, a method of immersing in a sizing liquid through a roller, a method of contacting a roller to which the sizing liquid is adhered, and a method of spraying the sizing liquid in a mist form. .
  • a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable.
  • it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the carbon fiber is uniformly attached within an appropriate range.
  • the drying temperature and drying time should be adjusted according to the amount of the compound attached, the time required for complete removal of the solvent used for applying the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented, and carbon
  • the drying temperature is preferably 130 ° C. or higher and 350 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower.
  • Examples of the solvent used for the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone, and the like. Water is preferable from the viewpoint of easy handling and disaster prevention. Therefore, when a compound insoluble or hardly soluble in water is used as a sizing agent, it is preferable to add an emulsifier, a surfactant or the like to make it water dispersible.
  • an anionic emulsifier such as styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate, sodium polyacrylate
  • Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc.
  • Nonionic emulsifiers having a small interaction are preferable.
  • the sizing agent adhesion amount is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 2% by mass with respect to the mass of the carbon fiber alone. More preferably, it is applied in an amount of mass% or less. If it is 0.01% by mass or less, the effect of improving adhesiveness is hardly exhibited. If it is 10 mass% or more, the mechanical properties may be lowered when the carbon fiber nonwoven fabric is formed into a carbon fiber composite material molded product.
  • the carbon fiber bundle is obtained by dividing the drape value, which is an index representing the hardness of the carbon fiber bundle, by the single yarn bending stiffness, and the drape value / single yarn bending stiffness is 1.4 ⁇ 10. It is preferably in the range of 3 to 4.0 ⁇ 10 3 cm / (Pa ⁇ cm 4 ), more preferably in the range of 1.5 ⁇ 10 3 to 3.0 ⁇ 10 3 cm / (Pa ⁇ cm 4 ). It is.
  • the fiber When the drape value / single yarn bending rigidity is less than 1.4 ⁇ 10 3 cm / (Pa ⁇ cm 4 ), the fiber has poor convergence, and the fibers are used in a process of obtaining a carbon fiber nonwoven fabric such as airlaid or carding described later. It is easy to open, and the moldability may deteriorate when a carbon fiber composite material is used.
  • the carbon fiber composite material exceeds 4.0 ⁇ 10 3 cm / (Pa ⁇ cm 4 )
  • the matrix resin is formed when the carbon fiber composite material is used. There is a possibility that the wettability will deteriorate and the mechanical properties will deteriorate.
  • Examples of the process for obtaining the carbon fiber nonwoven fabric include carding and airlaid.
  • Carding as used in the present invention refers to an operation of aligning discontinuous fibers or opening fibers by applying a force in approximately the same direction in a comb-like discontinuous fiber assembly. Say. Generally, it is carried out using a carding apparatus having a roll having a large number of needle-like projections on the surface and / or a roll around which a metallic wire having a saw-like projection of a saw is wound.
  • the rotation speed of the cylinder roll is preferably rotated at a high rotation speed such as 150 rpm or more.
  • the surface speed of the doffer roll is preferably a high speed such as 10 m / min or more.
  • the carding apparatus 1 includes a cylinder roll 2, a take-in roll 3 provided on the upstream side near the outer peripheral surface, and a downstream side opposite to the take-in roll 3. And a plurality of worker rolls provided close to the outer peripheral surface of the cylinder roll 2 between the take-in roll 3 and the doffer roll 4. 5, a stripper roll 6 provided close to the worker roll 5, a feed roll 7 and a belt conveyor 8 provided close to the take-in roll 3.
  • a discontinuous carbon fiber bundle 9 is supplied to the belt conveyor 8, and the carbon fiber bundle 9 is introduced onto the outer peripheral surface of the cylinder roll 2 through the outer peripheral surface of the feed roll and then the outer peripheral surface of the take-in roll 3. Up to this stage, the carbon fiber bundle is unwound and becomes an aggregate of cotton-like carbon fiber bundles. A part of the aggregate of cotton-like carbon fiber bundles introduced on the outer peripheral surface of the cylinder roll 2 is wound around the outer peripheral surface of the worker roll 5, and this carbon fiber is peeled off by the stripper roll 6 and again the cylinder roll. 2 is returned to the outer peripheral surface.
  • a large number of needles and protrusions are present on the outer peripheral surface of each of the feed roll 7, the take-up roll 3, the cylinder roll 2, the worker roll 5 and the stripper roll 6, and the carbon fiber is
  • the bundle is opened to a predetermined bundle by the action of the needle and oriented to some extent.
  • the fiber bundle is opened to a predetermined carbon fiber bundle, and moves on the outer peripheral surface of the doffer roll 4 as a sheet-like web 10 which is one form of the carbon fiber aggregate.
  • Airlaid is a method for producing a nonwoven fabric of short fibers, and a general one can be used without any particular limitation.
  • Examples of general airlaid methods include the Honshu Paper Manufacturing Method, the Croyer Method, the Dunweb Method, the J & J Method, the KC Method, and the Scott Method.
  • the airlaid device 11 includes a cylindrical drum 12 having pores that rotate in reverse to each other and a pin cylinder 13 installed in each drum 12, and a carbon fiber together with a large amount of air.
  • a single bundle or a carbon fiber bundle and a thermoplastic resin fiber are blown to the drum 12, opened by the pin cylinder 13 in the drum 12, discharged from the pores, and dropped onto the wire 14 that travels thereunder.
  • air used for air blowing is sucked into a suction box 15 installed under the wire 14, and the opened carbon fiber bundle alone or the opened carbon fiber bundle and the thermoplastic resin fiber remains on the wire 4.
  • Forming a carbon fiber nonwoven fabric is blown into a suction box 15 installed under the wire 14, and the opened carbon fiber bundle alone or the opened carbon fiber bundle and the thermoplastic resin fiber remains on the wire 4.
  • the carbon fiber non-woven fabric referred to here refers to a thin carbon fiber bundle that retains its shape due to entanglement or friction between fibers in a state where discontinuous carbon fiber bundles are opened and oriented by airlaid or carding. Examples thereof include sheet-like webs and nonwoven fabrics obtained by laminating and adhering webs as necessary.
  • the obtained carbon fiber non-woven fabric is preferably obtained by air laid from the viewpoint of preventing the carbon fiber from being bent or bent, and having a good flowability when the inter-fiber entanglement force is reduced to a carbon fiber composite material. From the viewpoint of sex, it is preferable to obtain by carding.
  • the carbon fiber nonwoven fabric may be composed only of carbon fibers, but may also contain thermoplastic resin fibers and / or thermoplastic resin particles.
  • thermoplastic resin fibers is preferable because the carbon fibers can be prevented from breaking in the airlaid and carding steps. Since carbon fiber is rigid and brittle, it is difficult to be entangled and easily broken. Therefore, there is a problem that a carbon fiber non-woven fabric made of only carbon fibers is easily cut during the production or the carbon fibers are easily dropped.
  • thermoplastic fibers and / or thermoplastic resin particles are contained, and heat fusion is performed by pressure bonding or heat treatment with a heat calender roller or heat embossing roller in a subsequent process, fibers with a needle punch, water jet needle, or the like.
  • the handling property of the carbon fiber nonwoven fabric can be improved by the method of entanglement.
  • a carbon fiber aggregate with high uniformity can be formed by including thermoplastic resin fibers that are flexible, difficult to break, and easily entangled.
  • the carbon fiber content in the carbon fiber aggregate is preferably 20 to 95% by mass, more preferably 50 to 95% by mass, More preferably, it is 70 to 95% by mass. If the proportion of carbon fibers is low, it will be difficult to obtain high mechanical properties when a carbon fiber composite material is used. Conversely, if the proportion of thermoplastic resin fibers is too low, the uniformity of the above-mentioned carbon fiber aggregate will be improved. The effect is not obtained.
  • the carbon fiber bundle in the carbon fiber nonwoven fabric has a number average x of the number of carbon fibers constituting the carbon fiber bundle (1) in which the number of carbon fibers constituting the carbon fiber bundle is 90 or more in the range of 90 to 1000. is there.
  • the number average x of the number of carbon fibers constituting the bundle is in the range of 90 to 600. It is preferably some, more preferably in the range of 90 to 500.
  • the number average x is preferably in the range of 300 to 1000, more preferably 500 to 1000.
  • the number average x of the carbon fiber bundles is less than 90, the number of entanglements between the fibers increases and the fluidity deteriorates.
  • the number exceeds 1000 the mechanical properties and the carbon fiber followability to fine parts such as ribs are deteriorated, and the variation in mechanical properties becomes large.
  • the carbon fiber bundle in the carbon fiber nonwoven fabric has a ratio of the carbon fiber bundle (1) having 90 or more carbon fibers constituting the carbon fiber bundle to the total carbon fiber weight in the carbon fiber nonwoven fabric of not less than 5% by weight. It is preferable that it is below wt%. From the viewpoint of improving the strength utilization rate of the carbon fiber and the surface appearance of the molded product, the content is preferably 5% by weight or more and 50% by weight or less, more preferably 5% by weight or more and 45% by weight or less. From the viewpoint of further improving the fluidity, increasing the carbon fiber content when the carbon fiber composite material is obtained, and obtaining a high elastic modulus, it is preferably more than 30% by weight and 80% by weight or less, more preferably 35% by weight.
  • the proportion of the carbon fiber bundle (1) is less than 5% by weight, the number of entangled fibers increases and the fluidity deteriorates. If it exceeds 80% by weight, the mechanical properties and the ability to follow carbon fibers to fine parts such as ribs are deteriorated, and the variation in mechanical properties becomes large.
  • the standard deviation ⁇ of the number xn of carbon fibers constituting the carbon fiber bundle described later satisfies the range of 50 ⁇ ⁇ ⁇ 500, and the carbon fiber bundle is a carbon fiber nonwoven fabric.
  • the standard deviation ⁇ is preferably in the range of 100 ⁇ ⁇ ⁇ 350, more preferably in the range of 150 ⁇ ⁇ ⁇ 350, and still more preferably in the range of 150 ⁇ ⁇ ⁇ 300.
  • the fiber length of the thermoplastic resin fiber is within a range in which the object of the present invention can be achieved such as maintaining the shape of the carbon fiber aggregate and preventing the carbon fiber from falling off. If there is no particular limitation, thermoplastic resin fibers of about 3 to 100 mm can be generally used. In addition, the fiber length of the thermoplastic resin fiber can be relatively determined according to the fiber length of the carbon fiber.
  • thermoplastic resin fiber for the purpose of enhancing the entanglement effect by the thermoplastic resin fiber.
  • the degree of crimp is not particularly limited as long as the object of the present invention can be achieved.
  • thermoplastic resin fibers having a number of crimps of about 5 to 25 crests / 25 mm and a crimp ratio of about 3 to 30%. Can be used.
  • thermoplastic resin particles When the thermoplastic resin particles are included in the carbon fiber aggregate, the thermoplastic resin particles may be spherical, strip-like, or cylindrical like pellets.
  • a preferable average particle diameter in the case of a sphere is 0.01 to 1000 ⁇ m.
  • the material of the thermoplastic resin fiber as described above is not particularly limited, and can be appropriately selected as long as the mechanical properties are not greatly deteriorated when the carbon fiber composite material is formed.
  • polyolefin resins such as polyethylene and polypropylene
  • polyamide resins such as nylon 6, nylon 6,6, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyether ketone, polyether sulfone, aromatic polyamide, etc.
  • a fiber obtained by spinning a resin of the above can be used. It is preferable that the material of the thermoplastic resin fiber is appropriately selected and used depending on the combination of matrix resins.
  • thermoplastic resin fiber using the same resin as the matrix resin, a resin compatible with the matrix resin, or a resin having high adhesiveness with the matrix resin is preferable because it does not deteriorate the mechanical properties of the carbon fiber reinforced plastic.
  • the thermoplastic resin fiber is preferably at least one fiber selected from the group consisting of polyamide fiber, polyphenylene sulfide fiber, polypropylene fiber, polyether ether ketone fiber and phenoxy resin fiber.
  • a carbon fiber nonwoven fabric containing a thermoplastic resin fiber is prepared, and the thermoplastic resin fiber contained in the carbon fiber nonwoven fabric may be used as it is as the matrix resin.
  • a carbon fiber non-woven fabric that does not contain thermoplastic resin fibers may be used as a raw material, and the matrix resin may be impregnated at an arbitrary stage for producing a carbon fiber composite material.
  • a matrix resin can also be impregnated in the arbitrary steps which manufacture a carbon fiber composite material.
  • the resin constituting the thermoplastic resin fiber and the matrix resin may be the same resin or different resins. When the resin constituting the thermoplastic resin fiber is different from the matrix resin, it is preferable that both have compatibility or higher affinity.
  • the carbon fiber nonwoven fabric as described above is impregnated with a thermoplastic resin as a matrix resin, and the impregnation step to make the carbon fiber composite material can be carried out using a press machine having a heating function.
  • the press machine is not particularly limited as long as it can realize the temperature and pressure necessary for impregnation with the matrix resin, and a normal press machine having a flat platen that moves up and down, and a mechanism in which a pair of endless steel belts travel.
  • a so-called double belt press machine having the following can be used.
  • the matrix resin can be formed into a sheet shape such as a film, a nonwoven fabric, or a woven fabric, and then laminated with the carbon fiber nonwoven fabric, and in that state, the matrix resin can be melted and impregnated using the above-described press machine or the like.
  • discontinuous fibers are produced using a matrix resin, and a carbon fiber nonwoven fabric containing matrix resin and inorganic fibers is produced by mixing with inorganic fibers in the process of producing the carbon fiber nonwoven fabric.
  • a method of heating and pressurizing using a press machine or the like can also be employed.
  • the number of carbon fiber single yarns x n Mn / (Ln ⁇ F) constituting the carbon fiber bundle is calculated for each bundle.
  • F is the fineness of the carbon fiber
  • x n is the number of single yarns constituting the carbon fiber bundle.
  • the carbon fiber bundle constituted a single yarn number x n is more than 90 pieces of carbon fiber bundle and carbon fiber bundle (1), the total weight as M 1, a bundle total number as N, measured.
  • the carbon fiber bundle under construction single yarn number x n is 90 present a fiber bundle (2), the total weight of the carbon fiber bundle (2) as M 2, is measured. Fiber bundles opened to such an extent that they cannot be extracted with tweezers were collectively measured and finally weighed.
  • the fiber length is classified at intervals of about 0.2 mm, the weight is measured for a bundle of a plurality of classified bundles, and an average value may be used. .
  • N is the total number of bundles of carbon fiber bundles (1).
  • the ratio of the carbon fiber bundle (A) to the total weight of the carbon fiber bundle is M 1 / (M 1+ M 2 ) ⁇ 100 Sought by.
  • Vf carbon fiber content in the carbon fiber composite material
  • Fiber strength utilization rate bending strength / Vf
  • Drape Value / Single Yarn Bending Rigidity By dividing the single yarn bending stiffness from the drape value representing the hardness of the carbon fiber bundle, it was used as an index of convergence of the sizing agent (Sz agent).
  • Drape value of carbon fiber bundle As shown in FIG. 3 (A), the carbon fiber bundle 21 drawn out from the bobbin without applying tension is cut to a length of 40 cm, one end is fixed with a stop tape 22, and a 100 g weight 23 is suspended at the other end. After correcting the twist and the bend, it is left for 30 minutes in the atmosphere of the measurement temperature. Next, the weight 23 is removed and, as shown in FIG. 3 (B), the carbon fiber bundle 25 is placed so that it protrudes 25 cm from the horizontal rectangular base 24 having a corner of 90 ° so that the 40 cm carbon fiber bundle does not break.
  • Friction coefficient (3 / 8 ⁇ ) ln (T 2 / T 1 ) T 1 : Yarn entry side tension T 2 : Yarn exit side tension
  • the resin component is 1% by weight as a sizing agent for a continuous carbon fiber bundle having a fiber diameter of 7 ⁇ m, a tensile elastic modulus of 230 GPa, a single yarn bending rigidity of 2.71 ⁇ 10 ⁇ 11 Pa ⁇ m 4 , and 24,000 filaments.
  • glycerol triglycidyl ether was diluted with dimethylformamide (hereinafter abbreviated as DMF) to prepare a sizing agent mother liquor, a sizing agent was applied to the carbon fiber by a dipping method, and drying was performed at 230 ° C.
  • the adhesion amount was 0.4% by weight.
  • Carbon fiber bundle (B) A carbon fiber bundle was obtained in the same manner as the carbon fiber bundle (A) except that the sizing agent was changed to glycerol diglycidyl ether.
  • Carbon fiber bundle (D) A carbon fiber bundle was obtained in the same manner as the carbon fiber bundle (A) except that the sizing agent was changed to diglycerol polyglycidyl ether.
  • Carbon fiber bundle (E) A carbon fiber bundle was obtained in the same manner as the carbon fiber bundle (A) except that the sizing agent was changed to diethylene glycol diglycidyl ether.
  • the carbon fiber bundle (A) is the same as the carbon fiber bundle (A) except that the sizing agent is changed to bisphenol A type diglycidyl ether having an aromatic ring, “Epicoat” 828 (epoxy compound having an aromatic ring) manufactured by Yuka Shell Epoxy Co., Ltd. Got a bunch.
  • Carbon fiber bundle (G) A carbon fiber bundle was obtained in the same manner as the carbon fiber bundle (A) except that it was changed to phenol novolak glycidyl ether and “Epicoat” 154 (epoxy compound having an aromatic ring) manufactured by Yuka Shell Epoxy.
  • Example 1 The carbon fiber bundle (A) was cut to a fiber length of 15 mm, and the cut carbon fiber bundle (A) and nylon 6 short fiber (short fiber fineness 1.7 dtex, cut length 51 mm, crimp number 12 peaks / 25 mm, crimp rate 15%) was mixed at a mass ratio of 90:10 and charged into a carding apparatus.
  • the web that came out was cross-wrapped to form a sheet-like carbon fiber nonwoven fabric having a weight per unit area of 100 g / cm 2 composed of a carbon fiber bundle (A) and nylon 6 fibers.
  • the ratio of the carbon fiber bundle (1) to the total weight of the carbon fibers in the carbon fiber nonwoven fabric was 18% by weight, the number average x of the number of carbon fibers constituting the bundle was 160, and the standard deviation ⁇ was 70.
  • the winding direction of the sheet-like carbon fiber nonwoven fabric is 0 °
  • the carbon fiber nonwoven fabric is laminated at 0 ° / 90 °
  • the volume ratio of the carbon fiber to the thermoplastic resin is 30:70 in the laminated carbon fiber nonwoven fabric as a whole.
  • Example 2 The carbon fiber non-woven fabric was formed such that the ratio of the carbon fiber bundle (1) to the total weight of the carbon fibers in the carbon fiber non-woven fabric was 40% by weight, the number average x of the number of carbon fibers constituting the bundle was 320, and the standard deviation ⁇ was 200. Except for this, the procedure was the same as in Example 1. When the bending strength and fluidity in the 0 ° and 90 ° directions of the obtained flat plate were measured, the average value of the bending strength in the 0 ° and 90 ° directions was 480 MPa, and the fiber strength utilization rate was 16.0 MPa /%, A good product having a CV value of less than 5% and a fluidity of 290% could be obtained.
  • Example 3 A carbon fiber non-woven fabric was formed in which the ratio of the carbon fiber bundle (1) to the total weight of the carbon fibers in the carbon fiber non-woven fabric was 62% by weight, the number average x of the number of carbon fibers constituting the bundle was 615, and the standard deviation ⁇ was 320. Except for this, the procedure was the same as in Example 1. When the bending strength and fluidity in the 0 ° and 90 ° directions of the obtained flat plate were measured, the average value of the bending strength in the 0 ° and 90 ° directions was 463 MPa, and the fiber strength utilization rate was 15.4 MPa /%, A good product having a CV value of less than 5% and a fluidity of 313% could be obtained.
  • Examples 4-7, Comparative Examples 1-2 Compared to Example 2, the carbon fiber bundle (A) is changed to carbon fiber bundles (B), (C), (D), (E), (F), and (G) as shown in Table 1 and Table 2. In the same manner as in Example 2, a carbon fiber composite material flat plate made of a carbon fiber nonwoven fabric and a carbon fiber nonwoven fabric was obtained. Conditions, measurements, and evaluation results are shown in Table 1 and Table 2 together.
  • Comparative Example 3 A carbon fiber nonwoven fabric having a carbon fiber bundle (1) ratio of 84% by weight with respect to the total weight of carbon fibers in the carbon fiber nonwoven fabric, a number average x of the number of carbon fibers constituting the bundle was 1100, and a standard deviation ⁇ was 630 was formed. Except for this, the procedure was the same as in Example 1.
  • the average value of the bending strength in the 0 ° and 90 ° directions was 300 MPa, and the fiber strength utilization rate was 10.0 MPa /%,
  • the CV value is less than 5%, the fluidity is 320%, and the fluidity is excellent, but the bending strength and fiber utilization are low, the variation is large, and the mechanical properties are inferior.
  • Carbon fiber bundle (A1) For a continuous carbon fiber bundle having a fiber diameter of 7 ⁇ m, a tensile elastic modulus of 230 GPa, a single yarn bending rigidity of 2.71 ⁇ 10 ⁇ 11 Pa ⁇ m 4 , and a number of filaments of 24,000, as a sizing agent, R in the above-mentioned formula [I] 2 is -CH 2 CH 2- , R 3 is -CH 3 , m is 2 and n is 2, and a sizing agent is added to the carbon fiber by dipping a 1% by weight water emulsion of the resin component of the sizing agent. And drying at 180 ° C. The adhesion amount was 0.8% by weight.
  • Carbon fiber bundle (B1) Carbon fiber bundle (A1) except that the sizing agent is changed to a sizing agent in which R 2 is -CH 2 CH 2- , R 3 is -CH 3 , m is 5 and n is 5 in the above-mentioned formula [I]. And a carbon fiber bundle was obtained.
  • Carbon fiber bundle (C1) Carbon fiber bundle (A1), except that the sizing agent is changed to a sizing agent in which R 2 is -CH 2 CH 2- , R 3 is -CH 3 , m is 10 and n is 10 in the above formula [I] And a carbon fiber bundle was obtained.
  • Carbon fiber bundle (D1) The carbon fiber bundle (A1) except that the sizing agent was changed to a sizing agent in which R 2 is —CH 2 CH 2 —, R 3 is —H, m is 15 and n is 15 in the formula [I] described above. In the same manner, a carbon fiber bundle was obtained.
  • Carbon fiber bundle (E1) The sizing agent is the same as the carbon fiber bundle (A1) except that in the above formula [I], R 2 is —CH 2 CH 2 —, R 3 is —CH 3 , m is 30 and n is 30, A carbon fiber bundle was obtained.
  • the sizing agent is a carbon fiber bundle (except for the above formula [I] except that R 1 is —OH, R 2 is —CH 2 CH 2 —, R 3 is —CH 3 , m is 15 and n is 15) A carbon fiber bundle was obtained in the same manner as in A1).
  • Carbon fiber bundle (G1) The sizing agent is the same as that of the carbon fiber bundle (A1) except that in the above formula [I], R 2 is —CH 2 CH 2 —, R 3 is —CH 3 , m is 1 and n is 1. A carbon fiber bundle was obtained.
  • Example 8 The carbon fiber bundle (A1) was cut to a fiber length of 15 mm, and the cut carbon fiber bundle (A) and nylon 6 short fiber (short fiber fineness 1.7 dtex, cut length 51 mm, crimp number 12 peaks / 25 mm, crimp rate 15%) was mixed at a mass ratio of 90:10 and charged into a carding apparatus.
  • the web that came out was cross-wrapped to form a sheet-like carbon fiber nonwoven fabric having a weight per unit area of 100 g / cm 2 composed of carbon fiber bundles (A1) and nylon 6 fibers.
  • the ratio of the carbon fiber bundle (1) to the total weight of the carbon fibers in the carbon fiber nonwoven fabric was 18% by weight, the number average x of the number of carbon fibers constituting the bundle was 160, and the standard deviation ⁇ was 70.
  • the winding direction of the sheet-like carbon fiber nonwoven fabric is 0 °
  • the carbon fiber nonwoven fabric is laminated at 0 ° / 90 °
  • the volume ratio of the carbon fiber to the thermoplastic resin is 30:70 in the laminated carbon fiber nonwoven fabric as a whole.
  • Example 9 The carbon fiber non-woven fabric was formed such that the ratio of the carbon fiber bundle (1) to the total weight of the carbon fibers in the carbon fiber non-woven fabric was 40% by weight, the number average x of the number of carbon fibers constituting the bundle was 320, and the standard deviation ⁇ was 200. Except for this, the procedure was the same as in Example 8. When the bending strength and fluidity in the 0 ° and 90 ° directions of the obtained flat plate were measured, the average value of the bending strength in the 0 ° and 90 ° directions was 461 MPa, the fiber utilization rate was 15.4 MPa /%, CV A good product having a value of less than 5% and a fluidity of 297% could be obtained.
  • Example 10 A carbon fiber non-woven fabric was formed in which the ratio of the carbon fiber bundle (1) to the total weight of the carbon fibers in the carbon fiber non-woven fabric was 62% by weight, the number average x of the number of carbon fibers constituting the bundle was 615, and the standard deviation ⁇ was 320. Except for this, the procedure was the same as in Example 8. When the bending strength and fluidity in the 0 ° and 90 ° directions of the obtained flat plate were measured, the average value of the bending strength in the 0 ° and 90 ° directions was 449 MPa, and the fiber strength utilization rate was 15.0 MPa /%, A good product having a CV value of less than 5% and a fluidity of 318% could be obtained.
  • Examples 11 to 14 and Comparative Examples 4 to 5 For Example 9, the carbon fiber bundle (A1) was changed to carbon fiber bundles (B1), (C1), (D1), (E1), (F1), and (G1) as shown in Tables 3 and 4 In the same manner as in Example 9, a carbon fiber composite material flat plate made of a carbon fiber nonwoven fabric and a carbon fiber nonwoven fabric was obtained. Conditions, measurements, and evaluation results are shown in Table 3 and Table 4 together.
  • Comparative Example 6 A carbon fiber nonwoven fabric having a carbon fiber bundle (1) ratio of 84% by weight with respect to the total weight of carbon fibers in the carbon fiber nonwoven fabric, a number average x of the number of carbon fibers constituting the bundle was 1100, and a standard deviation ⁇ was 630 was formed. Except for this, the procedure was the same as in Example 8.
  • the average value of the bending strength in the 0 ° and 90 ° directions was 300 MPa, and the fiber strength utilization rate was 10.0 MPa /%,
  • the CV value is less than 5%, the fluidity is 332%, and the fluidity is excellent, but the bending strength and fiber strength utilization rate are low, the variation is large, and the mechanical properties are inferior.
  • the adhesion amount, friction coefficient, and drape value of the sizing agent were measured, the adhesion amount was 0.9% by weight, the friction coefficient was 0.23, and the drape value was 5.5 cm.
  • the agent adhesion method was the same as that of the carbon fiber bundle (A2). When the adhesion amount, friction coefficient, and drape value of the sizing agent were measured, the adhesion amount was 0.6% by weight, the friction coefficient was 0.21, and the drape value was 5.0 cm.
  • the agent adhesion method was the same as that of the carbon fiber bundle (A2).
  • the adhesion amount, friction coefficient, and drape value of sizing were measured, the adhesion amount was 0.7% by weight, the friction coefficient was 0.35, and the drape value was 6.2 cm.
  • Example 15 The carbon fiber bundle (A2) is cut to a fiber length of 6 mm, and the cut carbon fiber bundle and nylon 6 short fiber (short fiber fineness 1.7 dtex, cut length 10 mm) are mixed at a mass ratio of 80:20, and airlaid Loaded into the device.
  • the resulting non-woven fabric was heat-treated to form a sheet-like carbon fiber non-woven fabric having a basis weight of 200 g / cm 2 made of carbon fiber and nylon 6 fiber.
  • the ratio of the carbon fiber bundle (1) to the total carbon fiber weight was 13% by weight
  • the number average x of the number of carbon fibers constituting the bundle was 160
  • the standard deviation ⁇ Was 70.
  • the winding direction of the sheet-like carbon fiber aggregate is set to 0 °, the carbon fiber aggregates are laminated in the same direction, and the volume ratio of the carbon fiber to the thermoplastic resin is 30:70 in the whole laminated carbon fiber aggregate.
  • CM1001 nylon resin melt blown nonwoven fabric
  • ⁇ r 2.3, manufactured by Toray Industries, Inc.
  • Examples 16 to 26 The flat plate of the carbon fiber composite material which consists of a carbon fiber nonwoven fabric and a carbon fiber nonwoven fabric was obtained like Example 15 except having changed conditions as shown in Table 5 and Table 6 with respect to Example 15.
  • FIG. Tables 5 and 6 show the conditions, measurements, and evaluation results.
  • Comparative Example 7 The carbon fiber bundle (D2) is cut to a fiber length of 15 mm, and the cut carbon fiber bundle and nylon 6 discontinuous fiber (short fiber fineness 1.7 dtex, cut length 10 mm) are mixed at a mass ratio of 80:20,
  • Example 15 was the same as Example 15 except that the carbon fiber bundle (1) was 23% by weight, the carbon fiber non-woven fabric had a quantity average x of the number of carbon fibers constituting the bundle of 250, and a standard deviation ⁇ of 200.
  • Table 7 shows the conditions, measurements, and evaluation results.
  • the obtained carbon fiber nonwoven fabric is inferior in fluidity.
  • Comparative Example 8 The carbon fiber bundle (E2) is cut to a fiber length of 15 mm, and the cut carbon fiber bundle and nylon 6 discontinuous fiber (short fiber fineness 1.7 dtex, cut length 10 mm) are mixed at a mass ratio of 80:20,
  • Example 15 was the same as Example 15 except that the carbon fiber bundle (1) was 22% by weight, the carbon fiber non-woven fabric had a number average x of the number of carbon fibers constituting the bundle of 260, and a standard deviation ⁇ of 210.
  • Table 7 shows the conditions, measurements, and evaluation results.
  • the obtained carbon fiber nonwoven fabric is inferior in fluidity.
  • Comparative Example 9 The carbon fiber bundle (A2) is cut into a fiber length of 15 mm, and the cut carbon fiber bundle and nylon 6 discontinuous fiber (short fiber fineness 1.7 dtex, cut length 10 mm) are mixed at a mass ratio of 80:20,
  • Example 15 is the same as Example 15 except that the carbon fiber bundle (1) is 80% by weight, the carbon fiber non-woven fabric has a quantity average x of the number of carbon fibers constituting the bundle of 1200, and a standard deviation ⁇ of 630.
  • Table 7 shows the conditions, measurements, and evaluation results.
  • the obtained carbon fiber nonwoven fabric has good fluidity, but also has a low fiber strength utilization rate and a large variation in physical properties.
  • the carbon fiber nonwoven fabric according to the present invention can be applied to the production of any carbon fiber reinforced molded product that cannot be achieved by the prior art and requires both high fluidity and mechanical properties, and small variations in mechanical properties.

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Abstract

L'invention concerne un non-tissé de fibres de carbone dans lequel : les fibres de carbone ont été dimensionnées avec un composé aromatique spécifique ou un composé aliphatique spécifique ayant une pluralité de groupes époxy ; la moyenne numérique x de fibres de carbone constituant un faisceau de fibres de carbone (1), dans lequel le nombre de fibres de carbone constituant le faisceau de fibres de carbone est de 90 ou plus, est dans la plage de 90 à 1 000 fibres par faisceau parmi les faisceaux de fibres de carbone dans le non-tissé de fibres de carbone ; et l'écart-type du nombre de fibres de carbone constituant le faisceau de fibres de carbone (1) est dans la plage de 50 à 500. Il est possible de fournir un non-tissé de fibres de carbone dans lequel une fluidité et des caractéristiques mécaniques élevées sont possibles lorsqu'un matériau composite de fibres de carbone doit être moulé, et qui a d'excellentes propriétés de façonnage pour un mat de fibres de carbone sans variabilité des caractéristiques mécaniques.
PCT/JP2014/057105 2013-03-26 2014-03-17 Non-tissé de fibres de carbone WO2014156760A1 (fr)

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JP2014512995A JP6108240B2 (ja) 2013-03-26 2014-03-17 炭素繊維不織布
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EP3269859A1 (fr) 2016-07-15 2018-01-17 Toray Carbon Fibers Europe Mat aléatoire de fibres de carbone et matériau composite de fibre de carbone
JP7500104B1 (ja) 2023-04-20 2024-06-17 竹本油脂株式会社 炭素繊維含有不織布製造用の処理剤、炭素繊維含有不織布、及び炭素繊維含有不織布の製造方法

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EP2980309A1 (fr) 2016-02-03
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