WO2020196153A1 - Matériau composite renforcé par des fibres de carbone à base de polychlorure de vinyle - Google Patents

Matériau composite renforcé par des fibres de carbone à base de polychlorure de vinyle Download PDF

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Publication number
WO2020196153A1
WO2020196153A1 PCT/JP2020/011966 JP2020011966W WO2020196153A1 WO 2020196153 A1 WO2020196153 A1 WO 2020196153A1 JP 2020011966 W JP2020011966 W JP 2020011966W WO 2020196153 A1 WO2020196153 A1 WO 2020196153A1
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Prior art keywords
vinyl chloride
carbon fiber
chloride resin
resin composition
composite material
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PCT/JP2020/011966
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English (en)
Japanese (ja)
Inventor
亮介 中尾
修平 冠
誉大 山本
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積水化学工業株式会社
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Priority claimed from JP2019057123A external-priority patent/JP7332313B2/ja
Priority claimed from JP2019057105A external-priority patent/JP7332312B2/ja
Priority claimed from JP2019155858A external-priority patent/JP7323384B2/ja
Priority claimed from JP2019155872A external-priority patent/JP7323385B2/ja
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Publication of WO2020196153A1 publication Critical patent/WO2020196153A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • the present invention relates to a carbon fiber reinforced composite material in which a carbon fiber base material is impregnated with a vinyl chloride resin composition.
  • CFRP carbon fiber reinforced composite material composed of carbon fiber and a matrix resin
  • CFRP has high specific strength and specific elastic modulus, excellent mechanical properties, and high functional properties such as weather resistance and chemical resistance. Has. Therefore, CFRP is attracting attention in aircraft structural members, wind turbine blades, automobile outer panels, and general industrial applications, and its demand is increasing year by year.
  • thermosetting resin typified by an epoxy resin which has a low viscosity when impregnated with carbon fibers and has excellent adhesion to carbon fibers has been conventionally known.
  • thermoplastic resins such as polyolefins and polyamide-based polymer alloys have been developed due to the demand for improved impact resistance, high productivity, and interest in recycling.
  • thermoplastic resins may undergo thermal decomposition under high temperature conditions, and many of them have high viscosities even in a molten state, which tends to cause problems such as insufficient resin impregnation.
  • the interfacial adhesiveness between carbon fiber and matrix resin is excellent.
  • the interfacial adhesiveness to carbon fibers is poor, and it is difficult to obtain the expected mechanical properties even if the propylene-based resin and carbon fibers are simply melt-kneaded.
  • a modified propylene resin in which maleic anhydride or the like is graft-bonded to a propylene resin has been developed, and by adding this, the interfacial adhesiveness between the propylene resin and the carbon fiber can be improved. It is planned.
  • CFRP using polyolefin or polyamide polymer alloy as a matrix resin has been put into practical use, but it still has chemical resistance and flame retardancy depending on the matrix resin. Inferior performance was sometimes a problem.
  • Vinyl chloride resin which is a general-purpose thermoplastic resin, is a material that has excellent flame retardancy, durability, oil resistance and chemical resistance, has extremely little creep deformation compared to ethylene-based resin and propylene-based resin, and has excellent mechanical strength. Is known to be.
  • vinyl chloride resin has a high melt viscosity among thermoplastic resins, and the molding processing temperature, that is, the processing temperature when impregnating carbon fibers with vinyl chloride resin is the thermal decomposition temperature of vinyl chloride resin in the production of CFRP. It is presumed that impregnation of carbon fiber is difficult because it is close to, and no practical example has been found.
  • the vinyl chloride resin is only treated as a mixture with a thermosetting resin that dissolves the vinyl chloride resin while remaining in the blending amount as an auxiliary component.
  • vinyl chloride resin is a polar polymer having a chlorine group, it is presumed that it has better interfacial adhesiveness with carbon fibers than propylene resin, which is a non-polar polymer.
  • vinyl chloride resin is prone to thermal decomposition and adhesion to the mold during molding, a heat stabilizer that suppresses the thermal decomposition reaction is blended, and screws and molds that need to be contacted during the molding process.
  • vinyl chloride resins In order to prevent adhesion to the metal surface such as, it is essential to add a lubricant or the like. Therefore, vinyl chloride resins generally have a higher content ratio of additives than other thermoplastic resins. As a result, it is not known at present how the high content of the additive affects the impregnation property and the interfacial adhesiveness of the vinyl chloride resin composition containing a large amount of the additive and the carbon fiber.
  • the vinyl chloride resin composition has a high melt viscosity, low thermal stability, and a high additive content ratio. Therefore, it is presumed that the vinyl chloride-based resin composition is difficult to impregnate the carbon fiber base material and is difficult to composite. At present, it has not been sufficiently investigated and elucidated what kind of vinyl chloride resin composition is suitable for CFRP preparation. Therefore, there is still a demand for a vinyl chloride resin composition having good impregnation property into the carbon fiber base material. Further, there is a demand for CFRP in which a carbon fiber base material is impregnated with such a vinyl chloride resin composition.
  • the vinyl chloride resin composition (A) contains a vinyl chloride resin and at least one additive.
  • the vinyl chloride resin composition (A) and the carbon fiber base material (B) have the following properties (1) and properties (2): -Characteristics (1):
  • the vinyl chloride resin composition (A) has a complex viscosity ⁇ at 200 ° C. and a frequency of 10 Hz of 1 ⁇ ⁇ 1500.
  • the dissolution index (Ra (pi)) calculated from the following formula (I), the Hansen solubility parameter ( ⁇ Di, ⁇ Pi, ⁇ Hi), and the carbon fiber base material (B)
  • the solubility index (Ra (ci)) calculated from the following formula (II) using the Hansen solubility parameter ( ⁇ Dc, ⁇ Pc, ⁇ Hc) of the above, and each additive contained in the vinyl chloride resin composition (A).
  • the value S calculated by the following formula (III) using the weight component C (i) of (i) is 150 or less.
  • ⁇ D, ⁇ P and ⁇ H indicate the dispersion term, the polarity term and the hydrogen bond term in the Hansen solubility parameter, respectively, and the unit is (MPa) 1/2 .
  • the vinyl chloride resin composition (A) has the following characteristics (3): -Characteristics (3): Hansen solubility parameter ( ⁇ Di, ⁇ Pi, ⁇ Hi) of each additive (i) contained in the vinyl chloride resin composition (A), and Hansen solubility parameter of the vinyl chloride resin (p) used.
  • the weight is calculated from the following formulas (IV), (V), and (VI).
  • the Hansen solubility parameter ( ⁇ Dp, ⁇ Pp, ⁇ Hp) of the vinyl chloride resin composition (A) is calculated using the fraction, and the solubility index (Ra) calculated from the following formula (VII) is 7.5 or less. There is.
  • the additives are heat stabilizers, lubricants, processing aids, impact modifiers, heat improvers, antioxidants, ultraviolet absorbers, antistatic agents, light stabilizers, fillers, pigments, flame retardants.
  • the carbon fiber reinforced composite material according to any one of [1] to [3], which is at least one selected from the group consisting of, and a plasticizer.
  • [5] The carbon fiber according to any one of [1] to [4], wherein the vinyl chloride resin composition (A) contains a vinyl chloride resin (p) having an average degree of polymerization of 400 or more and 1500 or less. Reinforced composite material.
  • the total content of the additives is 70 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin, according to [1] to [5].
  • the content of the heat stabilizer is 0.1 to 30 parts by mass, the content of the internal lubricant is 20 parts by mass or less, the content of the external lubricant is 10 parts by mass or less, and the content of the plasticizer is 30.
  • the carbon fiber reinforced composite material according to the present invention is a carbon fiber reinforced composite material composed of a vinyl chloride resin composition (A) and a carbon fiber base material (B). Further, the carbon fiber reinforced composite material according to the present invention is a vinyl chloride resin composition that covers at least a part of the surface of the composite material composed of the vinyl chloride resin composition (A) and the carbon fiber base material (B). It is preferable to further include (C). Further, the carbon fiber reinforced composite material according to the present invention is characterized by satisfying the following properties (1) and (2). The carbon fiber reinforced composite material according to the present invention preferably further satisfies the following property (3).
  • the vinyl chloride resin composition (A) has a complex viscosity ⁇ at 200 ° C. and a frequency of 10 Hz in the range of 1 ⁇ ⁇ 1500.
  • the vinyl chloride resin composition (A) preferably has a complex viscosity ⁇ at 200 ° C. and a frequency of 10 Hz of 10 ⁇ ⁇ ⁇ 1000 Pa ⁇ s, and preferably 20 ⁇ ⁇ ⁇ 800 Pa ⁇ s.
  • the complex viscosity ⁇ is less than 1500 Pa ⁇ s, the resin can be impregnated into the inside of the carbon fiber filament bundle, and the excellent mechanical properties of the carbon fiber can be utilized.
  • the complex viscosity ⁇ is more than 1 Pa ⁇ s, it is possible to obtain the mechanical strength of the matrix resin itself to the extent that the mechanical strength as CFRP is not impaired.
  • n a vinyl chloride resin (p.) ) And the product of Ra (pi) and Ra (ci) calculated with respect to the carbon fiber base material (B) and the weight fraction C (i).
  • the value n multiplied by the product is each.
  • the number of components of the additive (i) is shown.)
  • Hansen solubility parameter ( ⁇ Di, ⁇ Pi, ⁇ Hi) of each additive (i) contained in the vinyl chloride resin composition (A) Hansen solubility parameter of the vinyl chloride resin (p) used.
  • the weight is calculated from the following formulas (IV), (V), and (VI).
  • the Hansen solubility parameter ( ⁇ Dp, ⁇ Pp, ⁇ Hp) of the vinyl chloride resin composition (A) is calculated using the fraction, and the solubility index (Ra) calculated from the following formula (VII) is 7.5 or less.
  • x indicates the number of copies of the vinyl chloride resin added
  • y indicates the total number of copies of the vinyl chloride resin composition
  • z indicates the addition of each compounding agent. Indicates the number of copies.
  • ⁇ D, ⁇ P and ⁇ H indicate the dispersion term, the polarity term and the hydrogen bond term in the Hansen solubility parameter, respectively, and the unit is (MPa) 1/2 .
  • the vinyl chloride resin composition (A) should have excellent interfacial adhesiveness to the surface of the carbon fiber base material (B), that is, it should have high compatibility.
  • HSP Hansen solubility parameter
  • HSP Hansen solubility parameter
  • HSP represents the solubility in the three-dimensional space of the dispersion term ⁇ D, the polar term ⁇ P, and the hydrogen bond term ⁇ H.
  • the dispersion term ⁇ D indicates the effect due to the dispersion force
  • the polar term ⁇ P indicates the effect due to the dipole interdental force
  • the hydrogen bond term ⁇ H indicates the effect due to the hydrogen bond force.
  • the Hildebrand SP value ( ⁇ ) and the Hansen solubility parameter (HSP) are related by the following formula (VIII), and the SP value is the length of the vector of HSP with ⁇ D, ⁇ P, and ⁇ H as three components (totHSP). Corresponds to.
  • HSP is a better method in that it completely includes the information of Hildebrand SP value and can evaluate the solubility including the direction of the vector.
  • Hansen solubility parameter The definition and calculation of the Hansen solubility parameter can be found in Charles M. It is described in Hansen, Hansen Solubility Parameter: A Users Handbook (CRC Press, 2007).
  • HSP Hansen Solubility Parameters in Practice
  • the HSP of a certain solvent that was not used for measuring the HSP of the substance is ⁇ D, ⁇ P, ⁇ H
  • the points indicated by the coordinates are included inside the solubility sphere of the substance. If so, the solvent is considered to dissolve the above substances.
  • the coordinate point is outside the solubility sphere of the substance, it is considered that this solvent cannot dissolve the substance.
  • a carbon material that is insoluble in a general solvent is also a target substance, but in the latter case, the HSP is measured not by its solubility but by the dispersion of the carbon material and the degree of aggregation and sedimentation. Is calculated.
  • the following technical papers are referred to. C. M. Hansen, A. L. Smith, Using Hansen solubility parameters to correlate Solubility of C60 fullerene in organic solvents and carbon (42, pp1591-1597).
  • the distance (Ra) between HSPs in the HSP space is defined by the following mathematical formula (IX), which is a dissolution index of whether or not the two molecules are compatible.
  • ⁇ D1 and ⁇ D2 represent the dispersion terms of two specific molecules in the Hansen solubility parameter.
  • ⁇ P and ⁇ H each represent the polar term and the hydrogen bond term, respectively. The units are both. (MPa) 1/2 .)
  • the compatibility between the vinyl chloride resin composition (A) and the carbon fiber base material (B) is a target, but the present inventors consider vinyl chloride. Since the based resin composition (A) contains a large amount of various additives while containing the vinyl chloride resin (p) as the main component, compatibility between each additive (i) used and the vinyl chloride resin (p) used, It is important to pay attention to the compatibility between each additive (i) used and the carbon fiber base material (B), and the property (2) was invented.
  • the characteristic (2) the Hansen solubility parameter ( ⁇ Di, ⁇ Pi, ⁇ Hi) of each additive (i) contained in the vinyl chloride resin composition (A) and the vinyl chloride resin (p) used.
  • the Hansen solubility parameter ( ⁇ Dp, ⁇ Pp, ⁇ Hp) the dissolution index (Ra (pi)) calculated from the above formula (I), the Hansen solubility parameter ( ⁇ Di, ⁇ Pi, ⁇ Hi), and carbon.
  • Ra is preferably 7.5 or less. Further, Ra is more preferably 7.4 or less. When Ra is 7.5 or less, the influence of the additive (i) exuding near the surface of the vinyl chloride resin composition (A) can be reduced, and as a result, the vinyl chloride resin composition (A) and The interfacial adhesiveness of the carbon fiber base material (B) shall be sufficient.
  • the vinyl chloride resin used in the vinyl chloride resin composition (A) is not particularly limited, and in addition to the homopolymer of the vinyl chloride monomer, for example, (1) vinyl chloride monomer and vinyl chloride monomer. Copolymers with polymerizable monomers other than, (2) Graft copolymers obtained by grafting a vinyl chloride monomer or vinyl chloride resin on a polymer other than vinyl chloride resin, (3) Vinyl chloride type Examples thereof include a polymer alloy in which a vinyl chloride monomer or a vinyl chloride resin is mixed with a polymer other than the resin. Further, a chlorinated vinyl chloride resin obtained by chlorinating these vinyl chloride resins can also be mentioned. These vinyl chloride resins may be used alone or in combination of two or more.
  • the polymerizable monomer in the copolymer of the vinyl chloride monomer and the polymerizable monomer other than the vinyl chloride monomer is not particularly limited, but is an ⁇ -olefin having 2 or more and 16 or less carbon atoms (1).
  • ethylene, propylene, and butylene vinyl esters of aliphatic carboxylic acids having 2 or more and 16 or less carbon atoms (for example, vinyl acetate and vinyl propionate); alkyl vinyl ethers having 2 or more and 16 or less carbon atoms (for example, butyl vinyl ether and Cetyl vinyl ether); alkyl (meth) acrylates with 1 to 16 carbon atoms (eg, methyl (meth) acrylate, ethyl (meth) acrylate and butyl acrylate); aryl (meth) acrylate (eg, phenylmethacrylate); aromatic vinyl (For example, styrene and ⁇ -substituted styrene (eg, ⁇ -methylstyrene)); vinyl halides (eg, vinylidene chloride and vinylidene fluoride); and N-substituted maleimides (N-phenylmaleimide and N-cyclo
  • the polymer that gives the graft copolymer together with the vinyl chloride monomer or vinyl chloride resin is any polymer that can be graft-polymerized to the vinyl chloride monomer, regardless of whether it is a homopolymer or a copolymer. Things are also included.
  • a copolymer of ⁇ -olefin and vinyl ester eg, ethylene-vinyl acetate copolymer
  • a copolymer of ⁇ -olefin, vinyl ester and carbon monoxide eg, ethylene-vinyl acetate-monooxide
  • Carbon copolymer copolymer of ⁇ -olefin and alkyl (meth) acrylate (eg, ethylene-methylmethacrylate copolymer and ethylene-ethylacrylate copolymer); with ⁇ -olefin and alkyl (meth) acrylate Copolymer with carbon monoxide (eg, ethylene-butyl acrylate-carbon monoxide copolymer); Copolymer of two or more different ⁇ -olefins (eg, ethylene-propylene copolymer); Unsaturated nitrile Copolymers of and diene (eg, acrylonitrile-butadiene copolymers); polyurethanes; and chlorinated polyolefins (eg, chlorinated polyethylene and chlorinated polypropylene).
  • ⁇ -olefin and alkyl (meth) acrylate eg, ethylene-methylmethacrylate copolymer and ethylene-eth
  • thermosetting resin examples include epoxy resin, phenol resin, vinyl ester resin, benzoxazine resin, polyimide resin, oxetane resin, maleimide resin, unsaturated polyester resin, urea resin, and melamine resin.
  • thermoplastic resin examples include chlorinated resins such as chlorinated vinyl chloride and chlorinated polyethylene, polyolefin resins such as polyethylene resin and polypropylene resin, aliphatic polyamide resins such as polyamide 66, polyamide 6, and polyamide 12, and acid components.
  • aromatic polyester resin such as polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT), polycarbonate resin, polystyrene resin (polystyrene resin, AS resin, ABS) Resins, etc.), or aliphatic polyester-based resins such as polylactic acid-based resins.
  • PET polyethylene terephthalate resin
  • PBT polybutylene terephthalate resin
  • polycarbonate resin polystyrene resin (polystyrene resin, AS resin, ABS) Resins, etc.)
  • aliphatic polyester-based resins such as polylactic acid-based resins.
  • the compounding ratio of the vinyl chloride resin to the entire matrix resin may be 1 to 95% by mass, preferably 5 to 80% by mass, and further preferably 10 to 70% by mass. Within the range, effects such as improvement of heat resistance, strength, impact resistance, and flame retardancy can be obtained according to the performance of the matrix resin.
  • the average degree of polymerization of the vinyl chloride resin (p) is not particularly limited, but is preferably 400 or more and 1500 or less, and more preferably 600 or more and 1000 or less. When the average degree of polymerization is at least the above lower limit value, it is easy to obtain preferable mechanical properties (for example, toughness) of the vinyl chloride resin. When the average degree of polymerization is not more than the above upper limit value, it is easy to make the melt viscosity when impregnating the carbon fiber base material (B) suitable.
  • the vinyl chloride resin used in the vinyl chloride resin composition (C) is more average than the vinyl chloride resin used in the vinyl chloride resin composition (A) in order to improve the mechanical properties of the carbon fiber reinforced composite material.
  • the degree of polymerization can be increased.
  • the vinyl chloride resin used in the vinyl chloride resin composition (C) preferably has an average degree of polymerization of 600 or more, and more preferably 800 or more and 2000 or less.
  • the vinyl chloride resin used in the vinyl chloride resin composition (C) is mainly composed of a chlorinated vinyl chloride resin. It is good to select the one to be.
  • a chlorinated vinyl chloride resin composition has a higher melt viscosity than a vinyl chloride resin composition and is easily thermally decomposed, so that it is difficult to impregnate carbon fibers. Therefore, when a chlorinated vinyl chloride resin composition is used for the vinyl chloride resin composition (A), it is necessary to use a chlorinated vinyl chloride resin having a low degree of polymerization or increase the amount of additives added. , There is a risk of impairing mechanical properties.
  • At least a part of the surface of the composite material provided with the carbon fiber equipment (B) impregnated with the vinyl chloride resin composition (A) is a chlorinated vinyl chloride resin composition containing a chlorinated vinyl chloride resin ( By coating with C), CFRP that maintains the expected heat resistance and flame retardancy and mechanical properties can be obtained.
  • the degree of chlorination of the vinyl chloride resin used in the vinyl chloride resin compositions (A) and (C) is, for example, 56% by mass to 72% by mass.
  • the vinyl chloride-based resin composition is a vinyl chloride-based resin having a degree of chlorination of about 56.8% by mass, the viscosity of the carbon fiber base material (B) having a good impregnation property can be maintained. Further, when the degree of chlorination is about 60% by mass to 72% by mass, improvement in heat resistance and flame retardancy is expected.
  • the degree of chlorination of the vinyl chloride resin used in the vinyl chloride resin composition (C) for coating is determined by the vinyl chloride resin composition. It is preferably higher than the degree of chlorination of the vinyl chloride resin used in (A).
  • the chlorine content can be measured in accordance with JIS K7229.
  • the vinyl chloride resin composition (C) contains a vinyl chloride resin foam.
  • a foam can be obtained by chemical foaming by blending a foaming agent or physical foaming by injecting nitrogen.
  • these means are used for the resin to be impregnated in carbon fibers, bubbles are contained in the fibers. There is a risk of impairing the mechanical properties of the obtained CFRP.
  • a vinyl chloride resin composition (A) containing a vinyl chloride resin that is not a foam is used, and the outer layer thereof is a vinyl chloride resin composition containing a vinyl chloride resin foam.
  • CFRP having the expected light weight and soundproofing properties and mechanical properties can be obtained.
  • additives added to the vinyl chloride resin composition (A) include heat stabilizers, lubricants, processing aids, impact modifiers, heat resistance improvers, antioxidants, ultraviolet absorbers, antistatic agents, and light. Stabilizers, fillers, pigments, flame retardants, plasticizers and the like can be mentioned. Only one kind of the additive may be used, or two or more kinds may be used in combination.
  • the heat stabilizer is not particularly limited, and examples thereof include a heat stabilizer and a heat stabilization aid.
  • the heat stabilizer is not particularly limited, and examples thereof include an organotin-based stabilizer, a lead-based stabilizer, a calcium-zinc-based stabilizer, a barium-zinc-based stabilizer, and a barium-cadmium-based stabilizer.
  • organic tin stabilizer examples include dibutyl tin mercapto, dioctyl tin mercapto, dimethyl tin mercapto, dibutyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, dioctyl tin malate polymer, dibutyl tin laurate, and the like. Examples thereof include dibutyltin laurate polymer. Only one type of the stabilizer may be used, or two or more types may be used in combination.
  • the heat stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, phosphoric acid ester, polyol, hydrotalcite, and zeolite.
  • the heat stabilization aid only one kind may be used, or two or more kinds may be used in combination.
  • the content of the heat stabilizer contained in the vinyl chloride resin composition (A) is preferably 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin, and is preferably 10 parts by mass. It is more preferably 5 parts by mass or less, and further preferably 5 parts by mass or less.
  • the amount is small, the influence of exudation near the interface of the continuous carbon fiber base material (B) can be reduced, and deterioration of physical properties such as bending strength of the carbon fiber reinforced composite material can be suppressed.
  • the lubricant examples include an internal lubricant and an external lubricant.
  • the internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin during molding and preventing frictional heat generation.
  • the internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl alcohol, epoxy soybean oil, glycerin monostearate, stearic acid, and bisamide. Only one kind of the above-mentioned lubricant may be used, or two or more kinds may be used in combination.
  • the content of the internal lubricant contained in the vinyl chloride resin composition (A) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the vinyl chloride resin. It is more preferably 5 parts by mass or less.
  • the amount is small, the influence of exudation near the interface of the continuous carbon fiber base material (B) can be reduced, and deterioration of physical properties such as bending strength of the carbon fiber reinforced composite material can be suppressed.
  • the external lubricant is used for the purpose of enhancing the sliding effect between the molten resin and the metal surface during molding.
  • the external lubricant is not particularly limited, and examples thereof include paraffin wax, polyolefin wax, ester wax, and montanic acid wax. Only one kind of the above-mentioned lubricant may be used, or two or more kinds may be used in combination.
  • the processing aid is not particularly limited, and conventionally known processing aids can be used, and homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate, alkyl methacrylate, and methyl.
  • Copolymers with alkyl acrylates such as acrylates, ethyl acrylates and butyl acrylates, copolymers of alkyl methacrylates with aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene, alkyl methacrylates and acrylonitrile, methacrylonitrile.
  • Examples thereof include copolymers with vinyl cyanide compounds such as nitrile, and these can be used alone or in combination of two or more.
  • an alkyl acrylate-alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2 million can be preferably used.
  • Specific examples thereof include an n-butyl acrylate-methyl methacrylate copolymer and a 2-ethylhexyl acrylate-methyl methacrylate-butyl methacrylate copolymer.
  • the processing aid only one kind may be used, or two or more kinds may be used in combination.
  • the impact modifier is not particularly limited, and a conventionally known impact modifier can be used without particular limitation.
  • the heat resistance improving agent is not particularly limited, and examples thereof include ⁇ -methylstyrene-based resins and N-phenylmaleimide-based resins. Only one kind of the heat resistance improving agent may be used, or two or more kinds thereof may be used in combination.
  • the antioxidant is not particularly limited, and a phenolic antioxidant such as 4,4'-butylidenebis- (6-t-butyl-3-methylphenol), tris (mixed mono and dinonylphenyl) phos.
  • a phenolic antioxidant such as 4,4'-butylidenebis- (6-t-butyl-3-methylphenol), tris (mixed mono and dinonylphenyl) phos.
  • examples thereof include phosphite-based antioxidants such as phyto, and thioether-based antioxidants such as distearylthiodipropionate.
  • phenolic antioxidants such as 4,4'-butylidenebis- (6-t-butyl-3-methylphenol), which has a low high-temperature decomposition inhibitory function, are particularly preferable. Only one type of the antioxidant may be used, or two or more types may be used in combination.
  • the ultraviolet absorber is not particularly limited, and examples thereof include a salicylic acid ester-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. Only one kind of the ultraviolet absorber may be used, or two or more kinds may be used in combination.
  • the antistatic agent is not particularly limited, and conventionally known antistatic agents can be used, and anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like are used. I can do it.
  • Anionic surfactants include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, aliphatic amines, amide sulfates, dibasic fatty acid ester sulfates, fatty acid amide sulfonates, and alkylaryls. Examples thereof include sulfonates, formalin-condensed naphthalene sulfonates, and mixtures thereof.
  • Examples of the cationic surfactant include aliphatic amine salts, quaternary ammonium salts, alkylpyridium salts and mixtures thereof.
  • Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol esters, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, and mixtures thereof. be able to. It may be a mixture of a nonionic surfactant and an anionic surfactant or a cationic surfactant.
  • amphoteric surfactant examples include an imidazoline type, a higher alkylamino type (betaine type), a sulfate ester, a phosphoric acid ester type, and a sulfonic acid type. Only one type of antistatic agent may be used, or two or more types may be used in combination.
  • the light stabilizer is not particularly limited, and examples thereof include hindered amine-based light stabilizers. Only one kind of the light stabilizer may be used, or two or more kinds thereof may be used in combination.
  • the filler is not particularly limited, and carbonates such as talc, heavy calcium carbonate, precipitated calcium carbonate, and collagen carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, wollastonite, and zeolite. , Silica, zinc oxide, magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers, metal fibers and other inorganic fibers, as well as organic fibers such as polyamide and the like. Only one kind of the filler may be used, or two or more kinds thereof may be used in combination.
  • the pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments.
  • the organic pigment include an azo-based organic pigment, a phthalocyanine-based organic pigment, a slene-based organic pigment, and a dye lake-based organic pigment.
  • the inorganic pigments include oxide-based inorganic pigments, molybdenum chromate-based inorganic pigments, sulfide / selenium-based inorganic pigments, and ferrosinized inorganic pigments. Only one kind of the above pigment may be used, or two or more kinds may be used in combination.
  • the flame retardant examples include metal hydroxides, brominated compounds, triazine ring-containing compounds, zinc compounds, phosphorus compounds, halogen flame retardants, silicone flame retardants, intomescent flame retardants, antimony oxide and the like. , These can be used alone or in combination of two or more.
  • the plasticizer may be added for the purpose of improving workability during molding.
  • the plasticizer is not particularly limited, and conventionally known plasticizers can be used.
  • phthalate ester plasticizers and non-phthalate plasticizers can be used.
  • the phthalate ester plasticizer include dioctyl phthalate (DOP).
  • DOP dioctyl phthalate
  • non-phthalic acid-based plasticizers include trimellitic acid-based compounds, phosphoric acid-based compounds, adipic acid-based compounds, citric acid-based compounds, ether-based compounds, polyester-based compounds, soybean oil-based compounds, and cyclohexanedicarboxylate. Examples include system compounds and terephthalic acid compounds. Only one type of the plasticizer may be used, or two or more types may be used in combination.
  • the total content of the additive (i) contained in the vinyl chloride resin composition (A) is not particularly specified, but the weight fraction C (i) of each additive is included as a component of the formula (III). As can be seen from the above, it is preferable that the amount is small as long as there is no problem in manufacturing.
  • the total content of the additive (i) is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is more preferably parts or less, more preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and most preferably 10 parts by mass or less.
  • a small amount can reduce the influence of exudation near the interface of the carbon fiber base material (B).
  • the content of the plasticizer contained in the vinyl chloride resin composition (A) is preferably small because if it is contained in a large amount in the vinyl chloride resin composition (A), the mechanical strength of CFRP may be impaired.
  • the content of the plasticizer is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin. Yes, more preferably 1 part by mass or less, particularly preferably 0.1 part by mass or less, and most preferably the plasticizer is not contained.
  • a vinyl chloride resin containing a chlorinated vinyl chloride resin as a main component.
  • a chlorinated vinyl chloride resin composition has a higher melt viscosity than a vinyl chloride resin composition and is easily thermally decomposed, so that it is difficult to impregnate carbon fibers. Therefore, when a chlorinated vinyl chloride resin is used for the vinyl chloride resin composition (A), it is possible to use a chlorinated vinyl chloride resin having a low degree of polymerization or increase the amount of the additive added.
  • CFRP that maintains the expected heat resistance and flame retardancy and mechanical properties can be obtained.
  • Carbon fiber is a fiber composed of a material containing carbon. It is a concept that includes the case of using it together with other fibers and the case of using it alone.
  • the carbon fiber base material is a carbon fiber woven fabric in which a carbon fiber bundle composed of a plurality of carbon fibers is used as a warp bundle and a weft bundle.
  • Carbon fiber is a concept including short carbon fiber, long carbon fiber, and continuous carbon fiber.
  • the short carbon fiber is a carbon fiber having a fiber length of 1 mm or less.
  • the long carbon fiber is a carbon fiber having a fiber length of 5 cm or less.
  • Continuous carbon fibers are carbon fibers other than short fibers and long fibers.
  • the material of the carbon fiber is not particularly limited as long as it is a carbon fiber such as PAN (polyacrylonitrile) carbon fiber and pitch carbon fiber, and other fibers; metal fiber such as steel fiber; glass fiber, ceramic fiber, etc.
  • Inorganic fibers such as boron fiber; and organic fibers such as aramid, polyester, polyethylene, nylon, vinylon, polyacetal, polyparaphenylene benzoxazole, and high-strength polypropylene; used in combination with natural fibers such as kenaf and hemp. May be done. From the viewpoint of specific strength, it is preferable that it is composed of only carbon fibers.
  • carbon fiber used in the present invention short carbon fiber, long carbon fiber, and continuous carbon fiber can be appropriately used, but continuous carbon fiber is preferable from the viewpoint of the mechanical properties of the obtained CFRP.
  • the form of the fiber is not particularly limited as long as it is a continuous fiber, for example, a form in which the toe and the toe directions are aligned in one direction and held by a weft auxiliary thread, a form in which the fiber is used as a warp and a woven fabric (cross); Examples thereof include a form of a multi-axial warp knit in which a plurality of fiber sheets in which the directions of the above are aligned in one direction are woven and fastened with auxiliary threads so that the directions of the fibers are different from each other.
  • the carbon fiber base material (B) can be obtained by producing the carbon fiber by each production method based on the above-mentioned form.
  • Each carbon fiber is generally a single fiber, and a plurality of carbon fibers gather to form a carbon fiber bundle.
  • the number of carbon fibers constituting each carbon fiber bundle is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and even more preferably 5,000 to 25,000.
  • the fiber diameter of the filament is preferably 3 ⁇ m or more, and preferably 12 ⁇ m or less. Sufficient strength can be obtained when the fiber diameter is 3 ⁇ m or more, and for example, when the filament causes lateral movement on the surface of a roll, spool, etc. in various processing processes, it suppresses cutting or fluffing. it can.
  • the upper limit is usually about 12 ⁇ m because carbon fibers can be easily produced.
  • the plurality of carbon fiber bundles are not particularly limited, but are preferably in the form of a sheet.
  • the basis weight of the sheet-shaped carbon fiber bundle is, for example, preferably 100 g / m 2 or more and 600 g / m 2 or less, and more preferably 150 g / m 2 or more and 500 g / m 2 or less. It is preferable that the basis weight is at least the above lower limit value because it is efficient when the obtained CFRP sheets are laminated and secondary processed, and at least the above upper limit value is easy to obtain impregnation property. It is preferable in that.
  • the carbon fiber base material (B) it is preferable to use a carbon fiber bundle that has been pre-spread (hereinafter, may be referred to as a spread carbon fiber bundle) for the purpose of facilitating impregnation with the resin.
  • the fiber opening step is not particularly limited, and examples thereof include a method of including spacer particles, a method of squeezing the fiber with a round bar, a method of using an air flow, a method of vibrating the fiber with ultrasonic waves, and the like.
  • a method of including spacer particles is preferable, and by widening the interfiber distance in this way, even if a high tension is applied to the carbon fiber at the manufacturing stage, the interfiber distance is preliminarily widened. , Resin impregnation becomes easy. Further, even if tension is applied to the fibers, the distance between the fibers is unlikely to be narrowed.
  • the spacer particles enter between the carbon fibers in each fiber bundle, thereby opening the carbon fiber bundle.
  • the spacer particles that have entered between the carbon fibers may be crosslinked between the carbon fibers.
  • cross-linking means having a structure in which spacer particles that have entered between carbon fibers are arranged so as to bridge at least two carbon fibers.
  • the spacer particles may be adhered to carbon fibers via carbon allotropes existing on the particle surface.
  • the spacer particles are not particularly limited, but may contain, for example, carbon allotropes.
  • carbon allotropes include, for example, amorphous carbon, graphite, diamond and the like.
  • Amorphous carbon is mentioned as an amorphous carbon. Among these, amorphous carbon is preferable, and amorphous carbon is more preferable.
  • the carbon allotrope is preferably derived from the carbon of the thermosetting resin, that is, the carbon allotrope is preferably obtained by carbonizing the thermosetting resin.
  • the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, oxazine resin, etc., and strong amorphous carbon by carbonization treatment at low temperature.
  • Oxazine-based resin is preferable from the viewpoint of forming a film of.
  • the oxazine-based resin include benzoxazine resin and naphthoxazine resin.
  • the naphthoxazine resin is preferable from the viewpoint that it is easily carbonized at a lower temperature, and it is difficult to be excessively softened even under the temperature and pressure conditions at the time of CFRP production of the present invention. Therefore, a sufficient distance between fibers is secured, and the impregnation property of the resin is further improved.
  • the spacer particles may be carbon allotrope particles composed of carbon allotropes, but may be film particles containing core particles and carbon allotropes that coat the core particles.
  • the spacer particles are preferably coated particles from the viewpoint of resin impregnation.
  • the entire surface of the coated particles may be coated with a carbon allotrope, or a part of the surface thereof may be coated with a carbon allotrope.
  • the core particles can be used without particular limitation as long as they are not deformed or destroyed by the pressure and temperature when the carbon fiber bundle is impregnated with the thermoplastic resin.
  • inorganic particles, organic particles and the like can be used. it can.
  • inorganic particles or organic particles may be used alone, or both may be used in combination.
  • the average particle size of the spacer particles is preferably 1 to 20 ⁇ m. By using the spacer particles having a size in this range, the spacer particles can be easily inserted between the carbon fibers, and the carbon fiber bundle can be opened more widely.
  • the more preferable average particle size of the spacer particles is 2 to 20 ⁇ m, and particularly preferably 4 to 15 ⁇ m.
  • the total amount of spacer particles adhered to the spread-treated carbon fiber bundle is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the spread carbon fiber bundle.
  • the carbon fiber bundle can be appropriately opened. Further, by setting the adhesion amount to the upper limit value or less, it is possible to prevent the spread carbon fiber bundle from containing spacer particles more than necessary and deteriorating the mechanical properties.
  • the carbon fiber reinforced composite material according to the present invention can be produced by a method including (1) a base material preparation step and (2) a resin impregnation step.
  • a base material preparation step a base material preparation step
  • a resin impregnation step a resin impregnation step
  • the base material preparation step is a step of preparing the carbon fiber base material (B) described above.
  • the carbon fiber base material (B) is as described above, and for example, an appropriate carbon fiber material, form, and basis weight can be selected. Further, a woven fabric having a desired structure may be produced by using a commercially available carbon fiber bundle.
  • the carbon fiber base material preparation step preferably includes a step of opening the carbon fiber bundle.
  • the step of opening the carbon fiber bundle will be described.
  • the carbon fiber bundle may include spacer particles arranged between the carbon fibers. By arranging the spacer particles between the carbon fibers, the carbon fiber bundle is opened and the thermoplastic resin can be sufficiently impregnated into the carbon fiber woven fabric.
  • the fiber bundles are laterally opened, the pitch width of the woven fabric is increased, and the design of the fiber-reinforced composite material may be deteriorated.
  • the carbon fiber woven fabric composed of carbon fiber bundles having spacer particles on the surface of the carbon fiber as described above is not physically opened, it is possible to suppress deterioration of the design of the fiber reinforced composite material. It is considered that the impregnation property of the thermoplastic resin can be improved because the carbon fiber bundles are sufficiently opened by the spacer particles.
  • the spread carbon fiber bundle can be produced by bringing the carbon fiber bundle into contact with the spread fiber impregnating liquid and heating it. After opening the carbon fiber bundle, the carbon fiber woven fabric may be obtained by using the opened defibrated carbon fiber bundle, but after producing the carbon fiber woven fabric using the carbon fiber bundle, the carbon fiber bundle is opened by the above method. It is preferable to fiber.
  • the timing of contacting the carbon fiber bundle with the opening fiber impregnating liquid may be such that the carbon fiber bundle is brought into contact with the opening fiber impregnating liquid in advance before the carbon fiber woven fabric is produced, and the carbon fiber bundle is used as a warp yarn bundle and a weft yarn bundle.
  • the carbon fiber woven fabric may be woven and the obtained carbon fiber woven fabric may be brought into contact with the opening fiber impregnating liquid to open the carbon fiber bundle.
  • the contact of the opening fiber impregnating liquid may be performed by impregnating the carbon fiber bundle with the opening fiber impregnating liquid.
  • the spread fiber impregnating liquid may be sprayed or applied to the carbon fiber bundle, or the carbon fiber bundle may be immersed in the fiber spread impregnated liquid.
  • the resin particles enter the gaps between the carbon fibers of the carbon fiber bundles, whereby the carbon fiber bundles can be opened.
  • the fiber-spreading impregnated liquid used for opening the carbon fiber bundle contains a monomer (hereinafter, also simply referred to as "monomer") capable of forming a thermosetting resin.
  • the monomer reacts to become a thermosetting resin.
  • the thermosetting resin is preferably an oxazine-based resin as described above, but when the thermosetting resin is an oxazine-based resin, the monomers are, for example, phenols, formaldehyde, and amines.
  • a naphthoxazine resin is preferable.
  • Resin impregnation step (2) is a step of impregnating the carbon fiber base material (B) prepared above with the vinyl chloride resin composition (A).
  • the carbon fiber reinforced composite material according to the present invention can be produced by impregnating the carbon fiber woven fabric composed of the above-mentioned spread carbon fiber bundle with the vinyl chloride resin composition (A).
  • a film made of a vinyl chloride resin composition (A) is laminated on a carbon fiber base material (B) composed of open fiber carbon fiber bundles and heat-press molded, or on the carbon fiber base material (B).
  • the carbon fiber base material (B) can be impregnated with the vinyl chloride resin composition (A) by performing melt extrusion molding of the vinyl chloride resin composition (A).
  • a plurality of carbon fiber base materials (B) impregnated with the vinyl chloride resin composition (A) may be laminated, and at this time, the structure direction of each carbon fiber woven fabric is at a constant angle.
  • Extrusion molding or press molding can be used for the hot press, and a carbon fiber reinforced composite material having a desired shape can be obtained by using a molding die.
  • the temperature at which the hot press molding is performed can be set to a temperature higher than the temperature at which the vinyl chloride resin composition (A) to be used softens or melts.
  • the carbon fiber reinforced composite material according to the present invention has good bending strength.
  • the bending strength of the three-point bending test is preferably 300 MPa or more, more preferably 400 MPa or more, and 500 MPa or more. It is more preferable to have.
  • the bending strength is at least the above lower limit value, it can be suitably used in applications requiring high strength such as aircraft structural members, wind turbine blades, and automobile outer panels.
  • the three-point bending test conforms to JIS K 7074, and the distance between fulcrums (L) is (L) for a test piece having a length (l) of 40 ⁇ 1 mm, a width (b) of 15 ⁇ 0.2 mm, and a thickness of h. Is a measured value (MPa) with 40 ⁇ hmm.
  • the jig indenter radius of the bending test was 5 mm, and the indenter width was 2 mm.
  • Vf 100 x carbon fiber thickness (mm) ⁇ carbon fiber reinforced composite material thickness (mm)
  • ⁇ Test Example 1> ⁇ Making resin film> Vinyl chloride resin 1 (manufactured by Tokuyama Sekisui Kogyo, SL-P40, degree of polymerization of about 400) was dissolved in tetrahydrofuran so as to have a solution concentration of about 10%. Subsequently, 2 parts by mass of a heat stabilizer 1 (methyl tin mercapto, liquid stabilizer, AT5300 manufactured by Nitto Kasei Co., Ltd.) was added as an additive to 100 parts by mass of the vinyl chloride resin 1 to the solution. The mixture was stirred to obtain a vinyl chloride resin composition (A).
  • a heat stabilizer 1 methyl tin mercapto, liquid stabilizer, AT5300 manufactured by Nitto Kasei Co., Ltd.
  • the obtained vinyl chloride resin composition (A) was coated on a glass plate with a solution using a glass rod, and allowed to stand to volatilize the solvent to obtain a resin film. After the obtained resin film was peeled off from the glass plate, it was further dried in a traveling oven at 60 ° C. for about 3 hours to obtain a resin film for producing CFRP.
  • ⁇ Creation of carbon fiber base material (B)> A monomer consisting of 10 parts by mass of 1,5-dihydroxynaphthalene, 4 parts by mass of a 40% by mass methylamine aqueous solution, and 8 parts by mass of formalin (formaldehyde content: 37% by mass), and ethanol water (ethanol content: ethanol content:) as a solvent. 50 parts by mass) 800 parts by mass was uniformly mixed to prepare a monomer solution prepared by dissolving the monomer.
  • a carbon fiber woven fabric composed of PAN-based carbon fiber bundles (number of carbon fibers: 3000, average diameter of carbon fibers: 7 ⁇ m, grain: 200 g / m 2 , thickness: 0.19 mm, plain weave) was prepared.
  • the carbon fiber woven fabric was immersed in the above-mentioned opening fiber impregnating solution, pulled up, and then heated at 200 ° C. for 2 minutes. By this heating, the polymerization reaction of the naphthoxazine resin and carbonization occurred, and amorphous carbon derived from the naphthoxazine resin was produced, and a woven fabric of open fiber bundles was obtained.
  • the total amount of organic particles and carbon allotropes attached to the spread carbon fiber bundle was 1% by mass. This spread carbon fiber bundle was used as a carbon fiber base material (B).
  • Example 1 ⁇ Press molding of CFRP>
  • the carbon fiber base material (B) obtained above is sandwiched between the two resin films obtained above from above and below, pressed stepwise from 0 to 6 MPa at 200 ° C., and pressed for a total of 10 minutes. Obtained CFRP.
  • the obtained CFRP was used as a sample "Fruit-1" for physical property evaluation.
  • Example 2 CFRP was obtained by the same process as in Example 1 except that the amount of the heat stabilizer 1 was increased to 10 parts by mass in the preparation of the resin film. The obtained CFRP was used as a sample “Actual-2” for physical property evaluation.
  • Example 3 CFRP was obtained by the same process as in Example 1 except that the vinyl chloride resin 1 was changed to the vinyl chloride resin 2 (manufactured by Tokuyama Sekisui Kogyo Co., Ltd., TS-640M, degree of polymerization of about 640) in the preparation of the resin film.
  • the obtained CFRP was used as a carbon fiber base material sample "Actual-3" for physical property evaluation.
  • Example 4 CFRP was obtained by the same process as in Example 1 except that 5 parts by mass of external lubricant 1 (HIWAX220RKT polyethylene wax manufactured by Mitsui Chemicals, Inc.) was added in the preparation of the resin film. The obtained CFRP was used as a carbon fiber base material sample "Fruit-4" for physical property evaluation.
  • external lubricant 1 HIWAX220RKT polyethylene wax manufactured by Mitsui Chemicals, Inc.
  • Example 5 CFRP was obtained by the same process as in Example 1 except that 10 parts by mass of internal lubricant 1 (LOXIOL G60 glycerin monostearate manufactured by Emery Oleo Chemical Co., Ltd.) was added in the preparation of the resin film.
  • the obtained CFRP was used as a carbon fiber base material sample "Fruit-5" for physical property evaluation.
  • Example 6 CFRP was obtained by the same process as in Example 1 except that 0.1 part by mass of plasticizer 1 (dioctylphthalate manufactured by J-PLUS Co., Ltd.) was added in the preparation of the resin film. The obtained CFRP was used as a carbon fiber base material sample "Fruit-6" for physical property evaluation.
  • plasticizer 1 dioctylphthalate manufactured by J-PLUS Co., Ltd.
  • Example 7 CFRP was obtained by the same process as in Example 1 except that the heat stabilizer 1 was changed to 0.5 parts by mass in the preparation of the resin film. The obtained CFRP was used as a sample for physical property evaluation. The obtained CFRP was used as a sample "Fruit-7" for physical property evaluation.
  • Example 8 CFRP was obtained by the same process as in Example 1 except that the amount of the heat stabilizer 1 was increased to 20 parts by mass in the preparation of the resin film. The obtained CFRP was used as a sample "Fruit-8" for physical property evaluation.
  • Example 9 CFRP was obtained by the same process as in Example 1 except that 0.5 parts by mass of external lubricant 1 (HIWAX220RKT polyethylene wax manufactured by Mitsui Chemicals, Inc.) was added in the preparation of the resin film.
  • the obtained CFRP was used as a carbon fiber base material sample "Fruit-9" for physical property evaluation.
  • Example 10 CFRP was obtained by the same process as in Example 1 except that 2 parts by mass of the external lubricant 1 was added in the preparation of the resin film.
  • the obtained CFRP was used as a carbon fiber base material sample "Fruit-10" for physical property evaluation.
  • Example 11 CFRP was obtained by the same process as in Example 1 except that 5 parts by mass of external lubricant 2 (AC316 polyethylene oxide wax manufactured by Honeywell Co., Ltd.) was added in the preparation of the resin film. The obtained CFRP was used as a carbon fiber base material sample "Fruit-11" for physical property evaluation.
  • external lubricant 2 AC316 polyethylene oxide wax manufactured by Honeywell Co., Ltd.
  • Example 12 CFRP was obtained by the same process as in Example 1 except that 5 parts by mass of external lubricant 3 (SG22 ester wax manufactured by RIKEN Vitamin Co., Ltd.) was added in the preparation of the resin film.
  • the obtained CFRP was used as a carbon fiber base material sample "Fruit-12" for physical property evaluation.
  • Example 13 CFRP was obtained by the same process as in Example 1 except that 30 parts by mass of plasticizer 1 (dioctylphthalate manufactured by J-PLUS Co., Ltd.) was added in the preparation of the resin film. The obtained CFRP was used as a carbon fiber base material sample "Fruit-13" for physical property evaluation.
  • plasticizer 1 dioctylphthalate manufactured by J-PLUS Co., Ltd.
  • CFRP was obtained by the same process as in Example 1 except that the vinyl chloride resin 1 was changed to the vinyl chloride resin 3 (TS-1000R manufactured by Tokuyama Sekisui Kogyo Co., Ltd., degree of polymerization of about 1000) in the preparation of the resin film.
  • the obtained CFRP was used as a carbon fiber base material sample “ratio-2” for physical property evaluation.
  • the complex viscosity ⁇ of the vinyl chloride resin composition (A) used for producing the resin film was measured by the following method. The measurement results are shown in Tables 1 and 2.
  • the resin film is cut into a size of 30 (mm) ⁇ 90 (mm), weighed to about 5 g, heat-press molded at 170 ° C. for about 3 minutes, and cooled for about 1 minute.
  • a sample for measuring viscosity having a thickness of 1 mm was prepared.
  • a viscoelasticity measuring device manufactured by MCR102 Antonio Par was used for the measurement, and the diameter of the parallel plate was measured under the conditions of 25 mm, the parallel distance of 1 mm, the temperature of 200 ° C., and the angular frequency of 10 Hz, and the complex viscosity ⁇ was calculated.
  • a resin film (II) for preparing CFRP was prepared by the same process as the resin film prepared in Example 3 of Test Example 1 above.
  • ⁇ Making resin film (III)> The same applies to the preparation of the resin film (I), except that a chlorinated vinyl chloride resin (manufactured by Tokuyama Sekisui Kogyo, HA-05K, degree of polymerization of about 360, degree of chlorination of about 67%) is used instead of the vinyl chloride resin 1.
  • a resin film (III) for making CFRP was prepared by the process.
  • a resin film (V) for preparing CFRP was prepared by the same process as the resin film prepared in Comparative Example 2 of Test Example 1.
  • the carbon fiber base material (B) was prepared by the same process as the preparation of the carbon fiber base material (B) of Test Example 1 above.
  • Example 14 ⁇ Press molding of CFRP>
  • the carbon fiber base material (B) obtained above is sandwiched between two resin films (I) on the upper side and one resin film (I) and one resin film (II) on the lower side from above and below, and 200 CFRP was obtained by stepwise pressurizing from 0 to 6 MPa at ° C. and pressing for a total of 10 minutes.
  • the obtained CFRP was used as a sample "Fruit-14" for physical property evaluation.
  • Example 15 CFRP was obtained by the same process as in Example 14 except that the amount of the heat stabilizer was increased to 10 parts by mass in the preparation of the resin film (I) and the resin film (II). The obtained CFRP was used as a sample "Fruit-15" for physical property evaluation.
  • Example 16 In the preparation of the resin film (I), CFRP was obtained by the same process as in Example 14 except that 10 parts by mass of an internal lubricant (LOXIOL G60 glycerin monostearate manufactured by Emery Oleo Chemical Co., Ltd.) was added as an additive. The obtained CFRP was used as a carbon fiber base material sample "Fruit-16" for physical property evaluation.
  • an internal lubricant LOXIOL G60 glycerin monostearate manufactured by Emery Oleo Chemical Co., Ltd.
  • Example 17 CFRP was obtained by the same process as in Example 14 except that 0.1 part by mass of a plasticizer (dioctyl phthalate manufactured by J-PLUS Co., Ltd.) was added as an additive in the preparation of the resin film (I). The obtained CFRP was used as a carbon fiber base material sample "Fruit-17" for physical property evaluation.
  • a plasticizer dioctyl phthalate manufactured by J-PLUS Co., Ltd.
  • Example 18 In the press molding of CFRP of Example 1, the carbon fiber base material (B) obtained above was used, one resin film (I) and one resin film (III) on the upper side, and a resin film (III) on the lower side.
  • CFRP was obtained by the same process as in Example 14 except that I) and the resin film (III) were sandwiched between one each from above and below.
  • the obtained CFRP was used as a carbon fiber base material sample "Fruit-18" for physical property evaluation.
  • Example 19 In the press molding of CFRP of Example 1, the carbon fiber base material (B) obtained above was used, one resin film (I) and one resin film (IV) on the upper side, and a resin film (IV) on the lower side.
  • CFRP was obtained by the same process as in Example 1 except that I) was sandwiched between two sheets from above and below. The obtained CFRP was used as a carbon fiber base material sample "Fruit-19" for physical property evaluation.
  • Table 3 shows the index S calculated by the same method as in Test 1 above.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un CFRP à l'aide d'une composition de résine à base de chlorure de vinyle présentant une excellente aptitude à l'imprégnation dans un matériau de base en fibre de carbone. Ce matériau composite renforcé par des fibres de carbone comprend une composition de résine à base de chlorure de vinyle (A) et un matériau de base en fibre de carbone (B). La composition de résine à base de chlorure de vinyle (A) contient une résine à base de chlorure de vinyle et un ou plusieurs additifs. La composition de résine à base de chlorure de vinyle (A) et le matériau de base en fibre de carbone (B) satisfont la propriété (1) et la propriété (2) suivantes. Propriété physique (1) : La viscosité complexe η de la composition de résine à base de chlorure de vinyle (A) à 200 °C à une fréquence de 10 Hz satisfait 1 < η < 1500. Propriété physique (2) : Une valeur S calculée à l'aide d'un indice de solubilité (Ra(pi)), d'un indice de solubilité (Ra(ci)) et des fractions de poids C(i) des additifs (i) présents dans la composition de résine à base de chlorure de vinyle (A) est égale ou inférieure à 150, l'indice de solubilité (Ra(pi)) étant calculé à l'aide des paramètres de solubilité de Hansen des additifs respectifs (i) présents dans la composition de résine à base de chlorure de vinyle (A) et des paramètres de solubilité de Hansen de la résine à base de chlorure de vinyle (p) utilisés, et l'indice de solubilité (Ra(ci)) étant calculé à l'aide des paramètres de solubilité de Hansen des additifs respectifs (i) et des paramètres de solubilité de Hansen du matériau de base en fibres de carbone (B).
PCT/JP2020/011966 2019-03-25 2020-03-18 Matériau composite renforcé par des fibres de carbone à base de polychlorure de vinyle WO2020196153A1 (fr)

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JP2019057123A JP7332313B2 (ja) 2019-03-25 2019-03-25 ポリ塩化ビニル系炭素繊維強化複合材料
JP2019-057105 2019-03-25
JP2019057142 2019-03-25
JP2019057171 2019-03-25
JP2019057105A JP7332312B2 (ja) 2019-03-25 2019-03-25 ポリ塩化ビニル系炭素繊維強化複合材料
JP2019-057123 2019-03-25
JP2019-057142 2019-03-25
JP2019-057171 2019-03-25
JP2019155858A JP7323384B2 (ja) 2019-03-25 2019-08-28 ポリ塩化ビニル系炭素繊維強化複合材料
JP2019155872A JP7323385B2 (ja) 2019-03-25 2019-08-28 ポリ塩化ビニル系炭素繊維強化複合材料
JP2019-155872 2019-08-28
JP2019-155858 2019-08-28

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JPS4880170A (fr) * 1972-01-31 1973-10-26
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JPH0428534A (ja) * 1990-05-25 1992-01-31 Teijin Ltd 繊維強化複合成型物の製造法及びそれに用いる中間素材
JPH08267565A (ja) * 1995-03-31 1996-10-15 Sekisui Chem Co Ltd 繊維強化熱可塑性樹脂複合管の製造方法
JPH11291416A (ja) * 1998-04-13 1999-10-26 Asahi Glass Engineering Co Ltd 繊維補強塩化ビニル系樹脂成形体およびその製造方法
JP2002001811A (ja) * 2000-06-23 2002-01-08 Sekisui Chem Co Ltd 塩化ビニル系樹脂管の製造方法
JP2011213061A (ja) * 2010-04-01 2011-10-27 Mitsubishi Plastics Inc 積層体
JP2016092381A (ja) * 2014-11-11 2016-05-23 株式会社フジクラ 電磁波遮蔽用樹脂組成物、及び、ケーブル
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Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4880170A (fr) * 1972-01-31 1973-10-26
JPH03158211A (ja) * 1989-11-16 1991-07-08 Sekisui Chem Co Ltd 繊維強化ポリ塩化ビニル系樹脂複合材の製造方法
JPH0428534A (ja) * 1990-05-25 1992-01-31 Teijin Ltd 繊維強化複合成型物の製造法及びそれに用いる中間素材
JPH08267565A (ja) * 1995-03-31 1996-10-15 Sekisui Chem Co Ltd 繊維強化熱可塑性樹脂複合管の製造方法
JPH11291416A (ja) * 1998-04-13 1999-10-26 Asahi Glass Engineering Co Ltd 繊維補強塩化ビニル系樹脂成形体およびその製造方法
JP2002001811A (ja) * 2000-06-23 2002-01-08 Sekisui Chem Co Ltd 塩化ビニル系樹脂管の製造方法
JP2011213061A (ja) * 2010-04-01 2011-10-27 Mitsubishi Plastics Inc 積層体
JP2016092381A (ja) * 2014-11-11 2016-05-23 株式会社フジクラ 電磁波遮蔽用樹脂組成物、及び、ケーブル
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