WO2020196531A1 - Film de résine matricielle pour résines renforcées par des fibres, préimprégné, corps moulé en résine renforcée par des fibres de carbone et procédé de production d'un corps moulé en résine renforcée par des fibres de carbone - Google Patents

Film de résine matricielle pour résines renforcées par des fibres, préimprégné, corps moulé en résine renforcée par des fibres de carbone et procédé de production d'un corps moulé en résine renforcée par des fibres de carbone Download PDF

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WO2020196531A1
WO2020196531A1 PCT/JP2020/013045 JP2020013045W WO2020196531A1 WO 2020196531 A1 WO2020196531 A1 WO 2020196531A1 JP 2020013045 W JP2020013045 W JP 2020013045W WO 2020196531 A1 WO2020196531 A1 WO 2020196531A1
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Prior art keywords
resin
mass
resin composition
carbon fiber
prepreg
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PCT/JP2020/013045
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English (en)
Japanese (ja)
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宏和 飯塚
正嗣 大槻
真一郎 鈴木
陽 平田
雄介 菊本
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藤森工業株式会社
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Priority to JP2021509456A priority Critical patent/JP7426378B2/ja
Publication of WO2020196531A1 publication Critical patent/WO2020196531A1/fr

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    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture

Definitions

  • the present invention relates to a matrix resin film for a fiber reinforced resin, a prepreg, a carbon fiber reinforced resin molded body, and a method for producing a carbon fiber reinforced resin molded body.
  • the present application claims priority based on Japanese Patent Application No. 2019-057349 filed on March 25, 2019, the contents of which are incorporated herein by reference.
  • CFRP carbon fiber reinforced resin
  • a molded body using CFRP is obtained by molding a prepreg having a semi-cured curable resin and carbon fiber which is a reinforcing fiber, and curing the curable resin.
  • CFRP prepregs are produced, for example, by impregnating a carbon fiber woven fabric with a solution of curable resin, then removing the solvent from the solution, and then semi-curing the curable resin (eg, Patent Document). 1).
  • the present invention has been made in view of such circumstances, and is a matrix resin film for fiber reinforced resin, a prepreg, and a carbon fiber reinforced resin molded body capable of producing a molded body having high shear strength and few voids. , And a method for producing a carbon fiber reinforced resin molded body.
  • a matrix resin film for a fiber-reinforced resin having a first layer on one surface and a second layer on the other surface, wherein the first layer is composed of a first resin composition.
  • the second layer is composed of a second resin composition having a lower content of a cross-linking agent than the first resin composition, and the first resin composition is cross-linked with a main agent made of maleic acid-modified polyolefin.
  • the second resin composition contains a main agent made of maleic acid-modified polyolefin, and the solid content concentration of the main agent contained in the first resin composition is the first resin composition.
  • Matrix resin film for resin [2] The matrix resin film for a fiber reinforced resin according to [1], which has a thickness of 30 ⁇ m or more and 200 ⁇ m or less.
  • the prepreg according to [7] wherein the surface provided with the second layer is laminated so as to be in contact with the carbon fibers.
  • a matrix resin film for a fiber reinforced resin, a prepreg, a carbon fiber reinforced resin molded body, and a method for manufacturing a carbon fiber reinforced resin molded body, which enable the production of a molded body having high shear strength and few voids. can be provided.
  • the matrix resin film for fiber reinforced plastics of the present embodiment (hereinafter, may be referred to as “resin film”) has a first layer on one surface and a second layer on the other surface.
  • FIG. 1 shows a schematic view of a cross section of the resin film 11 of the present embodiment.
  • the resin film 11 includes a first layer 11A and a second layer 11B.
  • the first layer is composed of the first resin composition.
  • the second layer is composed of a second resin composition having a lower content of the cross-linking agent than the first resin composition.
  • the first resin composition contains a main agent composed of maleic acid-modified polyolefin and a cross-linking agent.
  • the second resin composition contains a main agent composed of maleic acid-modified polyolefin.
  • the first resin composition and the main agent constituting the second resin composition have thermoplasticity.
  • the maleic acid-modified polyolefin used as the main agent of the present embodiment is obtained by graft-modifying an unmodified polyolefin resin with either or both of maleic anhydride and maleic acid.
  • the “unmodified polyolefin resin” means a maleic anhydride or a polyolefin resin that has not been graft-modified with maleic acid.
  • Examples of the method for producing a maleic acid-modified polyolefin include the following two methods. (1) A method of graft-modifying an unmodified polyolefin resin with maleic anhydride or maleic acid by melt-kneading. (2) A method of copolymerizing an olefin monomer and an acid functional group-containing monomer. Either one or both of maleic anhydride and maleic acid is used as the "acid functional group-containing monomer".
  • the graft modification is preferably carried out in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.
  • a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.
  • the olefin monomer when copolymerized with maleic anhydride or maleic acid, or the olefin monomer constituting the unmodified polyolefin resin includes ethylene, propylene, 1-butene, isobutylene, 1-hexene, and the like.
  • One or more of 1-octene, ⁇ -olefin and the like can be mentioned.
  • Examples of the unmodified polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a copolymer of ethylene and propylene, a copolymer of propylene and 1-butene, and a random mixture of propylene and ethylene or ⁇ -olefin.
  • Examples thereof include one or more types such as a copolymer, a block copolymer of propylene and ethylene or ⁇ -olefin.
  • polypropylene-based resins such as homopolypropylene which is a homopolymer of propylene, a block copolymer of propylene-ethylene, a random copolymer of propylene-ethylene, and a propylene-1-butene copolymer are preferable. That is, in the present embodiment, the maleic acid-modified polypropylene-based resin is preferable as the maleic acid-modified polyolefin.
  • the monomer constituting the maleic acid-modified polyolefin contains 1-butene
  • the molecular movement of the main agent and the cross-linking agent constituting the resin film is promoted when the resin film is heated.
  • the main agent and the cross-linking agent have functional groups capable of reacting with each other, the chances of the functional groups of the main agent and the cross-linking agent coming into contact with each other increase, and as a result, the durability of the resin film and the adhesion to the adherend are further improved. To do.
  • maleic acid-modified polyolefin contains unreacted maleic acid or maleic anhydride
  • the adhesive strength may decrease. Therefore, as the main agent constituting the resin film, unreacted maleic acid or maleic anhydride-modified polyolefin containing no maleic anhydride is preferable.
  • the graft modification rate of maleic anhydride or maleic acid-modified polyolefin with maleic anhydride is 0.5% by mass or more and 3.0% by mass or less, and 0.5% by mass or more and 2.5% by mass or less. Is preferable.
  • the "graft denaturation rate" refers to a value obtained by measuring by the following method.
  • a film having a thickness of about 100 ⁇ m was prepared by hot-pressing a pellet-shaped sample of maleic anhydride, and the content of maleic acid (maleic acid content) was obtained from the absorption peak appearing at 1780 cm -1 in the infrared absorption spectrum and the separately obtained calibration curve. Mass%) is calibrated, and the obtained value is taken as the content rate (mass%) of total maleic anhydride. Let A be the obtained value.
  • the measurement sample After dissolving the pellet-shaped measurement sample in boiling xylene, the measurement sample is reprecipitated in methanol from the obtained solution. The precipitate is then vacuum dried at 80 ° C. for 6 hours to give a powdery sample.
  • the content of maleic anhydride contained in the obtained sample is calibrated by the same method as above, and the obtained value is taken as the content of maleic anhydride grafted on the polyolefin in the sample (mass%). Let B be the obtained value.
  • the content of graft-modified maleic anhydride (B) was divided by the content of total maleic anhydride (A), and the obtained value was expressed as a percentage ((B / A) ⁇ 100).
  • the graft denaturation rate (mass%) of maleic anhydride in the sample was expressed as a percentage ((B / A) ⁇ 100).
  • the graft denaturation rate may be measured by the following method.
  • the obtained sample is heat-pressed to prepare a film having a thickness of 100 ⁇ m.
  • the ratio of the absorption peak appearing at 1780 cm -1 to the absorption peak of polypropylene appearing at 840 cm -1 and the calibration curve of Ide et al. (Reference: Polymer Chemistry 25,167, 1968).
  • the obtained graft denaturation rate (mol%) can be converted into a graft denaturation rate (mass%) based on a separately obtained calibration curve.
  • a plurality of mixtures of polypropylene and maleic anhydride are prepared while changing the composition, and each mixture is heat-pressed to prepare a film having a thickness of 100 ⁇ m.
  • a calibration curve showing the correspondence between the content rate (mass%) of maleic anhydride contained in the film and the graft denaturation rate (mol%).
  • the acid value of the measurement sample of maleic acid-modified polyolefin can be obtained by an oxidation measurement method based on JIS K 0070, and the graft modification rate (mass%) can be obtained by converting the obtained acid value by the following formula. Good.
  • [Graft denaturation rate] [Acid value of maleic acid-modified polyolefin] ⁇ 11.4
  • Sample amount 1-2 g (fine scale)
  • Solvent Xylene (special grade reagent)
  • Indicator Phenolphthalein titrate: 0.05 mol / L KOH benzyl alcohol solution. Titrate in advance with 0.1 ml / L hydrochloric acid to determine the correct concentration.
  • a sample and 70 ml of solvent are added to a 100 ml Erlenmeyer flask, an air-cooled tube is attached, and the sample is heated in an oil bath at 135 ° C. for 15 minutes to obtain a xylene solution of the sample.
  • the melt viscosity of the maleic acid-modified polyolefin at a measurement temperature of 180 ° C. is preferably 1000 mPa ⁇ s or more and 50,000 mPa ⁇ s or less, and more preferably 5000 mPa ⁇ s or more and 20000 mPa ⁇ s or less.
  • the upper and lower limits of the melt viscosity can be arbitrarily combined.
  • the melt viscosity refers to a value measured by a method conforming to JIS K7199. Specifically, it refers to a value when measurement is performed using a rheometer (manufactured by AntonioPaar, device name: physicaMCR301) at a measurement temperature of 180 ° C., a strain amplitude of 3%, and a frequency of 1 Hz.
  • the melting point of the maleic acid-modified polyolefin is preferably 60 ° C. or higher and 130 ° C. or lower.
  • the melting point is preferably 70 ° C. or higher and 120 ° C. or lower, more preferably 75 ° C. or higher and 110 ° C. or lower, and further preferably 80 ° C. or higher and 100 ° C. or lower.
  • the weight average molecular weight of the maleic acid-modified polyolefin is not particularly limited, but is, for example, 10,000 to 800,000, preferably 50,000 to 650000, more preferably 80,000 to 550000, and even more preferably 100,000 to 450,000.
  • the first resin composition and the cross-linking agent constituting the second resin composition will be described.
  • the epoxy group-containing resin used as a cross-linking agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, glycidyl ether type epoxy resin, and glycidyl amine type epoxy resin. And so on.
  • the phenoxy resin is a polyhydroxypolyether resin synthesized from bisphenols and epichlorohydrin. The phenoxy resin can be used as a cross-linking agent when it has an epoxy group derived from epichlorohydrin as a raw material in its structure.
  • epoxy group-containing resin a phenol-type epoxy resin, a novolac-type epoxy resin, and a phenol novolac-type epoxy resin are preferable, and a phenol novolac-type epoxy resin is more preferable.
  • the epoxy group-containing resin bisphenol A type epoxy resin and bisphenol F type epoxy resin are also preferable.
  • the bisphenol A type epoxy resin means an epoxy resin having a bisphenol A skeleton.
  • the bisphenol F type epoxy resin means an epoxy resin having a bisphenol F skeleton.
  • a bisphenol type epoxy resin such as a bisphenol A type epoxy resin and a bisphenol F type epoxy resin is a compound having a bisphenol compound as a basic structure and an epoxy group introduced into a part of the structure. Since the bisphenol compound has two phenolic hydroxyl groups, the bisphenol type epoxy resin is usually a bifunctional epoxy resin having a bisphenol skeleton.
  • the phenol novolac type epoxy resin is a compound having a phenol novolac resin as a basic structure and an epoxy group introduced into a part of the structure.
  • the phenol novolac resin is generally also simply referred to as "novolak” and is obtained by condensing a phenolic compound and formaldehyde.
  • the amount of epoxy group introduced per molecule in the phenol novolac type epoxy resin is not particularly limited, but by reacting an epoxy group raw material such as epichlorohydrin with the phenol novolac resin, a large number of phenols present in the phenol novolac resin are present. Since a large number of epoxy groups are introduced into the sex hydroxyl group, it is usually a polyfunctional epoxy resin.
  • the phenolic compound constituting the phenol novolak resin may be any compound having a phenolic hydroxyl group, and a compound having no active hydrogen other than the hydroxyl group is preferable.
  • Specific examples of the phenolic compound include monophenolic compounds such as phenol (hydroxybenzene), cresol and naphthol, and bisphenol compounds such as bisphenol A, bisphenol E and bisphenol F.
  • the phenol novolac resin and the phenol novolac type epoxy resin constructed by using the bisphenol compound have a bisphenol skeleton.
  • a phenol novolac type epoxy resin having a bisphenol skeleton is preferable, and a phenol novolac type epoxy resin having a bisphenol A skeleton or bisphenol F is particularly preferable.
  • the epoxy equivalent of the epoxy group-containing resin is preferably 100 to 300, more preferably 200 to 300.
  • the epoxy equivalent (g / eq) corresponds to the weight average molecular weight of the epoxy group-containing resin per epoxy group, and the smaller this value is, the more epoxy groups are contained in the epoxy group-containing resin.
  • the weight average molecular weight of the epoxy group-containing resin constituting the cross-linking agent is preferably 300 or more and 50,000 or less, and preferably 10,000 or less.
  • the weight average molecular weight of the epoxy compound is 50,000 or less, the epoxy compound easily diffuses and moves easily in the main agent. Therefore, when the weight average molecular weight of the epoxy group-containing resin is not more than the above upper limit value, the reaction probability between the epoxy group of the cross-linking agent (epoxide group-containing resin) and the substituent of the main agent (maleic acid-modified polyolefin) increases. ..
  • the weight average molecular weight of the epoxy group-containing resin is not more than the above upper limit value
  • the epoxy group contained in the cross-linking agent is replaced with the surface of the fiber. The reaction probability with the group increases.
  • jER registered trademark
  • jER registered trademark
  • 157S70 jER
  • jER registered trademark
  • 157S65 Mitsubishi Chemical Co., Ltd .
  • EPICLON registered trademark
  • N-730A manufactured by DIC Co., Ltd.
  • EPICLON registered trademark
  • N-740 EPICLON (registered trademark) N-770
  • EPICLON registered trademark
  • N-775 all of which are trade names
  • the matrix resin film for the fiber-reinforced resin appropriately contains an additive, an additional resin, a plasticizer, a stabilizer, a colorant and the like which are miscible with the main agent and the cross-linking agent. Can be done.
  • the solid content concentration of the main agent contained in the first resin composition is 70% by mass or more and 99.5% by mass or less with respect to the total amount of the first resin composition.
  • the solid content concentration of the cross-linking agent contained in the first resin composition is 0.5% by mass or more and 30% by mass or less with respect to the total amount of the first resin composition.
  • the solid content concentration of the main agent contained in the second resin composition is 80% by mass or more and 100% by mass or less with respect to the total amount of the second resin composition.
  • the solid content concentration of the cross-linking agent contained in the second resin composition is smaller than the concentration of the cross-linking agent contained in the first resin composition, and is lower than the concentration of the cross-linking agent contained in the first resin composition. It is preferably 15% by mass less, more preferably 10% by mass less, and particularly preferably 5% by mass less. Further, the content of the cross-linking agent in the second resin composition may be 0% by mass.
  • a second sheet is formed by melt extrusion, and a coating liquid of a first resin composition containing a main agent and a cross-linking agent is formed on the second sheet. There is a method of applying and drying.
  • the film thickness of the resin film after drying is preferably 30 ⁇ m or more and 200 ⁇ m or less.
  • the film thickness of the resin sheet is preferably 20 ⁇ m or more and 150 ⁇ m or less, more preferably 30 ⁇ m or more and 100 ⁇ m or less, and most preferably 40 ⁇ m or more and 80 ⁇ m or less.
  • the ratio of the thickness of the first layer to the sum of the thicknesses of the first layer and the second layer is preferably 0.4 or less, more preferably 0.3 or less, and preferably 0.05 or more and 0.07 or more. ..
  • the coating liquid a coating liquid in which the main agent and the cross-linking agent are dissolved in a solvent is preferable.
  • the solvent an organic solvent having excellent drying property after coating, in addition to the solubility of the main agent and the cross-linking agent, is preferable.
  • the boiling point of the solvent is preferably, for example, 150 ° C. or lower.
  • the solvent include aromatics such as toluene, xylene, anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, simene and mesitylene.
  • aromatics such as toluene, xylene, anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, simene and mesitylene.
  • Aliphatic solvent such as n-hexane
  • Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone
  • Ester solvents such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol.
  • solvent used in the coating liquid one of the above-mentioned solvents may be used alone, or two or more of them may be used in combination.
  • a combination of an organic solvent that dissolves the main agent well and an organic solvent that dissolves the cross-linking agent well it is also preferable to use a combination of an organic solvent that dissolves the main agent well and an organic solvent that dissolves the cross-linking agent well.
  • a combination of toluene that dissolves the main agent well and methyl ethyl ketone that dissolves the cross-linking agent well is preferable.
  • the method for producing the coating liquid using the mixed solvent may be a method of dissolving the main agent and the cross-linking agent in the mixed solvent, or a method of mixing the solution of the main agent and the solution of the cross-linking agent.
  • the mixing ratio in the mixed solvent is not particularly limited as long as the main agent and the cross-linking agent can be dissolved well.
  • the mass ratio is preferably 60 to 95: 5 to 40, more preferably 70 to 90:10 to 30.
  • the resin film may be produced by melt extrusion using a known sheet die or T die.
  • the resin film to be produced is likely to be thickened as compared with the method of applying and drying the above-mentioned coating liquid.
  • the resin film of the present embodiment may include layers other than the first layer and the second layer as long as the effects of the present embodiment are not impaired.
  • the other layer is preferably a polyolefin-based layer.
  • the present embodiment is a prepreg in which the resin film of the present embodiment and carbon fibers are laminated.
  • FIG. 2 is a schematic cross-sectional view showing the prepreg of the present embodiment.
  • the prepreg 1 of the present embodiment includes a resin layer 10 and a carbon fiber layer 20.
  • the resin layer 10 contains the above-mentioned main agent and cross-linking agent.
  • the carbon fiber layer 20 is composed of a plurality of carbon fibers 29 buried in the resin layer 10.
  • the gaps 20a of the plurality of carbon fibers 29 are impregnated with the main agent and the cross-linking agent constituting the resin layer 10.
  • the resin film is used as the resin film 11.
  • the carbon fibers are preferably continuous fibers.
  • Continuous carbon fiber is a general term for fibrous carbon materials composed of substantially only carbon elements.
  • commonly known carbon fibers such as pitch-based carbon fiber and PAN-based carbon fiber can be used.
  • the carbon fiber as the continuous carbon fiber may be a single fiber or a twisted yarn.
  • the continuous fiber means a bundle of fibers continuous over the entire length of the prepreg.
  • the continuous fiber may be a woven fabric or a knitted fabric formed by using carbon fiber which is a continuous fiber.
  • woven fabric commonly known weaving methods such as plain weave, twill weave (oblique weave), and satin weave can be adopted.
  • the carbon fiber sheet 21 is a molded body in which carbon fibers are molded into a sheet shape.
  • a woven fabric having the same shape as the above-mentioned carbon fiber can be mentioned.
  • the resin film 11 is pressure-bonded to the carbon fiber sheet 21 to obtain a laminate 1B composed of the resin film 11, the carbon fiber sheet 21, and the resin film 11.
  • the resin film 11 is heated and melted in a temperature range equal to or higher than the softening point (softening temperature) of the resin film 11 and lower than the reaction start temperature of the cross-linking agent contained in the resin film 11. Further, the molten resin film 11 is pressed toward the carbon fiber sheet 21.
  • the "softening point of the resin film 11" is a softening point of the matrix resin for fiber reinforced resin constituting the resin film 11.
  • the resin constituting the resin film 11 is melted and penetrates into the gaps 20a of the plurality of carbon fibers 29 constituting the carbon fiber sheet 21.
  • prepreg 1 is generated.
  • the obtained prepreg 1 may be cooled after pressurization.
  • the cross-linking agent contained in the resin sheet 11 may unintentionally undergo a cross-linking reaction due to heating, and curing may proceed.
  • the unintended cross-linking reaction as described above can be suppressed or stopped.
  • the melted resin when the resins constituting the second layer 11B of each of the pair of resin films are melted, the melted resin has a low content of a cross-linking agent, so that it has high fluidity and is a carbon fiber sheet. It is easy to impregnate 21. Therefore, the generation of voids can be suppressed.
  • the cross-linking agents contained in the first layer 11A of each of the pair of resin films are easily cross-linked inside the carbon fiber sheet 21, and the strength of the manufactured molded product can be increased.
  • FIG. 7 An embodiment of a method for producing a prepreg will be described with reference to FIG.
  • the first layer 11A and the second layer 11B are laminated so as to be in contact with the carbon fiber sheet 21. Then pressurize and stick.
  • the cross-linking agent contained in the resin sheet is easily dispersed when laminated with carbon fibers and pressed, and can be cured in a short time.
  • the prepreg produced using the resin sheet of the present embodiment tends to have a gradient in the concentration of the cross-linking agent in the depth direction.
  • the present embodiment is a carbon fiber reinforced resin molded body in which the prepreg of the present embodiment is laminated.
  • the carbon fiber reinforced resin molded body may be simply referred to as a “molded body”.
  • the method for producing a carbon fiber reinforced resin molded product of the present embodiment includes a step of laminating prepregs to obtain a laminated body and a step of stampable molding the obtained laminated body.
  • the obtained prepreg 1 of the present embodiment is used as a stampable sheet.
  • the prepreg 1 can be molded by heating to produce a molded body.
  • the molded body is formed by performing so-called stampable molding, in which only one prepreg 1 or a laminated body obtained by laminating a plurality of prepregs 1 is heated and softened, and the softened prepreg 1 is pressed by a mold to be molded. Can be manufactured.
  • the prepreg 1 is heated to a temperature equal to or higher than the reaction start temperature of the cross-linking agent contained in the resin layer 10, so that the cross-linking reaction between the main agent constituting the resin layer 10 and the cross-linking agent proceeds and the prepreg 1 is cured. As a result, the desired molded body can be obtained.
  • the measurement sample was reprecipitated in methanol from the obtained solution. Then, the precipitate was vacuum dried at 80 ° C. for 6 hours to obtain a powdery sample.
  • the amount of maleic anhydride contained in the obtained sample was calibrated by the same method as above, and the obtained value was used as the amount of maleic anhydride grafted on the polyolefin in the sample.
  • the obtained value was designated as B.
  • the amount of maleic anhydride (B) that has been graft-modified is divided by the total amount of maleic anhydride (A), and the value obtained is expressed as a percentage ((B / A) x 100).
  • the graft modification rate (mass%) of the maleic anhydride-modified polyolefin by acid was used.
  • Examples 1 to 4 Comparative Examples 1 and 2
  • a resin film was produced according to the configuration shown in Table 1. Specifically, a toluene solution of a maleic acid-modified polypropylene resin as a main agent and a cross-linking agent was applied by bar coating on a PET base film that had been subjected to a mold release treatment, and dried to obtain a resin film. .. The film thickness of each resin film was the film thickness shown in Table 1.
  • the carbon fiber sheets shown in Table 1 were sandwiched between the two obtained resin films to form a laminate, and the obtained laminate was heated and pressed under the following conditions to produce a prepreg.
  • the thickness of the prepreg is shown in Table 1, respectively. Heating: 180 ° C Pressure: 30cm 2 corners per 0.5t load time: 1 minute
  • CF1 Carbon fiber plain woven fabric (trade name: Trading Card Cloth CO-6363, manufactured by Toray Industries, Inc.)
  • Epoxy Special novolak type epoxy resin (epoxy equivalent 200, softening point 70 ° C). It contains a bisphenol A skeleton in the molecule and contains an epoxy group with a novolak structure.
  • the resin permeability of the obtained prepreg was evaluated as follows. First, the prepreg 1 was cut in a direction intersecting the fiber direction of the carbon fibers to form a surface in which both the carbon fibers and the resin were present in the cross section of the prepreg 1 and the carbon fibers looked circular.
  • the region excluding the carbon fiber that looks circular was regarded as the resin portion or the gap portion where the resin did not penetrate.
  • the boundary between the resin part and the gap part was judged from the change in brightness of the image. That is, the set of parts where the contrast is suddenly darker than the vicinity where the contrast is adjacent is regarded as the gap part, and the other parts are regarded as the resin part.
  • the sudden darkening means a point where the brightness becomes three times or less when the movement corresponding to 0.5 ⁇ m is performed from an arbitrary point.
  • the set of the parts where the certain range is darkened is defined as the gap part.
  • the same operation was performed in the entire image area at intervals of 0.5 ⁇ m in the y-axis direction, and the boundary line between the gap portion and the resin portion was drawn from the obtained multiple boundary points.
  • the side with high brightness was the resin part and the side with low brightness was the gap part across the drawn boundary line.
  • the area Sp of the resin portion and the area Sv of the gap portion were obtained from the region excluding the carbon fibers that appeared to be circular in the captured image.
  • the resin permeability of the prepreg to the carbon fibers was evaluated according to the following items. “ ⁇ ”, “ ⁇ ” and “ ⁇ ” were evaluated as non-defective products, and “ ⁇ ” was evaluated as defective products. The results are shown in Table 1. “ ⁇ ”: The porosity was less than 1%. “ ⁇ ”: The porosity was 1% or more and less than 2%. “ ⁇ ”: The porosity was 2% or more and less than 5%. “X”: The porosity was 5% or more.
  • the interfacial shear strength was evaluated according to the following criteria. The results are shown in Table 1. " ⁇ ”: Interfacial shear strength is 30 MPa or more. “ ⁇ ”: Interfacial shear strength is 20 MPa or more and less than 30 MPa. “ ⁇ ”: Interfacial shear strength is 10 MPa or more and less than 20 MPa. “X”: Interfacial shear strength is less than 10 MPa.
  • the prepreg of the example had fewer voids and the interfacial shear strength was higher than that of the prepreg of the comparative example.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un film de résine matricielle pour des résines renforcées par des fibres, qui comprend une première couche dans une surface, tout en comprenant une seconde couche dans l'autre surface et qui est conçu de telle sorte que : la première couche est formée d'une première composition de résine ; la première composition de résine contient un matériau de base qui est composé d'une polyoléfine modifiée par l'acide maléique et d'un agent de réticulation ; une seconde composition de résine ; la concentration en matières solides du matériau principal contenu dans la première composition de résine est de 7 0% en masse à 99,5 % en masse (inclus) par rapport à la masse totale de la première composition de résine ; la concentration en matières solides de l'agent de réticulation contenu dans la première composition de résine est comprise entre 0,5 % en masse et 30 % en masse (inclus) par rapport à la masse totale de la première composition de résine ; et la concentration en matières solides du matériau principal contenu dans la seconde composition de résine est comprise entre 80 % en masse et 100 % en masse (inclus) par rapport à la masse totale de la seconde composition de résine.
PCT/JP2020/013045 2019-03-25 2020-03-24 Film de résine matricielle pour résines renforcées par des fibres, préimprégné, corps moulé en résine renforcée par des fibres de carbone et procédé de production d'un corps moulé en résine renforcée par des fibres de carbone WO2020196531A1 (fr)

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JP2017043672A (ja) * 2015-08-25 2017-03-02 三菱レイヨン株式会社 熱成形用複合材
JP2018135467A (ja) * 2017-02-22 2018-08-30 藤森工業株式会社 ホットメルト接着性樹脂積層体及び積層体

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WO2017006681A1 (fr) 2015-07-03 2017-01-12 東洋紡株式会社 Composition adhésive pour panneaux de structure de véhicule automobile à base de polyoléfine
JP7058073B2 (ja) 2017-02-16 2022-04-21 藤森工業株式会社 積層体及び積層体の製造方法
JP6937594B2 (ja) 2017-03-23 2021-09-22 日鉄ケミカル＆マテリアル株式会社 炭素繊維強化樹脂組成物用の密着性付与剤
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JP2017043672A (ja) * 2015-08-25 2017-03-02 三菱レイヨン株式会社 熱成形用複合材
JP2018135467A (ja) * 2017-02-22 2018-08-30 藤森工業株式会社 ホットメルト接着性樹脂積層体及び積層体

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JP7426378B2 (ja) 2024-02-01

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