WO2020241623A1 - Préimprégné en étoupes - Google Patents

Préimprégné en étoupes Download PDF

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WO2020241623A1
WO2020241623A1 PCT/JP2020/020693 JP2020020693W WO2020241623A1 WO 2020241623 A1 WO2020241623 A1 WO 2020241623A1 JP 2020020693 W JP2020020693 W JP 2020020693W WO 2020241623 A1 WO2020241623 A1 WO 2020241623A1
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Prior art keywords
epoxy resin
component
resin composition
components
tow preg
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PCT/JP2020/020693
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English (en)
Japanese (ja)
Inventor
都築正博
土田紘也
吉崎聡一
荒井信之
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東レ株式会社
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Priority to KR1020217036254A priority Critical patent/KR20220016051A/ko
Priority to JP2020529665A priority patent/JPWO2020241623A1/ja
Publication of WO2020241623A1 publication Critical patent/WO2020241623A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of 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
    • C08J2421/00—Characterised by the use of unspecified rubbers

Definitions

  • the present invention particularly relates to a tow preg that is suitably used for manufacturing a hollow container or cylinder made of a fiber-reinforced composite material. More specifically, the present invention relates to a tow preg that is easy to handle, has few voids, and can obtain a high-quality molded product.
  • Fiber reinforced composite materials using reinforced fibers such as carbon fiber and glass fiber are applied to many fields such as aerospace, automobiles, railroad vehicles, ships, civil engineering and construction and sporting goods due to their excellent light weight. There is. In particular, in applications where high performance is required, fiber-reinforced composite materials using continuous reinforcing fibers are used, carbon fibers having excellent specific strength and specific elastic modulus are used as reinforcing fibers, and thermosetting resins are used. , Epoxy resins having excellent adhesion to carbon fibers are often used.
  • filament winding is a method preferably used for manufacturing hollow containers such as pressure vessels and cylinders.
  • Toe prepregs and yarn prepregs in which thermosetting resin is pre-impregnated in the reinforcing fiber bundles instead of the conventional wet method in which the reinforcing fiber bundle unwound from the bobbin is immersed in a liquid thermoplastic resin and then wound onto a mold.
  • a method of supplying a narrow intermediate base material hereinafter referred to as tow prepreg
  • a strand prepreg or the like winding it on a mold is attracting attention from the viewpoint of productivity and quality.
  • the tow preg is usually supplied in the form of a bobbin in which hundreds to thousands of meters are wound around a paper tube, and is unraveled at high speed in the molding process of the fiber-reinforced composite material.
  • the bobbin does not slip off from the paper tube when the bobbin is erected, the bobbin is less tightly wound during unwinding, and the shape stability of the bobbin is good, the toe widening property during filament winding molding is improved. It is also required that it is good and that gaps are hard to form.
  • the epoxy resin is less deteriorated when the epoxy resin before being impregnated with the toe is stored for a long period of time.
  • Patent Document 1 discloses a tow preg obtained by impregnating a reinforcing fiber bundle with an epoxy resin composition in which a solid curing agent, dicyandiamide, is dispersed.
  • a paper tube when a bobbin is erected is disclosed. Although it does not slip off from the toe, there is a problem that the widening property of the toe during filament winding molding is poor and a gap is easily formed.
  • Patent Document 2 discloses a tow preg obtained by impregnating a reinforcing fiber bundle with an epoxy resin composition in which a boron halide amine complex is dissolved as a curing agent. Such a tow preg is used during filament winding molding. Although the tow has good widening property and it is difficult to form a gap, there is a problem that the bobbin slips off from the paper tube when it is erected.
  • the present invention states that the bobbin does not slip off from the paper tube when it is erected, that the bobbin is less tightly wound during unwinding and that the shape stability of the bobbin is good, and that the toe during filament winding molding is used.
  • An object of the present invention is to provide a tow preg that has good widening property and satisfies all the requirements that gaps are difficult to form.
  • the bobbin does not slip off from the paper tube when the bobbin is erected, the toe has good widening property during filament winding molding, and a gap is formed.
  • the challenge is to provide a tow preg that is both difficult and difficult.
  • the tow preg of the present invention is reinforced with an epoxy resin composition containing the following components [A] and [B], satisfying the condition (I), and further satisfying any one of the conditions (X) and (Y).
  • a tow preg made by impregnating a fiber bundle.
  • Epoxy resin curing agent compatible with epoxy resins [B] [A] (I) (i) Components [A], [B] and the following components [C], or (ii) component [A] ], [B] and the complex shear viscosity ( ⁇ 0.1) measured at 25 ° C.
  • Thixotropy index (TI 4 ) of an epoxy resin composition prepared by mixing the component [B] 4 days after preparing the main agent containing the hydrophobic rock denaturing agent (IV) components [A] and [C1].
  • ⁇ '0.1 / ⁇ ' 10) is 1.5 or more. (Here, eta '0.1, the components [A], by mixing the components [B] Four days after the preparation of the main component containing [C1], using a parallel plate vibration rheometer, 25 ° C., a frequency 0.
  • the content of the component (V) component [C1] is 1.0 to 7.0 parts by mass with respect to 100 parts by mass of the component [A].
  • the tow preg of the present invention has no slippage from the paper tube when the bobbin is erected, less tightening during unwinding and good shape stability of the bobbin, and widening of the toe during filament winding molding. Since it is good and all that it is difficult to form a gap is satisfied, it is possible to obtain a molded product having excellent handleability at the time of manufacturing a hollow container such as a pressure vessel by a filament winding method or a cylinder, and having few voids and good quality.
  • the tow preg of the present invention does not slip off from the paper tube when the bobbin is erected even when an epoxy resin stored for a long period of time is used, and the toe has good widening property during filament winding molding. Since it is possible to obtain a molded product having excellent handleability at the time of manufacturing a hollow container such as a pressure vessel or a cylinder by the filament winding method and having few voids, it is possible to obtain a good quality molded product.
  • the present invention has the following configuration. That is, the tow preg of the present invention is reinforced with an epoxy resin composition containing the following components [A] and [B], satisfying the condition (I), and further satisfying any one of the conditions (X) and (Y).
  • a tow preg made by impregnating a fiber bundle.
  • eta '0.1 the components [A], by mixing the components [B] Four days after the preparation of the main component containing [C1], using a parallel plate vibration rheometer, 25 ° C., a frequency 0. is the complex shear viscosity measured at 1 Hz, eta '10, the components [a], by mixing the components [B] four days after the preparation of the main component containing [C1], using a parallel plate vibration rheometer, 25 ° C. , Complex shear viscosity measured at a frequency of 10 Hz.
  • the content of the component (V) component [C1] is 1.0 to 7.0 parts by mass with respect to 100 parts by mass of the component [A].
  • the component [A] in the present invention is an epoxy resin.
  • the epoxy resin is not particularly limited, and is, for example, a bisphenol type epoxy resin such as bisphenol A type, bisphenol F type, or bisphenol S type, glycidyl aniline type, diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, and metaxylene.
  • Glycidylamine type epoxy resin such as diamine type, 1,3-bisaminomethylcyclohexane type, isocyanurate type, hydantin type, phenol novolac type, orthocresol novolac type, dicyclopentadiene novolac type, biphenyl type, trishydroxyphenylmethane type And tetraphenylol ethane type epoxy resin and the like.
  • epoxy resins may be used alone or in admixture as appropriate.
  • epoxy resins it has the effect of imparting stability to the epoxy resin composition and preventing thickening of the epoxy resin composition during the preparation process of the epoxy resin composition, the manufacturing process of the tow preg, and the storage period of the tow preg. Therefore, it is preferable to contain a glycidylamine type epoxy resin. By preventing the thickening of the epoxy resin composition in such a process and period, the impregnated state of the epoxy resin composition in the tow preg can be improved, and the unfoldability at the time of molding can be kept good.
  • Examples of the glycidylamine type epoxy resin include glycidylaniline type, diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, metaxylylenediamine type, and 1,3-bisaminomethylcyclohexane type.
  • Commercially available products of such glycidylamine type epoxy resin include GAN (N, N-diglycidylaniline, manufactured by Nippon Kayaku Co., Ltd.), GOT (N, N-diglycidyl-o-toluidin, Nippon Kayaku Co., Ltd.).
  • the content of the glycidylamine type epoxy resin is preferably 10 parts by mass or more, more preferably 10 to 80 parts by mass, and 20 to 60 parts by mass in 100 parts by mass of the component [A]. Especially preferable.
  • the content of the glycidylamine type epoxy resin is preferably 10 parts by mass or more out of 100 parts by mass of the component [A].
  • the effect of preventing the thickening of the epoxy resin composition can be obtained.
  • an epoxy resin composition for tow preg that provides a fiber-reinforced composite material having an excellent balance of mechanical properties can be obtained.
  • the component [B] in the present invention is an epoxy resin curing agent that is compatible with the component [A] contained in the epoxy resin composition in the tow preg of the present invention.
  • being compatible with the component [A] means that the epoxy resin composition to be impregnated with the tow preg does not contain substantially a solid epoxy resin curing agent, and can be observed with an optical microscope or used. If the particle component derived from the curing agent of the raw material is not detected by a method such as particle size distribution measurement by a light scattering method, it can be confirmed that the particles are compatible.
  • the component [B] can be dissolved in the component [A] in a temperature range in which a rapid reaction with the component [A] does not start, and can maintain a compatible state at 25 ° C., or at 25 ° C. It needs to be a liquid curing agent that can maintain a compatible state, and is more preferably liquid from the viewpoint of leaving no solid content.
  • the component [B] it is possible to obtain a toe preg having good toe widening property at the time of filament winding molding and having less gaps.
  • component [B] examples include aliphatic amines, aromatic amines, polyphenols, imidazoles, carboxylic acids, carboxylic acid anhydrides, carboxylic acid amides, mercaptans, and Lewis acids such as boron halide amine complexes. Further, these epoxy resin curing agents may be used alone or in an appropriate mixture.
  • aromatic amines are particularly preferably used because it is possible to obtain an epoxy resin composition for tow preg that provides a fiber-reinforced composite material having an excellent balance of mechanical properties.
  • an aromatic amine liquid at 25 ° C. is more preferable.
  • the aromatic amine is a general term for compounds having an amino group directly bonded to an aromatic ring.
  • the aromatic amine liquid at 25 ° C. include compounds having one aromatic ring such as aminobenzylamine and diethyltoluenediamine, and aromatic rings such as 3,3'-diethyl-4,4'-diaminodiphenylmethane. Examples thereof include a compound having two.
  • aromatic amines Commercially available products of such aromatic amines include ABAM (aminobenzylamine, Mitsui Kagaku Fine Co., Ltd.), "jER Cure (registered trademark)” WA (diethyltoluenediamine, manufactured by Mitsubishi Chemical Co., Ltd.), and “LONZACURE (registered). Trademarks) “DETDA80 (diethyltoluenediamine, manufactured by Ronza Japan Co., Ltd.),” KAYAHARD (registered trademark) "AA (3,3'-diethyl-4,4'-diaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.), etc. Can be mentioned.
  • the content of the aromatic amine liquid at 25 ° C. is preferably an amount in which active hydrogen is 0.7 to 2.0 equivalents with respect to the epoxy group of each epoxy resin component contained in the component [A]. , 0.7 to 1.8 equivalents, more preferably.
  • the epoxy resin composition impregnated in the tow preg of the present invention comprises (i) component [A], [B] and a component [C] described later, or (ii) component [A], [B] and a component described later.
  • the complex shear viscosity ( ⁇ 0.1 ) measured at 25 ° C. and a frequency of 0.1 Hz using a parallel plate vibration rheometer was 40 to 300 Pa ⁇ s. It is necessary that the frequency is 100 to 300 Pa ⁇ s, which is more preferable.
  • ⁇ 0.1 is 40 Pa ⁇ s or more, it is possible to suppress the bobbin from slipping off the paper tube when the bobbin is erected and the winding tightening at the time of unwinding. Further, when ⁇ 0.1 is 300 Pa ⁇ s or less, it is possible to prevent poor liquid feeding in the tow preg manufacturing process and poor formation of the resin coating film on the kiss roll.
  • condition (I) immediately after preparing the epoxy resin composition, when the epoxy resin composition contains (i) components [A] and [B] and a component [C] described later, the component [A] ] And [C], 1 hour after the main agent was prepared, and 30 minutes after the preparation of the epoxy resin composition was completed by further mixing the component [B], and similarly, the epoxy resin composition.
  • the substance contains (ii) component [A], [B] and component [C1] described later, one hour after preparing the main agent containing component [A] and [C1], further component [ It means that it is 30 minutes after the preparation of the epoxy resin composition is completed by mixing B].
  • the condition (X) is that the epoxy resin composition contains (i) components [A] and [B] and a component [C] described later, and satisfies the conditions (II) and (III).
  • [C] Immediately after preparing the epoxy resin composition containing the components [A], [B] and [C] of the shear modifier (II), it was measured at 25 ° C. and a frequency of 10 Hz using a parallel plate vibration rheometer. The complex shear viscosity ( ⁇ 10 ) is 50 Pa ⁇ s or less.
  • (III) Complex shear viscosity ( ⁇ 0.1 ) measured at 25 ° C.
  • the ratio ( ⁇ 0.1 / ⁇ 10 ) to the viscosity ( ⁇ 10 ) is 1.5 or more.
  • the component [C] in the present invention is a shake denaturing agent contained in the epoxy resin composition in the tow preg of the present invention.
  • the shaking denaturation means a phenomenon in which the apparent viscosity decreases by applying a shear stress and returns to the original apparent viscosity after a lapse of time after being allowed to stand. That is, it is a phenomenon that the viscosity is high under low frequency conditions and the viscosity is low under high frequency conditions.
  • the bobbin does not slip off from the paper tube when it is erected, the bobbin is less tightly wound during unwinding, and the shape stability of the bobbin is good. Filament winding molding It is possible to obtain a tow preg that has good widening property of the toe at the time and satisfies all the requirements that gaps are difficult to form.
  • the slipping off from the paper tube when the bobbin is erected means that the bobbin-shaped tow preg, which is made by winding a tow preg of several hundred to several thousand meters around the paper tube, is placed on the surface of the workbench in the longitudinal direction of the paper tube.
  • This is a phenomenon in which the toe preg slides down and the bobbin shape collapses when it is installed so as to be vertical to the other and left to stand.
  • FIG. 1 shows a schematic diagram showing the sliding-down phenomenon. Once the slip-off phenomenon occurs, the thread falls off at the end of the bobbin whose shape has collapsed, so that the toe cannot be unwound. Since the slip-off phenomenon is a deformation that occurs over a relatively long period of time, the occurrence can be suppressed if the epoxy resin composition impregnated in the reinforcing fiber bundle has a high viscosity under low frequency conditions.
  • the winding tightening at the time of unwinding is when a bobbin-shaped tow preg made by winding a toe preg of several hundred to several thousand meters on a paper tube is attached to the creel of a filament winding device and tension is applied to perform molding.
  • the bobbin is squeezed and deformed by the applied tension, causing unevenness on the bobbin surface and bulging of the bobbin end face.
  • FIG. 2 shows a schematic diagram showing the winding tightening phenomenon.
  • the winding tightening phenomenon occurs, the thread comes off at the end of the bobbin that has bulged out, and the toe preg cannot be unwound. Since the winding tightening phenomenon is a deformation that occurs over a relatively long period of time, the occurrence can be suppressed if the viscosity of the epoxy resin composition impregnated in the reinforcing fiber bundle is high under low frequency conditions.
  • the widening of the toe during filament winding molding is a phenomenon in which the width of the tow preg is widened by the pressure when the tow is wound around the liner of the pressure vessel or the mandrel used for molding the cylinder. If the tow preg has insufficient widening property, voids are generated in the molded product, especially when manufacturing a pressure vessel, near the mouthpiece, which causes a decrease in burst strength. Since the widening phenomenon is a deformation that occurs in a relatively short time, good widening property can be obtained if the viscosity of the epoxy resin composition impregnated in the reinforcing fiber bundle is low under high frequency conditions.
  • the bobbin does not slip off the paper tube when it is erected, the bobbin is less tightly wound during unwinding and the shape stability of the bobbin is good, and the toe widening property during filament winding molding is good.
  • the epoxy resin composition impregnated in the reinforcing fiber bundle has a high viscosity under low frequency conditions and a low viscosity under high frequency conditions. This can be achieved by the inclusion of an impartant.
  • rocking modifiers include organic substances such as amido wax and hydrogenated castor oil, silica, alumina, mixed oxides of aluminum and silicon, titanium oxide, light calcium carbonate, and smectite clay minerals (montmorillonite, bidelite, etc.). Bentonite, hectorite, saponite, etc.), sepiolite, carbon black and other inorganic substances can be mentioned.
  • these sway denaturing agents those having a large sway denaturing effect are desirable. From this point of view, it is preferable to contain at least one selected from the group consisting of bentonite, fine particle silica and amide wax, and more preferably to contain hydrophobic fine particle silica. Further, these sway denaturing agents may be used alone or in an appropriate mixture.
  • the amidowax-based rocking modifier is a rocking modifier having an amide structure in which a fatty acid and an amine are condensed.
  • Examples of commercially available products of such amidowax-based rock denaturing agents include "Disparon (registered trademark)" 6500 (manufactured by Kusumoto Kasei Co., Ltd.) and "Tarren (registered trademark)” VA-750B (manufactured by Kyoeisha Chemical Co., Ltd.). ..
  • the bentonite-based rock denaturing agent is a rocking denaturing agent made from a mineral having a layered structure.
  • an epoxy resin modified with an organic compound so as to have a large effect of imparting shaking modification is preferable. Further, it may be a mixture with a mineral having a structure other than the layered structure.
  • Commercially available products of such bentonite-based rock denaturing agents include "TIXOGEL (registered trademark)" MPZ (manufactured by BIC Chemie Japan Co., Ltd.) and "GARAMITE (registered trademark)” 7305 (manufactured by BIC Chemie Japan Co., Ltd.). Be done.
  • the fine particle silica-based shaking modification imparting agent is fine particle silica having a primary particle diameter of several nanometers to several tens of nanometers, and fumed silica obtained by a combustion heating decomposition method or the like is preferably used.
  • Examples of commercially available products of such a fine silica-based shake modification imparting agent include "AEROSIL (registered trademark)” 130 (manufactured by Nippon Aerosil Co., Ltd.) and "AEROSIL (registered trademark)” 300 (manufactured by Nippon Aerosil Co., Ltd.).
  • a shaking denaturing agent using hydrophobic fine particle silica subjected to a hydrophobic surface treatment is more preferable because it has a large shaking denaturing effect.
  • the hydrophobic surface treatment is a treatment in which an alkylsilyl group such as a dimethylsilyl group or a trimethylsilyl group or a hydrophobic substituent such as dimethylpolysiloxane is bonded to a silanol group on the surface of fine particle silica.
  • AEROSIL registered trademark
  • R972 manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL registered trademark
  • R812 manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL registered trademark
  • RY200S manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL registered trademark
  • R805 manufactured by Japan Aerosil Co., Ltd.
  • the content of the shaking denaturing agent is preferably 1.0 to 20 parts by mass, and more preferably 3.0 to 7 parts by mass with respect to 100 parts by mass of the component [A].
  • viscosity is evaluated using “complex shear viscosity” as an index.
  • the epoxy resin composition to be impregnated in the tow preg of the present invention has a frequency of 25 ° C. using a parallel plate vibration rheometer immediately after the epoxy resin composition containing the components [A], [B] and [C] is prepared.
  • the complex shear viscosity ( ⁇ 10 ) measured at 10 Hz needs to be 50 Pa ⁇ s or less, preferably 1.0 to 50 Pa ⁇ s, and more preferably 4 to 50 Pa ⁇ s.
  • ⁇ 10 is 50 Pa ⁇ s or less, the widening property of the toe during filament winding molding can be improved, and the lower the ⁇ 10 is, the better the widening property can be obtained. Further, by setting ⁇ 10 to 1.0 or more, it is possible to achieve both suppression of resin scattering and good toe widening property.
  • the epoxy resin composition to be impregnated in the tow preg of the present invention is a parallel plate vibration rheometer having a complex shear viscosity ( ⁇ 0.1 ) measured at 25 ° C. and a frequency of 0.1 Hz using a parallel plate vibration rheometer.
  • the ratio ( ⁇ 0.1 / ⁇ 10 ) to the complex shear viscosity ( ⁇ 10 ) measured at 25 ° C. and a frequency of 10 Hz needs to be 1.5 or more, preferably 3.0 or more.
  • the bobbin does not slip off from the paper tube when it is erected, there is little winding tightening at the time of unwinding, and the shape stability of the bobbin is good. It is possible to obtain a tow preg that has good toe widening property at the time of filament winding molding and that it is difficult to form a gap, and the larger ⁇ 0.1 / ⁇ 10 is, the better the balance between them can be obtained.
  • the upper limit is not particularly limited, but is usually 300 or less.
  • condition complex shear viscosity at (III) ( ⁇ 0.1) is a condition the complex shear viscosity was obtained by (I) ( ⁇ 0.1)
  • ⁇ 10 is the complex obtained by the condition (II) It means shear viscosity ( ⁇ 10 )
  • the epoxy resin composition contains (i) component [A], [B] and the following component [C], the complex shear viscosity ( ⁇ 0 ) obtained under the condition (I).
  • the ratio to the complex shear viscosity ( ⁇ 10 ) obtained under the condition (II) of 1.1) is specified.
  • the condition (Y) includes (ii) components [A] and [B] and the following component [C1], and satisfies the conditions (IV) and (V).
  • [C1] Thixotropy index (TI 4 ) of an epoxy resin composition prepared by mixing the component [B] 4 days after preparing the main agent containing the hydrophobic rock denaturing agent (IV) components [A] and [C1]. ⁇ '0.1 / ⁇ ' 10) is 1.5 or more.
  • the component [C1] in another aspect of the present invention is a hydrophobic rock denaturing agent contained in the epoxy resin composition in the tow preg of the present invention.
  • the rock denaturing agent in another aspect of the present invention is a hydrophobic rock denaturing agent in which the surface of the rock denaturing agent is treated with a hydrophobic surface treatment.
  • a hydrophobic surface treatment is a treatment for binding a hydrophobic functional group to a reactive functional group on the surface of the rock denaturing agent.
  • a hydrophobic functional group is an electrically neutral functional group that is less likely to be hydrated by hydrogen bonds.
  • hydrophobic functional group examples include alkylsilyl groups such as dimethylsilyl group, trimethylsilyl group, butylsilyl group and octylsilyl group, dimethylpolysiloxane and the like.
  • FIG. 3 illustrates the chemical structure when the surface of the rock denaturing agent is subjected to a hydrophobic surface treatment.
  • hydrophobic functional groups from the viewpoint of being able to further suppress the decay of rock denaturation over time, it is possible to bond a hydrophobic functional group containing four or more carbon atoms to the reactive functional group on the surface of the rock denaturing agent.
  • the hydrophobic functional group to be bonded include an alkylsilyl group such as a butylsilyl group and an octylsilyl group, and dimethylpolysiloxane.
  • the carbon content of the rocking modifier can be used as an index of the hydrophobicity of the rocking modifier.
  • the carbon content of the rock denaturing agent is 0.6% or more, the rock denaturing agent has hydrophobicity, so that the time-dependent change of rock denaturation in the epoxy resin composition can be suppressed.
  • the carbon content is 2.0% or more because the effect of suppressing the change with time of rock denaturation is large, and it is further preferable that the carbon content is 3.0% or more.
  • the carbon content of the commercially available rock denaturing agent is 10% or less, and it is preferable to use one in this range.
  • hydrophobic rock denaturing agent examples include silica and light calcium carbonate.
  • these hydrophobic swaying denaturing agents those having a large swaying denaturing effect are desirable in order to suppress slipping off immediately after the production of towpreg bobine. From this point of view, silica is preferable. Further, fine particle silica is more preferable from the viewpoint that the shaking denaturation with time is particularly small and the shaking denaturation of the epoxy resin composition can be maintained for a long period of time.
  • AEROSIL registered trademark
  • R972 dimethylsilyl-treated fumed silica, hydrophobic functional group carbon atom number: 2, manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL registered trademark
  • AEROSIL registered trademark
  • RY200S hydrophobic functional group has 400 carbon atoms
  • AEROSIL® hydrophobic functional group having 8 carbon atoms
  • the epoxy resin composition to be impregnated in the tow preg of the present invention is a thixotropy index (TI 4 ) of the epoxy resin composition prepared by mixing the component [B] 4 days after the main agent containing the components [A] and [C1] is prepared.
  • TI 4 thixotropy index
  • ⁇ '0.1 / ⁇ ' 10 is required to be 1.5 or more, preferably 3.0 or more.
  • the upper limit is not particularly limited, but is usually 300 or less.
  • the component [B] is mixed 4 days after the main agent containing the components [A] and [C1] is prepared, and the frequency is 0 at 25 ° C. using a parallel plate vibration rheometer.
  • TI thixotropic index
  • the inclusion of the rock denaturing agent greatly increases the viscosity of the epoxy resin composition at a frequency of 0.1 Hz.
  • the viscosity at a frequency of 0.1 Hz also decreases with time.
  • TI decreases over time. Maintaining a value above a certain level of TI means that the attenuation of the viscosity at a frequency of 0.1 Hz with time is small, and when the viscosity at a frequency of 0.1 Hz satisfies the condition (I), If the TI 4 is 1.5 or more, the tow preg prepared by using the epoxy resin stored for 4 days can also suppress the slip-off.
  • the content of the hydrophobic rock denaturing agent of the component [C1] needs to be 1.0 to 7.0 parts by mass with respect to 100 parts by mass of the component [A], and is 2.5 to 7.0 parts by mass. It is preferably 0 parts by mass.
  • the content of the hydrophobic swaying modifier is 1.0 part by mass or more, it is possible to suppress the bobbin from slipping off the paper tube when it is erected. Further, when the blending amount is 7.0 parts by mass or less, it is possible to prevent poor liquid feeding in the tow preg manufacturing process and poor formation of the resin coating film on the kiss roll.
  • the epoxy resin composition to be impregnated in the tow preg of the present invention is at 40 ° C. measured using an E-type viscometer immediately after preparing the epoxy resin composition containing the components [A], [B] and the component [C1].
  • the viscosity is preferably 40 Pa ⁇ s or less, and more preferably 0.5 to 40 Pa ⁇ s.
  • the towpreg can be produced by heating the epoxy resin composition to about 40 ° C., but if the epoxy resin composition has a high viscosity at 40 ° C., it is heated to a relatively high temperature for liquid feeding. It becomes necessary to reduce the viscosity. The higher the temperature, the faster the epoxy resin composition thickens, the shorter the pot life until the liquid cannot be sent, and the lower the productivity of the tow preg.
  • the viscosity at 40 ° C. is 40 Pa ⁇ s or less, it is not necessary to heat the epoxy resin composition to a high temperature, so that it is difficult to thicken the epoxy resin composition and the productivity of the tow preg is improved, which is preferable.
  • the epoxy resin composition used for the tow preg of the present invention preferably contains a core-shell rubber and / or a liquid rubber as a toughening agent as the component [D].
  • the toughening agent refers to an additive generally used to increase the toughness of a cured resin product.
  • Examples of the component [D] include core-shell rubber fine particles having a core-shell structure in which rubber fine particles such as acrylic rubber fine particles, butadiene rubber fine particles, butadiene-styrene rubber fine particles, and silicone rubber fine particles are coated with different polymers, and liquid NBR (nitrile-). It is preferable to select from liquid rubbers such as butadiene rubber), CTBN (terminal carboxy group modified NBR), ATBN (terminal amino group modified NBR), and carboxy group modified NBR in the main chain.
  • liquid rubbers such as butadiene rubber
  • CTBN terminal carboxy group modified NBR
  • ATBN terminal amino group modified NBR
  • carboxy group modified NBR carboxy group modified NBR in the main chain.
  • core-shell rubber particles are formed by graft-polymerizing a shell component polymer different from the core component on the surface of a particulate core component containing a crosslinked rubber-like polymer or an elastomer as a main component, thereby forming a surface of the particle core component. A part or the whole is coated with a shell component.
  • the blending amount of the component [D] is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the component [A].
  • the epoxy resin composition used for the tow preg of the present invention may contain various additives such as a thermoplastic resin, a rubber component, a defoaming agent, a stabilizer, a flame retardant, and a pigment as long as the effects of the present invention are not lost. it can.
  • the thermoplastic resin is preferably a thermoplastic resin that is soluble in the epoxy resin.
  • examples of the thermoplastic resin soluble in the epoxy resin include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyamide, polyimide, polyvinylpyrrolidone, and polysulfone.
  • the epoxy resin composition used for the tow preg of the present invention may be kneaded using a machine such as a kneader, a planetary mixer, a mechanical stirrer, a dissolver, or a three-roll, or it may be mixed by hand using a beaker and a spatula.
  • a machine such as a kneader, a planetary mixer, a mechanical stirrer, a dissolver, or a three-roll
  • a machine such as a kneader, a planetary mixer, a mechanical stirrer, a dissolver, or a three-roll
  • a beaker and a spatula for the shaking denaturing agent which is the component [C] of the present invention (including the hydrophobic shaking denaturing agent which is the component [C1])
  • an appropriate kneading method for developing the shaking denaturation is specified for each product used. Therefore, it is preferable to apply the optimum method as appropriate.
  • the tow preg of the present invention is obtained by impregnating a reinforcing fiber bundle with the epoxy resin composition used for the tow preg of the present invention.
  • a reinforcing fiber bundle composed of 1,000 to 70,000 filaments having a diameter of 3 to 100 ⁇ m is usually used.
  • Examples of the reinforcing fiber bundle used in the tow preg of the present invention include fiber bundles composed of glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like. Two or more of these fiber bundles may be mixed and used. Among these, it is preferable to use a carbon fiber bundle because a lightweight and highly rigid fiber-reinforced composite material can be obtained. Specific examples of such carbon fiber bundles include acrylic-based, pitch-based, and rayon-based carbon fiber bundles, and acrylic-based carbon fiber bundles having particularly high tensile strength are preferably used.
  • the mass content (Rc) of the epoxy resin composition in the tow preg of the present invention can be set without particular limitation depending on the intended purpose, but is preferably 20 to 40%, more preferably 20 to 30%. Most preferably 22-28%.
  • the mass ratio of the epoxy resin composition to the reinforcing fiber bundle is 20% or more, it is possible to suppress the occurrence of defects such as unimpregnated portions and voids inside the obtained fiber-reinforced composite material. Further, if it is 40% or less, the volume content of the reinforcing fiber bundle can be increased, so that the mechanical properties of the fiber-reinforced composite material can be effectively exhibited, which can contribute to weight reduction.
  • the tow preg of the present invention can be produced by various known methods. That is, a method in which the epoxy resin composition used for the tow preg of the present invention is impregnated by heating without using an organic solvent and the reinforcing fiber bundle is immersed, and the epoxy resin composition is heated to be reduced in viscosity. It can be manufactured by forming a coating film on a rotating roll or a release paper, then transferring it to one side or both sides of a reinforcing fiber bundle, and then applying pressure to impregnate it by passing it through a bending roll or a pressure roll.
  • the method for producing a tow preg of the present invention includes a step of bringing a rotary roll coated with an epoxy resin composition into contact with at least one side of a reinforcing fiber bundle.
  • the tow preg is usually supplied in the form of a bobbin with hundreds to thousands of meters wound around a paper tube.
  • the tow preg of the present invention can be used in many fields such as aerospace, automobiles, railroad vehicles, ships, civil engineering and sports equipment, and is particularly suitable for manufacturing hollow containers such as pressure vessels and cylinders. Can be used.
  • Epoxy resin curing agent compatible with component [B] [A] ⁇ "jER Cure (registered trademark)” WA (diethyl toluenediamine, manufactured by Mitsubishi Chemical Corporation) -"DYHARD (registered trademark)” Fluid 111 (Cyanamide, manufactured by AlzChem) ⁇ "KAYAHARD (registered trademark)” MCD (Methylnadic anhydride, manufactured by Nippon Kayaku Co., Ltd.) -Accelerator DY 9757 (boron trichloride amine complex, manufactured by Huntsman Japan Corporation).
  • the component [B] was added, and the mixture was stirred at 25 ° C. to 65 ° C. until the component [B] (curing agent) was compatible with the main agent to obtain an epoxy resin composition. It was confirmed by observation with an optical microscope that the component [B] was compatible with the component [A] and that there was no solid component. Further, the stirring temperature after the addition of the component [B] was carried out in a temperature range in which a rapid reaction did not start in consideration of the reactivity of the epoxy resin and the epoxy resin curing agent.
  • the component content ratios of Examples and Comparative Examples are shown in Tables 1 to 7.
  • the epoxy resin composition prepared by mixing the component [B] was prepared at 25 ° C. the complex shear viscosity at a frequency 0.1Hz ⁇ '0.1, 25 °C, the complex shear viscosity at a frequency 10 Hz eta' and denoted 10 and.
  • the measurement was carried out at a timing of 30 minutes after mixing the component [B] with the main agent to prepare an epoxy resin composition.
  • TI thixotropy index
  • TI 0 ⁇ 0.1 / ⁇ 10
  • TI 4 ⁇ '0.1 / ⁇ ' 10
  • ⁇ Epoxy resin composition stability evaluation method> As a method for evaluating the stability of the epoxy resin composition in the tow preg of the present invention, the viscosity of the epoxy resin composition prepared by mixing the main agent and the curing agent after being allowed to stand at 25 ° C. and 50% RH for 24 hours. was divided by the viscosity immediately after preparation (30 minutes after mixing the main agent and the curing agent), and the thickening ratio was used as an index.
  • the viscosity of the epoxy resin composition the complex shear viscosity ( ⁇ 10 ) measured at 25 ° C. and a frequency of 10 Hz using a parallel plate vibration rheometer was used, and in the table showing the results, “after 25 ° C. ⁇ 24 h”. The thickening ratio of ".
  • Rc of toupreg are bobbin mass of towpreg (W A), the paper tube mass (W B), the mass per unit length of the carbon fiber (W C), the length of the towpreg was wound around a bobbin (W D) Therefore, it was calculated according to the formula (1).
  • the Rc of Examples and Comparative Examples are shown in Tables 1, 2, 5 and 6.
  • a 7.5 L polyethylene liner was installed in the filament winding molding apparatus, and the tow preg of the present invention was wound around the entire liner.
  • a hoop layer forming ⁇ 89 ° with respect to the axial direction of the liner was wound so that its thickness was 1.4 mm.
  • a helical layer forming ⁇ 20 ° with respect to the axial direction of the liner was wound so as to have a thickness of 2.2 mm.
  • a hoop layer forming ⁇ 89 ° with respect to the axial direction of the liner was wound so as to have a thickness of 0.6 mm to obtain an intermediate.
  • the thickness of each layer was determined by measuring the outer diameter with a caliper.
  • the intermediate was cured at 110 ° C. for 6 hours while rotating in a curing furnace to obtain a pressure vessel.
  • Example 1 100 parts by mass of "jER®” 807 as component [A], 25.5 parts by mass of "jER Cure (registered trademark)" WA as component [B], and component [C] (also component [C1]]
  • An epoxy resin composition was prepared according to the above ⁇ Method for preparing epoxy resin composition> using 2.5 parts by mass of "AEROSIL” RY200S.
  • the kneading of the component [C] was carried out by pre-kneading using a kneader and then using three rolls.
  • the complex shear viscosity ( ⁇ 0.1 ) of this epoxy resin composition measured at 25 ° C.
  • TI 0 ⁇ 0.1 / ⁇ 10
  • the viscosity at 40 ° C. was 3.3 Pa ⁇ s
  • the thickening ratio after standing at 25 ° C. and 50% RH for 24 hours was 2.0.
  • towpregs were obtained according to the above ⁇ method for producing towpregs>.
  • the slip-off phenomenon was evaluated for this tow preg, the amount of movement of the lower end of the cylindrical bobbin of the toe preg was 9 mm, which was evaluated as B.
  • the TI was also calculated for the epoxy resin composition prepared by mixing the components [B] four days after the components [A] and [C1] were mixed, and the towpreg was prepared according to the above ⁇ Method for producing towpreg>. did.
  • the TI (TI 4 ) after 4 days of mixing was 17, and the amount of movement of the lower end of the cylindrical bobbin of the tow preg was 9 mm.
  • the degree of slippage of the tow preg did not change before and after storage of the epoxy resin.
  • the hydrophobic sway denaturing agent it was possible to suppress the deterioration of the epoxy resin and prevent the towpreg bobine from slipping off.
  • both the winding tightness and the widening property were evaluated as A.
  • Examples 2 to 3 As shown in Tables 1 and 3, the same method as in Example 1 except that the content of "AEROSIL®” RY200S, which is a component [C] (also applicable to the component [C1]), was changed. , Epoxy resin composition, tow preg, pressure vessel were prepared and evaluated. As for the evaluation results, as shown in Tables 1 and 3, good results were obtained in all the items.
  • Examples 4 to 9 As shown in Tables 1 and 4, the epoxy resin composition, towpreg, and pressure vessel were prepared in the same manner as in Example 1 except that the composition was changed so as to contain the glycidylamine type epoxy resin as the component [A]. Was prepared and evaluated. As for the evaluation results, as shown in Tables 1 and 4, good results were obtained in all the items. In particular, the evaluation result of the thickening ratio after standing at 25 ° C. and 50% RH for 24 hours is good, and the stability of the epoxy resin composition is excellent in these compositions containing the glycidylamine type epoxy resin. I understand.
  • Example 10 As shown in Table 2, "Disparon (registered trademark)" 6500 was used as the component [C], and the component was kneaded using a kneader at 90 ° C. for 30 minutes, except that other compositions were changed. , An epoxy resin composition, a tow preg, and a pressure vessel were prepared and evaluated by the same method as in Example 1. As for the evaluation results, as shown in Table 2, good results were obtained in all the items.
  • Example 12 As shown in Table 2, the epoxy resin composition, towpreg, and pressure vessel were used in the same manner as in Example 1 except that "GARAMITE (registered trademark)" 7305 was used as the component [C] and other compositions were changed. Was prepared and evaluated. As for the evaluation results, as shown in Table 2, good results were obtained in all the items.
  • GAAMITE registered trademark
  • Example 13 As shown in Tables 2 and 4, the epoxy resin composition was prepared in the same manner as in Example 1 except that "DYHARD (registered trademark)" Fluid 111 was used as the component [B] and other compositions were changed. Toupregs and pressure vessels were prepared and evaluated. As for the evaluation results, as shown in Tables 2 and 4, good results were obtained in all the items.
  • Example 14 As shown in Table 2, except that "DYHARD (registered trademark)" Fluid 111 was used as the component [B] and "AEROSIL (registered trademark)" 300 was used as the component [C].
  • Epoxy resin compositions, towpregs and pressure vessels were prepared and evaluated in the same manner. As for the evaluation results, as shown in Table 2, good results were obtained in all the items.
  • Example 15 As shown in Tables 2 and 4, "KAYAHARD (registered trademark)” MCD was used as the component [B], and "U-CAT (registered trademark)” SA 102 was used as the curing accelerator, and other compositions were changed.
  • An epoxy resin composition, a tow preg, and a pressure vessel were prepared and evaluated by the same method as in Example 1 except for the above. As for the evaluation results, as shown in Tables 2 and 4, good results were obtained in all the items.
  • Example 16 As shown in Tables 2 and 4, an epoxy resin composition, a tow preg, and a pressure vessel were prepared in the same manner as in Example 1 except that Accelerator DY 9757 was used as the component [B] and other compositions were changed. ,evaluated. As for the evaluation results, as shown in Tables 2 and 4, good results were obtained in all the items.
  • Example 18 As shown in Table 3, the epoxy resin composition, towpreg, were prepared in the same manner as in Example 1 except that “AEROSIL®” RY200S was changed to “AEROSIL®” R812 as the component [C1]. A pressure vessel was prepared and evaluated. As a result, ⁇ 0.1 was 145 Pa ⁇ s, and the tow preg bobine produced immediately after mixing the components [A] to [C1] did not cause the tow preg bobbin to slip off.
  • Example 19 As shown in Table 5, an epoxy resin composition, a tow preg, and a pressure vessel were prepared in the same manner as in Example 1 except that the composition was changed so as to contain the glycidylamine type epoxy resin as the component [A]. evaluated. As for the evaluation results, as shown in Table 5, good results were obtained in all the items.
  • Example 20 to 23 As shown in Table 5, an epoxy resin composition, a tow preg, and a pressure vessel were prepared and evaluated by the same method as in Example 1 except that the composition was changed so as to contain core-shell rubber particles as the component [D]. .. As shown in Table 5, the evaluation results are good in all items, and it can be seen that the bending fracture elongation of the cured resin product is excellent in these compositions containing the component [D].
  • Examples 24-26 As shown in Table 5, the epoxy resin composition and towpreg were prepared in the same manner as in Example 1 except that the composition was changed so as to include the terminal carboxyl group-modified butadiene nitrile rubber which is a liquid rubber as the component [D]. , A pressure vessel was prepared and evaluated. As shown in Table 5, the evaluation results are good in all items, and it can be seen that the bending fracture elongation of the cured resin product is excellent in these compositions containing the component [D]. However, when liquid rubber was used, the thixotropy index tended to be smaller than when core-shell rubber particles were used.
  • Example 27 As shown in Table 7, the same method as in Example 1 except that the component [C] "AEROSIL (registered trademark)" RY200S was changed to "AEROSIL (registered trademark)" 300 and the content thereof was changed.
  • Example 6 the epoxy resin composition and tow preg were prepared in the same manner as in Example 1 except that "jER Cure (registered trademark)" DICY7 was used as the epoxy resin curing agent and DCMU99 was used as the curing accelerator. , A pressure vessel was prepared and evaluated. As shown in Table 6, the evaluation results show that ⁇ 0.1 is 5.7 Pa ⁇ s and ⁇ 0.1 / ⁇ 10 is as low as 1.0, but the slip-off phenomenon and the winding phenomenon occur. It did not occur.
  • the widening property is evaluated as C, and when a solid epoxy resin curing agent that is not compatible with the component [A] such as "jER Cure (registered trademark)" DICY7 is used, the widening property of the tow preg is used. It turns out that is insufficient.
  • the widening property is evaluated as C, and when a solid epoxy resin curing agent that is not compatible with the component [A] such as "jER Cure (registered trademark)" DICY7 is used, the widening property of the tow preg is used. It turns out that is insufficient.

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Abstract

La présente invention vise à fournir un préimprégné en étoupes sans qu'un tube de papier ne glisse lorsqu'une bobine est levée, qui présente peu de retrait d'emballage lorsqu'il est déroulé et a une bonne stabilité de forme de bobine, et présente ainsi une facilité de manipulation supérieure, et qui présente également une bonne expansion d'étoupes pendant le moulage par enroulement de filament, et permet ainsi de produire un article moulé sans vide de bonne qualité.　Le préimprégné en étoupe est obtenu par imprégnation d'un faisceau de fibres de renforcement avec une composition de résine époxy qui contient le composant [A] une résine époxy et le composant [B] un agent de durcissement de résine époxy compatible avec [A], et qui satisfait à la condition (I) et à l'une des conditions (X) et (Y).
PCT/JP2020/020693 2019-05-29 2020-05-26 Préimprégné en étoupes WO2020241623A1 (fr)

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JPH06345884A (ja) * 1993-06-10 1994-12-20 Toray Ind Inc ヤーンプリプレグ用エポキシ樹脂組成物およびヤーンプリプレグ
JPH08283435A (ja) * 1995-02-14 1996-10-29 Toray Ind Inc ヤーンプリプレグおよび繊維強化複合材料
WO1997028210A1 (fr) * 1996-02-02 1997-08-07 Toray Industries, Inc. Compositions de resines pour materiaux composites a renfort de fibres et leurs procedes de fabrication, pre-impregnes, composites a renfort de fibres, et structures en nids d'abeilles
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