JP2007297487A - Yarn prepreg, fiber reinforced composite material, automatic laminate-molding method and process for producing fiber reinforced composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a yarn prepreg which excels in guide passableness and releasability, can be laminated on a molding jig, and can be cured by irradiation with active energy rays. <P>SOLUTION: The yarn prepreg comprises a reinforcing fiber bundle and a cationically polymerizable resin composition, wherein the cationically polymerizable resin composition comprises a cationically polymerizable compound, a cationic polymerization initiator, and a thermoplastic resin and has a viscosity at 30°C of 1×10<SP>4</SP>to 1×10<SP>6</SP>Pa s and a viscosity at 80°C of 1 to 300 Pa s. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a yarn prepreg, a fiber reinforced composite material, an automatic laminate molding method, and a method for manufacturing a fiber reinforced composite material used for aircraft members, satellites, rockets, spacecraft members such as spacecrafts, and automobile members. The present invention relates to a yarn prepreg that can be cured by irradiation with active energy rays, a fiber-reinforced composite material, an automatic laminate molding method, and a method for producing a fiber-reinforced composite material.

  Conventionally, a fiber reinforced composite material using a prepreg composed of a reinforced fiber and a resin composition is lightweight and excellent in mechanical properties such as strength, rigidity, and impact resistance, so that it is an aircraft member, spacecraft member, satellite member, It is applied to many fields such as automobile members, railway vehicle members, ship members, and sports equipment members. Examples of reinforcing fibers used include glass fibers, carbon fibers, and aramid fibers. Resin compositions include unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, cyanate resins, and bismaleimide resins. Can be mentioned.

  Of the fields in which fiber reinforced composite materials are used, aircraft members and spacecraft members require particularly excellent mechanical properties and heat resistance. Therefore, carbon fiber is generally used as the reinforcing fiber. The resin composition is preferably a thermosetting resin, and among them, a combination of an epoxy resin and a polyamine is more preferable from the viewpoints of heat resistance, elastic modulus, chemical resistance, and curing shrinkage.

  As the prepreg, a so-called yarn prepreg prepared by directly impregnating a carbon fiber bundle with a resin and winding it up without using a release paper or a release film is preferable. As yarn prepregs, those using thermosetting and thermoplastic resins are generally known, and have the advantages of a long winding length and excellent economic efficiency.

  The main method of manufacturing fiber reinforced composite materials using such yarn prepregs is heating and pressure molding using autoclaves, etc., but the cost is increased, the molding equipment is enlarged, the molding size is limited, and complex shapes are molded. However, there are problems such as difficulty in strength, a decrease in strength due to residual thermal stress in the molded product, and generation of cracks (for example, see Patent Document 1).

  Therefore, in recent years, establishment of a method for producing a fiber-reinforced composite material using an automatic lamination molding method that does not require a heating step has been regarded as important, and a yarn prepreg that is cured by an active energy ray such as ultraviolet light or visible light is used. A method has been developed.

As a yarn prepreg that is cured by active energy rays, a wet type that is always sticky (tackiness) using a resin composition having a viscosity at 30 ° C. of several Pa · s is known (for example, (See Patent Documents 2 to 4).
JP 2004-050574 A Japanese Patent Laid-Open No. 8-57971 Japanese Patent Laid-Open No. 2001-2760 JP-A-11-193322

  However, when the viscosity of the resin composition to be used is several Pa · s and the yarn prepreg is always sticky, it has excellent tackiness when pressed onto a forming jig, but guides in an automatic laminating apparatus, etc. There is a problem that the guide passage property is low and the guide passing property is low, and the single yarn breakage occurs when unwinding from the bobbin, so that it cannot be unwound.

  The object of the present invention has been made in view of the above points. When unwinding, the adhesiveness is small and the guide passing property and the unwinding property are excellent. Another object of the present invention is to provide a yarn prepreg which can be cured by irradiation with active energy rays, and a fiber reinforced composite material, an automatic laminate molding method and a fiber reinforced composite material manufacturing method using the yarn prepreg.

In order to solve the above problem, the invention according to claim 1 is:
In a yarn prepreg comprising a reinforcing fiber bundle and a cationic polymerizable resin composition,
The cationically polymerizable resin composition, the cationically polymerizable compound includes a cationic polymerization initiator and a thermoplastic resin, the viscosity viscosity at 30 ° C. is at ^{1 × 10 4 ~1 × 10 6} Pa · s, 80 ℃ 1 to 300 Pa · s.

The invention according to claim 2 is the yarn prepreg according to claim 1,
It hardens | cures by irradiating the active energy ray of wavelength 200-600nm, illumination intensity 0.1-20W / cm < ² >, and exposure amount 0.1-50J / cm < ² >.

The invention according to claim 3 is the yarn prepreg according to claim 1 or 2,
The cationic polymerizable resin composition has a glass transition temperature of −30 to 30 ° C.

The invention according to claim 4 is the yarn prepreg according to any one of claims 1 to 3,
The cationic polymerizable resin composition has a viscosity of 3 × 10 ^{4 to} 3 × 10 ⁵ Pa · s at 30 ° C. and a viscosity of 10 to 200 Pa · s at 80 ° C.

The invention according to claim 5 is the yarn prepreg according to any one of claims 1 to 4,
The thermoplastic resin is blended in an amount of 0.5 to 50 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.

The invention according to claim 6 is the yarn prepreg according to any one of claims 1 to 5,
The thermoplastic resin is at least one of polyvinyl formal, polyvinyl butyral, polyamide, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetherethersulfone, polyphenylsulfone, and polyurethane.

The invention according to claim 7 is the yarn prepreg according to any one of claims 1 to 6,
The cationic polymerization initiator is a iodonium salt of Lewis acid and / or a sulfonium salt of Lewis acid.

The invention according to claim 8 is the yarn prepreg according to any one of claims 1 to 7,
The cationic polymerizable resin composition includes a photosensitizer.

The invention according to claim 9 is a fiber-reinforced composite material,
A yarn prepreg according to any one of claims 1 to 8 is cured.

The invention described in claim 10 is characterized in that, in the automatic laminate molding method, the yarn prepreg according to any one of claims 1 to 8 is heated and laminated to give adhesiveness.

The invention according to claim 11 is a method for producing a fiber-reinforced composite material,
When the yarn prepreg according to any one of claims 1 to 8 is unwound from a bobbin, heated and softened to have adhesiveness, and pressed and laminated on a forming jig, each time one layer is laminated. It is characterized by being cured by irradiation with active energy rays.

Invention of Claim 12 in the manufacturing method of the fiber reinforced composite material of Claim 11,
The yarn prepreg is heated and pressed using a compaction roller heated to 40 to 150 ° C.

  According to the present invention, when unrolling from a bobbin, the adhesiveness is small and the guide passing property and the unwinding property are excellent. A yarn prepreg that can be cured can be provided. Moreover, the fiber reinforced composite material using the yarn prepreg according to the present invention can be provided. Furthermore, the yarn prepreg according to the present invention can be used to improve the productivity of the automatic lamination molding method and the method for manufacturing the fiber-reinforced composite material.

  The yarn prepreg according to the present invention includes at least a reinforcing fiber bundle and a cationic polymerizable resin composition, and the cationic polymerizable resin composition includes a cationic polymerizable compound, a cationic polymerization initiator, and a thermoplastic resin. Hereinafter, each component will be described.

  The reinforcing fiber bundle used in the present invention is obtained by combining or splitting reinforcing fibers. There is no restriction | limiting in particular as a reinforced fiber, The thing according to the field | area where a fiber reinforced composite material is used is applicable. Specific examples include carbon fiber, graphite fiber, aramid fiber, silicon carbide fiber, alumina fiber, boron fiber, tungsten carbide fiber, glass fiber, and the like, and these may be used in combination. Among these, carbon fibers having excellent specific strength and specific elastic modulus are preferably used in fields where weight reduction and high strength are required (for example, aircraft and spacecraft members).

  Any type of carbon fiber can be used for the carbon fiber depending on the application. From the standpoint of high impact resistance when used as the fiber's original tensile strength and fiber-reinforced composite material, the so-called high-strength carbon fiber is used. Is preferred. The high strength carbon fiber in the present invention is a carbon fiber having a strand tensile strength of 4 GPa or more, preferably 4.6 GPa or more. The higher the strand tensile strength, the better, but the fiber reinforced composite material obtained as long as it is about 6.0 GPa or more can be applied to various fields. On the other hand, when the strand tensile strength is 7.0 GPa or more, the processability of the obtained fiber-reinforced composite material may be deteriorated. Here, the strand tensile strength refers to the strength measured by a strand tensile test based on JIS R7601 (1986).

  Further, the tensile elongation at break of the carbon fiber is preferably 1.7% or more, and more preferably 1.8% or more. The higher the tensile elongation at break, the better, but if it is about 2.0%, it is applicable to the present invention.

  The number of single fibers constituting the reinforcing fiber bundle is 1000 to 500000 filaments, preferably 3000 to 50000 filaments. In order to obtain a thick reinforcing fiber bundle, a plurality of fiber bundles may be combined, and in order to obtain a fine reinforcing fiber bundle, one fiber bundle may be divided.

  The thickness of the reinforcing fiber is preferably in the range of 1 to 20 μm, more preferably in the range of 3 to 10 μm. When the thickness of the reinforcing fiber exceeds 20 μm, the tensile strength and the tensile modulus tend to decrease. On the other hand, when the thickness of the reinforcing fiber is less than 1 μm, the productivity of the reinforcing fiber bundle is lowered and the cost is increased.

  The cationically polymerizable resin composition used in the present invention contains at least a cationically polymerizable compound, a cationic polymerization initiator, and a thermoplastic resin.

  As the cationically polymerizable compound, a generally known monomer, oligomer or polymer having a cationically polymerizable group can be used without particular limitation. Examples include vinyl resins, epoxy resins, bicycloorthoester resins, spiroorthocarbonate resins, thiirane resins, oxetane resins, and the like. Among these, an epoxy resin, an oxetane resin, or a mixture thereof is preferable from the viewpoint of suitably having heat resistance and active energy ray curability.

  As epoxy resins, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2 -Dodecylene oxide, epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, limonene oxide, α-pinene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxy Monofunctional monomers such as methylcyclohexene oxide and 3-vinylcyclohexene oxide, 1,1,3-tetradecadiene dioxide, Nendioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylpentyl-3,4-epoxycyclohexanecarboxylate, di (3,4- Epoxycyclohexyl) adipate, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin , O-, m-, p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, naphthalene ring-containing epoxy resin, biphenyl type epoxy resin Poxy resin, biphenyl novolac type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin, triphenylmethane type epoxy resin, isocyanate modified epoxy resin containing oxazolidone ring, tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, tetra Glycidylamine type epoxy resin such as glycidylxylenediamine, glycidylaniline, glycidyl o-toluidine, polyglycidyl ether of polyhydric alcohol, K-62-722 (manufactured by Shin-Etsu Silicone) and UV9300 (manufactured by Toshiba Silicone) Examples thereof include polyfunctional epoxy resins such as epoxy silicone, and alicyclic epoxy resins.

  Oxetane resins include 3,3-dimethyloxetane, 3,3-bis (chloromethyl) oxetane, 2-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane, 3- Ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-3-oxetanyl) Ethyl) ether, m-xylylenebis (3-ethyl-3-oxetanylethylether), di [1-ethyl (3-oxetanyl)] methylether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3 -Ethyl-3-{[3- (triethoxysilyl) propoxy ] Methyl} oxetane, Oki Se Tani silsesquioxane, and the like phenol novolak type oxetane. These epoxy resins and oxetane resins may be used alone or in combination of two or more.

  The cationic polymerization initiator is capable of generating a Lewis acid or a proton acid by the action of active energy rays such as light, electron beam, X-ray or the like, or heat. Examples include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, Lewis acid selenonium salts, sulfonic acid esters, iron-arene compounds, silanol-aluminum complexes, and the like. Of these, Lewis acid iodonium salt compounds and / or Lewis acid sulfonium salt compounds are preferred from the viewpoints of active energy ray curability and thermal stability.

  The cationic polymerization initiator preferably has a potential below 100 ° C. Specific examples include Lewis acid iodonium salt compounds and / or Lewis acid sulfonium salt compounds. If it does not have the potential at less than 100 ° C., when the reinforcing fiber bundle is impregnated with the cationic polymerizable resin composition, a curing reaction due to heat proceeds and a resin runaway reaction may occur.

  Examples of the iodonium salt compound of Lewis acid and / or the sulfonium salt compound of Lewis acid include arylsulfonium complex salts described in US Pat. No. 4,231,951 and those described in US Pat. No. 4,256,828. Aromatic iodonium complex salts and aromatic sulfonium complex salts, aromatic sulfonium complex salts as described in JP-A-10-24496, aromatic iodonium complex salts as described in JP-A-11-263804, etc. These can be used alone or in combination.

（式中、Ｒ^１、Ｒ^２は水素原子、アルキル基、アルコキシ基のいずれかを示し、それぞれのＲ^１、Ｒ^２は互いに同一であっても異なっていてもよい。また、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、アルキル基のいずれかを示し、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は互いに同一であっても異なっていてもよい。さらに、ＸはＢ（Ｃ_６Ｆ_５）_４、ＳｂＦ_６、ＡｓＦ_６、ＰＦ_６、ＢＦ_４、ＣＦ_３ＳＯ_３、ＦＳＯ_３、ＣｌＯ_４、Ｆ_２ＰＯ_２のいずれかを示す。） As the cationic polymerization initiator, an iodonium salt compound of Lewis acid represented by the general formula (1) is preferable.

^(Wherein, R 1, ^{R 2} is a hydrogen atom, an alkyl group, any one of an alkoxy group, each of ^R 1, ^{R 2} may be the being the same or different. ^{Also, R} 3, R ⁴ , R ⁵ and R ^{6 each} represent a hydrogen atom or an alkyl group, and R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and X is B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , CF ₃ SO ₃ , FSO ₃ , ClO ₄ , or F ₂ PO ₂ .

Specific examples of the iodonium salt compound of Lewis acid represented by the general formula (1) include the following compounds. In the present invention, these compounds can be used alone or in combination.

  The compounding quantity of a cationic polymerization initiator is 0.01-20 weight part with respect to 100 weight part of cationic polymerizable compounds, Preferably it is 0.1-10 weight part. If the amount of the cationic polymerization initiator is less than the above range, the curability of the resulting cationic polymerizable resin composition may decrease, and if it exceeds the above range, mechanical properties after curing of the resulting cationic polymerizable resin composition may be reduced. May decrease.

  In the present invention, a photosensitizer may be added to the cationic polymerizable resin composition for the purpose of promoting the cationic polymerization initiation reaction. Examples of the photosensitizer include pigments such as acridine orange, acridine yellow, benzoflavin, cetoflavin T, and phosphine R, thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Diethylthioxanthone, 2,4-diisopropylthioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, anthracene, 1,2-benzanthracene, dibutoxyanthracene, dipropoxyanthracene, anthracene derivatives, perylene, perylene derivatives, benzophenone, benzophenone Derivatives, pyrene, pyrene derivatives, phenothiazine, 2-chlorophenothiazine, 2-methoxyphenothiazine, phenothiazine derivatives, co Nene, coronene derivatives, benzophenone, benzophenone derivatives, camphorquinone, anthraquinone, 2-ethylanthraquinone, 9,10-anthraquinone, anthraquinone derivatives, fluorenone, 9-fluorenone, fluorenone derivatives, tetracene, tetracene derivatives, etc. These can be used alone or in combination of two or more. Among them, thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, phenothiazine, 2-chlorophenothiazine, 2-methoxyphenothiazine, camphorquinone, Dibutoxyanthracene and dipropoxyanthracene are preferable because they have special light absorption in the visible region and become a visible light initiator when mixed with a cationic polymerization initiator.

  The molar ratio of the cationic polymerization initiator to the photosensitizer is (cationic polymerization initiator) / (photosensitizer) = 5/1 to 0.2 / 1, preferably 2/1 to 0.5. / 1. When the molar ratio between the cationic polymerization initiator and the photosensitizer is outside the above range, the photocurability of the resulting cationic polymerizable resin composition may be reduced, and the mechanical properties after curing may be reduced.

  Here, when a cationically polymerizable resin composition consisting only of a cationically polymerizable compound and a cationic polymerization initiator is used as a matrix resin, it is difficult to control the viscosity of the matrix resin, and the adhesiveness of the resulting yarn prepreg is controlled. However, there is a problem that the guide passing property and the unwinding property are lowered when the yarn prepreg is unwound from the bobbin. Further, since the drapability of the matrix resin is insufficient, there is a problem that resin powder is generated when the yarn prepreg is unwound from the bobbin.

  Therefore, in the present invention, by adding a thermoplastic resin to the cationic polymerizable resin composition, it is possible to control the viscosity of the matrix resin and to adjust the drapability of the yarn prepreg, and to improve the handleability of the yarn prepreg. is there. Further, by blending a thermoplastic resin, it is possible to reduce the adhesiveness when unwinding the yarn prepreg and improve the guide passing property and the unwinding property. Further, by imparting drape properties to the yarn prepreg, it is possible to prevent the generation of resin powder when unwinding from the bobbin. Furthermore, it is possible to obtain effects such as improved adhesion between the matrix resin and the reinforcing fibers, improved toughness of the matrix resin, and improved impact resistance of the matrix resin.

  The mechanism by which the thermoplastic resin exhibits such an effect is considered to be due to the entanglement of molecular chains between the cationic polymerizable compound and the dissolved thermoplastic resin. Therefore, the thermoplastic resin is preferably soluble in the cationically polymerizable compound. Moreover, in order for the molecular chain of a cationic polysynthetic compound and a thermoplastic resin to fully entangle, it is preferable that both have high compatibility.

  As an index of these solubility and compatibility, SP value which is a solubility parameter that can be calculated from the molecular structure can be used. In order to obtain sufficient solubility and compatibility, the absolute value of the difference in SP value between the thermoplastic resin and the cationic polymerizable compound should not exceed 5, preferably not exceed 3, more preferably 1. It must not exceed 5. If the absolute value of the difference in SP value exceeds 5, the thermoplastic resin will not be sufficiently dissolved in the cationically polymerizable compound. In order to reduce the absolute value of the difference in SP value, it is necessary to select the raw material of the cationic polymerizable compound, optimize the blending ratio, select the structure of the thermoplastic resin, and the like. In addition, when several types are mixed as a cationically polymerizable compound, the average value calculated as the sum total of the value which multiplied the SP value of each raw material by the weight fraction is used.

  Specific examples of the thermoplastic resin used in the present invention include polyvinyl formal, polyvinyl butyral, polyamide, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetherethersulfone, polyphenylsulfone, and polyurethane. . Moreover, as a commercial item, for example, “Denka Butyral” (registered trademark) and “Denka Formal” (registered trademark) (manufactured by Denki Kagaku Kogyo Co., Ltd.), “Vinyleck” (registered trademark) as polyvinyl butyral and polyvinyl formal. (Manufactured by Chisso Co., Ltd.), “Macromelt” (registered trademark) (manufactured by Henkel Hakusui Co., Ltd.), “Amilan” (registered trademark) CM4000 (manufactured by Toray Industries, Inc.), polyimide and polyetherimide “ “Meldin” (registered trademark) (Mitsui Chemicals) and “Ultem” (registered trademark) (manufactured by General Electric), “Matrimid” 5218 (manufactured by Ciba), polysulfone and polyethersulfone, “UDEL” ( Registered trademark) (manufactured by Teijin Amoco) and "Sumika Excel" (registered trader) ) (Manufactured by Sumitomo Chemical (Co., Ltd.)), "RADEL" (registered trademark) (Teijin Amoco Co., Ltd.), "Resamine" as polyurethane (registered trademark) (Dainichiseika Color & Chemicals Mfg. Co., Ltd.), and the like. In the present invention, these may be used alone or in combination.

  As the terminal functional group of the thermoplastic resin, a primary amine, a secondary amine, a hydroxyl group, a carboxyl group, a thiol group, an acid anhydride and the like are preferable because they can react with the cationic polymerizable compound. Examples of the terminal functional group having a hydroxyl group include “Sumika Excel” (registered trademark) 5003P (manufactured by Sumitomo Chemical Co., Ltd.), which is a commercially available polyethersulfone. Examples thereof include copolymer oligomers of polyethersulfone and polyetherethersulfone as described in Document 3. Examples of the terminal functional group containing both amine and acid anhydride include polyetherimide commercially available products “Ultem” 1000, “Ultem” 1010, “Ultem” 1040 (manufactured by General Electric). It is done.

  The glass transition point (Tg) of the thermoplastic resin needs to be 150 ° C. or higher, preferably 170 ° C. or higher in order to obtain good heat resistance. When the glass transition temperature is less than 150 ° C., it may be easily deformed by heat when used as a molded article.

  The glass transition temperature was precisely weighed about 10 mg of a thermoplastic resin and measured with a differential scanning calorimeter in accordance with JIS-K7121 under conditions of a temperature range of 25 ° C. to 350 ° C. and a temperature increase rate of 20 ° C./min. . Specifically, in the portion showing the step change of the obtained curve, the point where the straight line equidistant in the vertical axis direction from the extended straight line of each baseline intersects the curve of the step change portion of the glass transition Is the glass transition temperature, and the obtained glass transition temperature is a heat resistance index.

  The compounding quantity of a thermoplastic resin is 0.5-50 weight part with respect to 100 weight part of cationically polymerizable compounds, Preferably it is 1-30 weight part. When the blending amount of the thermoplastic resin is less than 0.5 parts by weight, the resulting cationically polymerizable resin composition has a low viscosity, which may increase the adhesiveness of the yarn prepreg at room temperature. On the other hand, when the blending amount exceeds 50 parts by weight, the viscosity of the cationic polymerizable resin composition is excessively increased, and there is a concern that workability is deteriorated and strength is decreased due to coarse separation in the cured product.

The viscosity of the cationic polymerizable resin composition used in the present invention is 1 × 10 ⁴ to 1 × 10 ⁶ Pa · s, preferably 3 × 10 ^{4 to} 3 × 10 ^{5 in} a working environment, that is, 30 ° C. or less. Pa · s, more preferably in the range of 5 × 10 ⁴ to 2 × 10 ⁵ Pa · s. By setting the viscosity of the cationic polymerizable resin composition at 30 ° C. within the above range, it is possible to reduce the adhesiveness of the obtained yarn prepreg and improve the guide passage property. Further, when the viscosity of the cationic polymerizable compound is higher than 1 × 10 ⁶ Pa · s, it takes time to impregnate the reinforcing fiber bundle with the cationic polymerizable resin composition, resulting in a decrease in productivity. There is a possibility that an unimpregnated portion of the cationic polymerizable resin composition may be formed in the yarn prepreg.

  Further, the viscosity at 80 ° C. of the cationic polymerizable resin composition increases the adhesiveness by heating at the time of automatic lamination, and presses and laminates on a forming jig, so that the viscosity is in the range of 1 to 300 Pa · s. Has been. When the viscosity is smaller than the above range, sufficient adhesiveness cannot be imparted even when heated during automatic lamination, and there is a possibility that it cannot be adhered to the lamination surface on the forming jig. On the other hand, when the viscosity is larger than the above range, it is difficult to impregnate the reinforcing fiber bundle with the cationic polymerizable resin composition, and an unimpregnated portion of the cationic polymerizable resin composition may be formed in the obtained yarn prepreg. The viscosity of the cationic polymerizable resin composition at 80 ° C. is preferably in the range of 10 to 200 Pa · s, more preferably in the range of 50 to 150 Pa · s.

Here, the viscosity is a viscoelasticity measuring device (ARES, manufactured by Rheometrics), a parallel plate radius of 20 mm, a parallel distance of 1.0 ± 0.1 mm, a measurement temperature of 30 ° C. or 80 ° C., It calculated | required from the value of the complex viscosity η ^{* on} the conditions of the measurement frequency of 0.5 Hz.

  The glass transition temperature of the cationic polymerizable resin composition is -30 to 30 ° C, preferably -20 to 25 ° C, more preferably -10 to 20 ° C. If the glass transition temperature is less than −30 ° C., the resulting yarn prepreg is very sticky when unwinding, and there is a risk that the guide passage property and the unwinding property will be lowered. On the other hand, when the glass transition temperature is higher than 30 ° C., the drapability of the yarn prepreg is insufficient, the shape wound around the bobbin is deteriorated, or resin powder is generated and unwound when unwinding from the bobbin. There is a fear.

  As for the glass transition temperature, about 15 mg of the obtained yarn prepreg is precisely weighed, and in accordance with JIS K7121 (2002), the temperature range is −50 ° C. to 100 ° C., and the heating rate is 10 ° C./min. Measurement was performed using an apparatus.

  The cationic polymerizable resin composition used in the present invention may further contain other components such as a polymerization accelerator, organic particles, and inorganic particles as optional components.

  As the polymerization accelerator, alcohols such as ethylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol, polyvinyl alcohol, benzyl alcohol, piperonyl alcohol, and ε-caprolactone polyol are preferably used. By blending such a polymerization accelerator, the active energy ray curability can be improved.

  As the organic particles, rubber particles, thermoplastic resins, or thermosetting resin particles are preferably used, and may be used alone or in combination. By blending such organic particles, there are effects such as improving the toughness of the cationic polymerizable resin composition and improving the impact resistance of the fiber-reinforced composite material.

  As the rubber particles, cross-linked rubber particles and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the cross-linked rubber particles are preferably used. Commercially available crosslinked rubber particles include FX-501 and FX-602 (manufactured by Nippon Synthetic Rubber Co., Ltd.), which are crosslinked products of carboxyl-modified butadiene-acrylonitrile copolymers, and CX-MN series (Japan). Catalyst Co., Ltd.), YR-500 series (Toto Kasei Co., Ltd.), etc. can be used. Commercially available core-shell rubber particles include, for example, “Paraloid” (registered trademark) EXL-2655 (manufactured by Kureha Chemical Industry Co., Ltd.), acrylic ester / methacrylic acid made of butadiene / alkyl methacrylate / styrene copolymer. "STAPHYLOID" (registered trademark) AC-3355 composed of ester copolymer, TR-2122 (manufactured by Takeda Pharmaceutical Co., Ltd.), "PARARAID" (registered trademark) composed of butyl acrylate / methyl methacrylate copolymer EXL-2611, EXL-3387 (manufactured by Rohm & Haas) and the like can be used.

  The thermoplastic resin particles include polyacrylate, polyvinyl acetate, vinyl resins such as polystyrol, polyamide, grillamide, polyaramid, polyester, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polyarylate, polybenzimidazole, polyimide. , Thermoplastic resins belonging to engineering plastics such as polyamideimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, hydrocarbon resins typified by polyethylene, polypropylene, cellulose acetate, and cellulose tangle A cellulose derivative, a copolymer consisting of methyl methacrylate-butyl acrylate-methyl methacrylate th (registered trademark) M22 (manufactured by Arkema Co., Ltd.), Nanostrength 123, Nanostrength 123, Nanostrength 250, Nanostrength012, Nanostrength E20, Nanostrength E40 (manufactured by Alstremath E40), which are copolymers of styrene-butadiene-methyl methacrylate It is done. Of these, polyamide or polyimide particles are preferably used. As commercially available polyamide particles, SP-500 (manufactured by Toray Industries, Inc.), “Orgasol” (registered trademark) (manufactured by ATOCHEM) and the like can be used.

  The thermosetting resin particle is a resin that is cured by an external energy such as heat, light, or electron beam to form a three-dimensional cross-linked body at least partially, and can be applied without particular limitation. Preferred thermosetting resin particles include epoxy resin, phenol resin, unsaturated polyester resin, amino resin, allyl resin, silicone resin, urethane resin, maleimide resin, polyimide resin, acetylene-terminated resin, allyl-terminated resin, Examples thereof include a resin having a nadic acid terminal and a resin particle having a cyanate terminal. Commercially available thermosetting resin particles include “Trepearl” (registered trademark) EP-B, “Trepearl” (registered trademark) EP-D, “Trepearl” (registered trademark) EP-C, and "Trepearl" (registered trademark) EP-R, "Trepearl" (registered trademark) EP-M (manufactured by Toray Industries, Inc.) and the like can be used.

  As the inorganic particles, silica, alumina, smectite, synthetic mica, calcium carbonate, talc, clay, glass powder, aluminum hydroxide, titanium oxide, barium oxide and the like are preferable. These inorganic particles mainly have effects of rheology control such as thickening of the obtained cationic polymerizable resin composition and imparting thixotropy. Further, as the inorganic particles, those acting as additives such as a surfactant, an internal release agent, a dye and a pigment may be added.

The yarn prepreg according to the present invention can be instantaneously cured by irradiation with active energy rays. The wavelength of light as the active energy ray is 200 to 600 nm, preferably 300 to 500 nm, more preferably 380 to 450 nm. When the wavelength is less than 200 nm, it is difficult to select a light source, and when it exceeds 600 nm, the photosensitivity of the cationic polymerizable resin composition becomes insufficient and the photocurability may be lowered. The illuminance of light is in the range of 0.1 to 10 W / cm ² . If the illuminance is less than 0.1 W / cm ² , the photocurability of the yarn prepreg is insufficient, and if it exceeds 10 W / cm ² , a resin runaway reaction may occur when the yarn prepreg is cured. The exposure amount is in the range of 0.1 to 50 J / cm ² . May exposure amount hardening degree of the fiber-reinforced composite material is less than 0.1 J / cm ² is lowered mechanical properties lower, a longer time required for curing exceeds 50 J / cm ^2, reduction in production efficiency To do.

  In the yarn prepreg according to the present invention, when the curing reaction has completely progressed, the degree of curing measured by a differential scanning calorimeter is 100. In the case of the present invention, after irradiating the yarn prepreg with active energy rays, only the surface of the yarn prepreg may be cured, and the inside of the yarn prepreg and the back surface may be uncured. The degree of cure of the yarn prepreg is preferably 50 or more, more preferably 70 or more. If the degree of cure is less than 50, it is difficult to maintain the form as a fiber-reinforced composite material, and workability in subsequent processing may be reduced.

  The yarn prepreg according to the present invention is produced by directly impregnating a reinforced fiber bundle with a cationic polymerizable resin composition without using a release paper or a release film and winding it around a bobbin as it is.

  The strength and elastic modulus of the fiber-reinforced composite material using the yarn prepreg according to the present invention greatly depend on the amount of reinforcing fibers. In other words, when a certain amount of reinforcing fiber is contained, the weight of the product can be reduced while maintaining the performance of the fiber-reinforced composite material and the final product almost constant as the amount of the cationic polymerizable resin composition is reduced. it can. For such purposes, the content of the reinforcing fiber with respect to the total weight of the yarn prepreg in the present invention is preferably 40 to 90% by weight, more preferably 50 to 80% by weight, and still more preferably 50 to 70% by weight. . When the content of the reinforcing fiber is less than 40% by weight, the amount of the cationic polymerizable resin composition is large and the weight reduction may not be sufficient. On the other hand, when the content of the reinforcing fiber exceeds 90% by weight, the amount of the cationic polymerizable resin composition is small, so that voids may remain in the fiber-reinforced composite material and the mechanical properties may be deteriorated.

  The thickness of the yarn prepreg is not particularly limited because it is determined in consideration of the mechanical properties required for the application, ease of laminating work, and the like, but is preferably 10 μm to 300 μm. If the thickness of the yarn prepreg is less than 10 μm, the yarn prepreg is likely to be cracked, and the handleability is remarkably deteriorated. If the thickness exceeds 300 μm, the cationic polymerizable resin composition may not be impregnated to the center in the thickness direction.

  The fiber-reinforced composite material according to the present invention is manufactured by curing the above-described yarn prepreg by irradiation with active energy rays and / or heat. For example, the yarn prepreg is laminated while being pressed one by one, and the cationic polymerizable resin composition is cured by irradiation with active energy rays and / or heat, or the laminated yarn prepreg is wrapped with pressure or bag film. Examples thereof include a method of curing the cationic polymerizable resin composition by irradiating active energy rays and / or heat after making the inside vacuum or reduced pressure. Thus, a fiber reinforced composite material having high fiber density and good adhesion can be obtained by curing and laminating the cationic polymerizable resin composition under pressure. Specific examples of the lamination method include a hand lay-up method, ATL (Automatic Tape Laying), ATP (Automatic Tape Placement), and AFP (Automatic Fiber Placement). The lamination method of ATL, ATP, and AFP is a method of automatically performing hand layup that has been performed manually, and is preferable because it is possible to manufacture large fiber reinforced composite materials such as aircraft. Is more preferable. In addition, a method of manufacturing while winding a yarn prepreg around a bobbin, such as filament winding, is preferable because the end of winding and the end of curing are simultaneously performed. Furthermore, after irradiating active energy rays as necessary, post-curing may be performed by performing a heat treatment at 40 ° C. to 180 ° C. for about 30 minutes to 20 hours.

  Next, the manufacturing method of the fiber reinforced composite material using the yarn prepreg of this invention is demonstrated. The following is one embodiment of the present invention and does not limit the scope of the invention.

  FIG. 1 is a flowchart showing a method for manufacturing a fiber-reinforced composite material of the present embodiment. FIG. 2 is a partially cutaway view of the automatic laminating apparatus 9 applied to the manufacturing method of the present embodiment as viewed from the front. A molding jig 13 on which the yarn prepreg 3 is laminated is provided below the automatic laminating apparatus 9. The forming jig 13 moves the yarn prepreg 3 laminated on the upper surface relative to the automatic laminating apparatus 9 and conveys it in the right direction in FIG.

  The automatic laminating apparatus 9 includes a supply unit 10 that sequentially feeds and supplies the yarn prepregs 3. The supply unit 10 is loaded with a cartridge 1 manufactured in a state where the yarn prepreg 3 is wound around a bobbin (not shown). The supply unit 10 is covered with a light shielding box 2 so that the inner yarn prepreg 3 is not irradiated with light from the outside.

  On the side of the supply unit 10, there is provided a laminate molding unit 11 that laminates the supplied yarn prepreg 3 on the upper surface of the molding jig 13. The lamination molding part 11 is provided with a compaction roller 4 that presses the yarn prepreg 3 on the upper surface of the molding jig 13. The compaction roller 4 is provided with a heating mechanism (not shown). Above the compaction roller 4, a belt-shaped guide portion 7 that guides the yarn prepreg 3 from the supply portion 10 to the compaction roller 4 is provided. Between the guide part 7 and the compaction roller 4, there is provided a winding guide 5 for winding the guided yarn prepreg 3 around the compaction roller 4 while shielding the light. In addition, an air cylinder 6 is provided above the guide portion 7 to move the guide portion 7 up and down together with the compaction roller 4 and the entrainment guide 5.

  In the direction of the relative movement of the yarn prepreg 3 on the side of the laminate forming portion 11, an illuminating portion 12 that irradiates the laminated yarn prepreg with light as active energy rays is provided. The illumination unit 12 is provided with a lamp 8 that irradiates light toward the upper surface of the forming jig 13.

  As shown in FIG. 1, the fiber reinforced composite material manufacturing method performed using the automatic laminating apparatus 9 is first performed at a normal working environment temperature (30 ° C. or less) by placing the yarn prepreg 3 in a light-shielding box ( The cartridge 1 made of a dark box is wound and filled (process P1). And the cartridge 1 is set to the supply part 10 of the automatic laminating apparatus 9 (process P2).

  Subsequently, the lamination molding unit 11 laminates the yarn prepreg 3 on the upper surface of the molding jig 13 by an automatic lamination molding method. At this time, the temperature of the compaction roller 4 is heated by a heating mechanism so as to be 40 ° C. to 150 ° C., preferably 60 ° C. to 80 ° C.

  Then, the supply unit 10 supplies the yarn prepreg 3 from the cartridge 1 to the lamination molding unit 11 (Step S1). The supplied yarn prepreg 3 is guided inside the laminated molding part 11 by the guide part 7 and is wound around the compaction roller 4 by the winding guide 5.

  Next, the yarn prepreg 3 wound around the compaction roller 4 is heated by conducting heat from the compaction roller 4 and thus is given tackiness, thereby increasing the adhesiveness (step S2).

  Then, the yarn prepreg 3 is sandwiched between the upper surface of the forming jig 13 by the rotation of the compaction roller 4. At this time, the air cylinder 6 moves the compaction roller 4 together with the guide portion 7 and the winding guide 5 downward. Then, the yarn prepreg 3 sandwiched between the compaction roller 4 and the forming jig 13 is pressed against the upper surface of the forming jig 13 by the compaction roller 4, and pressure is applied (step S3).

  Thereafter, the yarn prepreg 3 on the upper surface of the forming jig 13 moves relative to the automatic laminating apparatus 9 and is conveyed below the illumination unit 11. Then, the lamp 8 is turned on to irradiate the yarn prepreg 3 with light (step S4). When the yarn prepreg 3 is irradiated with light, the cationic polymerization reaction of the cationic polymerizable resin composition starts, and the yarn prepreg 3 is cured. Here, the irradiation of light as an active energy ray may be performed immediately before the yarn prepreg 3 is pressed against the upper surface of the forming jig 13 by the compaction roller 4. In this way, the yarn prepreg is laminated and formed on the lamination surface of the forming jig 13.

  Thereafter, by repeating step S1 to step S4, the yarn prepreg is laminated on the laminated surface, and when the required number of layers is reached, the automatic lamination molding step is finished, and the method for producing the fiber-reinforced composite material is finished.

  As described above, according to the automatic lamination molding method according to the present invention, tackiness can be imparted by winding the yarn prepreg 3 around the heated compaction roller 4, so that heating by an autoclave or the like is unnecessary, and the lamination molding unit 11. There is no need to keep the inside of the apparatus at a constant temperature and humidity, and the apparatus can be simplified and miniaturized. Further, by using the compaction roller 4, it is possible to cause the yarn prepreg 3 to be heated and pressure-loaded by one mechanism.

  Further, according to the method for producing a fiber reinforced composite material according to the present invention, the yarn prepreg 3 is cured every time one layer is laminated by the automatic lamination molding method, so that it is possible to produce a fiber reinforced composite material having a desired thickness. is there. Moreover, since it hardens | cures whenever it laminates | stacks one layer, it is not necessary to permeate | transmit an active energy ray to the inner side of the yarn prepreg 3, and the reinforcing fiber bundle which does not let light pass can also be used. Further, since the light prepreg 3 can be shielded until it is wound around the compaction roller 4 by using the light shielding box 2 or the like, the active energy rays are not unnecessarily irradiated.

Moreover, according to the yarn prepreg 3 according to the present invention, it is possible to handle it at a working environment temperature (about 30 ° C. or less) with a low adhesiveness. Therefore, the guide passage property and unwinding property of the yarn prepreg 3 can be improved, and handling is easy.
In addition, according to the yarn prepreg 3 according to the present invention, the adhesiveness can be increased by heating, and can be easily laminated by pressing the upper surface of the forming jig 13 after the heating. Then, the yarn prepreg 3 can be easily cured by irradiating the active energy ray after the lamination.
Further, since the yarn prepreg 3 according to the present invention does not require a release paper or a release film, it is not necessary to remove the release paper or the release film during automatic lamination molding.

  Furthermore, according to the fiber reinforced composite material according to the present invention, a desired thickness and degree of curing can be obtained, and mechanical properties and heat resistance are excellent, and it is suitably used for aircraft members, spacecraft members, automobile members, and the like. It is possible.

Hereinafter, the present invention will be described more specifically with reference to examples. The resin raw materials used in the examples, the preparation method of the yarn prepreg, the evaluation methods of the viscosity at 30 ° C. and 80 ° C., the degree of cure, the tackiness, the glass transition temperature, and the automatic laminating device passability are shown below. Table 1 shows the results of the composition of the resin composition used in each example, the viscosity at 30 ° C. and 80 ° C., the degree of cure, the tackiness, the glass transition temperature, and the passability of the automatic laminating apparatus.

<Resin raw material>
For the preparation of the cationic polymerizable resin composition, one selected from the following commercially available products and reagents was used.
(1) Cationic polymerizable compound “Epototo” (registered trademark) YD128 (manufactured by Toto Kasei Co., Ltd.): Bisphenol A type epoxy resin “Ceroxide” (registered trademark) 2021P (manufactured by Daicel Chemical Industries, Ltd.): Fat Cyclic epoxy resin “Epiclon” (registered trademark) EXA-1514 (Dainippon Ink Co., Ltd.): Bisphenol S type epoxy resin / NC-3000 (Nippon Kayaku Co., Ltd.): Biphenyl novolac type epoxy resin (2) Thermoplastic resin “SUMICA EXCEL” (registered trademark) 5003P (manufactured by Sumitomo Chemical Co., Ltd.): polyethersulfone “ULTEM” (registered trademark) 1010 (manufactured by General Electric Co., Ltd.): polyetherimide (3) Cationic polymerization initiator “Lordsil” (registered trademark) 2074 (manufactured by Rhodia Japan): One An iodonium salt compound represented by the general formula (2).
-3,3'-DAS (Mitsui Chemicals Fine Co., Ltd.): 3,3'-diaminodiphenyl sulfone (4) photosensitizer-"KAYACURE" (registered trademark) CTX (Nippon Kayaku Co., Ltd.) : 2-chlorothioxanthone

<Preparation of cationic polymerizable resin composition>
[Examples 1 to 3, Comparative Example 3]
The raw material of the cationic polymerizable compound mixed at a predetermined ratio shown in Table 1 was stirred until it became uniform while being heated to 100 ° C. to obtain a mixture of the cationic polymerizable compound. Next, the mixture of cationically polymerizable compounds was heated to 150 ° C., and a thermoplastic resin was added and stirred until it was uniformly dissolved. Subsequently, the temperature of the obtained mixture was lowered to 80 ° C., a cationic polymerization initiator was added and stirred until it was uniformly dissolved, and a cationically polymerizable resin composition was obtained.
[Example 4]
The raw material of the cationic polymerizable compound mixed at a predetermined ratio shown in Table 1 was stirred until it became uniform while being heated to 100 ° C. to obtain a mixture of the cationic polymerizable compound. Next, the mixture of cationically polymerizable compounds was heated to 150 ° C., and a thermoplastic resin was added and stirred until it was uniformly dissolved. Subsequently, the temperature of the obtained mixture was lowered to 80 ° C., a cationic polymerization initiator and a photosensitizer were added, and the mixture was stirred until it was uniformly dissolved to obtain a cationic polymerizable resin composition.
[Comparative Examples 1 and 2]
The raw material of the cationic polymerizable compound mixed at a predetermined ratio shown in Table 1 was stirred until it became uniform while being heated to 100 ° C. to obtain a mixture of the cationic polymerizable compound. Next, the temperature was lowered to 80 ° C., a cationic polymerization initiator was added, and the mixture was stirred until it was uniformly dissolved to obtain a cationic polymerizable resin composition.
[Comparative Example 4]
The raw material of the cationic polymerizable compound mixed at a predetermined ratio shown in Table 1 was stirred until it became uniform while being heated to 100 ° C. to obtain a mixture of the cationic polymerizable compound. Next, the mixture of cationically polymerizable compounds was heated to 150 ° C., and a thermoplastic resin was added and stirred until it was uniformly dissolved. Subsequently, the temperature of the obtained mixture was lowered to 80 ° C., a cationic polymerization initiator outside the range of the present invention was added and stirred until it was uniformly dissolved, and a cationic polymerizable resin composition was obtained.

<Production of yarn prepreg>
Using a kiss roll that controls the resin adhesion amount by the clearance between the rotatable grooved roll heated to 80 ° C. and the blade, the obtained cationic polymerizable resin composition is supplied to the groove portion of the grooved roll, A bundle of reinforcing fibers “Torayca” (registered trademark) T700G (manufactured by Toray Industries, Inc., tensile elastic modulus: 240 GPa, tensile strength: 4.9 GPa, number of filaments: 24000) is brought into contact with the groove of the grooved roll on the downstream side in the rotational direction. Then, a yarn prepreg having a carbon fiber basis weight of 1.6 g / m and a resin content of 40% by weight was wound around a bobbin.

<Viscosity at 30 ° C or 80 ° C>
The viscosity of the yarn prepreg at 30 ° C. or 80 ° C. can be substituted by measuring the viscosity of the cationic polymerizable resin composition, and was measured using a viscoelasticity measuring device. Measurement is made from a value of complex viscosity η ^* using a parallel plate having a radius of 20 mm, a parallel distance of 1.0 ± 0.1 mm, a measurement temperature of 30 ° C. or 80 ° C., and a measurement frequency of 0.5 Hz. did. In this example, ARES (manufactured by Rheometrics Co., Ltd.) was used as a viscoelasticity measuring device.

<Curing degree>
About 4 to 10 mg of the cationic polymerizable resin composition is precisely weighed and subjected to cationic polymerization with a differential scanning calorimeter in a temperature range of 25 ° C. to 350 ° C. and a heating rate of 20 ° C./min according to JIS K7121. The total calorific value (Ha) involved is measured. Specifically, the heat generation amount (Ha) is obtained from the area surrounded by the heat generation curve and the extension line of the base line. Subsequently, the produced yarn prepreg is used under a condition of a wavelength of 404 nm, an illuminance of 800 mW / cm ² , and an exposure amount of 10 J / cm ² using a conveyor type ultraviolet curing device using a metal halide lamp as a light source at a constant temperature (25 ° C.). Irradiate light to cure. About 10 mg of this cured product is precisely weighed, and in accordance with JIS K7121, a residual calorific value (Hb) (heat generation due to heating) in a differential scanning calorimeter under the conditions of a temperature range of 25 ° C. to 350 ° C. and a heating rate of 20 ° C./min. Measure). The remaining heat generation amount (Hb) is obtained from the area surrounded by the heat generation curve and the extension line of the base line. At this time, the curing degree = 100 × (Ha−Hb) / Ha. Therefore, when the curing reaction has completely proceeded, the degree of curing is 100. In this embodiment, it is assumed that the curing degree is 10 or more. In this embodiment, DSC3100SA (Bruker AXS Co., Ltd.) is used as the differential scanning calorimeter, and ECS-151S (I Graphics Co., Ltd.) is used as the conveyor type ultraviolet curing device. It was.

<Adhesiveness>
As the adhesiveness of the yarn prepreg, the force required for peeling after the yarn prepregs are pressure-bonded to each other is measured. This measurement method has many parameters such as load stress, speed, and time. These were appropriately determined as follows in consideration of the conditions used by the yarn prepreg. Regarding the evaluation of adhesiveness in this example, “Instron” 4201 universal material testing machine (manufactured by Instron Japan Co., Ltd.) was used as a measuring device.
・ Sample: 50x50mm
・ Temperature: 25 ℃
・ Load speed: 1 mm / min ・ Adhesive load: 0.12 MPa
・ Load time: 5 ± 2 seconds ・ Peeling speed: 10 mm / min

<Glass transition temperature>
The glass transition temperature is measured by weighing about 15 mg of the yarn prepreg and measuring the glass transition with a differential scanning calorimeter in a temperature range of -50 to 100 ° C. and a heating rate of 20 ° C./min according to JIS K7121 (2002). The temperature was measured. Specifically, in the portion showing the step change of the obtained curve, the point where the straight line equidistant in the vertical axis direction from the extended straight line of each baseline intersects the curve of the step change portion of the glass transition Was defined as the glass transition temperature. In this example, DSC3100SA (manufactured by Bruker AXS Co., Ltd.) was used as a differential scanning calorimeter.

<Passability of automatic laminating equipment>
The state when a 50 m yarn prepreg was pulled out from the bobbin at 3 m / min was measured. If the yarn prepreg can be smoothly unwound without breakage of the single yarn of the yarn prepreg or resin powder, the yarn prepreg may be cut, the yarn breakage, or the resin powder may fall off during unwinding, and the yarn prepreg cannot be unwound smoothly. X.

<Evaluation>
As shown in Table 1, each of the yarn prepregs of Examples 1 to 4 has excellent automatic lamination passability, is heated to 80 ° C. and softened to have adhesiveness, and is pressed onto a steel forming jig by a compaction roller. It was found that they can be laminated and then cured with active energy rays.
When all the yarn prepregs of Comparative Example 1 were unwound from the bobbin, the yarn prepregs were cut and the single yarn was broken and could not be unwound smoothly. In addition, the yarn prepreg is heated to 80 ° C. and softened to have adhesiveness, and pressed and laminated on a steel forming jig by a compaction roller. It could not be laminated on the jig.
Since the yarn prepreg of Comparative Example 2 had a low draping property of the cationic polymerizable resin composition, resin powder was generated when it was pulled out from the bobbin and could not be unraveled smoothly.
The yarn prepreg of Comparative Example 3 could be laminated by heating the yarn prepreg at 80 degrees to make it sticky and pressing it onto a steel forming jig with a compaction roller. However, when pulling out from the bobbin, the yarn prepreg was cut and the single yarn was broken, and could not be unwound smoothly.
The yarn prepreg of Comparative Example 4 was heated to 80 ° C. to give adhesiveness, and was pressed onto a steel forming jig by a compaction roller and laminated. However, an attempt was made to cure the yarn prepreg by irradiation with energy rays, but it did not cure.

It is a flowchart which shows the manufacturing method of the fiber reinforced composite material of this invention. It is a partially broken view in front view of the automatic lamination apparatus applied to the manufacturing method of the fiber reinforced composite material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cartridge 2 Shading box 3 Yarn prepreg 4 Compaction roller 5 Entrainment guide 6 Air cylinder 7 Guide part 8 Lamp 9 Automatic laminating device 10 Supply part 11 Lamination molding part 12 Illumination part

Claims (12)

In a yarn prepreg comprising a reinforcing fiber bundle and a cationic polymerizable resin composition,
The cationic polymerizable resin composition contains a cationic polymerizable compound, a cationic polymerization initiator, and a thermoplastic resin, and has a viscosity at 30 ° C. of 1 × 10 ⁴ to 1 × 10 ⁶ Pa · s and a viscosity at 80 ° C. Yarn prepreg characterized by being 1 to 300 Pa · s. Wavelength 200 to 600 nm, illuminance 0.1 to 20 / cm ^2, yarn prepreg according to claim 1, characterized in that the curing by irradiation with an active energy ray exposure 0.1~50J / cm ^2.   The yarn prepreg according to claim 1 or 2, wherein the cationic polymerizable resin composition has a glass transition temperature of -30 to 30 ° C. The cation polymerizable resin composition has a viscosity at 30 ° C. of 3 × 10 ^{4 to} 3 × 10 ⁵ Pa · s and a viscosity at 80 ° C. of 10 to 200 Pa · s. The yarn prepreg according to any one of the above.   The yarn prepreg according to any one of claims 1 to 4, wherein the thermoplastic resin is blended in an amount of 0.5 to 50 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.   The thermoplastic resin is at least one of polyvinyl formal, polyvinyl butyral, polyamide, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetherethersulfone, polyphenylsulfone, and polyurethane. The yarn prepreg according to any one of Items 1 to 5.   The yarn prepreg according to any one of claims 1 to 6, wherein the cationic polymerization initiator is a Lewis acid iodonium salt and / or a Lewis acid sulfonium salt.   The yarn prepreg according to any one of claims 1 to 7, wherein the cationic polymerizable resin composition contains a photosensitizer.   A fiber-reinforced composite material obtained by curing the yarn prepreg according to any one of claims 1 to 8.   An automatic laminate molding method, wherein the yarn prepreg according to any one of claims 1 to 8 is laminated by heating to give adhesiveness.   When the yarn prepreg according to any one of claims 1 to 8 is unwound from a bobbin, heated and softened to have adhesiveness, and pressed and laminated on a forming jig, each time one layer is laminated. A method for producing a fiber-reinforced composite material, wherein the active energy ray is irradiated and cured.   The method for producing a fiber-reinforced composite material according to claim 11, wherein the yarn prepreg is heated and pressed using a compaction roller heated to 40 to 150 ° C.

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