Molded body manufacturing method, resin impregnation device, and 3D printer

Abstract

The present invention pertains to: a method for manufacturing a molded article formed of a fiber reinforced composite material containing continuous reinforcing fibers and a cured product of a thermosetting resin or a thermosetting resin composition, the method including steps (I)-(III) in sequence; and a resin impregnating apparatus and a 3D printer suitable used for said manufacturing method.　Step (I): An application step for applying the thermosetting resin or the thermosetting resin composition on the surface of a continuous reinforcing fiber bundle. Step (II): A resin impregnating step for, after step (I), twisting said continuous reinforcing fiber bundle and obtaining a prepreg impregnated with the thermosetting resin or the thermosetting resin composition. Step (III): A thermal molding step for placing the prepreg obtained in step (II) and then heating same.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a molded body made of a fiber-reinforced composite material, a resin impregnation device, and a 3D printer. [Background technology]

[0002] In recent years, environmentally friendly natural gas vehicles (CNG vehicles) and fuel cell vehicles (FCVs) have become increasingly popular. Fuel cell vehicles are powered by fuel cells, so it is essential to develop hydrogen stations where the hydrogen fuel can be compressed to high pressure and filled into the vehicles. Steel tanks have been used up until now as high-pressure gas storage tanks used at hydrogen stations for fuel cell vehicles, or as on-board fuel tanks for CNG vehicles, fuel cell vehicles, etc. However, progress has been made in the development of lighter high-pressure gas storage tanks that use resin materials for the tank liner or outer layer. Reducing the weight of on-board fuel tanks has the advantage of improving the fuel efficiency of vehicles equipped with them.

[0003] Fiber-reinforced composites (hereinafter referred to as "FRPs (Fiber Reinforced Plastics)"), such as carbon fiber reinforced composites, are attracting attention as alternatives to metals due to their extremely high elastic modulus, strength, and light weight. Demand for FRPs is expected to accelerate in applications such as automotive structural materials, wind turbine blades, pressure vessels, and aerospace.

[0004] When FRPs using a cured product of a thermosetting resin such as an epoxy resin as the matrix resin are used for pressure vessel applications, molding by the filament winding method is known. For example, a reinforcing fiber yarn (tow prepreg) impregnated with a thermosetting resin composition such as an epoxy resin composition can be wound around the outer surface of a metal or resin liner to cover it, and then the composition can be cured and molded. However, the above method requires a liner or core material that serves as a mold for winding the reinforcing fiber yarn, making it difficult to manufacture a linerless pressure vessel made only of FRP.

[0005] On the other hand, a method using a 3D printer is also being considered as a method for three-dimensional modeling using a prepreg impregnated with a thermosetting resin composition without using a mold. For example, Patent Document 1 proposes a three-dimensional object molding system that includes a head having a supply unit that supplies a continuous material containing resin and fibers, and a robot arm that holds a molding unit in which the continuous material is supplied from the supply unit to mold a three-dimensional object, and that is capable of moving and rotating the molding unit and changing the position and orientation of the molding unit relative to the supply unit. Furthermore, Patent Document 1 proposes a head having a supply unit that supplies the continuous material containing resin and fibers, which includes a resin impregnation device that impregnates fibers with a thermosetting resin, and which includes a resin tank in which resin is stored. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2019-48398 Summary of the Invention [Problem to be solved by the invention]

[0007] As in Patent Document 1, conventional filament winding methods also employ a method in which reinforcing fiber yarns are impregnated with a thermosetting resin by immersing them in a resin tank containing a thermosetting resin or a thermosetting resin composition (hereinafter also referred to as "thermosetting resin or composition"). However, the above method has a problem in that it cannot be applied to thermosetting resins or compositions with a short pot life, since they will harden during the stage prior to molding, for example, while stored in a resin tank. On the other hand, when a method other than the immersion method is used as a method for impregnating the reinforcing fiber yarn with the thermosetting resin or composition, if the impregnation of the reinforcing fiber yarn with the thermosetting resin or composition is insufficient, problems such as a decrease in the physical properties of the resulting FRP may occur.

[0008] An object of the present invention is to provide a manufacturing method for a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and continuous reinforcing fibers, which method enables the use of a thermosetting resin or a thermosetting resin composition having a short pot life and provides good impregnation of a continuous reinforcing fiber bundle with the thermosetting resin or the thermosetting resin composition, as well as a resin impregnation device and a 3D printer that are suitable for use in the manufacturing method. [Means for solving the problem]

[0009] The present inventors have discovered that the above-mentioned problems can be solved by a manufacturing method that includes, in order, an application step (I) of applying a thermosetting resin or composition to the surface of a continuous reinforcing fiber bundle, a resin impregnation step (II) of twisting the continuous reinforcing fiber bundle after step (I) to obtain a prepreg impregnated with the thermosetting resin or composition, and a heat-molding step (III) of arranging and then heating the prepreg, as well as a resin impregnation device and a 3D printer that have a predetermined mechanism and are suitable for use in the manufacturing method. That is, the present invention relates to the following [1] to [3]. [1] A method for producing a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and continuous reinforcing fibers, the method comprising the following steps (I) to (III) in order: Step (I): A coating step of coating a thermosetting resin or a thermosetting resin composition on the surface of the continuous reinforcing fiber bundle. Step (II): A resin impregnation step in which the continuous reinforcing fiber bundles are twisted after step (I) to obtain a prepreg impregnated with the thermosetting resin or thermosetting resin composition. Step (III): A hot molding step in which the prepreg obtained in step (II) is arranged and then heated. [2] A resin impregnation device comprising: a mechanism for feeding a continuous reinforcing fiber bundle; a nozzle for ejecting a thermosetting resin or a thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle; and a mechanism for twisting the continuous reinforcing fiber bundle. [3] A 3D printer equipped with the resin impregnation device described in [2] above. [Effects of the Invention]

[0010] According to the present invention, in the production of a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or composition and continuous reinforcing fibers, it is possible to use a thermosetting resin or composition with a short pot life, and to improve the impregnation of the thermosetting resin or composition into the continuous reinforcing fiber bundle, and it is possible to provide a resin impregnation device and a 3D printer that are suitably used for the production method. According to the manufacturing method of the present invention, a linerless pressure vessel can be easily manufactured. The pressure vessel is suitable as a high-pressure gas storage tank for vehicles, and because it is lightweight, it can improve the fuel efficiency of the vehicle in which it is installed. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 4 is a schematic diagram illustrating one embodiment of the twisting step in step (II). [Figure 2] FIG. 1 is a cross-sectional schematic diagram showing one embodiment of a linerless pressure vessel. [Figure 3] 1 is a schematic diagram showing an embodiment of a resin impregnation device of the present invention and a 3D printer equipped with the same. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Method of manufacturing molded body] The method for producing a molded article of the present invention (hereinafter also simply referred to as "the production method of the present invention") is a method for producing a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and continuous reinforcing fibers, and comprises the following steps (I) to (III) in this order: Step (I): A coating step of coating a thermosetting resin or a thermosetting resin composition on the surface of the continuous reinforcing fiber bundle. Step (II): A resin impregnation step in which the continuous reinforcing fiber bundles are twisted after step (I) to obtain a prepreg impregnated with the thermosetting resin or thermosetting resin composition. Step (III): A hot molding step in which the prepreg obtained in step (II) is arranged and then heated.

[0013] In this specification, a thermosetting resin means a resin that can be thermoset independently, and a thermosetting resin composition means a thermosetting composition containing two or more resin components. A typical example of a thermosetting resin composition is a two-component thermosetting resin composition containing a main component (A) and a curing agent (B).

[0014] According to the manufacturing method of the present invention, in the manufacture of a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and continuous reinforcing fibers, it is possible to use a thermosetting resin or composition with a short pot life, and the impregnation of the thermosetting resin or composition into the continuous reinforcing fiber bundle is also good. The reason for this is not clear, but is presumed to be as follows. In the manufacturing method of the present invention, step (I) is a step (coating step) in which a thermosetting resin or a thermosetting resin composition is applied to the surface of a continuous reinforcing fiber bundle. Conventionally, a method of immersing a continuous reinforcing fiber bundle in a thermosetting resin bath has been used to impregnate a continuous reinforcing fiber bundle with a thermosetting resin, which is a matrix resin precursor. However, this method has the problem of the thermosetting resin bath curing during the manufacturing process. However, by performing step (I) in the present invention, even when a thermosetting resin or composition with a short pot life is used, curing of the resin during the manufacturing process can be avoided. Furthermore, for example, when a two-component thermosetting resin composition is used as the thermosetting resin composition, in the coating step, the main agent (A) or a composition containing it and the curing agent (B) or a composition containing it can be applied separately without premixing them. From this perspective, the manufacturing method of the present invention is also suitable for use with a thermosetting resin composition with a short pot life. In step (II) of the manufacturing method of the present invention, the continuous reinforcing fiber bundle coated with the thermosetting resin or composition in step (I) is twisted to cause the thermosetting resin or composition to flow and promote impregnation into the continuous reinforcing fiber bundle. When a two-component thermosetting resin composition is used, even if the main component (A) or a composition containing the main component and the curing agent (B) or a composition containing the main component are separately applied to the surface of the continuous reinforcing fiber bundle in step (I), the main component (A) and the curing agent (B) are thoroughly mixed within the continuous reinforcing fiber bundle in step (II). As a result, it is believed that a decrease in the Tg of the cured product due to insufficient mixing of the main component (A) and the curing agent (B) can be suppressed.

[0015] <Process (I): Coating process> In step (I), a thermosetting resin or a thermosetting resin composition is applied to the surface of the continuous reinforcing fiber bundle. By performing step (I), a fiber-reinforced composite material and a molded article can be produced without causing problems such as curing of the thermosetting resin or composition before molding, even if a thermosetting resin or composition with a short pot life is used.

[0016] (Thermosetting resin, thermosetting resin composition) The thermosetting resin used in the present invention is not particularly limited as long as it is a resin that can be cured by heating. The thermosetting resin composition used in the present invention is a composition containing the thermosetting resin. Examples of the thermosetting resin include at least one selected from the group consisting of epoxy resin, phenol resin, unsaturated polyester resin, urea resin, melamine resin, unsaturated polyimide resin, cyanate ester resin, silicon resin, urethane resin, casein resin, furan resin, alkyd resin, and xylene resin. Examples of two-component thermosetting resin compositions containing a main component (A) and a curing agent (B) include epoxy resin compositions in which the main component (A) is an epoxy resin and the curing agent (B) is an epoxy resin curing agent, and urethane resin compositions in which the main component (A) is a polyol and the curing agent (B) is a polyisocyanate. From the viewpoint of ease of impregnation into continuous reinforcing fiber bundles, and from the viewpoints of the heat resistance, strength, and gas barrier properties of the resulting cured product, such as hydrogen gas, two-component epoxy resin compositions in which the main component (A) is an epoxy resin and the curing agent (B) is an epoxy resin curing agent are preferred.

[0017] Among the above epoxy resin compositions, an epoxy resin composition in which the main component (A) is an epoxy resin (A1) and the curing agent (B) is an epoxy resin curing agent (B1) containing the reaction product (X) of the following components (x1) and (x2) is more preferred. This epoxy resin composition provides higher gas barrier properties and impact resistance, making it suitable for producing pressure vessels, as described below. (x1) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (x2) at least one selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.

[0018] The cured product of the epoxy resin composition has high gas barrier properties. For example, the hydrogen gas permeability coefficient of the cured product is preferably 8.0×10 -11 [cc·cm / (cm 2 ·s·cmHg)] or less, preferably 6.0 × 10 -11 [cc·cm / (cm 2 ·s·cmHg)] or less, more preferably 4.5 × 10 -11 [cc·cm / (cm 2·s·cmHg)] or less. The hydrogen gas permeability coefficient of the cured product of the epoxy resin composition can be measured under dry conditions at 23°C by the method described in the Examples.

[0019] [Epoxy resin (A1)] The epoxy resin (A1) (hereinafter simply referred to as "component (A1)") that is the main component (A) is not particularly limited as long as it is a polyfunctional epoxy resin having two or more epoxy groups. However, in consideration of the development of high gas barrier properties, a polyfunctional epoxy resin that contains an aromatic ring or an alicyclic structure in the molecule is preferred. Specific examples of such polyfunctional epoxy resins include at least one resin selected from the group consisting of epoxy resins having glycidylamino groups derived from meta-xylylenediamine, epoxy resins having glycidylamino groups derived from para-xylylenediamine, epoxy resins having glycidylamino groups derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from diaminodiphenylmethane, epoxy resins having glycidylamino groups and / or glycidyloxy groups derived from para-aminophenol, epoxy resins having glycidyloxy groups derived from bisphenol A, epoxy resins having glycidyloxy groups derived from bisphenol F, epoxy resins having glycidyloxy groups derived from phenol novolac, and epoxy resins having glycidyloxy groups derived from resorcinol. Two or more of the above epoxy resins can also be mixed in appropriate proportions to improve various properties such as flexibility, impact resistance, and moist heat resistance. Among the above, from the viewpoint of gas barrier properties, the epoxy resin (A1) is preferably one whose main component is at least one selected from the group consisting of epoxy resins having a glycidylamino group derived from meta-xylylenediamine, epoxy resins having a glycidylamino group derived from para-xylylenediamine, epoxy resins having a glycidyloxy group derived from bisphenol A, and epoxy resins having a glycidyloxy group derived from bisphenol F, and from the viewpoint of exhibiting high hydrogen gas barrier properties, one whose main component is an epoxy resin having a glycidylamino group derived from meta-xylylenediamine is more preferred. The term "main component" as used herein means that other components may be contained within the scope of the present invention, and preferably means 50 to 100% by mass of the total, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0020] [Epoxy resin curing agent (B1)] The epoxy resin curing agent (B1) (hereinafter also simply referred to as "component (B1)") contains a reaction product (X) of the following component (x1) and component (x2) from the viewpoint of exhibiting high gas barrier properties and impact resistance. (x1) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (x2) at least one selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.

[0021] [Reaction product (X)] The reaction product (X) is a reaction product of the component (x1) and the component (x2). The component (x1) is used from the viewpoint of gas barrier properties, and metaxylylenediamine is preferred from the viewpoint of gas barrier properties. One type of component (x1) may be used alone, or two types may be used in combination.

[0022] The component (x2) is at least one selected from the group consisting of unsaturated carboxylic acids and derivatives thereof represented by the general formula (1). 1 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. In addition, from the viewpoint of exhibiting high gas barrier properties and impact resistance, R 2 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0023] Examples of the derivative of the unsaturated carboxylic acid represented by the general formula (1) include esters, amides, acid anhydrides, and acid chlorides of the unsaturated carboxylic acid. As the ester of the unsaturated carboxylic acid, alkyl esters are preferred, and from the viewpoint of obtaining good reactivity, the number of alkyl carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0024] Examples of the unsaturated carboxylic acid represented by the general formula (1) and its derivatives include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, α-propylacrylic acid, α-isopropylacrylic acid, α-n-butylacrylic acid, α-t-butylacrylic acid, α-pentylacrylic acid, α-phenylacrylic acid, α-benzylacrylic acid, crotonic acid, 2-pentenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-heptenoic acid, 4-methyl-2-hexenoic acid, 5-methyl-2-hexenoic acid, 4,4-dimethyl-2-pentenoic acid, 4-phenyl-2-butenoic acid, cinnamic acid, o-methylcinnamic acid, m-methylcinnamic acid, p-methylcinnamic acid, and 2-octenoic acid, as well as esters, amides, acid anhydrides, and acid chlorides thereof. Among the above, from the viewpoint of exhibiting high gas barrier properties and impact resistance, component (x2) is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and derivatives thereof, more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and alkyl esters thereof, even more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof, even more preferably alkyl esters of acrylic acid, and even more preferably methyl acrylate. The component (x2) may be used alone or in combination of two or more.

[0025] When an unsaturated carboxylic acid, ester, or amide is used as component (x2), the reaction between component (x1) and component (x2) is carried out by mixing component (x1) and component (x2) at a temperature of 0 to 100°C, more preferably 0 to 70°C, and then carrying out a Michael addition reaction and an amide group-forming reaction by dehydration, dealcoholization, and deamination at a temperature of 100 to 300°C, preferably 130 to 250°C. In this case, during the amide group-forming reaction, the inside of the reaction apparatus can be reduced in pressure at the final stage of the reaction, if necessary, to complete the reaction. Furthermore, the reaction can be diluted with a non-reactive solvent, if necessary. Furthermore, a catalyst such as a phosphite ester can be added as a dehydrating agent or dealcoholizing agent.

[0026] On the other hand, when an acid anhydride or acid chloride of an unsaturated carboxylic acid is used as component (x2), the components are mixed at a temperature of 0 to 150°C, preferably 0 to 100°C, followed by the Michael addition reaction and the amide group formation reaction. In this case, during the amide group formation reaction, the reactor may be depressurized at the final stage of the reaction, if necessary, to complete the reaction. Furthermore, a non-reactive solvent may be used for dilution, if necessary. Furthermore, a tertiary amine such as pyridine, picoline, lutidine, or trialkylamine may also be added.

[0027] The amide group moiety formed by the reaction between component (x1) and component (x2) has high cohesive strength, and therefore, a cured product of an epoxy resin composition using an epoxy resin curing agent containing the reaction product (X) of component (x1) and component (x2) has high gas barrier properties and good adhesion to continuous reinforcing fibers.

[0028] In the reaction product (X), the reaction molar ratio of component (x2) to component (x1) [(x2) / (x1)] is preferably in the range of 0.3 to 1.0, more preferably 0.6 to 1.0. If the reaction molar ratio is 0.3 or more, a sufficient amount of amide groups is generated in the epoxy resin curing agent, resulting in high levels of gas barrier properties and adhesion to reinforcing fibers. On the other hand, if the reaction molar ratio is 1.0 or less, a sufficient amount of amino groups is available to react with the epoxy groups in the epoxy resin (A1), resulting in excellent heat resistance and solubility in organic solvents.

[0029] The reaction product (X) may be a reaction product of the components (x1) and (x2) with at least one compound selected from the group consisting of the following components (x3), (x4), and (x5): (x3)R 3 At least one (R ) selected from the group consisting of monocarboxylic acids represented by —COOH and derivatives thereof 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a hydroxyl group, or an aryl group having 6 to 12 carbon atoms. (x4) Cyclic carbonate (x5) Monoepoxy compound having 2 to 20 carbon atoms

[0030] Component (x3), R 3 The monocarboxylic acid represented by -COOH and its derivatives are used from the viewpoint of reducing the reactivity between the epoxy resin (A1) and the epoxy resin curing agent (B1) containing the reaction product (X) as needed, and improving workability, pot life, etc. R 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a hydroxyl group, or an aryl group having 6 to 12 carbon atoms; R 3 is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group. Also R 3 Derivatives of monocarboxylic acids represented by -COOH include, for example, esters, amides, acid anhydrides, and acid chlorides of the carboxylic acids. The esters of the carboxylic acids are preferably alkyl esters, and the number of alkyl carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2. Examples of the component (x3) include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, and benzoic acid, and derivatives thereof. The component (x3) may be used alone or in combination of two or more.

[0031] The cyclic carbonate component (x4) is used as needed to reduce the reactivity between the epoxy resin curing agent (B1) containing the reaction product (X) and the epoxy resin (A1) and to improve workability, pot life, etc. From the viewpoint of reactivity with component (x1), component (x4) is preferably a cyclic carbonate having a six-membered ring or less. Examples include ethylene carbonate, propylene carbonate, glycerin carbonate, 1,2-butylene carbonate, vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, 4-methoxymethyl-1,3-dioxolan-2-one, and 1,3-dioxan-2-one. Among these, from the viewpoint of gas barrier properties, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and glycerin carbonate is preferred. The component (x4) may be used alone or in combination of two or more.

[0032] The monoepoxy compound of component (x5) is a monoepoxy compound having 2 to 20 carbon atoms, and is used as needed to reduce the reactivity between the epoxy resin curing agent (B1) containing the reaction product (X) and the epoxy resin (A1) and to improve workability, pot life, etc. From the viewpoint of gas barrier properties, component (x5) is preferably a monoepoxy compound having 2 to 10 carbon atoms, and more preferably a compound represented by the following formula (2):

[0033] [ka] (In formula (2), R 4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, a chloromethyl group, or R 5 -O-CH2-, R 5 represents a phenyl group or a benzyl group. Examples of the monoepoxy compound represented by the formula (2) include ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, epichlorohydrin, phenyl glycidyl ether, and benzyl glycidyl ether. The component (x5) may be used alone or in combination of two or more.

[0034] When component (x3), component (x4), or component (x5) is used in the reaction product (X), any one compound selected from the group consisting of component (x3), component (x4), and component (x5) may be used alone, or two or more may be used in combination.

[0035] The reaction product (X) may be a reaction product obtained by reacting the components (x1) to (x5) with other components, as long as the effects of the present invention are not impaired. Examples of the other components include aromatic dicarboxylic acids and derivatives thereof. However, the amount of the "other components" used is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less of the total amount of the reaction components constituting the reaction product (X).

[0036] The reaction product of components (x1) and (x2) with at least one compound selected from the group consisting of components (x3), (x4), and (x5) can be obtained by reacting component (x1), a polyamine compound, with at least one compound selected from the group consisting of components (x3), (x4), and (x5) in combination with component (x2). In this reaction, components (x2) to (x5) may be added in any order and reacted with component (x1), or components (x2) to (x5) may be mixed and reacted with component (x1).

[0037] The reaction between component (x1) and component (x3) can be carried out under the same conditions as those for the reaction between component (x1) and component (x2). When component (x3) is used, component (x2) and component (x3) may be mixed and then reacted with component (x1), or component (x1) may be reacted with component (x2) first, and then component (x3) may be reacted. On the other hand, when component (x4) and / or component (x5) are used, it is preferable to first react component (x1) with component (x2), and then react component (x4) and / or component (x5). The reaction of component (x1) with component (x4) and / or component (x5) is carried out by mixing component (x1) with component (x4) and / or component (x5) at 25 to 200° C. and carrying out an addition reaction at 30 to 180° C., preferably 40 to 170° C. Furthermore, a catalyst such as sodium methoxide, sodium ethoxide, or potassium t-butoxide can be used as necessary. During the above reaction, in order to promote the reaction, the component (x4) and / or the component (x5) may be melted or diluted with a non-reactive solvent before use, if necessary.

[0038] When the reaction product (X) is a reaction product of the components (x1) and (x2) and at least one compound selected from the group consisting of the components (x3), (x4), and (x5), the molar ratio of the component (x2) to the component (x1), [(x2) / (x1)], is preferably in the range of 0.3 to 1.0, more preferably 0.6 to 1.0, for the same reasons as above. On the other hand, the molar ratio of the components (x3), (x4), and (x5) to the component (x1), [{(x3) + (x4) + (x5)} / (x1)], is preferably in the range of 0.05 to 3.1, more preferably 0.07 to 2.5, and even more preferably 0.1 to 2.0. However, from the viewpoints of gas barrier properties, workability, pot life, and the like, the reaction molar ratio of components (x2) to (x5) to component (x1), [{(x2)+(x3)+(x4)+(x5)} / (x1)], is preferably in the range of 0.35 to 2.5, and more preferably in the range of 0.35 to 2.0.

[0039] The epoxy resin curing agent (B1) may contain a curing agent component other than the reaction product (X). The "curing agent component other than the reaction product (X)" refers to a component other than the reaction product (X) that has two or more functional groups that can react with the epoxy groups in the epoxy resin (A1). From the viewpoints of reactivity with the epoxy resin (A1) and gas barrier properties, preferred components include polyamine compounds other than the component (x1) that have two or more amino groups in the molecule and modified polyamine compounds.

[0040] Examples of the polyamine compound include linear aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexamethylenediamine; polyamine compounds having an alicyclic structure such as 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, menthenediamine, isophoronediamine, norbornanediamine, and 1,4-diamino-3,6-diethylcyclohexane; polyamine compounds having an aromatic ring such as orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; polyamine compounds having a heterocyclic structure such as N-aminomethylpiperazine and N-aminoethylpiperazine; and polyetherpolyamine compounds. These compounds may be used alone or in combination of two or more. Among the above, the polyamine compound is more preferably at least one selected from the group consisting of 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine. Examples of modified polyamine compounds include reaction products of polyamine compounds and epoxy compounds, and Mannich reaction products of polyamine compounds, phenolic compounds, and aldehyde compounds.

[0041] However, from the viewpoint of achieving high gas barrier properties and impact resistance, it is preferable that the epoxy resin curing agent (B1) has a high content of the reaction product (X). From the above viewpoints, the content of the reaction product (X) in the epoxy resin curing agent (B1) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit is 100% by mass.

[0042] The ratio of epoxy resin (A1) to epoxy resin curing agent (B1) in the epoxy resin composition may be the standard ratio generally used when preparing an epoxy resin reaction product by reacting an epoxy resin with an epoxy resin curing agent. Specifically, the ratio of the number of active amine hydrogens in the epoxy resin curing agent (B1) to the number of epoxy groups in the epoxy resin (A1) (number of active amine hydrogens in the epoxy resin curing agent (B1) / number of epoxy groups in the epoxy resin (A1)) is preferably in the range of 0.2 to 12.0. From the viewpoint of achieving high gas barrier properties and impact resistance, the ratio (number of active amine hydrogens in the epoxy resin curing agent (B1) / number of epoxy groups in the epoxy resin (A1)) is more preferably 0.4 to 10.0, even more preferably 0.6 to 8.0, even more preferably 0.9 to 6.0, and even more preferably greater than 1.0 but not greater than 5.0. From the viewpoint of further improving impact resistance, (the number of active amine hydrogen atoms in the epoxy resin curing agent (B1) / the number of epoxy groups in the epoxy resin (A1)) is even more preferably 1.1 or more, and from the viewpoint of further improving the barrier property against hydrogen gas, it is more preferably 4.0 or less, and even more preferably 3.2 or less.

[0043] The epoxy resin composition may be an epoxy resin composition in which the main component (A) is an epoxy resin (A1) and the curing agent (B) is an epoxy resin curing agent that does not contain the reaction product (X). As the epoxy resin curing agent, from the viewpoints of reactivity with the epoxy resin (A1) and gas barrier properties, the above-mentioned polyamine compounds or modified products thereof are preferred, and the polyamine compound is more preferably at least one selected from the group consisting of 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine. In this case, the preferred range of the ratio of the number of active amine hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin (A1) (number of active amine hydrogens in the epoxy resin curing agent / number of epoxy groups in the epoxy resin (A1)) is the same as the range described above in (number of active amine hydrogens in the epoxy resin curing agent (B1) / number of epoxy groups in the epoxy resin (A1)).

[0044] 〔solvent〕 The composition of the main agent (A), the composition of the curing agent (B), and the thermosetting resin composition such as the epoxy resin composition used in step (I) may further contain a solvent from the viewpoint of lowering the viscosity of the composition to improve the impregnation ability into the continuous reinforcing fiber bundle, and from the viewpoint of adjusting the pot life. In the present invention, the term "solvent" is a concept that includes both reactive solvents such as reactive diluents and non-reactive solvents. From the viewpoint of improving the pot life, the solvent is preferably a non-reactive solvent.

[0045] Specific examples of non-reactive solvents include alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-propoxy-2-propanol; ester-based solvents such as ethyl acetate and butyl acetate; ketone-based solvents such as acetone and methyl isobutyl ketone; ether-based solvents such as diethyl ether and diisopropyl ether; hydrocarbon-based solvents such as toluene; and non-reactive diluents such as benzyl alcohol. One or more of these may be used. From the viewpoint of the solubility of the epoxy resin (A1) and the epoxy resin curing agent (B1) and the ease of removing the solvent, the solvent is preferably at least one non-reactive diluent selected from the group consisting of alcohol solvents, ester solvents, and hydrocarbon solvents having 8 or less carbon atoms, more preferably at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethyl acetate, and toluene, and even more preferably at least one selected from the group consisting of methanol and ethyl acetate.

[0046] When the composition of the main agent (A), the composition of the curing agent (B), or the thermosetting resin composition contains a solvent, the content thereof is not particularly limited, but from the viewpoint of improving the impregnation of the composition into the continuous reinforcing fiber bundle and adjusting the pot life, the content thereof in each composition is preferably 5% by mass or more, and from the viewpoint of facilitating removal of the solvent and controlling the amount of impregnation into the continuous reinforcing fiber bundle, the content thereof is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0047] In the production method of the present invention, a composition with a low solvent content and a solvent-free composition can also be used as the thermosetting resin composition. Generally, a thermosetting resin composition containing a non-reactive solvent can maintain a longer pot life, but since the production method of the present invention involves step (I), even a solvent-free composition with a short pot life can be applied. That is, the content of the solvent in the composition of the main agent (A) and the composition of the curing agent (B) used in the present invention can be reduced, and it is also possible to use no solvent. From the viewpoint of ease of solvent removal and control of the amount of impregnation into the continuous reinforcing fiber bundle, for example, the content of the solvent in the composition of the main agent (A), the composition of the curing agent (B), or the thermosetting resin composition can be more preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less. In particular, from the viewpoint of ease of solvent removal and control of the amount of impregnation into the continuous reinforcing fiber bundle, it is preferable that the composition of the main agent (A) is solvent-free. Also, it is preferable that the content of the solvent in the composition of the curing agent (B) is 40 mass% or less.

[0048] In the present invention, a thermosetting resin composition with a short pot life refers to, for example, a two-component thermosetting resin composition in which the pot life after mixing of the main component (A) and the curing agent (B) is preferably 1 hour or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, even more preferably 10 minutes or less, and even more preferably less than 10 minutes. More specifically, this refers to a thermosetting resin composition in which the time it takes for the main component (A) and the curing agent (B) to become gelled when left standing at 23°C after mixing is preferably 1 hour or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, even more preferably 10 minutes or less, and even more preferably less than 10 minutes. The gelation time can be measured using a rheometer. Specifically, the storage modulus G' and loss modulus G'' of the thermosetting resin or composition are measured using a rheometer at 23°C, a frequency of 1 Hz, and a plate distance of 0.5 mm, and the point where G' and G'' intersect is defined as the gelation time.

[0049] The thermosetting resin composition may further contain additives such as coupling agents, curing accelerators, wetting agents, rubbers, thermoplastic resins, tackifiers, antifoaming agents, rust inhibitors, lubricants, pigments, oxygen scavengers, ultraviolet absorbers, and antioxidants, as needed, within the scope of not impairing the effects of the present invention. When the composition contains additives, the total content of the additives in the composition is preferably 20.0 parts by mass or less, and more preferably 0.001 to 15.0 parts by mass, per 100 parts by mass of the thermosetting resin in the thermosetting resin composition (the total amount of the base resin (A) and the curing agent (B) in the case of a two-component type).

[0050] However, from the viewpoint of obtaining the effects of the present invention, the content of the thermosetting resin (main component (A) and curing agent (B) in the case of a two-component type) in the solid content of the thermosetting resin composition is preferably 60 mass % or more, more preferably 70 mass % or more, even more preferably 80 mass % or more, and even more preferably 85 mass % or more, with the upper limit being 100 mass %. The "solid content of the thermosetting resin composition" means the components excluding the solvent from the thermosetting resin composition.

[0051] (continuous reinforcing fiber) The continuous reinforcing fibers used in the present invention are reinforcing fibers having a fiber length of more than 100 mm. The continuous reinforcing fibers may be in the form of a tow, a sheet, a tape, etc., and the continuous reinforcing fibers constituting a sheet or tape may be unidirectional (UD) materials, woven fabrics, nonwoven fabrics, etc. From the viewpoint of obtaining a molded article by the manufacturing method of the present invention, the shape of the continuous reinforcing fiber is preferably a tow or a tape, and more preferably a tow (continuous reinforcing fiber yarn). As the continuous reinforcing fiber yarn, not only a fiber bundle having a substantially circular cross section but also a fiber bundle having a flat cross section (roving) can be used. As the single yarns constituting the continuous reinforcing fibers, fibers having a substantially circular cross section as well as fibers having a flat cross section can be used.

[0052] The number of fiber bundles (number of filaments) constituting the continuous reinforcing fiber bundle is preferably 0.3K to 60K, more preferably 3K to 60K, and even more preferably 6K to 50K, from the viewpoint of easily obtaining high strength and high elastic modulus. There are no particular restrictions on the average fiber length of the continuous reinforcing fiber bundles, but from the viewpoint of molding processability, it is preferably 100 to 100,000 m, more preferably 500 to 10,000 m. The larger the average fineness of the continuous reinforcing fiber bundles, the more efficient the production of molded articles. From the viewpoints of production efficiency, molding processability, and the ease of obtaining high strength and high elastic modulus, the average fineness of the continuous reinforcing fiber bundles is preferably 50 to 10,000 tex (g / 1,000 m), more preferably 200 to 7,500 tex, and even more preferably 500 to 5,000 tex. The average tensile modulus of the continuous reinforcing fiber bundles is preferably 100 to 1,000 GPa.

[0053] Examples of materials for the continuous reinforcing fibers include inorganic fibers such as glass fibers, carbon fibers, metal fibers, boron fibers, basalt fibers, and ceramic fibers, and organic fibers such as aramid fibers, polyoxymethylene fibers, aromatic polyamide fibers, polyparaphenylene benzobisoxazole fibers, and ultra-high molecular weight polyethylene fibers. Among these, inorganic fibers are preferred from the viewpoint of obtaining high strength, and at least one fiber selected from the group consisting of glass fibers, carbon fibers, and basalt fibers is more preferred because of its light weight, high strength, and high elastic modulus, with carbon fibers being even more preferred. Examples of carbon fibers include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, etc. Carbon fibers made from plant-derived materials such as lignin and cellulose can also be used.

[0054] The continuous reinforcing fibers used in the present invention may be treated with a treatment agent, such as a surface treatment agent or a sizing agent. The surface treatment agent is preferably a silane coupling agent, such as a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, a silane coupling agent having a (meth)acrylic group, or a silane coupling agent having a mercapto group.

[0055] Examples of the sizing agent include urethane-based sizing agents, epoxy-based sizing agents, acrylic-based sizing agents, polyester-based sizing agents, vinyl ester-based sizing agents, polyolefin-based sizing agents, polyether-based sizing agents, and carboxylic acid-based sizing agents, and these can be used alone or in combination of two or more. Examples of sizing agents that combine two or more types include urethane / epoxy-based sizing agents, urethane / acrylic-based sizing agents, and urethane / carboxylic acid-based sizing agents.

[0056] Among the above, from the viewpoint of improving the interfacial adhesion with a cured product of a thermosetting resin or composition, particularly a cured product of an epoxy resin composition, and further improving the strength and impact resistance of the resulting molded article, it is preferable that the continuous reinforcing fibers be treated with one or more selected from the group consisting of a urethane-based sizing agent, an epoxy-based sizing agent, and a urethane / epoxy-based sizing agent, and it is more preferable that the continuous reinforcing fibers be treated with an epoxy-based sizing agent.

[0057] The amount of the treatment agent is preferably 0.001 to 5 mass %, more preferably 0.1 to 3 mass %, and even more preferably 0.5 to 2 mass %, relative to the continuous reinforcing fibers, from the viewpoint of improving the interfacial adhesion with the thermosetting resin or the cured product of the thermosetting resin composition and further improving the strength and impact resistance of the resulting molded article.

[0058] Commercially available continuous reinforcing fibers can also be used. Examples of commercially available carbon fibers that are continuous reinforcing fibers include the "T300", "T300B", "T400HB", "T700SC", "T800SC", "T800HB", "T830HB", "T1000GB", "T100GC", "M35JB", "M40JB", "M46JB", "M50JB", "M55J", "M55JB", "M60JB", "M30SC", and "Z600" series of Toray carbon fibers manufactured by Toray Industries, Inc., and the "CO6142", "CO6151B", "CO6343", "CO6343B", "CO6347B", "CO6644B", "CK6244C", "CK6273C", "CK6261C", the "UT70" series, the "UM46" series, and the "BT70" series of Toray carbon fibers. Commercially available glass fibers include the "E Glass Yarn" series manufactured by Nitto Boseki Co., Ltd.

[0059] When a two-component thermosetting resin composition containing a main component (A) and a curing agent (B) is used, the application step in step (I) can be performed in two ways: by applying the main component (A) or a composition thereof to the surface of the continuous reinforcing fiber bundle and by applying the curing agent (B) or a composition thereof; or by premixing the main component (A) or a composition thereof with the curing agent (B) or a composition thereof and then applying the mixture to the surface of the continuous reinforcing fiber bundle. Examples of premixing the main component (A) and the curing agent (B) include mixing the main component (A) or a composition thereof with the curing agent (B) or a composition thereof using a mixer; or by sending the main component (A) or a composition thereof and the curing agent (B) or a composition thereof from both sides of a T-shaped pipe, respectively, and causing collision mixing of the main component (A) or a composition thereof with the curing agent (B) or a composition thereof. When a thermosetting resin composition having a short pot life is used, step (I) preferably comprises a step of applying a main agent (A) or a composition thereof to the surface of the continuous reinforcing fiber bundle, and a step of applying a curing agent (B) or a composition thereof.

[0060] In step (I), the method for applying the thermosetting resin or composition to the surface of the continuous reinforcing fiber bundle is not particularly limited, but examples include a method in which the main component (A), the curing agent (B), the thermosetting resin, or a composition thereof is ejected onto the surface of the continuous reinforcing fiber bundle from a nozzle capable of supplying the thermosetting resin or composition. When the method includes a step of applying a main agent (A) or a composition thereof to the surface of a continuous reinforcing fiber bundle and a step of applying a curing agent (B) or a composition thereof, it is preferable to dispense the main agent (A) or a composition thereof onto one side of the continuous reinforcing fiber bundle and dispense and apply the curing agent (B) or a composition thereof onto the other side, from the viewpoint of avoiding curing of the thermosetting resin composition during the manufacturing process. The "other side" preferably refers to the side opposite to the "one side".

[0061] <Step (II): Resin Impregnation Step> In step (II), the continuous reinforcing fiber bundles are twisted after step (I) and impregnated with a thermosetting resin or a thermosetting resin composition to obtain a prepreg. By performing step (II), the thermosetting resin or composition can be made to flow, facilitating impregnation into the continuous reinforcing fiber bundles. When a two-component thermosetting resin composition is used, even if the main agent (A) or a composition containing it and the curing agent (B) or a composition containing it are applied separately to the continuous reinforcing fiber bundle in step (I), the main agent (A) and the curing agent (B) are sufficiently mixed within the continuous reinforcing fiber bundle.

[0062] In step (II), the continuous reinforcing fiber bundle obtained in step (I) is twisted (twisting step). The twisting direction is preferably unidirectional, preferably a circumferential direction substantially perpendicular to the longitudinal direction of the continuous reinforcing fiber bundle. For example, when the continuous reinforcing fiber bundle is a tow, the continuous reinforcing fiber bundle is twisted in a circumferential direction substantially perpendicular to the longitudinal direction of the tow. This operation allows the thermosetting resin or composition applied in step (I) to be sufficiently impregnated into the continuous reinforcing fiber bundle. The number of rotations for twisting the continuous reinforcing fiber bundle is preferably 20 to 300 rotations, more preferably 50 to 200 rotations, and even more preferably 70 to 150 rotations per meter of continuous reinforcing fiber length, from the viewpoint of sufficiently impregnating the continuous reinforcing fibers with the thermosetting resin or composition applied in step (I).

[0063] The twisting step in step (II) can also be performed using the mechanism shown in FIG. 1. FIGS. 1(a) and 1(b) are schematic diagrams illustrating one embodiment of the twisting step in step (II), with FIG. 1(a) being a top view and FIG. 1(b) being a side view. In FIG. 1, A represents the continuous reinforcing fiber yarn after the thermosetting resin or thermosetting resin composition has been applied in step (I), and B1 and B2 represent take-up rolls. The continuous reinforcing fiber yarn A sandwiched between the two take-up rolls B1 and B2 is fed in the longitudinal direction (axial direction) of the continuous reinforcing fiber yarn A by the rotation of the take-up rolls. Here, by tilting the rotation axes of the two take-up rolls by θ° in opposite directions as shown in FIG. 1(a), the continuous reinforcing fiber yarn A can be rotated in the circumferential direction and taken up in the axial direction while being twisted.

[0064] Step (II) preferably includes a step of untwisting the continuous reinforcing fiber bundles after twisting them. By performing the untwisting step, the restoration of the twisted continuous reinforcing fiber bundles serves as a driving force to further flow the thermosetting resin or composition, thereby facilitating impregnation of the continuous reinforcing fiber bundles and mixing within the continuous reinforcing fiber bundles. The untwisting step is performed by twisting the continuous reinforcing fiber bundle in the opposite direction to the twisting direction in the twisting step. When using the twisting mechanism shown in Figure 1, the twist can be unwound by tilting the rotation axes of the two take-up rolls by θ° in the opposite direction to the twisting step. The untwisting step may be performed alternately with the twisting step. For example, in the twisting step, the continuous reinforcing fiber bundle is twisted once in the circumferential direction substantially perpendicular to the longitudinal direction of the continuous reinforcing fiber bundle, and then twisted once in the opposite direction to untwist the continuous reinforcing fiber bundle. By repeating this series of operations, the thermosetting resin or composition can be sufficiently impregnated into the continuous reinforcing fiber bundle. When the untwisting step is performed, the rotation speed is preferably the same as the rotation speed for twisting in the twisting step, and is preferably 20 to 300 rotations, more preferably 50 to 200 rotations, and even more preferably 70 to 150 rotations per meter of the continuous reinforcing fiber bundle. The twisting step and untwisting step in step (II) may be performed manually or mechanically using a device equipped with a twisting mechanism, such as a resin impregnation device described below.

[0065] After the twisting step, or if a twist unwinding step has been performed, a step of removing excess thermosetting resin or composition applied to the continuous reinforcing fiber bundle may be performed. In the following description, the step of removing excess thermosetting resin or composition is also referred to as the "squeezing step." By performing this step, the impregnation of the thermosetting resin or composition into the continuous reinforcing fiber bundle is further promoted. Furthermore, by performing this step, the cross section perpendicular to the running direction (longitudinal direction) of the continuous reinforcing fiber bundle becomes flat, such as an ellipse, thereby suppressing the occurrence of gaps due to steps (crimps) when laminating prepregs in the molding step (III), as well as a decrease in strength. The squeezing step can be performed, for example, using nip rolls.

[0066] Furthermore, after the twisting step, or after the untwisting step if performed, a step of removing the solvent and the like contained in the thermosetting resin composition (solvent removal step) may be performed as needed. From the viewpoint of productivity, the solvent removal step is usually performed under heating. The heating conditions are not particularly limited as long as they allow the solvent to be removed and do not cause excessive curing of the thermosetting resin, and can be appropriately selected depending on the type of thermosetting resin and solvent. For example, the heating temperature can be selected in the range of 30 to 100°C, and the heating time can be selected in the range of 10 seconds to 10 minutes. The solvent removal step can be carried out by a known method using a hot air dryer, heater, heated roll, hot plate, etc. Examples include a method of running the film through a heated atmosphere using a hot air dryer, heater, etc.; a method of contacting the film with a heating body such as a heated roll, hot plate, etc. Among these, the method using a hot air dryer is preferred.

[0067] By carrying out the above steps (I) and (II), a prepreg in which the continuous reinforcing fiber bundles are impregnated with the thermosetting resin or composition is obtained. The prepreg obtained in step (II) may be temporarily wound onto a bobbin or the like, but from the viewpoint of improving productivity, it is preferable to subject it to step (III) without winding.

[0068] From the viewpoint of productivity of the molded article, it is preferable that steps (I) and (II) are carried out using a resin impregnation device equipped with a mechanism for feeding out a continuous reinforcing fiber bundle, a nozzle for ejecting the thermosetting resin or thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle, and a mechanism for twisting the continuous reinforcing fiber bundle. The resin impregnation device will be described later.

[0069] <Process (III): Heat forming process> In step (III), the prepreg obtained in step (II) is arranged and then heated to obtain a molded body. "Arranging the prepreg" refers to laminating the prepreg so as to obtain the desired molded body shape. The method for arranging the prepreg can be appropriately selected depending on the shape of the prepreg and the resulting molded body. For example, when the prepreg is a tow prepreg, a braiding method, a winding method, a 3D printing method, etc. can be used. The braiding method and the winding method can be performed by a known method. When the 3D printing method is used, it is preferable to use the 3D printer of the present invention described later. From the viewpoint that it becomes possible to form a molded body such as a pressure vessel without using a core material such as a mandrel, the forming method in step (III) is preferably a braiding method or a 3D printing method, and from the viewpoint of forming a complex shape, a 3D printing method is more preferable.

[0070] The heating in step (III) is carried out by a known method at a temperature and for a time sufficient to cure the thermosetting resin contained in the prepreg after placement. From the viewpoint of improving productivity, the heating temperature is preferably in the range of 80 to 150°C, and the heating time is preferably in the range of 10 minutes to 5 hours.

[0071] By using the manufacturing method having the above steps (I) to (III) in order, a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and continuous reinforcing fibers can be efficiently manufactured.

[0072] The content of continuous reinforcing fibers in the molded article obtained by the manufacturing method of the present invention is not particularly limited, but from the viewpoint of high strength and high elastic modulus of the molded article, the volume fraction (Vf) of continuous reinforcing fibers is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and even more preferably 40% or more. Furthermore, from the viewpoint of gas barrier properties and impact resistance of the molded article, the volume fraction is preferably 98% or less, more preferably 95% or less, even more preferably 80% or less, and even more preferably 70% or less. The volume fraction Vf of the continuous reinforcing fibers in the molded body can be calculated from the following formula. Vf (%) = {mass (g) of continuous reinforcing fiber / specific gravity of continuous reinforcing fiber} ÷ [{mass (g) of continuous reinforcing fiber / specific gravity of continuous reinforcing fiber} + {mass (g) of cured thermosetting resin (composition) / specific gravity of cured thermosetting resin (composition)}] × 100 Furthermore, from the viewpoint of high strength and high elastic modulus of the molded body, the total content of the thermosetting resin or cured product of the composition and the continuous reinforcing fibers in the molded body is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, with the upper limit being 100% by mass.

[0073] <Pressure vessel> An example of a molded article produced by the production method of the present invention is a pressure vessel. In particular, when an epoxy resin composition in which the base resin (A) is the epoxy resin (A1) and the curing agent (B) is the epoxy resin curing agent (B1) is used as the thermosetting resin composition, the resulting pressure vessel has good gas barrier properties against hydrogen gas and the like, and is also lightweight, pressure-resistant, and impact-resistant. The material stored in the pressure vessel may be a gas or liquid at 25°C and 1 atm, preferably a gas at 25°C and 1 atm. Specific examples include hydrogen, oxygen, carbon dioxide, nitrogen, argon, LPG, chlorofluorocarbon alternatives, methane, etc. Among these, hydrogen is preferred from the viewpoint of effectiveness when the epoxy resin composition is used as a thermosetting resin composition. The pressure vessel may be (1) a pressure vessel having a liner and an outer layer for reinforcing the liner, or (2) a linerless pressure vessel, and the manufacturing method of the present invention can be applied to either pressure vessel (1) or (2). In the case of pressure vessel (1), the manufacturing method of the present invention can be applied to the manufacture of either the liner or the outer layer, or both. From the viewpoint of the effectiveness of the present invention and light weight, it is preferable that the pressure vessel be linerless.

[0074] The following description of pressure vessels will focus on linerless pressure vessels. The pressure vessel is generally hollow as long as it has a space therein that is filled with gas. The shape of the pressure vessel will be described with reference to the drawings. Fig. 2 is a cross-sectional schematic diagram showing one embodiment of a pressure vessel. In Fig. 2, a linerless pressure vessel 100 has a cylindrical portion 1 and two dome portions 2a, 2b that seal both ends (1a and 1b) of the cylindrical portion 1. Both dome sections 2a and 2b are hollow, and at least one of the dome sections (dome section 2a in FIG. 1) can be provided with an opening 3 at the top of the dome section for joining a valve or the like for a pressure vessel. A valve or the like for a pressure vessel may be installed in the dome section beforehand. The pressure vessel may be provided with any layer (not shown) such as a protective layer, a paint layer, or a rust-preventing layer, if necessary.

[0075] The fiber-reinforced composite material constituting the pressure vessel 100 is formed using the prepreg obtained in step (II). In step (III), the prepreg obtained in step (II), preferably a tow prepreg, is molded by a braiding method, a winding method, a 3D printing method, or the like to obtain the pressure vessel 100 made of a fiber-reinforced composite material having a helical structure, a braided structure, a spiral structure, or the like. That is, in step (III), the prepreg (preferably a tow prepreg) obtained in step (II) of the manufacturing method is arranged to form the shape of the pressure vessel having a helical structure, a braided structure, or a spiral structure. From the viewpoint of improving gas barrier properties, strength, impact resistance, etc., the fiber reinforced composite material that constitutes the pressure vessel 100 preferably has a braided or spiral structure. The braided and spiral structures are structures in which a cured prepreg composed of a thermosetting resin or composition and continuous reinforcing fiber bundles is tightly arranged in a braided or spiral shape, thereby forming the hollow pressure vessel 100.

[0076] In step (III), a pressure vessel having a braided structure can be produced by molding a tow prepreg composed of a thermosetting resin or composition and continuous reinforcing fiber bundles using a braiding method. Furthermore, a pressure vessel having a spiral structure can be produced by molding the tow prepreg using a unidirectional braiding method, a winding method, or a 3D printing method. Pressure vessels having a braided or spiral structure have excellent gas barrier properties, strength, and impact resistance, and are also advantageous in terms of productivity.

[0077] From the viewpoints of gas barrier properties, strength, impact resistance, and productivity, it is preferable that at least the cylindrical portion 1 constituting the pressure vessel 100 has a braided structure or a spiral structure. The dome portions 2a and 2b constituting the pressure vessel 100 may also be made of a fiber-reinforced composite material having a braided structure or a spiral structure, but are not particularly limited thereto.

[0078] 2 may be molded by separately manufacturing and joining the cylindrical portion and the dome portion, or may be molded by collectively molding the cylindrical portion and the dome portion. From the viewpoint of productivity, it is preferable that the cylindrical portion 1 and at least one dome portion are molded by collectively molding. If a braiding method, a winding method, or a 3D printing method is used in step (III), the cylindrical portion and the dome portion of the pressure vessel can be easily molded in one step.

[0079] When the dome portion of the pressure vessel is produced separately, the production method is not particularly limited, but for example, it can be produced by hot press molding a prepreg in which reinforcing fibers have been previously impregnated with a thermosetting resin or composition using a mold. If the thermosetting resin or composition used is a solventless type, it can also be produced by known molding methods such as Va-RTM (Vacuum assisted resin transfer molding), RTM (Resin transfer molding), and HP-RTM (High pressure resin transfer molding). In this case, the thermosetting resin or composition and reinforcing fibers constituting the dome portion may be the same as those constituting the cylindrical portion of the pressure vessel. When a component in which only the cylindrical portion of a pressure vessel or only one end of the cylindrical portion is sealed is molded using the manufacturing method of the present invention, a separately manufactured dome portion can be joined and sealed to one or both ends of the cylindrical portion to manufacture a pressure vessel.

[0080] The thickness of the pressure vessel 100 (t in FIG. 2) can be selected appropriately depending on the capacity and shape of the pressure vessel, the thickness of the continuous reinforcing fibers used, or the outer diameter of the fiber bundle, etc. From the viewpoint of ensuring sufficient gas barrier properties and pressure resistance for the pressure vessel against hydrogen gas, etc., the thickness of the pressure vessel is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 400 μm or more, and from the viewpoint of reducing the size and weight of the pressure vessel, the thickness is preferably 60 mm or less, more preferably 40 mm or less.

[0081] [Resin impregnation equipment] The present invention provides a resin impregnation device including a mechanism for feeding a continuous reinforcing fiber bundle, a nozzle for ejecting a thermosetting resin or a thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle, and a mechanism for twisting the continuous reinforcing fiber bundle. The resin impregnation device is suitably used in steps (I) and (II) of the production method of the present invention.

[0082] The resin impregnation device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing one embodiment of a resin impregnation apparatus and a 3D printer equipped with the same. In Fig. 3, the resin impregnation apparatus 200 includes a conveying roll 20 for feeding out the continuous reinforcing fiber bundle 11, nozzles 21 (21a, 21b) for discharging and applying a thermosetting resin or a thermosetting resin composition to the surface of the fed continuous reinforcing fiber bundle 11, and a twisting mechanism 22 for twisting the continuous reinforcing fiber bundle 11. The nozzle 21 is a mechanism for discharging and applying a thermosetting resin or a thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle 11, and is capable of carrying out step (I) in the manufacturing method of the present invention. Tanks 23 (23a, 23b) filled with a thermosetting resin or composition are connected to nozzle 21, and the thermosetting resin or composition is supplied from tank 23 to nozzle 21 via resin supply lines 24 (24a, 24b). When a two-component thermosetting resin composition containing a main component (A) and a curing agent (B) is used as the thermosetting resin composition, it is preferable to provide tank 23a for filling main component (A) or its composition, and tank 23b for filling curing agent (B) or its composition. This configuration makes it easy to use a thermosetting resin composition with a short pot life in step (I). 3, a resin supply line 24a and a nozzle 21a are connected in this order to a tank 23a, and a resin supply line 24b and a nozzle 21b are connected in this order to a tank 23b. The nozzles 21a and 21b are provided at opposing positions sandwiching the side surface of the continuous reinforcing fiber bundle 11, and the main agent (A) or a composition thereof can be discharged from the nozzle 21a onto one side surface of the continuous reinforcing fiber bundle 11, and the curing agent (B) or a composition thereof can be discharged from the nozzle 21b onto the other side surface, for application.

[0083] In an embodiment in which a two-component thermosetting resin composition containing a main component (A) and a curing agent (B) is used as the thermosetting resin composition, when the main component (A) or a composition thereof and the curing agent (B) or a composition thereof are mixed by collision and then applied to the surface of the continuous reinforcing fiber bundle 11, it is preferable to provide a confluence 25 (not shown) between a resin supply line 24a connected to a tank 23a and a resin supply line 24b connected to a tank 23b upstream of the nozzle 21. This allows the main component (A) or a composition thereof and the curing agent (B) or a composition thereof to be mixed at the confluence 25, and the resulting thermosetting resin composition to be supplied to the nozzle 21. The confluence 25 can be configured as a T-pipe or the like.

[0084] The resin impregnation device 200 includes a twisting mechanism 22. The twisting mechanism 22 can perform the step (II) in the manufacturing method of the present invention. The twisting mechanism 22 is provided downstream of the nozzle 21. The continuous reinforcing fiber bundle 11 to which the thermosetting resin or composition has been applied using the nozzle 21 is twisted, preferably in the circumferential direction substantially perpendicular to the running direction, by the twisting mechanism 22. This allows the thermosetting resin or composition to be sufficiently impregnated and mixed into the continuous reinforcing fiber bundle 11. In step (II) of the manufacturing method of the present invention, if the continuous reinforcing fiber bundle 11 is twisted in one direction, the step of untwisting can be carried out by twisting the continuous reinforcing fiber bundle 11 in the opposite direction using the twisting mechanism 22. The twisting mechanism 22 may be the twisting mechanism illustrated in FIG.

[0085] The resin impregnation device 200 may be provided with a nip roll 26 downstream of the twisting mechanism 22 for removing excess thermosetting resin or composition applied to the continuous reinforcing fiber bundle 11.

[0086] The resin impregnation device 200 may further include a drying mechanism 27, if necessary. The drying mechanism 27 is preferably provided downstream of the twisting mechanism 22 (downstream of the nip rolls 26, if provided). The drying mechanism 27 is provided to remove the solvent from the thermosetting resin composition impregnated into the continuous reinforcing fiber bundle 11, and may take the form of a hot air dryer, a heater, a heating roll, a hot plate, or the like. The continuous reinforcing fiber bundle 11 impregnated with the thermosetting resin composition containing the solvent passes through a drying mechanism 27, whereby the solvent is removed and a prepreg is formed.

[0087] [3D Printer] The present invention further provides a 3D printer equipped with the resin impregnation device, which is suitable for use in the manufacturing method of the present invention. The 3D printer of the present invention preferably includes at least the resin impregnation device and a robot arm. Steps (I) and (II) are performed using the resin impregnation device, and the resulting prepreg is then used by the robot arm to perform molding in step (III), thereby easily producing a three-dimensional molded body.

[0088] The 3D printer 400 shown in FIG. 3 includes a resin impregnation device 200 and a robot arm 300. The robot arm 300 is composed of a support table 30 for placing the prepreg obtained in step (II), and an arm unit 31 for holding the support table 30. The arm unit 31 holds the support table 30 and can freely change the position (X, Y, and Z directions), rotation direction, tilt, etc. of the support table 30 by mechanical control. The arm unit 31 is connected to, for example, the underside of the support table 30 so as to hold the support table 30.

[0089] The position, rotation direction, inclination, etc. of the support table 30 are freely changed by the operation of the arm unit 31, and by this operation, the prepreg supplied from the resin impregnation device 200 is arranged in a desired shape on the support table 30. The operation of the arm unit 31 is controlled, for example, by a control device (not shown) according to a program. The prepreg supplied from the resin impregnation device 200 toward the robot arm 300 is placed and laminated on the support table 30 while being pressed by the laminating roll 32, and is then molded into the desired shape. This method makes it possible to mold a linerless pressure vessel in one go without using a core material such as a mandrel.

[0090] Next, the laminate 33 obtained by placing the prepreg on the support table 30 is heated to obtain a molded article made of a fiber-reinforced composite material. The laminate 33 may be heated by being placed on the support table 30 and then subjected to a heating mechanism, or may be removed from the support table 30 and then subjected to a heating mechanism. [Example]

[0091] The present invention will now be described in detail with reference to examples, although the present invention is not limited to these examples in any way. In the present examples, measurements and evaluations were carried out by the following methods.

[0092] <Hydrogen gas permeability coefficient [cc·cm / (cm 2 ·s·cmHg)]> The mixture of base resin and curing agent solution (epoxy resin composition) used in Example 1 was applied to a 200 mm square sheet 100 μm thick using a bar coater on a smooth metal plate coated with a release agent, and then heated at 100°C for 5 minutes to cure, producing a cured product. The hydrogen gas permeability coefficient of this cured product was measured in a dry state at 23°C using a vapor permeability measuring device (GTR Tech Co., Ltd., "G2700T·F").

[0093] <Impregnability> In each example, the impregnation of the thermosetting resin composition into the continuous reinforcing fiber bundle was evaluated by the following method. A randomly selected vertical cross section was polished from the molded body and photographed using an ultra-deep color 3D shape measurement microscope. The region impregnated with the epoxy resin composition, a thermosetting resin composition, was selected from the resulting cross-sectional photograph using the image analysis software "ImageJ," and its area was measured. The impregnation rate was expressed as the area of ​​the region impregnated with the epoxy resin composition / (area of ​​the total region - area of ​​the region where continuous reinforcing fiber bundles are present) × 100 (%). The region impregnated with the epoxy resin composition refers to a region where the thermosetting resin composition has permeated between the continuous carbon fibers or continuous glass fibers and the air between the fibers has been removed. That is, in the region impregnated with the epoxy resin composition, a cured product of the thermosetting resin composition is present between the continuous carbon fibers or continuous glass fibers. The ultra-deep color 3D shape measurement microscope used was the Keyence VK-9500 (controller unit) / VK-9510 (measurement unit). The impregnation property was judged according to the following criteria. [Evaluation criteria] AA: Impregnation rate 100% A: Impregnation rate 95% or more but less than 100% B: Impregnation rate 90% or more but less than 95% C: Impregnation rate less than 90%

[0094] <Glass transition temperature (Tg)> The glass transition temperature Tg of the matrix resin (cured product of the epoxy resin composition) of the fiber reinforced composite material obtained in each example was measured using a differential scanning calorimeter ("DSC25" manufactured by TA Instruments). In a nitrogen atmosphere, approximately 5 mg of a sample (cured epoxy resin composition) was subjected to the following thermal history conditions. The thermal history conditions were a first temperature increase (heating rate of 10°C / min), followed by cooling (cooling rate of 10°C / min), followed by a second temperature increase (heating rate of 10°C / min). The heating temperature was from room temperature to 225°C, and the peak glass transition temperature observed during the second temperature increase was read and shown in Table 1. In examples using the same thermosetting resin composition, a higher Tg indicates that the base agent and curing agent in the thermosetting resin composition are more thoroughly mixed.

[0095] Manufacturing Example 1 (Preparation of Epoxy Resin Hardener Solution B-1) A reaction vessel was charged with 1 mol of metaxylylenediamine (MXDA). The temperature was raised to 60°C under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. The temperature was raised to 165°C while distilling off the resulting methanol, and the temperature was maintained at 165°C for 2.5 hours to obtain an epoxy resin curing agent, which was a reaction product of MXDA and methyl acrylate. Methanol was added dropwise to the mixture over 1.5 hours to obtain an epoxy resin curing agent solution B-1 containing 65% by mass of the epoxy resin curing agent and 35% by mass of methanol.

[0096] Example 1 (Production and Evaluation of Molded Product) The thermosetting resin composition used an epoxy resin having a glycidylamino group derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) as the main agent, the epoxy resin curing agent solution B-1 obtained in Production Example 1 as the curing agent, and a carbon fiber roving "T700SC-12000" manufactured by Toray Industries, Inc. (number of filaments: 12,000, fineness: 800 tex, cross-sectional shape of the carbon fiber roving: ellipse) as the continuous reinforcing fiber. First, the base resin was applied to one side of the carbon fiber roving so that the ratio of the active amine hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin was 1.2 and the total solid mass of the base resin and curing agent was 700 g / 1,000 m. Then, the curing agent solution B-1 was applied to the other side (step (I)). The resulting roving was twisted 100 times per meter in the circumferential direction and then untwisted 100 times per meter in the reverse direction, thereby impregnating and mixing the base resin and curing agent solution. Next, a nip roll was used to remove excess resin composition (base resin and curing agent solution) (squeezing step). The roving was then heated and dried in a hot air dryer at 60°C for 6 minutes to remove the solvent, yielding a tow prepreg (step (II)). The obtained tow prepreg was arranged in a spiral structure to form a tank shape, and then heat-cured at 120°C for 1 hour to produce a molded product made of a carbon fiber reinforced composite material (step (III)). The obtained molded body was evaluated by the above-mentioned method, and the results are shown in Table 1. The hydrogen gas permeability coefficient of the cured product of the mixture of the base resin and the curing agent solution (epoxy resin composition) used in Example 1, measured by the above method, was 3.9 × 10 -11 [cc·cm / (cm 2 ·s·cmHg)].

[0097] Example 2 A molded body was produced and evaluated in the same manner as in Example 1, except that the drawing step was not performed in step (II) of Example 1. The results are shown in Table 1.

[0098] Example 3 A molded article was produced and evaluated in the same manner as in Example 1, except that the step of unwinding the twist and the step of drawing were not carried out in step (II) of Example 1. The results are shown in Table 1.

[0099] Example 4 In Example 1, a liquid epoxy resin having glycidyloxy groups derived from bisphenol A ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / equivalent) was used as the main component of the thermosetting resin composition, and 1,3-bis(aminomethyl)cyclohexane (1,3-BAC, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as the curing agent in a ratio of the number of active amine hydrogen atoms in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin = 1.0. A molded article was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0100] Example 5 A molded body was produced and evaluated in the same manner as in Example 1, except that a bundle of 16 glass fiber rovings "E Glass Yarn ECG 75 1 / 0 0.7Z" (filament diameter: 9.1 μm, number of filaments: 400, fineness: 68.7 tex, cross-sectional shape: circular) manufactured by Nitto Boseki Co., Ltd. was used instead of the carbon fiber roving. The results are shown in Table 1.

[0101] Example 6 The thermosetting resin composition used an epoxy resin having a glycidylamino group derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) as the main agent, the epoxy resin curing agent solution B-1 obtained in Production Example 1 as the curing agent, and carbon fiber roving "T700SC-12000" manufactured by Toray Industries, Inc. as the continuous reinforcing fiber. A molded product was produced and evaluated in the same manner as in Example 2, except that in step (I) of Example 2, the base resin and curing agent solutions were impingement-mixed immediately before application to the carbon fiber roving, and then applied to the carbon fiber roving. The impingement mixing was performed by feeding the base resin from the left and the curing agent solution from the right into a T-shaped feed pipe (T-pipe) and causing them to collide at the branching point in the center of the T-pipe. The mixed liquid flowing out from the bottom of the T-pipe was applied to the carbon fiber roving. The results are shown in Table 1. The pot life of the epoxy resin composition obtained by impingement-mixing the base resin and curing agent solutions was 10 minutes. The pot life was measured using the method described in the specification.

[0102] Comparative Example 1 A molded body was produced and evaluated in the same manner as in Example 1, except that step (II) was not carried out. The results are shown in Table 1.

[0103] Comparative Example 2 The thermosetting resin composition used an epoxy resin having a glycidylamino group derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) as the main agent, the epoxy resin curing agent solution B-1 obtained in Production Example 1 as the curing agent, and a carbon fiber roving "T700SC-12000" manufactured by Toray Industries, Inc. as the continuous reinforcing fiber bundle. In step (I) of Comparative Example 1, the base agent and curing agent solutions were mixed by collision just before being applied to the carbon fiber roving, and then the carbon fiber roving was coated with the mixed solution. A molded body was produced and evaluated in the same manner as in Comparative Example 1. The collision mixing was carried out in the same manner as in Example 6. The results are shown in Table 1.

[0104] Comparative Example 3 A molded body was produced and evaluated in the same manner as in Comparative Example 1, except that a squeezing step using nip rolls was carried out after step (I) in Comparative Example 1. The results are shown in Table 1.

[0105] The shapes of the prepregs after step (II) are shown in Table 1. "Elliptical cylinder" and "cylindrical cylinder" refer to the cross-sectional shapes perpendicular to the running direction of the tow prepreg, respectively, which are elliptical and circular, and "spiral cylinder" refers to the twisted shape of the tow prepreg.

[0106] [Table 1]

[0107] From Table 1, it can be seen that the manufacturing method of this example, in which steps (I) to (III) defined in the present invention are carried out in order, improves the impregnation of the continuous reinforcing fiber bundle with the thermosetting resin composition, and even when the base resin and curing agent constituting the thermosetting resin composition are supplied separately, they are sufficiently mixed within the continuous reinforcing fiber bundle, thereby achieving a high Tg. In particular, by carrying out the untwisting step and the squeezing step in step (II), the impregnation of the thermosetting resin composition is further improved. [Industrial Applicability]

[0108] According to the present invention, in the production of a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and a continuous reinforcing fiber bundle, it is possible to provide a production method that enables the use of a thermosetting resin or composition with a short pot life and improves the impregnation of the thermosetting resin or composition into the continuous reinforcing fiber bundle, as well as a resin impregnation device and a 3D printer that are suitably used for the production method. According to the manufacturing method of the present invention, a linerless pressure vessel can be easily manufactured. The pressure vessel is suitable as a high-pressure gas storage tank for vehicles, and because it is lightweight, it can improve the fuel efficiency of the vehicle in which it is installed. [Explanation of symbols]

[0109] 100 Pressure vessel 1 Cylindrical part 1a, 1b End of cylindrical part 2a, 2b Dome section 3 Opening 11 Continuous reinforcing fiber bundle 200 Resin impregnation device 20 Transport roll 21, 21a, 21b nozzles 22 Twisting mechanism 23, 23a, 23b tanks 24, 24a, 24b Resin supply lines 26 Nip Roll 27 Drying mechanism 300 Robot Arm 30 Support stand 31 Arm section 32 Laminated roll 33 Prepreg Laminates 400 3D printers

Claims

1. A method for producing a molded article made of a fiber-reinforced composite material containing a cured product of a thermosetting resin or a thermosetting resin composition and continuous reinforcing fibers, the method comprising the following steps (I) to (III) in this order: Step (I): A coating step in which a thermosetting resin or a thermosetting resin composition is discharged from a nozzle capable of supplying a thermosetting resin or a thermosetting resin composition onto the surface of a continuous reinforcing fiber bundle sent out by a conveying roll, thereby coating the thermosetting resin or the thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle. Step (II): After step (I), the continuous reinforcing fiber bundles are twisted in a circumferential direction substantially perpendicular to the longitudinal direction of the continuous reinforcing fiber bundles to obtain a prepreg impregnated with the thermosetting resin or thermosetting resin composition. A resin impregnation step Step (III): A heat-molding step in which the prepreg obtained in step (II) is arranged and then the arranged prepreg is heated to cure the thermosetting resin or thermosetting resin composition.

2. The method for producing a molded article according to claim 1, wherein the thermosetting resin composition is a two-component thermosetting resin composition containing a main component (A) and a curing agent (B).

3. The method for producing a molded article according to claim 2, wherein a pot life after mixing the base agent (A) and the curing agent (B) is 10 minutes or less.

4. 4. The method for producing a molded article according to claim 2 or 3, wherein the main component (A) is an epoxy resin (A1), and the curing agent (B) is an epoxy resin curing agent (B1) containing a reaction product (X) of the following component (x1) and component (x2): (x1) At least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (x2) At least one member selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: 【Chemistry 1】 (In formula (1), R １ , R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.

5. The method for producing a molded article according to claim 4, wherein the epoxy resin (A1) is mainly composed of an epoxy resin having a glycidylamino group derived from metaxylylenediamine.

6. The method for producing a molded article according to any one of claims 2 to 5, wherein the step (I) comprises a step of applying the main agent (A) or a composition thereof to a surface of the continuous reinforcing fiber bundle, and a step of applying the curing agent (B) or a composition thereof.

7. The method for producing a molded article according to any one of claims 2 to 5, wherein the step (I) comprises a step of collision-mixing the main agent (A) or a composition thereof and the curing agent (B) or a composition thereof, and then applying the mixture to the surface of the continuous reinforcing fiber bundle.

8. The method for producing a molded article according to claim 6 or 7, wherein the content of the solvent in the composition of the curing agent (B) is 40 mass% or less.

9. The method for producing a molded article according to any one of claims 6 to 8, wherein the composition of the main component (A) is solvent-free.

10. The method for producing a molded body according to any one of claims 1 to 9, wherein the step (II) includes a step of twisting the continuous reinforcing fiber bundle and then untwisting it.

11. The step (I) and the step (II) are performed using a resin impregnation device equipped with a mechanism for feeding out the continuous reinforcing fiber bundle, a nozzle for discharging the thermosetting resin or thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle, and a mechanism for twisting the continuous reinforcing fiber bundle. The method for producing a molded body according to any one of claims 1 to 10.

12. The method for producing a molded body according to any one of claims 1 to 11, wherein the molding method in the step (III) is a 3D printing method.

13. The method for producing a molded article according to any one of claims 1 to 12, wherein the molded article is a pressure vessel.

14. The method for producing a molded article according to claim 13, wherein the pressure vessel is linerless.

15. A resin impregnation device comprising: a mechanism for feeding out a continuous reinforcing fiber bundle; a nozzle for ejecting a thermosetting resin or a thermosetting resin composition onto a surface of the continuous reinforcing fiber bundle; and a mechanism for twisting the continuous reinforcing fiber bundle, The mechanism for feeding the continuous reinforcing fiber bundle includes a conveying roll, the nozzle is a nozzle for discharging a thermosetting resin or a thermosetting resin composition onto the surface of the continuous reinforcing fiber bundle sent out by the conveying roll, a mechanism for twisting the continuous reinforcing fiber bundle provided downstream of the nozzle and twisting the continuous reinforcing fiber bundle in a circumferential direction substantially perpendicular to a longitudinal direction of the continuous reinforcing fiber bundle;

16. The resin impregnation device according to claim 15, further comprising a drying mechanism.

17. A 3D printer equipped with the resin impregnation device according to claim 15 or 16.

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