Prepregs, fiber-reinforced resin molded articles, and integrally molded articles

Abstract

The purpose of this invention is to provide a prepreg and fiber-reinforced resin molded article that has excellent bonding strength with other components, appropriate control of resin flow during welding, and excellent dimensional stability during welding. A prepreg having a thermoplastic resin layer comprising reinforcing fibers and thermoplastic resin, wherein the thermoplastic resin layer is present on at least one surface of the prepreg, the aforementioned thermoplastic resin layer comprising, with respect to 100% by mass of the total constituent units of thermoplastic resin, thermosetting resin and curing agent, 65.0 to 99.5% by mass of thermoplastic resin constituent units, and 0.5 to 35.0% by mass of thermosetting resin constituent units and curing agent constituent units.

Description

Technical Field

[0001] The present invention relates to a prepreg having a thermoplastic resin layer, a fiber-reinforced resin molded body formed from the prepreg, and an integrally molded article formed by bonding the fiber-reinforced resin molded body with other components. Prior Technology

[0002] Fiber-reinforced composites, which use thermosetting or thermoplastic resins as the matrix resin and combine them with reinforcing fibers such as carbon fiber and glass fiber, are used in numerous fields, including aerospace, automotive, railway vehicles, shipbuilding, civil engineering, and sporting goods, due to their excellent mechanical properties such as light weight, strength, and rigidity. However, these fiber-reinforced composites are not suitable for manufacturing parts or structures with complex shapes in a single molding step. In such applications, it is necessary to first fabricate components containing fiber-reinforced composites, and then integrate them with other components. In this case, resins with different properties are sometimes combined as needed.

[0003] As a method of integrating fiber-reinforced composite materials with other components, two main methods are used: mechanical bonding methods using bolts, rivets, and screws, and bonding methods using adhesives. Mechanical bonding methods require pre-processing steps such as drilling holes in the bonding area, thus increasing manufacturing time and costs, and also leading to a reduction in material strength due to drilling. Adhesive bonding methods require bonding and curing steps, including adhesive preparation and application, thus also increasing manufacturing time, and there are reliability issues regarding insufficient bond strength.

[0004] In addition to the methods mentioned above, fiber-reinforced composites using thermoplastic resins as the matrix resin can also be bonded together by hot-melt bonding, which has the potential to shorten the bonding time between components.

[0005] Here, Patent Document 1 discloses that a pre-impregnated sheet material comprising multiple resin fields of different thermoplastic resins is formed from a reinforcing fiber sheet layer aligned in a predetermined direction. Patent Document 2 discloses that a fiber-reinforced resin sheet is impregnated with multiple different thermoplastic resins on a nonwoven fabric composed of reinforcing fibers. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2012-246442 [Patent Document 2] International Publication No. 2014 / 103658 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] However, in recent years, the increasing complexity of shapes required for products using thermoplastic resins in fiber-reinforced composites with a matrix resin has necessitated the integration of various components to meet specific performance requirements. During the manufacture of such molded articles, the thermoplastic resin flows during welding, resulting in insufficient dimensional stability of the welded components. Consequently, adequate bond strength cannot be achieved under conditions that suppress this flow. Therefore, the object of this invention is to provide a prepreg and fiber-reinforced resin molded article that exhibits excellent bond strength with other components, while also providing appropriate control over resin flow during welding and excellent dimensional stability during welding. [Methods used to solve problems]

[0009] This invention relates to a prepreg having a thermoplastic resin layer comprising reinforcing fibers and thermoplastic resin, wherein the thermoplastic resin layer is present on at least one surface of the prepreg, and the aforementioned thermoplastic resin layer comprises 65.0 to 99.5% by mass of thermoplastic resin constituent units and 0.5 to 35.0% by mass of thermoplastic resin constituent units and curing agent constituent units, respectively, relative to 100% by mass of the total amount of thermoplastic resin constituent units, thermosetting resin constituent units and curing agent constituent units. [Effects of the Invention]

[0010] By using a fiber-reinforced resin molded body formed from a preform containing the prepreg of the present invention, it becomes possible to manufacture a one-piece molded article that has excellent adhesive strength and excellent dimensional stability during welding. Simple Explanation of the Diagram

[0011] Figure 1 is a schematic diagram of the composite prepreg described later, illustrating the method for determining the average roughness length RSm and average height Rc of the composite prepreg. Figure 2 is a schematic diagram of a cross-section of the composite prepreg perpendicular to a plane, which will be described later. It serves as an explanation of the method for determining the average roughness length RSm and average roughness height Rc of the composite prepreg. Implementation

[0012] [The form in which the invention is carried out]

[0013] The following description pertains to the prepreg of the present invention. In the following description, "~" is used to indicate a range encompassing both ends of the value. Furthermore, the term "~" sometimes refers to the resin composition occupying the area outside the reinforcing fibers in the prepreg (i.e., a composition comprising thermoplastic resin constituent units, thermosetting resin constituent units, and curing agent constituent units), or is collectively referred to as the resin composition occupying the area outside the reinforcing fibers in the fiber-reinforced resin molded article and described as the matrix resin. Also, when simply referred to as "thermoplastic resin layer," it means a thermoplastic resin layer comprising reinforcing fibers, thermoplastic resin, reaction product [A] and reaction product [B] described later (in the case of the composite prepreg described later, this is the first thermoplastic resin layer).

[0014] The prepreg of the present invention comprises reinforcing fibers and thermoplastic resin, and, relative to 100% by mass of the total constituent units of thermoplastic resin, thermosetting resin, and curing agent, contains 65.0 to 99.5% by mass of thermoplastic resin constituent units, and a thermoplastic resin layer containing a total of 0.5 to 35.0% by mass of thermosetting resin constituent units and curing agent constituent units exists on at least one surface of the prepreg. In this case, either the thermosetting resin constituent units or the curing agent constituent units may be 0 by mass.

[0015] Here, "constituent units of thermoplastic resin," "constituent units of thermosetting resin," and "constituent units of hardener" in the thermoplastic resin layer refer to the portions corresponding to the chemical structures of the thermoplastic resin, thermosetting resin, and hardener, respectively. That is, when the content is expressed as "mass % of constituent units," even if a portion of the components undergoes a reaction to generate reaction products from a simple mixture, the mass % of the constituent units remains unchanged as long as the total mass is preserved. The mass % of the constituent units of the thermoplastic resin, thermosetting resin, and hardener can be determined using well-known analytical methods such as solution or solid-state NMR, mass analysis, or combinations thereof.

[0016] By adopting this structure, compared to when the base resin is a simple thermoplastic resin, it is possible to obtain a one-piece molded product with appropriate thickening of the base resin and excellent adhesive strength, proper control of resin flow during welding, and excellent dimensional stability during welding.

[0017] If the constituent units of the thermoplastic resin are less than 65.0% by mass, or the constituent units of the thermosetting resin and the hardener become more than 35.0% by mass, the resulting integrally molded article will have insufficient adhesive strength. Furthermore, if the constituent units of the thermosetting resin and the hardener are less than 0.5% by mass, or the constituent units of the thermoplastic resin become more than 99.5% by mass, excessive resin flow will occur, resulting in insufficient dimensional stability during welding.

[0018] The prepreg of the present invention is a prepreg having a thermoplastic resin layer comprising reinforcing fibers and thermoplastic resin as described above, and has the following first to third preferred embodiments.

[0019] In the first preferred embodiment, the thermoplastic resin layer comprises the constituent units of the thermosetting resin and / or the constituent units of the curing agent in the form of a reaction product [A] of a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions. Hereinafter, "reaction product [A] of a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions" will sometimes be referred to simply as "reaction product [A]".

[0020] Here, "in the form of reaction product [A], the thermoplastic resin layer comprises the constituent units of thermosetting resin and / or the constituent units of a hardener" means that the thermoplastic resin layer comprises the reaction product [A] and the thermoplastic resin, which are made from a thermosetting resin monomer or prepolymer with two or more functions and a hardener with two or more functions. Here, "monomer" refers to the smallest unit constituting the prepolymer and polymer, becoming the constituent unit of the thermoplastic resin, thermosetting resin, and hardener. Furthermore, "prepolymer" refers to the intermediate product in which the polymerization or condensation reaction of the monomer is stopped at an appropriate point.

[0021] By adopting this configuration, not only can one-piece molded articles with excellent dimensional stability during welding be obtained, as mentioned above, but also the thermoplastic resin can be modified by the reaction product [A] of thermosetting resin monomers or prepolymers and hardeners as raw materials. Depending on the type of thermosetting resin monomers or prepolymers and hardeners, additional effects such as improved heat resistance and solvent resistance, and reduced water absorption can be obtained. At this time, the thermoplastic resin can be simply mixed with the reaction product [A], or a portion of the thermoplastic resin can react with a portion of the reaction product [A].

[0022] In the second preferred embodiment, the thermoplastic resin layer comprises the constituent units of the thermoplastic resin and / or the constituent units of the curing agent in the form of a reaction product [B] formed by the reaction of a thermoplastic resin with a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions. Hereinafter, "the reaction product [B] formed by the reaction of a thermoplastic resin with a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions" will sometimes be referred to simply as "reaction product [B]".

[0023] Here, "in the form of reaction product [B], the thermoplastic resin layer contains the constituent units of thermosetting resin and / or the constituent units of curing agent" means that the thermoplastic resin layer contains the reaction product [B] which is a thermoplastic resin with a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions as raw materials.

[0024] By adopting this structure, not only can one obtain a one-piece molded article with excellent dimensional stability during welding, as mentioned above, but also additional effects such as improved heat resistance and solvent resistance, and reduced water absorption can be obtained by modifying the thermoplastic resin with thermosetting resin monomers or prepolymers and / or hardeners, depending on the type of thermosetting resin monomers or prepolymers and / or hardeners.

[0025] In the third preferred embodiment, the thermoplastic resin layer comprises the constituent units of the thermoplastic resin and / or the constituent units of the aforementioned curing agent in the form of a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions.

[0026] Here, "the thermoplastic resin layer comprising thermoplastic resin constituent units and / or curing agent constituent units in the form of thermoplastic resin monomers or prepolymers with two or more functions and / or curing agents with two or more functions" means that the thermoplastic resin layer comprises a mixture of thermoplastic resin and thermoplastic resin monomers or prepolymers with two or more functions and / or curing agents with two or more functions. In this case, the thermoplastic resin monomers or prepolymers with two or more functions and / or curing agents with two or more functions can be dispersed in the thermoplastic resin or can be miscible with the thermoplastic resin, but from the perspective of the uniformity of the matrix resin thickening described later, miscibility is preferred.

[0027] By employing this configuration, during the molding of the fiber-reinforced resin molded body and / or during the welding with other components as described later, a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions reacts with a thermoplastic resin, a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions, or multiple reactions thereof. This allows for the production of an integrally molded article that achieves appropriate thickening of the base resin and excellent adhesive strength, while also ensuring proper control of resin flow during welding and excellent dimensional stability during welding. The following is a detailed description of each ingredient.

[0028] <Reinforced Fibers> The reinforcing fibers used in this invention include: glass fiber, carbon fiber, metal fiber, aromatic polyamide fiber, polyarylamide fiber, alumina fiber, silicon carbide fiber, boron fiber, basalt fiber, etc. These can be used alone or in combination of two or more. Carbon fiber is ideally chosen as the reinforcing fiber due to its low specific gravity, high strength, and high modulus of elasticity. Commercially available carbon fiber products include: Torayca T800G-24K, Torayca T800S-24K, Torayca T700G-24K, Torayca T700S-24K, Torayca T300-3K, and Torayca T1100G-24K (all manufactured by Toray Corporation).

[0029] Reinforcing fibers can also be those that have undergone surface treatment. Surface treatments include: metal adhesion treatment, treatment using coupling agents, treatment using sizing agents, and additive adhesion treatment. Furthermore, in this specification, the case of reinforcing fibers with an attached surface treatment agent is defined as reinforcing fibers containing a surface treatment agent.

[0030] Regarding the morphology and arrangement of reinforcing fibers, appropriate selection can be made from the arrangement of reinforcing fibers in one direction, the laminate of fibers arranged in one direction, or the morphology of the fabric. In order to obtain a laminate with a higher level of lightweight and durability, it is preferable to have a morphology of long fibers (fiber bundles) or continuous fibers such as fabric in which the reinforcing fibers are arranged in one direction in each prepreg.

[0031] The reinforcing fiber bundle can be composed of multiple fibers of the same shape or multiple fibers of different shapes. The number of reinforcing fibers constituting a reinforcing fiber bundle is usually 300 to 60,000, but considering the manufacturing of the substrate, it is preferably 300 to 48,000, and more preferably 1,000 to 24,000. It can also be a range defined by any combination of the upper and lower limits mentioned above.

[0032] Regarding the reinforcing fiber, if the tensile strength of the strand, as determined by the resin impregnation strand test method in JIS R7608 (2007), is 5.5 GPa or higher, it is preferable to obtain a laminate with excellent adhesive strength in addition to tensile strength. If the tensile strength of the strand is 5.8 GPa, it is even more preferable. The adhesive strength referred to here is the tensile shear adhesive strength determined according to ISO 4587:1995 (JIS K6850 (1994)).

[0033] The prepreg of this invention preferably has a reinforcing fiber content of 30 g / m² or more per unit area. If the reinforcing fiber content is 30 g / m² or more, the operation becomes easier in obtaining fiber-reinforced resin molded articles and integrally molded articles. There is no particular upper limit to the reinforcing fiber content, but as long as it is 2,000 g / m² or less, the matrix resin can be easily impregnated into the reinforcing fibers, and the lightweight nature of the prepreg can be maintained.

[0034] <Thermoplastic Resins> The type of thermoplastic resin used in this invention is not particularly limited, but for example, thermoplastic resins having bonds selected from the group consisting of carbon-carbon bonds, amide bonds, amide bonds, ester bonds, ether bonds, carbonate bonds, carbamate bonds, thioether bonds, ion bonds, and carbonyl bonds in their main chain can be used. The thermoplastic resin can be crystalline or amorphous. Furthermore, the thermoplastic resin can also be a copolymer or modified product of the above-mentioned resins, and / or a blend of two or more resins.

[0035] From the perspective of balancing processability, heat resistance, and mechanical properties, at least one thermoplastic resin selected from the group consisting of polyamide, polyurethane, polyetherurethane, polyetherimide, polyaryl sulfide, polyetherketone ketone, and polyaryl etherketone is preferred.

[0036] In this specification, the "melting point or glass transition temperature" of thermoplastic resins refers to the melting point in the case of thermoplastic resins with a melting point (typically crystalline thermoplastic resins), and to the glass transition temperature in the case of thermoplastic resins without a melting point (typically amorphous thermoplastic resins). Furthermore, this includes not only melting caused by heating a thermoplastic resin with a melting point above that melting point, but also softening caused by heating a thermoplastic resin without a melting point above its glass transition point, which may sometimes be expressed as "melting". Moreover, the melting point and glass transition temperature of the thermoplastic resins referred to herein can be determined using a differential scanning calorimeter (DSC) based on JIS K7121 (2012). 1–10 mg of sample was loaded into a 50 μL sealed sample container, and the temperature was increased at a rate of 10 °C / min. The difference between the high and low points of the DSC curve detected in the range of 30–400 °C was used as the glass transition temperature, and the endothermic peak was used as the melting point. Each temperature was designated as the glass transition temperature and melting point. When multiple melting points or glass transition temperatures were observed for mixtures, the highest melting point was designated as the melting point of the thermoplastic resin.

[0037] <Thermosetting resin monomers or prepolymers with two or more functionalities> The thermosetting resin monomers or prepolymers with two or more functionalities used in this invention are low molecular weight thermosetting resins (uncured) having two or more functional groups that react with the functional groups and / or chemical bonds of thermoplastic resins and / or curing agents. The phrase "react with functional groups and / or chemical bonds" here refers to any reaction with other functional groups and chemical bonds to form new covalent bonds. Examples of such combinations of functional groups include: epoxy group and amino group, epoxy group and carboxyl group, carboxyl group and amino group, amide bond and amino group, etc. The thermosetting resin monomers or prepolymers with two or more functionalities can also be compounds that react with the same monomers or prepolymers.

[0038] Furthermore, the term "low molecular weight compound" as used herein refers to compounds with a molecular weight calculated from their structural formula or a weight-average molecular weight determined by gel permeation chromatography of less than 10,000 g / mol. The preferred range for the aforementioned molecular weight or weight-average molecular weight is 8,000 g / mol or less, more preferably 5,000 g / mol or less, further preferably 3,000 g / mol or less, and most preferably 2,000 g / mol or less. The weight-average molecular weight referred to herein is the weight-average molecular weight converted to polystyrene as determined by gel permeation chromatography. If the aforementioned molecular weight or weight-average molecular weight is 10,000 g / mol or more, the reactions of the aforementioned functional groups become difficult to occur.

[0039] The thermosetting resin monomers or prepolymers with two or more functions used in this invention are not particularly limited as long as they react with heat to at least partially form a three-dimensional cross-linked structure. Examples of such thermosetting resins include epoxy resins, benzo[a]pyrene resins, bismaleimide resins, unsaturated polyester resins, vinyl ester resins, phenol resins, urea resins, melamine resins, and thermosetting polyimide resins. Modified versions of these resins and resins blended with two or more of these resins can also be used. Furthermore, these thermosetting resins can be self-curing upon heating, or they can be blended with curing agents and curing accelerators.

[0040] The epoxy resin used in this invention is not particularly limited, but examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol S type epoxy resin, and other bisphenol-type epoxy resins; brominated epoxy resins such as tetrabromobisphenol A diglycidyl ether; epoxy resins having a biphenyl backbone; epoxy resins having a naphthalene backbone; epoxy resins having a dicyclopentadiene backbone; phenolic varnish-type epoxy resins such as phenolic varnish-type epoxy resins and cresolic varnish-type epoxy resins; N,N,O-triepoxypropyl-m-aminophenol; N,N, O-Tricyclooxypropyl-p-aminophenol, N,N,O-Tricyclooxypropyl-4-amino-3-methylphenol, N,N,N',N'-Tetracyclooxypropyl-4,4'-methylenediphenylamine, N,N,N',N'-Tetracyclooxypropyl-2,2'-diethyl-4,4'-methylenediphenylamine, N,N,N',N'-Tetracyclooxypropyl-m-xylenediamine, N,N-dicyclooxypropylaniline, N,N-dicyclooxypropyl-o-toluidine and other epoxy propylene amine type epoxy resins, resorcinol dicyclooxypropyl ether, tricyclooxypropyl isocyanate, etc.

[0041] The curing agents with two or more functions used in this invention are not particularly limited as long as they react with heat to form covalent bonds. Examples of such curing agents include amine compounds, acid anhydrides, polyamides, organic acids such as amide hydrazides and isocyanates, which are used as curing agents for epoxy resins. Examples also include epoxy resins used as curing agents for benzo[a]ethylene]ethylene resins and phenolic compounds used as curing agents for bismaleimide resins.

[0042] Furthermore, it is preferable that the aforementioned thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities contain at least two compounds. In this case, in addition to the reaction between the thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities and the thermoplastic resin, the combination of covalent bonds formed by the aforementioned compounds through reaction is preferable because it efficiently thickens the matrix resin during welding. Examples of such combinations of thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities include epoxy resin and epoxy resin curing agents.

[0043] From the perspective of ease of reaction control, amine compounds are preferred among the aforementioned epoxy resin curing agents. Furthermore, from the perspective of heat resistance and mechanical properties, aromatic amine compounds are preferred, especially those with 1 to 4 phenyl groups within the molecule. From the perspective of heat resistance, aromatic polyamine compounds with two or more phenyl groups, specifically those with an amino group at the para-position, are ideally preferred, and those with a sulfur atom within the molecule are even more desirable. Specific examples of such aromatic polyamines include: m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylamine, tris(3-aminophenyl)phosphine oxide, m-xylenediamine, (p-phenylenemethyl)diphenylamine, and various derivatives of these compounds with alkyl substitutions and isomers with different amino group positions. Among these, the use of 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone is preferred, as they can yield reaction products with excellent heat resistance and elastic modulus in applications such as aviation and spacecraft, and even with minimal reduction in heat resistance due to linear expansion coefficient and moisture absorption. These aromatic amine compounds can be used alone or in combination of two or more.

[0044] The proportions of each component relative to the total amount of thermosetting resin monomers or prepolymers with two or more functions and hardeners with two or more functions (100% by mass) need to be adjusted appropriately depending on the type of compound used. However, it is better to set the aforementioned thermosetting resin monomers or prepolymers to a range of 60.0 to 99.5% by mass and the aforementioned hardeners to a range of 0.5 to 40.0% by mass, as this will appropriately increase the viscosity of the matrix resin during welding.

[0045] Furthermore, from the viewpoint of the uniformity of the matrix resin, it is preferable that at least a portion (more preferably all) of the aforementioned thermosetting resin monomer or prepolymer and the aforementioned curing agent are compatible with the thermoplastic resin.

[0046] The thermoplastic resin layer may also include: a reaction product generated by reacting a portion of the thermoplastic resin with a portion of a thermosetting resin monomer or prepolymer with two or more functions and a portion of a curing agent with two or more functions when impregnating the matrix resin with the reinforcing fiber.

[0047] <Reaction products of thermosetting resin monomers or prepolymers with two or more functionalities and curing agents with two or more functionalities [A]> The reaction product [A] used in this invention is a reaction product of the aforementioned thermosetting resin monomer or prepolymer with two or more functions and the aforementioned curing agent with two or more functions, and it is a compound in which the functional groups of the thermosetting resin monomer or prepolymer and the functional groups of the curing agent have reacted. Here, "functional groups have reacted" means the formation of new covalent bonds. Examples of such combinations of functional groups include: epoxy groups and amino groups, phenolic hydroxyl groups and epoxy groups generated by ring opening of the benzo[a] ring, maleic anhydride groups and amino groups, etc.

[0048] The reaction product [A] can be used alone or in combination with two or more reaction products. In the case of a thermosetting resin with one functional group per molecule, the glass transition temperature of the reaction product with the curing agent decreases, which may have an adverse effect on the heat resistance of the base resin. There are no particular limitations on the thermosetting resin monomers or prepolymers with two or more functional groups and the curing agents with two or more functional groups used as raw materials for the reaction product [A], but examples can be given as compounds exemplified in the description of the thermosetting resin monomers or prepolymers with two or more functional groups and the curing agents with two or more functional groups mentioned above.

[0049] The presence of reaction product [A] in the prepreg was confirmed using gel permeation chromatography (GPC) with hexafluoroisopropanol as the solvent. The sample was prepared by extracting the resin composition from a specified amount of prepreg using hexafluoroisopropanol. The chromatograms of the mixture of raw materials before mixing and the extract were compared, and the peak area originating from the reaction product was assessed to determine if there was an increase. When the thermoplastic resin is not dissolved in hexafluoroisopropanol, other appropriate solvents can be used for determination. When no solvent for dissolving the thermoplastic resin is available, a specified amount of matrix resin taken from the prepreg can be used as the sample, combined with known analytical methods such as solid-state NMR.

[0050] From the viewpoint of uniformity of the matrix resin and efficient thickening of the matrix resin, it is preferable that the reaction product [A] is miscible with the thermoplastic resin. A reaction can occur between the reaction product [A] and the thermoplastic resin, meaning that the thermoplastic resin layer can further contain the aforementioned reaction product of the thermoplastic resin and the reaction product [A]. From the viewpoint of uniformity of the matrix resin, it is preferable that the reaction product of the thermoplastic resin and the reaction product [A] is miscible with the thermoplastic resin.

[0051] The miscibility of thermoplastic resins with each reaction product was determined by staining thin sections of the prepared prepreg and obtaining transmission electron images at an appropriate magnification using a transmission electron microscope (Hitachi, H-7100) at an accelerating voltage of 100 kV to confirm the presence or absence of phase-separated structures. In this study, those without confirmed phase-separated structures were considered "miscible," while those with confirmed phase-separated structures were considered "phase-separated." OsO4 and RuO4 staining agents were used, depending on the resin composition, to provide sufficient contrast in morphology. Furthermore, when the structural period is greater than or equal to 1 nm but less than 10 nm, the appropriate multiplier is 50,000 times; when the structural period is greater than or equal to 10 nm but less than 100 nm, the appropriate multiplier is 20,000 times; when the structural period is greater than or equal to 100 nm but less than 1,000 nm, the appropriate multiplier is 2,000 times; and when the structural period is greater than or equal to 1,000 nm, the appropriate multiplier is 1,000 times.

[0052] In the thermoplastic resin layer, it is preferable that the reaction product [A] forms a semi-IPN structure or an IPN structure with the thermoplastic resin. Here, IPN is short for Interpenetrating Polymer Network, which is a type of polymer blend. The polymer component of the blend is a cross-linked polymer, and it refers to a structure in which different types of cross-linked polymers partially or entirely intertwine to form a multi-mesh structure. A semi-IPN is a structure with a multi-mesh structure formed by cross-linked polymers and linear polymers. By using a thermoplastic resin matrix resin that has undergone semi-IPN modification in the reaction product [A], excellent heat resistance and impact resistance can be imparted to the fiber-reinforced resin molded body.

[0053] From the viewpoint of effectively imparting the aforementioned additional effects by moderately thickening the thermoplastic resin in the thermoplastic resin layer, the reaction product [A] preferably contains 60.0 to 99.5% by mass of thermoplastic resin constituent units and 0.5 to 40.0% by mass of hardener constituent units relative to 100% by mass of the total amount of thermoplastic resin constituent units and hardener constituent units. Here, "thermoplastic resin constituent units" and "hardener constituent units" refer to the portions of the chemical structure of the thermoplastic resin monomer or prepolymer and hardener, respectively, that are the raw materials of the reaction product [A].

[0054] <Reaction products of thermoplastic resin reacting with thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities [B]> The reaction product [B] used in this invention is a reaction product of thermosetting resin monomers or prepolymers with two or more functions and / or curing agents with two or more functions with thermoplastic resins, and it is a compound in which the functional groups of the thermosetting resin and / or the functional groups of the curing agent have reacted with the functional groups of the thermoplastic resin.

[0055] The term "functional group reaction" as used here refers to the reaction of functional groups with other functional groups and chemical bonds to form new covalent bonds. Examples of such functional group combinations include: epoxy group and amino group, epoxy group and carboxyl group, carboxyl group and amino group, amide bond and amino group, etc.

[0056] The reaction product [B] can be used alone or in combination with two or more reaction products. In the case of a thermosetting resin with one functional group per molecule, the thickening effect of the reaction product [B] may be insufficient compared to the thermoplastic resin from which the reaction product [B] originates. The thermosetting resin monomers or prepolymers with two or more functional groups used in this invention are not particularly limited, but examples include epoxy resins, benzo[a]pyrene resins, and bismaleimide resins, etc., which are listed above.

[0057] In the case of a curing agent with only one functional group per molecule, the thickening effect of the reaction product [B] becomes insufficient compared to the thermoplastic resin from which the reaction product [B] originates. The curing agents with two or more functional groups used in this invention are not particularly limited, but examples include: amine compounds with two or more functional groups, epoxy resins used as curing agents for benzo[a]ethylene resins, and phenolic compounds used as curing agents for bismaleimide resins.

[0058] The presence of reaction product [B] in the prepreg can be confirmed using the same method as that used to confirm the presence of reaction product [A] in the prepreg. Gel permeation chromatography (GPC) using hexafluoroisopropanol as the solvent is employed. The sample is prepared by comparing the chromatograms of the mixture of raw materials before mixing with those of the extract. The peak area originating from the reaction product is assessed to determine if it has increased. If reaction product [B] is not dissolved in hexafluoroisopropanol, other solvents can be used for determination. If a solvent for dissolving reaction product [B] is unavailable, a sample prepared from a specified amount of matrix resin taken from the prepreg can be used, combined with known analytical methods such as solid-state NMR.

[0059] In a certain state of the prepreg of the present invention, the aforementioned reaction product [B] is soluble in the solvent. Here, "reaction product [B] is soluble in the solvent" means that a homogeneous solution can be obtained by mixing the reaction product [B] with the solvent. "Hybrid solution" means that a state in which no separation is visually apparent can be obtained. Specifically, "soluble" is defined as the situation in which 0.5% by mass of the reaction product [B] is added to at least one solvent and stirred at 30°C to obtain a solution in which no separation is visually apparent, and other situations are defined as "insoluble".

[0060] Furthermore, in other forms of the preimpregnated material of the present invention, the aforementioned reaction product [B] has a cross-linked structure. Here, "having a cross-linked structure" means that the molecular chains of the reaction product [B] adopt a mesh-like three-dimensional structure. The presence of the cross-linked structure can be confirmed by various analyses. Specifically, examples include: FT-IR, solid-state NMR, X-ray photoelectron spectroscopy, etc.

[0061] The thermoplastic resin layer in the prepreg of the present invention may also contain reaction product [A] while containing reaction product [B]. This allows reaction product [B] to efficiently increase viscosity. The reaction product [A] can be used alone or in combination with two or more reaction products.

[0062] From the perspective of uniformity of the matrix resin and efficient thickening of the matrix resin, it is preferable that reaction product [A] and reaction product [B] are miscible. The determination of the miscibility of reaction product [A] and reaction product [B] can be carried out using the same method as the determination of the miscibility of reaction product [A] and thermoplastic resin mentioned above.

[0063] From the viewpoint of effectively imparting the aforementioned additional effects by moderately thickening the thermoplastic resin in the thermoplastic resin layer, the reaction product [B] preferably contains 60.0 to 99.5% by mass of thermoplastic resin constituent units and 0.5 to 40.0% by mass of hardener constituent units relative to 100% by mass of the total constituent units of the thermoplastic resin and the hardener. Here, "constituent units of thermoplastic resin" and "constituent units of hardener" refer to the portions of the chemical structure of the thermoplastic resin and hardener, respectively, that are the raw materials of the reaction product [B].

[0064] The area weight of the thermoplastic resin layer in the prepreg of the present invention is preferably 10 g / m² or more. If the area weight of the thermoplastic resin layer is 10 g / m² or more, it is preferable to obtain a sufficient thickness for exhibiting excellent adhesive strength and a sufficient layer thickness for integration with other components. More preferably, it is 20 g / m² or more, and even more preferably, it is 50 g / m² or more. The upper limit is not particularly limited, but in order to obtain a fiber-reinforced resin substrate with excellent specific strength and specific modulus of elasticity without the amount of thermoplastic resin becoming excessive relative to the reinforcing fibers, it is preferably 1000 g / m² or less. Here, area weight refers to the mass (g) of thermoplastic resin contained in 1 m² of fiber-reinforced resin substrate.

[0065] <Composite Prepreg> The prepreg of the present invention, in addition to having the aforementioned thermoplastic resin layer (hereinafter referred to as the "first thermoplastic resin layer" in the description of this embodiment), may also have: a thermoplastic resin layer (hereinafter referred to as the "second thermoplastic resin layer" in the description of this embodiment) that forms an interface with and is bonded to the thermoplastic resin layer, comprising at least one thermoplastic resin having constituent units of a thermoplastic resin different from the thermoplastic resin contained in the first thermoplastic resin layer. Furthermore, in addition to having the first thermoplastic resin layer, it may also have: a thermosetting resin layer that forms an interface with and is bonded to the thermoplastic resin layer, comprising at least one thermosetting resin. Such embodiments are collectively referred to as "composite prepregs".

[0066] Especially in the prepreg of the present invention, it is preferable that the second thermoplastic resin layer or thermosetting resin layer and the first thermoplastic resin layer are respectively formed in layers and adjacent to each other. For example, as shown in FIG2, forming layers and being adjacent to each other means that in a cross-section obtained by cutting perpendicularly to the plane direction of the prepreg, the thermoplastic resin layer 3 and the thermosetting resin layer 4, which are continuous in the facing direction, exist in close contact while forming the interface 5. When the thermoplastic resin is not in a layered and continuous state, but exists in the form of particles, fibers, non-woven fabric, etc., the proportion of epoxy resin exposed on the surface increases, and the coverage of the thermoplastic resin on the outermost surface decreases, thus tending to reduce weldability.

[0067] In this invention, the thermoplastic resin contained in the second thermoplastic resin layer has thermoplastic resin constituent units that are different from those of the thermoplastic resin (or thermoplastic resin constituent units) contained in the first thermoplastic resin layer. The difference in resin types is determined by the similarity of the structure that gives characteristics to the thermoplastic resin. For example, polyamide resin is a resin having repeating units containing amide bonds, and polycarbonate resin is a resin having repeating units containing carbonate bonds; these are considered different because they are resins with repeating units having different bonds.

[0068] These composite prepregs preferably have a first thermoplastic resin layer on at least one surface, the first thermoplastic resin layer comprising continuous reinforcing fibers, and in a cross-section perpendicular to the surface direction, the reinforcing fibers are distributed in an area of ​​more than 80% of the thickness of each of the first thermoplastic resin layer and the second thermoplastic resin layer or the thermosetting resin layer.

[0069] The composite prepreg of the present invention allows for observation of the resin layer at the interface in a cross-section obtained by cutting perpendicularly to the plane of the fiber-reinforced resin substrate, and simultaneous evaluation of the adhesion force in the fiber axis direction and the direction perpendicular to it. Specifically, it is sufficient to observe, from a top view of the composite prepreg, a cross-section perpendicular to the plane of the fiber-reinforced resin substrate containing the aforementioned continuous reinforcing fibers, at an angle differing from the fiber direction of any continuous reinforcing fibers contained in the first thermoplastic resin layer by 45 degrees, is sufficient.

[0070] The composite prepreg of this invention preferably has a roughness average length RSm of 100 μm or less and a roughness average height Rc of 3.5 μm or more, as defined by JIS B0601 (2001) for the cross-sectional profile formed at the interface of the aforementioned two resin layers. If RSm is 100 μm or less, not only the chemical and / or physical bonding strength is increased, but also the mechanical bonding strength of interpenetration is increased, making it difficult to peel the aforementioned two resin layers apart. The lower limit of RSm is not particularly limited, but from the viewpoint of avoiding the reduction of mechanical bonding strength due to stress concentration, it is preferable to be 15 μm or more. Furthermore, with an Rc of 3.5 μm or more for the cross-sectional profile, not only is the mechanical bonding strength due to interpenetration evident, but the continuous reinforcing fibers existing at the interface also enhance the adhesion between the aforementioned two resin layers through chemical and / or physical bonding. A preferred range for Rc is 10 μm or more, where the continuous reinforcing fibers become easier to incorporate into the two resin layers and the adhesion is further improved; more preferably, it is 20 μm or more. The upper limit of Rc is not particularly limited, but from the viewpoint of avoiding a decrease in mechanical bonding strength due to stress concentration, it is preferably 100 μm or less.

[0071] Here, known methods can be used to determine the average roughness height Rc and average roughness length RSm of the profile curve. Examples include methods using cross-sectional images obtained from X-ray CT, methods using elemental analysis mapping images obtained by energy dispersive X-ray spectroscopy (EDS), and methods using cross-sectional observation images obtained by optical microscopy, scanning electron microscopy (SEM), or transmission electron microscopy (TEM). During observation, the two resin layers may also be stained to adjust contrast. In the images obtained using any of the above methods, the average roughness height Rc and average roughness length RSm of the profile curve are measured within a 500 μm × 500 μm range. The calculation of Rc and RSm from the cross-sectional observation image can be performed using the methods described in the examples below.

[0072] One method to optimize the average roughness height Rc and average roughness length RSm of the profile curve is to extend the pressing time by increasing the pressure rollers or similar components during the impregnation of thermoplastic resin with continuous reinforcing fibers. Other methods include increasing the pressure applied, setting the surface temperature of the heating and pressing components such as rollers to a high level, and reducing the viscosity of the thermoplastic resin.

[0073] <Pre-form> The prepreg of the present invention can be used alone or laminated with metal components, prepregs using thermosetting resins in the matrix resin, prepregs using thermoplastic resins in the matrix resin, etc., to form a preform.

[0074] <Fiber-reinforced resin molded parts> The fiber-reinforced resin molded body of the present invention can be manufactured by molding the aforementioned pre-molded body containing the prepreg of the present invention. Typically, it can be manufactured by stacking multiple layers of the prepreg and then heating and pressurizing it. As a method of heating and pressurizing, for example, pressure molding, autoclave molding, bagging molding, wrapping tape molding, internal pressure molding, etc.

[0075] More specific methods for forming the fiber-reinforced resin molded articles of the present invention include: methods of forming the aforementioned prepreg or composite prepreg of the present invention, either alone or together with other prepregs, by means of pressure molding, autoclave molding, bagging molding, cable ties, internal pressure molding, etc.; and methods of forming the composite prepreg of the present invention with other fiber-reinforced resin substrates or fiber substrates by means of hand-accumulation, filament winding, pultrusion, resin injection molding, resin transfer molding, etc.

[0076] <One-piece molded product> The fiber-reinforced resin molded body of the present invention can be thermally welded to other components (adhesive materials) through the aforementioned thermoplastic resin layer, thereby producing a monolithic article with good productivity. As an adhesive material, there are no particular limitations on any component that can be thermally welded to the aforementioned thermoplastic resin layer, including: components containing thermoplastic resin, metal components with thermoplastic resin disposed on their surfaces, and micro-processed components with thermoplastic resin embedded in their surfaces. Furthermore, the adhesive material can also be the fiber-reinforced resin molded body of the present invention. That is, the thermoplastic resin layers of the fiber-reinforced resin molded body of the present invention can also be bonded together to form a monolithic article. There are no particular limitations on the means of thermally welding the fiber-reinforced resin molded body and the adhesive material, including, for example: vibration welding, ultrasonic welding, laser welding, resistance welding, induction welding, insertion injection molding, and external insertion injection molding.

[0077] The strength of the bonded portion in a monolithic body can be evaluated based on ISO 4587:1995 (JIS K6850 (1994)) and ASTM D7291-07. The tensile shear bond strength measured according to ISO 4587:1995 is preferably 20 MPa or higher at a test ambient temperature of 23°C, more preferably 25 MPa or higher, and even more preferably 28 MPa or higher. [Example]

[0078] The present invention will be described in detail below by way of examples. However, the scope of the present invention is not limited to these examples. Furthermore, unless otherwise specified, all measurements of various properties are performed at an environment of 23°C and 50% relative humidity.

[0079] <Materials used in the examples and comparative examples> The materials used in each embodiment and comparative example are shown in Tables 1 to 11.

[0080] <Reinforced Fibers> • T800S: "Torayca (registered trademark)" T800SC-24000 (carbon fiber with 24,000 fibers, tensile strength 5.9 GPa, tensile modulus 294 GPa, elongation 2.0%, manufactured by Toray). • T700S: "Torayca (registered trademark)" Cloth CK6273C ("Torayca (registered trademark)" T700SC-12000 (carbon fiber with 12,000 fibers, tensile strength 4.9GPa, tensile elastic modulus 230GPa, tensile elongation 2.1%, plain weave, unit area weight 192g / m2, made of Toray (ply)).

[0081] • Continuous, grade E glass fiber with a total of 1,600 monofilaments after bundling treatment. Its characteristics are as follows.

[0082] Single fiber diameter: 13μm Tensile strength: 3400MPa Tensile modulus: 72 GPa Elongation: 3% Density: 2.6 g / cm³.

[0083] <Thermoplastic Resins> • "Amilan (registered trademark)" CM4000 (3-component copolymer polyamide resin, melting point 155°C, manufactured by Toray Co., Ltd.) • "Amilan (registered trademark)" CM1007 (Polyamide 6, melting point 225°C, manufactured by Toray) • Films containing reaction products of thermoplastic resins and thermosetting resin monomers or prepolymers with two or more functionalities, produced using the following methods The thermoplastic resin "Amilan (registered trademark)" CM1007 and the thermosetting resin monomer or prepolymer "jER (registered trademark)" 828 with more than two functions are mixed at a mass ratio of 90:10, and then melt-mixed at 260°C for 30 minutes before film formation.

[0084] • "SUMIKAEXCEL (registered trademark)" PES5003P (polyether ether, weight average molecular weight 47,000 g / mol, glass transfer temperature 225°C, manufactured by Sumitomo Chemical Co., Ltd.) • "Torelina (registered trademark)" A670T05 (polyphenylene sulfide, melting point 278°C, glass transition temperature 90°C, manufactured by Toray (stock) Co., Ltd.) • "KEPSTAN (registered trademark)" 7002 (polyetherketoneketone, melting point 331°C, glass transition temperature 162°C, manufactured by Arkema).

[0085] <Thermoplastic resin used in the second thermoplastic resin layer> • "KEPSTAN (registered trademark)" 7002 (polyetherketoneketone, melting point 331°C, glass transition temperature 162°C, manufactured by Arkema).

[0086] <Thermosetting resin monomers or prepolymers with two or more functionalities> • "jER (registered trademark)" 828 (Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.: epoxy equivalent 184~194g / eq, weight average molecular weight approximately 370g / mol) • "SUMI-EPOXY (registered trademark)" ELM434 (Tetraepoxypropyldiaminodiphenylmethane, manufactured by Sumitomo Chemical Co., Ltd.: epoxy equivalent 120g / eq, molecular weight 423g / mol) •Fa (Bisphenol F-aniline type benzo[a] resin, manufactured by Shikoku Chemical Industry Co., Ltd.: epoxy equivalent 184~194 g / eq, molecular weight 434.52 g / mol) • "Compimide (registered trademark)" MDAB (4,4'-bismaleimine-diphenylmethane, manufactured by Evonik Industries AG: molecular weight 358.35 g / mol) • "Compimide (registered trademark)" TDAB (2,4-bismaleimine-toluene, manufactured by Evonik Industries AG: molecular weight 282.25 g / mol).

[0087] SEIKACURE-S (4,4'-Diaminodiphenyl sulfone, manufactured by Wakayama Seika Kogyo Co., Ltd.: active hydrogen equivalent 62 g / eq, molecular weight 248 g / mol, used as a curing agent for epoxy resins) • (3-Aminophenyl)phosphine oxide (manufactured by Katayama Chemical Industry Co., Ltd.: active hydrogen equivalent 54 g / eq, molecular weight 323 g / mol, used as a curing agent for epoxy resins) ·DICY7 (Dicyandiamine, manufactured by Mitsubishi Chemical Co., Ltd., molecular weight 84 g / mol, used as a curing agent for epoxy resins) • "Araldite (registered trademark)" MY0610 (Tricyclooxypropyl-m-aminophenol type epoxy resin, manufactured by Huntsman Corporation: epoxy equivalent 114 g / eq, molecular weight 277.31 g / mol, used as a curing agent for benzo[a]pyrrolidone resin) • Compimide (registered trademark) TM124 (2,2'-bis(4-hydroxy-3-allylphenyl)propane, manufactured by Evonik Industries AG: molecular weight 308.41 g / mol, used as a curing agent for bismaleimide resins).

[0088] <Other materials used in thermosetting resin compositions> • "SUMIKAEXCEL (registered trademark)" PES5003P (polyether ether, manufactured by Sumitomo Chemical Co., Ltd.) • "Virantage (registered trademark)" VW10700RFP (polyether ether, manufactured by Solvay SA) • "Matrimid (registered trademark)" 9725 (polyimide, manufactured by Huntsman Advanced Materials) ·EPTS (Ethyl p-toluenesulfonate, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0089] <Reaction products of thermosetting resin monomers or prepolymers with two or more functionalities and curing agents with two or more functionalities [A]> • The reaction products (A-1 to A-7) prepared using the following method Using the proportions listed in Table 1, thermosetting resin monomers or prepolymers with two or more functionalities and curing agents with two or more functionalities were added to a mixing apparatus and heated and mixed at 180°C for 5 minutes to obtain reaction products A-1 to A-4, A-6, and A-7 of epoxy resins with two or more functionalities and amine compounds. Also, using the proportions listed in Table 1, "jER (registered trademark)" 828 and SEIKACURE-S were added to a mixing apparatus and heated and mixed at 50°C. The resulting mixture was heated in an oven at 180°C for 30 minutes to obtain reaction product A-5 of epoxy resins with two or more functionalities and amine compounds.

[0090] <Reaction products of thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities and thermoplastic resins [B]> • The reaction products (B-1~B-12) prepared using the following method Using the proportions shown in Table 5, "Amilan (registered trademark)" CM1007, thermosetting resin monomers or prepolymers with two or more functionalities, and / or curing agents with two or more functionalities were added to a mixing apparatus and heated and mixed at 260°C for 30 minutes to obtain reaction products B-1 to B-4 and B-11 of thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities and polyamide 6. Also, using the proportions shown in Table 5, "Amilan (registered trademark)" CM1007 and thermosetting resin monomers or prepolymers with two or more functionalities were added to a mixing apparatus and heated and mixed at 260°C for 30 minutes. Then, curing agents with two or more functionalities were added and heated and mixed at 260°C for 30 minutes to obtain reaction products B-5 to B-10 and B-12 of thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities and polyamide 6.

[0091] <Thermocurable Prepreg> In a kneader, the components and proportions listed in Table 3, namely "jER (registered trademark)" 828, "SUMI-EPOXY (registered trademark)" ELM434, and "SUMIKAEXCEL (registered trademark)" PES5003P, were added. While kneading, the temperature was raised to above 150°C and stirred for 1 hour to dissolve "SUMIKAEXCEL (registered trademark)" PES5003P, resulting in a transparent, viscous liquid. This liquid was then kneaded while cooling to below 100°C, and SEIKACURE-S was added for further kneading to obtain a thermosetting resin composition.

[0092] The thermosetting resin composition using benzo[a]pyrene resin was prepared by the following method: Araldite (registered trademark) MY0610 and Virantage (registered trademark) VW10700RFP were mixed in a kneader while being heated to above 150°C and stirred for 1 hour to dissolve the Virantage (registered trademark) VW10700RFP, resulting in a transparent viscous liquid. This liquid was then mixed while being cooled to below 100°C, and benzo[a]pyrene resin was added and further mixed until completely dissolved, yielding the thermosetting resin composition.

[0093] The thermosetting resin composition using bismaleimide resin was prepared by the following method: Compimide TM124 and Matrimid 9725 were mixed in a kneader while being heated to above 120°C and stirred for 1 hour to dissolve Matrimid 9725 and obtain a transparent viscous liquid. This liquid was then cooled to below 100°C while being mixed, and a mixture of Compimide MDAB and Compimide TDAB preheated to 140°C was added and further mixed to obtain the thermosetting resin composition.

[0094] The obtained thermosetting resin composition was coated onto release paper using a knife coating machine at a resin unit area weight of 50 g / m² to prepare a resin film. The resin film was then overlapped on both sides of a reinforcing fiber sheet (unit area weight 190 g / m²) in which the reinforcing fibers [A] were neatly arranged in one direction, and the thermosetting resin composition was impregnated using a heated roller while heating and pressing to obtain a thermosetting prepreg.

[0095] <Evaluation and Measurement Methods> (1) Methods for determining the melting point and glass transition temperature of thermoplastic resins The melting point and glass transition temperature of thermoplastic resins were determined using a differential scanning calorimeter (DSC) based on JIS K7121 (2012). 1–10 mg of sample was loaded into a 50 μL sealed sample container, and the temperature was increased at a rate of 10 °C / min. The difference between the high and low points of the DSC curve within the range of 30–400 °C was used as the glass transition temperature, and the endothermic peak was used as the melting point. Each temperature was designated as the glass transition temperature and melting point. When multiple melting points or glass transition temperatures were observed for mixtures, the highest melting point was used as the melting point of the thermoplastic resin.

[0096] (2) Method for manufacturing integrally molded articles for tensile shear bond strength testing Prepare 8 pre-impregnated materials cut to the specified size. Define the axial direction of the reinforcing fibers as 0° and the perpendicular direction of the axial direction as 90°, and construct a laminate with [0° / 90°] 2S (the symbol S indicates mirror symmetry). Place the laminate in a pressure molding metal mold heated to the melting point of the thermoplastic resin or the glass transition temperature +35°C. While maintaining the shape, apply a pressure of 1MPa with a press and heat for 12 minutes to obtain a fiber-reinforced resin molded body. Cut the prepared fiber-reinforced resin molded body into two pieces with a width of 250mm and a length of 92.5mm, with the 0° direction set as the length direction of the test piece, and dry them in a vacuum oven for 24 hours. Next, with the 0° direction set as the length direction, the two panels are overlapped with a 12.5 mm length from the ends of the two panels forming the bonding surface. A pressure of 1 MPa is applied at the welding temperature (melting point of thermoplastic resin + 25°C, or glass transfer temperature + 100°C if the melting point is not shown) as recorded in Tables 2-4 and 6-11, and held for 6 minutes to weld the overlapping surfaces, thereby obtaining a one-piece molded product for evaluating tensile shear bond strength.

[0097] (3) Method for determining tensile shear bond strength The monolithic article prepared in (2) above was labeled according to ISO 4587:1995 (JIS K6850 (1994)) and cut to a width of 25 mm to obtain the test piece. The obtained test piece was dried in a vacuum oven for 24 hours, and the tensile shear bond strength at an ambient temperature of 23°C was measured according to ISO 4587:1995 (JIS K6850 (1994)). The results were evaluated as follows. Above 28MPa: A 25MPa or higher but less than 28MPa: B 20MPa or higher but less than 25MPa: C Less than 20MPa: D (Unqualified).

[0098] (4) Evaluation method for dimensional stability during welding The dimensional stability during welding is determined by setting the average thickness of the two fiber-reinforced resin molded bodies before welding as T1 and T2, respectively, and the average thickness of the integral molded body after welding as T3. The change rate of thickness before and after welding is calculated by (T1+T2-T3) / (T1+T2)×100, and the evaluation is based on the calculation results as follows. Below 5%: A Greater than 5% and less than 8%: B Greater than 8% and less than 10%: C Greater than 10%: D (Unacceptable) Here, in an area with a length of 12.5 mm and a width of 250 mm corresponding to the adhesive surface before and after welding, the thickness is measured at 10 equal intervals in the width direction using a micrometer, and the average value is set as the average thickness.

[0099] (5) Roughness mean length RSm and roughness mean height Rc of composite prepreg Using a pre-fabricated composite prepreg, as shown in Figure 1, a test piece with an observation cross-section 7 is obtained by cutting the prepreg perpendicularly to its plane at a 45-degree angle from a top view, relative to the fiber direction 6 of the reinforcing fibers 2 contained in the first thermoplastic resin layer 3 and the second thermoplastic resin layer 4 or the thermosetting resin layer 4. The test piece is then embedded in epoxy resin and the observation cross-section is ground. Ten 1000x images are captured using an optical microscope in the obtained observation cross-section. The pattern of any 500μm × 500μm observation area in the obtained images is shown in Figure 2. In this observation image 7, the first thermoplastic resin layer 3 and the second thermoplastic resin layer 4 or the thermosetting resin layer 4 form an interface 5. Here, the end of the resin layer 4 is designated as the baseline 8, and vertical baselines 9 are drawn from the resin layer 4 towards the resin layer 3 at 5μm intervals. Plot the vertical baseline 9 from the point where the baseline 8 first intersects with the first thermoplastic resin layer 3. Connect the plotted points to define the profile curve 10. For the obtained profile curve 10, perform filtering based on JIS B0601 (2001) to calculate the average roughness height Rc and average roughness length RSm. Similarly, calculate the average roughness height Rc and average roughness length RSm from the image at point 10, and set the average values ​​as their respective values.

[0100] (6) Calculation of the mass percentage of each constituent unit in the thermoplastic resin layer A specified amount of thermoplastic resin layer was taken from the prepreg and used as a test sample. Solid-state NMR (Bruker AVANCE III 400) was performed to determine the mass ratio of each component unit of thermoplastic resin, thermosetting resin and hardener.

[0101] (7) Electron microscopic observation of pre-impregnated materials • Confirmation of the compatibility between the thermoplastic resin and reaction product [A] and observation of the structure of the mixture of the thermoplastic resin and reaction product [A]. • Confirmation of the miscibility between reaction product [A] and reaction product [B] • Confirmation of the compatibility between thermoplastic resins and thermosetting resin monomers or prepolymers with two or more functionalities and / or curing agents with two or more functionalities By staining thin sections of the prepared pre-impregnated material, transmission electron microscopy (Hitachi, H-7100) was used to acquire transmission electron images at an accelerating voltage of 100 kV and appropriate magnification to confirm the presence or absence of phase-separated structures and thus assess compatibility. Here, those without confirmed phase-separated structures were defined as "compatible," and those with confirmed phase-separated structures were defined as "phase-separated." The results are shown in Tables 2-4 and 6-11. OsO4 and RuO4 were used as staining agents, respectively, to provide sufficient contrast in morphology, depending on the resin composition. Furthermore, when the structural period is greater than 1 nm but less than 10 nm, the appropriate multiplier is set to 50,000 times; when the structural period is greater than 10 nm but less than 100 nm, the appropriate multiplier is set to 20,000 times; when the structural period is greater than 100 nm but less than 1,000 nm, the appropriate multiplier is set to 2,000 times; and when the structural period is greater than 1,000 nm, the appropriate multiplier is set to 1,000 times.

[0102] (8) Confirmation of the presence of reaction products [A] and [B] in the prepreg. The presence of reaction products [A] and [B] in the prepreg was confirmed using gel permeation chromatography (GPC) with hexafluoroisopropanol as the solvent. The sample was prepared by extracting the resin composition from a specified amount of prepreg using hexafluoroisopropanol. The chromatograms of the mixture of raw materials before mixing and the extract were compared. The peak area originating from the reaction product was assessed to determine whether there was an increase in the peak area.

[0103] (9) Evaluation of solubility when dissolved in solvent 100 mg of the reaction product [B] was stirred and mixed with 20 g of hexafluoroisopropanol at 30 °C, and the appearance of the resulting solution was visually confirmed. The case where no separation was observed visually was defined as "soluble", and the case where separation was observed was defined as "insoluble". The results are shown in Table 5.

[0104] (10) Confirmation of cross-linked structure Each raw material and the reaction product [B] (100 mg each) were stirred and mixed separately with 20 g of hexafluoroisopropanol at 30 °C. The appearance of the resulting solutions was visually confirmed. For the solutions of the aforementioned raw materials, no separation was observed visually. For the solution of the reaction product [B], separation was observed visually, which was defined as "having" a cross-linked structure. No separation was observed visually, which was defined as "not having" a cross-linked structure. The results are shown in Table 5.

[0105] <Example · Comparative Example> [Example 1] The prepreg was prepared using carbon fiber T800S as the reinforcing fiber, "Amilan (registered trademark)" CM1007 as the thermoplastic resin, and A-1 as listed in Table 1 as the reaction product [A].

[0106] According to the proportions shown in Table 2, thermoplastic resin and the aforementioned reaction product A-1 were added to a mixing apparatus and heated and mixed at 260°C for 5 minutes to obtain a mixture containing thermoplastic resin and reaction product [A]. Here, the mass % of thermoplastic resin is equivalent to: the mass % of the constituent units of thermoplastic resin relative to 100% of the total mass of the constituent units of thermoplastic resin, thermosetting resin, and curing agent. Furthermore, the mass % of reaction product [A] is equivalent to: the total mass % of the constituent units of thermosetting resin and curing agent relative to 100% of the total mass of the constituent units of thermoplastic resin, thermosetting resin, and curing agent.

[0107] Next, a sheet of reinforcing fiber (190 g / m²) with the reinforcing fibers neatly arranged in one direction is extracted. An aqueous dispersion of the previously mentioned mixture (100 g / m²) is coated and dried. The mixture is then heated by a roller at a temperature of 25°C above the melting point of the thermoplastic resin. While being heated and pressurized, the mixture is impregnated onto the continuous sheet of reinforcing fiber to obtain a pre-impregnated material.

[0108] Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 2.

[0109] [Example 2] The mixing time of the thermoplastic resin and the aforementioned reaction product A-1 was changed from 5 minutes to 30 minutes. Otherwise, the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 1. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 2.

[0110] [Examples 3-6] Using A-2 to A-5 as described in Table 1 as reaction products [A], the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 1. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 2.

[0111] [Example 7] The prepreg is made using T800S as the reinforcing fiber, "Amilan (registered trademark)" CM1007 as the thermoplastic resin, "jER (registered trademark)" 828 as a thermosetting resin monomer or prepolymer with more than two functions, and SEIKACURE-S as a curing agent with more than two functions.

[0112] In accordance with the proportions recorded in Table 3, thermoplastic resin, thermosetting resin monomers or prepolymers with two or more functions, and hardeners with two or more functions are added to a mixing apparatus and heated and mixed at 260°C for 5 minutes to obtain a mixture containing thermoplastic resin and reaction product [A].

[0113] Next, a sheet of reinforcing fiber (190 g / m²) with the reinforcing fibers neatly arranged in one direction is extracted. An aqueous dispersion of the previously mentioned mixture (100 g / m²) is coated and dried. The mixture is then heated by a roller at a temperature of 25°C above the melting point of the thermoplastic resin. While being heated and pressurized, the mixture is impregnated onto the continuous sheet of reinforcing fiber to obtain a pre-impregnated material.

[0114] Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 3.

[0115] [Example 8] Using "jER (registered trademark)" 828 and "SUMI-EPOXY (registered trademark)" ELM434 as thermosetting resin monomers or prepolymers with two or more functions, the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 7. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 3.

[0116] [Examples 9 and 10] The proportion of thermoplastic resin and reaction product [A] was set in a manner that was 100% by mass relative to the total amount of thermoplastic resin and reaction product [A] as shown in Table 3. Otherwise, the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 3. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 3.

[0117] [Examples 11 and 12] Using A-6 to A-7 as described in Table 1 as reaction products [A], the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 1. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 3.

[0118] [Example 13] The composite prepreg was prepared using carbon fiber T800S as the reinforcing fiber, "Amilan (registered trademark)" CM1007 as the thermoplastic resin, "KEPSTAN (registered trademark)" 7002 as the thermoplastic resin used in the second thermoplastic resin layer, and A-4 as listed in Table 1 as the reaction product [A].

[0119] A reinforcing fiber sheet (190 g / m²) with the reinforcing fibers neatly arranged in one direction is extracted. A film (50 g / m²) containing the thermoplastic resin used in the second thermoplastic resin layer is placed on one surface of the continuous fiber sheet. The thermoplastic resin used in the second thermoplastic resin layer is melted by heating with an IR heater and adhered to one side of the continuous reinforcing fiber sheet. Pressure is applied by three pairs of rollers at a temperature 100°C lower than the melting point of the thermoplastic resin used in the second thermoplastic resin layer, so that the resin is impregnated in the reinforcing fiber sheet, resulting in a semi-impregnated material with the fiber-reinforced sheet exposed on the other side.

[0120] Next, the thermoplastic resin and the aforementioned reaction product A-4 were added to a mixing apparatus in the proportions shown in Table 4 and heated and mixed at 260°C for 5 minutes to obtain a mixture containing the thermoplastic resin and reaction product [A]. An aqueous dispersion of the aforementioned mixture, which had been frozen and pulverized, was coated on the other side of the resulting semi-impregnated fabric (the unit area weight of the frozen and pulverized mixture was 100 g / m²). The mixture was heated and pressurized at a temperature of 25°C above the melting point of the thermoplastic resin, and then impregnated with a continuous reinforcing fiber sheet to obtain a composite prepreg.

[0121] Furthermore, according to (2) above, the laminated composite prepreg is subjected to a pressure of 1 MPa using a press and heated to 366°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 4.

[0122] [Example 14] The composite prepreg was prepared using carbon fiber T800S as the reinforcing fiber, "Amilan (registered trademark)" CM1007 as the thermoplastic resin, A-4 as listed in Table 1 as the reaction product [A], and the composition listed in Table 4 as the thermosetting resin composition.

[0123] According to the proportions recorded in Table 4, thermoplastic resin and the aforementioned reaction product A-4 were added to a mixing apparatus and heated and mixed at 260°C for 5 minutes to obtain a mixture containing thermoplastic resin and reaction product [A]. A reinforcing fiber sheet (weight per unit area 190 g / m²) with the reinforcing fibers neatly arranged in one direction was extracted. The aforementioned mixture (weight per unit area 100 g / m²) after being frozen and pulverized was spread on one side of the reinforcing fiber sheet. The mixture was heated and melted using an IR heater and adhered to one side of the continuous reinforcing fiber sheet. Pressure was applied using three pairs of rollers at a temperature maintained 100°C lower than the melting point or glass transition temperature of the thermoplastic resin to impregnate the reinforcing fiber sheet, resulting in a semi-impregnated material with the fiber-reinforced sheet exposed on the other side.

[0124] Next, a film containing an uncured thermosetting resin composition (weight per unit area of ​​50 g / m²) is overlapped on the other side of the obtained semi-impregnated material, and a heated roller is used to heat and pressurize the film containing the uncured thermosetting resin composition while impregnating the continuous reinforcing fiber sheet to obtain a composite prepreg.

[0125] Furthermore, prepare two pieces of the obtained composite prepreg cut to the specified size, and prepare six pieces of the thermosetting prepreg made using the above method cut to the same shape. Define the axial direction of the reinforcing fiber as 0° and the perpendicular direction of the axial direction as 90°. The prepreg is constructed in the form of [0° / 90°] 2S (the symbol S indicates mirror symmetry). The outermost layer is the aforementioned two pieces of composite prepreg (the thermoplastic resin layer is the outermost layer), and the inner layer is the aforementioned thermosetting prepreg.

[0126] The prepreg material that has been laminated is subjected to a pressure of 1 MPa by a press and heated at 230°C for 12 minutes to produce a fiber-reinforced resin molded body. In addition, according to (2) above, a pressure of 1 MPa is applied to the obtained fiber-reinforced resin molded body and held at 250°C for 6 minutes to fuse the overlapping surfaces and obtain an integral molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 4.

[0127] [Examples 15, 17] Using A-6 and A-7 as described in Table 1 as reaction products [A], the composite prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 13. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 4.

[0128] [Example 16] Using A-6 as described in Table 1 as the reaction product [A], the prepreg after lamination was subjected to a pressure of 1 MPa by a press, heated at 180°C for 1 hour, and then heated at 230°C for 1 hour, thereby producing a fiber-reinforced resin molded article. Otherwise, the composite prepreg, fiber-reinforced resin molded article, and integral molded article were produced in the same manner as in Example 14.

[0129] The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 4.

[0130] [Example 18] Using A-7 as described in Table 1 as reaction product [A], the prepreg after lamination was subjected to a pressure of 1 MPa by a press, heated at 140°C for 1 hour, heated at 180°C for 1 hour, and further heated at 230°C for 1 hour, thereby producing a fiber-reinforced resin molded article. Otherwise, the composite prepreg, fiber-reinforced resin molded article, and integral molded article were produced in the same manner as in Example 14. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 4.

[0131] [Comparative Example 1] The prepreg is made using carbon fiber T800S as the reinforcing fiber and "Amilan (registered trademark)" CM1007 as the thermoplastic resin, as follows.

[0132] Extract a sheet of reinforcing fibers (190 g / m²) with the reinforcing fibers neatly arranged in one direction. Coat the sheet with an aqueous dispersion of a frozen and pulverized thermoplastic resin (100 g / m² of the frozen and pulverized reaction product). After drying, heat the sheet with a roller at a temperature of 25°C above the melting point of the thermoplastic resin. While heating and pressurizing, impregnate the sheet with the aforementioned thermoplastic resin to obtain a prepreg.

[0133] Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 2.

[0134] [Compare Examples 2 and 3] The proportion of thermoplastic resin and reaction product [A] was set in a manner that was 100% by mass relative to the total amount of thermoplastic resin and reaction product [A] as shown in Table 3. Otherwise, the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 3. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 3.

[0135] By comparing Examples 1-10 with Comparative Example 1, it can be seen that when the thermoplastic resin layer contains 65.0-99.5% by mass of thermoplastic resin constituent units and a total of 0.5-35.0% by mass of thermoplastic resin constituent units and hardener constituent units in the form of reaction product [A] relative to the total of 100% by mass of thermoplastic resin constituent units, thermosetting resin constituent units and hardener constituent units, the balance between dimensional stability during welding and tensile shear bond strength at 23°C is excellent. However, when reaction product [A] is not included, or when the content of each constituent unit is outside the above range, the tensile shear bond strength at 23°C or the dimensional stability during welding is unacceptable.

[0136] The results of Examples 11-16 show that the thermoplastic resin layer contains the reaction product [A] and the content of each constituent unit meets the above range. Such a composite prepreg has an excellent balance between dimensional stability during welding and tensile shear bond strength at 23°C.

[0137] [Example 19] The prepreg was prepared using carbon fiber T800S as the reinforcing fiber and B-1 as described in Table 5 as the reaction product [B], as follows.

[0138] Extract a sheet of reinforcing fiber (190 g / m²) with the reinforcing fibers neatly arranged in one direction. Coat the sheet with an aqueous dispersion of B-1 that has been frozen and crushed (100 g / m² of the reaction product that has been frozen and crushed). After drying, heat the roller at a temperature of 25°C above the melting point of the thermoplastic resin of B-1 raw material. While heating and pressurizing, impregnate the aforementioned reaction product into the continuous reinforcing fiber sheet to obtain a prepreg.

[0139] Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 6.

[0140] [Examples 20-24] Using B-2 to B-6 as described in Table 5 as reaction products [B], the prepreg, fiber-reinforced resin molded body, and integral molded article were prepared in the same manner as in Example 19. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 6.

[0141] [Example 25] The prepreg was prepared using carbon fiber T800S as the reinforcing fiber, B-1 as described in Table 5 as the reaction product [B], "jER (registered trademark)" 828 as a thermosetting resin monomer or prepolymer with two or more functions, and SEIKACURE-S as a curing agent with two or more functions.

[0142] Using the proportions listed in Table 6, thermosetting resin monomers or prepolymers with two or more functions (B-1) and curing agents with two or more functions were added to a mixing apparatus and heated and mixed at 260°C for 5 minutes to obtain a mixture containing reaction product [A] of thermosetting resin monomers or prepolymers with two or more functions (B-1) and curing agents with two or more functions. A sheet of reinforcing fibers (190 g / m²) with the reinforcing fibers neatly arranged in one direction was extracted. An aqueous dispersion of the aforementioned mixture (100 g / m²) after freeze-crushing was applied, dried, and then heated by a roller at a temperature 25°C above the melting point of the thermoplastic resin of raw material B-1. While heating and pressurizing, the aforementioned mixture was impregnated onto the continuous sheet of reinforcing fibers to obtain a prepreg. Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 6.

[0143] [Examples 26-29] Using B-7, B-8, B-11 and B-12 as described in Table 5 as reaction products [B], the prepreg, fiber-reinforced resin molded body and integral molded article were prepared in the same manner as in Example 19. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 7.

[0144] [Compare Examples 4 and 5] Using B-9 and B-10 as described in Table 5 as reaction products [B], the prepreg, fiber-reinforced resin molded article, and integral molded article were prepared in the same manner as in Example 19.

[0145] The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 7.

[0146] [Example 30] The composite prepreg was prepared using carbon fiber T800S as the reinforcing fiber, B-5 ​​as described in Table 5 as the reaction product [B], and KEPSTAN (registered trademark) 7002 as the thermoplastic resin used in the second thermoplastic resin layer.

[0147] A reinforcing fiber sheet (190 g / m²) with the reinforcing fibers neatly arranged in one direction is extracted. A film (50 g / m²) containing the thermoplastic resin used in the second thermoplastic resin layer is placed on one surface of the continuous fiber sheet. The thermoplastic resin used in the second thermoplastic resin layer is melted by heating with an IR heater and adhered to one side of the continuous reinforcing fiber sheet. Pressure is applied by three pairs of rollers at a temperature 100°C lower than the melting point of the thermoplastic resin used in the second thermoplastic resin layer, so that the resin is impregnated in the reinforcing fiber sheet, resulting in a semi-impregnated material with the fiber-reinforced sheet exposed on the other side.

[0148] Next, the aqueous dispersion of the frozen and pulverized reaction product [B] is coated on the other side of the obtained semi-impregnated material (the unit area weight of the frozen and pulverized mixture is 100 g / m2). The mixture is heated and pressurized at a temperature of 25°C above the melting point of the thermoplastic resin of raw material B-5, and then impregnated with a continuous reinforcing fiber sheet to obtain a composite prepreg.

[0149] Furthermore, according to (2) above, the laminated composite prepreg is subjected to a pressure of 1 MPa using a press and heated to 366°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 8.

[0150] [Example 31] The composite prepreg was prepared using carbon fiber T800S as the reinforcing fiber, B-5 ​​as described in Table 5 as the reaction product [B], and the composition described in Table 8 as the thermosetting resin composition.

[0151] Extract a sheet of reinforcing fiber (190 g / m²) with the reinforcing fibers neatly arranged in one direction. Spread the previously described mixture (100 g / m²) on one side of the reinforcing fiber sheet after freezing and pulverizing. Melt the mixture using an IR heater and attach it to one side of the continuous reinforcing fiber sheet. Press it with three pairs of rollers at a temperature 100°C lower than the melting point or glass transition temperature of the thermoplastic resin of the B-5 raw material to impregnate it with the reinforcing fiber sheet, resulting in a semi-impregnated material with the fiber-reinforced sheet exposed on the other side.

[0152] Next, a film containing an uncured thermosetting resin composition (weight per unit area of ​​50 g / m²) is overlapped on the other side of the obtained semi-impregnated material, and a heated roller is used to heat and pressurize the film containing the uncured thermosetting resin composition while impregnating the continuous reinforcing fiber sheet to obtain a composite prepreg.

[0153] Furthermore, prepare two pieces of the obtained composite prepreg cut to the specified size, and prepare six pieces of the thermosetting prepreg made using the above method cut to the same shape. Define the axial direction of the reinforcing fiber as 0° and the perpendicular direction of the axial direction as 90°. The prepreg is constructed in the form of [0° / 90°] 2S (the symbol S indicates mirror symmetry). The outermost layer is the aforementioned two pieces of composite prepreg (the layer containing the reaction product [B] is the outermost layer), and the inner layer is the aforementioned thermosetting prepreg.

[0154] The prepreg material that has been laminated is subjected to a pressure of 1 MPa by a press and heated at 230°C for 12 minutes to produce a fiber-reinforced resin molded body. In addition, according to (2) above, a pressure of 1 MPa is applied to the obtained fiber-reinforced resin molded body and held at 250°C for 6 minutes to fuse the overlapping surfaces and obtain an integral molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 8.

[0155] [Examples 32, 34] Using B-11 and B-12 as described in Table 5 as reaction products [B], the composite prepreg, fiber-reinforced resin molded article, and integral molded article were prepared in the same manner as in Example 30. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 8.

[0156] [Example 33] Using B-11 as described in Table 5 as the reaction product [B], the prepreg after lamination was subjected to a pressure of 1 MPa by a press, heated at 180°C for 1 hour, and then heated at 230°C for 1 hour, thereby producing a fiber-reinforced resin molded article. Otherwise, the composite prepreg, fiber-reinforced resin molded article, and integral molded article were produced in the same manner as in Example 31. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 8.

[0157] [Example 35] Using B-12 as described in Table 5 as the reaction product [B], the prepreg after lamination was subjected to a pressure of 1 MPa by a press, heated at 140°C for 1 hour, heated at 180°C for 1 hour, and further heated at 230°C for 1 hour, thereby producing a fiber-reinforced resin molded article. Otherwise, the composite prepreg, fiber-reinforced resin molded article, and integral molded article were produced in the same manner as in Example 31. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 8.

[0158] Comparing Examples 19-29 with Comparative Examples 1, 4, and 5, it can be seen that when the thermoplastic resin layer, in the form of reaction product [B], contains 65.0-99.5% by mass of thermoplastic resin constituent units and a total of 0.5-35.0% by mass of thermoplastic resin constituent units and hardener constituent units, respectively, relative to 100% by mass of the total constituent units of thermoplastic resin, thermosetting resin, and hardener, the balance between dimensional stability during welding and tensile shear bond strength at 23°C is excellent. However, when reaction product [B] is not included, or when the content of each constituent unit is outside the above range, the tensile shear bond strength at 23°C and the dimensional stability during welding are both unacceptable.

[0159] The results of Examples 30-35 show that the thermoplastic resin layer contains the reaction product [B] and the content of each constituent unit meets the above range. Such a composite prepreg has an excellent balance between dimensional stability during welding and tensile shear bond strength at 23°C.

[0160] [Example 36] The prepreg is made using carbon fiber T800S as the reinforcing fiber, "Amilan (registered trademark)" CM1007 as the thermoplastic resin, and "jER (registered trademark)" 828 as a thermosetting resin monomer or prepolymer with more than two functions, as follows.

[0161] The "jER (registered trademark)" 828 was heated to 50°C and coated onto a film (50 g / m²) containing "Amilan (registered trademark)" CM1007 using a coating machine. When using two or more thermosetting resin monomers or prepolymers with two or more functions, or when using one or more thermosetting resin monomers or prepolymers with two or more functions, and other components, the thermosetting resin monomers or prepolymers with two or more functions, and other components (only added when used) are added to a kneader beforehand and heated and mixed at 50°C to obtain a mixture. The mixture is then coated onto a film containing a thermoplastic resin using a coating machine. Furthermore, regarding the "SUMIKAEXCEL (registered trademark)" PES5003P used in Examples 42 and 44, since it is a powder, it is added to the kneader and mixed together with the thermosetting resin monomers or prepolymers with two or more functions. At this time, it is set as follows: relative to 100% by mass of the total amount of thermoplastic resin and thermosetting resin monomers or prepolymers with two or more functions, it includes 90.0% by mass of thermoplastic resin and 10.0% by mass of thermosetting resin monomers or prepolymers with two or more functions.

[0162] Next, a sheet of reinforcing fibers (190 g / m²) with the reinforcing fibers neatly arranged in one direction is extracted. On both sides of the continuous reinforcing fiber sheet, the side of the aforementioned film coated with thermosetting resin monomers or prepolymers with two or more functions is overlapped. The film is heated and pressed at a temperature of 25°C above the melting point of the thermoplastic resin, and the aforementioned film is impregnated in the continuous reinforcing fiber sheet to obtain a prepreg.

[0163] Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0164] [Example 37] EPTS of 0.1% by mass relative to 100% by mass of the total amount of thermoplastic resin and thermosetting resin monomers or prepolymers with two or more functions was used as other components. Otherwise, the prepreg, fiber-reinforced resin molded article and integral molded article were prepared in the same manner as in Example 36. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0165] [Example 38] Extract a sheet of reinforcing fibers (190 g / m²) with the reinforcing fibers neatly arranged in one direction. Overlap a film (50 g / m²) containing the reaction product of the aforementioned thermoplastic resin and thermosetting resin monomers or prepolymers with two or more functions on both sides of the continuous reinforcing fiber sheet. Heat the film with a roller at a temperature of 25°C above the melting point of the thermoplastic resin, and impregnate the continuous reinforcing fiber sheet while heating and pressurizing. Otherwise, the prepreg, fiber-reinforced resin molded body, and integral molded article are produced in the same manner as in Example 36. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0166] [Comparative Example 6] The proportion of thermoplastic resin and thermosetting resin monomers or prepolymers with two or more functions is set in a manner that is 100% by mass relative to the total amount of thermoplastic resin and thermosetting resin monomers or prepolymers with two or more functions as described in Table 9. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 36. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0167] [Example 39] Using T800S as the reinforcing fiber, Amilan CM1007 (registered trademark) as the thermoplastic resin, jER 828 (registered trademark) as a thermosetting resin monomer or prepolymer with two or more functionalities, and SEIKACURE-S as a curing agent with two or more functionalities, the prepreg was prepared in the same manner as in Example 36. In this case, the composition was set such that, relative to 100% by mass of the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functionalities, and curing agent with two or more functionalities, the composition included 65.0% by mass of thermoplastic resin, 25.9% by mass of thermosetting resin monomer or prepolymer with two or more functionalities, and 9.1% by mass of curing agent with two or more functionalities. Furthermore, the proportions of thermosetting resin monomer or prepolymer with two or more functionalities and curing agent with two or more functionalities relative to 100% by mass of the total amount of thermosetting resin monomer or prepolymer with two or more functionalities and curing agent with two or more functionalities were set to 74% by mass and 26% by mass, respectively. Furthermore, according to (2) above, the prepreg that has been laminated is subjected to a pressure of 1 MPa using a press and heated to 260°C for 12 minutes to produce a fiber-reinforced resin molded body. The resulting fiber-reinforced resin molded body is subjected to a pressure of 1 MPa and held at 250°C for 6 minutes to fuse the overlapping surfaces, thereby obtaining an integrally molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0168] [Examples 40, 41] The proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions are set in a manner that is 100% by mass relative to the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions as described in Table 9. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 39. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0169] [Example 42] Using "Amilan (registered trademark)" CM1007 and "SUMIKAEXCEL (registered trademark)" PES5003P as thermoplastic resins, the proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions were set in the manner described in Table 9, relative to 100% by mass of the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article were produced in the same manner as in Example 39. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0170] [Example 43] A mixture of thermosetting resin monomers or prepolymers with two or more functionalities diluted with isopropanol is coated onto a film containing a thermoplastic resin. The isopropanol is then dried to remove it, thereby obtaining a film coated with thermosetting resin monomers or prepolymers with two or more functionalities. The proportions of the thermoplastic resin, thermosetting resin monomers or prepolymers with two or more functionalities, and curing agents with two or more functionalities are adjusted to the mass percentages listed in Table 9 relative to 100% of the total mass of the thermoplastic resin, the thermosetting resin monomers or prepolymers with two or more functionalities, and the curing agents with two or more functionalities. Otherwise, prepregs, fiber-reinforced resin molded articles, and integrally molded articles are produced in the same manner as in Example 39. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0171] [Comparative Example 7] The proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions are set in a manner that is 100% by mass relative to the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions as described in Table 9. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 39. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0172] [Comparative Example 8] The proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions are set in the manner described in Table 9, relative to 100% by mass of the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 43. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 9.

[0173] [Example 44] Using "jER (registered trademark)" 828 and "SUMI-EPOXY (registered trademark)" ELM434 as thermosetting resin monomers or prepolymers with two or more functions, the proportions of thermoplastic resin, thermosetting resin monomers or prepolymers with two or more functions, and hardeners with two or more functions are set in the manner described in Table 10 as a mass percentage relative to 100% of the total mass of thermoplastic resin, thermosetting resin monomers or prepolymers with two or more functions, and hardeners with two or more functions. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 42. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0174] [Example 45] DICY7 was used as a curing agent with two or more functions, and the proportions of the thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions were set in a manner that was 100% by mass relative to the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions as described in Table 10. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article were produced in the same manner as in Example 41. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0175] [Example 46] "Amilan (registered trademark)" CM1007 was used as the thermoplastic resin, benzo[a]pyrene resin Fa was used as a thermosetting resin monomer or prepolymer with two or more functions, and "Araldite (registered trademark)" MY0610 was used as a curing agent with two or more functions. The proportions of the thermoplastic resin, the thermosetting resin monomer or prepolymer with two or more functions, and the curing agent with two or more functions were set in a manner that was 100% by mass relative to the total mass of the thermoplastic resin, the thermosetting resin monomer or prepolymer with two or more functions, and the curing agent with two or more functions as described in Table 10. Otherwise, the prepreg, the fiber-reinforced resin molded article, and the integral molded article were produced in the same manner as in Example 39. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0176] [Example 47] "Amilan (registered trademark)" CM1007 was used as the thermoplastic resin, "Compimide (registered trademark)" MDAB and "Compimide (registered trademark)" TDAB were used as thermosetting resin monomers or prepolymers with two or more functions, and "Compimide (registered trademark)" TM124 was used as a curing agent with two or more functions. The proportions of the thermoplastic resin, thermosetting resin monomers or prepolymers with two or more functions, and curing agents with two or more functions were set in a manner that was 100% by mass relative to the total mass of the thermoplastic resin, the thermosetting resin monomers or prepolymers with two or more functions, and the curing agents with two or more functions as described in Table 10. Otherwise, the prepreg, the fiber-reinforced resin molded article, and the integral molded article were produced in the same manner as in Example 39. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0177] [Example 48] Using "Amilan (registered trademark)" CM4000 as the thermoplastic resin, a fiber-reinforced resin molded body was made at 190°C, and a one-piece molded article was made at 180°C. Otherwise, the prepreg, fiber-reinforced resin molded body, and one-piece molded article were made in the same manner as in Example 41. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0178] [Comparative Example 9] The proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions are set in a manner that is 100% by mass relative to the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions as described in Table 10. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 48. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0179] [Example 49] Using "Torelina (registered trademark)" A670T05 as the thermoplastic resin, a fiber-reinforced resin molded body was made at 313°C, and a one-piece molded article was made at 303°C. Otherwise, the prepreg, fiber-reinforced resin molded body, and one-piece molded article were made in the same manner as in Example 41. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0180] [Comparative Example 10] The proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions are set in a manner that is 100% by mass relative to the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions as described in Table 10. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 49. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0181] [Example 50] Using "KEPSTAN (registered trademark)" 7002 as the thermoplastic resin, a fiber-reinforced resin molded body was made at 366°C, and a one-piece molded article was made at 356°C. Otherwise, the prepreg, fiber-reinforced resin molded body, and one-piece molded article were made in the same manner as in Example 41. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0182] [Comparative Example 11] The proportions of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions are set in a manner that is 100% by mass relative to the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functions, and curing agent with two or more functions as described in Table 10. Otherwise, the prepreg, fiber-reinforced resin molded article, and integral molded article are produced in the same manner as in Example 50. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0183] [Example 51] Continuous E-grade glass fiber was used to replace carbon fiber T800S as the reinforcing fiber, and otherwise, the prepreg was obtained in the same manner as in Example 41. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0184] [Example 52] The reinforcing fiber sheet, which aligns the reinforcing fibers in one direction, was replaced with carbon fiber fabric "Torayca (registered trademark)" Cloth CK6273C as the reinforcing fiber. Otherwise, the prepreg was obtained in the same manner as in Example 41. The evaluation results of the physical properties of the prepreg, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 10.

[0185] [Example 53] The composite prepreg is made using carbon fiber T800S as the reinforcing fiber, "Amilan (registered trademark)" CM1007 as the thermoplastic resin, "KEPSTAN (registered trademark)" 7002 as the thermoplastic resin used in the second thermoplastic resin layer, "jER (registered trademark)" 828 as a thermosetting resin monomer or prepolymer with more than two functions, and SEIKACURE-S as a curing agent with more than two functions.

[0186] A reinforcing fiber sheet (190 g / m²) with the reinforcing fibers neatly arranged in one direction is extracted. A film (50 g / m²) containing the thermoplastic resin used in the second thermoplastic resin layer is placed on one surface of the continuous fiber sheet. The thermoplastic resin used in the second thermoplastic resin layer is melted by heating with an IR heater and adhered to one side of the continuous reinforcing fiber sheet. Pressure is applied by three pairs of rollers at a temperature 100°C lower than the melting point of the thermoplastic resin used in the second thermoplastic resin layer, so that the resin is impregnated in the reinforcing fiber sheet, resulting in a semi-impregnated material with the fiber-reinforced sheet exposed on the other side.

[0187] Using the same method as in Example 36, a thermosetting resin monomer or prepolymer with two or more functionalities and a curing agent with two or more functionalities are coated onto a film containing thermoplastic resin (100 g / m²). In this case, the composition is set such that, relative to 100% by mass of the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functionalities, and curing agent with two or more functionalities, the composition comprises 95.0% by mass of thermoplastic resin, 3.7% by mass of thermosetting resin monomer or prepolymer with two or more functionalities, and 1.3% by mass of curing agent with two or more functionalities. Furthermore, the proportions of the thermosetting resin monomer or prepolymer with two or more functionalities and the curing agent with two or more functionalities relative to 100% by mass of the total amount of thermosetting resin monomer or prepolymer with two or more functionalities and curing agent with two or more functionalities are set to 74% by mass and 26% by mass, respectively.

[0188] The side of the film coated with a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions is overlapped onto the other side of the resulting semi-impregnated material. A heating roller is used to heat and pressurize the film while impregnating a continuous reinforcing fiber sheet to obtain a composite prepreg. Furthermore, according to (2) above, the laminated prepreg is subjected to a pressure of 1 MPa using a press and heated to 366°C for 12 minutes to produce a fiber-reinforced resin molded body. A pressure of 1 MPa is applied to the resulting fiber-reinforced resin molded body, and it is held at 250°C for 6 minutes to fuse the overlapping surfaces, obtaining an integrally molded product for evaluating tensile shear bond strength. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 11.

[0189] [Example 54] Carbon fiber T800S was used as the reinforcing fiber, "Amilan (registered trademark)" CM1007 was used as the thermoplastic resin, "jER (registered trademark)" 828 was used as a thermosetting resin monomer or prepolymer with two or more functions, SEIKACURE-S was used as a curing agent with two or more functions, and the composition listed in Table 11 was used as the thermosetting resin composition.

[0190] A sheet of reinforcing fibers (190 g / m²) with the reinforcing fibers neatly aligned in one direction is extracted. Using the same method as in Example 36, a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions are coated. At this time, the proportions of each component are set as described in Table 11.

[0191] The film, coated with a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions, is placed on the surface of a continuous fiber sheet. The film is then heated and melted using an IR heater, adhering to one side of the continuous reinforcing fiber sheet. Pressure is applied using three pairs of rollers maintained at a temperature 100°C lower than the melting point or glass transition temperature of the thermoplastic resin, impregnating the reinforcing fiber sheet to obtain a semi-impregnated material with the fiber-reinforced sheet exposed on the other side. A film containing an uncured thermosetting resin composition (50 g / m²) is overlapped onto the other side of the resulting semi-impregnated material, and heated rollers are used to impregnate the continuous reinforcing fiber sheet while heating and pressurizing, resulting in a composite prepreg.

[0192] Prepare two pieces of the obtained composite prepreg cut to the specified size, and prepare six pieces of the thermosetting prepreg made as described above cut to the same shape. Define the axial direction of the reinforcing fiber as 0° and the perpendicular direction of the axial direction as 90°. The prepreg is constructed in the form of [0° / 90°] 2S (the symbol S indicates mirror symmetry). The outermost layer is the aforementioned two pieces of composite prepreg (containing the thermoplastic resin layer as the outermost layer), and the inner layer is the aforementioned thermosetting prepreg.

[0193] The prepreg material that has been laminated is subjected to a pressure of 1 MPa by a press and heated at 230°C for 12 minutes to produce a fiber-reinforced resin molded body. In addition, according to (2) above, a pressure of 1 MPa is applied to the obtained fiber-reinforced resin molded body and held at 250°C for 6 minutes to fuse the overlapping surfaces and obtain an integral molded article for evaluating tensile shear bond strength. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 11.

[0194] [Example 55] "Amilan (registered trademark)" CM1007 was used as the thermoplastic resin, benzo[a]pyrene resin Fa was used as a thermosetting resin monomer or prepolymer with two or more functions, and "Araldite (registered trademark)" MY0610 was used as a curing agent with two or more functions. The proportions of the thermoplastic resin, the thermosetting resin monomer or prepolymer with two or more functions, and the curing agent with two or more functions were set in the manner described in Table 11, relative to 100% by mass of the total amount of the thermoplastic resin, the thermosetting resin monomer or prepolymer with two or more functions, and the curing agent with two or more functions. Otherwise, the composite prepreg, the fiber-reinforced resin molded article, and the integral molded article were prepared in the same manner as in Example 53. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 11.

[0195] [Example 56] Using "Amilan (registered trademark)" CM1007 as the thermoplastic resin, benzo[a]pyrene resin Fa as a thermosetting resin monomer or prepolymer with two or more functionalities, and "Araldite (registered trademark)" MY0610 as a curing agent with two or more functionalities, the composition listed in Table 11 was used as the thermosetting resin composition. The prepreg, after being laminated, was subjected to a pressure of 1 MPa using a press, heated at 180°C for 1 hour, and then heated at 230°C for 1 hour to produce a fiber-reinforced resin molded article. Otherwise, the composite prepreg, the fiber-reinforced resin molded article, and the integrally molded article were produced in the same manner as in Example 54. At this time, the proportions of the thermoplastic resin, the thermosetting resin monomer or prepolymer with two or more functionalities, and the curing agent with two or more functionalities were set as shown in Table 11, relative to 100% by mass of the total amount of thermoplastic resin, thermosetting resin monomer or prepolymer with two or more functionalities, and curing agent with two or more functionalities. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 11.

[0196] [Example 57] "Amilan (registered trademark)" CM1007 was used as the thermoplastic resin, "Compimide (registered trademark)" MDAB and "Compimide (registered trademark)" TDAB were used as thermosetting resin monomers or prepolymers with two or more functions, and "Compimide (registered trademark)" TM124 was used as a curing agent with two or more functions. The proportions of the thermoplastic resin, thermosetting resin monomers or prepolymers with two or more functions, and curing agents with two or more functions were set in a manner that was 100% by mass relative to the total mass of the thermoplastic resin, the thermosetting resin monomers or prepolymers with two or more functions, and the curing agents with two or more functions as described in Table 11. Otherwise, the composite prepreg, the fiber-reinforced resin molded article, and the integral molded article were produced in the same manner as in Example 53.

[0197] The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 11.

[0198] [Example 58] Using "Amilan (registered trademark)" CM1007 as the thermoplastic resin, "Compimide (registered trademark)" MDAB and "Compimide (registered trademark)" TDAB as thermosetting resin monomers or prepolymers with two or more functions, "Compimide (registered trademark)" TM124 as a curing agent with two or more functions, and the composition listed in Table 11 as the thermosetting resin composition, the prepreg after lamination was subjected to a pressure of 1 MPa by a press, heated at 140°C for 1 hour, heated at 180°C for 1 hour, and further heated at 230°C for 1 hour, thereby producing a fiber-reinforced resin molded body. Otherwise, the composite prepreg, fiber-reinforced resin molded body, and integral molded article were produced in the same manner as in Example 54. The evaluation results of the physical properties of composite prepregs, fiber-reinforced resin molded articles, and integral molded articles are shown in Table 11.

[0199] From the comparison of Examples 36-38 with Comparative Example 6, and the comparison of Examples 39-43 with Comparative Example 7, it can be seen that when the thermoplastic resin layer contains more than 35.0% by mass of thermoplastic resin constituent units and hardener constituent units relative to 100% by mass of thermoplastic resin constituent units, thermoplastic resin constituent units and hardener constituent units, the dimensional stability during welding is good to particularly good, but the tensile shear bond strength at 23°C is unacceptable.

[0200] Comparison of Examples 36-38 with Comparative Example 1, and comparison of Examples 39-43 with Comparative Example 8, shows that when the thermoplastic resin layer contains only less than 0.5% by mass of thermoplastic resin monomers or prepolymers and hardeners relative to the total mass percentage of thermoplastic resin constituent units, thermoplastic resin constituent units, and hardener constituent units (100% by mass), the tensile shear bond strength at 23°C is particularly good, but the dimensional stability during welding is unacceptable.

[0201] A comparison of Examples 36-38 with Examples 39-43 shows that prepregs containing thermosetting resin monomers or prepolymers with two or more functions that can form covalent bonds through reaction and hardeners with two or more functions have excellent dimensional stability during welding.

[0202] By comparing Example 48 with Comparative Example 9, Example 49 with Comparative Example 10, and Example 50 with Comparative Example 11, it can be seen that when the thermoplastic resin layer contains only less than 0.5% by mass of thermoplastic resin monomers or prepolymers and hardeners relative to the total mass percentage of thermoplastic resin constituent units, thermoplastic resin constituent units, and hardener constituent units (100% by mass), the tensile shear bond strength at 23°C is good to particularly good, but the dimensional stability during welding is unacceptable.

[0203] From the results of Examples 53-58, it can be seen that: the thermoplastic resin layer contains thermosetting resin monomers or prepolymers with two or more functions and a curing agent with two or more functions, and relative to the total mass percentage of thermoplastic resin constituent units, thermosetting resin constituent units and curing agent constituent units, it contains 65.0 to 99.5% by mass of thermoplastic resin constituent units and a total of 0.5 to 35.0% by mass of thermosetting resin constituent units and curing agent constituent units. Such a composite prepreg has an excellent balance between dimensional stability during welding and tensile shear bond strength at 23°C.

[0204] [Table 1] [Table 1] A-1 A-2 A-3 A-4 A-5 A-6 A-7 Thermosetting resin monomers or prepolymers with two or more functions jER® 828 quality% 95.0 75.0 60.0 24.0 75.0 - - SUMI-EPOXY® ELM434 - - - 44.0 - - - Fa - - - - - 60.0 - Compimide® MDAB - - - - - - 40.0 Compimide® TDAB - - - - - - 27.0 Hardeners with 2 or more functions SEIKACURE-S quality% 5.0 25.0 40.0 32.0 25.0 - - Araldite® MY0610 - - - - - 40.0 - Compimide® TM124 - - - - - - 33.0 Mixing temperature ℃ 180 180 180 180 180 180 180 Mixed practice time point 5 5 5 5 30 5 5

[0205] [Table 2] [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S T800S thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% 90.0 90.0 90.0 90.0 90.0 90.0 100.0 Thermosetting resin monomers or prepolymers with two or more functions The reaction product with a hardener with two or more functional groups [A] - A-1 A-1 A-2 A-3 A-4 A-5 - quality% 10.0 10.0 10.0 10.0 10.0 10.0 - Thermosetting resin monomers or prepolymers with two or more functions jER® 828 quality% - - - - - - - SUMI-EPOXY® ELM434 - - - - - - - Hardeners with 2 or more functions SEIKACURE-S quality% - - - - - - - Mixing temperature ℃ 260 260 260 260 260 260 - Mixed practice time point 5 30 5 5 5 5 - The presence or absence of reaction product [A] - have have have have have have none Compatibility of thermoplastic resin with reaction product [A] - Miscible Miscible Miscible Miscible Miscible Phase separation - Structure of the mixture of thermoplastic resin and reaction product [A] - Half IPN IPN Half IPN Half IPN Half IPN islands - Welding temperature ℃ 250 250 250 250 250 250 250 Dimensional stability during welding determination C B B C B C D % 8.8 7.4 7.1 8.1 6.7 9.9 14.8 Tensile shear bond strength at 23°C determination A A A A A A A MPa 30.5 29.6 28.8 30.2 28.0 28.3 28.7

[0206] [Table 3] [Table 3] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 2 Comparative Example 3 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S T800S T800S thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% 90.0 90.0 65.0 99.0 90.0 90.0 60.0 99.9 Thermosetting resin monomers or prepolymers with two or more functions The reaction product with a hardener with two or more functional groups [A] - - - A-2 A-2 A-6 A-7 A-2 A-2 quality% - - 35.0 1.0 10.0 10.0 40.0 0.1 Thermosetting resin monomers or prepolymers with two or more functions jER® 828 quality% 7.5 2.4 - - - - - - SUMI-EPOXY® ELM434 - 4.4 - - - - - - Hardeners with 2 or more functions SEIKACURE-S quality% 2.5 3.2 - - - - - - Mixing temperature ℃ 260 260 260 260 260 260 260 260 Mixed practice time point 5 5 5 5 5 5 5 5 The presence or absence of reaction product [A] - have have have have have have have have Compatibility of thermoplastic resin with reaction product [A] - Miscible Miscible Miscible Miscible Miscible Miscible Phase separation Miscible Structure of the mixture of thermoplastic resin and reaction product [A] - Half IPN Half IPN Half IPN Half IPN Half IPN Half IPN islands Half IPN Welding temperature ℃ 250 250 250 250 250 250 250 250 Dimensional stability during welding determination A A A B B B A D % 4.5 2.8 1.6 7.5 7.0 6.9 1.4 13.0 Tensile shear bond strength at 23°C determination B B C A A A D A MPa 27.4 25.3 20.3 34.0 29.0 28.5 18.9 29.0

[0207] [Table 4] [Table 4] Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% 90.0 90.0 90.0 90.0 90.0 90.0 Thermosetting resin monomers or prepolymers with two or more functions The reaction product with a hardener with two or more functional groups [A] - A-4 A-4 A-6 A-6 A-7 A-7 quality% 10.0 10.0 10.0 10.0 10.0 10.0 Thermoplastic resin used in the second thermoplastic resin layer KEPSTAN® 7002 (Melting point: 331℃) - ○ - ○ - ○ - Thermosetting resin composition (proportion relative to 100% by mass of the total amount of thermosetting resin composition) jER® 828 quality% - twenty two - - - - SUMI-EPOXY® ELM434 - 41 - - - - SEIKACURE-S - 28 - - - - SUMIKAEXCEL® PES5003P - 9 - - - - Fa - - - 57 - - Araldite® MY0610 - - - 38 - - Virantage® VW10700RFP - - - 5 - - Compimide® MDAB - - - - - 39 Compimide® TDAB - - - - - 26 Compimide® TM124 - - - - - 32 Matrimid® 9725 - - - - - 2 The presence or absence of reaction product [A] - have have have have have have Compatibility of thermoplastic resin with reaction product [A] - Miscible Miscible Miscible Miscible Miscible Miscible Structure of the mixture of thermoplastic resin and reaction product [A] - Half IPN Half IPN Half IPN Half IPN Half IPN Half IPN Roughness average length RSm of prepreg μm 53 47 50 43 54 50 The average height of the roughness of the pre-impregnated material, Rc μm 18 twenty four 16 twenty two 20 26 Welding temperature ℃ 250 250 250 250 250 250 Dimensional stability during welding determination A A A A A A % 2.5 0.5 2.9 0.6 2.8 0.6 Tensile shear bond strength at 23°C determination A A A A A A MPa 28.9 28.2 30.2 29.9 29.7 29.3

[0208] [Table 5] [Table 5] B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 B-12 Thermosetting resin monomers or prepolymers with two or more functions jER® 828 quality% 10.0 - - - 7.5 2.4 26.3 0.7 30.0 0.07 - - SUMI-EPOXY® ELM434 - - 10.0 - - 4.4 - - - - - - Fa - - - - - - - - - - 6.0 - Compimide® MDAB - - - - - - - - - - - 4.0 Compimide® TDAB - - - - - - - - - - - 2.7 Hardeners with 2 or more functions SEIKACURE-S quality% - 10.0 - - 2.5 3.2 8.8 0.3 10.0 0.03 - - (3-aminophenyl)phosphine oxide - - - 10.0 - - - - - - - - Araldite® MY0610 - - - - - - - - - - 4.0 - Compimide® TM124 - - - - - - - - - - - 3.3 thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% 90.0 90.0 90.0 90.0 90.0 90.0 65.0 99.0 60.0 99.9 90.0 90.0 Mixing temperature ℃ 260 260 260 260 260 260 260 260 260 260 260 260 Mixed practice time point 30 30 30 30 30+30 30+30 30+30 30+30 30+30 30+30 30 30+30 Solubility in hexafluoroisopropanol - soluble soluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Insoluble Cross-linked structure - none none have have have have have have have have have have

[0209] [Table 6] [Table 6] Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Comparative Example 1 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S T800S T800S Thermosetting resin monomers or prepolymers with two or more functions and / or the reaction product of a hardener with two or more functionalities and a thermoplastic resin [B] - B-1 B-2 B-3 B-4 B-5 B-6 B-1 - quality% 100.0 100.0 100.0 100.0 100.0 100.0 95.0 - Thermosetting resin monomers or prepolymers with two or more functions jER® 828 quality% - - - - - - 3.0 - SUMI-EPOXY® ELM434 - - - - - - - - Hardeners with 2 or more functions SEIKACURE-S quality% - - - - - - 2.0 - thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% - - - - - - - 100.0 The presence or absence of reaction product [A] - none none none none none none have none Compatibility of [A] and [B] - - - - - - - Miscible - Welding temperature ℃ 250 250 250 250 250 250 250 250 Dimensional stability during welding determination B C A B A A A D % 7.4 8.8 4.8 5.7 4.1 3.0 3.2 14.8 Tensile shear bond strength at 23°C determination A A B A B C B A MPa 30.8 30.0 25.6 28.5 27.4 24.8 25.1 28.7

[0210] [Table 7] [Table 7] Example 26 Example 27 Example 28 Example 29 Comparative Example 4 Comparative Example 5 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S Thermosetting resin monomers or prepolymers with two or more functions and / or the reaction product of a hardener with two or more functionalities and a thermoplastic resin [B] - B-7 B-8 B-11 B-12 B-9 B-10 quality% 100.0 100.0 100.0 100.0 100.0 100.0 Thermosetting resin monomers or prepolymers with two or more functions jER® 828 quality% - - - - - - SUMI-EPOXY® ELM434 - - - - - - Hardeners with 2 or more functions SEIKACURE-S quality% - - - - - - thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% - - - - - - The presence or absence of reaction product [A] - none none none none none none Compatibility of [A] and [B] - - - - - - - Welding temperature ℃ 250 250 250 250 250 250 Dimensional stability during welding determination A B B B A D % 1.4 7.0 6.5 6.2 1.1 12.8 Tensile shear bond strength at 23°C determination C A A A D A MPa 20.4 33.7 28.3 28.0 17.0 28.4

[0211] [Table 8] [Table 8] Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S Thermosetting resin monomers or prepolymers with two or more functions and / or the reaction product of a hardener with two or more functionalities and a thermoplastic resin [B] - B-5 B-5 B-11 B-11 B-12 B-12 quality% 100.0 100.0 100.0 100.0 100.0 100.0 Thermoplastic resin used in the second thermoplastic resin layer KEPSTAN® 7002 (Melting point: 331℃) - ○ - ○ - ○ - Thermosetting resin composition (proportion relative to 100% by mass of the total amount of thermosetting resin composition) jER® 828 quality% - twenty two - - - - SUMI-EPOXY® ELM434 - 41 - - - - SEIKACURE-S - 28 - - - - SUMIKAEXCEL® PES5003P - 9 - - - - Ago - - - 57 - - Araldite® MY0610 - - - 38 - - Virantage® VW10700RFP - - - 5 - - Compimide® MDAB - - - - - 39 Compimide® TDAB - - - - - 26 Compimide® TM124 - - - - - 32 Matrimid® 9725 - - - - - 2 The presence or absence of reaction product [A] - none none none none none none Compatibility of [A] and [B] - - - - - - - Roughness average length RSm of prepreg μm 48 42 45 44 50 46 The average height of the roughness of the pre-impregnated material, Rc μm 12 18 12 11 15 12 Welding temperature ℃ 250 250 250 250 250 250 Dimensional stability during welding determination A A A A A A % 1.9 0.2 1.9 0.2 1.7 0.2 Tensile shear bond strength at 23°C determination A A A A A A MPa 28.4 28.0 29.0 28.9 28.8 28.5

[0212] [Table 9] [Table 9] Example 36 Example 37 Example 38 Comparative Example 6 Comparative Example 1 Example 39 Example 40 Example 41 Example 42 Example 43 Comparative Example 7 Comparative Example 8 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S T800S T800S T800S T800S T800S T800S thermoplastic resin Amilan® CM4000 (Melting point: 155℃) quality% - - - - - - - - - - - - Amilan® CM1007 (Melting point: 225℃) 90.0 90.0 90.0 60.0 100.0 65.0 80.0 95.0 94.5 99.0 60.0 99.9 SUMIKAEXCEL® PES5003P (Glass transfer temperature: 225℃) - - - - - - - - 0.5 - - - Torelina® A670T05 (Melting point: 278℃) - - - - - - - - - - - - KEPSTAN® 7002 (Melting point: 331℃) - - - - - - - - - - - - Thermosetting resin monomers or prepolymers with two or more functions...① jER® 828 quality% 10.0 10.0 10.0 40.0 - 25.9 14.8 3.7 3.7 0.7 29.6 0.07 SUMI-EPOXY® ELM434 - - - - - - - - - - - - Hardeners with 2 or more functions...② SEIKACURE-S quality% - - - - - 9.1 5.2 1.3 1.3 0.3 10.4 0.03 DICY - - - - - - - - - - - - Other components (proportions relative to the total amount of thermoplastic resin, ①, and ②, 100% by mass) EPTS quality% - 0.1 - - - - - - - - - - The proportion of ① relative to the total of ① and ② (100% by mass) quality% - - - - - 74 74 74 74 74 74 74 The proportion of ② relative to the total of ① and ② (100% by mass) - - - - - 26 26 26 26 26 26 26 The reactivity of ① and ② - - - - - - have have have have have have have The compatibility of thermoplastic resin with ① and ② - Miscible Miscible Miscible Phase separation - Miscible Miscible Miscible Miscible Miscible Phase separation Miscible The presence or absence of reaction product [B] - none none have none - none none none none none none none Welding temperature ℃ 250 250 250 250 250 250 250 250 250 250 250 250 Dimensional stability during welding determination C B B B D A A A A B A D % 9.2 5.8 7.4 6.2 14.8 1.5 3.0 5.0 4.8 7.7 1.1 13.5 Tensile shear bond strength at 23°C determination A A A D A C B A A A D A MPa 30.5 31.0 30.8 19.5 28.7 20.1 25.2 31.2 32.0 35.3 18.9 29.4

[0213] [Table 10] [Table 10] Example 44 Example 45 Example 46 Example 47 Example 48 Comparative Example 9 Example 49 Comparative Example 10 Example 50 Comparative Example 11 Example 51 Example 52 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S T800S T800S T800S T800S Fiberglass T700S thermoplastic resin Amilan® CM4000 (Melting point: 155℃) quality% - - - - 95.0 100.0 - - - - - - Amilan® CM1007 (Melting point: 225℃) 94.5 95.0 90.0 90.0 - - - - - - 95.0 95.0 SUMIKAEXCEL® PES5003P (Glass transfer temperature: 225℃) 0.5 - - - - - - - - - - - Torelina® A670T05 (Melting point: 278℃) - - - - - - 95.0 100.0 - - - - KEPSTAN® 7002 (Melting point: 331℃) - - - - - - - - 95.0 100.0 - - Thermosetting resin monomers or prepolymers with two or more functions...① jER® 828 quality% 1.2 4.9 - - 3.7 - 3.7 - 3.7 - 3.7 3.7 SUMI-EPOXY® ELM434 2.2 - - - - - - - - - - - Ago - - 6.0 - - - - - - - - - Compimide® MDAB - - - 4.0 - - - - - - - - Compimide® TDAB - - - 2.7 - - - - - - - - Hardeners with 2 or more functions...② SEIKACURE-S quality% 1.6 - - - 1.3 - 1.3 - 1.3 - 1.3 1.3 DICY - 0.1 - - - - - - - - - - Araldite® MY0610 - - 4.0 - - - - - - - - - Compimide® TM124 - - - 3.3 - - - - - - - - Other components (in 100% by mass relative to the total amount of thermoplastic resin, ① and ②) EPTS quality% - - - - - - - - - - - - The proportion of ① relative to the total of ① and ② (100% by mass) quality% 69 97 60 67 74 - 74 - 74 - 74 74 The proportion of ② relative to the total of ① and ② (100% by mass) 31 3 40 33 26 - 26 - 26 - 26 26 The reactivity of ① and ② - have have have have have - have - have - have have The compatibility of thermoplastic resin with ① and ② - Miscible Miscible Miscible Miscible Miscible - Miscible - Miscible - Miscible Miscible The presence or absence of reaction product [B] - none none none none none - none - none - none none Welding temperature ℃ 250 250 250 250 180 180 303 303 356 356 250 250 Dimensional stability during welding determination A B B B A D B D B D B A % 4.1 7.5 7.8 7.5 4.8 16.2 7.8 13.9 7.2 11.1 5.5 4.6 Tensile shear bond strength at 23°C determination A A A A A A B B A A A A MPa 32.3 32.7 33.0 32.5 33.7 34.8 27.5 27.9 30.2 30.6 30.5 28.3

[0214] [Table 11] [Table 11] Example 53 Example 54 Example 55 Example 56 Example 57 Example 58 Reinforced Fibers variety T800S T800S T800S T800S T800S T800S thermoplastic resin Amilan® CM1007 (Melting point: 225℃) quality% 95.0 95.0 90.0 90.0 90.0 90.0 Thermosetting resin monomers or prepolymers with two or more functions...① jER® 828 quality% 3.7 1.2 - - - - SUMI-EPOXY® ELM434 - 2.2 - - - - Fa - - 6.0 6.0 - - Compimide® MDAB - - - - 4.0 4.0 Compimide® TDAB - - - - 2.7 2.7 Hardeners with 2 or more functions...② SEIKACURE-S quality% 1.3 1.6 - - - - SUMI-EPOXY® ELM434 - - - - - - Araldite® MY0610 - - 4.0 4.0 - - Compimide® TM124 - - - - 3.3 3.3 Thermoplastic resin used in the second thermoplastic resin layer KEPSTAN® 7002 (Melting point: 331℃) - ○ - ○ - ○ - Thermosetting resin composition (proportion relative to 100% by mass of the total amount of thermosetting resin composition) jER® 828 quality% - twenty two - - - - SUMI-EPOXY® ELM434 - 41 - - - - SEIKACURE-S - 28 - - - - SUMIKAEXCEL® PES5003P - 9 - - - - Ago - - - 57 - - Araldite® MY0610 - - - 38 - - Virantage® VW10700RFP - - - 5 - - Compimide® MDAB - - - - - 39 Compimide® TDAB - - - - - 26 Compimide® TM124 - - - - - 32 Matrimid® 9725 - - - - - 2 The proportion of ① relative to the total of ① and ② (100% by mass) quality% 74% 69% 60% 60% 67% 67% The proportion of ② relative to the total of ① and ② (100% by mass) 26% 31% 40% 40% 33% 33% The reactivity of ① and ② - have have have have have have The compatibility of thermoplastic resin with ① and ② - Miscible Miscible Miscible Miscible Miscible Miscible The presence or absence of reaction product [B] - none none none none none none Roughness average length RSm of prepreg μm 51 45 46 40 48 46 The average height of the roughness of the pre-impregnated material, Rc μm 15 twenty two 20 twenty four twenty one twenty two Welding temperature ℃ 250 250 250 250 250 250 Dimensional stability during welding determination A A A A A A % 2.0 0.3 2.1 0.3 2.3 0.3 Tensile shear bond strength at 23°C determination A A A A A A MPa 30.3 29.8 31.0 30.5 30.7 31.2

[0215] 1: Composite prepreg 2: Reinforced Fibers 3: First thermoplastic resin layer 4: Second thermoplastic resin layer or thermosetting resin layer 5: Interface 6: Strengthen the fiber direction 7: Observe the cross-section 8: Baseline 9: Vertical baseline 10: Profile Curve

Claims

1. A prepreg having a thermoplastic resin layer comprising reinforcing fibers and a thermoplastic resin, wherein the thermoplastic resin layer is present on at least one surface of the prepreg, the thermoplastic resin layer comprising, with respect to 100% by mass, 65.0-99.5% by mass of thermoplastic resin constituent units, and a total of 0.5-35.0% by mass of thermoplastic resin constituent units and curing agent constituent units; the reinforcing fiber being selected from one or more of glass fiber, carbon fiber, metal fiber, aromatic polyamide fiber, polyarylamide fiber, alumina fiber, silicon carbide fiber, boron fiber, and basalt fiber. The thermoplastic resin has bonds selected from the group consisting of carbon-carbon bonds, amide bonds, amide bonds, ester bonds, ether bonds, carbonate bonds, carbamate bonds, thioether bonds, ion bonds, and carbonyl bonds in its main chain. The thermosetting resin is epoxy resin, benzo[a]ethylene resin, bismaleimide resin, unsaturated polyester resin, vinyl ester resin, phenol resin, urea resin, melamine resin, and thermosetting polyimide resin, as well as modified versions of these and resins blended with two or more of them. The curing agent is a curing agent with two or more functions.

2. The prepreg of claim 1 is in the form of a reaction product [A] of a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions, such that the thermoplastic resin layer contains the constituent units of the thermosetting resin and / or the constituent units of the curing agent.

3. The prepreg of claim 2, wherein the reaction product [A] is compatible with the thermoplastic resin.

4. The prepreg of claim 2, wherein the reaction product [A] forms a semi-IPN structure or an IPN structure with the thermoplastic resin.

5. The prepreg of claim 1 is in the form of a reaction product [B] formed by reacting the thermoplastic resin with a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions, such that the thermoplastic resin layer contains the constituent units of the thermosetting resin and / or the constituent units of the curing agent.

6. The prepreg of claim 5, wherein the reaction product [B] is soluble in the solvent.

7. The prepreg of claim 5, wherein the reaction product [B] has a cross-linked structure.

8. The prepreg of claim 1 is in the form of a thermosetting resin monomer or prepolymer with two or more functions and / or a curing agent with two or more functions, such that the thermoplastic resin layer contains the constituent units of the thermosetting resin and / or the constituent units of the curing agent.

9. The prepreg of claim 8, wherein the thermosetting resin monomer or prepolymer with two or more functions and / or the curing agent with two or more functions is compatible with the thermoplastic resin.

10. The prepreg of claim 8, wherein the molecular weight calculated from the structural formula or the weight average molecular weight determined by gel permeation chromatography of the thermosetting resin monomer or prepolymer and / or the curing agent with more than two functions is less than 3,000 g / mol.

11. The prepreg of claim 8, wherein the thermoplastic resin is tackified by reaction of a thermosetting resin monomer or prepolymer with two or more functions and a curing agent with two or more functions.

12. The prepreg of claim 11, wherein the tackification of the thermoplastic resin occurs by heating the prepreg.

13. The prepreg of claim 12, wherein the thickening of the thermoplastic resin occurs during the molding of the fiber-reinforced resin molded article.

14. The prepreg of claim 12, wherein the tackification of the thermoplastic resin occurs during the manufacture of the integrally molded article.

15. The prepreg of claim 11, wherein at a temperature of 25°C above the melting point of the thermoplastic resin (or 100°C above the glass transition temperature if the melting point is not specified), the viscosity of the tackified thermoplastic resin is 2 to 2000 times that of the untackified thermoplastic resin.

16. The prepreg of claim 1, 2, 5 or 8, wherein the thermoplastic resin is selected from the group consisting of polyamide, polyurethane, polyetherurethane, polyetherimide, polyaryl sulfide, polyetherketone ketone and polyaryl ether ketone.

17. The prepreg as claimed in items 1, 2, 5 or 8, wherein the thickness direction of the prepreg encompasses the thermoplastic resin layer throughout.

18. The prepreg as claimed in items 1, 2, 5 or 8, wherein the reinforcing fiber is carbon fiber.

19. The prepreg of claim 1, 2, 5 or 8, wherein, relative to 100% by mass of the total constituent units of the thermosetting resin and the constituent units of the hardener, it comprises 60.0 to 99.5% by mass of the thermosetting resin constituent units and 0.5 to 40.0% by mass of the hardener constituent units.

20. The prepreg of claim 2, 5 or 8, wherein the thermosetting resin monomer or prepolymer with two or more functions is at least one epoxy resin monomer or prepolymer.

21. The prepreg of claim 2, 5 or 8, wherein the curing agent with two or more functions is an amine compound with two or more functions.

22. The prepreg of claim 21, wherein the amine compound with two or more functions is an aromatic polyamine compound.

23. The prepreg of claim 1, 2, 5 or 8, having the thermoplastic resin layer and any of the following layers bonded to each other at an interface with the thermoplastic resin layer: (1) a second thermoplastic resin layer comprising reinforcing fibers and at least one thermoplastic resin having constituent units different from the thermoplastic resin; or (2) a thermosetting resin layer comprising reinforcing fibers and at least one thermosetting resin and / or a curing agent.

24. The prepreg of claim 23, wherein in the thickness direction, the roughness mean length RSm of the profile curve formed by the interface is less than 100 μm and the roughness mean height Rc is more than 3.5 μm.

25. The prepreg of claim 1, comprising the thermoplastic resin layer and a thermosetting resin layer containing reinforcing fibers and at least one thermosetting resin and / or a hardener bonded to the thermoplastic resin layer at an interface: the thermoplastic resin layer is in the form of a reaction product of a thermosetting resin monomer or prepolymer with two or more functions and an amine compound with two or more functions, or in the form of a reaction product [B] of the thermoplastic resin reacting with a thermosetting resin monomer or prepolymer with two or more functions and / or an amine compound with two or more functions, or in the form of a thermosetting resin monomer or prepolymer with two or more functions and / or an amine compound with two or more functions, containing the constituent units of the thermosetting resin and / or the constituent units of the hardener; and the thermosetting resin layer is a layer with the thermosetting resin monomer or prepolymer with two or more functions and the amine compound with two or more functions as the main components.

26. A fiber-reinforced resin molded article formed by molding a preform comprising a prepreg as claimed in claims 1, 2, 5 or 8.

27. A fiber-reinforced resin molded article, which is formed by molding a preform comprising a prepreg as claimed in claim 23.

28. The fiber-reinforced resin molded article of claim 27, wherein when a pressure of 1 MPa is applied and held for 6 minutes at a temperature of 25°C above the melting point of the thermoplastic resin (or 100°C above the glass transition temperature if the melting point is not specified), the dimensional stability at the time of welding is less than 10% (here, the dimensional stability at the time of welding is expressed as the rate of change of thickness before and after welding, calculated by (T1+T2-T3) / (T1+T2)×100, when the average thickness of the two fiber-reinforced resin molded articles before welding is set as T1 and T2 respectively, and the average thickness of the integral molded article after welding is set as T3).

29. A monolithic article formed by fusing a fiber-reinforced resin molded body as claimed in any one of claims 26 to 28 with other components through the thermoplastic resin layer.

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