Materials for molding fiber-reinforced plastics and methods for manufacturing laminated articles

Abstract

A fiber-reinforced plastic molding material and a method for manufacturing a laminated body. The manufacturing method is characterized by: laminating a fiber-reinforced plastic molding material having phenyloxy resin as a matrix resin and a fiber-reinforced plastic molding material having polycarbonate resin as a matrix resin, and performing molding processing at a temperature above 260°C. The fiber-reinforced plastic laminated body contains phenyloxy resin and polycarbonate resin, and reinforcing fibers, and comprises multiple layers, including one or more interlayer bonding sites where layers containing the phenyloxy resin and layers containing the polycarbonate resin are bonded at their lamination interfaces through a cross-linking reaction.

Description

[0001] This application is a divisional application of application number 202080021806.2, filed on March 25, 2020, entitled Resin Composition, Hardened Molded Article, Molding Material, Fiber Reinforced Plastic, Laminated Article and Method for Manufacturing the Same. Technical Field

[0002] This invention relates to a resin composition, a cured molded article using the resin composition, a material for molding fiber-reinforced plastics, fiber-reinforced plastics, fiber-reinforced plastic laminates, and a method for manufacturing the same. Background Technology

[0003] Carbon fiber reinforced plastic (CFRP), representing fiber reinforced plastic (FRP), is a lightweight and high-strength material widely used in various components of sporting goods such as bicycles or tennis rackets, as well as automobiles, railway vehicles, and aircraft.

[0004] Phenoxy resin, as a thermoplastic resin, possesses good formability, excellent adhesion, and, through the use of a crosslinking agent, can exhibit properties similar to those of thermosetting resins with high heat resistance. As a technique utilizing phenoxy resin, for example, the following method is proposed: a powder of phenoxy resin or a resin composition of phenoxy resin mixed with a crystalline epoxy resin and an anhydride as a crosslinking agent is applied to a fiber-reinforced substrate by a powder coating method to produce a prepreg, which is then molded and cured by hot pressing to manufacture fiber-reinforced plastic (FRP) (Patent Document 1).

[0005] On the other hand, polycarbonate resin, as a thermoplastic resin, possesses excellent mechanical strength and heat resistance, and can be widely used in various industrial applications such as electrical and electronic machinery and automobiles. Furthermore, polycarbonate resin reinforced with glass fiber is used for frames in various electrical and electronic machinery due to its superior strength and rigidity.

[0006] To improve the mechanical strength and other properties of FRP, for example, a scheme has been proposed to mix a small amount of one or more hydroxyl-containing polymers selected from phenoxy resins or epoxy resins into polycarbonate resin (Patent Document 2). Another scheme has been proposed to mix a small amount of phenoxy resin into aromatic condensation polymers such as polyaryl ether sulfone, polyaryl ether ketone, polycarbonate, and polyetherimide (Patent Document 3).

[0007] In Patent Document 2, it is argued that if the proportion of hydroxyl-containing polymers in the resin component exceeds 50% by weight, sufficient mechanical strength cannot be obtained. In Patent Document 3, the concentration of phenoxy resin is set to approximately 30% by weight or less of the total composition, including fibers, which is less than that in Patent Document 2. Furthermore, Patent Document 3 does not disclose specific examples of adding phenoxy resin to polycarbonate resin.

[0008] However, in recent years, efforts have been made to utilize thermoplastic resins to impart impact resistance or recyclability to CFRP. For example, proposals have been made not only to simply replace the matrix resin with a thermoplastic resin, but also to incorporate thermoplastic resin microparticles into the epoxy resin matrix, or to configure a thermoplastic resin film in the intermediate layer of the CFRP (Patent Document 4).

[0009] In addition, it has been proposed that the outermost layer of a CFRP made of thermoplastic resin be configured as an adhesive layer (Patent Document 5), or that a CFRP molding material in which two different thermoplastic resins are configured on each side of a pad-shaped substrate containing short fibers and reinforcing fibers is used (Patent Document 6).

[0010] The polycarbonate resin described as a preferred resin in Patent Documents 4 to 6 is characterized by its particularly excellent impact resistance among thermoplastic resins, but it has the disadvantage of slightly poor adhesion to other resins. Therefore, in applications for structural components, there is a risk of peeling due to external stress, resulting in a significant reduction in the strength of the structure, thus limiting its use or application.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: International Publication No. WO2016 / 152856

[0014] Patent Document 2: Japanese Patent No. 2968388

[0015] Patent Document 3: Japanese Patent Publication No. 2005-536597

[0016] Patent Document 4: Japanese Patent No. 6278286

[0017] Patent Document 5: International Publication No. WO2018 / 124215

[0018] Patent Document 6: Japanese Patent No. 5626330 Summary of the Invention

[0019] The problem that the invention aims to solve

[0020] The purpose of this invention is to provide a novel resin composition and its uses that have excellent heat resistance and mechanical strength, and can be effectively used as a material such as FRP.

[0021] Technical means to solve the problem

[0022] The resin composition of the present invention is a resin composition containing a first resin and a second resin different from the first resin, and exhibiting curing properties through thermal crosslinking.

[0023] In the resin composition of the present invention, the first resin is selected from one or more of the group consisting of difunctional epoxy resins and phenoxy resins having a weight average molecular weight of 4,000 or more, and the second resin is a polycarbonate resin.

[0024] In the resin composition of the present invention, the content ratio of the first resin to the second resin (first resin: second resin) by weight can be in the range of 9:1 to 3:7.

[0025] In the resin composition of the present invention, both the first resin and the second resin may have an intramolecular bisphenol backbone.

[0026] In the resin composition of the present invention, the hardened product formed by thermally crosslinking the resin composition may have a glass transition temperature (Tg) of 100°C or higher as determined by dynamic viscoelasticity measurement (dynamic thermomechanical analysis, DMA), and the hardened product may also not have a melting point (Tm).

[0027] In the resin composition of the present invention, the displacement of the probe after the hardened product formed by thermal crosslinking of the resin composition is measured in a dynamic viscoelasticity test (DMA) at a temperature in the range of 25°C to 300°C, can be less than -1 mm from the reference temperature before the test.

[0028] The cured molded articles of the present invention comprise cured articles of the resin compositions described in any one of the claims.

[0029] The fiber-reinforced plastic molding material of the present invention comprises a reinforcing fiber substrate and a powder of any of the resin compositions attached to the reinforcing fiber substrate.

[0030] The fiber-reinforced plastic of the present invention has a reinforcing fiber substrate and a hardened form of any of the resin compositions attached to the reinforcing fiber substrate.

[0031] Furthermore, the fiber-reinforced plastic laminate of the present invention is a fiber-reinforced plastic laminate containing phenoxy resin and polycarbonate resin, and reinforcing fibers, and comprising multiple layers. The fiber-reinforced plastic laminate of the present invention is characterized by comprising one or more interlayer bonding sites where layers containing the phenoxy resin and layers containing the polycarbonate resin are bonded at their lamination interfaces through a crosslinking reaction.

[0032] In the fiber-reinforced plastic laminate of the present invention, the layers containing the phenoxy resin and the layers containing the polycarbonate resin can be alternately laminated.

[0033] In the fiber-reinforced plastic laminate of the present invention, the interlaminar shear strength of the interlaminar bonding sites joined by the crosslinking reaction can be 40 MPa or more as measured by the interlaminar shear strength (ILSS) method.

[0034] In the fiber-reinforced plastic laminate of the present invention, the reinforcing fiber may be a continuous fiber selected from at least one of carbon fiber, glass fiber, ceramic fiber, metal fiber and organic fiber.

[0035] The first aspect of the present invention discloses a method for manufacturing a fiber-reinforced plastic laminate, wherein the method manufactures any of the fiber-reinforced plastic laminates, characterized in that:

[0036] A fiber-reinforced plastic molding material having phenyl oxy resin as a matrix resin and a fiber-reinforced plastic molding material having polycarbonate resin as a matrix resin are laminated and molded at a temperature of 260°C or higher.

[0037] The second aspect of the present invention discloses a method for manufacturing a fiber-reinforced plastic laminate, wherein the method comprises:

[0038] The steps for preparing a fiber-reinforced plastic molding material in which one side of a plurality of reinforcing fiber substrates is coated with phenylene oxide resin and the other side is coated with polycarbonate resin; and

[0039] The step of laminating multiple fiber-reinforced plastic molding materials in a manner that includes the lamination boundary between phenoxy resin and polycarbonate resin, and performing molding processing at a temperature of 260°C or higher.

[0040] In the second aspect of the present invention, the method for manufacturing a fiber-reinforced plastic laminated article allows fiber-reinforced plastic molding materials having phenyloxy resin as a matrix resin and / or fiber-reinforced plastic molding materials having polycarbonate resin as a matrix resin to exist separately between a plurality of said fiber-reinforced plastic molding materials and to be laminated.

[0041] In the second aspect of the present invention, the method for manufacturing a fiber-reinforced plastic laminated article allows for the interposition of a phenoxy resin film and / or a polycarbonate resin film between a plurality of said fiber-reinforced plastic molding materials and their lamination.

[0042] The third aspect of the present invention discloses a method for manufacturing a fiber-reinforced plastic laminate, wherein the method for manufacturing the fiber-reinforced plastic laminate is characterized by:

[0043] A fiber-reinforced plastic molding material having phenyloxy resin as the matrix resin and a polycarbonate resin film are laminated and molded at a temperature above 260°C.

[0044] The fourth aspect of the present invention discloses a method for manufacturing a fiber-reinforced plastic laminate, wherein the method for manufacturing the fiber-reinforced plastic laminate is characterized by:

[0045] A fiber-reinforced plastic molding material having polycarbonate resin as the matrix resin and a phenylene oxide film are laminated and molded at a temperature above 260°C.

[0046] The fiber-reinforced plastic molding material of the present invention includes: a reinforcing fiber substrate, a phenoxy resin coating layer formed on one side of the reinforcing fiber substrate, and a polycarbonate resin coating layer formed on the other side of the reinforcing fiber substrate.

[0047] In the fiber-reinforced plastic molding material of the present invention, the reinforcing fiber substrate may be a woven fabric containing continuous fibers or a unidirectional (UD) material in which the continuous fibers are unidirectionally aligned.

[0048] The effects of the invention

[0049] The resin composition according to the present invention provides a resin material with excellent heat resistance and mechanical strength. Therefore, the resin composition of the present invention is preferably used to manufacture various resin molded articles or composite materials such as FRP that require heat resistance or strength. Attached Figure Description

[0050] Figure 1 This is a schematic diagram illustrating a method for manufacturing an FRP laminated molded article according to an embodiment of the present invention.

[0051] Figure 2 This is a schematic diagram illustrating a method for manufacturing an FRP laminated article according to another embodiment of the present invention.

[0052] Figure 3 This is a schematic diagram illustrating a method for manufacturing an FRP laminated article according to another embodiment of the present invention.

[0053] Figure 4 This is a schematic diagram illustrating a method for manufacturing an FRP laminated molded article according to yet another embodiment of the present invention.

[0054] Figure 5 This is a graph showing the results of viscosity measurements of the resin compositions obtained in the examples and comparative examples.

[0055] [Explanation of Symbols]

[0056] 10: Materials for Phenoxy Resin FRP Molding

[0057] 20: Materials for FRP molding of polycarbonate resin

[0058] 30: FRP laminated body (prepreg laminate)

[0059] 40: Polycarbonate resin film

[0060] 50A, 50B: FRP laminated bodies (membrane insertion laminates)

[0061] 60: Phenoxy resin film

[0062] 70: Reinforced fiber substrate

[0063] 80: Materials for hybrid FRP molding

[0064] 90: FRP laminated body (mixed prepreg laminate) Detailed Implementation

[0065] The embodiments of the present invention will now be described in detail.

[0066] [Resin Composition]

[0067] The resin composition of this embodiment is a resin composition containing a first resin and a second resin different from the first resin, and exhibits curing properties through thermal crosslinking.

[0068] The first resin is selected from one or more of a difunctional epoxy resin (hereinafter sometimes referred to as "difunctional epoxy resin") with a weight average molecular weight of 4,000 or more, and a phenoxy resin. The second resin is a polycarbonate resin.

[0069] The resin composition of this embodiment uses either or both of the first resin and the second resin as the main component. Here, "main component" refers to the component contained most abundantly in the resin composition. In order to exhibit the effects of the invention, in the resin composition of this embodiment, the total amount of the first resin and the second resin is preferably 50 parts by weight or more, more preferably 80 parts by weight or more and 100 parts by weight or less, relative to the total amount of 100 parts by weight of the resin composition. Furthermore, the "resin composition" includes thermoplastic resins or thermosetting resins other than difunctional epoxy resins, phenoxy resins, and polycarbonate resins, but does not include non-resin components such as crosslinking agents.

[0070] <Difunctional epoxy resin>

[0071] The term "difunctional epoxy resin with a weight average molecular weight of 4,000 or more" as the primary resin specifically refers to a linear high molecular weight epoxy resin with a weight average molecular weight (Mw) between 4,000 and 10,000, and which has epoxy groups at both ends of the molecular chain. Epoxy resins with a Mw of less than 4,000 are unsuitable because they have a low softening point, are prone to sticking, and make workability during mixing and processing into resin compositions difficult. Furthermore, difunctional epoxy resins with a Mw of 10,000 or more are generally treated as thermoplastic resins referred to later as phenoxy resins.

[0072] Furthermore, Mw represents the value obtained by gel permeation chromatography and conversion using a standard polystyrene calibration curve.

[0073] As previously explained, any existing known difunctional epoxy resin can be used as the first resin, provided it is a linear difunctional epoxy resin with a weight average molecular weight of 4,000 or more. A difunctional epoxy resin with a softening point of 90°C or higher and having a bisphenol backbone is preferred. Furthermore, the softening point of the difunctional epoxy resin is preferably 100°C or higher, and more preferably 110°C or higher.

[0074] Examples of such difunctional epoxy resins with a bisphenol backbone include: bisphenol A type epoxy resins (e.g., Epotohto YD-014, YD-017, YD-019 manufactured by Nippon Steel Chemical & Materials Co., Ltd., and JER1010 manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol F type epoxy resins (e.g., Epotohto YDF-2005RL manufactured by Nippon Steel Chemical & Materials Co., Ltd., and JER4007P, JER4009P manufactured by Mitsubishi Chemical Co., Ltd.), and bisphenol sulfide type epoxy resins (e.g., YSLV-120TE manufactured by Nippon Steel Chemical & Materials Co., Ltd.), but are not limited to these, and may also be used in combination of two or more of these.

[0075] Furthermore, although the preferred high molecular weight derivatives as the first resin, namely difunctional epoxy resin and phenoxy resin, have roughly the same chemical structure, they are distinguished in the following aspects.

[0076] (1) The Mw of the phenoxy resin is 10,000 or more (more generally, Mw is 40,000 or more), while the Mw of this epoxy resin is less than 10,000 (more generally, Mw is around 4,000 to 6,000).

[0077] (2) The number of grams of epoxy groups containing one gram equivalent of the high molecular weight difunctional epoxy resin, i.e., the epoxy equivalent, is 700 g / eq to 5,000 g / eq, which is more than 6,000 g / eq relative to the phenoxy resin.

[0078] (3) Phenoxy resins, due to their large molecular weight (Mw), exhibit strong thermoplastic properties and can generally be used without a curing agent. In contrast, difunctional epoxy resins, being high molecular weight compounds, typically require a curing agent in their applications. However, when a difunctional epoxy resin is used in the resin composition of this embodiment, no curing agent is used.

[0079] <Phenoxy Resin>

[0080] The phenoxy resin used as the first resin is a thermoplastic polyhydroxy polyether resin obtained by condensation reaction of a divalent phenol compound with an epihaloalcohol or by addition polymerization reaction of a divalent phenol compound with a difunctional epoxy resin, and can be obtained in a solvent or without a solvent by existing known methods.

[0081] The phenoxy resin preferably used in this invention is solid at room temperature, and its melt viscosity at temperatures above 200°C is preferably below 3,000 Pa·s, more preferably below 2,000 Pa·s, further preferably below 1,500 Pa·s, and most preferably below 1,000 Pa·s. If the melt viscosity exceeds 3,000 Pa·s, the resin's fluidity decreases during molding, the resin cannot be fully distributed throughout the material, and porosity is formed, which is undesirable.

[0082] Examples of divalent phenolic compounds used in the manufacture of phenoxy resins include: hydroquinone, resorcinol, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ketone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, and 1,1-bis(4-hydroxyphenyl)propane. Examples of bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,3-bis(2-(4-hydroxyphenyl)propyl)benzene, 1,4-bis(2-(4-hydroxyphenyl)propyl)benzene, 2,2-bis(4-hydroxyphenyl)-1,1,1-3,3,3-hexafluoropropane, 9,9'-bis(4-hydroxyphenyl)fluorene, etc.

[0083] Of these, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ketone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), or 9,9'-bis(4-hydroxyphenyl)fluorene are particularly preferred.

[0084] In addition, examples of difunctional epoxy resins used in the manufacture of phenoxy resins include epoxy oligomers obtained by the condensation reaction of the divalent phenol compound with epihaloalcohol, such as hydroquinone diglycidyl ether, resorcinol diglycidyl ether, bisphenol S type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, methyl hydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl oxide diglycidyl ether, 2,6-dihydroxynaphthalene diglycidyl ether, dichlorobisphenol A diglycidyl ether, tetrabromobisphenol A type epoxy resin, and 9,9'-bis(4-hydroxyphenyl)fluorene diglycidyl ether.

[0085] Among these, bisphenol A type epoxy resin, bisphenol S type epoxy resin, hydroquinone diglycidyl ether, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, or 9,9'-bis(4-hydroxyphenyl)fluorene diglycidyl ether are preferred.

[0086] The manufacture of phenoxy resin can be carried out in the absence of a solvent or in the presence of a reaction solvent. As a reaction solvent, aprotic organic solvents such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, and sulfolane are preferably used. Furthermore, the phenoxy resin obtained in the solvent reaction can be prepared into a solvent-free solid resin by undergoing a solvent removal treatment. In the manufacture of phenoxy resin, known polymerization catalysts such as alkali metal hydroxides, tertiary amine compounds, tetraammonium compounds, triphosphine compounds, and tetraphosphonium compounds are preferably used as reaction catalysts.

[0087] The average molecular weight of phenoxy resin, expressed as weight average molecular weight (Mw), is typically 10,000 to 200,000, but preferably 20,000 to 100,000, more preferably 30,000 to 100,000, and most preferably 40,000 to 80,000. If the Mw of the phenoxy resin is too low, the strength of the molded article will be poor; if it is too high, the workability or processability will easily deteriorate. Furthermore, Mw represents the value determined by gel permeation chromatography and converted using a standard polystyrene calibration curve.

[0088] The hydroxyl equivalent (g / eq) of phenoxy resin is typically 1000 or less, but preferably 750 or less, and particularly preferably 500 or less. More specifically, the hydroxyl equivalent (g / eq) of phenoxy resin is typically 50 to 1000, but preferably 100 to 750, and particularly preferably 200 to 500. If the hydroxyl equivalent is too low, the number of hydroxyl groups increases, leading to increased water absorption and a potential decrease in mechanical properties. If the hydroxyl equivalent is too high, the crosslinking density is insufficient, resulting in decreased heat resistance of the cured material, which is undesirable. Furthermore, if the hydroxyl equivalent is too high, there are fewer hydroxyl groups, thus reducing the wettability with the reinforcing fiber matrix, especially carbon fibers, and therefore, sufficient reinforcing effect cannot be expected when reinforcing carbon fibers. Here, the hydroxyl equivalent referred to in this specification refers to the secondary hydroxyl equivalent. Moreover, the terminal functional groups of the polymer chain of phenoxy resin may have either epoxy groups or hydroxyl groups, or both.

[0089] The glass transition temperature (Tg) of the phenoxy resin is preferably 65°C or higher and 200°C or lower, more preferably 180°C or lower, and more preferably within the range of 65°C to 180°C. If the Tg of the phenoxy resin is higher than 200°C, the melt viscosity becomes higher, making it difficult to impregnate the resin composition of this embodiment into the reinforcing fiber substrate without defects such as pores when applied to, for example, FRP. In addition, if the Tg exceeds 200°C, the fluidity of the resin during molding and processing becomes lower, requiring processing at higher temperatures, which is therefore less desirable. On the other hand, there is no particular limitation on the lower limit of Tg as long as there are no problems with processability; a value of approximately 65°C is acceptable. If the glass transition temperature is lower than 65°C, the formability is good, but there is a risk of a decrease in the retention rate of the tensile elastic modulus or the retention rate of dimensional change.

[0090] Furthermore, the glass transition temperature of phenoxy resin is determined using a differential scanning calorimeter under a heating rate of 10℃ / min within a range of 20℃ to 280℃, and the value is obtained by taking the peak value from a second scan.

[0091] Commercially available phenoxy resins can be used, such as: bisphenol A type phenoxy resins (e.g., Phenoto YP-50, Phenoto YP-50S, Phenoto YP-55U manufactured by Nippon Steel Chemicals & Materials Co., Ltd.), bisphenol F type phenoxy resins (e.g., Phenoto FX-316 manufactured by Nippon Steel Chemicals & Materials Co., Ltd.), copolymerized phenoxy resins of bisphenol A and bisphenol F (e.g., YP-70 manufactured by Nippon Steel Chemicals & Materials Co., Ltd.), and other special phenoxy resins such as brominated phenoxy resins, phosphorus-containing phenoxy resins, and sulfone-containing phenoxy resins (e.g., Phenoto YPB-43C, Phenoto FX293, YPS-007, etc. manufactured by Nippon Steel Chemicals & Materials Co., Ltd.). These can be used alone or in combination.

[0092] <Polycarbonate resin>

[0093] The polycarbonate resin used as a second resin can be obtained, for example, by reacting divalent phenol, or divalent phenol and a small amount of polyhydroxy compound with a carbonate precursor.

[0094] There are no particular limitations on the manufacturing method of polycarbonate resin; it can be manufactured using existing known methods such as the phosgene method (interfacial polymerization) or the melt method (transesterification).

[0095] In polycarbonate resins, considering compatibility with difunctional epoxy resins or phenoxy resins, aromatic polycarbonate resins obtained from aromatic dihydroxy compounds are preferred. Examples of aromatic dihydroxy compounds include: 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,2-bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,1-bis(4-hydroxyphenyl-3-tert-butylphenyl)propane, 1,2 ... (4-Hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, etc. These can be used alone or in combination of two or more.

[0096] In addition, examples of carbonate precursors include carbonyl halide, carbonyl ester, or haloformate, specifically phosgene, diphenyl carbonate, dihaloformates of divalent phenol, and mixtures thereof. When manufacturing polycarbonate resins, appropriate molecular weight regulators or catalysts to promote the reaction may also be used. Two or more aromatic polycarbonate resins thus obtained may also be mixed.

[0097] Polycarbonate resins can be linear or branched. To obtain a branched polycarbonate resin, a portion of the divalent phenol can be substituted using, for example, the following branching agents: pyrogallol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-3-heptene, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, or compounds such as 3,3-bis(4-hydroxyaryl)hydroxyindole (=isatinbisphenol), 5-chloroindigo, 5,7-dichloroindigo, 5-bromoindigo. The amount of these substituted compounds used relative to divalent phenol is typically 0.01 mol% to 10 mol%, preferably 0.1 mol% to 2 mol%.

[0098] As the polycarbonate resin, it is preferably a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane, or a polycarbonate copolymer derived from 2,2-bis(4-hydroxyphenyl)propane and other dihydroxy compounds. Alternatively, it may be a copolymer with polycarbonate resin as the main component, such as a copolymer with a polymer or oligomer having a siloxane structure.

[0099] When using a melt method to obtain polycarbonate resin, the amount of OH groups at the ends of the polymer chains can be adjusted, but the end structure of the polycarbonate resin is not particularly limited in this invention. Therefore, the end groups can remain in their original state or be sealed using an end-capping agent, and the sealing can be single-end or double-end sealing.

[0100] There is no particular limitation on the weight average molecular weight (Mw) of the polycarbonate resin, but from the viewpoint of ensuring the mechanical strength of the molded article, it is preferably in the range of 10,000 to 250,000, more preferably in the range of 15,000 to 200,000, and most preferably in the range of 15,000 to 100,000. If the Mw of the polycarbonate resin is too low, the mechanical properties or heat resistance of the molded article may deteriorate; if it is too high, the workability or processability may easily deteriorate. If the Mw is less than 10,000, the strength of the molded article is poor; if it is too high, the workability or processability may easily deteriorate. Furthermore, Mw represents the value obtained by measuring using gel permeation chromatography and converting it using a standard polystyrene calibration curve.

[0101] The polycarbonate resin preferably used in this invention is solid at room temperature, and its melt viscosity at temperatures above 260°C, such as 280°C, is preferably 3,000 Pa·s or less, more preferably 2,000 Pa·s or less, and even more preferably 1,500 Pa·s or less. If the melt viscosity exceeds 3,000 Pa·s, the resin's fluidity decreases during molding, the resin cannot be sufficiently distributed throughout the material, and porosity or impregnation becomes insufficient, resulting in insufficient appearance or mechanical strength, which is therefore undesirable. The lower limit of the melt viscosity is preferably above 100 Pa·s, more preferably above 300 Pa·s, and most preferably above 500 Pa·s. When the melt viscosity is below 100 Pa·s, the matrix resin becomes brittle, and therefore sometimes it is not possible to obtain sufficient mechanical strength such as flexural properties.

[0102] The glass transition temperature (Tg) of the polycarbonate resin only needs to be below 200°C, preferably in the range of 140°C to 170°C, and more preferably in the range of 145°C to 165°C. If the Tg of the polycarbonate resin is higher than 200°C, the melt viscosity becomes higher, and when the resin composition of this embodiment is applied to, for example, FRP, it is difficult to impregnate the reinforcing fiber substrate without defects such as pores. On the other hand, there is no particular limitation on the lower limit of Tg as long as it does not cause problems with processability, and it is considered that it only needs to be about 140°C or higher.

[0103] Furthermore, regarding the melting point (Tm) of polycarbonate resin, although a precise Tm is not explicitly defined, it can be in the range of 200°C to 300°C, preferably 220°C to 280°C, and more preferably 240°C to 260°C. If the melting point is less than 200°C, for example, in the case of FRP, there is a risk that the crosslinking reaction will begin before the reinforcing fiber substrate is sufficiently impregnated. If the melting point exceeds 300°C, a molding machine with a higher temperature rating will be required during processing.

[0104] <Composition Ratio>

[0105] The resin composition preferably has a weight ratio (first resin: second resin) of 9:1 to 3:7 for the first resin and the second resin. Within this range, the cured product formed by thermal crosslinking of the resin composition exhibits excellent heat resistance and mechanical properties. According to this viewpoint, the weight ratio (first resin: second resin) is more preferably in the range of 9:1 to 4:6, further preferably in the range of 8:2 to 4:6, and most preferably in the range of 8:2 to 5:5. If the weight ratio (first resin: second resin) deviates from 3:7 with less first resin, or deviates from 9:1 with less second resin, the crosslinking density of the crosslinked cured product of the first and second resins decreases, thus failing to achieve a significant improvement in heat resistance or mechanical strength.

[0106] A particularly preferred combination of the first and second resins is a combination of resins in which both the first and second resins have an intramolecular bisphenol backbone. By ensuring that both the first and second resins have an intramolecular bisphenol backbone, compatibility is improved, and a uniform cured product is easily obtained.

[0107] <Any ingredient>

[0108] The resin composition of this embodiment may include, without compromising the effects of the invention, any thermoplastic resin or thermosetting resin other than difunctional epoxy resin, phenoxy resin and polycarbonate resin as an arbitrary component.

[0109] Regarding thermoplastic resins as any component, there are no particular limitations on their properties such as crystallinity or amorphousness. For example, one or more of the following can be used: polyolefins and their acid-modified derivatives, polystyrene, polymethyl methacrylate, acrylonitrile-styrene (AS) resin, acrylonitrile butadiene-styrene (ABS) resin, polyethylene terephthalate or polybutylene terephthalate, etc., as well as polyimide, polyamide, polyamide-imide, polyetherimide, polyethersulfone, polyphenylene ether and its modified derivatives, polyphenylene sulfide, polyoxymethylene, polyarylate, polyetherketone, polyetheretherketone, polyetherketoneketone, etc.

[0110] Furthermore, regarding the thermosetting resin as an arbitrary component, one or more selected from vinyl ester resin, phenolic resin, urethane resin, etc., may preferably be used.

[0111] Regarding the resin composition, since it is necessary to impart excellent heat resistance and mechanical strength to its cured product, it is preferable that the total amount of other thermoplastic resins or thermosetting resins as optional components is less than 50 parts by weight relative to 100 parts by weight of the total amount of the resin component, more preferably 0 to 20 parts by weight or less. If the total amount of the resin as an optional component is 50 parts by weight or more, the effect of the invention may be compromised.

[0112] In addition, the resin composition of this embodiment may contain, without compromising the effects of the invention, any components such as organic solvents, crosslinking agents, inorganic fillers, extender pigments, colorants, antioxidants, UV stabilizers, flame retardants, and flame retardant additives.

[0113] <Morphology of Resin Compositions>

[0114] In addition to being solid or powdery, the resin composition of this embodiment can be obtained in any form, such as liquid, using a suitable solvent. Examples of solvents capable of dissolving the first and second resins include methanol, ethanol, butanol, dichloromethane, chloroform, tetrahydrofuran, toluene, xylene, acetone, ethyl acetate, dimethylformamide, N-methyl-2-pyrrolidone, and dimethylacetamide.

[0115] The melt viscosity of the resin composition in the temperature range below 260°C is below 3000 Pa·s. If the melt viscosity in the temperature range below 260°C exceeds 3000 Pa·s, the fluidity of the resin composition decreases, resulting in porosity after processing, which is undesirable.

[0116] Furthermore, the resin composition exhibits a melt viscosity of 8,000 Pa·s or higher in the temperature range of 260°C or higher, preferably 280°C or higher, more preferably 10,000 Pa·s to 1,000,000 Pa·s, and more preferably 20,000 Pa·s to 1,000,000 Pa·s. The resin composition begins to thicken at temperatures 10°C to 20°C above the melting point of the polycarbonate resin (approximately 250°C), and its viscosity increases sharply at temperatures above 260°C, reaching a range of 10,000 Pa·s.

[0117] Furthermore, from the viewpoint of molding and processing, the increase in melt viscosity of the resin composition, for example at a temperature of 280°C, preferably reaches 10,000 Pa·s or more within 30 minutes, and more preferably reaches 10,000 Pa·s or more within 20 minutes.

[0118] Thus, the resin composition exhibits behavior similar to that of a thermosetting resin through thermal crosslinking, curing at temperatures above 260°C to form a cured product. That is, although both the first and second resins constituting the resin composition are thermoplastic resins, they are irreversibly cured by heating the resin composition to temperatures above 260°C, for example, 280°C to 320°C, preferably 280°C to 300°C, subsequently exhibiting characteristic behavior of being substantially non-melting. The curing mechanism in this case is not yet clear, but it is speculated that a three-dimensional network structure is obtained through transesterification between the main secondary hydroxyl groups contained in the difunctional epoxy resin or phenoxy resin and the ester groups contained in the polycarbonate resin, thereby forming crosslinks between the difunctional epoxy resin chains or phenoxy resin chains and the polycarbonate resin chains, and thus curing occurs.

[0119] <Preparation of Resin Compositions>

[0120] The resin composition of this embodiment can be easily prepared by mixing the first resin and the second resin, and further, any other components as needed. There are no particular limitations on the mixing method; examples include: mixing the first resin and the second resin in a powder state (dry blending); heating and melting the first resin and the second resin and then mixing them; or dissolving the first resin and the second resin in a solvent and then mixing them.

[0121] Furthermore, when mixing the components, various blenders or mixers, dry mills, single-shaft or twin-shaft extruders, kneaders, etc., can be used depending on the appropriate mixing method. Moreover, when heating and melting followed by mixing, it is preferable to perform the process at a temperature before the hardened material described later is formed. If the first resin and the second resin are mixed and the temperature is increased, thickening begins from a temperature 10°C to 20°C above the melting point of the polycarbonate resin (approximately 250°C). Therefore, the mixing temperature (mixing in the unhardened state) used to prepare the resin composition is preferably, for example, below 240°C, and more preferably within the range of 200°C to 240°C.

[0122] [Hardened materials and hardened molded products]

[0123] The cured product of this embodiment is obtained by curing the resin composition through thermal crosslinking. The cured product of this embodiment can be obtained by heat-treating the resin composition at a temperature of 260°C or higher, preferably 280°C or higher. During heat treatment, the resin composition can be shaped into a desired shape, for example, by compression molding or injection molding or extrusion molding using a single-shaft or bi-shaft extruder, kneader, etc.

[0124] Furthermore, since the resin composition hardens through a crosslinking reaction and becomes non-flowable, the time from melting to forming is, for example, within 20 minutes after reaching 280°C, preferably within 10 minutes.

[0125] In this embodiment, the glass transition temperature (Tg) of the cured material, as measured by dynamic viscoelasticity measurement (DMA), is 100°C or higher. For example, in the DMA of the cured material, when the amount of difunctional epoxy resin or phenoxy resin (first resin) is greater than that of polycarbonate resin (second resin) (the content ratio of phenoxy resin to polycarbonate resin is 8:2 or 9:1), the Tg of the first resin is detected (e.g., about 110°C to 120°C), but the Tg of the second resin (e.g., about 160°C to 170°C) is not detected, until it disappears. When the Tg of the cured material shifts towards the high-temperature side as the amount of the second resin increases, it is approximately the same as the Tg of the polycarbonate resin used as the second resin alone.

[0126] Furthermore, when the thermal crosslinking temperature of the cured material is below 280°C, the tanδ peak representing the Tg of the first resin separates from the tanδ peak representing the Tg of the second resin, becoming distinct two peaks at least below 240°C.

[0127] Furthermore, it was confirmed that the storage elastic coefficient E' and loss elastic coefficient E” of the cured material are significantly increased compared to the first resin alone or the second resin alone, and the storage elastic coefficient E' exhibits stable behavior even in the region with a higher temperature than the Tm of the polycarbonate resin. The cured material of the resin composition of the present invention does not have a melting point and remains in a solid state even when heated.

[0128] Furthermore, in this embodiment, the displacement of the probe after being measured in DMA at temperatures ranging from 25°C to 300°C is less than -1 mm compared to the initial measurement. This means that the hardened material does not melt or soften even at 300°C, exhibiting high heat resistance.

[0129] As described above, the hardened material of this embodiment exhibits excellent heat resistance and mechanical strength. Therefore, the hardened molded material, formed into various shapes, can be used for a wide range of applications, including aircraft parts, automotive parts, electrical and electronic components, building components, various containers, sporting goods, daily necessities, household goods, and hygiene products. In particular, it is preferably used for applications requiring high heat resistance or mechanical strength, such as aircraft engine peripheral parts, aircraft parts, automotive body parts or engine peripheral parts, intake and exhaust system parts, engine cooling water system parts, frame parts for personal computers (PCs) or input boards, smartphones, and heat dissipation components for light-emitting diode (LED) lighting, as well as other electrical and electronic machine components.

[0130] Furthermore, the hardened material of this embodiment can also preferably be used as the matrix resin in fiber-reinforced plastics, for example. In this case, the hardened material has excellent adhesion and affinity to fibers from the first resin, and therefore has good impregnation properties with the reinforcing fiber substrate regardless of whether sizing treatment is performed, thus obtaining fiber-reinforced plastics with excellent mechanical strength.

[0131] [Fiber-reinforced plastic molding materials]

[0132] The fiber-reinforced plastic molding material of this embodiment (hereinafter, sometimes referred to as "FRP molding material") contains a reinforcing fiber substrate and a powder of the resin composition attached to the reinforcing fiber substrate.

[0133] In the FRP molding material of this embodiment, there are no particular limitations on the reinforcing fiber. For example, carbon fiber, boron fiber, silicon carbide fiber, glass fiber, aramid fiber, etc., are preferred, and carbon fiber is more preferred. Regarding the type of carbon fiber, for example, any polyacrylonitrile (PAN) based or pitch based fiber can be used. These can be used alone or in combination depending on the purpose or application. In addition, as the reinforcing fiber substrate, for example, non-woven substrate using chopped fiber or fabric using continuous fiber, unidirectional reinforcing fiber substrate (UD material), etc., can be used. However, in terms of reinforcement effect, fabric or UD material is preferred. When using fabric or UD material, it is preferable to use fibers called filaments that have undergone fiber-opening treatment.

[0134] The preferred area weight of the reinforced fiber substrate is 40 g / m². 2 ~250g / m 2 Within the range. If the weight per unit area is less than 40g / m². 2 If the number of reinforcing fibers in the molded part is too small, the desired mechanical properties cannot be obtained. Furthermore, if it exceeds 250 g / m², the required reinforcing fibers will be insufficient. 2 If the resin is not fully impregnated within the reinforced fiber substrate, the result is unsatisfactory.

[0135] Furthermore, reinforced fiber substrates can be used regardless of whether they have been sized.

[0136] In the FRP molding material of this embodiment, the resin composition is attached to the reinforcing fiber substrate in powder form. The FRP molding material is preferably prepared, for example, by a powder coating method in which micropowder of the resin composition is attached to the reinforcing fiber substrate. In the powder coating method, the raw resin composition is in the form of microparticles, which makes it easy to melt, and the coated film has appropriate porosity, thus providing an escape path for air and preventing the resin from easily forming pores after melting.

[0137] Examples of powder coating methods include electrostatic coating, fluidized bed coating, and suspension coating. Among these, electrostatic coating and fluidized bed coating are suitable for thermoplastic resins, and are simple to operate and have good productivity, so they are preferred. In particular, in electrostatic coating, the micro-powdered raw material resin composition exhibits good uniform adhesion to the reinforced fiber substrate, making it the most preferred method.

[0138] The average particle size of the micro-powdered raw material resin composition used in powder coating is preferably in the range of 10 μm to 100 μm, more preferably in the range of 40 μm to 80 μm, and most preferably in the range of 40 μm to 50 μm. If the average particle size of the micro-powder exceeds 100 μm, the energy of the micro-powder colliding with the fiber increases during powder coating in an electrostatic field, resulting in a decrease in the adhesion rate to the reinforcing fiber substrate. Furthermore, if the average particle size of the micro-powder is less than 10 μm, the particles are dispersed by the accompanying airflow, reducing the adhesion efficiency. In addition, the micro-powdered raw material resin suspended in the atmosphere may cause a deterioration of the working environment. The micro-powdering of the raw material resin is preferably performed using a pulverizing and mixing machine such as a low-temperature drying pulverizer (centrifugal dry mill), but is not limited to these. Furthermore, during the pulverization of the raw material resin, multiple components of the raw material may be pulverized and mixed, or multiple components may be pre-mixed and then pulverized.

[0139] In powder coating, it is preferable to apply the resin powder to the reinforcing fiber substrate in an amount (resin ratio: RC) ranging from 20% to 50%, more preferably from 25% to 45%, and even more preferably from 25% to 40%. If the RC exceeds 50%, the mechanical properties of CFRP, such as tensile and flexural elasticity, decrease. If it is less than 20%, the amount of resin adhering is very small, resulting in insufficient impregnation of the resin into the reinforcing fiber substrate, which may lead to a decrease in both thermal and mechanical properties.

[0140] [Fiber-reinforced plastics]

[0141] The fiber-reinforced plastic (hereinafter, sometimes referred to as "FRP") of this embodiment has a hardened form of a reinforcing fiber substrate and a resin composition of a matrix resin attached to the reinforcing fiber substrate.

[0142] The manufacturing method of FRP is not particularly limited, and can include impregnation, film stacking, etc. Preferably, it is prepared by heating and pressurizing an FRP molding material (prepreg) having the resin composition described in the embodiment. In the heating and pressurizing process, the powdered raw resin composition is completely melted and becomes liquid by heating, and then impregnated into the prepreg by pressurization. Within the prepreg, where the air permeability is controlled to a specified degree, an escape path for air is ensured. Thus, the molten resin impregnates while simultaneously expelling air, completing impregnation in a short time at relatively low pressure, and also avoiding the formation of pores.

[0143] In the FRP of the present invention, the fiber volume fraction (Vf) of the reinforcing fiber is preferably in the range of 40% to 65%. Vf can be adjusted according to the application of the FRP, more preferably 45% to 65%, and even more preferably 45% to 60%. If Vf exceeds 65%, the amount of matrix resin is insufficient, which reduces the strength of the FRP. In addition, if Vf is less than 40%, the reinforcing effect of the reinforcing fiber is reduced.

[0144] To ensure that the micronized powder of the raw resin composition is completely melted and impregnated into the entirety of the reinforcing fiber substrate, the heat-pressurization treatment is preferably performed at a temperature above the melting point of the polycarbonate resin used as the second resin, approximately in the range of 230°C to 350°C. More preferably, within this temperature range, it is performed at the melting point (Tm) of the polycarbonate resin used as the second resin plus 10°C to 60°C. If the upper limit temperature is exceeded, excessive heat will be applied, which may cause resin decomposition. If the lower limit temperature is exceeded, the melt viscosity is high, which not only risks insufficient impregnation of the reinforcing fiber substrate but also prevents the crosslinking reaction between the first and second resins from occurring, thus failing to obtain a cured product with the desired strength and heat resistance.

[0145] Furthermore, when the melting point of the polycarbonate resin used as the second resin cannot be clearly determined, the glass transition temperature (Tg) +100°C or higher becomes the standard for the heating and pressurization treatment temperature.

[0146] The pressure for the heat-pressurization treatment is preferably 3 MPa or higher, more preferably in the range of 3 MPa to 5 MPa. If the upper limit is exceeded, excessive pressure will be applied, which may cause deformation or damage, and if the lower limit is exceeded, the impregnation of the reinforcing fiber substrate will be poor.

[0147] The heating and pressurizing treatment time is preferably at least 5 minutes, and more preferably within the range of 5 minutes to 20 minutes.

[0148] It can also be formed into a specified shape while being heated and pressurized. The forming process can also be carried out by quickly placing the material preheated to a specified temperature into a low-temperature press forming machine.

[0149] Alternatively, after the heating and pressurizing treatment, any treatment such as post-cure can be performed. Post-cure is preferably performed at a temperature of, for example, 260°C or higher, preferably 280°C or higher, for about 10 to 30 minutes.

[0150] [Fiber-reinforced plastic laminated body]

[0151] A fiber-reinforced plastic laminate (hereinafter, sometimes referred to as "FRP laminate") according to one embodiment of the present invention contains phenoxy resin, polycarbonate resin, and reinforcing fibers. In the FRP laminate of this embodiment, the phenoxy resin and polycarbonate resin are laminated in a layered manner, and include an interlayer bonding site where one or more layers containing phenoxy resin (hereinafter, sometimes referred to as "phenoxy resin-containing layers") and layers containing polycarbonate resin (hereinafter, sometimes referred to as "polycarbonate resin-containing layers") are bonded at the lamination interface by a crosslinking reaction. The FRP laminate of this embodiment preferably has an interlaminar shear strength of 40 MPa or more as measured by the ILSS method.

[0152] The so-called ILSS method is an evaluation method for interlaminar shear strength as specified in Japanese Industrial Standards (JIS) K 7078. In this embodiment, the interlaminar shear strength measured by the method is 40 MPa or higher.

[0153] FRP laminates are generally made by stacking multiple sheets of FRP material called prepregs and heating and pressing them using a hot press or autoclave. However, if the interlaminar shear strength is less than 40 MPa, interlaminar delamination will occur when external stress is applied to the FRP laminate, resulting in a significant reduction in the strength of the FRP laminate.

[0154] Furthermore, if the interlaminar shear strength is too high, it may lead to a decrease in impact resistance. Therefore, it is preferably in the range of 40MPa to 65MPa, and more preferably in the range of 45MPa to 60MPa.

[0155] The FRP laminate of this embodiment preferably has a matrix resin having a layered state of phenoxy resin and polycarbonate resin. The layering state can be any structure depending on the desired characteristics of the FRP laminate; it can be a state of alternating layers of phenoxy resin and polycarbonate resin, or a state of random layering. In the case of random layering of phenoxy resin and polycarbonate resin layers, as long as the layering includes at least one interlayer bonding portion formed by bonding phenoxy resin and polycarbonate resin layers, it is acceptable to laminate in such a way that the layers are joined together. However, in order to achieve excellent mechanical strength of the FRP laminate, it is preferable that at least 10%, more preferably at least 50%, and even more preferably at least 70% and less than 100% of all interlayer bonding portions be interlayer bonding portions formed by bonding phenoxy resin and polycarbonate resin layers.

[0156] In addition, the phenoxy resin layer and the polycarbonate resin layer preferably each contain at least a portion of reinforcing fibers, but it is also possible that only one of the resin layers contains reinforcing fibers.

[0157] The FRP laminate of this embodiment may include layers made of any resin other than phenylene oxide resin and polycarbonate resin (e.g., layers of FRP molding material made from any resin, layers of resin film made from any resin, etc.) without impairing the effects of the invention. Here, there are no particular limitations on the type of resin, but resins with good adhesion to phenylene oxide resin and polycarbonate resin are preferred. On the other hand, to maintain excellent mechanical strength, the FRP laminate of this embodiment is preferably composed of, for example, 50% or more, more preferably 70% or more and 100% or less, relative to the total number of layers constituting the FRP laminate.

[0158] The fiber volume fraction (Vf) in the FRP laminate of this embodiment is preferably within, for example, a range of 45% to 67%. Here, Vf refers to the volume fraction of reinforcing fibers contained in the FRP laminate. From the viewpoint of the mechanical properties of the FRP laminate, it is preferable to set Vf within the aforementioned range. If Vf is too high, it is sometimes impossible to fill the voids in the reinforcing fiber substrate with thermoplastic resin, and mechanical properties commensurate with the fiber content cannot be obtained.

[0159] The FRP laminate of this embodiment includes interlayer bonding sites where phenoxy resin and polycarbonate resin, layered in a stacked manner, are firmly bonded at their interface through a crosslinking reaction. This crosslinking reaction was confirmed by a significant increase in the melt viscosity of the mixture of phenoxy resin and polycarbonate resin, and the cured product exhibits a higher modulus of elasticity than polycarbonate resin alone. The crosslinking reaction becomes significant when subjected to a thermal process at 260°C or higher, for example, 280°C, for more than 10 minutes, and is widely observed at phenoxy resin to polycarbonate resin mixing ratios of 9:1 to 3:7. The details of the reaction mechanism are not currently clear, but since the crosslinking reaction does not occur in the end structure of the polycarbonate resin without particular restriction, it is presumed to be caused by the transesterification reaction of the phenoxy resin and the polycarbonate resin. That is, it is believed that through the transesterification reaction of the carbonate groups (-O (C=O)-O-) of the polycarbonate resin with the hydroxyl groups (-OH) present at the end or side chain of the phenoxy resin, a three-dimensional cross-linking is formed between the polymer chains of the phenoxy resin and the polycarbonate resin. Therefore, a cross-linked cured product with stronger strength and higher heat resistance than phenoxy resin monomers and polycarbonate resin monomers can be obtained. Moreover, the FRP laminate of this embodiment is used to improve mechanical strength by inducing the cross-linking reaction at the interface between the phenoxy resin and the polycarbonate resin.

[0160] The details of the phenoxy resin-containing layer, the polycarbonate resin-containing layer, and the reinforcing fiber constituting the FRP laminate of this embodiment are described below.

[0161] [Layer containing phenoxy resin]

[0162] The phenoxy resin-containing layer may contain reinforcing fibers (substrate), and may also contain other components as needed, without compromising the effects of the present invention. Examples of other components that may be included include: flame retardants such as brominated phenoxy resin, mold release agents, dyes and pigments, antistatic agents, anti-drip agents, impact strength modifiers, and other thermoplastic resins (polyamide resins or polycarbonate resins, fluororesins, etc.). The phenoxy resin-containing layer is most preferably free of other resin components, containing only phenoxy resin. However, if other resin components are present, it is preferable to contain 60 parts by weight or more of phenoxy resin relative to 100 parts by weight of all resin components in the phenoxy resin-containing layer; more preferably, it contains 80 parts by weight or more; and even more preferably, it contains 90 parts by weight or more.

[0163] [Layer containing polycarbonate resin]

[0164] The polycarbonate resin-containing layer may contain reinforcing fibers (substrate), and may also contain other components as needed, without impairing the effects of the present invention. Examples of other components that may be included include: phosphoric acid, phosphoric acid, phosphite esters, phosphate esters, and other phosphorus-based heat stabilizers or hindered phenolic antioxidants, mold release agents, ultraviolet absorbers, dyes and pigments, antistatic agents, flame retardants, anti-drip agents, impact strength modifiers, and other thermoplastic resins (such as phenoxy resins). The polycarbonate resin-containing layer is most preferably free of other resin components, containing only polycarbonate resin. However, if other resin components are included, the layer preferably contains 80 parts by weight or more of polycarbonate resin, more preferably 90 parts by weight or more, relative to 100 parts by weight of all resin components in the polycarbonate resin-containing layer.

[0165] [Reinforced Fibers]

[0166] In the FRP laminated body of this embodiment, the reinforcing fiber can be widely selected from reinforcing fibers such as carbon fiber or glass fiber, boron or alumina, ceramic fibers such as silicon carbide, metal fibers such as stainless steel, and organic fibers such as aramid. Commercially available reinforcing fibers such as Tyranno fiber (registered trademark) can also be used. Among these, carbon fiber and glass fiber are preferred, and carbon fiber with high strength and good thermal conductivity is most preferred. Carbon fiber can be either pitch-based or PAN-based. Pitch-based carbon fiber not only has high strength but also high thermal conductivity, thus allowing heat to dissipate rapidly, making it more preferable than PAN-based carbon fiber in applications requiring heat dissipation. The form of the reinforcing fiber substrate is not particularly limited. Preferably, a woven fabric containing continuous fibers or a UD material with continuous fibers unidirectionally aligned can be used, such as unidirectional materials, plain or twill fabrics, three-dimensional fabrics, or fiber bundles containing thousands or more filaments. One type of these reinforcing fiber substrates can be used, or two or more types can be used in combination.

[0167] To improve the wettability or processability of the matrix resin on the reinforcing fiber, the surface of the reinforcing fiber may be coated with surface treatment agents such as sizing agents (bundling agents) or coupling agents, or subjected to oxidation treatment.

[0168] Examples of sizing agents include maleic anhydride compounds, carbamate compounds, acrylic compounds, epoxy compounds, phenolic compounds, or derivatives of these compounds. Examples of coupling agents include amino-based, epoxy-based, chlorinated-based, mercapto-based, and cationic silane coupling agents.

[0169] Relative to 100 parts by weight of reinforcing fiber, the content of sizing agent and coupling agent as surface treatment agent is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.5 parts by weight to 6 parts by weight. If the content of sizing agent and coupling agent is 0.1 parts by weight to 10 parts by weight, the wettability and processability with the matrix resin are better.

[0170] [Manufacturing Method of FRP Laminated Articles]

[0171] The FRP laminated molded body of this embodiment is obtained, for example, by the manufacturing methods described in (1) to (3) below. Hereinafter, details of these manufacturing methods will be described as representative examples, but the manufacturing methods of the FRP laminated molded body of this embodiment are not limited to these.

[0172] [Manufacturing Method (1)]

[0173] Prepreg stacking:

[0174] The method is as follows, i.e. Figure 1As shown, multiple sheet-shaped phenoxy resin FRP molding materials 10 containing phenoxy resin as a matrix resin and reinforcing fiber substrate, and sheet-shaped polycarbonate resin FRP molding materials 20 containing polycarbonate resin as a matrix resin and reinforcing fiber substrate are prepared. The two are alternately or randomly stacked, and FRP laminated bodies 30 are obtained by heating and pressing at the same time.

[0175] The phenoxy resin FRP molding material 10 and polycarbonate resin FRP molding material 20 used in manufacturing method (1) can be used without particular problems as long as they are obtained by known methods, but it is preferred that they are manufactured by a method without using a solvent. Examples of such methods include, for example, a method of pressurizing and impregnating a resin composition into a reinforcing fiber substrate (film deposition method), a method of dispersing and coating a powdered resin composition onto a reinforcing fiber substrate (powder coating method), and a method of weaving a continuous fiber obtained by spinning a resin composition with a reinforcing fiber (commingle method).

[0176] Regarding the resin ratio (RC) of the phenyl oxy resin FRP molding material 10 or the polycarbonate resin FRP molding material 20, in order to reliably form a melt-mixed state of phenyl oxy resin and polycarbonate resin at these layer boundaries in the subsequent heating and pressing molding step, it is preferably in the range of 25% to 50%, more preferably in the range of 30% to 50%.

[0177] The phenoxy resin FRP molding material 10 and the polycarbonate resin FRP molding material 20 are alternately or randomly stacked in a manner that achieves the desired molded body thickness, and then heated and pressurized to form the FRP laminated molded body 30 of this embodiment. When the phenoxy resin FRP molding material 10 and the polycarbonate resin FRP molding material 20 are randomly stacked, it is sufficient to stack them in a manner that includes at least one stack boundary where phenoxy resin and polycarbonate resin are in contact. However, in order to produce an FRP laminated molded body 30 with excellent mechanical strength, it is preferable to stack them in a manner where at least 10%, more preferably at least 50%, and even more preferably at least 70% and less than 100% of all stack boundaries are stack boundaries where phenoxy resin and polycarbonate resin are in contact.

[0178] Alternatively, an FRP molding material or resin film formed of resins other than phenylene resin and polycarbonate resin may be embedded in the interlayer between the phenylene resin FRP molding material 10 and the polycarbonate resin FRP molding material 20, as needed. In this case, it is sufficient to laminate in such a way that at least a portion of the laminated boundary between the phenylene resin and the polycarbonate resin is included. However, in order to ensure excellent mechanical strength of the manufactured FRP laminated molded body 30, it is preferable to laminate in such a way that at least 70% of all laminated boundaries, more preferably at least 75% and less than 100%, are laminated boundaries between the phenylene resin and the polycarbonate resin.

[0179] During forming, a flat-plate hot press, belt press, roller press, autoclave, or other pressure forming machine can be used for FRP forming, but a forming temperature of 260°C or higher and processing time of 5 minutes or more are required. The preferred processing conditions are a forming temperature in the range of 260°C to 300°C and a processing time of 5 to 30 minutes, more preferably in the range of 280°C to 290°C and a processing time of 10 to 20 minutes.

[0180] Furthermore, if the molding temperature is less than 260°C or the processing time is less than 5 minutes, the cross-linking reaction between phenoxy resin and polycarbonate resin becomes insufficient, resulting in a fragile interface between the two, which prevents the FRP laminate from achieving sufficient mechanical strength.

[0181] [Manufacturing Method (2)]

[0182] Membrane insertion:

[0183] The method is as follows, i.e. Figure 2 or Figure 3 As shown, phenoxy resin FRP molding material 10 or polycarbonate resin FRP molding material 20, and any resin film not used for FRP molding are prepared and alternately stacked, and then heated and pressurized to obtain FRP laminated body 50A or FRP laminated body 50B. That is, in manufacturing method (2), as... Figure 2 As shown, an FRP laminate 50A can be manufactured by laminating a polycarbonate resin film 40 onto a phenylene resin FRP molding material 10, or as... Figure 3 As shown, an FRP laminate 50B can also be manufactured by laminating a phenoxy resin film 60 onto a polycarbonate resin FRP molding material 20.

[0184] The phenoxy resin FRP molding material 10 and polycarbonate resin FRP molding material 20 used in manufacturing method (2) can be the same as those used in manufacturing method (1). Furthermore, there are no particular limitations on the manufacturing method of the phenoxy resin film 60 or the polycarbonate resin film 40; for example, they can be made by T-molding or inflation, or commercially available films can be used. There are no particular restrictions on the thickness of the phenoxy resin film 60 and the polycarbonate resin film 40, but...

[0185] a) Ensure sufficient resin quantity for achieving a adequate melt-mix state at the interface with the phenoxy resin FRP molding material 10 or the polycarbonate resin FRP molding material 20.

[0186] b) Minimize the thickness of the portion containing only resin without reinforcing fibers, ensuring mechanical strength without significantly reducing the Vf of the obtained FRP laminate 50A and FRP laminate 50B.

[0187] From this perspective, the preferred range is 10 μm to 200 μm, and more preferably 20 μm to 150 μm.

[0188] In manufacturing method (2), similarly to manufacturing method (1), FRP molding material and resin film are alternately or randomly laminated in a manner that achieves the desired molded body thickness, and then heated and pressurized to process the FRP laminated body 50A and FRP laminated body 50B of this embodiment. When FRP molding material and resin film are randomly laminated, it is sufficient to laminate in a manner that includes at least one laminated boundary where phenylene resin and polycarbonate resin are in contact. However, if the laminated resin film does not contain reinforcing fibers, the Vf of the FRP laminated body 50A and FRP laminated body 50B will decrease. Therefore, in order to make the manufactured FRP laminated body 50A and FRP laminated body 50B have excellent mechanical strength, it is preferable to laminate in a manner where at least 25% of all laminated boundaries, more preferably at least 25% and less than 100%, are laminated boundaries where phenylene resin and polycarbonate resin are in contact.

[0189] Alternatively, FRP molding materials or resin films formed from resins other than phenylene resin and polycarbonate resin may be embedded into the interlayer as needed. In this case, it is sufficient to laminate in such a way that at least a portion of the laminate boundary where phenylene resin and polycarbonate resin meet is included. However, in order to obtain excellent mechanical strength of the manufactured FRP laminate 50A and FRP laminate 50B, it is preferable to laminate in such a way that at least 25% of all laminate boundaries, more preferably at least 25% and less than 100%, are laminate boundaries where phenylene resin and polycarbonate resin meet.

[0190] During forming, a flat-plate hot press, belt press, roller press, autoclave, or other pressure forming machine can be used for FRP forming, but a forming temperature of 260°C or higher and processing time of 5 minutes or more are required. The preferred processing conditions are a forming temperature in the range of 260°C to 300°C and a processing time of 5 to 30 minutes, more preferably in the range of 280°C to 290°C and a processing time of 10 to 20 minutes.

[0191] Furthermore, if the molding temperature is less than 260°C or the processing time is less than 5 minutes, the cross-linking reaction between the phenylene oxide resin and the polycarbonate resin becomes insufficient, resulting in a fragile interface between the two. Consequently, the FRP laminate 50A and FRP laminate 50B cannot obtain sufficient mechanical strength.

[0192] [Manufacturing Method (3)]

[0193] Use of materials for hybrid molding:

[0194] The method is as follows, i.e. Figure 4 As shown, a mixed FRP molding material 80 is prepared, in which one side of the reinforced fiber substrate 70 is covered with phenyl oxy resin and the other side is covered with polycarbonate resin. The mixed FRP molding material 80 is stacked in multiple layers and heated and pressed to form an FRP laminate 90.

[0195] Unlike manufacturing methods (1) and (2), the hybrid FRP molding material 80 used in manufacturing method (3) is formed by covering one side of the reinforcing fiber substrate 70 with phenylene oxide resin and the other side with polycarbonate resin. Here, the phenylene oxide resin coating layer on one side of the hybrid FRP molding material 80 is the part of the FRP laminate 90 that is called the "phenylene oxide resin layer", and the polycarbonate resin coating layer on the other side is the part of the FRP laminate 90 that is called the "polycarbonate resin layer".

[0196] The phenoxy resin and polycarbonate resin coating the reinforcing fiber substrate 70 can be coated on the surface of the reinforcing fiber substrate 70 in a film form, or they can be coated on the surface of the reinforcing fiber substrate 70 in a state of being piled up and attached with resin powder. However, in terms of the productivity of the mixed FRP molding material 80, it is preferable to coat it in a film form.

[0197] The hybrid FRP molding material 80 is obtained by applying pressure to the surface of the reinforcing fiber substrate 70 while heating the phenoxy resin and polycarbonate resin to temperatures above their melting or softening temperatures, thereby coating the surface of the reinforcing fiber substrate 70. Specifically, examples include:

[0198] (i)If Figure 4As shown by the downward arrow, a method is used to impregnate the reinforcing fiber substrate 70 with a phenylene resin film 60 and a polycarbonate resin film 40 overlapping on both sides of the reinforcing fiber substrate 70 in the thickness direction, while simultaneously heating and pressurizing to melt the resin components.

[0199] (ii) such as Figure 4 As shown by the upward arrow, a method is used to integrate phenoxy resin FRP molding material 10 and polycarbonate resin FRP molding material 20 by overlapping them while heating and pressurizing to melt and impregnate the resin components.

[0200] As equipment for implementing the method, a pressure forming machine, a belt press, or a roll press may preferably be used, for example.

[0201] Furthermore, in steps (i) and (ii), the process is carried out at a temperature below 260°C, preferably between 200°C and 240°C, where the phenoxy resin and polycarbonate resin are melted and impregnated in the reinforcing fiber substrate 70. If processing is performed at a temperature above 260°C, the phenoxy resin and polycarbonate resin undergo a cross-linking reaction, thus reducing the shapeability of the mixed FRP molding material 80, which is undesirable.

[0202] In order to reliably form a molten mixture of phenoxy resin and polycarbonate resin in the subsequent heating and pressing molding step, the resin ratio (RC) of the mixed FRP molding material 80 is preferably in the range of 25% to 50%, and more preferably in the range of 30% to 50%.

[0203] Similar to manufacturing methods (1) and (2), the FRP molding material 80 is mixed and laminated to achieve the desired thickness of the molded body. At this time, there is no particular limitation on the inside and outside direction of the mixed FRP molding material 80, as long as the lamination is carried out in such a way that at least a portion of the lamination boundary where the phenylene resin and the polycarbonate resin meet is included. However, in order to make the manufactured FRP laminated molded body 90 have excellent mechanical strength, it is preferable to laminate in such a way that at least 50% of all lamination boundaries, more preferably at least 75% and less than 100%, are lamination boundaries where the phenylene resin and the polycarbonate resin meet.

[0204] Alternatively, depending on the need, FRP molding materials or resin films formed of phenyl oxy resin or polycarbonate resin, or FRP molding materials or resin films formed of resins other than phenyl oxy resin and polycarbonate resin, can be embedded into the interlayer spaces of multiple mixed FRP molding materials 80. In this case, it is sufficient to laminate in such a way that at least a portion of the laminated boundary between phenyl oxy resin and polycarbonate resin is included. However, in order to ensure excellent mechanical strength of the manufactured FRP laminated body 90, it is preferable to laminate in such a way that at least 50% and more preferably 75% and less than 100% of all laminated boundaries are laminated boundaries between phenyl oxy resin and polycarbonate resin.

[0205] The FRP laminated body 90 of this embodiment is processed by heating and pressurizing a laminate containing multiple mixed FRP molding materials 80. During molding, a pressure molding machine generally used for FRP molding, such as a flat-plate hot press, belt press, roller press, or autoclave, can be used, but a molding temperature of 260°C or higher and processing time of 5 minutes or more are required. The preferred processing conditions are a molding temperature in the range of 260°C to 300°C and a processing time of 5 to 30 minutes, more preferably in the range of 280°C to 290°C and a processing time of 10 to 20 minutes.

[0206] Furthermore, if the molding temperature is less than 260°C or the processing time is less than 5 minutes, the cross-linking reaction between the phenoxy resin and the polycarbonate resin becomes insufficient, resulting in a fragile interface between the two and an inability to obtain sufficient mechanical strength for the FRP laminate 90.

[0207] In addition, by heating and pressing, near the center of the mixed FRP molding material 80 in the thickness direction (inside the reinforcing fiber substrate 70), the impregnated phenyl oxy resin and the mixed polycarbonate resin are sometimes mixed and cross-linked, but the interior of the reinforcing fiber substrate 70 is not included in the "interlayer bonding area".

[0208] The FRP laminates 30, 50A, 50B, and 90 obtained in the manner described above can be further processed by painting, punching for fastening with other parts, or embedding into an injection molding die for rib forming or other post-processing.

[0209] The FRP laminates 30, 50A, 50B, and 90 obtained in this manner are formed by layering phenylene resin-containing layers with polycarbonate resin-containing layers. At the bonding sites, the phenylene resin and polycarbonate resin are mixed, resulting in a stable and strong interlayer bonding and high mechanical properties. Therefore, the FRP laminates 30, 50A, 50B, and 90 combine the excellent impact resistance characteristic of polycarbonate resin with the good adhesion to other components characteristic of phenylene resin, and also exhibit excellent processability such as bending. Therefore, the FRP laminates 30, 50A, 50B, and 90 are preferably used as mounting components for applications such as automotive components, electrical and electronic machine frames, and aircraft components.

[0210] The application of the FRP laminated molded body in this embodiment is not particularly limited. Examples include: sporting goods or portable information terminals and electrical and electronic machine parts, civil engineering and building material parts, structural parts for automobiles and two-wheeled vehicles, and aircraft parts. However, from the viewpoint of its mechanical properties, it can be more preferably used for electrical and electronic machine frames that require high mechanical strength, structural materials for bicycles and sporting goods, and interior and exterior decoration components for automobiles and aircraft.

[0211] Example

[0212] The following examples illustrate the invention in more detail, but the invention is not limited to these examples. Furthermore, the testing and measurement methods for various physical properties in the examples are as follows.

[0213] [Average Particle Size (D50)]

[0214] Regarding the average particle size, the particle size was measured using a laser diffraction-scattering particle size distribution measuring device (Microtrac MT3300EX, manufactured by Nikkiso Corporation) when the cumulative volume was 50% based on volume.

[0215] [Dynamic Viscoelasticity Measurement (DMA)]

[0216] The measurements were performed using a dynamic viscoelasticity measuring device (DMA 7e manufactured by Perkin Elmer).

[0217] Regarding the probe displacement of the hardened material, the displacement of the probe after DMA measurement will be compared with the position before measurement at a temperature ranging from 25°C to 300°C.

[0218] Regarding the Tg of the hardened material, test pieces with a width of 10 mm and a length of 10 mm were cut from the hardened material using a diamond cutter. The Tg was measured under a heating rate of 5 °C / min in the range of 25 °C to 300 °C. The maximum peak value of the obtained tanδ was set as Tg.

[0219] [Melt viscosity]

[0220] Using a rheometer (Anton Paar MCR302), approximately 300 mg of the test sample was clamped between parallel plates and heated to 280 °C at a rate of 50 °C / min. The temperature was then maintained at 280 °C under the specified conditions. The minimum melt viscosity and the melt viscosity above 280 °C were measured under the following conditions: frequency: 1 Hz, swing angle: 0.5%, and normal force: 0.1 N.

[0221] [Resin Ratio (RC: %)]

[0222] The weight of the reinforcing fiber substrate before resin attachment (W1) and the weight of the CFRP molding material after resin attachment (W2) are calculated using the following formula.

[0223] Resin ratio (RC:%) = (W2 - W1) / W2 × 100

[0224] W1: Weight of the reinforced fiber substrate before resin adhesion

[0225] W2: Weight of the CFRP molding material after resin adhesion

[0226] [Fiber volume content (Vf:%)]

[0227] Based on JIS K 7075:1991 Test method for fiber content and void ratio of carbon fiber reinforced plastics, the determination was carried out using the combustion method.

[0228] [Determination of Mechanical Strength]

[0229] Based on JIS K 7074:1988, the mechanical properties (fracture stress and elastic modulus) of the obtained CFRP molded articles were determined.

[0230] Specifically, the self-layered molded product was cut into strips with a total length of 80 mm and a width of 15 mm to serve as the test specimen, with the distance between the support points set at 40 mm. The testing was conducted using a Tensilon universal testing machine (RTA250, manufactured by A&D) at a testing speed of 2 mm / min.

[0231] [Determination of interlaminar shear strength]

[0232] Based on JIS K 7078:1991 Interlaminar shear test method for carbon fiber reinforced plastics, a universal strength testing machine (Autograph AG-Xplus100kN, manufactured by Shimadzu Corporation) was used to measure the strength of a test piece with a length of 21mm × width of 10mm × thickness of 3mm.

[0233] [Evaluation of the mechanical strength of FRP laminated articles]

[0234] The mechanical properties (flexural strength, flexural modulus) of the obtained FRP laminate were determined based on JIS K 7074:1988, a bending test method for carbon fiber reinforced plastics.

[0235] [Determination of Flexural Temperature]

[0236] Based on Method C in JIS K 7191-2:2015 Plastics—Determination of Flexural Temperature, the flexural temperature of a test piece with a length of 80 mm, a width of 10 mm, and a thickness of 1 mm was determined using an HDT tester 3M-2V manufactured by Toyo Seiki Co., Ltd.

[0237] <Phenoxy Resin>

[0238] A-1:

[0239] Phenoto YP-50S (Bisphenol A type manufactured by Nippon Steel Chemicals & Materials Co., Ltd., Mw = 60,000, hydroxyl equivalent = 284 g / eq), melt viscosity at 200°C = 400 Pa·s, Tg = 84°C

[0240] <Difunctional epoxy resin>

[0241] A-2:

[0242] Epotohto YP-017 (Bisphenol A type manufactured by Nippon Steel Chemicals & Materials Co., Ltd., Mw=4000), softening point=117℃

[0243] <Polycarbonate resin>

[0244] B-1:

[0245] Iupilon S3000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Mw = 45000), melt viscosity at 280°C = 1,020 Pa·s, Tg = 149°C, Tm = 240°C

[0246] B-2:

[0247] Novarax 7022R (manufactured by Mitsubishi Engineering Plastics Corporation, Mw = 21,000), melt viscosity at 280°C = 1,200 Pa·s, Tg = 160°C, Tm = 230°C~260°C

[0248] [Example 1]

[0249] Prepare 90 parts by weight of phenoxy resin A-1 and 10 parts by weight of polycarbonate resin B-1, pulverize and classify them respectively to prepare powder with an average particle size D50 of 80 μm, and dry blend the obtained powder using a dry powder mixer (manufactured by Aichi Electric Co., Ltd., rocking mixer) to prepare resin composition E1.

[0250] Alternatively, the obtained resin composition E1 was mixed at 280°C for 15 minutes using a Labo plastomill (manufactured by Toyo Seiki Co., Ltd.), thereby hardening it to obtain the hardened product E1.

[0251] [Examples 2 to 7]

[0252] The mixing ratio of phenoxy resin A-1 and polycarbonate resin B-1 was varied as shown in Table 1, and resin compositions E2 to E7 and cured products E2 to E7 were obtained in the same manner as in Example 1.

[0253] [Example 8]

[0254] By using B-2 instead of polycarbonate resin B-1, and making the mixing ratio the same as in Example 2, resin composition E8 and cured product E8 were obtained in the same manner as in Example 1.

[0255] [Example 9]

[0256] Using a difunctional epoxy resin A-2 instead of phenoxy resin A-1, and using B-2 instead of polycarbonate resin B-1, the mixing ratio was the same as in Example 3. Otherwise, the resin composition E9 and the cured product E9 were obtained in the same manner as in Example 1.

[0257] [Example 10, Example 11]

[0258] The mixing ratio of phenoxy resin A-1 and polycarbonate resin B-1 was varied as shown in Table 1, and resin compositions E10 and E11 were prepared in the same manner as in Example 1.

[0259] In addition, the obtained resin composition E10 and resin composition E11 were mixed at 280°C for 15 minutes using a Labo plastomill (manufactured by Toyo Seiki Co., Ltd.), thereby hardening them to obtain hardened products E10 and hardened products E11.

[0260] For the resin compositions E1 to E11 and the cured products E1 to E11 obtained in Examples 1 to 11, DMA and melt viscosity were measured. The results are shown in Table 1. In each example, it was confirmed that the melt viscosity increased due to the crosslinking reaction between the phenoxy resin and the polycarbonate resin. In particular, cured products E1 to E9 did not have a melting point and remained in a solid state even when heated.

[0261] [Comparative Example 1]

[0262] The DMA and melt viscosity of the cured product R1 of phenoxy resin A-1 were determined. The results are shown in Table 1.

[0263] [Comparative Example 2]

[0264] The DMA and melt viscosity of the cured polycarbonate resin B-1, R2, were determined. The results are shown in Table 1.

[0265] [Comparative Example 3]

[0266] Resin composition R3 was prepared in the same manner as in Example 1, except that polyamide resin (polyamide 6, CM1013 manufactured by Toray) was used instead of polycarbonate resin B-1 and the mixing ratio was set as shown in Table 1.

[0267] The obtained resin composition R3 was kneaded at 280°C for 15 minutes in the same manner as in Example 1, but no particularly large thickening was observed. Therefore, cured product R3 was obtained by direct cooling. The results are shown in Table 1.

[0268] [Refer to Example 1, Refer to Example 2]

[0269] The resin composition E2 obtained in Example 2 was kneaded at 260°C (Reference Example 1) and 240°C (Reference Example 2) for 15 minutes respectively, thereby hardening it to obtain hardened products R4 and R5. The results are shown in Table 1.

[0270] [Table 1]

[0271]

[0272] In addition, for the resin compositions E1 to E11, R1, and R2 obtained in Examples 1 to 11, Comparative Examples 1 and 2, the viscosity was measured using a rheometer at 0 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, and 100 minutes after reaching 280°C. The results are shown below. Figure 5 .

[0273] [Example 12]

[0274] For the resin composition E1 obtained in Example 1, SA3202 (a plain-woven open-fiber carbon fiber fabric manufactured by Sakai Ovex Co., Ltd., with the sizing agent removed) was used as the reinforcing fiber substrate. Powder coating was performed in an electrostatic field with a charge of 60 kV and an air spray rate of 60 L / min, with the Vf of the formed product being 60%. Subsequently, the resin composition was thermally fused to the carbon fiber by heating and melting in an oven at 250°C for 3 minutes, thereby producing a CFRP prepreg A with a thickness of 0.9 mm and a resin ratio (RC) of 30%.

[0275] Using 13 pieces of the obtained CFRP prepreg A, a CFRP molded body X1 was produced by pressing at 5 MPa for 10 minutes using a press heated to 280°C. The mechanical properties (fracture stress and elastic modulus) of the obtained CFRP molded body X1 were measured after cooling. The results are shown in Table 2.

[0276] [Examples 13-22, Comparative Examples 4-6]

[0277] Using the resin compositions (or resins) obtained in Examples 2 to 11 and Comparative Examples 1 to 3, except that CFRP prepregs B to K of the Examples and CFRP prepregs L to N of the Comparative Examples were prepared in the same manner as in Example 12, CFRP molded bodies X2 to X11 of the Examples and CFRP molded bodies W1 to W3 of the Comparative Examples were then prepared, and their mechanical properties (fracture stress and elastic modulus) were measured. The results are shown in Table 2. Furthermore, the correspondence with the resin compositions used is also shown in Table 2.

[0278] [Refer to Example 3 and Example 4]

[0279] Using the resin composition E2 obtained in Example 2, CFRP prepreg B was prepared in the same manner as in Example 12, except that the pressing temperature was changed to 260°C (Reference Example 3) or 240°C (Reference Example 4). CFRP molded bodies W4 and W5 were prepared in the same manner as in Example 12, and their mechanical properties (fracture stress and elastic modulus) were measured. The results are shown in Table 2. Furthermore, the correspondence with the resin composition used is also shown in Table 2.

[0280] [Table 2]

[0281]

[0282] [Examples 23-33, Comparative Example 7, Comparative Example 8]

[0283] SA3202 without removing the sizing agent was used as the reinforcing fiber substrate. Otherwise, the same procedures were carried out as in Examples 12 to 22, Comparative Examples 4 and 5 to obtain CFRP prepregs a to k of the examples, CFRP prepreg l of the comparative examples and CFRP prepreg m of the comparative examples.

[0284] Using the obtained CFRP prepregs a to k, l, and m, CFRP prepregs were pressed at 5 MPa for 10 minutes using a press heated to 280°C, thereby producing CFRP molded bodies Y1 to Y11 of the examples, and CFRP molded bodies Z1 and Z2 of the comparative examples. Their mechanical properties (fracture stress and elastic modulus) were then measured. The results are shown in Table 3. Furthermore, the correspondence with the resin compositions used is also shown in Table 3.

[0285] [Table 3]

[0286]

[0287] In addition, the interlaminar shear strength and load flexural temperature were measured for the CFRP molded body X2 obtained in Example 13 and the CFRP molded body X10 obtained in Example 21. The results are shown in Table 4.

[0288] [Table 4]

[0289] Example 13 Example 21 CFRP molded body X2 X10 Interlaminar shear strength [MPa] 59.3 39.2 Flexural temperature under load [°C] ＞300 ＞300

[0290] [Example 34]

[0291] Phenoxy resin and polycarbonate resin were separately pulverized and graded to prepare two matrix resin powders with an average particle size D50 of 80 μm. Next, a plain-woven reinforcing fiber substrate containing split carbon fibers (manufactured by Toray Industries, Inc., T700) was prepared. In an electrostatic field with a charge of 100 kV and an air spray pressure of 0.1 MPa, powder coating was performed using the respective matrix resin powders. Then, the phenoxy resin was heated to 200°C and the polycarbonate resin to 260°C in an oven for 3 minutes each, allowing the resins to thermally fuse, thereby obtaining phenoxy resin FRP molding materials and polycarbonate resin FRP molding materials. The resin ratio (RC) of the obtained FRP molding materials was 33% for the phenoxy resin FRP molding material and 32% for the polycarbonate resin FRP molding material.

[0292] The phenoxy resin FRP molding material and the polycarbonate resin FRP molding material were alternately laminated with the phenoxy resin FRP molding material as the outermost layer. The FRP laminate was then heated and pressurized using a hot press at 5 MPa, 280°C, and 10 min, and the various physical properties of the resulting FRP laminate were measured. These results are shown in Table 5.

[0293] [Example 35]

[0294] The heating and pressing molding temperature was set to 260°C, and the FRP laminate was fabricated in the same manner as in Example 34, and various physical properties were measured. These results are shown in Table 5.

[0295] [Example 36]

[0296] For phenoxy resin A-1, a 20μm thick phenoxy resin film was obtained using a T-die extrusion molding machine with a die width of 150mm, a coat hanger die, and a die lip width of 0.2mm.

[0297] The polycarbonate resin FRP molding material prepared in Example 34 is laminated with the phenoxy resin film such that the outermost layer is the polycarbonate resin FRP molding material.

[0298] Furthermore, regarding the polycarbonate resin FRP molding material and the phenoxy resin film, it is set that when three pieces of polycarbonate resin FRP molding material are stacked, one piece of phenoxy resin film is stacked, and the two are stacked in total of 51 pieces.

[0299] Subsequently, the laminate was heated and pressurized using a hot press at 5 MPa, 280 °C, and 10 min, and the various physical properties of the obtained FRP laminate were measured. These results are shown in Table 5.

[0300] [Example 37]

[0301] The polycarbonate resin FRP molding material and the phenoxy resin film were arranged such that four pieces of polycarbonate resin FRP molding material were on the outermost layer, and one piece of phenoxy resin film was stacked for every six pieces of polycarbonate resin FRP molding material, for a total of 46 pieces. Otherwise, the FRP laminate was prepared in the same manner as in Example 36, and various physical properties were measured. These results are shown in Table 5.

[0302] [Comparative Example 9]

[0303] The heating and pressing molding temperature was set to 240°C, and the FRP laminate was fabricated in the same manner as in Example 34, and various physical properties were measured. These results are shown in Table 5.

[0304] [Comparative Example 10]

[0305] The heating and pressing molding temperature was set to 240°C, and the FRP laminate was fabricated in the same manner as in Example 36, and various physical properties were measured. These results are shown in Table 5.

[0306] [Comparative Example 11]

[0307] The heating and pressing molding temperature was set to 240°C, and the FRP laminate was fabricated in the same manner as in Example 37, and various physical properties were measured. These results are shown in Table 5.

[0308] [Reference Example 5]

[0309] Using only phenoxy resin FRP molding material, FRP laminates were fabricated in the same manner as in Example 34, and various physical properties were measured. These results are shown in Table 5.

[0310] [Reference Example 6]

[0311] FRP laminates were fabricated using only polycarbonate resin FRP molding materials, in the same manner as in Example 34, and various physical properties were measured. These results are shown in Table 5.

[0312] [Table 5]

[0313]

[0314] The FRP laminate of the present invention forms a strong bonding interface through the crosslinking reaction between phenyl oxy resin and polycarbonate resin. Therefore, compared with the FRP laminate in the insufficient crosslinking state of Comparative Example 9, it has a large interlayer shear strength and can exert high mechanical properties that can also be used as structural materials.

[0315] The embodiments of the present invention have been described in detail above for illustrative purposes, but the present invention is not limited to the embodiments described.

Claims

1. A method for producing a fiber-reinforced plastic laminate molded body, characterized by: laminating a fiber-reinforced plastic molding material having phenoxy resin as a matrix resin and a fiber-reinforced plastic molding material having polycarbonate resin as a matrix resin, and performing molding processing at a temperature of 260°C or higher and for a time of 5 minutes or more.

2. The method for producing a fiber-reinforced plastic laminate molded body according to claim 1, wherein the fiber-reinforced plastic laminate molded body contains phenoxy resin and polycarbonate resin, and a reinforcing fiber, and comprises a plurality of layers, and wherein an interlayer bonding site at which one or more layers containing the phenoxy resin and layers containing the polycarbonate resin are bonded to each other through a cross-linking reaction at an interface between the layers is included.

3. The method for producing a fiber-reinforced plastic laminate molded body according to claim 2, wherein at least one of the fiber-reinforced plastic molding material having phenoxy resin as a matrix resin and the fiber-reinforced plastic molding material having polycarbonate resin as a matrix resin is interposed between and laminated with a plurality of the fiber-reinforced plastic molding materials.

4. The method for producing a fiber-reinforced plastic laminate molded body according to claim 2, wherein at least one of a phenoxy resin film and a polycarbonate resin film is interposed between and laminated with a plurality of the fiber-reinforced plastic molding materials.

2. A method of producing a fiber-reinforced plastic laminated molded body, characterized by 5. A method for producing a fiber-reinforced plastic laminate molded body, characterized by: laminating a fiber-reinforced plastic molding material having phenoxy resin as a matrix resin and a polycarbonate resin film, and performing molding processing at a temperature of 260°C or higher and for a time of 5 minutes or more.

6. A method for producing a fiber-reinforced plastic laminate molded body, characterized by: laminating a fiber-reinforced plastic molding material having polycarbonate resin as a matrix resin and a phenoxy resin film, and performing molding processing at a temperature of 260°C or higher and for a time of 5 minutes or more. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 7. A fiber-reinforced plastic molding material for forming a fiber-reinforced plastic laminated molded body, comprising: a reinforcing fiber base material; a coating layer of phenoxy resin formed on one face of the reinforcing fiber base material; and a coating layer of polycarbonate resin formed on the other face of the reinforcing fiber base material, the fiber-reinforced plastic molding material being laminated in such a manner that at least a part of a laminated boundary where the phenoxy resin and the polycarbonate resin are in contact is included when a plurality of pieces are laminated.

8. The fiber-reinforced plastic molding material according to claim 7, wherein the reinforcing fiber base material is a woven fabric including continuous fibers or a unidirectional material in which continuous fibers are unidirectionally aligned. ​

Images