Method for manufacturing fiber-reinforced resin molded product, system for manufacturing fiber-reinforced resin molded product, and fiber-reinforced resin molded product

Abstract

To provide a method for manufacturing a fiber-reinforced resin molded product with a high degree of freedom in design.SOLUTION: A method for manufacturing a fiber-reinforced resin molded product includes: a patterning step of impregnating a fiber sheet with ink containing a flexible resin composition containing at least a flexible material and patterning the sheet; a spraying step of spraying a matrix resin onto an area of the fiber sheet that is not impregnated with the ink to obtain a fiber-reinforced resin composite; and a molding step of heating and pressurizing the fiber-reinforced resin composite to obtain a fiber-reinforced resin molded product. The flexible material is filled inside the fiber sheet in the fiber-reinforced resin molded product.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a fiber-reinforced resin molded product, a system for manufacturing a fiber-reinforced resin molded product, and a fiber-reinforced resin molded product. [Background technology]

[0002] Fiber-reinforced plastic molded products are lightweight and strong, and are therefore used in the aerospace industry, mobility applications such as automobiles, and sporting goods. While fiber-reinforced plastic molded products have excellent strength, they can be prone to cracking, making improving their impact resistance a challenge. Therefore, a technology has been devised that combines fiber-reinforced plastic molded products with flexible materials that have excellent impact resistance, achieving both high strength and impact resistance.

[0003] For example, Patent Document 1 discloses an FRP molded product having high strength, high elastic modulus, and excellent impact resistance, and a method for manufacturing the same. Specifically, it discloses that a buffer material (acrylic resin) is disposed on at least one surface of a fiber-containing fiber substrate.

[0004] However, Patent Document 1 has a problem in that the degree of freedom in design is low. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a method for producing a fiber-reinforced resin molded article having a high degree of freedom in design. [Means for solving the problem]

[0006] The method for producing a fiber-reinforced resin molding of the present invention as a means for solving the above-mentioned problems includes a patterning step of patterning a fiber sheet with an ink containing a flexible resin composition including at least a flexible material, an application step of applying a matrix resin to the patterned fiber sheet to obtain a fiber-reinforced resin composite, and a molding step of molding the fiber-reinforced resin composite to obtain a fiber-reinforced resin molding, wherein the flexible material and matrix resin are filled inside the fiber sheet in the fiber-reinforced resin molding. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a method for producing a fiber-reinforced resin molded article with a high degree of freedom in design. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a flowchart showing a method for producing a fiber-reinforced resin molded product according to one embodiment of the present invention. [Figure 2] 1 is a schematic diagram of a manufacturing system for a fiber-reinforced resin molded product according to an embodiment of the present invention. [Figure 3] 1 is a schematic diagram showing the change before and after the molding step in a method for producing a fiber-reinforced resin molded product according to one embodiment of the present invention. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0009] The method for producing a fiber-reinforced resin molded product of the present invention includes a patterning step of patterning a fiber sheet with an ink containing a flexible resin composition that includes at least a flexible material, an application step of applying a matrix resin to the patterned fiber sheet to obtain a fiber-reinforced resin composite, and a molding step of molding the fiber-reinforced resin composite to obtain a fiber-reinforced resin molded product, and may further include other steps as necessary.

[0010] Other steps include a drying step of drying the fiber sheet and a lamination step of laminating a plurality of the fiber-reinforced resin composites before the application step.

[0011] The manufacturing system for fiber-reinforced resin moldings of the present invention includes a patterning device that performs a patterning process, a drying device that performs a drying process, an application device that performs an application process, a lamination device that performs a lamination process, and a molding device that performs a molding process, and may further include other devices as necessary.

[0012] The method for manufacturing a fiber-reinforced resin molded product according to one embodiment of the present invention can be suitably carried out by the system for manufacturing a fiber-reinforced resin molded product of the present invention, and the patterning step can be carried out by a patterning device, the drying step can be carried out by a drying device, the application step can be carried out by an application device, the lamination step can be carried out by a lamination device, and the molding step can be carried out by a molding device.

[0013] In the present invention, the term "fiber-reinforced resin composite" refers to a product in which a flexible resin composition containing at least a flexible material and a matrix resin are applied to a fiber sheet. Also included in the term "fiber-reinforced resin composite" is a product in which multiple fiber-reinforced resin composites are laminated by a lamination process. The term "fiber-reinforced resin molded product" refers to a molded fiber-reinforced resin composite.

[0014] The present invention will now be described in detail with reference to the drawings.

[0015] (Method of manufacturing fiber-reinforced resin molded product) FIG. 1 is a flowchart showing a method for producing a fiber-reinforced resin molded product according to one embodiment of the present invention. The method for producing a fiber-reinforced resin molded product according to one embodiment of the present invention includes a patterning step S1, a drying step S2, an applying step S3, a laminating step S4, and a molding step S5, which are carried out in this order.

[0016] <Patterning process> In the patterning step S1, a pattern is formed on a fiber sheet using an ink containing a flexible resin composition that includes at least a flexible material. By adjusting the area impregnated with the ink in the patterning step S1, i.e., the pattern arrangement, the physical properties of the fiber-reinforced resin molded product, such as its strength and impact resistance, can be adjusted.

[0017] The patterning method is not particularly limited as long as it is a method that can impregnate the ink onto the fiber sheet, and can be selected appropriately depending on the purpose. For example, the ink can be ejected onto the fiber sheet using an inkjet nozzle, or the ink can be applied to the fiber sheet by hand.

[0018] The pattern arrangement may be such that the ink is impregnated onto the fiber sheet in a regular manner or in an irregular manner, such as only in the center of the fiber sheet, only on both ends of the fiber sheet, etc. Examples of pattern arrangements in which the ink is impregnated onto the fiber sheet in a regular manner include stripes and a grid.

[0019] [Soft resin composition] The flexible resin composition contains at least a flexible material. Furthermore, the flexible resin composition contains a crosslinking agent, a chain transfer agent, an emulsifier, a polymerization initiator, a solvent, and other components as needed. The flexible resin composition is preferably, for example, a resin emulsion, in which resin particles are dispersed in an aqueous medium. The resin particles are solid or liquid. The aqueous medium as a solvent contains water or a hydrophilic solvent as a main component, and may contain both water and a hydrophilic solvent.

[0020] -Flexible material- The flexible material is a material that improves the impact resistance of the fiber-reinforced resin molding, and is, for example, resin particles.

[0021] The resin particles are not particularly limited and can be appropriately selected depending on the purpose. Examples include acrylic resin particles, polyester resin particles, urethane acrylic resin particles, silicone resin particles, vinyl acetate acrylic resin particles, polyurethane resin particles, and polyester resin particles. Among these, acrylic resin particles are preferred from the viewpoint of design freedom. Examples of acrylic resin particles include acrylic esters, methacrylic esters, aromatic vinyl monomers, unsaturated nitriles, conjugated diolefins, multifunctional vinyl monomers, amide monomers, hydroxyl group-containing monomers, caprolactone addition monomers, amino group-containing monomers, glycidyl group-containing monomers, acid monomers, and vinyl monomers. Examples of acrylic ester resin particles include methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, hexyl acrylate, and 2-ethylhexyl acrylate. Examples of polyester resin particles include polyethylene terephthalate and 1,6-hexanediol dimethacrylate. The soft material may be a single type of resin particle or a combination of two or more types.

[0022] -Crosslinking agent- The crosslinking agent reacts with the flexible material, polymerizing the flexible materials together to form a crosslinked structure. The crosslinking agent improves the strength of the fiber-reinforced resin molded product. In the present invention, the crosslinking agent does not react with the flexible material until the molding process. The crosslinking reaction progresses due to the application of heat and pressure in the molding process, forming a crosslinked structure.

[0023] The type of crosslinking agent is not particularly limited and can be selected appropriately depending on the purpose. However, an alkoxysilane-based crosslinking agent is preferred because it can maintain a non-crosslinked state until the molding process by adjusting the pH when preparing the flexible resin composition.

[0024] The type of alkoxysilane crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose, but examples include vinyltriethoxysilane, vinyltrimethoxysilane, etc. Among them, vinyltriethoxysilane and vinyltrimethoxysilane are preferred from the viewpoint of design freedom. These may be used alone or in combination of two or more.

[0025] The content of the crosslinking agent is preferably 3% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass, based on the total amount of the flexible resin composition. A content of the crosslinking agent of 5% by mass to 10% by mass is preferable in that it allows for both high filling of the flexible material into the fiber sheet and strength of the resulting fiber-reinforced resin molded product.

[0026] - Chain transfer agent - The chain transfer agent adjusts the molecular weight of the polymerization. The chain transfer agent is not particularly limited, and examples thereof include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecyl mercaptan, 1-dodecanethiol, and thioglycerol. The chain transfer agent may be used alone or in combination of two or more. The chain transfer agent is preferably contained in an amount of 1 to 30 parts by mass relative to the total mass of the ink.

[0027] -emulsifier- The emulsifier is not particularly limited, and both non-reactive emulsifiers and reactive emulsifiers can be used, but it is preferable to use a reactive emulsifier. The use of a reactive emulsifier improves the storage stability of the ink. The reactive emulsifier is not particularly limited and can be selected appropriately depending on the purpose, but it is particularly preferable to use an emulsifier having a radically polymerizable double bond. Examples of reactive emulsifiers include an aqueous solution of polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate and sodium alkanesulfonate. The emulsifier may be used alone or in combination of two or more types. The emulsifier is preferably contained in an amount of 1 to 30 parts by mass relative to the total mass of the ink.

[0028] -Polymerization initiator- The polymerization initiator initiates polymerization of the flexible material. Radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators can be used as the polymerization initiator, but it is preferable to use radical polymerization initiators. The use of a polymerization initiator improves dispersion stability. Furthermore, the polymerization initiator is preferably contained in an amount of 1 to 30 parts by mass relative to the total mass of the ink in order to obtain a sufficient polymerization rate. Examples of the radical polymerization initiator include aqueous ammonium persulfate solutions, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, alkylamine compounds, azo compounds, and hexaarylbiimidazole. Examples of the cationic polymerization initiator include photoacid generators that generate acid upon irradiation with light, such as onium salt types and triarylsulfonium salt types having a sulfonium ion or an iodonium ion as the cation moiety. Examples of anionic polymerization initiators include photobase generators that generate a base upon irradiation with light. Photobase generators include ionic types that generate a strong base and nonionic types that have excellent solubility and stability. The polymerization initiator may be used alone or in combination of two or more kinds.

[0029] [Fiber sheet] The fiber sheet is a sheet containing fibers and formed into a flat shape. The type of fiber is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include glass fiber, carbon fiber, boron fiber, and aramid fiber. Among these, glass fiber or carbon fiber is preferred because it improves the strength of the fiber-reinforced resin molded product. The fiber sheet may contain one type of fiber alone or two or more types of fibers in combination.

[0030] [ink] The ink contains a soft resin composition and a solvent, and may further contain other components as required. The solvent contained in the ink preferably contains water and an organic solvent.

[0031] -Organic solvents- The organic solvent is not particularly limited, and any water-soluble organic solvent can be used, including, for example, polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, propylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, and 1,6-pentanediol. Polyhydric alcohols such as hexanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethyl ether, ethylene glycol monobutyl ether, diethyl ether, ethylene glycol monoethyl ... Examples of the alkyl ether include polyhydric alcohol alkyl ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; propylene carbonate; and ethylene carbonate. It is preferable to use an organic solvent having a boiling point of 250° C. or less, since it not only functions as a wetting agent but also provides good drying properties.

[0032] The content of the organic solvent in the ink is not particularly limited and can be selected appropriately depending on the purpose. From the viewpoint of the drying property and ejection reliability of the ink, however, the content is preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass or less.

[0033] -water- The water content in the ink is not particularly limited and can be selected appropriately depending on the purpose. From the viewpoint of the drying property and ejection reliability of the ink, however, it is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 60% by mass or less.

[0034] <Drying process> In the drying process S2, the fiber sheet impregnated with ink in the specified areas is dried. In the drying process, the resin emulsion as the flexible material becomes gel-like. More specifically, in the patterning process, the flexible material was patterned as a resin emulsion on the fiber sheet, but in the drying process, a resin film as the flexible material is formed on the fiber sheet. Therefore, the viscosity of the flexible material is higher in the drying process than in the patterning process. Furthermore, in the drying process, the flexible material and the crosslinking agent do not react, and no crosslinked structure is formed.

[0035] The drying method is not particularly limited as long as it can remove the solvent contained in the ink impregnated into the fiber sheet, and any known method can be used, such as a method using a hot air dryer or a vacuum dryer.

[0036] The drying temperature is not particularly limited, but is preferably 100°C or higher and 180°C or lower, more preferably 150°C or higher and 180°C or lower, so long as the crosslinking reaction does not proceed and from the viewpoint of filling properties in the molding step.

[0037] <Application process> In the applying step S3, a matrix resin is applied onto the patterned fiber sheet to obtain a fiber reinforced resin composite.

[0038] The application method is not particularly limited as long as it can apply the matrix resin onto the patterned fiber sheet, and can be appropriately selected depending on the purpose, and the matrix resin may be applied manually.

[0039] [Matrix resin] The matrix resin means a resin in a fiber reinforced resin composite that is different from the flexible material in the flexible resin composition.

[0040] The melting point of the matrix resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 265° C. or lower, and more preferably 250° C. or lower. A melting point of 265° C. or lower is preferable because the matrix resin and the soft resin composition can be uniformly filled into the fiber sheet.

[0041] The type of matrix resin is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyamide resins, urethane resins, polyester resins, acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins. Among these, polyamide resins are preferred. The matrix resins may be used alone or in combination of two or more.

[0042] <Lamination process> In the lamination step S4, a plurality of fiber reinforced resin composites are laminated. By changing the number of fiber reinforced resin composites to be laminated, a fiber reinforced resin composite having a desired thickness can be obtained.

[0043] The lamination method is not particularly limited as long as it allows a plurality of fiber-reinforced resin composites to be laminated, and can be appropriately selected depending on the purpose.

[0044] <Forming process> In the molding step S5, the fiber reinforced resin composite is molded to obtain a molded fiber reinforced resin composite, for example, by heating, pressing, etc.

[0045] The heating and pressurizing in the molding process causes the flexible material contained in the flexible resin composition to react with the crosslinking agent to form a crosslinked structure. For example, since a resin film is formed on the fiber sheet as the flexible material in the drying process, the crosslinking agent reacts with this resin film to form a crosslinked structure. The molding process fills the interior of the fiber sheet with the flexible material and matrix resin. The molding conditions in the molding step can be appropriately selected depending on the reactivity between the soft material contained in the soft resin composition and the crosslinking agent.

[0046] The molding method is not particularly limited as long as the reaction between the flexible material contained in the flexible resin composition and the crosslinking agent proceeds by heating and pressurizing, and any known method can be used, such as a method using a heat press machine.

[0047] (Manufacturing system for fiber-reinforced plastic moldings) FIG. 2 is a schematic diagram of a manufacturing system for a fiber-reinforced resin molded product according to one embodiment of the present invention. The manufacturing system 1 for a fiber-reinforced resin molded product according to one embodiment of the present invention includes a patterning device 100, a drying device 200, an application device 300, a lamination device 400, and a molding device 500.

[0048] The patterning device 100 performs a patterning step of patterning a fiber sheet with ink containing a flexible resin composition that includes at least a flexible material. As the patterning device, for example, an inkjet printer (IPSiO GX e5500, manufactured by Ricoh Co., Ltd.) can be suitably used.

[0049] The drying device 200 performs a drying process to dry the fiber sheet. As the drying device, a commonly used hot air dryer or vacuum dryer can be suitably used.

[0050] The application device 300 applies a matrix resin onto the patterned fiber sheet to perform an application step of obtaining a fiber reinforced resin composite. As the application device, for example, an electromagnetic feeder (manufactured by Sinfonia Technology Co., Ltd.) can be suitably used.

[0051] The laminating device 400 performs a laminating step of laminating a plurality of fiber reinforced resin composites.

[0052] As the molding device 500, a heat press machine (manufactured by Sintokogio Co., Ltd.) can be suitably used as a molding device for performing the molding step of molding a fiber reinforced resin composite to obtain a fiber reinforced resin molded product.

[0053] (fiber reinforced resin molding) 3A and 3B are schematic diagrams showing the changes before and after the molding step in a method for producing a fiber-reinforced resin molded product according to one embodiment of the present invention, where Fig. 3A shows the fiber-reinforced resin composite before the molding step, and Fig. 3B shows the fiber-reinforced resin molded product after the molding step. 3(A) shows a state in which a flexible resin composition 11 and a matrix resin 12 are disposed on a fiber sheet 10. Before the molding process, the flexible material contained in the flexible resin composition 11 has not reacted with the crosslinking agent, and the flexible resin composition 11 is in a non-crosslinked state. In other words, the interior of the fiber sheet 10 is not filled with the flexible resin composition 11 and the matrix resin 12. On the other hand, in FIG. 3(B), the interior of the fiber sheet 10 is filled with a flexible resin composition 11 and a matrix resin 12. By molding in the molding process, the flexible material is filled into the interior of the fiber sheet 10 together with the matrix resin 12. At the same time, a reaction with the crosslinking agent progresses, resulting in crosslinking. By filling the interior of the fiber sheet 10 with the flexible material, the strength of the resulting fiber-reinforced resin molded product is improved. In addition, by adjusting the region to be impregnated with ink in the patterning process, the physical properties of the fiber-reinforced resin molded product, such as strength and impact resistance, can be adjusted. Furthermore, FIG. 3(B) shows a fiber-reinforced resin molded product in which the flexible material is arranged in a predetermined region on the fiber sheet 10 and the matrix resin 12 is arranged in a region other than the predetermined region, and the bending strength of the fiber-reinforced resin molded product is 1 N / mm 2 That's all. 3 shows a state in which the flexible resin composition 11 is disposed in the center of the predetermined region on the fiber sheet 10, and the matrix resin 12 is disposed on both ends of the fiber sheet 10 excluding the center. Alternatively, the flexible resin composition 11 may be disposed on both ends of the predetermined region on the fiber sheet 10, and the matrix resin 12 may be disposed in the center of the fiber sheet 10 excluding the ends. [Example]

[0054] Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, "parts" means "parts by mass" unless otherwise specified.

[0055] (Preparation Example 1) -Preparation of Ink 1- The acetate buffer solution was adjusted in advance to pH 4.0 using ion-exchanged water, acetic acid, and sodium acetate. 41.0 parts by mass of methyl methacrylate (MMA) and 51.5 parts by mass of 2-ethylhexyl acrylate (EHA) were used as raw materials for the flexible material, 7.5 parts by mass of vinyltriethoxysilane (VTES) as a crosslinking agent, 0.2 parts by mass of 1-octanethiol (NOM) as a chain transfer agent, 1.8 parts by mass of polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate aqueous solution (AR-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) as an emulsifier, and 50.0 parts by mass of an acetate buffer solution were emulsified in a homomixer to obtain a uniform milky white emulsion. In a 1 L flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser, 87.0 parts by mass of acetate buffer solution was placed, and the temperature was raised to 70° C. while introducing nitrogen. Next, 2.8 parts by mass of 10% by mass polyoxyethylene styrenated propenyl phenyl ether sulfate ester ammonium (Aqualon AR-10 (Dai-ichi Kogyo Seiyaku Co., Ltd.)) as an emulsifier and 2.6 parts by mass of 5% by mass ammonium persulfate aqueous solution (APS) as a polymerization initiator were added. The emulsion was then added dropwise continuously over 2.5 hours. Furthermore, 0.6 parts by mass of 5% by mass ammonium persulfate aqueous solution was added every hour for 3 hours from the start of the addition. After the addition was completed, the mixture was aged at 70°C for 2 hours and then cooled to obtain a resin particle dispersion. 50 parts by mass of the obtained resin particle dispersion and 50 parts by mass of propylene glycol as a solvent were mixed and stirred. Thereafter, the mixture was filtered under pressure using a cellulose acetate membrane filter with an average pore size of 0.8 μm to remove coarse particles, and ink 1 was obtained.

[0056] (Preparation Example 2) -Preparation of Ink 2- Ink 2 was obtained in the same manner as in Preparation Example 1, except that the amount of 2-ethylhexyl acrylate added was changed to 54.0 parts by mass and the amount of vinyltriethoxysilane added was changed to 5.0 parts by mass.

[0057] (Preparation Example 3) -Preparation of Ink 3- Ink 3 was obtained in the same manner as in Preparation Example 1, except that the amount of 2-ethylhexyl acrylate added was changed to 49.0 parts by mass and the amount of vinyltriethoxysilane added was changed to 10.0 parts by mass.

[0058] (Preparation Example 4) -Preparation of Ink 4- Ink 4 was obtained in the same manner as in Preparation Example 1, except that vinyltriethoxysilane was changed to vinyltrimethoxysilane.

[0059] (Preparation Example 5) -Preparation of Ink 5- Ink 5 was obtained in the same manner as in Preparation Example 2, except that vinyltriethoxysilane was changed to vinyltrimethoxysilane.

[0060] (Preparation Example 6) -Preparation of Ink 6- Ink 6 was obtained in the same manner as in Preparation Example 3, except that vinyltriethoxysilane was changed to vinyltrimethoxysilane (VTMS).

[0061] (Preparation Example 7) -Preparation of Ink 7- The raw materials for the flexible material were 41.0 parts by mass of methyl methacrylate and 51.5 parts by mass of 2-ethylhexyl acrylate, 7.5 parts by mass of vinyltriethoxysilane as a crosslinking agent, 0.2 parts by mass of 1-octanethiol as a chain transfer agent, 1.8 parts by mass of an aqueous solution of polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate (Aqualon AR-10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)) as an emulsifier, and 50.0 parts by mass of ion-exchanged water as a solvent, and the mixture was emulsified in a homomixer to obtain a uniform, milky white emulsion. In a 1 L flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser, 87.0 parts by mass of ion-exchanged water was placed, and the temperature was raised to 70° C. while introducing nitrogen. Next, 2.8 parts by weight of a 10% by weight aqueous solution of Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier and 2.6 parts by weight of a 5% by weight aqueous solution of ammonium persulfate as an initiator were added, and the emulsion was then continuously added dropwise over 2.5 hours. Furthermore, 0.6 parts by weight of a 5% by weight aqueous solution of ammonium persulfate was added every hour for 3 hours after the start of the addition. After the addition was completed, the mixture was aged at 70°C for 2 hours and then cooled to obtain a resin particle dispersion. 50 parts by mass of the obtained resin particle dispersion and 50 parts by mass of propylene glycol as a solvent were mixed and stirred. Thereafter, the mixture was filtered under pressure using a cellulose acetate membrane filter with an average pore size of 0.8 μm to remove coarse particles, thereby obtaining ink 7.

[0062] (Preparation Example 8) -Preparation of Ink 8- Ink 8 was obtained in the same manner as in Preparation Example 7, except that the crosslinking agent in Preparation Example 7 was changed from vinyltriethoxysilane to vinyltrimethoxysilane.

[0063] (Preparation Example 9) -Preparation of Ink 9- Ink 9 was obtained in the same manner as in Preparation Example 7, except that the crosslinking agent in Preparation Example 7 was changed from vinyltriethoxysilane to 1,6-hexanediol dimethacrylate.

[0064] (Preparation Example 10) -Preparation of Ink 10- Ink 10 was obtained in the same manner as in Preparation Example 9, except that the amount of 2-ethylhexyl acrylate added as the raw material for the soft material was changed to 54.0 parts by mass and the amount of 1,6-hexanediol dimethacrylate added was changed to 5.0 parts by mass.

[0065] (Preparation Example 11) -Preparation of Ink 11- Ink 11 was obtained in the same manner as in Preparation Example 9, except that the amount of 2-ethylhexyl acrylate added as the softening material was changed to 49.0 parts by mass and the amount of 1,6-hexanediol dimethacrylate added was changed to 10.0 parts by mass.

[0066] Example 1 -Production of fiber reinforced resin molding 1- In the patterning process, ink 1 was applied to the center of a carbon fiber sheet (carbon fiber nonwoven fabric, Takayasu Co., Ltd., 100 mm x 100 mm) using an inkjet printer (IPSiO GX e5500, manufactured by Ricoh Co., Ltd.) as a patterning device. Next, in the drying process, the carbon fiber sheet coated with ink 1 was dried at 120 °C for 40 minutes using a dryer (manufactured by Yamato Scientific Co., Ltd.). Next, in the application process, polyamide resin (PA2200, manufactured by EOS Corporation) was applied as a matrix resin to both ends of the carbon fiber sheet except for the central area where ink 1 was applied using an electromagnetic feeder (manufactured by Sinfonia Technology Co., Ltd.), obtaining a fiber-reinforced resin composite. Then, in the lamination process, 22 fiber-reinforced resin composites were manually stacked. In the molding process, the laminated fiber-reinforced resin composite was heated and pressurized for 300 seconds at a temperature of 200°C and a load of 2.5 kN using a heat press machine (manufactured by Shinto Kogyo Co., Ltd.), and then water-cooled while maintaining the load at 2.5 kN. The upper and lower heating plates of the heat press machine were water-cooled to 45°C, and the pressure was released, yielding a fiber-reinforced resin molded product 1.

[0067] Examples 2 to 11 -Production of fiber-reinforced resin moldings 2 to 11- Fiber reinforced resin molded products 2 to 11 were obtained in the same manner as in Example 1, except that the ink used in Example 1 was changed to the ink shown in Table 1.

[0068] (Comparative Examples 1 and 2) -Production of fiber reinforced resin molded product 12- The patterning and drying processes were omitted. In the application process, polyamide resin (PA2200, manufactured by EOS) was applied as a matrix resin to the entire surface of a carbon fiber sheet (carbon fiber nonwoven fabric, manufactured by Takayasu Co., Ltd., 100 mm × 100 mm) using an electromagnetic feeder (manufactured by Sinfonia Technology Co., Ltd.). The lamination process and molding process were performed in the same manner as in Example 1, and a fiber-reinforced resin molded product 12 was obtained.

[0069] -Production of fiber reinforced resin molding 13- In the patterning step, ink 1 was applied to the entire surface of a carbon fiber sheet (carbon fiber nonwoven fabric, manufactured by Takayasu Co., Ltd., 100 mm x 100 mm) using an inkjet printer (manufactured by Ricoh Co., Ltd.). In the application step, polyamide resin (PA2200, manufactured by EOS) was applied as a matrix resin to the entire surface of the carbon fiber sheet on which ink 1 had been applied using an electromagnetic feeder (manufactured by Sinfonia Technology Co., Ltd.). The drying step, lamination step, and molding step were performed in the same manner as in Example 1, and a fiber-reinforced resin molded product 13 was obtained.

[0070] For the fiber-reinforced resin moldings 1 to 13 obtained in Examples 1 to 11 and Comparative Examples 1 and 2, the ink filling property and the bending strength of the moldings were evaluated to confirm the degree of freedom in design. The results are shown in Table 1. If the ink is filled to 80% or more, the flexible material can be sufficiently arranged in the target area, ensuring the degree of freedom in design, and the bending strength of the moldings is 1 N / mm 2 If the strength is above this level, there is no practical problem, and the degree of freedom in design can be ensured.

[0071] <Filling ability of flexible materials> The fiber-reinforced resin molding was observed under an optical microscope, and the area ratio occupied by the flexible material was evaluated as the filling rate of the flexible material in the carbon fiber sheet. [Evaluation criteria] ◎: Filling rate is 90% or more ○: Filling rate is 80% or more but less than 90% ×: Filling rate less than 80%

[0072] <Flexural strength of molded product> The fiber-reinforced resin molded product (thickness 1 mm) was cut into a piece of 75 mm x 6 mm, and a three-point bending test was performed using a strength testing machine (AG-5kNX, manufactured by Shimadzu Corporation). [Evaluation criteria] ◎: Bending strength is 5N / mm 2 End 〇: Bending strength is 1N / mm 2 More than 5N / mm 2 less than ×: Bending strength is 1N / mm 2 less than

[0073] [Table 1]

[0074] The fiber reinforced resin moldings of Examples 1 to 11 were all filled with 80% or more of a flexible material and had a bending strength of 1 N / mm 2 As a result, by adjusting the pattern arrangement of the flexible material, it is possible to arrange the flexible material in the desired area and ensure strength that does not pose any practical problems, so there is a high degree of freedom in the design of fiber-reinforced resin moldings. On the other hand, when no flexible material is applied, the strength of the resulting fiber-reinforced resin molded product is insufficient, as shown in Comparative Example 1. Furthermore, even when the flexible material is not arranged in a pattern and the flexible material and matrix resin are applied to the entire surface of the fiber sheet, as shown in Comparative Example 2, the strength of the resulting fiber-reinforced resin molded product is also insufficient.

[0075] The embodiments of the present invention are as follows, for example. <1> a patterning step of patterning a fiber sheet with an ink containing a soft resin composition including at least a soft material; an application step of applying a matrix resin onto the patterned fiber sheet to obtain a fiber-reinforced resin composite; and a molding step of molding the fiber reinforced resin composite to obtain a fiber reinforced resin molded product, The method for producing a fiber-reinforced resin molded product is characterized in that the soft material and matrix resin are filled inside the fiber sheet in the fiber-reinforced resin molded product. <2> The patterning step includes patterning a predetermined region of the fiber sheet, The application step is characterized in that the application is performed on an area different from the predetermined area. <1> 1. A method for producing the fiber-reinforced resin molded article according to claim 1. <3> The method further comprises a lamination step of laminating a plurality of the fiber-reinforced resin composites. <1> from <2> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <4> The method further comprises a drying step of drying the fiber sheet before the applying step. <1> from <3> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <5> The flexible material in the patterning process is a resin emulsion. <1> from <4> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <6> The soft resin composition contains a crosslinking agent, and the crosslinking agent is an alkoxysilane-based crosslinking agent. <1> from <5> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <7> The content of the crosslinking agent contained in the soft resin composition is 5% by mass or more and 10% by mass or less. <1> from <6> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <8> The fiber sheet contains glass fiber or carbon fiber. <1> from <7> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <9> The matrix resin has a melting point of 265°C or less. <1> from <8> 1. A method for producing a fiber-reinforced resin molded article according to any one of claims 1 to 9. <10> a patterning device that patterns a fiber sheet with an ink containing a soft resin composition that includes at least a soft material; a drying device for drying the fiber sheet; an application device for applying a matrix resin onto the patterned fiber sheet to obtain a fiber-reinforced resin composite; a lamination device for laminating a plurality of the fiber reinforced resin composites; a molding device for molding a plurality of stacked fiber reinforced resin composites to obtain a fiber reinforced resin molded product; The manufacturing system for a fiber-reinforced resin molding is characterized in that the soft material and matrix resin are filled inside the fiber sheet in the fiber-reinforced resin molding. <11> A flexible material is placed in a predetermined area on the fiber sheet, and a matrix resin is placed in the area other than the predetermined area, and the bending strength is 1 N / mm 2 The above is a fiber reinforced resin molded product. [Explanation of symbols]

[0076] 1. Fiber-reinforced plastic molding manufacturing system 10 Fiber sheet 11 Soft resin composition 12 Matrix resin 100 Patterning device 200 Drying equipment 300 Granting Device 400 Stacking Device 500 Molding equipment [Prior art documents]

Charter Documents

[0077] [Patent Document 1] Patent No. 7048956

Claims

1. a patterning step of patterning a fiber sheet with an ink containing a soft resin composition including at least a soft material; an application step of applying a matrix resin onto the patterned fiber sheet to obtain a fiber-reinforced resin composite; and a molding step of molding the fiber reinforced resin composite to obtain a fiber reinforced resin molded product, A method for producing a fiber-reinforced resin molding, characterized in that the soft material and matrix resin are filled inside the fiber sheet in the fiber-reinforced resin molding.

2. The patterning step includes patterning a predetermined region of the fiber sheet, The method for producing a fiber-reinforced resin molding according to claim 1 , wherein the applying step applies the resin to an area different from the predetermined area.

3. The method for producing a fiber-reinforced resin molded article according to claim 1, further comprising a lamination step of laminating a plurality of the fiber-reinforced resin composites.

4. The method for producing a fiber-reinforced resin molding according to claim 1, further comprising a drying step of drying the fiber sheet before the applying step.

5. 2. The method for producing a fiber-reinforced resin molded product according to claim 1, wherein the flexible material in the patterning step is a resin emulsion.

6. 2. The method for producing a fiber-reinforced resin molded article according to claim 1, wherein the flexible resin composition contains a crosslinking agent, and the crosslinking agent is an alkoxysilane-based crosslinking agent.

7. 2. The method for producing a fiber-reinforced resin molded product according to claim 1, wherein the content of the crosslinking agent contained in the soft resin composition is 5% by mass or more and 10% by mass or less.

8. 2. The method for producing a fiber-reinforced resin molding according to claim 1, wherein the fiber sheet contains glass fiber or carbon fiber.

9. 2. The method for producing a fiber-reinforced resin molding according to claim 1, wherein the matrix resin has a melting point of 265° C. or lower.

10. a patterning device that patterns a fiber sheet with an ink containing a soft resin composition that includes at least a soft material; a drying device for drying the fiber sheet; an application device for applying a matrix resin onto the patterned fiber sheet to obtain a fiber-reinforced resin composite; a lamination device for laminating a plurality of the fiber reinforced resin composites; a molding device for molding a plurality of stacked fiber reinforced resin composites to obtain a fiber reinforced resin molded product; A manufacturing system for a fiber-reinforced resin molded product, characterized in that the soft material and matrix resin are filled inside the fiber sheet in the fiber-reinforced resin molded product.

11. A flexible material is placed in a predetermined area on the fiber sheet, and a matrix resin is placed in the area other than the predetermined area, and the bending strength is 1 N / mm ２ The above fiber reinforced resin molded product.

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