JP2006044261A - Fiber-reinforced composite material, its production method and integrally structured material using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fiber-reinforced composite material to which another material can easily and strongly be adhered by an RTM molding method using a continuous reinforcing fiber material and to provide a continuous reinforcing fiber material. <P>SOLUTION: The method comprises a lamination process setting a thermoplastic material mainly composed of a thermoplastic resin on at least a part of the surface of a continuous reinforcing fiber material, a preheating process melting the thermoplastic material to form a film of a thermoplastic resin on a surface of the continuous reinforcing fiber material and a curing process introducing/curing a thermosetting resin. In the continuous reinforcing fiber material, a thermoplastic coating layer is formed on at least a part of the surface of the continuous reinforcing fiber material, and this material is useful as a material for coating a surface of a composite material for forming a thermoplastic resin layer on a surface of a molded article obtained from a continuous reinforcing fiber material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a fiber reinforced composite material obtained by impregnating and curing an uncured matrix resin in a reinforced fiber base material. Furthermore, the present invention relates to a fiber reinforced composite material, an integrated structure member obtained by joining the fiber reinforced composite material and another member, and a method for manufacturing the same.

  Fiber reinforced composite materials are excellent in moldability, thin wall, light weight, high rigidity, productivity, and economical efficiency. Electrical / electronic equipment parts, automotive equipment parts, personal computers, OA equipment, AV equipment, mobile phones, telephones, facsimiles, home appliances. It is frequently used in parts and casings of electrical and electronic equipment such as products and toy supplies.

  As a material superior in thickness, light weight, and high rigidity, there is a fiber-reinforced composite material using continuous reinforcing fibers. A typical method for manufacturing fiber reinforced composite materials is a method of stacking and curing fiber reinforced prepregs in which continuous reinforced fibers are impregnated with uncured resin, but it is easy to mass-produce molded products with complex shapes. It was unsuitable for production.

  As another manufacturing method, there is a so-called resin transfer molding (RTM) molding method in which a fiber base material is shaped into a mold, an uncured resin is injected, the base material is impregnated, and then cured. Since this molding method forms a base material that is not impregnated with resin, it is possible to produce a molded product having a relatively complicated shape. However, it is often difficult to cope with complex shapes as compared to injection molded products and metal molded products.

Therefore, in order to obtain a molded product having a complicated shape, a technique for integrally joining a fiber-reinforced plastic plate, a metal plate, or the like with another molded product or the like is required. Patent Document 1 describes a method of filling a mold with a reinforcing fiber base having at least a part of the surface coated with a thermoplastic resin, and injecting a thermosetting resin. In particular, it is intended to impart toughness to the fiber reinforced composite material, and since a thermoplastic resin is contained inside the molded product, a separate adhesive is required for joining with another member. In general, when using known adhesives, the man-hours and lead time required for the bonding process increase costs and reduce productivity, and above all, the bond strength cannot be fully expressed, and the characteristics of fiber-reinforced composite materials with high strength and high rigidity Is a problem. In addition, mechanical joining methods such as bolts and screws not only require a separate machining process, but are limited in design and limited in application, and above all, the characteristics of fiber-reinforced composite materials such as lightness are impaired. There is a problem.
JP-A-8-300395

    The present invention eliminates the problems of the prior art, and can be easily and firmly bonded to another member. The reinforced fiber base material is impregnated with an uncured matrix resin, represented by RTM molding. A method for producing a fiber-reinforced composite material and a continuous reinforcing fiber substrate are obtained.

The present invention adopts the following means in order to solve the problems. That is,
(1) Laminating step of disposing a thermoplastic base material mainly composed of a thermoplastic resin on at least a part of the surface of the continuous reinforcing fiber base material, and melting the thermoplastic base material on the surface of the continuous reinforcing fiber base material A method for producing a fiber-reinforced composite material, comprising: a curing step of forming a resin film and simultaneously injecting and curing a thermosetting resin composition.
(2) Laminating step in which a thermoplastic base material mainly composed of a thermoplastic resin is arranged on at least a part of the surface of the continuous reinforcing fiber base material, and the thermoplastic base material is melted to thermoplastic the continuous reinforcing fiber base surface. A method for producing a fiber-reinforced composite material, comprising: a preheating step for forming a resin film; and a curing step for injecting and curing a thermosetting resin.
(3) A continuous reinforcing fiber base material for a composite material surface layer in which a thermoplastic resin is disposed on at least a part of the surface of a base material made of continuous reinforcing fibers and has a capability of forming a thermoplastic resin layer on the surface of a molded product.
(4) The continuous reinforcing fiber base material for a composite material surface layer according to (3), wherein a thermoplastic resin is fused to at least a part of the surface of the base material made of the continuous reinforcing fibers.
(5) The continuous reinforcing fiber substrate for a composite material surface layer according to any one of (3) and (4), wherein the Gurley seconds defined in the present specification are in the range of 100 to 10,000 s.
(6) A continuous reinforcing fiber base material for a composite material surface layer, wherein a thermoplastic resin coating is formed on at least a part of the surface of the base material made of continuous reinforcing fibers, and has the ability to form a thermoplastic resin layer on the surface of the molded product.
(7) The continuous reinforcing fiber base material for a composite material surface layer according to any one of (3) to (6), wherein the drapeability defined in the present specification is in the range of 5 to 50 cm.
(8) The continuous reinforcing fiber base material for a composite material surface layer according to any one of (6) and (7), wherein an intrusion surface of the thermoplastic resin film is uneven in a thickness direction.
(9) The continuous reinforcing fiber base material for a composite material surface layer according to any one of (6) to (8), wherein the maximum thickness Tpf of the thermoplastic resin coating is in the range of 10 to 1000 μm.
(10) The continuous reinforcing fiber base material for a composite material surface layer according to any one of (6) to (9), wherein an average thickness of the thermoplastic resin coating is 0.01 to 1000 μm.
(11) The continuous reinforcing fiber base material for a composite material surface layer according to any one of (3) to (10), wherein the continuous reinforcing fiber is a carbon fiber.
(12) The continuous reinforcing fiber substrate for a composite material surface layer according to any one of (3) to (11), wherein the continuous reinforcing fiber substrate is a woven fabric substrate.
(13) The thermoplastic resin on the continuous reinforcing fiber base material for the composite material surface layer in which the thermoplastic resin is disposed on at least a part of the surface of the base material made of continuous reinforcing fibers is melted, and a pressure of 0.01 to 10 MPa is applied. The continuous reinforcing fiber base material for a composite material surface layer according to any one of (6) to (12), which is obtained by applying.
(14) The continuous reinforcing fiber base material for a composite material surface layer according to any one of (3) to (13) is a surface on which a thermoplastic resin is disposed as an outermost surface, and a predetermined number of continuous reinforcing fiber base materials are used. The manufacturing method of the fiber reinforced composite material including the lamination process to arrange | position, and the hardening process to inject | pour and cure reaction of thermosetting resin.
(15) A film of a thermoplastic resin is formed on at least a part of the surface of the base material made of continuous reinforcing fibers, and the entering surface of the film of the thermoplastic resin is uneven in the thickness direction, and The fiber reinforced composite material according to any one of (1), (2), and (14), wherein a continuous reinforcing fiber base material for a composite material surface layer having a maximum thickness Tpf of a thermoplastic resin coating in the range of 10 to 1000 μm is used. Manufacturing method.
(16) The fiber according to any one of (1), (2), (14), and (15), wherein a continuous reinforcing fiber base material for a composite material surface layer having an average thickness of 0.01 to 1000 μm is used. A method for producing a reinforced composite material.
(17) Production of a fiber-reinforced composite material according to any one of (1), (2) and (14) to (16) using a continuous reinforcing fiber base material for a composite material surface layer, wherein the continuous reinforcing fibers are carbon fibers. Method.
(18) The fiber-reinforced composite according to any one of (1), (2), and (14) to (17), wherein the continuous reinforcing fiber base material is a woven base material. Material manufacturing method.
(19) The method for producing a fiber-reinforced composite material according to (2), wherein the preheating step is performed in a state where a pressure of 0.01 to 10 MPa is applied.
(20) A fiber-reinforced composite material obtained by the production method according to any one of (1), (2), and (14) to (19), wherein the interface between the thermosetting resin and the thermoplastic resin Is a fiber-reinforced composite material with an irregular shape.
(21) An integrated structural member in which the fiber-reinforced composite material according to (20) and another member are joined via the thermoplastic resin.
(22) The integrated structural member according to (21), wherein a vertical adhesive strength of a joint surface between the fiber-reinforced composite material and another member is 6 MPa or more at 25 ° C.
(23) Integration according to any one of (21) or (22) used for any one of a part, member, casing or outer plate of an electrical / electronic device, OA device, home appliance, automobile or building material. Structural member.
(24) In the integrated structural member according to any one of (21) to (23), bonding of the fiber-reinforced composite material and another member may be performed by heat welding, vibration welding, ultrasonic welding, laser welding, or insert. A method for manufacturing an integrated structural member formed by at least one method selected from the group consisting of injection molding and outsert injection molding.

  According to the production method of the present invention, a fiber reinforced composite material obtained by impregnating and curing an uncured matrix resin on a reinforced fiber base material represented by RTM molding or the like is used and bonded to another member with high adhesive strength. An integrated structural member can be obtained easily.

  Below, the manufacturing method of the fiber reinforced composite material of this invention and the continuous reinforcement fiber base material for composite material surface layers are demonstrated in detail with desirable embodiment.

  FIG. 1 shows a method for molding a fiber-reinforced composite material according to an embodiment of the present invention. Reference numeral 1 denotes a mold, and an uneven cavity 2 is formed inside by clamping the upper mold 1a and the lower mold 1b. In the cavity 2, the continuous reinforcing fiber base 3 and the thermoplastic base 4 are arranged in a predetermined form when the fiber reinforced composite material is molded. After the lamination, a thermosetting resin is injected from the injection port, and a curing reaction is performed at a predetermined temperature. The form of the continuous reinforcing fiber base 3 is not particularly limited, and a reinforcing fiber bundle composed of a large number of reinforcing fibers, a woven fabric composed of the fiber bundle, and a reinforcing fiber bundle in which a large number of reinforcing fibers are arranged in one direction. (Unidirectional fiber bundles), unidirectional woven fabrics composed of the unidirectional fiber bundles, and the like, combinations thereof, and multi-layer arrangements. Of these, woven fabrics and unidirectional fiber bundles are preferred from the viewpoint of substrate productivity. The reinforcing fiber group may be composed of a plurality of fiber bundles having the same form, or may be composed of a plurality of fiber bundles having different forms. The number of reinforcing fibers constituting one reinforcing fiber group is usually 300 to 48,000, but considering the production of the base material, it is preferably 300 to 24,000, more preferably 1,000. ~ 12,000.

  Here, the reinforcing fiber group is composed of a large number of reinforcing fibers continuous in a length of 10 mm or more, preferably 20 mm or more in at least one direction. The reinforcing fiber group does not need to be continuous over the entire length in the length direction of the fiber reinforced composite material or the entire width in the width direction of the fiber reinforced composite material, and may be divided in the middle.

    Examples of the fiber material of the reinforcing fiber group used include glass fiber, carbon fiber, metal fiber, aromatic polyamide fiber, polyaramid fiber, alumina fiber, silicon carbide fiber, boron fiber, and basalt fiber. These are used alone or in combination of two or more. These fiber materials may be subjected to surface treatment. Examples of the surface treatment include oxidation treatment by heating, electrolysis and the like, metal deposition treatment, treatment with a coupling agent, treatment with a sizing agent, and additive adhesion treatment. Among these fiber materials, conductive fiber materials are also included. As the fiber material, carbon fiber having a small specific gravity, high strength and high elastic modulus is preferably used.

    Moreover, as a thermoplastic resin which comprises a thermoplastic base material, it is preferable that solubility parameter (delta) (SP value) is 8-16, More preferably, it is 9-16, More preferably, it is 10-15, Most preferably, it is 11-11. 14. By setting it within the above range, the cohesive force of the thermoplastic resin is large, and it is effective in increasing the adhesive strength which is one of the objects of the present invention.

  Examples of the thermoplastic resin that can achieve the solubility parameter δ include amide bonds, ester bonds, urethane bonds, ether bonds, amino groups, hydroxyl groups, carboxyl groups, acid anhydride groups, sulfonic acid groups, aromatic rings, imide rings, and the like. And those having a bond, functional group or structure having a polarity higher than that of the hydrocarbon skeleton. Examples of the thermoplastic resin composition include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), liquid crystal polyester, and other styrene resins. And polyamide (PA), polycarbonate (PC), polymethylene methacrylate (PMMA), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI) ), Polysulfone (PSU), modified PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyether Ketonketon (PEKK), polyarylate (PAR), polyether nitrile (PEN), modified polypropylene, these resins obtained by blending at least two kinds.

  In order to improve impact resistance, the thermoplastic resin may be added with an elastomer or a rubber component, and from the viewpoint of enhancing functionality, a filler or an additive may be added. For example, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat stabilizers, mold release agents, antistatic agents Plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, and coupling agents. In particular, when an inorganic substance is added, a smaller dispersion size is more preferable from the viewpoint of impregnation into the reinforcing fiber group. In particular, those having a nano-order dispersion size are more preferable from the viewpoint that the effect can be exhibited by addition of a small amount.

  As a form of the base material made of the thermoplastic resin, there are a nonwoven fabric, a woven fabric, particles and a film, and these are preferably used alone or in combination of two or more. By adopting the above form, the reinforced fiber base material can be sufficiently impregnated with the thermoplastic resin, and the surface of the fiber reinforced composite material can be appropriately covered, and a strong adhesive force with another member can be expressed. it can.

It is preferable that the non-woven fabric or woven fabric has a void area of 0 to 50 mm ² . More preferably 0~40mm ^2, especially preferably 0~30mm ^2. The void area is an area of a void portion surrounded by fibers forming a thermoplastic base material in a nonwoven fabric and a woven fabric. The void area can be measured from an optical microscope or SEM observation. By setting the void area in the above range, a fiber-reinforced composite material uniformly coated with a thermoplastic resin can be obtained without causing the thermosetting resin injected at the time of molding to exude to the surface. The lower limit of the void area is not particularly limited, and a fiber-reinforced composite material that is uniformly coated with a thermoplastic resin can be obtained even in the form of a film having a void area of 0 mm ² .

  The average particle diameter of the particles is preferably 1000 μm or less, more preferably 700 μm or less, and particularly preferably 500 μm or less. By setting it within the above range, the reinforcing fiber base material can be impregnated with the thermoplastic resin without unevenness, and the surface of the fiber-reinforced composite material can be appropriately covered.

The interval between adjacent particles of the particles is preferably 5 mm or less, more preferably 4 mm or less, and particularly preferably 3 mm or less. The interval between adjacent particles is a value (mm) obtained by measuring 100 or more intervals between adjacent particles and dividing the sum of the measurement values by the number of measurements. The interval between adjacent particles can be measured from an optical microscope or SEM observation. By setting the interval between adjacent particles in the above range, a fiber-reinforced composite material uniformly coated with a thermoplastic resin can be obtained without causing the thermosetting resin injected at the time of molding to exude to the surface. Preferably further the basis weight of the thermoplastic base material is 10 to 500 g / ^{m 2,} more preferably 20 to 400 g / ^{m 2,} more preferably from 40~200g / ^{m 2.} By making it within the above range, the reinforcing fiber base material can be sufficiently impregnated with the thermoplastic resin, and the surface of the fiber reinforced composite material can be properly covered, and a strong adhesive force with another member can be expressed. Can do.

  Examples of the thermosetting resin used include unsaturated polyester, vinyl ester, epoxy, phenol (resol type), urea / melamine, polyimide, urethane, copolymers thereof, and modified products. In particular, an epoxy resin is preferable from the viewpoint of mechanical properties.

The first production method of the present invention includes a lamination step in which the thermoplastic substrate 4 is disposed on at least a part of the surface 5 side of the continuous reinforcing fiber substrate, and then the thermoplastic substrate is melted and a thermosetting resin is injected. -It is important to perform the curing reaction in the same process. By simultaneously injecting and curing the thermosetting resin and melting the thermoplastic base material, the continuous reinforcing fiber base material is impregnated with the thermoplastic resin and a film is formed on the surface. Possible fiber-reinforced composite materials can be created.
The second production method of the present invention includes a lamination step in which the thermoplastic base material 4 is disposed on at least a part of the surface 5 side of the continuous reinforcing fiber base material, and then the thermoplastic base material is melted to obtain a continuous reinforcing fiber base material. It is important to have a preheating step of forming a thermoplastic resin film on the substrate, and then a step of injecting and curing the thermosetting resin. Fiber reinforced composite that can be firmly bonded to another member by injecting and curing the thermosetting resin in order to impregnate the continuous reinforcing fiber substrate with the thermoplastic resin in the preheating process and form a film on the surface. Materials can be created.

  Moreover, in a preheating process, in order to efficiently impregnate a continuous reinforcement fiber base material with a thermoplastic resin, it is preferable to carry out in the state which applied 0.01-10 Mpa of pressure. More preferably, it is 0.03-5 MPa. The pressure can be applied by a method such as temporarily closing the mold.

  In the first continuous reinforcing fiber base material for a composite material surface layer of the present invention, a thermoplastic resin is disposed on at least a part of the surface of the base material composed of continuous reinforcing fibers, and the molded article obtained from the continuous reinforcing fiber base material It is important to form a layer of thermoplastic resin on the surface. By obtaining a composite material having a surface of a thermoplastic resin layer, it is possible to firmly adhere to another member. Further, from the viewpoint of handling of the substrate, it is preferable that the thermoplastic resin is fused to at least a part of the surface of the substrate made of continuous reinforcing fibers.

  The continuous reinforcing fiber base material for the second composite material surface layer of the present invention is a base material for forming a layer of a thermoplastic resin on the surface of a molded product obtained from the continuous reinforcing fiber base material. It is important that at least a part of the surface of the base material, the base material made of continuous reinforcing fibers is impregnated with the thermoplastic resin, and a film of the thermoplastic resin is formed on the surface. A base material made of continuous reinforcing fibers is impregnated with a thermoplastic resin, and a thermoplastic resin film is formed on the surface. Then, the reinforcing fiber base material is impregnated with an uncured matrix resin and cured. A fiber-reinforced composite material having a surface of a plastic resin can be obtained, and strong adhesion to another member becomes possible.

  The first continuous reinforcing fiber base material for the composite material surface layer can be preferably used as a precursor of the second continuous reinforcing fiber base material for the composite material surface layer.

  As a preferred method of forming the second continuous reinforcing fiber base material for the composite material surface layer from the continuous reinforcing fiber base material for the first composite material surface layer, for example, heating the continuous reinforcing fiber base material for the first composite material surface layer, By melting the thermoplastic resin and applying a pressure of 0.01 to 10 MPa, the continuous reinforcing fiber base material can be impregnated with the thermoplastic resin and a film can be formed on the surface.

  The third production method of the present invention is a continuous reinforcing fiber base material in which a thermoplastic resin is disposed on at least a part of the surface of the base material made of continuous reinforcing fibers, and is a molded article obtained from the continuous reinforcing fiber base material. The continuous reinforcing fiber base material for the composite material surface layer for forming a thermoplastic resin layer on the surface of the composite material is disposed so that the side on which the thermoplastic resin of the continuous reinforcing fiber base material for the composite material surface layer is disposed is the outermost surface Subsequently, a fiber reinforced composite material that can be firmly bonded to another member by including a laminating step of arranging a predetermined number of continuous reinforcing fiber bases and a curing step of injecting and curing a thermosetting resin. Can be obtained.

  FIG. 2 shows a schematic view of the continuous reinforcing fiber base 6 for the composite material surface layer. It is important that the continuous reinforcing fiber 7 is impregnated with the thermoplastic resin 8 and a film of the thermoplastic resin is previously formed on the surface. Here, the maximum thickness Tpf-max of the region where the thermoplastic resin coating is present is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 40 μm or more. The maximum thickness Tpf-max is the outermost (surface side) reinforcing fiber 9b-out in contact with the thermoplastic resin 8 resin in the thickness direction of the thermoplastic resin 8 and the thermoplastic resin 8 resin. The distance (Tpf-max) between the innermost reinforcing fiber 9b-in-max in contact with the resin of the thermoplastic resin 8 at the portion where the penetration thickness from the surface to the continuous reinforcing fiber base is the largest Defined. The maximum thickness Tpf-max can be measured in a SEM or TEM photograph of a cross section of the continuous reinforcing fiber base material. If the maximum thickness Tpf-max is 1,000 μm at the maximum, the effect of the present invention is sufficiently achieved.

  In the thickness direction of the thermoplastic resin 8, it is important that the entering surface is uneven at the site where the surface of the thermoplastic resin 8 enters the continuous reinforcing fiber base. Since the entry surface is uneven, a fiber-reinforced composite material that can be firmly bonded to another member can be created. The entering surface of the coating can be measured by SEM or TEM photograph of the cross section of the continuous reinforcing fiber substrate.

  Moreover, it is preferable that the average thickness of the film formed is 0.01-1,000 micrometers, it is more preferable that it is 0.1-200 micrometers, and it is still more preferable that it is 1-50 micrometers. The average thickness of the coating is defined by the distance between the outermost (surface side) reinforcing fiber 9b-out in contact with the thermoplastic resin 8 shown in FIG. When the thickness of the film is not constant, measurement is performed at an arbitrary number of points, and the average value of the obtained measured values is taken as the average thickness of the film. When the average thickness is in the above-mentioned preferable range, a fiber-reinforced composite material that can express adhesive force more reliably is obtained. The average thickness of the coating can be evaluated not only by observing the cross section of the continuous fiber reinforced base material but also by observing the cross section of the fiber reinforced composite material.

  In the third production method, from the viewpoint of productivity, a continuous reinforcing fiber base for a second composite material surface layer, which is obtained by impregnating a surface of a continuous reinforcing fiber base with a thermoplastic resin in advance and further forming a film of the thermoplastic resin. It is preferable to use a material.

  Further, in any one of the first to third manufacturing methods, from the viewpoint of productivity, a lamination step of arranging the second continuous reinforcing fiber base material for the composite material surface layer so that the coating film of the thermoplastic resin becomes the outermost surface; It is also a preferable manufacturing method.

Moreover, it is preferable that the continuous reinforcement fiber base material which forms the said film exists in the range whose Gurley second number is 100-10000 s. The Gurley seconds are required for 10 ml of air to pass from the surface of the fiber-reinforced substrate having a diameter of 2.5 cm under the conditions of a pressure of 600 mmH ₂ O and a temperature of 23 ° C. using a B-type Gurley type electrometer. Defined as time. The Gurley seconds is an index that correlates with the fiber density of the fiber base material. A short time corresponds to a large gap between the fibers of the fiber base material, and a long time indicates a gap between the fibers of the fiber base material. Corresponds to being. That is, if it is 100 s or more, the gaps between the fibers are moderately clogged (not opened too much), so that the thermoplastic resin can easily form a coating, and if it is 10000 s or less, the gaps between the fibers are moderately opened. Therefore, the fiber base material is preferably impregnated with the thermoplastic resin quickly. For this reason, 120 to 7500 s is more preferable, and 150 to 5000 s is particularly preferable. By being in the above range, a fiber-reinforced composite material uniformly coated with a thermoplastic resin can be obtained without causing the thermosetting resin injected at the time of molding to ooze out to the surface.

  Moreover, it is preferable that the continuous reinforcement fiber base material which forms the said film exists in the range whose drape property is 5-50 cm. More preferably, it is 5-40 cm, More preferably, it is 5-30 cm. When the drapability is within the above range, the continuous reinforcing fiber base material is easy to handle, and the formability of the continuous reinforcing fiber base material at the time of molding is good, so that the moldability is excellent. Such drape measurement is performed as follows. The reinforcing fiber base material is cut into a width of 1 cm and a length of 100 cm, and the reinforcing fiber base material 17 is extruded in the longitudinal direction at a speed of 1 cm / second from the measurement start point (16) on the upper side of the measurement base 15 in FIG. . The amount of extrusion (cm) of the sample from the measurement start point when the tip of the sample is bent by its own weight and comes into contact with the hypotenuse (18) is defined as drape.

  The integrally molded product of the present invention is obtained by joining the fiber reinforced composite material 11 molded by the above manufacturing method and another member. FIG. 3 shows a joint portion between the fiber reinforced composite material and another member 12. The figure which expanded the cross section of is shown. FIG. 3 is a diagram created based on a photograph obtained by using a scanning electron micrograph (SEM). In FIG. 3, the fiber reinforced composite material 11 includes a large number of continuous reinforcing fibers 9 a and 9 b and a thermosetting resin 8 as main components. And it has the thermoplastic resin 8 in the junction part with another member 12, and this thermoplastic resin 8 includes the group of reinforcing fibers 5b. Here, it is preferable that the thermoplastic resin 8 has an uneven shape at the thermosetting resin 13 and its interface 14 and is integrated.

  In order to obtain an excellent adhesive effect when the integrated molded body of the present invention is joined to another member to form an integrally molded product, the thermoplastic resin provided on the surface of the fiber-reinforced composite material is used. It is preferable to join with another member.

  In the integrally molded product of the present invention, the other member is not particularly limited as long as it is made of a material having thermal adhesiveness at the joint portion with the fiber reinforced composite material.

  For example, another member having the same configuration as that of the fiber reinforced composite material and having a thermoplastic resin disposed at the joint is preferable from the viewpoint of manufacturing an integrally molded product having excellent mechanical properties.

  Moreover, if another member is a member comprised from the thermoplastic resin composition, it is preferable from a viewpoint which can shape | mold a more complicated shape. There is no restriction | limiting in particular as a thermoplastic resin to be used. Examples of the thermoplastic resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyester such as liquid crystal polyester, polyethylene (PE), polypropylene ( PP), polyolefins such as polybutylene, styrene resins, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethylene methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide ( PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), modified PSU, polyester Tersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), polyethernitrile (PEN), phenolic resin, Fluoropolymers such as phenoxy resin and polytetrafluoroethylene, polystyrene-based, polyolefin-based, polyurethane-based, polyester-based, polyamide-based, polybutadiene-based, polyisoprene-based, fluorine-based thermoplastic elastomers, etc. There are coalesced, modified and blended resins of at least two of these. An elastomer or a rubber component may be added to the thermoplastic resin in order to improve impact resistance. In particular, from the viewpoint of heat resistance and chemical resistance, PPS resin is used from the viewpoint of molded product appearance and dimensional stability, polycarbonate resin and styrene resin are used, and polyamide resin is used from the viewpoint of strength and impact resistance of the molded product. Preferably used.

  Further, it is more preferable that reinforcing fibers are added to the thermoplastic resin from the viewpoint of improving the mechanical properties. Examples of such reinforcing fibers include polyacrylonitrile-based, rayon-based, lignin-based, pitch-based carbon fibers, graphite fibers, glass fibers, aluminum fibers, brass fibers, stainless fibers, and other metal fibers, silicon carbide fibers, and siliconite. There are inorganic fibers such as ride fibers. Furthermore, a filler and an additive may be added to the thermoplastic resin from the viewpoint of enhancing the functionality. For example, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat stabilizers, mold release agents, antistatic agents Plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, and coupling agents.

  Furthermore, if another member is a member made of a metal material, it is preferable from the viewpoint of enhancing the fastness. The metal material may be a metal material obtained by subjecting aluminum, iron, magnesium, titanium, copper, an alloy thereof, or the like to a thermal adhesive surface treatment.

  The method for integrating the integrally molded product of the present invention is not particularly limited. For example, the manufacturing method includes joining, attaching, and cooling another member at a temperature equal to or higher than the melting point or softening point of the thermoplastic resin film constituting the fiber-reinforced composite material.

  The procedure in the joining is not particularly limited. For example, (i) a method in which a fiber reinforced composite material is preliminarily molded and the two members are simultaneously molded and joined together, or (ii) a fiber reinforced composite material and another member There is a method in which they are separately molded in advance, and both are joined and integrated.

  As a method of integration, a method of mechanically fitting and integrating a fiber reinforced composite material and another member, a method of integrating both using mechanical coupling means such as bolts, screws, rivets, There is also a method of integrating the two using chemical bonding means such as an adhesive. These methods for integrating may be used in combination as necessary.

  As a specific example of the integration method (i), a fiber reinforced composite material is molded, processed or post-processed to a predetermined size as necessary, then inserted into an injection mold, and then another member is formed. There is a technique of injection molding a material to be molded into a mold.

  As a specific example of the integration method (ii), a fiber reinforced composite material is molded, prepared by processing or post-processing to a predetermined size as necessary, and separately molding another member, Are integrated by thermal welding, vibration welding, ultrasonic welding, or the like. Further, if any member has laser permeability, it can be integrated by laser welding.

  Among the above-mentioned integration methods, insert injection molding and outsert injection molding in the integration method (i) are preferably used from the viewpoint of mass productivity of an integrated molded product. From the viewpoint of shape stability and precision of the bonded portion, the integration method (ii) is preferably used, and heat welding, vibration welding, ultrasonic welding, and laser welding can be preferably used.

  Further, if necessary, as the integration method, a method in which the fiber reinforced composite material and another member are mechanically fitted and integrated, and both are integrated using a mechanical coupling means such as a bolt, a screw, and a rivet. There is also a technique for integrating the two using chemical bonding means such as an adhesive. These methods of integrating may be used together as necessary.

  Since the integrated molded product is a field in which the application mainly requires strength, the vertical adhesive strength at 25 ° C. is preferably 6 MPa or more from the viewpoint of adhesive strength that can withstand its use. The pressure is more preferably 8 MPa or more, and further preferably 10 MPa or more. When the vertical adhesive strength at 25 ° C. is less than 6 MPa, the integrated molded product may be destroyed at the joint between the fiber-reinforced composite material and another member when subjected to a strong impact such as dropping. Although there is no restriction | limiting in particular about the upper limit of the perpendicular | vertical adhesive strength in 25 degreeC, if it is 30 Mpa or less, the effect of this invention can fully be achieved.

  As an application of the integrally molded product of the present invention, there is a product in a field where mechanical properties are required with light weight. For example, fuel pipes such as fuel tanks, intake manifolds, fuel pumps, instrument panels, interior materials, spoilers, pillars, door panels, bonnets, engine covers, automobile parts such as various beams and shock absorbers, structures such as windmill blades, cowls Bicycles such as bicycle cranks, bicycle parts, landing gear pods, monocoques, winglets, spoilers, edges, ladders, elevators, failings, ribs and other aircraft related parts, parabolic antennas, laptop computers, mobile phones, digital still cameras , Parts of PDA, portable MD, plasma or other electrical or electronic equipment, components and housing, telephone, facsimile, VTR, copy machine, TV, iron, hair dryer, rice cooker, microwave oven, audio equipment, cleaning , Toiletries, laser discs, compact discs, lighting, refrigerators, air conditioners, typewriters, home or office product parts such as word processors, parts and housings, pachinko machines, slot machines, game machines and other entertainment or entertainment product parts , Members and housings, microscopes, binoculars, cameras, watches and other optical equipment, precision machine parts, members and housings, medical applications such as X-ray cassettes, sports related to tennis rackets, golf club heads, boards, yachts, etc. These include parts, building materials and panels.

  In particular, it is suitably used for parts, members or casings of electric / electronic devices, OA devices, home appliances, automobiles or building materials that require light weight and high rigidity.

[Evaluation / Measurement Method]
(1) Gurley Second Using a Gurley Densometer (manufactured by Toyo Seiki Seisakusho: B-type Gurley-type Denso Meter) under a pressure of 600 mmH ₂ O and a temperature of 23 ° C. The time required for 10 ml of air to pass through was measured as Gurley seconds.
(2) Maximum film thickness Tpf
The cross section of the reinforcing fiber substrate was observed with a TEM and measured as follows. Among the reinforcing fibers embedded in the thermoplastic resin in the thickness direction of the thermoplastic resin impregnated in the reinforcing fiber base, as viewed from the surface (10 in FIG. 2) of the thermoplastic resin (8 in FIG. 2) From the surface closest to the surface (9b-out in FIG. 2) and the reinforcing fiber buried or in contact with the thermoplastic resin at the portion where the penetration depth from the surface of the thermoplastic resin is the largest. The distance in the thickness direction from a distance (9b-in in FIG. 2) is measured as Tpf.
(3) Average thickness of coating The cross section of the reinforcing fiber substrate was observed with TEM and measured as follows. Among the reinforcing fibers embedded in the thermoplastic resin in the thickness direction of the thermoplastic resin impregnated in the reinforcing fiber base, as viewed from the surface (10 in FIG. 2) of the thermoplastic resin (8 in FIG. 2) The distance in the thickness direction between the closest surface (9b-out in FIG. 2) and the surface (8 in FIG. 2) of the thermoplastic resin (8 in FIG. 2) is measured as the average thickness of the coating.
(4) Drapability A reinforcing fiber base material is cut into a width of 1 cm and a length of 100 cm to obtain a sample for evaluation. If the length of the reinforcing fiber base is not enough, adjust the width and length of the sample by proportional distribution. The reinforcing fiber base 17 is extruded in the longitudinal direction at a speed of 1 cm / sec from the measurement start point (16 in FIG. 4) on the upper side of the measurement base 15 in FIG. The amount of extrusion (cm) of the sample from the measurement start point when the tip of the sample is bent by its own weight and touches the hypotenuse (18 in FIG. 4) is defined as drape. When the width of the sample is adjusted, the push-out distance of the sample is also calculated by proportional distribution according to the adjustment width.
(5) Vertical Adhesive Strength A vertical adhesive strength evaluation sample (FIG. 5) was cut out in a size of 10 mm × 10 mm from the portion where the fiber reinforced composite material and another member were joined from the integrated structural member.

  Next, the sample was fixed to a jig (23a and 23b in FIG. 6) of the measuring apparatus. As the measuring apparatus, “Instron (registered trademark)” 5565 type universal material testing machine (manufactured by Instron Japan Co., Ltd.) was used. For fixing the sample, if the sample can be held by an Instron chuck, the sample is held in the chuck as it is and a tensile test is performed. If the sample cannot be held, an adhesive (ThreeBond 1782, manufactured by ThreeBond Co., Ltd.) is applied to the sample. It may be allowed to stand for 4 hours at ± 5 ° C. and 50 ± 5% RH to adhere to the jig.

  The tensile test was performed at an ambient temperature of 25 ° C. in a test chamber in which the ambient temperature can be adjusted.

 Before starting the test, after the sample has been kept in the test chamber for at least 5 minutes without being subjected to a tensile test load, and a thermocouple is placed on the sample to ensure that it is equivalent to the ambient temperature A tensile test was performed.

The tensile test was performed by pulling from the adhesion surface of both at 90 ° direction at a tensile speed of 1.27 mm / min, and the value obtained by dividing the maximum load by the adhesion area was defined as the vertical adhesion strength (unit: MPa). The number of samples was n = 5.
(6) Determination of Solubility Parameter δ (SP Value) In the present invention, the solubility parameter δ (SP value) refers to the value of the polymer repeating unit at 25 ° C. determined by the method of Fedors. This method is described in documents 1 and 2. That is, in the structural formula of the desired compound, it is determined by the following formula from the evaporation energy and molar volume data of atoms and atomic groups.
Solubility parameter δ (SP value) = (ΣΔei / ΣΔvi) ^{1/2 where} Δei and Δvi represent the evaporation energy and molar volume of the atom or atomic group, respectively. The structural formula of the compound to be determined is determined using a general structural analysis technique such as IR, NMR, and mass spectrum.
RFFedors, Polym.Eng.Sci., 14 (2), 147 (1974) Mukai Shinji and Kaneshiro Noriyuki “Practical Polymers for Engineers” (Kodansha, published on October 1, 1981), pp. 66-87 (7) Fabrication and thickness of continuous reinforcing fiber substrate JIS R 7602 According to the measurement method, the mass per unit area (hereinafter abbreviated as basis weight) and thickness of the continuous reinforcing fiber substrate were measured. (8) Non-woven fabric and void area of woven fabric The surface of the nonwoven fabric and woven fabric is observed with an optical microscope. Subsequently, the obtained surface photograph is binarized by image processing, and the fiber portion (25 in FIG. 7) is set to white and the other portions are set to black. The area of an independent black part (26 in FIG. 7) surrounded by fibers was defined as one void area. More than 100 void areas were measured, and the value obtained by dividing the sum of the measured values by the number of measurements was defined as the void area (mm2). (9) Spacing between adjacent particles The surface of the continuous reinforcing fiber substrate for forming a thermoplastic resin surface (27 in FIG. 8) is observed with an optical microscope. Subsequently, the length (29 in FIG. 8) between adjacent particles (28 in FIG. 8) was measured from the obtained surface photograph, and set as the interval (mm) between adjacent particles. The interval between adjacent particles was measured at 100 or more, and the value obtained by dividing the sum of the measured values by the measured number was defined as the interval (mm) between adjacent particles. (10) 90 parts by weight of matrix resin “Epicoat (registered trademark)” 828 (manufactured by Japan Epoxy Resin), 10 parts by weight of “ERISYS (registered trademark)” GE-20 (manufactured by CVC), “Ancamine (registered trademark)” A resin mixed with 32 parts by weight of 2049 (manufactured by PTI Japan) was used. [Example 1] Plate-like integrated structural member (fiber reinforced composite material) "Torayca (registered trademark) woven fabric" CO6343 (weight per unit area (W) 200 g / m 2, thickness (t) 0 of fiber reinforced base material) .29 mm) are cut into a predetermined size and six reinforcing fiber base materials are laminated in a mold, and a terpolymer polyamide resin CM4000 (nylon 6) manufactured by Toray Industries, Inc. as a thermoplastic resin composition on the outermost surface. / 66/610, melting point 150 ° C., solubility parameter δ (SP value) 13.3) film (weight per unit 60 g / m 2) cut into the same size as the molded product, stacked and laminated It was. Next, after the mold temperature is heated to 155 ° C., the matrix resin preheated to 60 ° C. is injected into the mold at an injection pressure of 0.2 MPa using a resin injection device and impregnated into the reinforcing fiber base I let you. The thickness of the molded product was adjusted to 1.1 mm so that the volume content of the reinforcing fiber was 60%. After impregnation, it was held at a temperature of 155 ° C. for 2 hours, then cooled to a temperature of 30 ° C., and demolded to obtain a fiber-reinforced composite material. The obtained fiber reinforced composite material was 1.1 mm in thickness, Tpf was 30 μm, and the average thickness of the coating was 10 μm.

(Other parts)
The same fiber reinforced composite material as above was used as another member.

(Integrated)
The above fiber-reinforced composite material and another member are heated on a hot plate at 160 ° C. for 3 minutes, and then the surfaces having the thermoplastic resin composition are bonded together as a joining surface and held at a pressure of 20 MPa for 2 minutes to be integrated. A plate-like integrated structural member was obtained. Attempts were made to evaluate the vertical bond strength of the obtained integrated structural member. At 6 MPa, the fixed part by the adhesive between the sample and the jig peeled off before the bonded part peeled off. It was evaluated that there was.
[Example 2] Plate-like integrated structural member (fiber reinforced composite material)
Toray Industries, Inc. “Torayca (registered trademark)” CO6343 (weight per unit area (W) 200 g / m 2, fiber reinforced base material thickness (t) 0.29 mm) cut to a predetermined size with a reinforcing fiber base material made of gold Six sheets are laminated in the mold, and a terpolymer polyamide resin CM4000 (nylon 6/66/610, melting point 150 ° C., solubility parameter δ (SP value) 13 manufactured by Toray Industries, Inc. as a thermoplastic resin composition on the outermost surface. .3) films (weight per unit area: 60 g / m ² ) cut into the same size as the molded body were stacked and laminated, and the molds were clamped. Next, after the mold temperature is heated to 155 ° C. and held for 5 minutes, the matrix resin preheated to 60 ° C. is injected into the mold at an injection pressure of 0.2 MPa using a resin injection device and strengthened. The fiber substrate was impregnated. The thickness of the molded product was adjusted to 1.1 mm so that the volume content of the reinforcing fibers was 60%. After impregnation, it was held at a temperature of 155 ° C. for 2 hours, then cooled to a temperature of 30 ° C., and demolded to obtain a fiber-reinforced composite material. The obtained fiber reinforced composite material was 1.1 mm in thickness, Tpf was 40 μm, and the average thickness of the coating was 10 μm.

(Other parts)
The same fiber reinforced composite material as above was used as another member.

(Integrated)
The above fiber-reinforced composite material and another member are heated on a hot plate at 160 ° C. for 3 minutes, and then the surfaces having the thermoplastic resin composition are bonded together as a joining surface and held at a pressure of 20 MPa for 2 minutes to be integrated. A plate-like integrated structural member was obtained. Attempts were made to evaluate the vertical bond strength of the obtained integrated structural member. At 6 MPa, the fixed part by the adhesive between the sample and the jig peeled off before the bonded part peeled off. It was evaluated that there was.
[Example 3] Electronic equipment casing (continuous reinforcing fiber base)
One reinforced fiber base material obtained by cutting “Torayca (registered trademark) fabric” CO6343 (weight per unit area (W) 200 g / m 2, thickness of fiber reinforced base material (t) 0.29 mm) manufactured by Toray Industries, Inc. Further, as a thermoplastic resin, a film of a terpolymer polyamide resin CM4000 (nylon 6/66/610, melting point 150 ° C., solubility parameter δ (SP value) 13.3) manufactured by Toray Industries, Inc. (weight per unit: 60 g / m ²⁾ ) Was laminated and arranged. Subsequently, it was press-molded at a pressure of 1 MPa for 2 minutes at a temperature of 160 ° C. to obtain a fiber reinforced base material in which a thermoplastic resin was previously coated on one surface. The fiber-reinforced substrate had a Gurley second of 1000 s, a Tpf of 50 μm, an average thickness of the coating of 10 μm, and a drape property of 8 cm.

(Fiber reinforced composite material)
Toray Industries, Inc. “Torayca (registered trademark)” CO6343 (weight per unit area (W) 200 g / m 2, fiber reinforced base material thickness (t) 0.29 mm) cut to a predetermined size with a reinforcing fiber base material made of gold Five sheets were laminated in the mold, and the above-mentioned reinforcing fiber base material was laminated and laminated so that the thermoplastic resin continuously impregnated on the outermost surface was disposed, and the mold was clamped. Next, after the mold temperature is heated to 155 ° C., the matrix resin preheated to 60 ° C. is injected into the mold at an injection pressure of 0.2 MPa using a resin injection device and impregnated into the reinforcing fiber base I let you. The thickness of the molded product was adjusted to 1.1 mm so that the volume content of the reinforcing fibers was 60%. After impregnation, it was held at a temperature of 155 ° C. for 2 hours, then cooled to a temperature of 30 ° C., and demolded to obtain a fiber-reinforced composite material. The resulting fiber reinforced composite material was 1.1 mm thick.

(Other parts / integration)
The fiber reinforced composite material is inserted into a mold for injection molding, and as a separate member, the fiber reinforced composite material having a thermoplastic resin has a long fiber pellet TLP1146 (polyamide resin matrix, carbon 9) was molded and integrated by injection molding to obtain an electronic device casing as shown in FIG. The injection molding machine uses J350EIII manufactured by Nippon Steel, Ltd., and the injection molding is screw rotation 60 rpm, cylinder temperature 280 ° C., injection speed 90 mm / sec, injection pressure 200 MPa, back pressure 0.5 MPa, mold temperature 55 Performed at ° C. Attempts were made to evaluate the vertical adhesive strength of the electronic device casing, which is an integrated structural member, and the fixed portion by the adhesive between the sample and the jig peeled before the joint portion peeled at 6 MPa. Therefore, it was evaluated as 6 MPa or more.
[Example 4] Plate-like integrated structural member (continuous reinforcing fiber base material)
Toray Industries, Inc. “Torayca (registered trademark)” CO6343 (weight per unit (W) 200 g / m 2, fiber reinforced base material thickness (t) 0.29 mm) cut to a predetermined size A1 reinforcing fiber base material Further, particles of terpolymer polyamide resin CM4000 (nylon 6/66/610, melting point 150 ° C., solubility parameter δ (SP value) 13.3) manufactured by Toray Industries, Inc. as a thermoplastic resin (average particle diameter 200 μm) 80 g / m ² was sprayed and arranged to obtain a continuous reinforcing fiber substrate B. Then, it heated for 2 minutes at the temperature of 160 degreeC, and the thermoplastic resin fuse | melted to the continuous reinforcement fiber base material, It was the continuous reinforcement fiber base material C (2 mm of adjacent particle | grains) excellent in the handleability. Subsequently, press molding was performed at a pressure of 1 MPa for 2 minutes at a temperature of 160 ° C. to obtain a fiber reinforced base D in which a thermoplastic resin was previously coated on one surface, and the Gurley second number of the fiber reinforced base was 700 s, Tpf was 70 μm, the average thickness of the coating was 15 μm, and the drapability was 18 cm.

(Fiber reinforced composite material)
Toray Industries, Inc. “Torayca (registered trademark)” CO6343 (weight per unit area (W) 200 g / m 2, fiber reinforced base material thickness (t) 0.29 mm) is reinforced fiber base material A cut to a predetermined size Five sheets were laminated in a mold, and the above-mentioned reinforcing fiber base D was laminated and laminated so that the thermoplastic resin continuously impregnated on the outermost surface was disposed, and the mold was clamped. Next, after the mold temperature is heated to 155 ° C., the matrix resin preheated to 60 ° C. is injected into the mold at an injection pressure of 0.2 MPa using a resin injection device and impregnated into the reinforcing fiber base I let you. The thickness of the molded product was adjusted to 1.1 mm so that the volume content of the reinforcing fibers was 60%. After impregnation, it was held at a temperature of 155 ° C. for 2 hours, then cooled to a temperature of 30 ° C., and demolded to obtain a fiber-reinforced composite material. The resulting fiber reinforced composite material was 1.1 mm thick.

(Other parts)
The same fiber reinforced composite material as above was used as another member.

(Integrated)
The above fiber-reinforced composite material and another member are heated on a hot plate at 160 ° C. for 3 minutes, and then the surfaces having the thermoplastic resin composition are bonded together as a joining surface and held at a pressure of 20 MPa for 2 minutes to be integrated. A plate-like integrated structural member was obtained. Attempts were made to evaluate the vertical bond strength of the obtained integrated structural member. At 6 MPa, the fixed part by the adhesive between the sample and the jig peeled off before the bonded part peeled off. It was evaluated that there was.

It is one embodiment illustration of the metal mold | die which produces the fiber reinforced composite material of this invention. It is a schematic diagram of the continuous reinforcement fiber base material for composite material surface layers which has a film of this invention. It is a cross-sectional schematic diagram of the integrally molded product of this invention. It is a schematic diagram of the drape property evaluation jig in this invention. It is a schematic diagram of a vertical adhesive strength evaluation sample. It is a schematic diagram of the jig for vertical adhesive strength evaluation. It is a schematic diagram of the space | gap part of the nonwoven fabric in this invention. It is a schematic diagram of the 2nd continuous reinforcement fiber base material for thermoplastic resin surface formation which the thermoplastic resin of this invention consists of particle | grains. It is a perspective view of the electronic device housing | casing concerning the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a: Upper mold | type 1b: Lower mold | type 2: Cavity 3: Continuous reinforcement fiber base material 4: Thermoplastic base material 5: Surface 6: Continuous fiber reinforcement base material 7 with a film | membrane: Continuous reinforcement fiber 8: Thermoplastic resin 9a: Reinforcement Fiber 9b: Reinforcing fiber 9b-out: Outermost (surface side) reinforcing fiber 9b-in-max in contact with the resin of the thermoplastic resin 8: Innermost reinforcement in contact with the resin of the thermoplastic resin 8 Fiber 10: Coating surface 11: Fiber reinforced composite material 12: Another member 13: Thermosetting resin 14: Interface between thermoplastic resin and thermosetting resin 15: Measurement base 16: Measurement start point 17: Reinforced fiber substrate 18: hypotenuse of measurement pedestal 19: vertical adhesive strength evaluation sample 20: fiber reinforced composite material 21: another member 22: bonding surface 23a: tension jig 23b: tension jig 24a: tension direction arrow 24b: tension direction arrow 25: Fiber part 26: fiber Enclosed independent part 27: continuous reinforcing fiber base material 28: thermoplastic composed of a resin particle 29: the fiber reinforced composite material 30: Another member

Claims (24)

A lamination step of disposing a thermoplastic base material mainly composed of a thermoplastic resin on at least a part of the surface of the continuous reinforcing fiber base; and a coating of the thermoplastic resin on the surface of the continuous reinforcing fiber base by melting the thermoplastic base And a curing step in which a thermosetting resin composition is injected and cured at the same time. Laminating step of disposing a thermoplastic base material mainly composed of a thermoplastic resin on at least a part of the surface of the continuous reinforcing fiber base, and coating the thermoplastic resin on the surface of the continuous reinforcing fiber base by melting the thermoplastic base A method for producing a fiber-reinforced composite material, which includes a preheating step for forming a resin and a curing step for injecting and curing a thermosetting resin. A continuous reinforcing fiber base material for a composite material surface layer in which a thermoplastic resin is disposed on at least a part of the surface of a base material made of continuous reinforcing fibers and has a capability of forming a thermoplastic resin layer on the surface of a molded product. The continuous reinforcing fiber base material for a composite material surface layer according to claim 3, wherein a thermoplastic resin is fused to at least a part of the surface of the base material made of the continuous reinforcing fibers. The continuous reinforcing fiber base material for a composite material surface layer according to any one of claims 3 and 4, wherein the Gurley seconds defined in the present specification are in the range of 100 to 10,000 s. A continuous reinforcing fiber base material for a composite material surface layer, wherein a thermoplastic resin film is formed on at least a part of the surface of a base material made of continuous reinforcing fibers, and has the ability to form a thermoplastic resin layer on the surface of a molded product. The continuous reinforcing fiber base material for a composite material surface layer according to any one of claims 3 to 6, wherein the drapeability defined in the present specification is in the range of 5 to 50 cm. The continuous reinforcing fiber base material for a composite material surface layer according to any one of claims 6 and 7, wherein an intrusion surface of the thermoplastic resin coating film is uneven in a thickness direction. The continuous reinforcing fiber base material for a composite material surface layer according to any one of claims 6 to 8, wherein a maximum thickness Tpf of the thermoplastic resin coating is in a range of 10 to 1000 µm. 10. The continuous reinforcing fiber substrate for a composite material surface layer according to claim 6, wherein an average thickness of the thermoplastic resin coating is 0.01 to 1000 μm. The continuous reinforcing fiber base material for a composite material surface layer according to any one of claims 3 to 10, wherein the continuous reinforcing fiber is a carbon fiber. The continuous reinforcing fiber substrate for a composite material surface layer according to any one of claims 3 to 11, wherein the continuous reinforcing fiber substrate is a woven fabric substrate. The thermoplastic resin on the continuous reinforcing fiber base material for the composite material surface layer in which the thermoplastic resin is arranged on at least a part of the surface of the base material made of continuous reinforcing fibers is melted, and a pressure of 0.01 to 10 MPa is applied. The continuous reinforcing fiber base material for a composite material surface layer according to any one of claims 6 to 12. A lamination step in which the continuous reinforcing fiber substrate for the composite material surface layer according to any one of claims 3 to 13 is the outermost surface on which the thermoplastic resin is disposed, and a predetermined number of continuous reinforcing fiber substrates are disposed. A method for producing a fiber-reinforced composite material, comprising injection of a thermosetting resin and a curing step for causing a curing reaction. A thermoplastic resin coating is formed on at least a part of the surface of the base material made of continuous reinforcing fibers, and the surface of the thermoplastic resin coating is uneven in the thickness direction, and the thermoplastic resin The manufacturing method of the fiber reinforced composite material in any one of Claims 1, 2, or 14 using the continuous reinforcement fiber base material for composite material surface layers in which the maximum thickness Tpf of the film of this is the range of 10-1000 micrometers. The manufacturing method of the fiber reinforced composite material in any one of Claims 1, 2, 14, or 15 using the continuous reinforcing fiber base material for composite material surface layers whose average thickness of the said film is 0.01-1000 micrometers. The manufacturing method of the fiber reinforced composite material in any one of Claims 1, 2, and 14-16 using the continuous reinforcing fiber base material for composite material surface layers whose continuous reinforcing fiber is carbon fiber. The manufacturing method of the fiber reinforced composite material in any one of Claims 1, 2, and 14-17 using the continuous reinforcing fiber base material for composite material surface layers whose continuous reinforcing fiber base material is a textile base material. The manufacturing method of the fiber reinforced composite material of Claim 2 which performs a preheating process in the state which provided the pressure of 0.01-10 Mpa. 20. A fiber-reinforced composite material obtained by the production method according to claim 1, wherein the interface between the thermosetting resin and the thermoplastic resin has an uneven shape. material. 21. An integrated structural member in which the fiber-reinforced composite material according to claim 20 and another member are joined via the thermoplastic resin. The integrated structural member according to claim 21, wherein a vertical adhesive strength of a joint surface between the fiber-reinforced composite material and another member is 6 MPa or more at 25 ° C. The integrated structural member according to any one of claims 21 and 22, which is used for any one of a part, a member, a casing, or an outer plate of an electric / electronic device, an OA device, a household electrical appliance, an automobile, or a building material. 24. The joint between the fiber-reinforced composite material and another member in the integrated structure member according to any one of claims 21 to 23, including thermal welding, vibration welding, ultrasonic welding, laser welding, insert injection molding, and outsert injection. A method for producing an integrated structural member formed by at least one method selected from the group consisting of molding.

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