Continuous Fiber Reinforced Resin Composite Material and Method for Producing the Same

Abstract

To provide a fiber reinforced resin composite material in which a thickness of an interfacial resin is thin enough, and which has a high bending fatigue characteristic and a physical-property recovering characteristic, and a method for manufacturing the same.SOLUTION: A continuous fiber reinforced resin composite material contains a continuous reinforcing fiber and a thermoplastic resin. An interfacial resin coverage of the continuous reinforcing fiber after melting of the resin is 44% or less. There is also provided a method for manufacturing the continuous fiber reinforced resin composite material.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a continuous fiber reinforced resin composite material and a method for manufacturing the same.

Background Art

[0002] Fiber reinforced resin composite materials in which a reinforcing material such as glass fiber is added to a matrix resin material are used for various structural parts such as various machines and automobiles, pressure vessels, and tubular structures. As this fiber reinforced resin composite material, there are those that devise the resin of the interface layer between the surface of the reinforcing fiber and the resin (for example, see Patent Document 1 below), those that devise the porosity at the interface (for example, see Patent Document 2 below), and those that increase the GF coating rate at the interface (for example, see Non-Patent Documents 1 and 2 below)

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0004]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the conventional fiber reinforced resin composite materials, in all cases, the amount of resin covering the reinforcing fiber is large and the thickness of the interfacial resin is thick, so there is room for improvement in that the flexural fatigue characteristics are not sufficient.

[0006] In view of such a prior art level, the problem to be solved by the present invention is to provide a fiber-reinforced resin composite material having a sufficiently thin interfacial resin and high flexural fatigue characteristics and physical property recovery characteristics, and a method for manufacturing the same.

Means for Solving the Problem

[0007] As a result of intensive studies and repeated experiments to solve such problems, the inventors of the present invention unexpectedly found that the above problems can be solved by adjusting the wettability between the reinforcing fiber and the resin and the impregnation rate of the reinforcing fiber and the resin, and devising the interfacial resin coating rate after resin dissolution of the fiber-reinforced resin composite material, and thus completed the present invention.

[0008] That is, the present invention is as follows. [1] A continuous fiber-reinforced resin composite material containing continuous reinforcing fibers and a thermoplastic resin, characterized in that the coating rate of the interfacial resin on the continuous reinforcing fibers after resin dissolution is 44% or less. [2] The continuous fiber-reinforced resin composite material according to [1], wherein the exposure degree of the continuous reinforcing fibers after resin dissolution is 55% or more. [3] The continuous fiber-reinforced resin composite material according to [1] or [2], wherein the relative elemental concentration of interfacial nitrogen in the continuous reinforcing fibers after resin dissolution is 6.70 or less. [4] The continuous fiber-reinforced resin composite material according to any one of [1] to [3], wherein the relative elemental concentration of interfacial carbon in the continuous reinforcing fibers after resin dissolution is 46.7 or less. [5] The continuous fiber-reinforced resin composite material according to any one of [1] to [4], wherein the relative elemental concentration of interfacial aluminum in the continuous reinforcing fibers after resin dissolution is 1.80 or more. [6] The continuous fiber-reinforced resin composite material according to any one of [1] to [5], wherein the relative elemental concentration of interfacial silicon in the continuous reinforcing fibers after resin dissolution is 8.30 or more. [7] The continuous fiber-reinforced resin composite material according to any one of [1] to [6], wherein the relative elemental concentration of interfacial calcium in the continuous reinforcing fiber after resin dissolution is 2.60 or more. [8] The continuous fiber-reinforced resin composite material according to any one of [1] to [7], wherein the relative elemental concentration of interfacial oxygen in the continuous reinforcing fiber after resin dissolution is 33.1 or more. [9] A method for producing a continuous fiber-reinforced resin composite material according to any one of [1] to [8], wherein the contact angle in the static wettability test between the continuous reinforcing fiber after resin dissolution and the thermoplastic resin is 70 to 130% of the contact angle in the static wettability test between the continuous reinforcing fiber treated only with a coupling agent and the thermoplastic resin, and the impregnation rate of the thermoplastic resin with respect to the continuous reinforcing fiber is 32% / min or more. [Advantages of the Invention]

[0009] The continuous fiber-reinforced resin composite material according to the present invention can exhibit high flexural fatigue characteristics because the interfacial resin is sufficiently thin. [Modes for Carrying Out the Invention]

[0010] Hereinafter, modes for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

[0011] [Continuous Fiber-Reinforced Resin Composite Material] The continuous fiber-reinforced resin composite material of the present embodiment (hereinafter also simply referred to as "composite material") includes continuous reinforcing fibers and a resin.

[0012] In the composite material of the present embodiment, the coating rate of the interfacial resin in the continuous reinforcing fiber after resin dissolution is 44% or less. The above coating rate is preferably 40% or less, more preferably 37% or less, and still more preferably 35% or less. The above coating rate is preferably 3% or more, more preferably 10% or more, and even more preferably 20% or more.

[0013] The coating rate of the interfacial resin of the continuous reinforcing fiber after resin dissolution can be obtained, for example, by dissolving the thermoplastic resin contained in the continuous fiber reinforced resin in a solvent, removing the solvent, washing the remaining continuous reinforcing fiber with the fresh solvent, removing substances other than the resin bonded to the continuous reinforcing fiber, drying, and then determining from the ratio of the thermoplastic resin component to the continuous reinforcing component in the thermoplastic resin component when measured by X-ray photoelectron spectroscopy (XPS). There is no particular limitation on the method of dissolving the thermoplastic resin contained in the continuous fiber reinforced resin in a solvent, removing the solvent, washing the remaining continuous reinforcing fiber with the fresh solvent, removing substances other than the resin bonded to the continuous reinforcing fiber, and drying, but the following treatment methods can be mentioned. (a) Cut the continuous fiber reinforced resin composite material into thin flakes. (b) Put 100 mg of the thin flakes of the continuous fiber reinforced resin composite material and 20 mL of a solvent selected according to the resin into a mixing rotor and stir for 5 hours. (c) Remove the solvent by suction filtration, sprinkle 40 mL of the fresh solvent on the filter to wash the continuous reinforcing fiber, and then air-dry it. (d) Put the continuous reinforcing fiber obtained in (c) and 20 mL of the fresh solvent into a mixing rotor and stir for 2 hours. (e) Remove the solvent by suction filtration, sprinkle 40 mL of the fresh solvent on the filter to wash the continuous reinforcing fiber, and then dry it with nitrogen blowing. (f) Put the continuous reinforcing fiber obtained in (e) and 20 mL of the fresh solvent into a mixing rotor and stir for 2 hours. (g) Remove the solvent by suction filtration, sprinkle 40 mL of the fresh solvent on the filter to wash the continuous reinforcing fiber, and then air-dry it. (h) Dry overnight in a vacuum dryer set at room temperature.

[0014] In the above-described processing method, as the solvent selected according to the resin, a solvent in which the thermoplastic resin contained in the composite material dissolves with a high solubility (the solubility is preferably 0.10 g / mL or more, more preferably 0.15 g / mL or more) shall be appropriately selected. For example, in the case of polyamide, hexafluoroisopropanol (HFIP) may be selected; in the case of polypropylene, hot xylene may be selected; and in the case of polyphenylene ether, chloroform may be selected.

[0015] Whether the continuous reinforcing fiber is a glass fiber or a carbon fiber, as long as the continuous reinforcing fiber used is substantially insoluble (the solubility is less than 0.1 mg / mL) in the solvent selected according to the above resin, the operation of the above processing method does not need to be changed.

[0016] When the thermoplastic resin contained in the composite material is different, it may be carried out in the same manner as the above processing method except that the solvent is changed according to the solvent.

[0017] And, for example, when the resin is polyamide and the continuous reinforcing fiber is a glass fiber, the coating rate can be obtained by (coating rate)=[N] / ([N]+[Si]). Here, [N] is the relative elemental concentration of nitrogen obtained by XPS measurement for the continuous reinforcing fiber after resin dissolution, and [Si] is the relative elemental concentration of silicon obtained in the same manner.

[0018] For example, when the resin is polyamide and the continuous reinforcing fiber is a carbon fiber, the coating rate can be obtained by (coating rate)=[N] / ([N]+[O]). Here, [N] is the relative elemental concentration of nitrogen obtained by XPS measurement for the continuous reinforcing fiber after resin dissolution, and [O] is the relative elemental concentration of oxygen obtained by XPS measurement in the same manner.

[0019] For example, when the resin is polypropylene and the continuous reinforcing fiber is glass fiber, the coating rate can be determined by (coating rate) = ([C] - [C0]) / ([C] - [C0] + [Si]). Here, [C] is the relative elemental concentration of carbon obtained when XPS measurement is performed on the continuous reinforcing fiber after resin dissolution. [C0] is the relative elemental concentration of carbon obtained when XPS measurement is performed on the continuous reinforcing fiber, which is a raw material not containing a sizing agent, after the same treatment. [Si] is the relative elemental concentration of silicon obtained when XPS measurement is performed on the continuous reinforcing fiber after resin dissolution. Here, the continuous reinforcing fiber as the material refers to the continuous reinforcing fiber itself as the raw material.

[0020] Note that the XPS measurement is performed as described in the examples in detail.

[0021] When the coating rate of the interfacial resin of the continuous reinforcing fiber after resin dissolution is within the above range, high flexural vibration fatigue characteristics can be exhibited.

[0022] In order to adjust the coating rate to the above range, for example, the contact angle by the static wettability test of the continuous reinforcing fiber after resin dissolution and the thermoplastic resin is 70 to 130% of the contact angle by the static wettability test of the continuous reinforcing fiber, which is a material treated only with a coupling agent, and the thermoplastic resin, and the impregnation rate of the thermoplastic resin with respect to the continuous reinforcing fiber is 32% / min or more. Here, the continuous reinforcing fiber as the material refers to the continuous reinforcing fiber itself as the raw material.

[0023] The contact angle is preferably 80 to 120%, and more preferably 90 to 110%. If the contact angle is within the above range, the compatibility between the thermoplastic resin and the coupling agent is improved, extra components that do not contribute to interface formation contained in the sizing agent can be removed, and the interface thickness becomes sufficiently thin. The contact angle by the static wettability test can be measured, for example, by sandwiching a single filament of continuous reinforcing fiber and a film of thermoplastic resin between glass covers, raising the temperature above the melting point of the thermoplastic resin, and observing the contact angle between the continuous reinforcing fiber and the thermoplastic resin immediately before starting cooling with an optical microscope. Specifically, it can be measured by the method described in the examples.

[0024] The impregnation rate is preferably 48% / min or more, and more preferably 64% / min or more. The impregnation rate can be measured by the following method. Specifically, it can be measured by the method described in the examples. That is, a continuous reinforcing fiber base material and a thermoplastic resin base material are laminated, and a heating press and a cooling press are performed so that the time during which the thermoplastic resin becomes equal to or higher than the melting point through heating and cooling is 60 seconds. Specifically, the mold temperature is set to an appropriate temperature so that the maximum temperature inside the mold becomes the melting point of the thermoplastic resin + 6 to 25°C, the molding pressure is set to 5 MPa, the heating press is performed, and then water cooling is performed to perform a cooling press at a pressure of 5 MPa. Thereafter, the obtained continuous reinforcing fiber composite material is cut and polished with a band saw or the like, and the impregnation rate (%) (described later) obtained for the cut surface is divided by the time (minutes) during which the thermoplastic resin was equal to or higher than the melting point during the heating press molding to obtain the impregnation rate. Here, the impregnation rate (%) can be determined by the ratio of the voids in the continuous reinforcing fibers in the cross section observed by SEM of the continuous fiber reinforced resin composite material. Specifically, for example, after cutting and polishing the continuous fiber reinforced resin composite material at an arbitrary position and performing SEM observation, the image of the cut surface obtained is subjected to image analysis using analysis software to calculate the area of the region surrounded by the outer contour line of the continuous reinforcing fiber, which is a bundle of single filaments (filaments), and the area of the voids contained in the region surrounded by the outer contour line of the continuous reinforcing fiber. The impregnation rate (%) is defined as follows when a predetermined area is set to 100%: Impregnation rate (%) = [1 - {void area / (area of the region surrounded by the outer contour line of the continuous reinforcing fiber)}] × 100 is calculated. Then, for 10 consecutive reinforcing fibers in the obtained cross-sectional image, calculate each impregnation rate, and the average value thereof may be used as the impregnation rate.

[0025] The exposure degree of the continuous reinforced resin (hereinafter, also referred to as "interface-exposed reinforcing fiber") after the resin dissolution is preferably 55% or more, more preferably 62% or more, still more preferably 66% or more, and even more preferably 72% or more. The exposure degree of the interface-exposed reinforcing fiber is preferably 95% or less, more preferably 90% or less, still more preferably 85% or less, and even more preferably 80% or less. The exposure degree of the interface-exposed reinforcing fiber can be obtained, for example, by dissolving the thermoplastic resin contained in the continuous fiber-reinforced resin in a solvent in the same manner as the treatment method in the measurement of the coating rate of the interfacial resin of the continuous reinforcing fiber after resin dissolution, removing the solvent, then washing the remaining continuous reinforcing fiber with the fresh solvent, removing substances other than the resin bonded to the continuous reinforcing fiber, drying, and measuring by X-ray photoelectron spectroscopy (XPS), and dividing the relative elemental concentration of the element derived from the obtained continuous reinforcing fiber by the relative elemental concentration of the element derived from the raw continuous reinforcing fiber not treated with the sizing agent.

[0026] More specifically, when the continuous reinforcing fiber is a glass fiber, the exposure degree of the continuous reinforced resin (interface-exposed reinforcing fiber) after resin dissolution is obtained, for example, by (ratio of interface-exposed reinforcing fiber) = [Al] / [Al0]. [Al] is the relative elemental concentration of aluminum obtained when XPS measurement is performed on the continuous reinforcing fiber after resin dissolution as described above. [Al0] is the relative elemental concentration of aluminum obtained when XPS measurement is performed on the continuous reinforcing fiber after treating the continuous reinforcing fiber, which is a raw material not containing a sizing agent, in the same manner. When the continuous reinforcing fiber is a carbon fiber, for example, (the ratio of the interfacial exposed reinforcing fiber) = [O] / [O0] is obtained. [O] is the relative elemental concentration of oxygen obtained when XPS measurement is performed on the continuous reinforcing fiber after resin dissolution as described above. [O0] is the relative elemental concentration of oxygen obtained when XPS measurement is performed on the continuous reinforcing fiber that has been similarly processed using a raw material that does not contain a sizing agent, after the treatment.

[0027] When the exposure degree of the interfacial exposed reinforcing fiber is within the above range, high strength can be exhibited under high-temperature conditions.

[0028] In order to adjust the exposure degree to the above range, for example, the contact angle in the static wettability test of the continuous reinforcing fiber and the thermoplastic resin is set to 70 to 130% of the contact angle in the static wettability test of the continuous reinforcing fiber treated only with a coupling agent and the thermoplastic resin, and the impregnation rate of the continuous reinforcing fiber and the thermoplastic resin is set to 32% / min or more.

[0029] For continuous reinforcing fibers that do not contain a sizing agent (hereinafter also referred to as "sizing agent-free continuous reinforcing fibers"), "not containing a sizing agent" means that when the total amount of sizing agent-free continuous reinforcing fibers is 100% by mass, the content of the sizing agent (sizing agent) described below is 0.45% by mass or less, and in the zeta potential measurement, the isoelectric point is less than pH = 3 and negative at pH = 3 to 8. The zeta potential can be obtained, for example, by using a dedicated zeta potential meter for solids and adjusting the pH with hydrochloric acid or potassium hydroxide.

[0030] Examples of methods for obtaining sizing agent-free continuous reinforcing fibers include a method of not treating the continuous reinforcing fibers with a sizing agent (sizing agent) during production, and a method of removing the sizing agent (sizing agent) of the continuous reinforcing fibers containing a sizing agent using an electric furnace or the like.

[0031] In the composite material of this embodiment, the relative elemental concentration of interfacial nitrogen after resin dissolution is preferably 6.70 or less, more preferably 5.70 or less, still more preferably 5.20 or less, and even more preferably 5.00 or less. The relative elemental concentration of interfacial nitrogen after resin dissolution is preferably 2.90 or more, more preferably 3.50 or more, and still more preferably 4.00 or more.

[0032] In the composite material of this embodiment, the relative elemental concentration of interfacial carbon after resin dissolution is preferably 46.7 or less, more preferably 45.0 or less, still more preferably 42.0 or less, and even more preferably 40.0 or less. The relative elemental concentration of interfacial carbon after resin dissolution is preferably 30.0 or more, and more preferably 35.0 or more.

[0033] In the composite material of this embodiment, the relative elemental concentration of interfacial aluminum after resin dissolution is preferably 1.80 or more, more preferably 2.00 or more, still more preferably 2.10 or more, and even more preferably 2.30 or more. The relative elemental concentration of interfacial aluminum after resin dissolution is preferably 3.00 or less, more preferably 2.90 or less, and still more preferably 2.80 or less.

[0034] In the composite material of this embodiment, the relative elemental concentration of interfacial silicon after resin dissolution is preferably 8.30 or more, more preferably 9.00 or more, and still more preferably 9.30 or more. The relative elemental concentration of interfacial silicon after resin dissolution is preferably 12.0 or less, more preferably 11.5 or less, still more preferably 11.0 or less, and even more preferably 10.5 or less.

[0035] In the composite material of this embodiment, the relative elemental concentration of calcium at the interface after resin dissolution is preferably 2.60 or more, more preferably 2.70 or more, still more preferably 2.90 or more, even more preferably 3.00 or more, and particularly preferably 3.20 or more. The relative elemental concentration of calcium at the interface after resin dissolution is preferably 3.40 or less, and more preferably 3.35 or less.

[0036] In the composite material of this embodiment, the relative elemental concentration of oxygen at the interface after resin dissolution is preferably 33.1 or more, more preferably 35.0 or more, still more preferably 37.0 or more, even more preferably 38.0 or more, and particularly preferably 39.0 or more. The relative elemental concentration of oxygen at the interface after resin dissolution is preferably 47.0 or less, and more preferably 45.0 or less.

[0037] In the composite material of this embodiment, when the relative elemental concentrations of the respective elements in the continuous reinforcing fibers after resin dissolution are within the above ranges, high strength and modulus of elasticity can be exhibited.

[0038] In order to adjust the relative elemental concentrations of the respective elements in the continuous reinforcing fibers after resin dissolution to the above ranges, for example, the contact angle in the static wettability test of the continuous fibers and the thermoplastic resin is 70 to 130% of the contact angle in the static wettability test of the continuous fibers treated only with the coupling agent and the thermoplastic resin, and the impregnation rate of the continuous fibers and the thermoplastic resin is 32% / min or more. Examples thereof include a method of using a silane coupling agent as the coupling agent. More specifically, when the contact angle in the static wettability test of the continuous fibers and the thermoplastic resin is increased and the difference from the contact angle in the static wettability test of the continuous fibers treated only with the coupling agent and the thermoplastic resin is increased, the relative elemental concentration of nitrogen at the interface tends to increase. The difference between the contact angle obtained from the static wettability test of the continuous fiber and the thermoplastic resin and the contact angle obtained from the static wettability test of the continuous fiber treated only with the coupling agent and the thermoplastic resin is increased, and when the impregnation rate of the continuous fiber and the thermoplastic resin is decreased, the relative elemental concentration of the interfacial carbon tends to increase. When the difference between the contact angle obtained from the static wettability test of the continuous fiber and the thermoplastic resin and the contact angle obtained from the static wettability test of the continuous fiber treated only with the coupling agent and the thermoplastic resin is decreased, the impregnation rate of the continuous fiber and the thermoplastic resin is increased, and a silane coupling agent is used as the coupling agent, the relative elemental concentration of the interfacial aluminum tends to increase. When a silane coupling agent is used as the coupling agent, the relative elemental concentration of the interfacial silicon tends to increase. When the difference between the contact angle obtained from the static wettability test of the continuous fiber and the thermoplastic resin and the contact angle obtained from the static wettability test of the continuous fiber treated only with the coupling agent and the thermoplastic resin is decreased, the impregnation rate of the continuous fiber and the thermoplastic resin is increased, and a silane coupling agent is used as the coupling agent, the relative elemental concentration of the interfacial calcium tends to increase. When the difference between the contact angle obtained from the static wettability test of the continuous fiber and the thermoplastic resin and the contact angle obtained from the static wettability test of the continuous fiber treated only with the coupling agent and the thermoplastic resin is decreased, the impregnation rate of the continuous fiber and the thermoplastic resin is increased, and a silane coupling agent is used as the coupling agent, the relative elemental concentration of the interfacial oxygen tends to increase.

[0039] [Form of continuous fiber reinforced resin composite material] The form of the continuous fiber reinforced resin composite material is not particularly limited, and the following various forms can be mentioned. For example, a form in which a fabric or knitted fabric of continuous reinforcing fibers, a braided cord, a pipe-shaped object and a thermoplastic resin are combined, a form in which continuous reinforcing fibers aligned in one direction and a thermoplastic resin are combined, a form in which yarns composed of continuous reinforcing fibers and a thermoplastic resin are aligned in one direction and shaped, a form in which yarns composed of continuous reinforcing fibers and a thermoplastic resin are made into a fabric, knitted fabric, braided cord, pipe shape, etc. The continuous fiber reinforced resin composite material of this embodiment may be a flat plate and may be a laminate including a layer of continuous reinforcing fibers and a layer of thermoplastic resin. For example, the longitudinal direction of the continuous reinforcing fibers may be arranged substantially parallel to the surface of the flat plate. Note that the layer of continuous reinforcing fibers is a layer including continuous reinforcing fibers (for example, a continuous reinforcing fiber base material), and may be a layer in which the continuous reinforcing fibers are impregnated with a thermoplastic resin inside. The form of the intermediate material before shaping of the continuous fiber reinforced resin composite material is not particularly limited, and examples include a mixed fiber yarn of continuous reinforcing fibers and resin fibers, a coating yarn in which a bundle of continuous reinforcing fibers is coated with resin around it, a tape obtained by previously impregnating continuous reinforcing fibers with resin, a structure in which continuous reinforcing fibers are sandwiched between resin films, a structure in which resin powder is adhered to continuous reinforcing fibers, a structure in which a bundle of continuous reinforcing fibers is used as a core material and the periphery is woven with resin fibers like a braid, a structure in which resin is previously impregnated between reinforcing fibers, a structure in which continuous reinforcing fibers are brought into contact with molten resin, and the like.

[0040] [Method for manufacturing continuous fiber reinforced resin composite material] The method for manufacturing the continuous fiber reinforced resin composite material of this embodiment is not particularly limited, and the following various methods can be mentioned.

[0041] In the manufacturing process, the contact angle by the static wettability test between the continuous reinforcing fibers after dissolving the resin and the thermoplastic resin is set to 70 to 130% of the contact angle by the static wettability test between the continuous reinforcing fibers, which are the material treated only with a coupling agent, and the thermoplastic resin, and the impregnation rate of the thermoplastic resin with respect to the continuous reinforcing fibers is set to 32% / min or more. As described above, this is preferable for obtaining a desired composite material. Here, the continuous reinforcing fibers as the material refer to the continuous reinforcing fibers themselves as raw materials.

[0042] In one method, for example, a base material (for example, a base material made of continuous reinforcing fibers, a base material made of thermoplastic resin) constituting the continuous fiber reinforced resin composite material is cut or shaped according to the desired composite material, stacked in the required number or laminated in the required number considering the thickness of the target product, and set in a mold according to the mold shape.

[0043] The base material may be cut one by one, or may be cut after stacking a desired number of sheets. From the viewpoint of productivity, it is preferable to cut in a stacked state. The cutting method may be any method, and examples thereof include a water jet, a blade press machine, a hot blade press machine, a laser, a plotter, etc. Among them, a hot blade press machine is preferable because it has an excellent cross-sectional shape and, furthermore, the handleability is improved by welding the end faces when cutting a plurality of stacked sheets. An appropriate cutting shape can be adjusted by repeating trial and error, but it is preferably set by performing a simulation by CAE (computer aided engineering) according to the shape of the mold.

[0044] The shaping of the base material may be performed by any method. For example, it may be shaped into a sheet shape.

[0045] After setting the base material in the mold, the mold is closed and compressed. Then, the mold is temperature-controlled to a temperature equal to or higher than the melting point of the thermoplastic resin constituting the continuous fiber reinforced resin composite material to melt and shape the thermoplastic resin. There is no particular regulation on the clamping pressure, but it is preferably 1 MPa or more, more preferably 3 MPa or more. Also, in order to vent gas, etc., the mold may be clamped once, and after compression molding, the clamping pressure of the mold may be released once. From the viewpoint of strength development, the compression molding time is preferably long within the range where the thermoplastic resin used does not undergo thermal degradation, but from the viewpoint of productivity, it is preferably within 2 minutes, more preferably within 1 minute.

[0046] The continuous fiber reinforced resin composite material may be further injection-filled with a thermoplastic resin composition for hybrid to form a hybrid composite material. In the manufacturing process of the hybrid composite material, the above base material is set in the mold, the mold is closed and pressurized, and after a predetermined time, a predetermined thermoplastic resin composition for hybrid is further injection-filled and molded to bond the thermoplastic resin of the base material and the predetermined thermoplastic resin composition for hybrid, thereby manufacturing a hybrid composite material.

[0047] The timing of injecting and filling a predetermined thermoplastic resin composition for hybridization greatly affects the interfacial strength between the two thermoplastics. The timing of injecting and filling a predetermined thermoplastic resin composition for hybridization is preferably within 30 seconds after setting the base material in the mold and closing the mold, and then raising the mold temperature to equal to or higher than the melting point or glass transition temperature of the thermoplastic resin constituting the base material.

[0048] The mold temperature when injecting and filling a predetermined thermoplastic resin composition for hybridization is preferably equal to or higher than the melting point or glass transition temperature of the thermoplastic resin constituting the base material, which is to be joined with the thermoplastic resin composition for hybridization. More preferably, it is equal to or higher than the melting point + 10°C or glass transition temperature + 10°C of the thermoplastic resin constituting the base material, which is to be joined with the thermoplastic resin composition for hybridization. Even more preferably, it is equal to or higher than the melting point + 20°C or glass transition temperature + 20°C, and even more preferably equal to or higher than the melting point + 30°C or glass transition temperature + 30°C.

[0049] In the hybrid composite material, the joint portion between the thermoplastic resin constituting the base material and the thermoplastic resin composition for hybridization formed by injection molding preferably has an uneven structure in which they are mixed with each other. Setting the mold temperature to be equal to or higher than the melting point of the thermoplastic resin composition for hybridization to be injected, and making the resin holding pressure during injection molding high, for example, 1 MPa or more, is effective in increasing the interfacial strength. To increase the interfacial strength, it is preferably set the holding pressure to 5 MPa or more, and more preferably 10 MPa or more. Also, keeping the holding pressure time long, for example, 5 seconds or more, preferably 10 seconds or more, and more preferably holding for the time until the mold temperature becomes equal to or lower than the melting point of the thermoplastic resin composition, is preferable from the viewpoint of increasing the interfacial strength.

[0050] The thermoplastic resin composition for hybridization for injection molding used to manufacture the hybrid composite material is not particularly limited as long as it is a thermoplastic resin composition used for general injection molding. The thermoplastic resin contained in the thermoplastic resin composition for hybrid is not limited to the following, but for example, polyethylene, polypropylene, polyvinyl chloride, acrylic resin, styrene resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyphenylene ether, modified polyphenylene ether resin, wholly aromatic polyester, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide resin, polysulfone, polyetheretherketone, polyetherketone, etc., or a mixture of one or more of these thermoplastic resins may be mentioned.

[0051] Various fillers may be blended in the thermoplastic resin composition for hybrid. The thermoplastic resin composition for hybrid may be a black resin composition containing a colorant. Examples of the various fillers include short fibers and long fiber materials, which are discontinuous reinforcing materials of the same kind of material as the above continuous reinforcing fibers. When using short glass fibers or long fibers as the discontinuous reinforcing material, the same sizing agent as that applied to the continuous reinforcing fibers constituting the continuous fiber reinforced resin composite material of the present embodiment may be used. The sizing agent (sizing agent) preferably consists of a silane coupling agent, a lubricant, and a binder. Regarding the types of the silane coupling agent, the lubricant, and the binder, the same ones as those of the sizing agent for the continuous reinforcing fibers can be used.

[0052] From the viewpoint of the interfacial strength with the thermoplastic resin to be joined, the thermoplastic resin contained in the thermoplastic resin composition for hybrid used in injection molding is preferably of a similar type to the thermoplastic resin on the joining surface constituting the continuous fiber reinforced resin composite material, and more preferably of the same type. Specifically, when polyamide 66 is used for the thermoplastic resin on the joining surface, the resin material of the thermoplastic resin composition for hybrid for injection molding is preferably polyamide 66.

[0053] As other methods, there are a molding method in which a base material is placed in a mold and compressed by a double-belt press machine, a method in which a mold is installed so as to surround the four sides of the installed base material and is pressurized and molded by a double-belt press machine, a compression molding machine set at one or more temperatures for heating, and a compression molding machine set at one or more temperatures for cooling. Examples include a molding method in which a mold with a base material installed is sequentially inserted into the compression molding machine for molding.

[0054] (Continuous reinforcing fiber) As the continuous reinforcing fiber, those used in ordinary continuous fiber reinforced resin composite materials may be used. The continuous reinforcing fiber is not limited to the following, but examples include glass fiber, carbon fiber, plant fiber, aramid fiber, ultra-high strength polyethylene fiber, polybenzazole-based fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, ceramic fiber, etc. From the viewpoints of mechanical properties, thermal properties, and versatility, glass fiber, carbon fiber, plant fiber, and aramid fiber are preferable, and from the viewpoint of productivity, glass fiber is preferable. The above continuous reinforcing fiber may be used alone or in combination of two or more.

[0055] -Sizing agent- When using continuous reinforcing fiber, a sizing agent may be used. The sizing agent (sizing agent) may contain one or more selected from the group consisting of a coupling agent, a lubricant, and a binder, and preferably contains at least a binder or a coupling agent. Further, the sizing agent may be composed of a coupling agent and a binder, or may be composed of a coupling agent, a lubricant, and a binder. Examples of the coupling agent include silane coupling agent, polymer coupling agent, polymerizable coupling agent, etc. By being a sizing agent that forms a strong bond between the continuous reinforcing fiber and the resin coating its surroundings, a continuous fiber reinforced resin composite material with a low porosity can be obtained. The bundling agent may be externally added to the materials used or may be internally contained in the materials used. For example, the lubricant may be contained in commercially available products of the thermoplastic resin used.

[0056] --Silane coupling agent-- Silane coupling agents are usually used as surface treatment agents for glass fibers and contribute to improving the interfacial adhesion strength. Examples of silane coupling agents include, but are not limited to, aminosilanes such as γ-aminopropyltrimethoxysilane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxy silanes; vinyl silanes, maleic acids, etc. When using polyamide as the thermoplastic resin, it is preferable to select those that are likely to bind to the carboxyl group or amino group which are the end groups of the polyamide-based resin, and aminosilanes are preferred. Examples of polymer coupling agents include, but are not limited to, diamines, polycarboxylic acids, epoxies, etc. From the perspective of compatibility with thermoplastic resins, diamines and polycarboxylic acids are preferred. Examples of polymerizable coupling agents include, but are not limited to, epoxies, phenols, ethers, lactones, etc. From the perspective of compatibility with thermoplastic resins, phenols and lactones are preferred.

[0057] --Lubricant-- The lubricant contributes to improving the fibrillability of glass fibers. As the lubricant, any ordinary liquid or solid lubricating material according to the purpose can be used as long as it does not inhibit the silane coupling agent and the binding agent. Examples include, but are not limited to, waxes of animal and plant or mineral origin such as carnauba wax and lanolin wax; surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

[0058] --Sizing agent-- The sizing agent contributes to improving the bundling property of glass fibers and the interfacial adhesion strength. As the sizing agent, a polymer according to the purpose, and a thermoplastic resin other than the thermoplastic resin as the main material of the continuous fiber reinforced resin composite material can be used. The polymer as the sizing agent is not limited to the following, but examples include homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines. Further, for example, polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate, and polyester-based or polyether-based diols are also preferably used. The homopolymer of acrylic acid preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000. The copolymerizable monomers constituting the copolymer of acrylic acid and other copolymerizable monomers are not limited to the following, but examples include one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid among the monomers having a hydroxyl group and / or a carboxyl group (however, the case of only acrylic acid is excluded). It is preferable to have one or more ester-based monomers as the copolymerizable monomers. The salts of the homopolymers and copolymers of acrylic acid with primary, secondary, and tertiary amines are not limited to the following, but examples include triethylamine salts, triethanolamine salts, and glycine salts. From the viewpoint of improving the stability of the mixed solution with other co-used agents (such as silane coupling agents) and reducing the amine odor, the degree of neutralization is preferably 20 to 90%, more preferably 40 to 60%. The weight average molecular weight of the polymer of acrylic acid that forms a salt is not particularly limited, but a range of 3,000 to 50,000 is preferred. From the viewpoint of improving the bundling property of glass fibers, 3,000 or more is preferred, and from the viewpoint of improving the properties when forming a composite body, 50,000 or less is preferred. When using polyamide as the thermoplastic resin, it is preferable to use a resin that has good wettability with the polyamide resin or a resin with a similar surface tension as the binder. Specifically, for example, an emulsion of a polyurethane resin, an emulsion of a polyamide resin, or a modified product thereof can be selected.

[0059] The thermoplastic resin used as the binder is not limited to the following, but examples include polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, thermoplastic fluorine-based resins, and modified thermoplastic resins obtained by modifying these. The thermoplastic resin used as the binder is preferably the same type of thermoplastic resin and / or modified thermoplastic resin as the resin that coats the continuous reinforcing fiber, because the adhesiveness between the glass fiber and the thermoplastic resin is improved after forming a composite material.

[0060] Furthermore, when further improving the adhesiveness between the continuous reinforcing fiber and the thermoplastic resin coating it and attaching the bundling agent to the glass fiber as an aqueous dispersion, from the viewpoint of reducing the ratio of the emulsifier component or making the emulsifier unnecessary, the thermoplastic resin used as the binder is preferably a modified thermoplastic resin. Here, the modified thermoplastic resin means a resin obtained by copolymerizing different monomer components for the purpose of changing the properties of the thermoplastic resin in addition to the monomer components that can form the main chain of the thermoplastic resin, and modifying the hydrophilicity, crystallinity, thermodynamic properties, etc. The modified thermoplastic resin used as the binder is not limited to the following, but examples include modified polyolefin resins, modified polyamide resins, modified polyester resins, etc.

[0061] The modified polyolefin resin as a finishing agent is a copolymer of an olefin monomer such as ethylene or propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid and / or its ester form, or a homopolymer of a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid and / or its ester form, and can be produced by a known method. It may be a random copolymer obtained by copolymerizing an olefin monomer with an unsaturated carboxylic acid and / or its ester form, or a graft copolymer obtained by grafting an unsaturated carboxylic acid onto an olefin. Examples of the olefin monomer include, but are not limited to, ethylene, propylene, 1-butene, etc. These may be used alone or in combination of two or more. Examples of the monomer copolymerizable with an olefin monomer include unsaturated carboxylic acids such as acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and esterified products of these unsaturated carboxylic acids (such as methyl ester, ethyl ester, etc.). These may be used alone or in combination of two or more. When the modified polyolefin resin is a copolymer of an olefin monomer and a monomer copolymerizable with the olefin monomer, the monomer ratio is preferably 60 to 95% by mass of the olefin monomer and 5 to 40% by mass of the monomer copolymerizable with the olefin monomer, with the total mass of the copolymer being 100% by mass. More preferably, it is 70 to 85% by mass of the olefin monomer and 15 to 30% by mass of the monomer copolymerizable with the olefin monomer. If the olefin monomer is 60% by mass or more, the affinity with the matrix is good. If the mass percentage of the olefin monomer is 95% by mass or less, the water dispersibility of the modified polyolefin resin is good, and it is easy to uniformly apply it to the continuous reinforcing fiber.

[0062] The modified polyolefin resin used as a binder may have modified groups such as carboxyl groups introduced by copolymerization neutralized with a basic compound. Examples of the basic compound include, but are not limited to, alkalis such as sodium hydroxide and potassium hydroxide; ammonia; and amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin used as a binder is not particularly limited, but is preferably from 5,000 to 200,000, more preferably from 50,000 to 150,000. From the viewpoint of improving the bundling property of glass fibers, it is preferably 5,000 or more, and from the viewpoint of emulsion stability in the case of water dispersibility, it is preferably 200,000 or less.

[0063] The modified polyamide resin used as a binder is a modified polyamide compound having a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component introduced into the molecular chain, and can be produced by a known method. When introducing a polyalkylene oxide chain into the molecular chain, for example, it is produced by copolymerizing a modified product of part or all of polyethylene glycol, polypropylene glycol, etc. with diamine or dicarboxylic acid. When introducing a tertiary amine component, for example, it is produced by copolymerizing aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylamino ε-caprolactam, etc.

[0064] The modified polyester resin used as a binder is a copolymer of a polycarboxylic acid or its anhydride and a polyol, and is a resin having a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of the hydrophilic group include a polyalkylene oxide group, a sulfonate, a carboxyl group, and neutral salts thereof. Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and polycarboxylic acids having three or more functional groups. Examples of the aromatic dicarboxylic acid include, but are not limited to, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, phthalic anhydride, etc. Examples of the sulfonate-containing aromatic dicarboxylic acid include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, 5-sulfoorthophthalate, etc. Examples of the aliphatic dicarboxylic acid or alicyclic dicarboxylic acid include, but are not limited to, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, maleic anhydride, etc. Examples of the polycarboxylic acid having three or more functional groups include, but are not limited to, trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, etc. Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Further, from the viewpoint of the emulsion stability when the modified polyester resin is made into an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

[0065] Examples of the polyol constituting the modified polyester resin include diol, polyol having three or more functional groups, etc. Examples of the diol include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or its alkylene oxide adduct, etc. Examples of the polyol having three or more functional groups include trimethylolpropane, glycerin, pentaerythritol, etc.

[0066] As the copolymerization ratio of the polycarboxylic acid or its anhydride and the polyol that constitute the modified polyester resin, it is preferably 40 to 60% by mass of the polycarboxylic acid or its anhydride and 40 to 60% by mass of the polyol, with the total mass of the copolymerization components being 100% by mass. More preferably, it is 45 to 55% by mass of the polycarboxylic acid or its anhydride and 45 to 55% by mass of the polyol. The weight average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, more preferably 10,000 to 30,000. From the perspective of improving the bundling property of glass fibers, it is preferably 3,000 or more, and from the perspective of emulsion stability when making it water-dispersible, it is preferably 100,000 or less.

[0067] The polymer and the thermoplastic resin used as the binder may be used alone, only one kind, or in combination of two or more kinds. Taking the total amount of the binder as 100% by mass, it is preferable to use 50% by mass or more of one or more polymers selected from homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary, and tertiary amines. More preferably, it is 60% by mass or more.

[0068] When the bundling agent consists of a silane coupling agent and a binder, the bundling agent is preferably applied and adhered in an amount of 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and even more preferably 0.2 to 1% by mass, as the total mass of the silane coupling agent and the binder, based on 100% by mass of the glass fiber. From the perspective of controlling the bundling property of glass fibers and improving the interfacial adhesion strength, the adhesion amount of the bundling agent is preferably 0.1% by mass or more, as the total mass of the silane coupling agent and the binder, based on 100% by mass of the glass fiber, and preferably 3% by mass or less from the perspective of the handleability of the yarn. Also, when the sizing agent consists of a silane coupling agent, a lubricant, and a binder, the sizing agent is preferably applied and adhered in an amount of 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and still more preferably 0.2 to 1% by mass, as the total mass of the silane coupling agent, the lubricant, and the binder, based on 100% by mass of the glass fiber. From the viewpoints of controlling the bundling property of the glass fiber and improving the interfacial adhesion strength, the adhesion amount of the sizing agent is preferably 0.1% by mass or more, as the total mass of the silane coupling agent, the lubricant, and the binder, based on 100% by mass of the glass fiber, and preferably 3% by mass or less from the viewpoint of the handleability of the yarn.

[0069] --Composition of sizing agent for glass fiber-- The compounding amount of the silane coupling agent in the sizing agent for glass fiber is preferably 0.1 to 2% by mass, more preferably 0.1 to 1% by mass, and still more preferably 0.2 to 0.5% by mass, from the viewpoints of improving the bundling property of the glass fiber, improving the interfacial adhesion strength, and improving the mechanical strength of the composite molded body. The compounding amount of the lubricant in the sizing agent for glass fiber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of imparting sufficient lubricity, and preferably 1% by mass or less, more preferably 0.5% by mass or less, from the viewpoints of improving the interfacial adhesion strength and improving the mechanical strength of the composite molded body. The compounding amount of the binder in the sizing agent for glass fiber is preferably 1 to 25% by mass, more preferably 3 to 15% by mass, and still more preferably 3 to 10% by mass, from the viewpoints of controlling the bundling property of the glass fiber, improving the interfacial adhesion strength, and improving the mechanical strength of the composite molded body.

[0070] When using glass fiber as the continuous reinforcing fiber and the sizing agent consists of a silane coupling agent, a lubricant, and a binder, in the sizing agent for the glass fiber, it is preferable to contain 0.1 to 2% by mass of the silane coupling agent, 0.01 to 1% by mass of the lubricant, and 1 to 25% by mass of the binder, respectively, and it is preferable to dilute these components with water and adjust the total mass to 100% by mass.

[0071] --Usage mode of sizing agent for glass fiber-- Depending on the usage mode, the sizing agent for glass fibers can be adjusted into any form such as an aqueous solution, a colloidal dispersion form, an emulsion form using an emulsifier, etc. However, from the viewpoints of improving the dispersion stability and heat resistance of the sizing agent, it is preferable to use it in the form of an aqueous solution. The glass fibers as continuous reinforcing fibers constituting the continuous fiber reinforced resin composite material of the present embodiment are obtained continuously by applying the above-described sizing agent to the glass fibers using a known method such as a roller-type applicator in a known glass fiber manufacturing process and then drying the produced glass fibers.

[0072] Also, when carbon fibers are selected as the continuous reinforcing fibers, a sizing agent may be used as well. The sizing agent preferably consists of a coupling agent, a lubricant, and a binder. As the coupling agent, one having good compatibility with the hydroxyl groups present on the surface of the carbon fibers can be selected, and as the binder, one having good wettability with the selected thermoplastic resin or having a similar surface tension can be selected. Examples of coupling agents preferably used for carbon fibers include diamines such as 1,6-hexanediamine and polycarboxylic acids. As the lubricant, one that does not inhibit the coupling agent and the binder can be selected. There are no particular restrictions on the type of sizing agent used for carbon fibers, and known ones can be used. Specifically, for example, those described in JP-A-2015-101794 can be used.

[0073] When using other continuous reinforcing fibers, the type and application amount of the sizing agent that can be used for glass fibers and carbon fibers can be appropriately selected according to the characteristics of the continuous reinforcing fibers, and it is preferable to use the type and application amount of the sizing agent similar to those used for carbon fibers.

[0074] (Shape of continuous reinforcing fibers) The continuous reinforcing fibers are multifilaments composed of a plurality of filaments, and the number of single filaments is preferably 30 to 15,000 from the viewpoint of handleability. The single filament diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, still more preferably 6 to 20 μm, and most preferably 8 to 18 μm, from the viewpoints of strength and handleability. The product RD of the single filament diameter R (μm) and the density D (g / cm 3 ) of the continuous reinforcing fiber is preferably 5 to 100 μm·g / cm 3 , more preferably 10 to 50 μm·g / cm 3 , still more preferably 15 to 45 μm·g / cm 3 , even more preferably 20 to 45 μm·g / cm 3 .

[0075] The density D can be measured by a hydrometer. On the other hand, the single filament diameter R (μm) can be calculated from the density D (g / cm 3 ), the fineness (dtex), and the number of single filaments (pieces) by the following formula:

Equation

[0076] To make the product RD of the continuous reinforcing fiber within a predetermined range, for commercially available continuous reinforcing fibers, the fineness (dtex) and the number of single filaments (pieces) may be appropriately selected according to the density of the continuous reinforcing fiber. For example, when using glass fiber as the continuous reinforcing fiber, since the density is about 2.5 g / cm 3 , those with a single filament diameter of 2 to 40 μm may be selected. Specifically, when the single filament diameter of the glass fiber is 9 μm, by selecting a glass fiber with a fineness of 660 dtex and 400 single filaments, the product RD becomes 23. Also, when the single filament diameter of the glass fiber is 17 μm, by selecting a glass fiber with a fineness of 11,500 dtex and 2,000 single filaments, the product RD becomes 43. When using carbon fiber as the continuous reinforcing fiber, since the density is about 1.8 g / cm 3Therefore, those with a single fiber diameter of 2.8 to 55 μm can be selected. Specifically, when the single fiber diameter of the carbon fiber is 7 μm, by selecting carbon fiber with a fineness of 2,000 dtex and 3,000 single fibers, the product RD is 13. When using aramid fiber as the continuous reinforcing fiber, the density is about 1.45 g / cm 3 Therefore, those with a single fiber diameter of 3.4 to 68 μm can be selected. Specifically, when the single fiber diameter of the aramid fiber is 12 μm, by selecting aramid fiber with a fineness of 1,670 dtex and 1,000 single fibers, the product RD is 17.

[0077] Continuous reinforcing fibers, such as glass fibers, are produced by weighing and mixing raw materials of glass, melting them into molten glass in a melting furnace, spinning them into glass filaments, applying a sizing agent, and passing through a spinning machine to be wound in forms such as direct wind roving (DWR), cake, and twisted yarn. The form of the continuous reinforcing fiber can be in any form, but it is preferable to wind it into yarn, cake, or DWR because the productivity and production stability in the process of coating with resin will be increased. From the perspective of productivity, DWR is the most preferable.

[0078] The form of the continuous reinforcing fiber is not particularly limited, and various forms can be mentioned, such as woven fabric, knitted fabric, braided cord, pipe-shaped, non-crimp fabric, unidirectional material, etc. Preferably, it is in the form of woven fabric, non-crimp fabric, or unidirectional material. (Thermoplastic resin)

[0079] The thermoplastic resin is not limited to the following, and examples include polyolefin resins such as polyethylene and polypropylene; polyamide resins such as polyamide 6, polyamide 66, polyamide 46, polyamide 612, polyamide 6I, polyamide 6T, polyamide 6I / 6T, polyamide MXD6, polyamide 11, polyamide 12, polyamide 610, and polyamide 1010; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate; polyacetal resins such as polyoxymethylene; polycarbonate resins; polyether resins such as polyether ketone, polyether ether ketone, polyether glycol, polypropylene glycol, and polytetramethylene ether glycol; polyether sulfone; polyphenylene sulfide; thermoplastic polyether imide; thermoplastic fluorine resins such as tetrafluoroethylene-ethylene copolymer; polyurethane resins; acrylic resins; and modified thermoplastic resins obtained by modifying these resins.

[0080] Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, and thermoplastic fluorine resins are preferred. Polyolefin resins, modified polyolefin resins, polyamide resins, polyester resins, polyurethane resins, and acrylic resins are more preferred from the viewpoints of mechanical properties and versatility. Considering the viewpoint of thermal properties, polyamide resins and polyester resins are even more preferred. Further, polyamide resins are even more preferred from the viewpoint of durability against repeated load.

[0081] - Polyamide resin - The polyamide resin means a high molecular compound having a -CO-NH- (amide) bond in the main chain. Examples include aliphatic polyamides, aromatic polyamides, and wholly aromatic polyamides.

[0082] Examples of polyamide resins include, but are not limited to, polyamides obtained by ring-opening polymerization of lactams, polyamides obtained by self-condensation of ω-aminocarboxylic acids, polyamides obtained by condensing diamines and dicarboxylic acids, and copolymers thereof. The polyamide resin may be used alone or as a mixture of two or more. Examples of lactams include, but are not limited to, pyrrolidone, caprolactam, undecanolactam, and dodecanolactam. Examples of ω-aminocarboxylic acids include, but are not limited to, ω-amino fatty acids which are ring-opening compounds of lactams with water. Lactams or ω-aminocarboxylic acids may be condensed by using two or more monomers in combination. Examples of diamines (monomers) include, but are not limited to, linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; branched aliphatic diamines such as 2-methylpentanediamine and 2-ethylhexamethylenediamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine. Examples of dicarboxylic acids (monomers) include, but are not limited to, aliphatic dicarboxylic acids such as adipic acid, pimelic acid, and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The diamine and dicarboxylic acid as monomers may be condensed either alone or in combination of two or more.

[0083] Examples of polyamide resins include, but are not limited to, aliphatic polyamides such as polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 1010; semi-aromatic polyamides such as polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonane methylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide MXD6, polyamide 6I / 6T; and copolyamide containing these as constituent components, etc. Examples of copolyamides include, but are not limited to, copolymers of hexamethylene adipamide and hexamethylene terephthalamide, copolymers of hexamethylene adipamide and hexamethylene isophthalamide, and copolymers of hexamethylene terephthalamide and 2-methylpentanediamine terephthalamide.

[0084] - Polyester resin - The polyester resin means a polymer compound having a -CO-O- (ester) bond in the main chain. Examples of polyester resins include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, etc. The polyester resin may be a homopolyester or a copolyester. In the case of a copolyester, it is preferably a homopolyester copolymerized with a third component as appropriate. The third component is not limited to the following, but examples include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid. In addition, a polyester resin using a raw material derived from biomass resources can also be used. The examples are not limited to the following, but include aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and aromatic polyester resins such as polybutylene adipate terephthalate.

[0085] [Additives] The continuous fiber reinforced resin composite material of this embodiment may contain additives as necessary. The composite material of this embodiment may contain, for example, colorants, anti-aging agents, antioxidants, weathering agents, metal deactivators, light stabilizers, heat stabilizers, ultraviolet absorbers, antibacterial and antifungal agents, deodorants, conductivity imparting agents, dispersants, softeners, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanization aids, foaming agents, foaming aids, flame retardants, vibration damping agents, nucleating agents, neutralizing agents, lubricants, anti-blocking agents, dispersants, fluidity improvers, mold release agents and other additives. The content of the additive may be 3% by mass or less based on 100% by mass of the composite material.

[0086] (Colorant) Examples of the colorant include carbon black, nigrosine, aluminum pigment, titanium dioxide, ultramarine, cyanine blue, cyanine green, quinacridone, diatomaceous earth, monoazo salt, perylene, disazo, condensed azo, isoindoline, valve pattern, nickel titanium yellow, diketopyrrolopyrrole, metal salt, perylene red, metal oxide, bismuth vanadate, cobalt green, cobalt blue, anthraquinone, phthalocyanine green, phthalocyanine blue, etc. Among them, black colorants are preferred, and carbon black and nigrosine are more preferred.

[0087] The continuous fiber reinforced resin composite material of this embodiment preferably has a content of continuous reinforcing fibers of 90 to 525 parts by mass and a content of components other than these of 0 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. More preferably, with respect to 100 parts by mass of the thermoplastic resin, the content of continuous reinforcing fibers is 150 to 340 parts by mass, and the content of components other than these is 0 to 1 part by mass.

[0088] [Applications of continuous fiber reinforced resin composite materials] The continuous fiber reinforced resin composite material of this embodiment can be suitably used for structural material applications such as aircraft, automobiles, building materials, and robots. In the case of automotive applications, although not limited to the following, for example, it can be used for chassis / frames, undercarriages, drive system components, interior components, exterior components, functional components, and other components. Specifically, steering shaft, mount, sunroof, step, surf trim, door trim, trunk, boot lid, bonnet, seat frame, seat back, retractor, retractor support bracket, clutch, gear, pulley, cam, argay, elastic beam, buffering, lamp, reflector, glazing, front end module, back door inner, brake pedal, steering wheel, electrical components, sound absorbing material, door exterior, interior panel, instrument panel, rear gate, ceiling rib, seat, seat frame assembly, wiper pillar, EPS (Electric Power Steering), small motor, heat sink, ECU (Engine Control Unit) box, ECU housing, steering gear box housing, plastic housing, housing for EV (Electric Vehicle) motor, wire harness, in-vehicle meter, combination switch, small motor, spring, damper, wheel, wheel cover, frame, sub-frame, side frame, two-wheeled frame, fuel tank, oil pan, intake manifold, propeller shaft, drive motor, monocoque, hydrogen tank, electrode of fuel cell, panel, floor panel, outer panel, door, cabin, roof, hood, valve, EGR (Exhaust GasRecirculation valve, variable valve timing unit, connecting rod, cylinder bore, members (engine mounting, front floor cross, footwell cross, seat cross, inner side, rear cross, suspension, pillar reinforcement, front side, front panel, upper, dash panel cross, steering), tunnel, fastening insert, crash box, crash rail, corrugate, roof rail, upper body, side rail, bradding, door surround assembly, airbag member, body pillar, dash to pillar gasket, suspension tower, bumper, body pillar lower, front body pillar, reinforcement (instrument panel, rail, roof, front body pillar, roof rail, roof side rail, rocker, door belt line, front floor under, front body pillar upper, front body pillar lower, center pillar, center pillar hinge, door outer panel), side outer panel, front door window frame, MICS (Minimum Intrusion CabinSystem) Bulk, torque box, radiator support, radiator fan, water pump, fuel pump, electronic control throttle body, engine control ECU, starter, alternator, manifold, transmission, clutch, dashboard, dashboard insulator pad, door side impact protection beam, bumper beam, door beam, bulkhead, outer pad, inner pad, rear seat rod, door panel, door trim bodysubassembly, energy absorber (bumper, shock absorption), shock absorber, shock absorption garnish, pillar garnish, roof side inner garnish, resin rib, side rail front spacer, side rail rear spacer, seat belt pretensioner, airbag sensor, arm (suspension, lower, hood hinge), suspension link, shock absorption bracket, fender bracket, inverter bracket, inverter module, hood inner panel, hood panel, cowl louver, cowl top outer front panel, cowl top outer panel, floor silencer, dump seat, hood insulator, fender side panel protector, cowl insulator, cowl top ventilator loop, cylinder head cover, tire deflector, fender support, strut tower bar, mission center tunnel, floor tunnel, radicore support, luggage panel, luggage floor, accelerator pedal, accelerator pedal base, etc. can be suitably used as parts.

[0089] [Molding of composite material] The continuous fiber reinforced resin composite material of this embodiment can be further molded. Examples of the above method include cutting the continuous fiber reinforced resin composite material of this embodiment into a predetermined size, heating it with an infrared heater, and performing hot compression pressing with a press molding machine.

Example

[0090] Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to these examples, and it goes without saying that various modifications can be made and implemented within the scope of the gist of the present invention.

[0091] [Coating rate of the interfacial resin of continuous reinforcing fibers, exposure degree of interfacial exposed reinforcing fibers, relative element concentration] 100 mg of the continuously reinforced fiber-reinforced resin composite cut into flakes and 20 mL of a solvent selected according to the resin used in each example were placed in a mixing rotor and stirred for 5 hours. Then, the solvent was removed by suction filtration, and 40 mL of fresh solvent was poured onto the filter to wash the continuous reinforcing fibers, followed by air drying. The obtained continuous reinforcing fibers and 20 mL of fresh solvent were placed in a mixing rotor and stirred for 2 hours. Then, the solvent was removed by suction filtration, and 40 mL of fresh solvent was poured onto the filter to wash the continuous reinforcing fibers, followed by drying with nitrogen blowing. The obtained continuous reinforcing fibers and 20 mL of fresh solvent were placed in a mixing rotor and stirred for 2 hours. The solvent was removed by suction filtration, and 40 mL of fresh solvent was poured onto the filter to wash the continuous reinforcing fibers, followed by air drying and drying overnight in a vacuum dryer set at room temperature. The obtained continuous reinforcing fibers were pressed into a flat plate, 2-mm small pieces were taken out, and using XPS (Versa probe II, ULVAC-PHI, Inc.), with excitation source mono.AlKα 20 kV×5 mA 100 W, analysis size 100 μm×1.4 mm, photoelectron extraction angle 45°, capture region (Survey scan): 117.4 eV, (Narrow scan): C1s, O1s, N1s, Si2p, Ca2p, Al2p, Pass Energy (Survey scan): 117.4 eV, (Narrow scan): 46.95 eV, measurements were performed to determine the relative element concentrations of carbon, oxygen, nitrogen, silicon, aluminum, and calcium. The coating rate of the interfacial resin of the continuous reinforcing fibers was determined by the following formula (1) when polyamide was used as the resin and glass fibers were used as the continuous reinforcing fibers, by the following formula (2) when polyamide was used as the resin and carbon fibers were used as the continuous reinforcing fibers, and by the following formula (3) when polypropylene was used as the resin and glass fibers were used as the continuous reinforcing fibers. The details in the formulas are as described above. (Coating rate)=[N] / ([N]+[Si]) (1) (Coating rate)=[N] / ([N]+[O]) (2) (Coating rate)=([C]-[C0]) / ([C]-[C0]+[Si]) When using glass fiber as the continuous reinforcing fiber, the exposure degree of the interface-exposed reinforcing fiber was determined by the following formula (4), and when using carbon fiber as the continuous reinforcing fiber, it was determined by the following formula (5). The details in the formulas are as described above. (Exposure degree of interface-exposed reinforcing fiber)=[Al] / [Al0] (4) (Exposure degree of interface-exposed reinforcing fiber)=[O] / [O0] (5)

[0092] [Static wettability] A thermoplastic resin film and a single reinforcing fiber were sandwiched between cover glasses, heated to 280°C at 100°C / min on a hot plate, left for 5 minutes, and then the angle (contact angle) (°) formed between the surface of the reinforcing fiber and the thermoplastic resin was observed with an optical microscope and measured at 4 points, and the average value was obtained. It was evaluated that the smaller this angle, the better the static wettability.

[0093] [Impregnation rate] As the molding machine, a hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons was used. Five continuous reinforcing fiber fabrics and a thermoplastic resin film were laminated, and the laminate was placed inside a mold equipped with a temperature sensor, and the mold temperature was set to the melting temperature of the thermoplastic resin + 65°C and put into a hot press molding machine. Heat press molding was performed at a pressure of 5 MPa while monitoring the temperature. The laminate was taken out of the hot press molding machine 30 seconds after the temperature inside the mold reached the melting point of the thermoplastic resin, put into a cooling press machine, and cooled by water cooling at a pressure of 5 MPa. The obtained continuous reinforcing fiber composite material was cut and polished with a band saw, and the impregnation rate (%) (described later) obtained for the cut surface was divided by the time (minutes) during which the thermoplastic resin was above the melting point during the hot press molding to obtain the impregnation rate (% / min). In the above operation, the time during which the thermoplastic resin was above the melting point was 60 seconds. The impregnation rate (%) was calculated by the following method. The obtained continuous fiber-reinforced resin composite material was cut at an arbitrary position, and polishing was performed while taking care not to damage the continuous reinforcing fibers. The cross-section was observed by SEM, and the obtained image was analyzed by analysis software (product name: ImageJ) to calculate the area of the region surrounded by the outer contour line of the continuous reinforcing fibers, which are bundles of single filaments (filaments), and the area of the voids contained in the region surrounded by the outer contour line of the continuous reinforcing fibers. And, the following formula: Impregnation rate (%) = [1 - {void area / (area of the region surrounded by the outer contour line of the continuous reinforcing fibers)}] × 100 was calculated. The impregnation rate was calculated for 10 continuous reinforcing fibers in the obtained image of the cut surface, and the average value was calculated as the impregnation rate.

[0094] [Flexural Fatigue Test] Test specimens of ASTM-D671 Type A were prepared from the continuous fiber-reinforced resin composite material, and a vibration fatigue test was carried out using a repeated vibration fatigue testing machine (B-70, Toyo Seiki Seisakusho Co., Ltd.) at a test temperature of 23°C, a frequency of 20 Hz, and a sine wave waveform. The number of judgment cycles of the vibration fatigue test at a stress corresponding to 35% of the flexural strength of the continuous fiber-reinforced resin composite material of each example was determined.

[0095] [Flexural Strength at 23°C, Flexural Strength at 120°C] Strip-shaped test specimens with a length of 100 mm, a width of 10 mm, and a thickness of 2 mm were cut out from the continuous fiber-reinforced resin composite material. Using an Instron universal testing machine and a fixture for three-point bending, with the span set to 32 mm and a speed of 1 mm / min, the flexural strength (MPa) was measured in an environment of 23°C and 50% RH, and in an environment of 120°C and 50% RH, respectively.

[0096] The materials used in the examples and comparative examples are as follows.

[0097] [Continuous Reinforcing Fibers] (Glass Fibers) Glass fiber 1 (GF1): Glass fiber 100% by mass with a fineness of 1.15 g / m and 2000 filaments per single yarn was produced with 0.10% by mass of a sizing agent attached. The winding form was DWR, and the average single yarn diameter was about 18 μm. The above sizing agent was prepared by adjusting with deionized water so that it contained 1.5% by mass of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 1% by mass of carnauba wax, and 3% by mass of a copolymer compound having a weight average molecular weight of 10,000 obtained by copolymerizing 50% by mass of maleic anhydride and 50% by mass of methyl methacrylate. Glass fiber 2 (GF2): The glass fiber obtained by treating GF1 in an electric furnace at 650°C for 3 hours was immersed in a 1.5% by mass aqueous solution of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) for 30 minutes and dried at 110°C for 3 hours. Glass fiber 3 (GF3): GF1 was treated in an electric furnace at 650°C for 3 hours to obtain GF without a sizing agent. Glass fiber 4 (GF4): Glass fiber 100% by mass with a fineness of 1.15 g / m and 2000 filaments per single yarn was produced with 0.10% by mass of a sizing agent attached. The winding form was DWR, and the average single yarn diameter was about 18 μm. The above sizing agent was prepared by adjusting with deionized water so that it contained 1.5% by mass of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 1% by mass of carnauba wax, and 3% by mass of a copolymer compound having a weight average molecular weight of 13,000 obtained by copolymerizing 50% by mass of maleic anhydride and 50% by mass of styrene. Glass fiber 5 (GF5): Glass fiber with a fineness of 1.15 g / m and 2000 filaments per single yarn, with 100% by mass of glass fiber, was attached with a mixture of 0.3% by mass of 3-glycidoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.), 1.5% by mass of an epoxy resin emulsion, and 0.2% by mass of carnauba wax as a sizing agent

[0098] (Carbon fiber) Carbon Fiber 1: A PAN-based carbon fiber with a single filament count of 12,000 was produced by attaching 0.1% by mass of a sizing agent. The sizing agent was prepared by mixing 1.5% by mass of 1,6-hexanediamine, 1.5% by mass of diphenylphosphoric acid azide, 1% by mass of carnauba wax, and 3% by mass of a copolymer compound with a weight average molecular weight of 10,000 obtained by copolymerizing 50% by mass of maleic anhydride and 50% by mass of methyl methacrylate, and adjusting with deionized water. Carbon Fiber 2: A PAN-based carbon fiber with a single filament count of 12,000 was immersed in an aqueous solution containing 1.5% by mass of 1,6-hexanediamine and 1.5% by mass of diphenylphosphoric acid azide at 60°C for 12 hours, and then dried at 110°C for 6 hours. Carbon Fiber 3: A PAN-based carbon fiber with a single filament count of 12,000 (without a sizing agent)

[0099] [Production of Continuous Reinforced Fiber Substrate] Glass Cloth: A glass cloth was produced using a repair loom (loom width 1 m), with the above Glass Fiber 1 used as the warp and weft. The woven form of the obtained glass cloth was plain weave, with a weave density of 6.5 threads / 25 mm and a basis weight of 640 g / m 2 ) Carbon Fiber Cloth: A carbon fiber cloth was produced using a repair loom (loom width 1 m), with the above Carbon Fiber 1 used as the warp and weft. The woven form of the obtained carbon fiber cloth was plain weave, with a weave density of 6.5 threads / 25 mm and a basis weight of 425 g / m 2

[0100] [Thermoplastic Resin] Resin 1: Polyamide 66 The polymerization reaction of polyamide was carried out as follows by the "thermal melt polymerization method". A salt containing adipic acid (Wako Pure Chemical Industries) and hexamethylenediamine (Tokyo Chemical Industry) in a molar ratio of 55:45: 1500 g and adipic acid: 150 g were dissolved in distilled water: 1500 g to prepare a 52 mass% homogeneous aqueous solution of the raw material monomers. This aqueous solution was charged into an autoclave with an internal volume of 6.2 L and purged with nitrogen. While stirring at a temperature of 110°C or higher and 140°C or lower, water vapor was gradually removed to concentrate the solution to a concentration of 69 mass%. Then, the internal temperature was raised to 225°C. At this time, the pressure in the autoclave increased to 1.9 MPa. While maintaining the pressure at 1.9 MPa by gradually removing water vapor, the reaction was carried out for 50 minutes until the internal temperature reached 245°C for 2 hours. Next, the pressure was reduced over 1.5 hours. Then, the inside of the autoclave was maintained under a reduced pressure of 650 torr for 11 minutes with a vacuum device. At this time, the final internal temperature of the polymerization was 265°C. Then, it was pressurized with nitrogen and formed into strands from the lower spinning orifice (nozzle), cooled with water, cut, and discharged in pellet form, and dried at 100°C in a nitrogen atmosphere for 12 hours to obtain Resin 1 (polyamide 66). Mw = 31000, Mw / Mn = 1.95, melting point (Tm) = 265°C, glass transition temperature (Tg) = 50°C.

[0101] Resin 2: 0.05 mass% of copper iodide and 0.2 mass% of potassium iodide were dry-blended with respect to 100 mass% of Resin 1, kneaded in a twin-screw kneader (TEM26SS, Toshiba Machine) set at 280°C, cooled with water, cut, and discharged in pellet form, and dried at 100°C in a nitrogen atmosphere for 12 hours to obtain Resin 2.

[0102] Resin 3: Polyamide 6I The polymerization reaction of polyamide was carried out as follows by the "thermal melt polymerization method". A salt containing an equimolar salt of isophthalic acid (Wako Pure Chemical Industries, Ltd.) and hexamethylenediamine in a molar ratio of 55:45: 1500 g, and 100 g of isophthalic acid were dissolved in 1500 g of distilled water to prepare a homogeneous aqueous solution. While stirring at a temperature of 110°C or higher and 140°C or lower, water vapor was gradually removed until the solution concentration reached 68% by mass to concentrate the solution. Then, the internal temperature was raised to 235°C. While maintaining the pressure constant by gradually removing water vapor, the reaction was carried out for 50 minutes until the internal temperature reached 245°C. Next, the pressure was reduced over 60 minutes. Then, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum device for 10 minutes. At this time, the final internal temperature of the polymerization was 265°C. Then, it was pressurized with nitrogen and formed into strands from the lower spinning nozzle (nozzle), cooled with water, cut, and discharged in pellet form. The pellets were dried at 100°C in a nitrogen atmosphere for 12 hours to obtain Resin 3 (polyamide 6I). The obtained Resin 3 (polyamide 6I) had Mw = 22000 and Mw / Mn = 1.9.

[0103] Resin 4: Resin 1 and Resin 3 were dry-blended at a mass ratio of 7:3.

[0104] Resin 5: Maleated PP (Mw = 42000, acid value: 40 eq / g)

[0105] [Production of Thermoplastic Resin Film] A thermoplastic resin film was obtained by molding using a T-die extrusion molding machine (manufactured by Soken Chemical & Engineering Co., Ltd.). The thickness of the thermoplastic resin film was 180 μm.

[0106] [Example 1] Using Resin 1, Thermoplastic Resin Film 1 was obtained by the above method. Five glass cloths 1 and six thermoplastic resin films 1 were prepared, and the glass cloth 1 and the thermoplastic resin film 1 were alternately stacked so that the thermoplastic resin film 1 was on the surface, and molding was performed to obtain a continuous fiber reinforced resin composite material. As a molding machine, a continuous compression molding machine was used. The glass cloth and the thermoplastic resin film 1 were stacked as described above and installed in the molding machine. The temperature of the heating zone in the molding machine was 350 °C, the temperature of the cooling zone was adjusted by oil cooling, and compression molding was performed at a pressure of 5 MPa and a belt speed of 0.5 m / min. Table 1 shows the results of the impregnation rate test, which are the physical properties of the obtained continuous fiber reinforced resin composite material and the results of the static wettability test of GF2, GF3 and resin 1.

[0107] [Example 2] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that resin 2 was used as the thermoplastic resin. Table 1 shows the results of the impregnation rate test, which are the physical properties of the obtained continuous fiber reinforced resin composite material and the results of the static wettability test of GF2, GF3 and resin 2.

[0108] [Example 3] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that resin 3 was used as the thermoplastic resin. Table 1 shows the results of the impregnation rate test, which are the physical properties of the obtained continuous fiber reinforced resin composite material and the results of the static wettability test of GF2, GF3 and resin 3.

[0109] [Example 4] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that resin 4 was used as the thermoplastic resin. Table 1 shows the results of the impregnation rate test, which are the physical properties of the obtained continuous fiber reinforced resin composite material and the results of the static wettability test of GF2, GF3 and resin 4.

[0110] [Example 5] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that a carbon fiber cloth was used as the continuous reinforcement fiber base material. In addition, a film with a thickness of 118 μm was used as the thermoplastic resin film. Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite materials, the results of the static wettability tests of CF2, CF3 and Resin 1, and the results of the impregnation rate tests.

[0111] [Example 6] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that Resin 5 was used as the thermoplastic resin and GF4 was used as the continuous reinforcing fiber. Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite materials, the results of the static wettability tests of GF2, GF3 and Resin 5, and the results of the impregnation rate tests.

[0112] [Comparative Example 1] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that a glass cloth with a plain weave, a weft density of 6.5 threads / 25 mm, and a basis weight of 600 g / m 2 was manufactured and used. Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite materials, the results of the static wettability tests of GF2, GF3 and Resin 1, and the results of the impregnation rate tests.

[0113] [Comparative Example 2] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that GF3 was used. Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite materials, the results of the static wettability tests of GF2, GF3 and Resin 1, and the results of the impregnation rate tests.

[0114] [Comparative Example 3] The same evaluation as in Example 1 was carried out using "Tepex dynalite 101" manufactured by Bond Laminate, in which polyamide 66 was impregnated into a glass cloth. Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite materials.

[0115]

Table 1

Industrial Applicability

[0116] The continuous fiber reinforced resin composite material of this embodiment is industrially applicable as a reinforcing material for materials that require high-level mechanical properties, such as structural parts of various machines and automobiles, and as a composite molded body material with a thermoplastic resin composition.

Claims

**Claim 1** A method for manufacturing a continuous fiber reinforced resin composite material comprising continuous reinforcing fibers and a thermoplastic resin, wherein the contact angle by a static wettability test between the continuous reinforcing fibers after resin dissolution and the thermoplastic resin is 70 to 130% of the contact angle by a static wettability test between the continuous reinforcing fibers and the thermoplastic resin of a material treated only with a coupling agent, and the impregnation rate of the thermoplastic resin with respect to the continuous reinforcing fibers is 32% / min or more. The method for manufacturing a continuous fiber reinforced resin composite material, wherein the continuous reinforcing fibers are continuous reinforcing fibers treated with a sizing agent containing an amino-silane-based silane coupling agent. **Claim 2** The method for manufacturing a continuous fiber reinforced resin composite material according to Claim 1, wherein the coverage rate of the interfacial resin in the continuous reinforcing fibers after resin dissolution is 44% or less. **Claim 3** A step of setting the continuous reinforcing fibers and the thermoplastic resin in a mold; A melting step of melting the thermoplastic resin; A compression step of compressing the mold to shape the continuous fiber reinforced resin composite material, the method for manufacturing a continuous fiber reinforced resin composite material according to Claim 1 or 2. **Claim 4** The method for manufacturing a continuous fiber reinforced resin composite material according to Claim 3, wherein the mold clamping pressure in the compression step is 1 MPa or more. **Claim 5** A step of installing the continuous reinforcing fibers and the thermoplastic resin in a mold and compressing them with a double belt press, or a step of installing a mold frame so as to surround the four sides of the installed continuous reinforcing fibers and the thermoplastic resin and compressing them with a double belt press, the method for manufacturing a continuous fiber reinforced resin composite material according to Claim 1 or 2. **Claim 6** A method for manufacturing a continuous fiber reinforced resin composite material according to Claim 1 or 2, comprising a step of preparing a compression molding machine set at one or more temperatures for heating and a compression molding machine set at one or more temperatures for cooling, and sequentially feeding a mold in which the continuous reinforcing fibers and the thermoplastic resin are installed into the compression molding machines for molding.

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