Continuous fiber-reinforced resin composite material and method for manufacturing the same

Abstract

To provide a continuous fiber-reinforced resin composite material and a method for producing the same that has good acoustic emission signal and high strength, elastic modulus and water absorption property.SOLUTION: Provided is a continuous fiber-reinforced resin composite material that contains a continuous reinforcing-fiber and a thermoplastic resin and in which, characterized, the acoustic emission (AE) count A calculated by the following formula is 0.16 or less. (AE count A)=(number of AE signals having amplitude of 40 dB or more and duration of 3500 μ seconds or less) / (total number of AE signals).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] Composite material molded bodies in which reinforcing materials such as glass fibers are added to a matrix resin material are used for various structural parts of machines, automobiles, etc., pressure vessels, and tubular structures. In particular, from the viewpoint of strength, a continuous fiber reinforced resin composite material in which the reinforcing fibers are continuous fibers is desired. As this continuous fiber reinforced resin composite material, there are those that devise a sizing agent added to the reinforcing fibers (for example, see Patent Document 1 below), those that devise the difference between the melting point and the crystallization temperature (for example, see Patent Document 2 below), those that add an organic salt to the resin material (for example, see Patent Document 3 below), those that laminate a fabric of a preform with a thermoplastic resin (for example, see Patent Document 4 below), and those that have good adhesive strength, affinity, etc. at the interface between the continuous reinforcing fibers and the resin (for example, see Patent Document 5 below).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the continuous fiber reinforced resin composites of the prior art, none of them have good acoustic emission (AE) signals generated during physical property tests, and there is room for improvement in that the physical properties such as strength and elastic modulus and water absorption characteristics are not sufficient.

[0005] In view of such a prior art level, the problem to be solved by the present invention is to provide a continuous fiber reinforced resin composite material having a good acoustic emission signal, high strength, elastic modulus, and water absorption characteristics, and a manufacturing method thereof.

Means for Solving the Problem

[0006] As a result of intensive studies and repeated experiments to solve such problems, the inventors of the present invention have unexpectedly found that by adjusting the interface amount, heating rate, and cooling rate of the continuous fiber reinforced resin composite material during manufacturing and devising the acoustic emission signal of the continuous fiber reinforced resin composite material, the above problems can be solved, and the present invention has been completed.

[0007] That is, the present invention is as follows. [1] A continuous fiber reinforced resin composite material comprising a continuous reinforcing fiber base material and a thermoplastic resin, wherein the acoustic emission (AE) count A of the continuous fiber reinforced resin composite material obtained by the following formula is 0.16 or less, the interface amount of the continuous fiber reinforced resin composite material is 100,000 m -1 or more, the crystallinity of the thermoplastic resin is 20 to 40%, and the basis weight of the continuous reinforcing fiber base material is 637 g / m 2 or more ru child A continuous fiber reinforced resin composite material, characterized by the above. (AE count A) = (number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less) / (total number of AE signals) [2] The continuous fiber-reinforced resin composite material according to [1], wherein the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less is 100,000 or less. [3] A continuous fiber-reinforced resin composite material according to [1] or [2], wherein the number of AE signals with an amplitude of 25-30 dB and a duration of 1000 μs or less is 1,000 or more. [4] A continuous fiber-reinforced resin composite material according to any one of [1] to [3], wherein the total number of AE signals is 500,000 or more. [5] The AE count B calculated using the following formula is 1.1 × 10 -3 The continuous fiber-reinforced resin composite material described in any of [1] to [4] above. (AE count B) = (Number of AE signals with amplitude 25-30 dB and duration 1000 μs or less) / (Total number of AE signals) [6] The continuous fiber-reinforced resin composite material according to any one of [1] to [5], wherein the thermoplastic resin is a polyamide resin. [7] A method for producing a continuous fiber-reinforced resin composite material according to any one of [1] to [6], The interface volume of the continuous fiber-reinforced resin composite material is 100,000 m -1 The above is true, with a heating rate of 200-330°C / min and a cooling rate of 10-120°C / min. The degree of crystallinity of the thermoplastic resin is 20-40%, and The basis weight of the aforementioned continuous reinforced fiber base material is 637 g / m². 2 That's all. ru child A manufacturing method characterized by the following. [Effects of the Invention]

[0008] The continuous fiber-reinforced resin composite material according to the present invention exhibits good acoustic emission signals and can demonstrate high strength, elastic modulus, and water absorption properties. [Modes for carrying out the invention]

[0009] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0010] [Continuous fiber-reinforced resin composite material] The continuous fiber-reinforced resin composite material of this embodiment (hereinafter also simply referred to as "composite material") includes continuous reinforcing fibers and resin, and the AE count A, calculated by the following formula in the acoustic emission signal during a bending test, is 0.16 or less. (AE Count A) = (Number of AE signals with amplitude of 40 dB or more and duration of 3,500 μs or less) / (Total number of AE signals) The above AE count A is preferably 0.10 or less, and more preferably 0.05 or less. When the AE count A is within this range, the adhesion between the continuous reinforcing fibers contained in the continuous fiber-reinforced resin composite material and the thermoplastic resin is good, making it difficult for both to break, and allowing for the expression of excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warp properties. As a method for adjusting the number of signals to the range, for example, in a method for manufacturing a continuous fiber-reinforced resin composite material, the interface amount of the continuous fiber-reinforced resin composite material is set to 100,000 m -1 The above examples include methods that set the heating rate to 200-330°C / min and the cooling rate to 10-120°C / min. In this disclosure, the acoustic emission signal of the continuous fiber-reinforced resin composite material can be obtained by attaching an acoustic emission sensor to a bending test fixture and sensing the sound emitted from the continuous fiber-reinforced resin composite material during the bending test. The AE count A is obtained by measuring the number of acoustic emission signals generated in the range of amplitude 40 dB or more and duration 3,500 μs or less, and the total number of AE signals, and in detail, it can be determined by the method described in the embodiments below.

[0011] In this embodiment, the continuous fiber-reinforced resin composite material preferably has 100,000 or fewer acoustic emission signals with an amplitude of 40 dB or more and a duration of 3,500 μs or less during a bending test, more preferably 80,000 or fewer, even more preferably 60,000 or fewer, and even more preferably 50,000 or fewer. When the number of signals is within this range, the adhesion between the continuous reinforcing fibers and the resin in the continuous fiber-reinforced resin composite material is good, making fracture of both less likely, and enabling the material to exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warping properties. A method for adjusting the number of signals to the aforementioned range is, for example, to set the interface amount of the continuous fiber-reinforced resin composite material to 100,000 m -1 In summary, the basis weight of the continuous reinforced fiber base material is 637 g / m². 2 The above-mentioned method involves a thermoplastic resin filling volume of 45% or more, a heating rate of 200-330°C / min, a cooling rate of 10-120°C / min, and a thermoplastic resin end group concentration of 70 μmol / g or more.

[0012] In the continuous fiber-reinforced resin composite material of this embodiment, the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of 1,000 μs or less during a bending test is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. When the number of signals is within this range, the adhesion between the continuous reinforcing fibers and the resin in the continuous fiber-reinforced resin composite material is good, making fracture of both less likely, and enabling the material to exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warping properties. A method for adjusting the number of signals to the aforementioned range includes, for example, setting the cooling rate during the manufacturing of the continuous fiber-reinforced resin composite material to 10 to 120°C / min, the degree of crystallinity of the resin contained in the continuous fiber-reinforced resin composite material to 20 to 40%, the proportion of thermoplastic resin in the filling volume to 45% or more, and the cooling and compression time to 1 to 10 minutes.

[0013] In the acoustic emission signal during the bending test of the continuous fiber reinforced resin composite material of the present embodiment, the total number of AE signals is preferably 500,000 or more, more preferably 750,000 or more, and even more preferably 1,000,000 or more. When the number of signals is within this range, the adhesion between the continuous reinforcing fibers and the resin contained in the continuous fiber reinforced resin composite material is good, and the breakage of both is unlikely to occur, and excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics can be exhibited. As a method for adjusting the number of signals to the above range, for example, a method of making the interface amount of the continuous fiber reinforced resin composite material 100,000 m -1 or more, the crystallinity of the resin contained in the continuous fiber reinforced resin composite material 20 - 40%, the cooling compression time 1 - 10 minutes, and the end group concentration of the thermoplastic resin 70 μmol / g or more can be mentioned.

[0014] In the acoustic emission signal during the bending test of the continuous fiber reinforced resin composite material of the present embodiment, the AE count B obtained by the following formula is preferably 1.1×10 -3 or more, more preferably 2.0×10 -3 or more, and even more preferably 3.0×10 -3 or more. (AE count B) = (number of AE signals with amplitude 25 - 30 dB and duration 1000 μs or less) / (total number of AE signals) When the number of signals is within this range, the adhesion between the continuous reinforcing fibers and the resin contained in the continuous fiber reinforced resin composite material is good, and the breakage of both is unlikely to occur, and excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics can be exhibited. As a method for adjusting the number of signals to the above range, for example, a method of making the interface amount of the continuous fiber reinforced resin composite material 100,000 m -1 or more, the heating rate is 200 - 330 °C / min, the cooling rate is 10 - 120 °C / min, and the end group concentration of the thermoplastic resin is 70 μmol / g or more can be mentioned.

[0015] The atmospheric equilibrium water absorption rate of the continuous fiber-reinforced resin composite material of this embodiment is preferably 0.75% by mass or less, and more preferably 0.70% by mass or less. The atmospheric equilibrium water absorption rate refers to the water absorption rate under conditions of 23°C and 50% humidity. When the atmospheric equilibrium water absorption rate is within this range, excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warp properties can be achieved.

[0016] [Forms of continuous fiber-reinforced resin composite materials] The form of the continuous fiber-reinforced resin composite material is not particularly limited, and various forms can be cited below. For example, a form in which continuous reinforced fibers are combined with a thermoplastic resin in the form of a woven, knitted, braided, or pipe-shaped material; a form in which continuous reinforced fibers aligned in one direction are combined with a thermoplastic resin; a form in which yarn made of continuous reinforced fibers and thermoplastic resin is aligned in one direction and shaped; and a form in which yarn made of continuous reinforced fibers and thermoplastic resin is formed into a woven, knitted, braided, or pipe-shaped material. The continuous fiber-reinforced resin composite material of this embodiment may be a flat plate, or 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. The layer of continuous reinforcing fibers is a layer containing continuous reinforcing fibers (for example, a continuous reinforcing fiber substrate), and may be a layer in which thermoplastic resin is impregnated inside the continuous reinforcing fibers. The form of the intermediate material before shaping of the continuous fiber-reinforced resin composite material is not particularly limited, and examples include a blended yarn of continuous reinforcing fibers and resin fibers, a coated yarn in which a bundle of continuous reinforcing fibers is covered with resin, continuous reinforcing fibers pre-impregnated with resin and made into a tape, continuous reinforcing fibers sandwiched between resin films, continuous reinforcing fibers with resin powder attached, a core material of continuous reinforcing fibers surrounded by a braided cord of resin fibers, reinforcing fibers pre-impregnated with resin, and a form in which continuous reinforcing fibers are in contact with molten resin.

[0017] [Method for manufacturing continuous fiber-reinforced resin composite materials] The method for producing the continuous fiber-reinforced resin composite material of this embodiment is not particularly limited and includes various methods such as those listed below.

[0018] In one method, for example, a base material constituting a continuous fiber-reinforced resin composite material (for example, a base material made of continuous reinforcing fibers, a base material made of thermoplastic resin) is cut or shaped to match the desired composite material, the required number of pieces are stacked or the required number of sheets are laminated considering the thickness of the target product, and then set in a mold according to the shape of the mold.

[0019] The base material may be cut one sheet at a time, or a desired number of sheets may be stacked and cut at once. From a productivity standpoint, it is preferable to cut the sheets in a stacked state. Any cutting method is acceptable, such as a water jet, blade press, hot blade press, laser, or plotter. Among these, a hot blade press is preferred because it offers excellent cross-sectional shape and improves handling by welding the edges when cutting multiple sheets in a stack. The appropriate cutting shape can be adjusted through trial and error, but it is preferable to set it by performing a simulation using CAE (computer-aided engineering) in accordance with the shape of the mold.

[0020] The base material may be shaped in any way; for example, it may be shaped into a sheet.

[0021] After setting the substrate in the mold, the mold is closed and compressed. Then, the mold temperature is controlled to a temperature above the melting point of the thermoplastic resin constituting the continuous fiber-reinforced resin composite material to melt the thermoplastic resin and shape it. There are no specific requirements for the mold clamping pressure, but it is preferably 1 MPa or higher, more preferably 3 MPa or higher. Alternatively, the mold may be clamped once for degassing, etc., and the mold clamping pressure may be released after compression molding. From the viewpoint of strength development, it is preferable for the compression molding time to be as long as possible so as not to cause thermal degradation of the thermoplastic resin used, but from the viewpoint of productivity, it is preferably within 2 minutes, more preferably within 1 minute.

[0022] In the method for manufacturing a continuous fiber-reinforced resin composite material of this embodiment, the interface amount of the continuous fiber-reinforced composite material is 100,000 m -1 The above conditions are met, and it is preferable that the heating rate is 200-330°C / min and the cooling rate is 10-120°C / min. Furthermore, the degree of crystallinity of the resin contained in the continuous fiber-reinforced resin composite material is 20-40%, and the basis weight of the continuous reinforcing fiber base material is 637 g / m². 2 The above conditions are met, and it is more preferable that the volume proportion of the thermoplastic resin is 45% or more of the total raw materials, the cooling and compression time is 1 to 10 minutes, and the end group concentration of the thermoplastic resin is 70 μmol / g or more.

[0023] The interface volume of a continuous fiber-reinforced composite material is the amount of interface between the continuous reinforcing fibers and the matrix resin, and can be calculated using the following formula. (Interface amount (m -1 )) = (Volume of reinforcing fibers in continuous fiber-reinforced resin composite material (m³) 3 )) × (density of reinforcing fibers (g / m³) 3 )) × (Number of single fibers of reinforcing fiber) × (Diameter of reinforcing fiber (m)) × π / (Fineness of reinforcing fiber (g / m)) / (Volume of continuous fiber-reinforced resin composite material (m³) 3 )) The interface volume is 100,000 m -1 Preferably, it is 120,000 m -1 It is more preferable that it be greater than or equal to 130,000 m -1 It is even more preferable that it be greater than or equal to the above. Furthermore, there is no specific upper limit, but 1,000,000 m -1 Preferably, the following: 500,000 m -1 The following is more preferable: The larger the interface area of ​​the continuous fiber-reinforced composite material, the smaller the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less tend to be, the larger the number of AE signals with an amplitude of 25-30 dB and a duration of 1000 μs or less tend to be, and the larger the total AE count tends to be.

[0024] The heating rate of a continuous fiber-reinforced composite material refers to the rate at which the substrate material is heated after it has been set in the molding machine. The heating rate is preferably 200-330°C / min, more preferably 230-300°C / min, and even more preferably 250-280°C / min. The slower the heating rate, the smaller the AE count A tends to be, the smaller the number of acoustic emission signals with an amplitude of 40 dB or more and a duration of 3,500 μs or less tends to be, and the larger the AE count B tends to be.

[0025] The cooling rate of a continuous fiber-reinforced composite material refers to the rate at which the base material constituting the continuous fiber-reinforced composite material is cooled by water cooling or other means after it has been set in a molding machine, melted, and compressed. The cooling rate is preferably 10 to 120°C / min, more preferably 20 to 100°C / min, and even more preferably 30 to 90°C / min. As the cooling rate decreases, the AE count A tends to decrease, the number of acoustic emission signals with an amplitude of 40 dB or more and a duration of 3,500 μs or less tends to decrease, and the number of acoustic emission signals with an amplitude of 25-30 dB and a duration of 1,000 μs or less tends to increase, and the AE count B tends to increase.

[0026] The degree of crystallinity of the resin contained in a continuous fiber-reinforced resin composite material refers to the degree of crystallinity when the material is in its continuous fiber-reinforced composite state, and represents the proportion of the crystalline region within the entire resin. The degree of crystallinity is preferably 20-40%, more preferably 25-35%, and even more preferably 28-33%. The lower the degree of crystallinity, the greater the number of acoustic emission signals with an amplitude of 25-30 dB and a duration of 1,000 μs or less, and the greater the total number of AE signals. The degree of crystallinity of the resin contained in the continuous fiber-reinforced resin composite material can be measured using a differential scanning calorimeter, and specifically, it can be measured by the method described in the examples below.

[0027] The basis weight of a continuous reinforced fiber base material refers to the weight per meter of the continuous reinforced fiber base material (such as fiber cloth) used in the manufacture of continuous fiber reinforced resin composite materials. 2 This is the mass per unit. The basis weight of the continuous reinforced fiber base material is 637 g / m². 2 Preferably, it is 640-700 g / m². 2 It is more preferable that it be 650-690 g / m² 2 It is even more preferable that this be the case. The larger the basis weight of the continuous fiber-reinforced substrate, the smaller the number of AE signals in the continuous fiber-reinforced composite material with an amplitude of 40 dB or more and a duration of 3500 μs or less tends to be, the larger the number of AE signals with an amplitude of 25-30 dB and a duration of 1000 μs or less tends to be, and the larger the total AE count tends to be.

[0028] The proportion of thermoplastic resin in the raw material volume refers to the ratio of the volume of thermoplastic resin to the total volume of raw materials used in the manufacture of continuous fiber-reinforced resin composite materials. The proportion of thermoplastic resin in the filling volume is preferably 45% or more, and more preferably 50% or more. There is no particular upper limit, but it is preferably 75% or less, and more preferably 65% ​​or less. The larger the proportion of thermoplastic resin in the compounding volume, the smaller the number of AE signals with amplitudes of 40 dB or more and durations of 3500 μs or less tend to be in continuous fiber-reinforced composite materials, the larger the number of AE signals with amplitudes of 25-30 dB and durations of 1000 μs or less tend to be, and the larger the total AE count tends to be.

[0029] Cooling and compression time refers to the time it takes to cool and compress the base material constituting the continuous fiber-reinforced composite material after it has been set in a molding machine, melted, and compressed, using methods such as water cooling. The cooling and compression time is preferably 1 to 10 minutes, more preferably 2 to 9 minutes, and even more preferably 3 to 8 minutes. The shorter the cooling and compression time, the smaller the number of AE signals with amplitudes of 40 dB or more and durations of 3500 μs or less tend to be in continuous fiber-reinforced composite materials, the larger the number of AE signals with amplitudes of 25-30 dB and durations of 1000 μs or less tend to be, and the larger the total AE count tends to be.

[0030] The end group concentration of a thermoplastic resin is the amount of end groups present in 1 gram of resin. The end group concentration of the thermoplastic resin is preferably 70 μmol / g or more, preferably 100 to 300 μmol / g, and more preferably 120 to 270 μmol / g. The higher the end group concentration of the thermoplastic resin, the greater the number of AE signals with an amplitude of 25-30 dB and a duration of 1000 μs or less, and the greater the total AE count tends to be. The end group concentration of thermoplastic resins is 1 The measurement can be performed using 1H-NMR, and specifically, by the method described in the examples below.

[0031] The continuous fiber-reinforced resin composite material may be further injected with a hybrid thermoplastic resin composition to produce a hybrid composite material. In the manufacturing process of the hybrid composite material, the above-mentioned base material may be set in a mold, the mold may be closed and pressurized, and after a predetermined time, a predetermined hybrid thermoplastic resin composition may be injected and molded to bond the thermoplastic resin of the base material with the predetermined hybrid thermoplastic resin composition, thereby producing the hybrid composite material.

[0032] The timing of injection filling of the predetermined hybrid thermoplastic resin composition significantly affects the interfacial strength between the two thermoplastic resins. Preferably, the injection filling of the predetermined hybrid thermoplastic resin composition should be done within 30 seconds after the mold temperature has risen above the melting point or glass transition temperature of the thermoplastic resin constituting the substrate, following the setting of the substrate in the mold and closing of the mold. The mold temperature when injecting and filling a predetermined hybrid thermoplastic resin composition is preferably above the melting point or glass transition temperature of the thermoplastic resin constituting the substrate to which the hybrid thermoplastic resin composition is bonded. More preferably, the temperature is above the melting point + 10°C or glass transition temperature of the thermoplastic resin constituting the substrate to which the hybrid thermoplastic resin composition is bonded, even more preferably above the melting point + 20°C or glass transition temperature + 20°C, and even more preferably above the melting point + 30°C or glass transition temperature + 30°C.

[0033] In hybrid composite materials, it is preferable that the joint between the thermoplastic resin constituting the base material and the hybrid thermoplastic resin composition formed by injection molding has a mixed uneven structure. Setting the mold temperature above the melting point of the hybrid thermoplastic resin composition to be injected, and increasing the resin holding pressure during injection molding, for example to 1 MPa or higher, is effective in increasing interfacial strength. To further increase interfacial strength, it is preferable to set the holding pressure to 5 MPa or higher, and more preferably to 10 MPa or higher. Furthermore, extending the holding time, for example 5 seconds or more, preferably 10 seconds or more, and more preferably until the mold temperature falls below the melting point of the thermoplastic resin composition, is preferable from the viewpoint of increasing interfacial strength.

[0034] (Hybrid thermoplastic resin composition) The hybrid thermoplastic resin composition used for injection molding to manufacture hybrid composite materials is not particularly limited, as long as it is a thermoplastic resin composition used in general injection molding. The thermoplastic resins included in the hybrid thermoplastic resin composition are not limited to the following, but include, for example, one or more thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, acrylic resin, styrene resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyphenylene ether, modified polyphenylene ether resin, fully aromatic polyester, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide resin, polysulfone, polyetheretherketone, and polyetherketone, as well as mixtures of two or more such thermoplastic resins.

[0035] The thermoplastic resin composition for hybrid applications may contain various fillers. The thermoplastic resin composition for hybrid applications may be a black resin composition containing a coloring agent. Examples of fillers include short fibers, long fibers, and other discontinuous reinforcing materials of the same type as the continuous reinforcing fibers mentioned above. When using short or long glass fibers in the discontinuous reinforcement material, the same sizing agent as that applied to the continuous reinforcing fibers constituting the continuous fiber-reinforced resin composite material of this embodiment may be used. The sizing agent (sizing agent) preferably consists of a silane coupling agent, a lubricant, and a binding agent. The types of silane coupling agent, lubricant, and binding agent can be the same as those used for the sizing agent of the continuous reinforcing fibers described above.

[0036] The thermoplastic resin included in the hybrid thermoplastic resin composition used for injection molding is preferably similar to, and more preferably of the same type as, the thermoplastic resin at the bonding surface constituting the continuous fiber-reinforced resin composite material, from the viewpoint of interfacial strength with the thermoplastic resin being bonded. Specifically, when polyamide 66 is used as the thermoplastic resin at the bonding surface, the resin material of the hybrid thermoplastic resin composition for injection molding is preferably polyamide 66.

[0037] Other methods include a molding method in which the base material is placed in a mold and compressed by a double-belt press, a molding method in which a mold frame is set up to surround the placed base material on all four sides and molded by applying pressure with a double-belt press, and a molding method in which one or more heating compression molding machines set to different temperatures and one or more cooling compression molding machines set to different temperatures are prepared, and the molds in which the base material is placed are fed into the compression molding machines in sequence for molding.

[0038] (Continuous reinforced fiber) As the continuous reinforcing fibers, those commonly used in continuous fiber-reinforced resin composite materials may be used. Examples of continuous reinforcing fibers include, but are not limited to, glass fibers, carbon fibers, plant fibers, aramid fibers, ultra-high-strength polyethylene fibers, polybenzazole fibers, liquid crystal polyester fibers, polyketone fibers, metal fibers, and ceramic fibers. From the viewpoints of mechanical properties, thermal properties, and versatility, glass fibers, carbon fibers, plant fibers, and aramid fibers are preferred, and from the viewpoint of productivity, glass fibers are preferred. The above-mentioned continuous reinforcing fibers may be used individually or in combination of two or more types.

[0039] - Stimulant - When glass fibers are selected as the continuous reinforcing fibers, a sizing agent may be used. The sizing agent may contain one or more selected from the group consisting of silane coupling agents, lubricants, and binding agents, and it is preferable that it contains at least a binding agent or a silane coupling agent. Furthermore, the sizing agent may consist of a silane coupling agent and a binding agent, or it may consist of a silane coupling agent, a lubricant, and a binding agent. By acting as a sizing agent that creates a strong bond between glass fibers and the resin coating surrounding them, it is possible to obtain a continuous fiber-reinforced resin composite material with a low porosity. The sizing agent may be added externally to the material being used, or it may be contained internally within the material being used. For example, a lubricant may be included in a commercially available thermoplastic resin being used.

[0040] --Silane coupling agent-- Silane coupling agents are typically used as surface treatment agents for glass fibers and contribute to improving interfacial adhesion strength. Examples of silane coupling agents include, but are not limited to, aminosilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes; maleic acids, etc. When using polyamide as the thermoplastic resin, it is preferable to select one that readily bonds with the carboxyl group or amino group, which are terminal groups of the polyamide resin, and aminosilanes are preferred.

[0041] --Lubricant-- The lubricant contributes to improving the fiber-opening properties of glass fibers. As a lubricant, any ordinary liquid or solid lubricating material can be used depending on the purpose, as long as it does not inhibit the silane coupling agent and binding agent. Examples of such lubricants include, but are not limited to, animal or plant-based or mineral waxes such as carnauba wax and lanolin wax; and surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

[0042] --Binding agent-- The binding agent contributes to improving the bundleability of glass fibers and enhancing the interfacial adhesion strength. As a binding agent, a polymer suitable for the purpose, or a thermoplastic resin other than the thermoplastic resin used as the main material in continuous fiber-reinforced resin composite materials, can be used. Polymers used as binders are 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. In addition, polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate, and polyester or polyether diols are also suitably used. The acrylic acid homopolymer preferably has a weight-average molecular weight of 1,000 to 90,000, and 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 include, for example, one or more monomers having a hydroxyl group and / or carboxyl group, 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 (except in the case of acrylic acid alone). It is preferable to have one or more ester monomers as copolymerizable monomers. The salts of acrylic acid homopolymers and copolymers with primary, secondary, and tertiary amines are not limited to the following, but examples include triethylamine salts, triethanolamine salts, and glycine salts. The degree of neutralization is preferably 20-90%, and more preferably 40-60%, from the viewpoint of improving the stability of the mixed solution with other concomitant agents (such as silane coupling agents) and reducing amine odor. The weight-average molecular weight of the acrylic acid polymer that forms the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. From the viewpoint of improving the bundling properties of the glass fibers, it is preferable to have a molecular weight of 3,000 or more, and from the viewpoint of improving the properties when a composite molded article is formed, it is preferable to have a molecular weight of 50,000 or less. When using polyamide as the thermoplastic resin, it is preferable to use a resin with good wettability or a surface tension similar to that of the polyamide resin as the binding agent. Specifically, for example, polyurethane resin emulsions, polyamide resin emulsions, or modified versions thereof can be selected.

[0043] Examples of thermoplastic resins used as binding agents include, but are not limited to, polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, polyether ketones, polyether ether ketones, polyether sulfones, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluorine resins, and modified thermoplastic resins obtained by modifying these. It is preferable that the thermoplastic resin used as a binding agent is the same type of thermoplastic resin and / or modified thermoplastic resin as the resin covering the continuous reinforcing fibers, as this improves the adhesion between the glass fibers and the thermoplastic resin after the composite material is formed.

[0044] Furthermore, to further improve the adhesion between the continuous reinforcing fibers and the thermoplastic resin coating them, and to allow for a reduction in the ratio of emulsifier components or even elimination of the need for emulsifiers when the sizing agent is attached to the glass fibers as an aqueous dispersion, a modified thermoplastic resin is preferred as the thermoplastic resin used as the sizing agent. Here, a modified thermoplastic resin refers to a thermoplastic resin in which, in addition to the monomer components that can form the main chain of the thermoplastic resin, different monomer components are copolymerized with the purpose of changing the properties of the thermoplastic resin, thereby modifying its hydrophilicity, crystallinity, thermodynamic properties, etc. Modified thermoplastic resins used as binding agents are not limited to the following, but examples include modified polyolefin resins, modified polyamide resins, and modified polyester resins.

[0045] Modified polyolefin resins used as binding agents are copolymers of olefin monomers such as ethylene and propylene with monomers copolymerizable with olefin monomers, such as unsaturated carboxylic acids and / or their esters, or homopolymers of monomers copolymerizable with olefin monomers, such as unsaturated carboxylic acids and / or their esters, and can be produced by known methods. They may be random copolymers obtained by copolymerizing olefin monomers with unsaturated carboxylic acids and / or their esters, or graft copolymers obtained by grafting unsaturated carboxylic acids onto olefins. Examples of olefin monomers include, but are not limited to, ethylene, propylene, and 1-butene. These may be used individually or in combination of two or more. Examples of monomers copolymerizable with olefin monomers 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, and mesaconic acid, as well as esterified products of these unsaturated carboxylic acids (methyl esters, ethyl esters, etc.). These may be used individually or in combination of two or more. When a modified polyolefin resin is a copolymer of an olefin monomer and a monomer copolymerizable with the olefin monomer, the monomer ratio is preferably 60-95% by mass of the olefin monomer and 5-40% by mass of the monomer copolymerizable with the olefin monomer, with the total mass of the copolymer being 100% by mass, and more preferably 70-85% by mass of the olefin monomer and 15-30% 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, and if the mass percentage of the olefin monomer is 95% by mass or less, the water dispersibility of the modified polyolefin resin is good, making it easy to uniformly apply it to continuous reinforcing fibers.

[0046] Modified polyolefin resins used as binding agents may have modified groups, such as carboxyl groups, introduced by copolymerization, neutralized with a basic compound. Examples of basic compounds, though not limited to the following, include 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 binding agent is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. From the viewpoint of improving the bundling properties of glass fibers, a molecular weight of 5,000 or more is preferred, and from the viewpoint of emulsification stability when water dispersibility is required, a molecular weight of 200,000 or less is preferred.

[0047] Modified polyamide resins used as binding agents are modified polyamide compounds in which hydrophilic groups such as polyalkylene oxide chains or tertiary amine components are introduced into the molecular chain, and can be manufactured by known methods. When introducing polyalkylene oxide chains into the molecular chain, for example, they are produced by copolymerizing a part or all of polyethylene glycol or polypropylene glycol modified with a diamine or dicarboxylic acid. When introducing tertiary amine components, for example, they are produced by copolymerizing aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam, etc.

[0048] Modified polyester resins used as binding agents are copolymers of polycarboxylic acid or its anhydride with polyols, and are resins having hydrophilic groups in their molecular skeleton, including the terminals, and can be manufactured by known methods. Examples of hydrophilic groups include polyalkylene oxide groups, sulfonates, carboxyl groups, and their neutralized salts. Examples of polycarboxylic acids or their anhydrides include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and polycarboxylic acids with three or more functions. Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride. Examples of sulfonate-containing aromatic dicarboxylic acids include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate. Examples of aliphatic dicarboxylic acids or alicyclic dicarboxylic acids 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, and the like. Examples of polycarboxylic acids with three or more functionalities include, but are not limited to, trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride. 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. Furthermore, from the viewpoint of emulsification stability when the modified polyester resin is dispersed in water, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

[0049] Examples of polyols that make up modified polyester resins include diols and polyols with three or more functionalities. Examples of diols, but not limited to those listed below, include 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 adducts. Examples of polyols with three or more functions include trimethylolpropane, glycerin, and pentaerythritol.

[0050] The copolymerization ratio of polycarboxylic acid or its anhydride and polyol constituting the modified polyester resin is preferably 40-60% by mass of polycarboxylic acid or its anhydride and 40-60% by mass of polyol, with the total mass of copolymerized components being 100% by mass, and more preferably 45-55% by mass of polycarboxylic acid or its anhydride and 45-55% by mass of polyol. The weight-average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. From the viewpoint of improving the bundling properties of glass fibers, a molecular weight of 3,000 or more is preferred, and from the viewpoint of emulsification stability when water dispersibility is required, a molecular weight of 100,000 or less is preferred.

[0051] The polymers and thermoplastic resins used as binding agents may be used individually or in combination of two or more types. It is preferable to use 50% or more by mass of one or more polymers selected from acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines, with the total amount of the binding agent being 100% by mass, and more preferably 60% or more by mass.

[0052] When the sizing agent consists of a silane coupling agent and a binding agent, the sizing agent is applied and attached to the glass fibers 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, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent and binding agent. From the viewpoint of controlling the bundling properties of the glass fibers and improving the interfacial adhesion strength, it is preferable that the amount of sizing agent applied is 0.1% by mass or more, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent and binding agent, and from the viewpoint of ease of handling the yarn, it is preferable that it is 3% by mass or less. Furthermore, when the sizing agent consists of a silane coupling agent, a lubricant, and a binder, the sizing agent is applied and attached 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, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent, lubricant, and binder. From the viewpoint of controlling the bundling properties of the glass fibers and improving the interfacial adhesion strength, it is preferable that the amount of sizing agent applied is 0.1% by mass or more, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent, lubricant, and binder, and from the viewpoint of ease of handling the yarn, it is preferable that it is 3% by mass or less.

[0053] --Composition of fiber optic sizing agent-- The amount of silane coupling agent in a sizing agent for glass fibers is preferably 0.1 to 2% by mass, more preferably 0.1 to 1% by mass, and even more preferably 0.2 to 0.5% by mass, from the viewpoint of improving the bundling ability of glass fibers, improving interfacial adhesion strength, and improving the mechanical strength of the composite molded article. The amount of lubricant in a fiber sizing agent for glass fibers is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of providing sufficient lubricity, and preferably 1% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of improving interfacial adhesion strength and the mechanical strength of the composite molded article. The amount of binding agent in a sizing agent for glass fibers is preferably 1 to 25% by mass, more preferably 3 to 15% by mass, and even more preferably 3 to 10% by mass, from the viewpoint of controlling the sizing properties of glass fibers, improving interfacial adhesion strength, and improving the mechanical strength of the composite molded article.

[0054] When glass fibers are used as continuous reinforcing fibers, and the sizing agent consists of a silane coupling agent, a lubricant, and a binder, it is preferable that the glass fiber sizing agent contains 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 to adjust the total mass to 100% by mass.

[0055] --Methods of use for fiber optic scrubbers-- The sizing agent for glass fibers may be prepared in any form, such as an aqueous solution, a colloidal dispersion, or an emulsion using an emulsifier, depending on the intended use. However, from the viewpoint 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, which constitute the continuous reinforcing fibers of the continuous fiber-reinforced resin composite material of this embodiment, are continuously obtained by applying the above-mentioned 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 manufactured glass fibers.

[0056] Similarly, when carbon fibers are selected as the continuous reinforcing fibers, a sizing agent may also be used, and the sizing agent preferably consists of a coupling agent, a lubricant, and a binding agent. The coupling agent can be selected to have good compatibility with the hydroxyl groups present on the surface of the carbon fibers, the binding agent can be selected to have good wettability with the selected thermoplastic resin or to have a similar surface tension, and the lubricant can be selected to not inhibit the coupling agent and binding agent. There are no particular restrictions on the type of sizing agent used for carbon fibers; known types can be used. Specifically, for example, those described in Japanese Patent Publication No. 2015-101794 can be used.

[0057] When using other continuous reinforcing fibers, the type and amount of sizing agent that can be used with glass fibers and carbon fibers should be appropriately selected according to the characteristics of the continuous reinforcing fibers, and it is preferable to use a type and amount of sizing agent similar to that used with carbon fibers.

[0058] (Shape of continuous reinforcing fibers) Continuous reinforcing fibers are multifilaments consisting of multiple filaments, and the number of single filaments is preferably 30 to 15,000 from the viewpoint of handling. The single filament diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, even more preferably 6 to 20 μm, and most preferably 8 to 18 μm, from the viewpoint of strength and handling. Single filament diameter R (μm) and density D (g / cm³) of continuous reinforced fibers. 3 The product RD of the ) is preferably 5 to 100 μm·g / cm² from the viewpoint of the handling of continuous reinforcing fibers and the strength of the composite material. 3 More comfortably, 10-50 μm·g / cm² 3 More preferably 15-45 μm·g / cm² 3 More preferably 20-45 μm·g / cm² 3 That is the case.

[0059] Density D can be measured using a hydrometer. On the other hand, the diameter of the single filament R (μm) is equal to the density D (g / cm³). 3 From the ) and fineness (dtex) and number of single filaments (strands), the following formula is used:

number

[0060] To set the product RD of continuous reinforcing fibers within a specified range, the fineness (dtex) and number of single fibers (strands) should be appropriately selected from commercially available continuous reinforcing fibers according to the density of the continuous reinforcing fibers. For example, when using glass fibers as continuous reinforcing fibers, the density is approximately 2.5 g / cm³. 3 Therefore, it is sufficient to select fibers with a single filament diameter of 2 to 40 μm. Specifically, if the single filament diameter of the glass fiber is 9 μm, selecting glass fibers with a fineness of 660 dtex and 400 single filaments will result in a product RD of 23. Also, if the single filament diameter of the glass fiber is 17 μm, selecting glass fibers with a fineness of 11,500 dtex and 2,000 single filaments will result in a product RD of 43. When using carbon fiber as the continuous reinforcing fiber, the density is approximately 1.8 g / cm³. 3 Therefore, it is sufficient to select fibers with a single filament diameter of 2.8 to 55 μm. Specifically, if the single filament diameter of the carbon fiber is 7 μm, selecting carbon fibers with a fineness of 2,000 dtex and 3,000 single filaments will result in a product RD of 13. When using aramid fibers as continuous reinforcing fibers, the density is approximately 1.45 g / cm³.3 Therefore, it is sufficient to select fibers with a single filament diameter of 3.4 to 68 μm. Specifically, if the single filament diameter of the aramid fiber is 12 μm, selecting an aramid fiber with a fineness of 1,670 dtex and 1,000 single filaments will result in a product RD of 17.

[0061] Continuous reinforced fibers, such as glass fibers, are manufactured by weighing and mixing raw glass, melting it in a melting furnace to form molten glass, spinning it into glass filaments, applying a sizing agent, and then passing it through a spinning machine to produce winding forms such as direct-wound roving (DWR), cakes, or twisted yarn. The continuous reinforcing fibers can be in any form, but it is preferable if they are wound into yarn, cake, or DWR, as this increases productivity and production stability in the resin coating process. From a productivity standpoint, DWR is the most preferable.

[0062] The form of the continuous reinforcing fibers is not particularly limited and can take various forms such as woven fabrics, knitted fabrics, braided cords, pipe-shaped materials, non-crimped fabrics, and unidirectional materials. Preferably, the form is that of a woven fabric, non-crimped fabric, or unidirectional material.

[0063] (thermoplastic resin) The thermoplastic resin constituting the continuous fiber-reinforced resin composite material of this embodiment preferably has a peak temperature of loss tangent tanδ of 80°C or higher, more preferably 85°C or higher, even more preferably 90°C or higher, and even more preferably 100°C or higher. When the peak temperature of tanδ of the thermoplastic resin is within the above range, the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less in the continuous fiber-reinforced composite material tends to be small, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μs or less tends to be large, and the total AE count tends to be large. The peak temperature of the loss tangent tanδ of a thermoplastic resin refers to the temperature at which the value of tanδ is maximum when tanδ is measured at various temperatures. The peak temperature of tanδ can be determined, for example, by applying a specific frequency of vibration to a single filament of continuous reinforcing fiber in a cross-section perpendicular to the length direction of the continuous reinforcing fiber contained in a thermoplastic resin film, and performing nanoindentation (nanoDMA). Specifically, it can be measured by the method described in the examples below. One method for adjusting the tanδ of a thermoplastic resin to the above range is to adjust the concentration of aromatic rings in the resin. Increasing the concentration of aromatic rings in the resin tends to raise the peak temperature of tanδ.

[0064] The thermoplastic resin of this embodiment has a Raman peak (peak in the Raman spectrum) of 950 to 1050 cm⁻¹. -1 It is preferable to have it at 970-1030 cm -1 It is more preferable to have this. When the Raman peak of the thermoplastic resin is within the above range, the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less in the continuous fiber-reinforced composite material tends to be small, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μs or less tends to be large, and the total AE count tends to be large. The Raman peak of the thermoplastic resin in this embodiment can be determined, for example, by measuring the Raman spectrum of the resin region in a cross-section perpendicular to the longitudinal direction of the continuous reinforcing fibers contained in the thermoplastic resin film using a laser-Raman microscope. Specifically, it can be measured by the method described in the examples below.

[0065] The thermoplastic resin in this embodiment may be of two or more types, and the difference between the saturated water absorption rates of the two or more thermoplastic resins with the highest and lowest saturated water absorption rates is preferably 2.0% by mass or more, more preferably 2.5% by mass or more, and even more preferably 2.8% by mass or more. When the saturated water absorption rates are within this range, the continuous fiber-reinforced resin composite material can exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warp properties.

[0066] When there are two or more types of thermoplastic resins, the resin with the largest mass proportion is preferably no more than five times the mass proportion of the resin with the second largest mass proportion, more preferably no more than four times, and even more preferably no more than three times, from the viewpoint of high-temperature properties and water absorption properties. When the mass proportion of thermoplastic resins is within the above range, the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) of the continuous fiber-reinforced resin composite material tend to improve.

[0067] Thermoplastic resins are not limited to the following, but examples include: polyolefin resins such as polyethylene and polypropylene; polyamide resins such as polyamide 6, polyamide 66, polyamide 46, polyamide 612, and polyamide 6I; 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 polyetherimide; thermoplastic fluorine resins such as tetrafluoroethylene-ethylene copolymer; polyurethane resins; acrylic resins; and modified thermoplastic resins obtained by modifying these.

[0068] Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyethersulfone, polyphenylene sulfide, thermoplastic polyetherimide, 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 viewpoint of mechanical properties and versatility. When thermal properties are also considered, polyamide resins and polyester resins are even more preferred. Furthermore, polyamide resins are even more preferred from the viewpoint of durability against repeated loading.

[0069] -Polyester resin- Polyester resins refer to polymer compounds that have -CO-O- (ester) bonds in their main chain. Examples of polyester resins, though not limited to those listed below, include polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate. The polyester resin may be homopolyester or copolymer polyester. In the case of copolymerized polyesters, it is preferable to copolymerize a homopolyester with an appropriate third component. 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 sulfisoisophthalic acid. Furthermore, polyester resins made from biomass resources can also be used, and are not limited to the following, but examples include aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and aromatic polyester resins such as polybutylene adipate terephthalate.

[0070] -Polyamide resin- Polyamide resins refer to polymer compounds that have -CO-NH- (amide) bonds in their main chain. Examples include aliphatic polyamides, aromatic polyamides, and fully aromatic polyamides.

[0071] 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 condensation of diamines and dicarboxylic acids, and copolymers thereof. Polyamide resins may be used individually or as a mixture of two or more types. Examples of lactams, though not limited to those listed below, include pyrrolidone, caprolactam, undecanlactam, and dodecalactam. 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 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. Diamines and dicarboxylic acids as monomers may be condensed individually or in combination of two or more.

[0072] Examples of polyamide resins, though not limited to those listed below, include aliphatic polyamides such as polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), polyamide 12 (polydodecaneamide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, and polyamide 612; semi-aromatic polyamides such as polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonanemethylene terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide); and copolymer polyamides containing these as constituent components. Examples of copolymerized polyamides 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.

[0073] When using a polyamide resin, it is preferable that the thermoplastic resin contains (A) 50 to 99 parts by mass of an aliphatic polyamide and (B) 1 to 50 parts by mass of a semi-aromatic polyamide containing dicarboxylic acid units containing at least 75 mol% isophthalic acid units and diamine units containing at least 50 mol% diamine units having 4 to 10 carbon atoms. When the thermoplastic resin contains (A) aliphatic polyamide and (B) semi-aromatic polyamide within the above range, the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) of the continuous fiber-reinforced resin composite material tend to improve compared to when the polyamide contains only (A) aliphatic polyamide. The total content of (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to 100% by mass of thermoplastic resin.

[0074] The weight-average molecular weight (Mw) of the thermoplastic resin containing (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably 15,000 to 35,000, more preferably 17,000 to 35,000, even more preferably 20,000 to 35,000, even more preferably 22,000 to 34,000, particularly preferably 24,000 to 33,000, and most preferably 25,000 to 32,000. When the weight-average molecular weight (Mw) of the thermoplastic resin is within the above range, the strength and rigidity tend to improve. Furthermore, in the above thermoplastic resin, (A) the weight-average molecular weight Mw of the aliphatic polyamide A (B) The weight-average molecular weight Mw of the semi-aromatic polyamide. B It is preferable that it be 1.5 times or more, and more preferably 2 times or more. Mw A Mw B When the ratio is 1.5 times or more, there is a tendency for strength and rigidity to improve. The weight-average molecular weight (Mw) of the thermoplastic resin, (A) aliphatic polyamide, and (B) semi-aromatic polyamide can be measured by gel permeation chromatography (GPC), and specifically, can be observed by the method described in the examples below.

[0075] The above (A) aliphatic polyamides are not limited to the following, but examples include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, etc. The content of (A) aliphatic polyamide in 100% by mass of polyamide in the thermoplastic resin is preferably 50 to 99% by mass, more preferably 60 to 90% by mass, and even more preferably 70 to 80% by mass.

[0076] The above (B) semi-aromatic polyamides are not limited to the following, but examples include polyamide 6I, polyamide 9I, polyamide 10I, etc. The total amount of isophthalic acid units and diamine units having 4 to 10 carbon atoms is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, based on 100 mol% of the total constituent units of the semi-aromatic polyamide (B). The proportion of monomer units constituting (B) semi-aromatic polyamide can be measured, for example, by 13C nuclear magnetic resonance spectroscopy (NMR).

[0077] (B) In the semi-aromatic polyamide, the proportion of isophthalic acid units in the dicarboxylic acid units is at least 75 mol%, preferably 85 mol% or more, and more preferably 90 mol% or more. When the proportion of isophthalic acid units in the dicarboxylic acid units is within the above range, high-temperature properties and water absorption properties tend to improve.

[0078] (B) In the semi-aromatic polyamide, the proportion of diamine units having 4 to 10 carbon atoms in the diamine units is at least 50 mol%, preferably 60 mol% or more, and more preferably 70 mol% or more. When the proportion of diamine units having 4 to 10 carbon atoms in the diamine units is within the above range, high-temperature properties and water absorption properties tend to improve.

[0079] The content of (B) semi-aromatic polyamide in 100% by mass of polyamide in the thermoplastic resin is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 20 to 30% by mass.

[0080] The above (A) aliphatic polyamide and (B) semi-aromatic polyamide may be end-capping with known end-capping agents, and the total amount of encapsulated ends of (A) aliphatic polyamide and (B) semi-aromatic polyamide, expressed as an equivalent amount per 1 g of the combined polyamide, is preferably 5 to 180 μequivalents / g, more preferably 10 to 170 μequivalents / g, even more preferably 20 to 160 μequivalents / g, particularly preferably 30 to 140 μequivalents / g, and most preferably 40 to 140 μequivalents / g. When the amount of encapsulated ends is within the above range, the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) tend to improve. Here, the amount of sealed ends refers to the total amount of amino and carboxyl ends sealed by the sealing agent. The amount of sealed ends is 1 The measurement can be performed using 1H-NMR, and specifically, by the method described in the examples below.

[0081] (A) The terminal group concentration of the aliphatic polyamide is preferably 1 / 2 or less of the terminal group concentration of the semi-aromatic polyamide (B), and more preferably 2 / 5 or less. When the terminal group concentration of the aliphatic polyamide (A) is 1 / 2 or less of the terminal group concentration of the semi-aromatic polyamide (B), the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) tend to improve. The terminal group concentrations of (A) aliphatic polyamides and (B) semi-aromatic polyamides are: 1 The measurement can be performed using 1H-NMR, and specifically, by the method described in the examples below.

[0082] The difference in tanδ peak temperature between (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably 45 to 100°C, more preferably 50 to 90°C, and even more preferably 60 to 90°C. When the difference in tanδ peak temperature between (A) aliphatic polyamide and (B) semi-aromatic polyamide is within the above range, high-temperature properties and water absorption properties tend to improve. The peak temperature of tanδ of (A) aliphatic polyamide and (B) semi-aromatic polyamide can be measured, for example, using a viscoelasticity analyzer, and specifically, by the method described in the examples below.

[0083] (A) The difference in viscosity between the aliphatic polyamide and (B) the semi-aromatic polyamide is preferably 3 times or more, and more preferably 4 times or more, from the viewpoint of strength, rigidity, moldability, and appearance. The viscosity of thermoplastic resins can be determined by MFR measurement (in accordance with ISO 1133), and specifically, it can be observed by the method described in the examples below.

[0084] [Additives] The continuous fiber-reinforced resin composite material of this embodiment may contain additives as needed. 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 imparters, dispersants, softeners, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanizing aids, foaming agents, foaming aids, flame retardants, vibration damping agents, nucleating agents, neutralizing agents, lubricants, anti-blocking agents, dispersants, flow improvers, and release agents. The additive content may be 3% by mass or less per 100% by mass of the composite material.

[0085] (Coloring agent) Examples of colorants include carbon black, nigrosine, aluminum pigment, titanium dioxide, ultramarine, cyanine blue, cyanine green, quinacridone, diatomaceous earth, monoazo salts, perylene, disazo, condensed azo, isoindoline, red iron oxide, nickel titanium yellow, diketone pyrrolopyrrole, metal salts, perylene red, metal oxides, bismuth vanadate, cobalt green, cobalt blue, anthraquinone, phthalocyanine green, and phthalocyanine blue. Among these, black colorants are preferred, with carbon black and nigrosine being more preferred.

[0086] The continuous fiber-reinforced resin composite material of this embodiment preferably contains 90 to 525 parts by mass of continuous reinforcing fibers and 0 to 2 parts by mass of other components per 100 parts by mass of thermoplastic resin, and more preferably contains 150 to 340 parts by mass of continuous reinforcing fibers and 0 to 1 part by mass of other components per 100 parts by mass of thermoplastic resin.

[0087] [Applications of continuous fiber-reinforced resin composite materials] The continuous fiber-reinforced resin composite material of this embodiment can be suitably used as a structural material for aircraft, automobiles, construction materials, robots, and the like. In automotive applications, it can be used in, but is not limited to, the chassis / frame, suspension, drivetrain components, interior components, exterior components, functional components, and other parts. Specifically, this includes the steering shaft, mount, sunroof, step, soffit trim, door trim, trunk, boot lid, bonnet, seat frame, seat back, retractor, retractor support bracket, clutch, gear, pulley, cam, AG, elastic beam, baffling, lamp, reflector, glazing, front end module, back door inner, brake pedal, steering wheel, electrical materials, sound-absorbing materials, door exterior, interior panel, instrument panel, rear gate, ceiling beam, seat, seat frame, wiper support, EPS (Electric Power Steering), small motor, heat sink, ECU (Engine Control Unit) box, ECU housing, steering gearbox housing, plastic housing, EV (Electric Vehicle) Motor housing, wire harness, onboard meter, combination switch, small motor, spring, damper, wheel, wheel cover, frame, subframe, side frame, two-wheel frame, fuel tank, oil pan, intake manifold, propeller shaft, drive motor, monocoque, hydrogen tank, fuel cell electrodes, panel, floor panel, exterior panel, door, cabin, roof, hood, valve, EGR (Exhaust Gas Recirculation)Recirculation valves, variable valve timing unit, connecting rods, cylinder bores, members (engine mounting, front floor cloth, footwell cloth, seat cloth, inner side, rear cloth, suspension, pillar reinforcement, front side, front panel, upper, dash panel cloth, steering), tunnel, fastening inserts, crash boxes, crash rails, corrugated panels, roof rails, upper body, side rails, braiding, door surround assembly, airbag components, body pillars, dash-to-pillar gussets, suspension towers, bumpers, lower body pillars, front body pillars, reinforcements (instrument panel, rails, roof, front body pillars, roof rails, roof side rails, rockers, door beltlines, front floor under, upper front body pillars, lower front body pillars, center pillars, center pillar hinges, door outside panels), side outer panels, front door window frames, MICS (Minimum Intrusion CabinSystem) Bulkhead, torque box, radiator support, radiator fan, water pump, fuel pump, electronic throttle body, engine control ECU, starter, alternator, manifold, transmission, clutch, dash panel, dash panel insulator pad, door side impact protection beam, bumper beam, door beam, bulkhead, outer pad, inner pad, rear seat rod, door panel, door trim body sub-assembly, energy absorber (bumper, impact absorber), impact absorber, impact absorbing garnish, pillar garnish, roof side inner garnish, resin rib, side rail front spacer, side rail rear spacer, seat belt pretensioner, airbag It can be suitably used as a component such as sensors, arms (suspension, lower, hood hinge), suspension links, impact absorption brackets, fender brackets, inverter brackets, inverter modules, hood inner panels, hood panels, cowl louvers, cowl top outer front panels, cowl top outer panels, floor silencers, dump sheets, hood insulators, fender side panel protectors, cowl insulators, cowl top ventilator louvers, cylinder head covers, tire deflectors, fender supports, strut tower bars, transmission center tunnels, floor tunnels, radiator core supports, luggage panels, luggage floors, accelerator pedals, and accelerator pedal bases.

[0088] [Molding of composite materials] The continuous fiber-reinforced resin composite material of this embodiment can be further molded. Examples of such methods include cutting the continuous fiber-reinforced resin composite material of this embodiment to a predetermined size, heating it with an infrared heater, and then heat-compressing it with a press molding machine. [Examples]

[0089] The present invention is described below in the following examples. Reference example,The present invention will be explained in detail using comparative examples, but it goes without saying that the present invention is not limited to these examples and can be implemented in various ways within the scope of the gist of the present invention.

[0090] [Interface amount] The interface volume (m) of a continuous fiber-reinforced resin composite material is calculated using the following formula. -1 ) was sought. (Interface amount (m -1 )) = (Volume of reinforcing fibers in continuous fiber-reinforced resin composite material (m³) 3 )) × (density of reinforcing fibers (g / m³) 3 )) × (Number of single fibers of reinforcing fiber) × (Diameter of reinforcing fiber (m)) × π / (Fineness of reinforcing fiber (g / m)) / (Volume of continuous fiber-reinforced resin composite material (m³) 3 ))

[0091] [Tensile strength, tensile strength retention rate] Strip-shaped test pieces measuring 70 mm in length, 10 mm in width, and 2 mm in thickness were cut from a continuous fiber-reinforced resin composite material and dried in a vacuum dryer at 80°C for more than 18 hours. Subsequently, the test pieces were chucked at 30 mm intervals along their longitudinal direction in an Instron universal testing machine, and the tensile strength (MPa) was measured at a speed of 5 mm / min under conditions of 23°C, 50% RH and 80°C, 50% RH. The tensile strength retention rate (%) at 80°C was calculated using the following formula. Tensile strength retention rate at 80°C = (Tensile strength at 80°C, 50%RH / Tensile strength at 23°C, 50%RH) × 100

[0092] [Bending strength, bending modulus, bending strength retention rate, bending modulus retention rate] Strip-shaped test pieces measuring 100 mm in length, 10 mm in width, and 2 mm in thickness were cut from a continuous fiber-reinforced resin composite material and dried in a vacuum dryer at 80°C for more than 18 hours. Subsequently, using an Instron universal testing machine with a three-point bending jig, the bending strength (MPa) and bending modulus (GPa) were measured at a speed of 1 mm / min under conditions of 23°C, 50% RH and 80°C, 50% RH. The flexural strength retention rate (%) and flexural modulus retention rate (%) at 80°C were determined using the following formulas. Bending strength retention rate at 80°C = (Bending strength at 80°C, 50%RH / Bending strength at 23°C, 50%RH) × 100 Retention rate of flexural modulus at 80°C = (Flexural modulus at 80°C, 50%RH / Flexural modulus at 23°C, 50%RH) × 100

[0093] [Water absorption properties] Strip-shaped test pieces measuring 100 mm in length, 10 mm in width, and 2 mm in thickness were cut from a continuous fiber-reinforced resin composite material. These were immersed in an 80°C constant temperature water bath for 18 hours, and then left in a constant temperature and humidity chamber at 80°C and 57% RH for more than 150 hours until the mass became constant. These were used as test pieces for water absorption. Tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the dry and water-absorbed test pieces were measured under conditions of 23°C and 50% RH using the method described above. The tensile strength retention rate (%), flexural strength retention rate (%), and flexural modulus retention rate (%) after water absorption were determined using the following formulas. Tensile strength retention rate after water absorption = (Tensile strength after water absorption / Tensile strength after drying) × 100 Bending strength retention rate after water absorption = (Bending strength after water absorption / Bending strength when dry) × 100 Retention rate of flexural modulus when water is absorbed = (Flexural modulus when water is absorbed / Flexural modulus when dry) × 100

[0094] [Impact strength] Test specimens measuring 60 mm in length, 60 mm in width, and 2 mm in thickness were cut from a continuous fiber-reinforced resin composite material. These specimens were tested using a high-speed impact testing machine (Shimadzu HYDRO SHOT HITS-P10, Shimadzu Corporation) in accordance with JIS K7211-2;2006, with a striker diameter of 20 mmφ, a receiving diameter of 40 mmφ, a test speed of 4.4 m / sec, a test temperature of 23°C, and a test number of n=5. A graph of the test force against displacement was drawn, and the maximum impact strength (kN) obtained from this graph was divided by the thickness of the test specimen to obtain the average value (kN / mm) of the 5 samples.

[0095] [Acoustic Emission Measurement] An acoustic emission measurement system (USB AE NODE AE measurement system, 1 channel, manufactured by PAC Corporation) was used. An acoustic emission sensor (R6a) was mounted in the center of the three-point bending jig used for the bending strength test, and the acoustic emission signal was acquired simultaneously with the start of the bending test in an environment of 23°C and 50% RH. The test was stopped when the load reached 80% of the maximum load after the test specimen broke. Acoustic emission signals with an amplitude of 40 dB or more and a duration of 3500 μs or less were counted as Count 1, and acoustic emission signals with an amplitude of 25 to 30 dB and a duration of 1000 μs or less were counted as Count 2. Counts 1, Count 2, and the total number of signals were measured, and AE Count A and AE Count B were calculated using the following formulas. (AE Count A) = (Number of AE signals with amplitude of 40 dB or more and duration of 3500 μs or less) / (Total number of AE signals) (AE count B) = (Number of AE signals with amplitude 25-30 dB and duration 1000 μs or less) / (Total number of AE signals)

[0096] [Vibration fatigue test] Test specimens of ASTM-D1822 tensile impact dumbbell Type S were prepared from continuous fiber-reinforced resin composite material, and vibration fatigue tests were conducted using an EHF-EB50kN-40L(RV) (Shimadzu Corporation) at a test temperature of 23°C, a frequency of 20Hz, a sinusoidal waveform, and a chuck distance of 35mm. Tests with a vibration fatigue test count of 250MPa were judged as "○ (good)" if they exceeded 20,000 cycles, and as "× (poor)" if they exceeded 20,000 cycles.

[0097] [Measurement of water absorption rate] Continuous fiber-reinforced resin composite material was dried in a vacuum dryer at 80°C for 24 hours, and its mass was measured to obtain the mass in the completely dry state. Subsequently, it was immersed in a constant temperature water bath set at 80°C for 18 hours, and its mass was measured again. The saturation water absorption rate (mass after 18 hours of water absorption / mass in the completely dry state) (%) was obtained by comparing it with the mass in the completely dry state. Then, it was left in a constant temperature and humidity bath at 80°C and 57% RH for more than 150 hours to regulate the humidity until the mass became constant, and the atmospheric equilibrium water absorption rate (mass after regulation / mass in the completely dry state) (%) was determined from the mass at that time and the mass in the completely dry state.

[0098] [Crystallization] Using a differential scanning calorimeter (Shimadzu DSC-60), the sample volume was approximately 5 mg, representing the resin content of the continuous fiber-reinforced resin composite material. Under conditions of an atmospheric gas flow rate of 30 mL / min and a heating rate of 10 °C / min, the sample was heated from room temperature (25 °C) to a temperature above the expected melting point. The degree of crystallinity (%) was determined by dividing the measured heat of fusion by the total heat of fusion. The total heat of fusion was assumed to be 188 J / g.

[0099] Examples, Reference example, The materials used in the comparative example are as follows: [Continuous Reinforced Fiber] (Glass fiber) Glass fiber 1: ER1200T-423 (Nippon Electric Glass Co., Ltd.) (2000 single filaments, 17 μm diameter, 1.15 g / m fineness) Glass fiber 2: A sizing agent was attached to 0.45% by mass of glass fiber 100% by mass of glass fiber with a fineness of 1.15 g / m and 1500 single filaments. The winding form was DWR, and the average single filament diameter was approximately 17 μm. The sizing agent was prepared by mixing 0.5% by mass of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 1% by mass of carnauba wax, 2% by mass of polyurethane resin (Y65-55, manufactured by ADEKA Corporation), and 3% by mass of a copolymer compound (a copolymer compound with a weight-average molecular weight of 20,000, obtained by copolymerizing 40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate). (Carbon fiber) Toray T300 (Toray Industries, Inc.) (12,000 single filaments, 9 μm diameter, 2.58 g / m fineness)

[0100] [Fabrication of continuous reinforced fiber substrates] Glass cloth 1 and glass cloth 2: Glass cloths were manufactured by weaving using a rapier loom (weaving width 1m) with the above glass fiber 1 used as warp and weft threads. The weave form of the obtained glass cloth was glass cloth 1 (plain weave, weave density 6.5 threads / 25mm, weight 640g / m). 2 ), Glass cloth 2 (plain weave, weave density 6.5 threads / 25mm, weight 660g / m) 2 ) was. Glass cloth 3: Glass cloth 3 was manufactured by weaving using the above-mentioned glass fibers 2 as warp and weft threads on a rapier loom (weaving width 1m). The resulting glass cloth 3 has a plain weave, a weave density of 6.5 threads / 25mm, and a weight of 500g / m 2 That was the case. Carbon fiber cloth: Carbon fiber cloth was manufactured by weaving using the above carbon fibers as warp and weft threads on a rapier loom (weaving width 1m). The resulting carbon fiber cloth has a plain weave, a weave density of 6.5 threads / 25mm, and a weight of 425g / m². 2 That was the case.

[0101] [Thermoplastic resin] Resin 1: PA66 (Leona 1300S, Asahi Kasei Corporation) (carboxyl-terminal group content 70 μmol / g, amino-terminal group concentration 30 μmol / g, tanδ peak temperature: 50°C) Dry blend of resin 2: resin 1 and PA6I (Leona 7000, Asahi Kasei Corporation) (PA66:PA6I = 2:1) (carboxyl terminal group concentration 120 μmol / g, amino terminal group concentration 40 μmol / g, tanδ peak temperature: 110°C) Resin 3: Polypropylene (Prime Polymer Co., Ltd.) (Peak temperature at terminal group concentration of 0 μmol / gtanδ: 0°C) Resin 4: Maleic acid-modified polypropylene (Riken Vitamin Co., Ltd.) (End group concentration 21 μmol / g, tanδ peak temperature: 0°C) Resin 5: PA6 (1011FB, Ube Industries, Ltd.) (carboxyl terminal group concentration 60 μmol / g, amino terminal group concentration 30 μmol / g, tanδ peak temperature: 50°C) Resin 6: PA6I (Leona 7000, Asahi Kasei Corporation) (carboxyl terminal group concentration 200 μmol / g, amino terminal group concentration 60 μmol / g, tanδ peak temperature: 130°C) Resin 7: PPS (Toray Industries, Inc.) (Peak temperature of tanδ: 90°C) (End group concentration of thermoplastic resins) The end group concentrations of each thermoplastic resin are: 1 The measurements were performed using 1H-NMR under the following conditions. 1 Measurement conditions for H-NMR Equipment: JEOL-ECA500 (JEOL Ltd.) Observation nucleus: 1 H Observation frequency: 500MHz Measurement method: Single-Plus Pulse width: 30° Waiting time: 10 seconds Total number of times: 256 Solvent: D2SO4 Sample concentration: 1.25% by mass Chemical shift reference: PA66 main chain 3.04 ppm

[0102] [Fabrication of thermoplastic resin films] A thermoplastic resin film was obtained by molding using a T-die extrusion molding machine (manufactured by Soken Co., Ltd.). The thickness of the thermoplastic resin film was 200 μm.

[0103] [Example 1] A thermoplastic resin film 1 was obtained using resin 1 by the method described above. Five sheets of glass cloth 1 and six sheets of thermoplastic resin film 1 were prepared. The glass cloth 1 and thermoplastic resin film 1 were alternately layered so that the thermoplastic resin film 1 was on the surface, and molding was performed to obtain a continuous fiber-reinforced resin composite material. At this time, the proportion of thermoplastic resin in the volume of the preparation was 50%. A double-belt press was used as the molding machine. The glass cloth and thermoplastic resin film 1 were stacked as described above and placed in the molding machine. Compression was performed at a heating rate of 280°C / min, a pressure of 3 MPa, and a belt speed of 0.5 m / min. Then, the cooling rate was set to 80°C / min, and the material was cooled and compressed at 3 MPa for 3 minutes to complete the molding process. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0104] [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 properties of the obtained continuous fiber-reinforced resin composite material.

[0105] [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 properties of the obtained continuous fiber-reinforced resin composite material.

[0106] [ reference Example 4] A continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 2, except that carbon fiber cloth was used as the continuous reinforcing fiber base material. The proportion of thermoplastic resin added was 50%. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0107] [Example 5] A continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1, except that glass cloth 2 was used as the continuous reinforcing fiber base material. The proportion of thermoplastic resin in the filling volume was 50%. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0108] [Example 6] 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 properties of the obtained continuous fiber-reinforced resin composite material.

[0109] [Example 7] 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. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0110] [ reference Example 8] A continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1, except that resin 6 was used as the thermoplastic resin. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0111] [Example 9] Using the glass fibers (100% by mass) described above, a mixture of 0.3% by mass of 3-glycidoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.), 1.5% by mass of epoxy resin emulsion, and 0.2% by mass of carnauba wax is attached as a sizing agent. The resulting fabric is plain weave with a weave density of 6.5 strands / 25 mm and a basis weight of 640 g / m². 2 Glass cloth was manufactured. Five layers of this glass cloth were stacked and placed in a mold. A mixed resin of 16g ​​of bisphenol A type liquid epoxy resin (jER828, Mitsubishi Chemical Corporation) and 1.6g of bisphenol A (4,4′-(propane-2,2-diyl)diphenol) was poured into the mold. The temperature inside the molding machine was set to 40°C, and compression molding was performed for 3 days with a clamping force of 5MPa. The material was then cooled for 8 minutes at a cooling rate of 80°C / min and a clamping force of 5MPa to obtain a continuous fiber-reinforced resin composite material. The proportion of thermoplastic resin in the volume of the mixture was 50%. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0112] [Example 10] A continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1, except that resin 7 was used as the thermoplastic resin. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0113] [Example 11] Resin 2 is used as the thermoplastic resin, and glass fiber 1 is used as the continuous reinforcing fiber base material with a basis weight of 640 g / m². 2 A continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1, except that the material used was aligned in such a way. The proportion of thermoplastic resin in the filling volume was 50%. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0114] [Comparative Example 1] Using the glass fibers (100% by mass) described above, a mixture of 0.3% by mass of 3-glycidoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.), 1.5% by mass of epoxy resin emulsion, and 0.2% by mass of carnauba wax is attached as a sizing agent. The resulting fabric is plain weave with a weave density of 6.5 strands / 25 mm and a basis weight of 600 g / m². 2 A continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1, except that a glass cloth was manufactured and used. The proportion of thermoplastic resin in the filling volume was 50%. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0115] [Comparative Example 2] The same evaluation as in Example 1 was performed using Bond Laminate's "Tepex dynalite 101," which is glass cloth impregnated with polyamide 66. Table 1 shows the properties of the obtained continuous fiber-reinforced resin composite material.

[0116] [Table 1] [Industrial applicability]

[0117] The continuous fiber-reinforced resin composite material of this embodiment can be used industrially as a reinforcing material for materials requiring high levels of mechanical properties, such as structural components for various machines and automobiles, and as a composite molded material with thermoplastic resin compositions.

Claims

1. A continuous fiber-reinforced resin composite material comprising a continuous fiber substrate and a thermoplastic resin, The acoustic emission (AE) count A of the continuous fiber-reinforced resin composite material, calculated using the following formula, is 0.16 or less. The interface volume of the continuous fiber-reinforced resin composite material is 100,000 m －１ That's all. The degree of crystallinity of the thermoplastic resin is 20 to 40%, and The basis weight of the aforementioned continuous reinforced fiber base material is 637 g / m². ２ That's all. A continuous fiber-reinforced resin composite material characterized by the following features. (AE Count A) = (Number of AE signals with amplitude of 40 dB or more and duration of 3500 μs or less) / (Total number of AE signals)

2. The continuous fiber-reinforced resin composite material according to claim 1, wherein the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less is 100,000 or less.

3. The continuous fiber-reinforced resin composite material according to claim 1 or 2, wherein the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1,000 μs or less is 1,000 or more.

4. The continuous fiber-reinforced resin composite material according to any one of claims 1 to 3, wherein the total number of AE signals is 500,000 or more.

5. The AE count B calculated using the following formula is 1.1 × 10 －３ The continuous fiber-reinforced resin composite material according to any one of claims 1 to 4. (AE count B) = (Number of AE signals with amplitude 25-30 dB and duration 1000 μs or less) / (Total number of AE signals)

6. The continuous fiber-reinforced resin composite material according to any one of claims 1 to 5, wherein the thermoplastic resin is a polyamide resin.

7. A method for producing a continuous fiber-reinforced resin composite material according to any one of claims 1 to 6, The interface volume of the continuous fiber-reinforced resin composite material is 100,000 m －１ The above is true, with a heating rate of 200-330°C / min and a cooling rate of 10-120°C / min. The degree of crystallinity of the thermoplastic resin is 20 to 40%, and The basis weight of the aforementioned continuous reinforced fiber base material is 637 g / m². ２ That's all. A manufacturing method characterized by the following features.

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