Continuous fiber reinforced resin composite material and its manufacturing method

Abstract

To provide a continuous fiber-reinforced resin composite material which has a good acoustic emission signal, and has high strength, elastic modulus and water absorption characteristics, and a method for producing the same.SOLUTION: A continuous fiber-reinforced resin composite material contains a continuous reinforcement fiber, and a thermoplastic resin, wherein an acoustic emission (AE) count A determined by the following expression is 0.30 or less. (AE count A)=(number of AE signals with amplitude of 40 dB or more and retention time of 3,500 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 producing the same. [Background technology]

[0002] Composite material molded articles in which a reinforcing material such as glass fiber is added to a matrix resin material are used in structural components of various machines and automobiles, pressure vessels, tubular structures, and the like. Continuous fiber-reinforced resin composite materials in which the reinforcing fibers are continuous fibers are particularly desirable from the standpoint of strength. Proposed continuous fiber-reinforced resin composite materials include those that utilize a sizing agent added to the reinforcing fibers (see, for example, Patent Document 1 below), those that utilize a difference between the melting point and crystallization temperature (see, for example, Patent Document 2 below), those that incorporate an organic salt into the resin material (see, for example, Patent Document 3 below), those in which a molding precursor fabric is laminated with a thermoplastic resin (see, for example, Patent Document 4 below), and those that exhibit good adhesive strength, affinity, and the like at the interface between the continuous reinforcing fibers and the resin (see, for example, Patent Document 5 below). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-238213 [Patent Document 2] Patent No. 5987335 [Patent Document 3] Japanese Patent Application Publication No. 2017-222859 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-19202 [Patent Document 5] International Publication No. 2019 / 208586 Summary of the Invention [Problem to be solved by the invention]

[0004] However, all of the conventional continuous fiber reinforced resin composite materials have room for improvement in that they produce poor acoustic emission (AE) signals during physical property testing, and their physical properties such as strength and elastic modulus, as well as their water absorption characteristics, are insufficient.

[0005] In view of the state of the prior art, an object of the present invention is to provide a continuous fiber reinforced resin composite material that exhibits a good acoustic emission signal and has high strength, elastic modulus, and water absorption properties, and a method for producing the same. [Means for solving the problem]

[0006] The inventors of the present invention have conducted extensive research and experiments to solve these problems. As a result, they unexpectedly discovered that the above problems can be solved by adjusting the interface amount, heating rate, cooling rate, and compatibility between the continuous reinforcing fibers and the thermoplastic resin in the continuous fiber reinforced resin composite material, and by devising the acoustic emission signal of the continuous fiber reinforced resin composite material, which led to the completion of the present invention.

[0007] That is, the present invention is as follows. [1] Contains continuous reinforcing fibers and a thermoplastic resin, The acoustic emission (AE) count A calculated using the following formula must be 0.30 or less. A continuous fiber reinforced resin composite material characterized by: (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 [1], wherein the number of AE signals having an amplitude of 40 dB or more and a duration of 3500 μsec or less is 600 or less. [3] The continuous fiber reinforced resin composite material according to [1] or [2], wherein the number of AE signals having an amplitude of 25 to 30 dB and a duration of 1000 μsec or less is 200 or more. [4] The continuous fiber reinforced resin composite material according to any one of [1] to [3], wherein the AE count B calculated by the following formula is 0.12 or more. (AE count B) = (number of AE signals with amplitude between 25 and 30 dB and duration of 1000 μs or less) / (total number of AE signals) [5] The continuous fiber reinforced resin composite material according to any one of [1] to [4], wherein the total number of AE signals is 2000 or more. [6] A method for producing a continuous fiber reinforced resin composite material according to any one of [1] to [5], treating the continuous reinforcing fibers with a surface treatment agent that includes a binder to produce continuous reinforcing fibers that include a surface treatment agent; The interface volume of the continuous fiber reinforced resin composite material is 100,000 m -1 The manufacturing method is characterized in that the temperature rise rate is 200 to 330°C / min, the cooling rate is 10 to 120°C / min, and the difference in SP value between the binder and the thermoplastic resin is 0.01 to 5. [Effects of the Invention]

[0008] The continuous fiber reinforced resin composite material according to the present invention has a good acoustic emission signal, and can exhibit high strength, elastic modulus, and water absorption properties. It is also preferable that it has fatigue properties, physical property stability, warpage properties, and shape conformability. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram showing a single continuous reinforcing fiber and a resin ball (μ drop) of thermoplastic resin attached to the single continuous reinforcing fiber. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0011] [Continuous fiber reinforced resin composite material] The continuous fiber reinforced resin composite material (hereinafter also simply referred to as "composite material") of this embodiment contains continuous reinforcing fibers and a resin, and in an acoustic emission signal during a bending test, the AE count A calculated by the following formula is 0.30 or less. The continuous reinforcing fibers preferably contain a surface treatment agent. (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 AE count A is preferably 0.25 or less, and more preferably 0.21 or less. When the AE count A is within this range, the binder in the surface treatment agent for the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material diffuses into the thermoplastic resin, promoting bonding between the thermoplastic resin and the aminosilane, and increasing the concentration of active sites in the surface treatment agent improves adhesion between the continuous reinforcing fibers and the thermoplastic resin, making them less susceptible to breakage, and allowing the composite to exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, warpage properties, physical property stability, and shape conformability. As a method for adjusting the number of signals to the above range, for example, in a method for producing a continuous fiber reinforced resin composite material, the interface volume of the continuous fiber reinforced resin composite material is adjusted to 100,000 m -1 Examples of such methods include a heating rate of 200 to 330°C / min, a cooling rate of 10 to 120°C / min, and a difference in the SP value (described below) between the binder contained in the continuous reinforcing fibers and the thermoplastic resin of 0.01 to 5. In the present disclosure, the acoustic emission signal of a continuous fiber-reinforced resin composite material can be obtained by attaching an acoustic emission sensor to a bending test jig and using the sensor to detect 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 within a range of 40 dB or more in amplitude and 3,500 μsec or less in duration, as well as the total number of AE signals. Specifically, the AE count A can be determined by the method described in the Examples below.

[0012] In the continuous fiber reinforced resin composite material of this embodiment, the number of acoustic emission signals having an amplitude of 40 dB or more and a duration of 3,500 μsec or less during a bending test is preferably 600 or less, more preferably 550 or less, and even more preferably 500 or less. 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 two are less likely to break, and the material can exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warpage properties. As a method for adjusting the number of signals to the above range, for example, the interface amount of the continuous fiber reinforced resin composite material is adjusted to 100,000 m -1 The weight of the continuous reinforcing fiber base material is 637 g / m 2 The above methods include a method in which the volumetric ratio of the thermoplastic resin is 45% or more, the heating rate is 200 to 330°C / min, the cooling rate is 10 to 120°C / min, the end group concentration of the thermoplastic resin is 70 μmol / g or more, and the interfacial shear strength between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin is 0.8 to 1.2 times the interfacial shear strength between the coupling agent-treated continuous reinforcing fiber treated only with a coupling agent instead of the surface treatment agent and the thermoplastic resin.

[0013] In the continuous fiber reinforced resin composite material of this embodiment, the number of acoustic emission signals during a bending test that have an amplitude of 25 to 30 dB and a duration of 1,000 μsec or less is preferably 200 or more, more preferably 300 or more, and even more preferably 350 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 two are less likely to break, and the material can exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warpage properties. Examples of methods for adjusting the number of signals within the above range include a method in which the cooling rate during production of the continuous fiber reinforced resin composite material is 10 to 120°C / min, the crystallinity of the resin contained in the continuous fiber reinforced resin composite material is 20 to 40%, the charged volume ratio of the thermoplastic resin is 45% or more, and the cooling and compression time is 1 to 10 minutes.

[0014] In the continuous fiber reinforced resin composite material of this embodiment, the total number of AE signals in the acoustic emission signal during a bending test is preferably 2000 or more, more preferably 2500 or more, and even more preferably 3000 or more. The total number of AE signals is preferably 25000 or less, more preferably 20000 or less, even more preferably 10000 or less, and even more preferably 5000 or less. 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 two are less likely to break, and the material can exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warpage properties. As a method for adjusting the number of signals to the above range, for example, the interface amount of the continuous fiber reinforced resin composite material is adjusted to 100,000 m -1 As mentioned above, there can be mentioned a method in which the crystallinity of the resin contained in the continuous fiber reinforced resin composite material is 20 to 40%, the cooling and compression time is 1 to 10 minutes, the μ droplet contact angle between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin measured by the μ droplet method is 0.4 to 0.7 times the μ droplet contact angle between the surface treatment agent-free continuous reinforcing fiber not containing the surface treatment agent and the thermoplastic resin, and the terminal group concentration of the thermoplastic resin is 70 μmol / g or more.

[0015] In the continuous fiber reinforced resin composite material of this embodiment, the AE count B calculated by the following formula in the acoustic emission signal during a bending test is preferably 0.12 or more, more preferably 0.15 or more, and even more preferably 0.20 or more. (AE count B) = (number of AE signals with amplitude between 25 and 30 dB and duration of 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 two are less likely to break, and the material can exhibit excellent strength, elastic modulus, water absorption properties, high-temperature properties, fatigue properties, impact properties, and warpage properties. As a method for adjusting the number of signals to the above range, for example, the interface amount of the continuous fiber reinforced resin composite material is adjusted to 100,000 m -1 As described above, the method may be such that the heating rate is 200 to 330° C. / min, the cooling rate is 10 to 120° C. / min, and the terminal group concentration of the thermoplastic resin is 70 μmol / g or more.

[0016] The atmospheric equilibrium water absorption 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 in an environment of 23°C and 50% humidity. When the atmospheric equilibrium water absorption is within this range, excellent strength, elastic modulus, water absorption properties, high temperature properties, fatigue properties, impact properties, and warpage properties can be exhibited.

[0017] [Form of continuous fiber reinforced resin composite material] The form of the continuous fiber reinforced resin composite material is not particularly limited, and various forms can be mentioned as follows: For example, a form in which a woven or knitted fabric, a non-crimp fabric, a braided cord, or a pipe-shaped continuous reinforcing fiber is combined with a thermoplastic resin, a form in which a unidirectionally aligned continuous reinforcing fiber and a thermoplastic resin are combined, a form in which a yarn made of a continuous reinforcing fiber and a thermoplastic resin is aligned in one direction and shaped, or a form in which a woven fabric, a knitted fabric, a braided cord, or a pipe-shaped continuous reinforcing fiber and a thermoplastic resin are combined. 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 length direction of the continuous reinforcing fibers may be arranged approximately parallel to the surface of the flat plate. The continuous reinforcing fiber layer may be a layer including continuous reinforcing fibers (e.g., a continuous reinforcing fiber substrate) and may be a layer in which the interior of the continuous reinforcing fibers is impregnated with a thermoplastic resin. The form of the intermediate material before shaping of the continuous fiber reinforced resin composite material is not particularly limited, and examples thereof include a mixed yarn of continuous reinforcing fibers and resin fibers, a coated yarn in which a bundle of continuous reinforcing fibers is coated with resin, continuous reinforcing fibers pre-impregnated with resin and formed into a tape, continuous reinforcing fibers sandwiched between resin films, continuous reinforcing fibers with resin powder attached, a braided cord made of a bundle of continuous reinforcing fibers surrounded by resin fibers as a core material, reinforcing fibers pre-impregnated with resin, and forms in which continuous reinforcing fibers are in contact with molten resin.

[0018] [Method of manufacturing continuous fiber reinforced resin composite material] The method for producing the continuous fiber reinforced resin composite material of this embodiment is not particularly limited, and the following various methods can be mentioned.

[0019] In one method, for example, a substrate (e.g., a substrate made of continuous reinforcing fibers, a substrate made of thermoplastic resin) that constitutes a continuous fiber reinforced resin composite material is cut or shaped to fit the desired composite material, and the required number of pieces or sheets are stacked in consideration of the thickness of the desired product, and then set in a mold according to the mold shape. In this specification, the laminate (the laminate placed in the mold immediately before heat molding) in which the substrates constituting the continuous fiber reinforced resin composite material are superimposed and set in the mold may be referred to as the raw material laminate.

[0020] The substrate may be cut one by one, or after stacking the desired number of sheets. From the viewpoint of productivity, it is preferable to cut the substrate in a stacked state. Any cutting method may be used, for example, a water jet, a blade press, a hot blade press, a laser, a plotter, etc. Among these, a hot blade press is preferred, as it provides an excellent cross-sectional shape and, further, improves handling by welding the end faces when cutting multiple sheets stacked together. An appropriate cut shape can be adjusted by repeated trial and error, but it is preferable to set it by performing simulations using CAE (computer-aided engineering) in accordance with the shape of the mold.

[0021] The substrate may be shaped by any method, for example, into a sheet shape.

[0022] After the substrate (for example, a raw material laminate) is set in a mold, the mold is closed and compressed. The temperature of the mold is then adjusted to a temperature equal to or higher than the melting point of the thermoplastic resin that constitutes the continuous fiber reinforced resin composite material, to melt the thermoplastic resin and form it. There are no particular restrictions on the mold clamping pressure, but it is preferably 1 MPa or higher, more preferably 3 MPa or higher. The mold may also be clamped once to allow for degassing or the like, and the mold clamping pressure may be released once after compression molding. From the viewpoint of strength development, the compression molding time is preferably as long as possible within a range that does not 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.

[0023] The method for producing a continuous fiber-reinforced resin composite material of this embodiment preferably includes treating the continuous reinforcing fibers with a surface treatment agent containing a binder to produce continuous reinforcing fibers containing a surface treatment agent.

[0024] In the method for producing 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 temperature rise rate is preferably 200 to 330°C / min and the cooling rate is preferably 10 to 120°C / min. Furthermore, it is preferable that the difference in SP value between the binder of the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material and the thermoplastic resin is 0.01 to 5. Furthermore, the degree of crystallinity of the resin contained in the continuous fiber reinforced resin composite material is 20 to 40%, and the basis weight of the continuous reinforcing fiber substrate is 637 g / m 2 More preferably, the volume ratio 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.

[0025] The interface amount of a continuous fiber reinforced composite material is the amount of interface where the continuous reinforcing fibers contact the matrix resin, and is calculated by the following formula. (Interface amount (m-1 )) = (Volume of reinforcing fibers in continuous fiber reinforced resin composite material (m 3 )) × (density of reinforcing fiber (g / m 3 )) × (number of reinforcing fiber single strands) × (reinforcing fiber diameter (m)) × π / (reinforcing fiber fineness (g / m)) / (volume of continuous fiber reinforced resin composite material (m 3 )) The interface volume is 100,000m -1 It is preferable that the maximum length is 120,000m or more. -1 More preferably, it is 130,000m or more. -1 It is more preferable that the thickness is 1,000,000 m or more. -1 Preferably, it is less than 500,000 m -1 More preferably, it is: As the interfacial content of the continuous fiber reinforced composite material increases, the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less tends to decrease, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μs or less tends to increase, and the total AE count number tends to increase.

[0026] The temperature rise rate of the continuous fiber reinforced composite material is the rate at which the temperature of the substrate constituting the continuous fiber reinforced composite material is raised after the substrate is set in a molding machine. The temperature rise rate is preferably 200 to 330° C. / min, more preferably 230 to 300° C. / min, and even more preferably 250 to 280° C. / min. As the temperature rise rate decreases, 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 μsec or less tends to decrease, and AE count B tends to increase.

[0027] The cooling rate of a continuous fiber reinforced composite material is the rate at which the substrate constituting the continuous fiber reinforced composite material is set in a molding machine, melted, compressed, and then cooled by water cooling or the like. 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, 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 μsec or less tends to decrease, the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of 1,000 μsec or less tends to increase, and AE count B tends to increase.

[0028] The SP values ​​of the binder of the continuous reinforcing fibers and the thermoplastic resin contained in the continuous fiber reinforced resin composite material are values ​​relating to the solubility of each substance. The difference in SP value between the binder of the continuous reinforcing fibers and the thermoplastic resin is preferably 0.01 to 5, more preferably 0.01 to 4, even more preferably 0.01 to 3, and even more preferably 0.01 to 2. The smaller the difference in SP value between the binder of the continuous reinforcing fibers and the thermoplastic resin, the smaller the AE count A tends to be. The difference in SP value may be the absolute value of the difference between the SP value of the binder for the continuous reinforcing fibers and the SP value of the thermoplastic resin. The SP value can be measured by the method described in the examples below.

[0029] The degree of crystallinity of the resin contained in the continuous fiber reinforced resin composite material is the degree of crystallinity when in the state of a continuous fiber reinforced composite material, and is the proportion of crystalline regions in the entire resin. The crystallinity is preferably from 20 to 40%, more preferably from 25 to 35%, and even more preferably from 28 to 33%. The lower the crystallinity, the greater the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of 1,000 μsec or less, and the greater the total number of AE signals. The crystallinity of the resin contained in the continuous fiber reinforced resin composite material can be measured using a differential scanning calorimeter, specifically, by the method described in the examples below.

[0030] The basis weight of continuous reinforcing fiber substrate is the weight per meter of continuous reinforcing fiber substrate (fiber cloth, etc.) used in the production of continuous fiber reinforced resin composite materials. 2 is the mass per unit mass. The weight of the continuous reinforcing fiber base material is 637 g / m 2 It is preferable that the density is 640 to 700 g / m or more. 2 More preferably, it is 650 to 690 g / m 2 It is more preferable that: As the basis weight of the continuous reinforcing fiber substrate increases, the number of AE signals of the continuous fiber reinforced composite material with an amplitude of 40 dB or more and a duration of 3500 μsec or less tends to decrease, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μsec or less tends to increase, and the total AE count tends to increase.

[0031] The ratio of the charged volume of the thermoplastic resin is the ratio of the volume of the raw material thermoplastic resin to the total volume of the raw materials charged when producing a continuous fiber reinforced plastic composite material. The ratio of the volume of the thermoplastic resin charged is preferably 45% or more, more preferably 50% or more, and although there is no particular upper limit, it is preferably 75% or less, more preferably 65% ​​or less. As the ratio of the thermoplastic resin volume charged increases, the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μs or less for continuous fiber reinforced composite materials tends to decrease, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μs or less tends to increase, and the total AE count tends to increase.

[0032] The cooling and compression time is the time required for the substrate constituting the continuous fiber reinforced composite material to be set in a molding machine, melted and compressed, and then cooled by water cooling or the like and compressed. The cold 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 an amplitude of 40 dB or more and a duration of 3500 μs or less for continuous fiber-reinforced composite materials tends to be, while the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μs or less tends to be, and the larger the total AE count tends to be.

[0033] The terminal group concentration of a thermoplastic resin is the amount of terminal groups present in 1 g of resin. The terminal group concentration of the thermoplastic resin is preferably 70 μmol / g or more, more preferably 100 to 300 μmol / g, and even more preferably 120 to 270 μmol / g. As the end group concentration of the thermoplastic resin increases, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μsec or less tends to increase, and the total AE count number tends to increase. The end group concentration of the thermoplastic resin is 1 It can be measured using H-NMR, specifically by the method described in the Examples below.

[0034] The continuous fiber reinforced resin composite material may be further filled with a thermoplastic resin composition for hybrid use to form a hybrid composite material. In the process for producing the hybrid composite material, the substrate is set in a mold, the mold is closed, pressure is applied, and after a predetermined time, a predetermined thermoplastic resin composition for hybrid use is further injected and filled to form a mold, thereby bonding the thermoplastic resin of the substrate and the predetermined thermoplastic resin composition for hybrid use to form a hybrid composite material.

[0035] The timing of injection of the specified thermoplastic resin composition for hybrid use greatly affects the interfacial strength between the thermoplastic resin substrates, and the timing of injection of the specified thermoplastic resin composition for hybrid use is preferably within 30 seconds, more preferably within 20 seconds, and even more preferably within 15 seconds after the substrate is set in the mold. The mold temperature when injecting and filling a predetermined thermoplastic resin composition for hybrid use is preferably not higher than the crystallization temperature or glass transition temperature of the thermoplastic resin constituting the substrate to be bonded with the thermoplastic resin composition for hybrid use, more preferably not higher than the crystallization temperature or glass transition temperature of the thermoplastic resin constituting the substrate to be bonded with the thermoplastic resin composition for hybrid use minus 20°C, even more preferably not higher than the crystallization temperature or glass transition temperature minus 50°C, and even more preferably not higher than the crystallization temperature or glass transition temperature minus 70°C.

[0036] In the hybrid composite material, the joint between the thermoplastic resin constituting the substrate and the thermoplastic resin composition for hybrid formed by injection molding preferably has an uneven structure in which they are mixed together. In order to enhance the interfacial strength, it is effective to set the mold temperature at or above the melting point of the thermoplastic resin composition for hybrid to be injected and to set the resin dwell pressure during injection molding at a high level, for example, at 1 MPa or higher. To enhance the interfacial strength, the dwell pressure is preferably set at 5 MPa or higher, and more preferably at 10 MPa or higher. From the viewpoint of enhancing interfacial strength, it is also preferable to maintain the pressure for a long time, for example, 5 seconds or more, preferably 10 seconds or more, and more preferably for a time until the mold temperature becomes equal to or lower than the melting point of the thermoplastic resin composition.

[0037] (Thermoplastic resin composition for hybrids) The thermoplastic resin composition for hybrid use for injection molding used to produce a hybrid composite material is not particularly limited as long as it is a thermoplastic resin composition that is generally used for injection molding. The thermoplastic resin contained in the thermoplastic resin composition for hybrids is not limited to the following, but examples include polyethylene, polypropylene, polyvinyl chloride, acrylic resin, styrene-based resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyphenylene ether, modified polyphenylene ether resin, wholly aromatic polyester, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide-based resin, polysulfone, polyetheretherketone, and mixtures of two or more thermoplastic resins such as polyetherketone.

[0038] The thermoplastic resin composition for hybrid use may contain various fillers. The thermoplastic resin composition for hybrid use may be a black resin composition containing a colorant. Examples of various fillers include short fiber and long fiber materials, which are discontinuous reinforcing materials of the same type as the above-mentioned continuous reinforcing fibers. When short glass fibers or long glass fibers are used as the discontinuous reinforcing material, the same sizing agent as that applied to the continuous reinforcing fibers constituting the continuous fiber-reinforced resin composite material of this embodiment may be used. The sizing agent (sizing agent) is preferably at least one selected from the group consisting of a silane coupling agent, a lubricant, and a binder. The types of silane coupling agent, lubricant, and binder that can be used are the same as those of the sizing agent for the continuous reinforcing fibers.

[0039] From the viewpoint of interfacial strength with the thermoplastic resin to be joined, the thermoplastic resin contained in the thermoplastic resin composition for hybrid use used in injection molding is preferably similar to, and more preferably the same type as, the thermoplastic resin at the joining surfaces constituting the continuous fiber reinforced resin composite material. Specifically, when polyamide 66 is used as the thermoplastic resin at the joining surfaces, the resin material of the thermoplastic resin composition for hybrid use used in injection molding is preferably polyamide 66.

[0040] Other methods include a molding method in which the substrate is placed in a mold and compressed using a double belt press, a method in which a mold frame is placed so as to surround the placed substrate on all sides and the substrate is pressurized and molded using a double belt press, a molding method in which a heating compression molding machine set to one or more temperatures and a cooling compression molding machine set to one or more temperatures are prepared, and the molds in which the substrate is placed are sequentially placed into the compression molding machines and molded, and a method in which the substrate is pressurized and molded using a continuous compression molding machine. In the method of molding by pressurizing using a double belt press or a continuous compression molding machine, the material of the belt or mold is different from that of the continuous fiber reinforced resin composite material to be molded, and is preferably metal or ceramic from the viewpoint of durability. The continuous reinforcing fiber substrate and the thermoplastic resin to be introduced may be laminated.

[0041] (continuous reinforcing fiber) As the continuous reinforcing fibers, those used in ordinary 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 continuous reinforcing fibers may be used alone or in combination of two or more. The continuous reinforcing fibers may be treated with a surface treatment agent (preferably a sizing agent, which will be described later).

[0042] -Sizing agent- The continuous reinforcing fibers preferably have a sizing agent attached thereto. When glass fibers are selected as the continuous reinforcing fibers, a sizing agent may be used as a surface treatment agent. The sizing agent may contain one or more selected from the group consisting of a coupling agent (e.g., a silane coupling agent), a lubricant, and a binder, and preferably contains at least a binder or a silane coupling agent. However, this does not include those consisting only of silane coupling agents. The sizing agent may be made of a silane coupling agent and a binder, or may be made of a silane coupling agent, a lubricant, and a binder. By acting as a sizing agent that creates a strong bond between continuous reinforcing fibers (for example, glass fibers) and the resin coating around them, it is possible to obtain continuous fiber reinforced resin composite materials with low void ratio. The sizing agent may be added externally to the material being used, or may be contained internally in the material being used, for example, a lubricant may be included in the commercial product of the thermoplastic resin being used. Coupling agents are compounds that bond materials with different properties, mainly inorganic and organic materials. Examples of coupling agents include, but are not limited to, silane coupling agents, polymer coupling agents, and polymerizable coupling agents. From the viewpoint of compatibility between the thermoplastic resin and the continuous reinforcing fibers, silane coupling agents are preferred.

[0043] --Silane coupling agent-- Silane coupling agents are usually used as surface treatment agents for continuous reinforcing fibers (for example, glass fibers or carbon fibers), and contribute to improving the interfacial adhesive 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 polyamide is used as the thermoplastic resin, it is preferable to select one that easily bonds with the carboxyl group or amino group that is the terminal group of the polyamide resin, and aminosilanes are preferred. Examples of polymer coupling agents include, but are not limited to, diamines, polycarboxylic acids, and epoxies, with diamines and polycarboxylic acids being preferred from the viewpoint of compatibility with thermoplastic resins. Examples of polymerizable coupling agents include, but are not limited to, epoxies, phenols, ethers, lactones, etc., and from the viewpoint of compatibility with thermoplastic resins, phenols and lactones are preferred.

[0044] --Lubricant-- The lubricant contributes to improving the openability of continuous reinforcing fibers (for example, glass fibers). As the lubricant, any ordinary liquid or solid lubricating material can be used depending on the purpose, as long as it does not interfere with the silane coupling agent and the binder. Examples of the lubricant include, but are not limited to, animal, vegetable, or mineral waxes such as carnauba wax and lanolin wax; surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers; and the like.

[0045] --Binding agent-- The binder contributes to improving the bundling property of continuous reinforcing fibers (for example, glass fibers) and improving the interfacial adhesive strength. As the binder, polymers according to the purpose, and thermoplastic resins other than the thermoplastic resins as the main material of the continuous fiber reinforced resin composite material can be used. Examples of polymers that can be used as binders include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, copolymers of acrylic acid esters and / or methacrylic acid esters and copolymerizable monomers, and salts of these with primary, secondary, and tertiary amines. 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 suitable. The homopolymer of acrylic acid preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000. The copolymerizable monomer constituting the copolymer of acrylic acid and other copolymerizable monomers is not limited to the following, but examples thereof include, among monomers having a hydroxyl group and / or a carboxyl group, one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid (excluding the case where only acrylic acid is used). It is preferable to have one or more ester-based monomers as the copolymerizable monomer. Salts of acrylic acid homopolymers and copolymers with primary, secondary, and tertiary amines include, but are not limited to, triethylamine salts, triethanolamine salts, glycine salts, etc. The degree of neutralization is preferably 20 to 90%, more preferably 40 to 60%, from the viewpoints of improving the stability of a mixed solution with other concomitant chemicals (such as a silane coupling agent) and reducing the 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 ability of continuous reinforcing fibers (for example, glass fibers), it is preferably 3,000 or more, and from the viewpoint of improving the properties of a composite molded article, it is preferably 50,000 or less. When polyamide is used as the thermoplastic resin, it is preferable to use a resin as the binder that has good wettability or a surface tension similar to that of the polyamide resin. Specifically, for example, an emulsion of a polyurethane resin, an emulsion of a polyamide resin, or a modified product thereof can be selected.

[0046] Thermoplastic resins used as binders include, but are not limited to, polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluorine-based resins, and modified thermoplastic resins obtained by modifying these resins. If the thermoplastic resin used as the binder is the same type of thermoplastic resin and / or modified thermoplastic resin as the resin that coats the continuous reinforcing fibers, the adhesion between the glass fibers and the thermoplastic resin is improved after the composite material is formed, which is preferable.

[0047] Furthermore, a modified thermoplastic resin is preferred as the thermoplastic resin used as a binder, from the viewpoints of further improving the adhesion between the continuous reinforcing fibers and the thermoplastic resin coating them, and reducing the proportion of emulsifier components or eliminating the need for an emulsifier when the sizing agent is attached to the continuous reinforcing fibers (e.g., glass fibers) as an aqueous dispersion. Here, the modified thermoplastic resin means a thermoplastic resin obtained by copolymerizing a different monomer component other than a monomer component capable of forming the main chain of the thermoplastic resin, in order to change the properties of the thermoplastic resin, thereby modifying the hydrophilicity, crystallinity, thermodynamic properties, etc. The modified thermoplastic resin used as the binder is not limited to the following, but examples thereof include modified polyolefin resins, modified polyamide resins, modified polyester resins, and the like.

[0048] The modified polyolefin resin used as a binder is a copolymer of an olefin monomer such as ethylene or propylene with a monomer copolymerizable with the olefin monomer, such as an unsaturated carboxylic acid and / or its ester, or a homopolymer of a monomer copolymerizable with the olefin monomer, such as an unsaturated carboxylic acid and / or its ester, and can be produced by a known method. It may be a random copolymer in which an olefin monomer is copolymerized with an unsaturated carboxylic acid and / or its ester, or a graft copolymer in which an unsaturated carboxylic acid is grafted onto an olefin. Examples of olefin monomers include, but are not limited to, ethylene, propylene, 1-butene, etc. These may be used alone or in combination of two or more. Examples of monomers copolymerizable with olefin-based monomers include unsaturated carboxylic acids such as acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, and esters of these unsaturated carboxylic acids (methyl esters, ethyl esters, and the like). These may be used alone or in combination of two or more. When the modified polyolefin resin is a copolymer of an olefin monomer and a monomer copolymerizable with the olefin monomer, the monomer ratio is preferably 60 to 95 mass% of the olefin monomer and 5 to 40 mass% of the monomer copolymerizable with the olefin monomer, and more preferably 70 to 85 mass% of the olefin monomer and 15 to 30 mass% of the monomer copolymerizable with the olefin monomer, with the total mass of the copolymer being 100 mass%. If the olefin monomer is 60 mass% or more, the affinity with the matrix is ​​good, and if the mass% of the olefin monomer is 95 mass% or less, the water dispersibility of the modified polyolefin resin is good and it is easy to apply it uniformly to the continuous reinforcing fibers.

[0049] In the modified polyolefin resin used as a binder, modified groups such as carboxyl groups introduced by copolymerization may be neutralized with a basic compound. Examples of basic compounds include, but are not limited to, alkalis such as sodium hydroxide and potassium hydroxide; ammonia; and amines such as monoethanolamine and diethanolamine. The weight-average molecular weight of the modified polyolefin resin used as a binder is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. From the viewpoint of improving the bundling ability of continuous reinforcing fibers (e.g., glass fibers), a molecular weight of 5,000 or more is preferred, and from the viewpoint of emulsion stability when the resin is made water-dispersible, a molecular weight of 200,000 or less is preferred.

[0050] The modified polyamide resin used as a binder is a modified polyamide compound having a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component introduced into the molecular chain, and can be produced by a known method. When a polyalkylene oxide chain is introduced into the molecular chain, for example, it is produced by copolymerizing a polyethylene glycol, a polypropylene glycol, or the like, which is partially or completely modified with a diamine or a dicarboxylic acid.When a tertiary amine component is introduced, it is produced by copolymerizing, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylamino ε-caprolactam, or the like.

[0051] The modified polyester resin used as a binder is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and has hydrophilic groups in the molecular skeleton including the terminals, and can be produced by a known method. Examples of hydrophilic groups include polyalkylene oxide groups, sulfonate salts, carboxyl groups, and neutralized salts thereof. Examples of polycarboxylic acids or anhydrides thereof include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, trifunctional or higher functional polycarboxylic acids, and the like. 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 the aliphatic dicarboxylic acid or alicyclic dicarboxylic acid include, but are not limited to, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, and maleic anhydride. Examples of tri- or higher functional polycarboxylic acids 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 components be aromatic dicarboxylic acids, and from the viewpoint of emulsion stability when the modified polyester resin is made into an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid components be sulfonate-containing aromatic dicarboxylic acids.

[0052] Examples of polyols constituting the modified polyester resin include diols and tri- or higher functional polyols. Examples of diols include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof, etc. Examples of tri- or higher functional polyols include trimethylolpropane, glycerin, pentaerythritol, etc.

[0053] The copolymerization ratio of the polycarboxylic acid or its anhydride and the polyol that constitutes the modified polyester resin is preferably 40 to 60 mass% of the polycarboxylic acid or its anhydride and 40 to 60 mass% of the polyol, and more preferably 45 to 55 mass% of the polycarboxylic acid or its anhydride and 45 to 55 mass% of the polyol, where the total mass of the copolymerization components is 100 mass%. 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 ability of continuous reinforcing fibers (for example, glass fibers), it is preferably 3,000 or more, and from the viewpoint of emulsion stability when it is made water-dispersible, it is preferably 100,000 or less.

[0054] The polymer or thermoplastic resin used as the binder may be used alone or in combination of two or more kinds. With the total amount of the binder taken as 100% by mass, it is preferable to use at least 50% by mass, and more preferably at least 60% by mass, of one or more polymers selected from homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, copolymers of acrylic acid esters and / or methacrylic acid esters and copolymerizable monomers, and salts of these with primary, secondary, and tertiary amines.

[0055] When the sizing agent is composed of a silane coupling agent and a binder, the sizing agent is applied and attached in a total amount of 0.1 to 3 mass%, more preferably 0.2 to 2 mass%, and even more preferably 0.2 to 1 mass% based on 100 mass% of continuous reinforcing fibers (e.g., glass fibers) as the total amount of the silane coupling agent and binder. From the viewpoint of controlling the bundling property of the continuous reinforcing fibers (e.g., glass fibers) and improving the interfacial adhesive strength, the amount of the sizing agent attached is preferably 0.1 mass% or more based on 100 mass% of the continuous reinforcing fibers (e.g., glass fibers) as the total amount of the silane coupling agent and binder, and from the viewpoint of yarn handleability, it is preferably 3 mass% or less. When the sizing agent is composed of a silane coupling agent, a lubricant, and a binder, the sizing agent is applied and attached in a total amount (total attached mass ratio) of the silane coupling agent, lubricant, and binder relative to 100% by mass of the continuous reinforcing fibers (e.g., glass fibers) of preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and even more preferably 0.2 to 1% by mass. The total attached mass ratio is preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.2% by mass, and even more preferably 0.03 to 0.15% by mass. From the viewpoint of controlling the bundling property of continuous reinforcing fibers (e.g., glass fibers) and improving the interfacial adhesive strength, the amount of the sizing agent attached is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, as the total mass of the silane coupling agent, lubricant, and binder, relative to 100% by mass of continuous reinforcing fibers (e.g., glass fibers); from the viewpoint of yarn handleability, it is preferably 3% by mass or less, and more preferably 0.3% by mass or less. The amount of the coupling agent attached is preferably 0.05 to 1 mass %, more preferably 0.1 to 0.9 mass %, relative to 100 mass % of the continuous reinforcing fibers.

[0056] --Composition of sizing agent for glass fibers-- The amount of the silane coupling agent in the glass fiber sizing agent is preferably 0.1 to 2 mass %, more preferably 0.1 to 1 mass %, and even more preferably 0.2 to 0.5 mass %, relative to 100 mass % of the sizing agent, from the viewpoints of improving the glass fiber bundling ability, improving the interfacial adhesive strength, and improving the mechanical strength of the composite molded body. The amount of lubricant in the glass fiber sizing agent is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of providing sufficient lubrication, and is preferably 1.5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, from the viewpoint of improving the interfacial adhesive strength and the mechanical strength of the composite molded product. The blending amount of the binder in the glass fiber sizing agent is preferably 1 to 25 mass %, more preferably 3 to 15 mass %, and even more preferably 3 to 10 mass %, from the viewpoints of controlling the bundling property of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite molded body.

[0057] When glass fibers are used as the continuous reinforcing fibers and the sizing agent is composed of a silane coupling agent, a lubricant, and a binder, the glass fiber sizing agent preferably contains 0.1 to 2 mass% of the silane coupling agent, 0.01 to 1.5 mass% of the lubricant, and 1 to 25 mass% of the binder, respectively, and more preferably contains 0.1 to 2 mass% of the silane coupling agent, 0.01 to 1 mass% of the lubricant, and 1 to 25 mass% of the binder, and it is preferable to dilute these components with water to adjust the total mass to 100 mass%.

[0058] --Use of glass fiber sizing agent-- 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 mode of use. From the viewpoint of improving the dispersion stability and heat resistance of the sizing agent, however, it is preferably in the form of an aqueous solution. The glass fibers as the continuous reinforcing fibers that constitute the continuous fiber-reinforced resin composite material of this embodiment can be continuously obtained by applying the above-mentioned sizing agent to glass fibers using a known method such as a roller-type applicator in a known glass fiber manufacturing process, and then drying the produced glass fibers. The glass fiber sizing agent can be used in various ways, including immersing the glass fibers in a liquid containing the sizing agent, and immersing the glass fiber substrate in a liquid containing the sizing agent.

[0059] Similarly, when carbon fibers are selected as the continuous reinforcing fibers, a sizing agent may be used. The sizing agent preferably comprises a coupling agent (e.g., a silane coupling agent), a lubricant, and a binder. The coupling agent can be selected to have good compatibility with the hydroxyl groups present on the surface of the carbon fibers, the binder can be selected to have good wettability with the selected thermoplastic resin or a surface tension similar to that of the selected thermoplastic resin, and the lubricant can be selected to not interfere with the coupling agent and binder. Examples of coupling agents suitable for use with carbon fibers include diamines such as 1,6-hexadiamine and polycarboxylic acids. The lubricant can be selected so as not to interfere with the coupling agent and the binder. The type of sizing agent used for the carbon fibers is not particularly limited, and any known sizing agent can be used. Specifically, for example, the one described in JP 2015-101794 A can be used.

[0060] When other continuous reinforcing fibers are used, the type and amount of sizing agent that can be used for glass fibers and carbon fibers may be appropriately selected depending on the characteristics of the continuous reinforcing fibers, and it is preferable to use the same type and amount of sizing agent as those used for carbon fibers.

[0061] (shape of continuous reinforcing fibers) The continuous reinforcing fiber is a multifilament consisting of a plurality of filaments, and the number of single fibers is preferably 30 to 15,000 from the viewpoint of handling. From the viewpoints of strength and ease of handling, the single filament diameter R of the continuous reinforcing fibers 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. Single fiber diameter R (μm) and density D (g / cm 3 ) is preferably 5 to 100 μm g / cm from the viewpoint of the ease of handling of the continuous reinforcing fibers and the strength of the composite material. 3 , more preferably 10 to 50 μm g / cm 3 , and more preferably 15 to 45 μm g / cm 3, and even more preferably 20 to 45 μm g / cm 3 is.

[0062] The density D can be measured by a hydrometer. On the other hand, the single fiber diameter R (μm) is related to the density D (g / cm 3 ) and the fineness (dtex), the number of single yarns (threads) are calculated using the following formula:

number

[0063] To set the RD of the continuous reinforcing fibers within a predetermined range, the fineness (dtex) and the number of single fibers (strands) of commercially available continuous reinforcing fibers can be appropriately selected according to the density of the continuous reinforcing fibers. For example, when glass fibers are used as the continuous reinforcing fibers, the density of the continuous reinforcing fibers is about 2.5 g / cm. 3 Therefore, it is sufficient to select a glass fiber with a single filament diameter of 2 to 40 μm. Specifically, when the single filament diameter of the glass fiber is 9 μm, selecting a glass fiber with a fineness of 660 dtex and a single filament count of 400 will result in a RD product of 23. Also, when the single filament diameter of the glass fiber is 17 μm, selecting a glass fiber with a fineness of 11,500 dtex and a single filament count of 2,000 will result in a RD product of 43. When carbon fiber is used as the continuous reinforcing fiber, the density is approximately 1.8 g / cm. 3 Therefore, it is sufficient to select a carbon fiber with a single filament diameter of 2.8 to 55 μm. Specifically, when the single filament diameter of the carbon fiber is 7 μm, by selecting a carbon fiber with a fineness of 2,000 dtex and 3,000 single filaments, the product RD becomes 13. When aramid fiber is used as the continuous reinforcing fiber, the density is about 1.45 g / cm. 3 Therefore, it is sufficient to select one with a single yarn diameter of 3.4 to 68 μm. Specifically, when the single yarn diameter of the aramid fiber is 12 μm, by selecting an aramid fiber with a fineness of 1,670 dtex and 1,000 single yarns, the product RD becomes 17.

[0064] Continuous reinforcing fibers, for example, glass fibers, are produced by measuring and mixing raw glass materials, molten glass in a melting furnace, spinning the molten glass into glass filaments, applying a sizing agent to the filaments, and passing them through a spinning machine to be wound into direct wound rovings (DWRs), cakes, twisted yarns, or other wound forms. The continuous reinforcing fibers may be in any form, but are preferably wound into yarn, cake, or DWR, as this increases productivity and production stability in the resin coating process. From the viewpoint of productivity, DWR is the most preferred.

[0065] The form of the continuous reinforcing fibers is not particularly limited, and various forms such as woven fabrics, knitted fabrics, braided cords, pipe-shaped materials, non-crimp fabrics, and unidirectional materials are possible, with woven fabrics, non-crimp fabrics, and unidirectional materials being preferred.

[0066] (thermoplastic resin) The thermoplastic resin constituting the continuous fiber reinforced resin composite material of this embodiment preferably has a loss tangent tanδ peak temperature 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 higher and a duration of 3500 μsec or shorter from the continuous fiber reinforced composite material tends to be smaller, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μsec or shorter tends to be larger, and the total AE count tends to be larger. The peak temperature of the loss tangent tanδ of a thermoplastic resin refers to the temperature at which tanδ reaches its maximum value when tanδ is measured at each temperature while changing the temperature. The peak temperature of tanδ can be determined, for example, by nanoindentation (nanoDMA) using a nanoindenter to apply vibrations of a specific frequency to a single continuous reinforcing fiber in a cross section perpendicular to the longitudinal direction of the continuous reinforcing fiber contained in a thermoplastic resin film. Specifically, it can be measured by the method described in the Examples below. One method for adjusting the tan δ of a thermoplastic resin within the above range is to adjust the aromatic ring concentration in the resin. Increasing the aromatic ring concentration in the resin tends to increase the peak temperature of tan δ.

[0067] Examples of thermoplastic resins include, but are not limited to, 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; polyethersulfone; polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluorine-based resins such as tetrafluoroethylene-ethylene copolymers; polyurethane resins; acrylic resins, and modified thermoplastic resins obtained by modifying these. The thermoplastic resin may be used alone or as a mixture of two or more kinds.

[0068] Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyethersulfone, polyphenylene sulfide, thermoplastic polyetherimide, and thermoplastic fluorine-based resins are preferred, and 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, and polyamide resins and polyester resins are even more preferred from the viewpoint of thermal properties. Furthermore, polyamide resins are even more preferred from the viewpoint of durability against repeated loads.

[0069] -Polyester resin- The polyester resin refers to a polymer compound having an --CO--O-- (ester) bond in the main chain. Examples of polyester resins include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate. The polyester resin may be a homopolyester or a copolymer polyester. In the case of copolymer polyesters, those obtained by copolymerizing a homopolyester with an appropriate third component are preferred. Examples of the third component include, but are not limited to, diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid. In addition, polyester-based resins using raw materials derived from biomass resources can also be used, and examples thereof include, but are not limited to, aliphatic polyester-based resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and aromatic polyester-based resins such as polybutylene adipate terephthalate.

[0070] -Polyamide resin- The polyamide resin refers to a polymer compound having an —CO—NH— (amide) bond in the main chain, and examples thereof include aliphatic polyamides, aromatic polyamides, and wholly 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 condensing diamines and dicarboxylic acids, and copolymers thereof. The polyamide resin may be used alone or as a mixture of two or more kinds. Examples of lactams include, but are not limited to, pyrrolidone, caprolactam, undecane lactam, and dodecalactam. Examples of ω-aminocarboxylic acids include, but are not limited to, ω-amino fatty acids, which are compounds obtained by ring-opening lactams with water. Two or more types of lactam or ω-aminocarboxylic acid may be condensed together. Examples of diamines (monomers) include, but are not limited to, linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; branched aliphatic diamines such as 2-methylpentanediamine and 2-ethylhexamethylenediamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine. Examples of dicarboxylic acids (monomers) include, but are not limited to, aliphatic dicarboxylic acids such as adipic acid, pimelic acid, and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The diamine and dicarboxylic acid monomers may be condensed either individually or in combination of two or more.

[0072] Examples of polyamide resins include, but are not limited to, aliphatic polyamides such as polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, and polyamide 1010; semi-aromatic polyamides such as polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide MXD6, and polyamide 6I / 6T; and copolymer polyamides containing these as constituent components. Examples of copolymerized polyamides include, but are not limited to, a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and a copolymer of hexamethylene terephthalamide and 2-methylpentanediamine terephthalamide.

[0073] [Additives] The continuous fiber-reinforced resin composite material of this embodiment may contain additives as needed. The composite material of this embodiment may contain additives such as colorants, antioxidants, antioxidants, weathering agents, metal deactivators, light stabilizers, heat stabilizers, UV absorbers, antibacterial and antifungal agents, deodorizers, conductivity-imparting agents, dispersants, softeners, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanization aids, foaming agents, foaming aids, flame retardants, vibration dampers, nucleating agents, neutralizing agents, lubricants, antiblocking agents, dispersants, flow improvers, and mold release agents. The additives mentioned above refer to components other than those mentioned above (e.g., the thermoplastic resin, the continuous reinforcing fibers, the components contained in the thermoplastic resin composition for hybrids, and the components contained in the bundling agent). The content of the additive may be 3% by mass or less relative to 100% by mass of the composite material.

[0074] (coloring agent) Examples of colorants include carbon black, nigrosine, aluminum pigments, 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, phthalocyanine blue, etc. Among these, black colorants are preferred, and carbon black and nigrosine are more preferred.

[0075] The continuous fiber reinforced resin composite material of this embodiment preferably has a continuous reinforcing fiber content of 90 to 525 parts by mass and a content of other components of 0 to 2 parts by mass per 100 parts by mass of thermoplastic resin, and more preferably has a continuous reinforcing fiber content of 150 to 340 parts by mass and a content of other components of 0 to 1 part by mass per 100 parts by mass of thermoplastic resin.

[0076] [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, cars, construction materials, robots, and the like. In automotive applications, the material can be used for, but not limited to, chassis / frames, undercarriage, drivetrain parts, interior parts, exterior parts, functional parts, and other parts. Specifically, steering shafts, mounts, sunroofs, steps, suspension trim, door trim, trunks, boot lids, bonnets, seat frames, seat backs, retractors, retractor support brackets, clutches, gears, pulleys, cams, argon, elastic beams, baffling, lamps, reflectors, glazing, front end modules, back door inners, brake pedals, steering wheels, electrical materials, sound absorbing materials, door exteriors, interior panels, instrument panels, rear gates, ceiling sills, seats, seat frames, wiper posts, EPS (Electric Power Steering), small motors, heat sinks, ECU (Engine Control Unit) boxes, ECU housings, steering gear box housings, plastic housings, EV (Electric Vehicle motor housings, wire harnesses, on-board meters, combination switches, small motors, springs, dampers, wheels, wheel covers, frames, subframes, side frames, motorcycle frames, fuel tanks, oil pans, intake manifolds, propeller shafts, drive motors, monocoques, hydrogen tanks, fuel cell electrodes, panels, floor panels, exterior panels, doors, cabins, roofs, hoods, valves, EGR (Exhaust GasRecirculation valves, variable valve timing units, connecting rods, cylinder bores, members (engine mountings, front floor cloth, footwell cloth, seat cloth, inner side, rear cloth, suspension, pillar reinforcement, front side, front panel, upper, dash panel cloth, steering), tunnels, fastening inserts, crash boxes, crash rails, corrugated roof rails, upper body, side rails, braiding, door surround assemblies, airbag components, body pillars, dash-to-pillar gussets, suspension towers, bumpers, body pillar lowers, front body pillars, reinforcements (instrument panels, rails, roofs, front body pillars, roof rails, roof side rails, rockers, door belt lines, front floor unders, front body pillar uppers, front body pillar lowers, center pillars, center pillar hinges, door outside panels), side outer panels, front door window frames, MICS (Minimum Intrusion CabinSystem bulk, torque box, radiator support, radiator fan, water pump, fuel pump, electronically controlled 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 board sub-assembly, energy absorber (bumper, impact absorption), impact absorber, impact absorption garnish, pillar garnish, roof side inner garnish, resin rib, side rail front spacer, side rail rear spacer, seat belt pretensioner, airbag They can be suitably used as parts such as sensors, arms (suspension, lower, hood hinge), suspension links, shock absorbing 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 seats, hood insulators, fender side panel protectors, cowl insulators, cowl top ventilator loopers, cylinder head covers, tire deflectors, fender supports, strut tower bars, transmission center tunnels, floor tunnels, radio core supports, luggage panels, luggage floors, accelerator pedals, and accelerator pedal bases.

[0077] [Molding of composite materials] The continuous fiber reinforced resin composite material of this embodiment may be further molded. Examples of the above method include a method in which the continuous fiber reinforced resin composite material of this embodiment is cut to a predetermined size, heated with an infrared heater, and hot-compressed and pressed with a press molding machine, or injection hybrid molding in which the continuous fiber reinforced resin composite material is heated with an infrared heater, hot-compressed and pressed with a press molding machine, and then the resin is injection molded. [Example]

[0078] The present invention will be specifically explained below with reference to examples and comparative examples, but it goes without saying that the present invention is not limited to these examples and can be practiced with various modifications within the scope of the gist of the present invention.

[0079] [Interface amount] The interfacial mass (m -1 ) was sought. (Interface amount (m -1 )) = (Volume of reinforcing fibers in continuous fiber reinforced resin composite material (m 3 )) × (density of reinforcing fiber (g / m 3 )) × (number of reinforcing fiber single strands) × (reinforcing fiber diameter (m)) × π / (reinforcing fiber fineness (g / m)) / (volume of continuous fiber reinforced resin composite material (m 3 ))

[0080] [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 the continuous fiber-reinforced resin composite material and dried for at least 18 hours in a vacuum dryer at 80°C. After that, the test pieces were chucked at 30 mm intervals in the longitudinal direction using an Instron universal testing machine, and the tensile strength (MPa) was measured at a speed of 5 mm / min in an environment of 23°C, 50% RH, and in an environment of 80°C, 50% RH, and the average value of five samples was calculated. The tensile strength retention rate (%) at 80°C was calculated using the following formula. Tensile strength retention at 80°C = (tensile strength at 80°C, 50% RH / tensile strength at 23°C, 50% RH) x 100

[0081] [Flexural strength, flexural modulus, flexural strength retention rate, flexural modulus retention rate] Strip-shaped test pieces measuring 100 mm in length, 10 mm in width, and 2 mm in thickness were cut from the continuous fiber-reinforced resin composite material and dried for at least 18 hours in a vacuum dryer at 80°C. After that, using an Instron universal testing machine, a three-point bending jig was used to measure the bending strength (MPa) and bending modulus (GPa) at a speed of 1 mm / min under an environment of 23°C, 50% RH, and an environment of 80°C, 50% RH, and the average values ​​of five samples were calculated. The flexural strength retention rate (%) and flexural modulus retention rate (%) at 80°C were calculated using the following formulas. Flexural strength retention at 80°C = (flexural strength at 80°C, 50% RH / flexural strength at 23°C, 50% RH) x 100 Flexural modulus retention at 80°C = (flexural modulus at 80°C, 50% RH / flexural modulus at 23°C, 50% RH) x 100

[0082] [Water absorption properties] A rectangular test piece measuring 100 mm in length, 10 mm in width, and 2 mm in thickness was cut from the continuous fiber-reinforced resin composite material, immersed in a constant-temperature water bath at 80°C for 18 hours, and then left in a constant-temperature, constant-humidity bath at 80°C and 57% RH for 150 hours or more, and the moisture content was adjusted until the mass became constant. This was used as the test piece after water absorption. Using the methods described above, the tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the test pieces in the dry and water-absorbed state were measured under an environment of 23°C and 50% RH. The tensile strength retention rate (%), flexural strength retention rate (%), and flexural modulus retention rate (%) upon water absorption were calculated using the following formulas. Tensile strength retention rate when absorbing water = (tensile strength when absorbing water / tensile strength when dry) x 100 Bending strength retention rate when absorbing water = (bending strength when absorbing water / bending strength when dry) x 100 Flexural modulus retention rate when absorbing water = (flexural modulus when absorbing water / flexural modulus when dry) x 100

[0083] [Impact strength] Test pieces measuring 60 mm in length, 60 mm in width, and 2 mm in thickness were cut from the continuous fiber reinforced resin composite material and 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 mm, a receiving diameter of 40 mm, a test speed of 4.4 m / sec, a test temperature of 23°C, and n = 5. A graph of the test force versus displacement was drawn, and the maximum impact strength (kN) obtained from the graph was divided by the thickness of the test piece to obtain the average value (kN / mm) of the five samples.

[0084] [Acoustic Emission Measurement] Using an acoustic emission measurement system (USB AE NODE AE measurement system 1ch, manufactured by PAC Corporation), an acoustic emission sensor (R6a) was attached to the center of the three-point bending jig for the bending strength test via silicone grease (Shin-Etsu Silicone HIVAC-G, Shin-Etsu Chemical Co., Ltd.) and fixed with vinyl tape. 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. The number of acoustic emission signals with an amplitude of 40 dB or more and a duration of 3500 μsec or less was defined as Count 1, and the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of 1000 μsec or less was defined as Count 2. Count 1, Count 2, and the total number of signals were measured, and AE Count A and AE Count B were calculated using the following formula. (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 between 25 and 30 dB and duration of 1000 μs or less) / (total number of AE signals) Measurements were made using N5, and the average values ​​were used as each value.

[0085] [Vibration fatigue test] ASTM-D1822 tensile impact dumbbell Type S test pieces were prepared from continuous fiber reinforced resin composite materials and subjected to vibration fatigue testing using an EHF-EB50kN-40L(RV) (Shimadzu Corporation) at a test temperature of 23°C, a frequency of 20Hz, a sine wave waveform, and a chuck distance of 35mm. Test pieces that failed after 20,000 or more cycles at 250MPa were rated as "good" (good), and those that failed after fewer than 20,000 cycles were rated as "poor" (poor).

[0086] [Crystallization] Using a differential scanning calorimeter (Shimadzu DSC-60), the sample amount was approximately 5 mg of the resin content contained in the continuous fiber reinforced resin composite material, and the sample was heated from room temperature (25°C) to a temperature above the expected melting point under the conditions of an atmospheric gas flow rate of 30 mL / min and a temperature rise rate of 10°C / min. The heat of fusion measured when the sample was melted was divided by the heat of complete fusion to determine the degree of crystallinity (%). The heat of complete fusion was calculated to be 188 J / g.

[0087] [μ droplet contact angle, interfacial shear strength] A thermoplastic resin was placed in the heating furnace of a composite interfacial property evaluation device (HM410, Toei Sangyo Co., Ltd.), and the furnace temperature was set to the melting point of the thermoplastic resin + 15°C. The resin was applied to a single continuous reinforcing fiber to create a μ-droplet. The μ-droplet thus created had an ellipsoidal shape, elongated along the length of the reinforcing fiber, with the reinforcing fiber at its center. After cooling to room temperature, the contact angle between the continuous reinforcing fiber and the thermoplastic resin μ-droplet (see α in Figure 1) was measured, and the μ-droplet contact angle (°) was calculated from the median contact angle obtained for 100 μ-droplets with a fiber axial length L of 95 to 105 μm. In addition, after measuring the diameter d (μm) of the continuous reinforcing fiber and the length L (μm) of the μ droplet in the fiber axial direction of the continuous reinforcing fiber, a shear test was performed on a μ drop of 95 to 105 μm, and the shear load F (N) when scraping off the resin droplet with a blade was measured, and the interfacial shear strength τ (MPa) was calculated using the following formula (1). The number of measurement points was 100, and the median value of the 100 points was calculated. τ=F / πdL (1) Measurements were performed to determine the interfacial strength ratio and contact angle ratio using continuous reinforcing fiber with the surface treatment agent used in each example, glass fiber without the surface treatment agent obtained by treating the glass fiber used in each example in an electric furnace at 650°C for 3 hours, and coupling agent-treated continuous reinforcing fiber treated with a surface treatment agent prepared by dissolving 0.5 mass% of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) in deionized water on glass fiber without the surface treatment agent, to obtain the interfacial strength ratio and contact angle ratio. (Interface strength ratio) = (Interface strength measured using continuous reinforcing fibers with a surface treatment agent) / (Interface strength measured using reinforcing fibers treated with a coupling agent) (Contact angle ratio) = (contact angle measured using continuous reinforcing fiber with surface treatment agent) / (contact angle measured using glass fiber without surface treatment agent)

[0088] [Physical stability] The bending strength test was carried out on 50 test pieces to measure the bending strength. The average value of the bending strength was designated as A, and the bending strength of the i-th test piece (i = 1 to 50) was designated as Ai. The coefficient of variation was calculated according to the following formula to determine the variation.

number

[0089] [Warpage characteristics] A dial gauge was fixed to the arm, and the plate of continuous fiber reinforced resin composite material obtained in each example was traced to read the difference between the maximum and minimum values.

[0090] [Shape following ability] A 150mm x 150mm test piece was cut from the continuous fiber-reinforced resin composite material obtained in each example using a band saw and heated to the melting temperature of the resin used in each example +25°C using an infrared heater (Infrastein H7GS-71298NGK, NGK, wavelength 3-7μm). It was then placed in a mold heated to 180°C with a 100mm x 100mm flat surface, 25mm x 100mm wall, and a wall radius of 10°, and pressed at a pressure of 10MPa. The maximum gap between the wall and the mold of the resulting box-shaped molded body was evaluated as "Excellent" if it was 0mm or more but less than 1mm, "Good" if it was 1mm or more but less than 3mm, and "Poor" if it was 3mm or more.

[0091] [SP value measurement] The SP value was calculated using the formula below based on the structure of the binder components of the resin and continuous reinforcing fiber used in each example. The evaporation energy and molar volume were calculated using the Fedors method. When multiple types of components are used, the SP value was calculated by adding up the values ​​obtained by multiplying the mass ratio of the components by the SP value. (SP value) = {(total vaporization energy of atoms or atomic groups contained in each component) / (molar volume of atoms or atomic groups contained in each component)}^(1 / 2)

[0092] The materials used in the examples and comparative examples are as follows. [Continuous reinforcing fiber] (glass fiber) Glass fiber 1: 100% by mass of glass fiber with a fineness of 1.15 g / m and 1,500 single fibers was produced by attaching 0.45% by mass of a sizing agent to the glass fiber. The winding method was DWR, and the average single fiber 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.) as a coupling agent, 1% by mass of carnauba wax as a lubricant, 2% by mass of polyurethane resin (Y65-55, manufactured by ADEKA Corporation) as a binder, 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) with deionized water. The SP value of the binder was 14.0. Glass fiber 2: 100% by mass of glass fiber with a fineness of 1.15 g / m and 1,500 single fibers was produced by applying 0.45% by mass of a sizing agent. The winding method was DWR, and the average single fiber 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.) as a coupling agent, 0.5% by mass of carnauba wax as a lubricant, 1.8% by mass of polyurethane resin (Y65-55, manufactured by ADEKA Corporation) as a binder, and 5.7% by mass of a copolymer compound (a copolymer compound with a weight-average molecular weight of 20,000, obtained by copolymerizing 51% by mass of maleic anhydride, 39% by mass of methyl acrylate, and 10% by mass of methyl methacrylate) with deionized water. The SP value of the binder was 15.5. Glass fiber 3: 100% by mass of glass fiber with a fineness of 1.15 g / m and 1,500 single fibers was produced by attaching 0.45% by mass of sizing agent to the glass fiber. The winding method was DWR, and the average single fiber 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.) as a coupling agent, 0.5% by mass of carnauba wax as a lubricant, 4% by mass of maleic anhydride-modified polypropylene resin as a binder, and 1.4% by mass of a copolymer compound (a copolymer compound with a weight-average molecular weight of 20,000, obtained by copolymerizing 71% by mass of methyl acrylate and 29% by mass of methyl methacrylate) with deionized water. The SP value of the binder was 11.1. (carbon fiber) A carbon fiber composite was produced by attaching 0.45% by mass of a sizing agent to 100% by mass of carbon fiber (12,000 single fibers, 9 μm diameter, 2.58 g / m fineness). The sizing agent was prepared by mixing 1% by mass of carnauba wax as a lubricant, 2% by mass of polyurethane resin (Y65-55, manufactured by ADEKA Corporation) as a binder, 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) with deionized water. The SP value of the binder was 14.0.

[0093] [Preparation of continuous reinforcing fiber substrate] Glass cloth 1, glass cloth 2: Glass cloths were produced by weaving using a rapier loom (weaving width 1 m) and the above glass fiber 1 as warp and weft. The weaving form of the obtained glass cloths was Glass cloth 1 (plain weave, weaving density 6.5 threads / 25 mm, basis weight 640 g / m 2 ), Glass Cloth 2 (plain weave, weave density 6.5 threads / 25 mm, basis weight 660 g / m 2 ) was. Glass cloth 3: A glass cloth was produced by weaving the glass fibers 2 as warp and weft using a rapier loom (weaving width 1 m). The weaving form of the obtained glass cloth was Glass cloth 3 (plain weave, weaving density 6.5 threads / 25 mm, basis weight 640 g / m2 ) was. Glass cloth 4: A glass cloth was produced by weaving the above-mentioned glass fiber 3 as warp and weft. The weaving form of the obtained glass cloth was Glass cloth 4 (plain weave, weaving density 6.5 threads / 25 mm, basis weight 640 g / m 2 ) was. Carbon fiber cloth: A carbon fiber cloth was produced by weaving the above carbon fibers as warp and weft yarns using a rapier loom (weaving width 1 m). The weaving form of the obtained carbon fiber cloth was plain weave, with a weaving density of 6.5 threads / 25 mm and a basis weight of 425 g / m 2 It was.

[0094] [Thermoplastic resin] Resin 1: PA66 (carboxyl end group amount 70 μmol / g, amino end group concentration 30 μmol / g, tanδ peak temperature: 50°C, SP value: 12.4, melting point: 265°C, crystallization temperature: 209°C) Resin 2: Dry blend of Resin 1 and PA6I (PA66:PA6I = 2:1) (carboxyl end group concentration 120 μmol / g, amino end group concentration 40 μmol / g, tanδ peak temperature: 110°C, SP value: 12.6, melting point: 260°C, crystallization temperature: 168°C) Resin 3: Polypropylene (end group concentration 0 μmol / g, tanδ peak temperature: 0°C, SP value: 8.4, melting point: 180°C, crystallization temperature: 133°C) Resin 4: Maleic acid-modified polypropylene (end group concentration 21 μmol / g, tanδ peak temperature: 0°C, SP value: 10.1, melting point: 180°C, crystallization temperature: 132°C) Resin 5: PA6 (carboxyl end group concentration 60 μmol / g, amino end group concentration 30 μmol / g, tanδ peak temperature: 50°C, SP value: 12.3, melting point: 225°C, crystallization temperature: 175°C) Resin 6: PA6I (carboxyl end group concentration 200 μmol / g, amino end group concentration 60 μmol / g, tanδ peak temperature: 130°C, SP value: 12.9, glass transition temperature: 135°C) Resin 7: PPS (Toray Industries, Inc.) (tan δ peak temperature: 90°C, SP value: 11.7, melting point: 280°C, crystallization temperature: 231°C) Resin 8: PA610 (carboxyl end group amount 70 μmol / g, amino end group concentration 30 μmol / g, tanδ peak temperature: 50°C, SP value: 11.5, melting point: 222°C, crystallization temperature: 170°C) Resin 9: Dry blend of resin 3 and resin 4 (resin 3:resin 4=90:10) (end group concentration 2 μmol / g, tanδ peak temperature: 0°C, SP value: 8.6, melting point: 180°C, crystallization temperature: 132°C) Resin 10: PA12 (carboxyl end group amount 60 μmol / g, amino end group concentration 60 μmol / g, tanδ peak temperature: 50°C, SP value: 10.5, melting point: 179°C, crystallization temperature: 130°C) (Terminal group concentration of thermoplastic resin) The end group concentration of each thermoplastic resin is 1 Measurement was performed using H-NMR under the following measurement conditions. 1 H-NMR measurement conditions Equipment: JEOL-ECA500 (JEOL Ltd.) Observation kernel: 1 H Observation frequency: 500MHz Measurement method: Single-Plus Pulse width: 30° Wait time: 10 seconds Accumulation count: 256 times Solvent: D2SO4 Sample concentration: 1.25% by mass

[0095] [Preparation of thermoplastic resin film] 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.

[0096] [Preparation of hybrid molded body] The continuous fiber reinforced resin composite material obtained in each example was cut into a 200 x 300 mm rectangle, and the resin used in each example was press-injection hybrid molded to obtain a box-shaped continuous fiber reinforced resin composite material molded product with short sides of 192 mm and long sides of 292 mm, and with 4 mm high standing walls made of polypropylene A on each side and cross-shaped ribs connecting each short side and halfway along the long side in the direction parallel to the long sides. The hybrid molded body was molded by heating the resin in each example to the melting point (glass transition temperature for resins without a melting point) + 35°C using an infrared heater (Infrastein H7GS-71298NGK, NGK, wavelength 3 to 7 μm), inserting the continuous fiber reinforced resin composite material that had been preheated for 60 seconds into a mold maintained at 150°C and pressing it with a press pressure of 10 MPa, then setting the injection pressure to 120 MPa and the injection temperature to the melting point (glass transition temperature for resins without a melting point) + 35°C of the resin in each example, and injection molding the resin used in each example within 10 seconds of setting the continuous fiber reinforced resin composite material in the mold.

[0097] [Example 1] Using Resin 1, Thermoplastic Resin Film 1 was obtained by the method described above. Five sheets of glass cloth 1 and six sheets of thermoplastic resin film 1 were prepared, and the glass cloth 1 and the thermoplastic resin film 1 were alternately stacked so that the thermoplastic resin film 1 was on the surface and molded to obtain a continuous fiber reinforced resin composite material. At this time, the charged volume ratio of the thermoplastic resin was 50%. A double belt press was used as the molding machine. The glass cloth and the thermoplastic resin film 1 were placed on top of each other as described above and placed in the molding machine, and compressed at a heating rate of 280°C / min, a pressure of 3 MPa, and a belt speed of 0.5 m / min. Thereafter, the cooling rate was changed to 80°C / min, and the mixture was cooled and compressed at 3 MPa for 3 minutes to be molded. A hybrid molded body was produced from the obtained continuous fiber reinforced resin composite material using the above method, and a piece 100 mm long and 10 mm wide was cut out. The ribs were removed using abrasive paper so as not to damage the continuous fiber reinforced resin composite material, and acoustic emission measurements were carried out using the above method. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0098] [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. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0099] [Example 3] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that Resin 9 was used as the thermoplastic resin and Glass Cloth 4 was used as the glass cloth. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0100] [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 substrate. The charged volume ratio of the thermoplastic resin was 50%. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0101] [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 substrate. The charged volume ratio of the thermoplastic resin was 50%. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0102] [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 and Glass Cloth 4 was used as the glass cloth. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0103] [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. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0104] [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. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0105] [Example 9] The glass fiber 1 (100% by mass) was coated with 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 as a sizing agent. The glass fiber was then woven in a plain weave with a density of 6.5 strands / 25 mm and a basis weight of 640 g / m. 2 A glass cloth of the same size was produced. Five sheets of this glass cloth were stacked and placed in a mold. A mixed resin of 16 g of bisphenol A liquid epoxy resin (jER828, Mitsubishi Chemical Corporation) and 1.6 g of bisphenol A (4,4'-(propane-2,2-diyl)diphenol) was added to the mixture. The temperature inside the molding machine was set to 40°C, and compression molding was performed for 3 days at a mold clamping force of 5 MPa. The mixture was then cooled for 8 minutes at a cooling rate of 80°C / min at a mold clamping force of 5 MPa to obtain a continuous fiber-reinforced resin composite material. The volume ratio of the thermoplastic resin charged was 50%. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0106] [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. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0107] [Example 11] Resin 2 was used as the thermoplastic resin, and glass fiber 1 was used as the continuous reinforcing fiber substrate with a basis weight of 640 g / m 2 A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that the fibers were aligned so that the volume ratio of the thermoplastic resin charged was 50%. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0108] [Example 12] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that Glass Cloth 3 was used as the glass cloth. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0109] [Example 13] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that Resin 8 was used as the thermoplastic resin. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0110] [Example 14] A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that Resin 10 was used as the thermoplastic resin. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0111] [Comparative Example 1] The glass fiber 1 (100% by mass) was coated with 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 as a sizing agent. The glass fiber was then woven in a plain weave with a density of 6.5 strands / 25 mm and a basis weight of 600 g / m. 2 A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that the glass cloth manufactured and used was the same as in Example 1. The charged volume ratio of the thermoplastic resin was 50%. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0112] Comparative Example 2 The same evaluation as in Example 1 was carried out using "Tepex dynalite 101" manufactured by Bond Laminate, which is glass cloth impregnated with polyamide 66. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0113] Comparative 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 and Glass Cloth 3 was used as the glass cloth. The physical properties of the obtained continuous fiber reinforced resin composite material are shown in Table 1.

[0114] [Table 1] [Industrial Applicability]

[0115] The continuous fiber reinforced resin composite material of the present embodiment can be industrially used as a reinforcing material for materials that require high levels of mechanical properties, such as structural parts for various machines and automobiles, and as a composite molded product material with a thermoplastic resin composition. [Explanation of symbols]

[0116] 1: Continuous reinforced fiber monofilament 2: Thermoplastic resin beads (μ Drop) α:μ droplet contact angle d: diameter of single continuous reinforcing fiber L: Length of the resin ball (μ drop) in the fiber axial direction of the continuous reinforcing fiber

Claims

1. Contains continuous reinforcing fibers and a thermoplastic resin, A method for producing a continuous fiber reinforced resin composite material, wherein the acoustic emission (AE) count A calculated by the following formula is 0.30 or less, (AE count A) = (number of AE signals with an amplitude of 40 dB or more and a duration of 3500 μsec or less) / (total number of AE signals) treating the continuous reinforcing fibers with a surface treatment agent that includes a binder to produce continuous reinforcing fibers that include a surface treatment agent; A method for producing a continuous fiber reinforced resin composite material, characterized in that the interfacial volume of the continuous fiber reinforced resin composite material is 100,000 m -1 or more, the heating rate is 200 to 330°C / min, the cooling rate is 10 to 120°C / min, and the difference in SP value between the binder and the thermoplastic resin is 0.01 to 5.

2. 2. The method for producing a continuous fiber reinforced resin composite material according to claim 1, wherein the number of AE signals having an amplitude of 40 dB or more and a duration of 3500 μsec or less is 600 or less.

3. The method for producing a continuous fiber reinforced resin composite material according to claim 1 or 2, wherein the number of AE signals having an amplitude of 25 to 30 dB and a duration of 1000 μsec or less is 200 or more.

4. The method for producing a continuous fiber reinforced resin composite material according to any one of claims 1 to 3, wherein the AE count B calculated by the following formula is 0.12 or more. (AE count B) = (number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 μsec or less) / (total number of AE signals)

5. The method for producing a continuous fiber reinforced resin composite material according to any one of claims 1 to 4, wherein the total number of AE signals is 2000 or more.

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