Continuous fiber reinforced resin composite material and its manufacturing method

Abstract

To provide a continuous fiber-reinforced resin composite material having an excellent balance between a water absorption property and fluidity, and a method for manufacturing the same.SOLUTION: There is provided a continuous fiber-reinforced resin composite material containing a continuous reinforced fiber and a thermoplastic resin. When a 1H-NMR measurement of the continuous fiber-reinforced resin composite gives a peak A2.6-2.8 having a peak top at 2.6 to 2.8 ppm, and a peak B5.2-5.8 having a peak top at 5.2 to 5.8 ppm, and when an integrated intensity of the peak A2.6-2.8 is set to 1, an integrated intensity of the peak B5.2-5.8 is 0.5 to 3.0, and the number of peaks having peak tops between 1.7 and 2.0 ppm is 1 or less.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 for structural parts, pressure vessels, tubular structures, etc. In particular, from the viewpoint of strength, continuous fiber reinforced resin composite materials in which the reinforcing fiber is continuous fiber are desired. 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 the difference between the melting point and crystallization temperature of the resin material (see, for example, Patent Document 2 below), those that add an organic salt to the resin material (see, for example, Patent Document 3 below), those that laminate a molding precursor fabric with a thermoplastic resin (see, for example, Patent Document 4 below), and those that utilize a modified interface between the continuous reinforcing fibers and the resin material (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, as a result of intensive research conducted by the present inventors, it was found that in the continuous fiber reinforced resin composite materials of the prior art, the balance between the concentrations of amide groups and amino terminal groups contained in the continuous fiber reinforced resin composite materials was not sufficient, and there was room for improvement in the balance between water absorption properties and fluidity.

[0005] In view of the state of the prior art, the problem to be solved by the present invention is to provide a continuous fiber reinforced resin composite material having an excellent balance between water absorption properties and fluidity, and a method for producing the same. [Means for solving the problem]

[0006] As a result of extensive research and experiments to solve this problem, the inventors have unexpectedly discovered that a continuous fiber-reinforced resin composite material with an excellent balance between water absorption properties and fluidity can be obtained by setting the ratio of integrated intensities of the peak having a peak top at 2.6 to 2.8 ppm to the peak having a peak top at 5.2 to 5.8 ppm, and the number of peaks having a peak top at 1.7 to 2.0 ppm, within specific ranges, and have thus completed the present invention.

[0007] That is, the present invention is as follows. [1] A continuous fiber reinforced resin composite material containing continuous reinforcing fibers and a thermoplastic resin, the continuous reinforcing fibers are glass fibers, the thermoplastic resin is a polyamide-based resin, The continuous fiber reinforced resin composite material 1 In H-NMR measurements, Peak A with a peak top at 2.6 to 2.8 ppm 2.6~2.8 and peak B, which has a peak top at 5.2 to 5.8 ppm. 5.2~5.8 and the peak A 2.6~2.8 When the integrated intensity of peak B is set to 1, 5.2~5.8 The integrated intensity is 0.5 to 3.0, There is one or less peak with a peak top between 1.7 and 2.0 ppm. A continuous fiber reinforced resin composite material. [2] The peak having a peak top at 1.7 to 2.0 ppm is a peak C having a peak top at 1.9 to 2.0 ppm. 1.9~2.0 and Peak C 1.9~2.0 When the integrated intensity of the peak A is set to 1, 2.6~2.8 The continuous fiber reinforced resin composite material according to [1], wherein the integrated strength is 1.0 to 3.0. [3] The continuous fiber reinforced resin composite material 1 In H-NMR measurement, peak D with a peak top at 8.0 to 8.1 ppm 8.0~8.1 and peak E having a peak top at 2.4 ppm or more and less than 2.6 ppm. 2.4以上2.6未満 and the peak A 2.6~2.8 When the integrated intensity of the peak D is set to 1, 8.0~8.1 and the integrated intensity of the peak E 2.4以上2.6未満 and the integrated intensity of the continuous fiber reinforced resin composite material according to [1] or [2], wherein the sum of the integrated intensity of the continuous fiber reinforced resin composite material and the integrated intensity of the continuous fiber reinforced resin composite material is 1.0 to 3.0. [4] Peak A 2.6~2.8 When the integrated intensity of the peak E is set to 1, 2.4以上2.6未満 The continuous fiber reinforced resin composite material according to [3], wherein the integrated strength is 1.5 to 3.0. [5] The continuous fiber reinforced resin composite material according to any one of [1] to [4], wherein the glass fibers are glass fibers to which a sizing agent is attached. [6] The continuous fiber reinforced resin composite material according to [5], wherein the sizing agent contains a silane coupling agent of an aminosilane. [7] The continuous fiber reinforced resin composite material according to [5], wherein the sizing agent contains γ-aminopropyltrimethoxysilane. [ 8 ] [1]~[ 7

[0023] A method for producing a continuous fiber reinforced resin composite material according to any one of [1] to

[10] , The thermoplastic resin 1 In H-NMR measurements, Peak a with a peak top at 2.6-2.8 ppm 2.6~2.8 and peak b with a peak top at 5.2 to 5.8 ppm. 5.2~5.8 and the peak a 2.6~2.8When the integrated intensity of the peak b is set to 1, 5.2~5.8 The integrated intensity is 0.5 to 3.0, There is one or less peak with a peak top between 1.7 and 2.0 ppm. A method for producing a continuous fiber reinforced resin composite material, comprising: [ 9 ] The peak a of the thermoplastic resin 2.6~2.8 When the integrated intensity of the peak b is set to 1, 5.2~5.8 The integrated intensity of the peak A of the continuous fiber reinforced resin composite material 2.6~2.8 When the integrated intensity of the peak B is set to 1, 5.2~5.8 is 0.8 to 1.2 times the integrated intensity of 8 ] A method for producing a continuous fiber reinforced resin composite material according to the present invention. [ 10 ] The continuous fiber reinforced resin composite material 1 In H-NMR measurement, peak D with a peak top at 8.0 to 8.1 ppm 8.0~8.1 and peak E having a peak top at 2.4 ppm or more and less than 2.6 ppm. 2.4以上2.6未満 There are some things that The thermoplastic resin 1 In H-NMR measurement, peak d has a peak top at 8.0 to 8.1 ppm. 8.0~8.1 and peak e having a peak top between 2.4 ppm and 2.6 ppm. 2.4以上2.6未満 There are some things that The peak d of the thermoplastic resin 8.0~8.1 and the integrated intensity of the peak e 2.4以上2.6未満 The sum of the integrated intensity of peak b and the integrated intensity of peak b is set to 1. 5.2~5.8 The integrated intensity of the peak D of the continuous fiber reinforced resin composite material 8.0~8.1 and the integrated intensity of the peak E 2.4以上2.6未満 The sum of the integrated intensity of peak B and the integrated intensity of peak B is set to 1. 5.2~5.8 is 0.2 to 0.9 times the integrated intensity of 8 ] or [ 9 ] A method for producing a continuous fiber reinforced resin composite material according to the present invention. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a continuous fiber reinforced resin composite material having an excellent balance between water absorption properties and fluidity, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content.

[0010] [Continuous fiber reinforced resin composite material] In this specification, the continuous fiber reinforced resin composite material of this embodiment may be simply referred to as a "composite material." The continuous fiber reinforced resin composite material of this embodiment is a continuous fiber reinforced resin composite material containing continuous reinforcing fibers and a thermoplastic resin, and 1 In H-NMR measurement, peak A has a peak top at 2.6 to 2.8 ppm. 2.6~2.8 and peak B, which has a peak top at 5.2 to 5.8 ppm. 5.2~5.8 Peak A 2.6~2.8 When the integrated intensity of peak B is set to 1, 5.2~5.8 The integrated intensity is 0.5 to 3.0, and the number of peaks having a peak top at 1.7 to 2.0 ppm is one or less. Peak A 2.6~2.8 Peak B when the integrated intensity of 5.2~5.8 The integrated intensity is preferably 1.0 to 2.0, and more preferably 1.22 to 1.5. Peak A 2.6~2.8 Peak B when the integrated intensity of 5.2~5.8 When the integrated intensity and the number of peaks having peak tops at 1.7 to 2.0 ppm are within the above ranges, the resulting continuous fiber reinforced resin composite material has an excellent balance between water absorption properties and fluidity.

[0011] Peak A 2.6~2.8 Peak B when the integrated intensity of 5.2~5.8Examples of methods for adjusting the integrated intensity of the continuous fiber reinforced resin composite material within the above range include adjusting the amide group concentration of the thermoplastic resin that is the material for the continuous fiber reinforced resin composite material. Specifically, the amide group concentration per mol of the thermoplastic resin is preferably 80 to 300 / mol, more preferably 90 to 200 / mol, or the amide group concentration per gram of the thermoplastic resin is preferably 5.5 to 9.9 mmol / g, more preferably 6.5 to 9.0 mmol / g. Another method includes adjusting the ratio of the amide group concentration to the amino terminal group concentration of the thermoplastic resin that is the material for the continuous fiber reinforced resin composite material. The amide group concentration is preferably 100 to 500 times, more preferably 150 to 300 times, the amino terminal group concentration. Furthermore, a coupling agent contained in a bundling agent added to the continuous reinforcing fibers may be used that has reactive terminal groups that are poorly reactive with the amino groups of the thermoplastic resin. The use of such a coupling agent can improve the peak A intensity. 2.6~2.8 Peak B versus integrated intensity of 5.2~5.8 The integrated intensity of the ion beam tends to decrease. In addition, examples of a method for adjusting the number of peaks having a peak top at 1.7 to 2.0 ppm to one or less include a method of purifying a thermoplastic resin, which is a material for the continuous fiber reinforced resin composite material, to remove impurities.

[0012] In the continuous fiber reinforced resin composite material of this embodiment, when there is one peak having a peak top at 1.7 to 2.0 ppm, the peak is a peak C having a peak top at 1.9 to 2.0 ppm. 1.9~2.0 It is preferable that: Further, the continuous fiber reinforced resin composite material of this embodiment is 1 In H-NMR measurement, peak C 1.9~2.0 If there is a peak C 1.9~2.0 When the integrated intensity of peak A is set to 1, 2.6~2.8 The integrated intensity is preferably 1.0 to 3.0, more preferably 1.5 to 3.0, and even more preferably 1.5 to 2.0. Peak C 1.9~2.0 Peak A when the integrated intensity of 2.6~2.8When the integrated strength is within the above range, the continuous fiber reinforced resin composite material tends to have excellent fluidity. Peak C 1.9~2.0 Peak A when the integrated intensity of 2.6~2.8 Examples of methods for adjusting the integrated intensity of peak C to within the above range include a method for adjusting the molecular weight of the thermoplastic resin and a method for adjusting the amount of end-capping of the thermoplastic resin. The higher the molecular weight of the thermoplastic resin is, or the lower the amount of end-capping of the thermoplastic resin is, the more the integrated intensity of peak C is. 1.9~2.0 Peak A when the integrated intensity of 2.6~2.8 The integrated intensity of tends to be large.

[0013] The continuous fiber reinforced resin composite material of this embodiment is 1 In H-NMR measurement, peak D with a peak top at 8.0 to 8.1 ppm 8.0~8.1 and peak E having a peak top at 2.4 ppm or more and less than 2.6 ppm. 2.4以上2.6未満 Peak A 2.6~2.8 When the integrated intensity of peak D is set to 1, 8.0~8.1 Integrated intensity and peak E 2.4以上2.6未満 The sum of the integrated intensity is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and even more preferably 1.0 to 1.5. Peak A 2.6~2.8 Peak D when the integrated intensity of 8.0~8.1 Integrated intensity and peak E 2.4以上2.6未満 When the sum of the integrated strength and the water absorption property is within the above range, the continuous fiber reinforced resin composite material tends to have an excellent balance between water absorption property and fluidity. Peak A 2.6~2.8 Peak D when the integrated intensity of 8.0~8.1 Integrated intensity and peak E 2.4以上2.6未満 and the integrated intensity of peak A are adjusted to fall within the above range, for example, by adjusting the balance of the end groups of the thermoplastic resin, or by adjusting the amount of end-capping of the thermoplastic resin. With regard to the balance of the end groups of the thermoplastic resin, the more the amount of carboxyl end groups is increased or the more the amount of end-capping of the thermoplastic resin is decreased, the more the peak A 2.6~2.8 Peak D when the integrated intensity of 8.0~8.1Integrated intensity and peak E 2.4以上2.6未満 The sum of the integrated intensity of the

[0014] The continuous fiber reinforced resin composite material of this embodiment is 1 In H-NMR measurement, peak A 2.6~2.8 When the integrated intensity of peak E is set to 1, 2.4以上2.6未満 The integrated intensity is preferably 1.5 to 3.0, more preferably 2.0 to 3.0, and even more preferably 2.5 to 3.0. Peak A 2.6~2.8 When the integrated intensity of peak E is set to 1, 2.4以上2.6未満 When the integrated strength is within the above range, the continuous fiber reinforced resin composite material tends to have an excellent balance between water absorption properties and fluidity. Peak A 2.6~2.8 When the integrated intensity of peak E is set to 1, 2.4以上2.6未満 As a method for adjusting the integrated intensity of peak A to be within the above range, for example, a method for adjusting the balance of the terminal groups of the thermoplastic resin can be mentioned. With regard to the balance of the terminal groups of the thermoplastic resin, the more the amount of carboxyl terminal groups is increased, the more the integrated intensity of peak A 2.6~2.8 When the integrated intensity of peak E is set to 1, 2.4以上2.6未満 The integrated intensity of tends to be large.

[0015] In the present disclosure, the continuous fiber reinforced resin composite material 1 For H-NMR measurements, the continuous fiber reinforced resin composite material was dissolved in a solvent consisting of a 1:1 mixture of deuterated sulfuric acid and deuterated trifluoroacetic acid by mass ratio, and the resulting solution was analyzed by nuclear magnetic resonance spectroscopy. 1 It can be obtained by H-NMR measurement (see JP 2020-56773 A), and specifically, it can be measured by the method described in the examples below. As for the nuclear magnetic resonance apparatus and the number of accumulations, it is preferable to use a high-resolution nuclear magnetic resonance apparatus with an accumulation number of 512, and it is more preferable to use a superconducting pulse Fourier transform type with a frequency of 500 MHz with an accumulation number of 512. In addition, the above peak A 2.6~2.8 , Peak B 5.2~5.8 , Peak C 1.9~2.0 , Peak D8.0~8.1 , Peak E 2.4以上2.6未満 For each of the above, if there are multiple peaks (for example, if there are two peaks with peak tops at 2.6 to 2.8 ppm), it is possible that there are peaks derived from the thermoplastic resin and peaks derived from impurities contained in the thermoplastic resin. Therefore, the peak derived from the thermoplastic resin can be identified from the integrated intensity ratio with other peaks (for example, peaks derived from the main chain skeleton of the thermoplastic resin), or the amount of terminal groups can be quantified by neutralization titration or the like and each peak can be identified to match the amount, or the thermoplastic resin can be purified to remove impurities so that only the peak derived from the thermoplastic resin can be seen, thereby identifying the peak derived from the thermoplastic resin as Peak A. 2.6~2.8 , Peak B 5.2~5.8 , Peak C 1.9~2.0 , Peak D 8.0~8.1 , Peak E 2.4以上2.6未満 It is assumed that the peaks are

[0016] (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, knitted, braided or pipe-shaped continuous reinforcing fiber is combined with a thermoplastic resin, a form in which continuous reinforcing fibers aligned in one direction are combined with a thermoplastic resin, a form in which threads made of continuous reinforcing fibers and a thermoplastic resin are aligned in one direction and molded, and a form in which threads made of continuous reinforcing fibers and a thermoplastic resin are molded into a woven, knitted, braided or pipe-shaped fabric. 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, and in this case, the cross section of the continuous fiber reinforced resin composite material perpendicular to the length direction of the continuous reinforcing fibers may be the thickness direction cross section of the continuous fiber reinforced resin composite material. 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. Examples of the form of the intermediate material before molding of the continuous fiber reinforced resin composite material 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 core material made of a bundle of continuous reinforcing fibers braided with resin fibers, and reinforcing fibers pre-impregnated with resin.

[0017] (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. For example, the substrate that constitutes the continuous fiber reinforced resin composite material (e.g., a substrate made of continuous reinforcing fibers, a substrate made of thermoplastic resin) 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.

[0018] 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. The substrate may be shaped by any method, for example, into a sheet shape.

[0019] After the substrate is set in the mold, the mold is closed and compressed. Then, the temperature of the mold is adjusted to a temperature equal to or higher than the melting point of the thermoplastic resin constituting the continuous fiber reinforced resin composite material, to melt 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. In addition, the mold may be clamped once 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 the thermoplastic resin used does not undergo thermal degradation, but from the viewpoint of productivity, it is preferably within 2 minutes, more preferably within 1 minute.

[0020] 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 and the predetermined thermoplastic resin composition for hybrid use to form a hybrid composite material.

[0021] The timing of injection of the specified thermoplastic resin composition for hybrid use greatly affects the interfacial strength between the two thermoplastic resins, and the timing of injection of the specified thermoplastic resin composition for hybrid use is preferably within 30 seconds after the substrate is set in the mold, the mold is closed, and the mold temperature is raised to or above the melting point or glass transition temperature of the thermoplastic resin constituting the substrate. The mold temperature when injecting and filling a predetermined thermoplastic resin composition for hybrid use is preferably equal to or higher than the melting point or glass transition temperature of the thermoplastic resin constituting the substrate to be bonded with the thermoplastic resin composition for hybrid use, more preferably equal to or higher than the melting point or glass transition temperature of the thermoplastic resin constituting the substrate to be bonded with the thermoplastic resin composition for hybrid use + 10°C, even more preferably equal to or higher than the melting point or glass transition temperature + 20°C, and even more preferably equal to or higher than the melting point or glass transition temperature + 30°C.

[0022] 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.

[0023] (Hybrid thermoplastic resin composition for injection molding) 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. Thermoplastic resins contained in the thermoplastic resin composition for hybrids include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, acrylic resins, styrene-based resins, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyphenylene ether, modified polyphenylene ether resins, wholly aromatic polyesters, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide-based resins, polysulfone, polyetheretherketone, and mixtures of two or more of polyetherketones.

[0024] 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, a sizing agent similar to that applied to the continuous reinforcing fibers constituting the continuous fiber reinforced resin composite material of this embodiment may be used. The sizing agent preferably comprises a silane coupling agent, a lubricant, and a binder. The types of silane coupling agent, lubricant, and binder can be the same as those of the binder for continuous reinforcing fibers described below.

[0025] 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.

[0026] 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 around the placed substrate on all four sides and the substrate is pressed and molded using a double belt press, and 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 placed in the compression molding machines in order to mold the molds.

[0027] (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.

[0028] The content of the continuous reinforcing fibers relative to 100 parts by mass of the thermoplastic resin is preferably 90 to 525 parts by mass, more preferably 150 to 340 parts by mass, and even more preferably 200 to 300 parts by mass. The volume fraction Vf (%) of continuous reinforcing fibers in the continuous fiber reinforced resin composite material is preferably 30 to 70%, more preferably 35 to 65%, and even more preferably 40 to 60%.

[0029] -Sizing agent- When glass fibers are selected as the continuous reinforcing fibers, a sizing agent may be used. The sizing agent may contain one or more selected from the group consisting of a silane coupling agent, a lubricant, and a binder, and preferably contains at least a binder or a silane coupling agent, and more preferably consists of a silane coupling agent, a lubricant, and a binder. By using a sizing agent that forms a strong bond with the resin coating around the continuous reinforcing fibers, a continuous fiber-reinforced resin composite material with low porosity can be obtained. 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.

[0030] --Silane coupling agent-- Silane coupling agents are usually used as surface treatment agents for glass 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 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 such as γ-aminopropyltrimethoxysilane, maleic acids, and epoxysilanes are preferred.

[0031] --Lubricant-- The lubricant contributes to improving the opening property of the 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.

[0032] --Binding agent-- The binder contributes to improving the bundling property of the 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 with other 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 the glass fibers, it is preferably 3,000 or more, and from the viewpoint of improving the properties of a composite material, it is preferably 50,000 or less.

[0033] 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. 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.

[0034] 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 the emulsifier component or eliminating the need for an emulsifier when the sizing agent is attached to the 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.

[0035] 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, 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.

[0036] 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. The copolymerization ratio of the olefinic monomer and the monomer copolymerizable with the olefinic monomer is preferably 60 to 95 mass% of the olefinic monomer and 5 to 40 mass% of the monomer copolymerizable with the olefinic monomer, and more preferably 70 to 85 mass% of the olefinic monomer and 15 to 30 mass% of the monomer copolymerizable with the olefinic monomer, where the total mass of the copolymerization components is 100 mass%. If the olefinic monomer is 60 mass% or more, the affinity with the matrix is ​​good, and if the mass% of the olefinic 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.

[0037] 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 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 the 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.

[0042] 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 binder being 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, and salts of these with primary, secondary, and tertiary amines.

[0043] When the sizing agent is composed of a silane coupling agent and a binder, the sizing agent is applied and attached in an amount of preferably 0.1 to 3 mass%, more preferably 0.2 to 2 mass%, and even more preferably 0.2 to 1 mass% as the total mass of the silane coupling agent and binder relative to 100 mass% of the glass fibers. From the viewpoint of controlling the bundling ability of the glass fibers and improving the interfacial adhesive strength, the amount of the sizing agent applied is preferably 0.1 mass% or more as the total mass of the silane coupling agent and binder relative to 100 mass% of the glass fibers, and from the viewpoint of yarn handleability, it is preferably 3 mass% or less. Furthermore, when the sizing agent is composed of a silane coupling agent, a lubricant, and a binder, the sizing agent is applied and attached in an amount of preferably 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 the glass fibers, as the total mass of the silane coupling agent, lubricant, and binder. From the viewpoint of controlling the bundling ability of the glass fibers and improving the interfacial adhesive strength, the amount of the sizing agent applied is preferably 0.1 mass% or more based on 100 mass% of the glass fibers, as the total mass of the silane coupling agent, lubricant, and binder, and from the viewpoint of yarn handleability, it is preferably 3 mass% or less.

[0044] --Composition of sizing agent for glass fibers-- When glass fibers are used as the continuous reinforcing fibers, the glass fiber sizing agent preferably contains 0.1 to 2 mass% of a silane coupling agent, 0.01 to 1 mass% of a lubricant, and 1 to 25 mass% of a binder, and these components are preferably diluted with water to adjust the total mass to 100 mass%. 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 %, from the viewpoints of improving the glass fiber bundling ability, improving the interfacial adhesive strength, and improving the mechanical strength of the composite material. The reactive terminal group of the silane coupling agent preferably has poor reactivity with an amino group, and is particularly preferably an amino group.

[0045] 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% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of improving the interfacial adhesive strength and the mechanical strength of the composite material. The blending amount of the binder in the sizing agent for glass fibers 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 material.

[0046] --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.

[0047] Similarly, when carbon fibers are selected as the continuous reinforcing fibers, a sizing agent may be used, and the sizing agent preferably comprises a 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 the binder. The type of sizing agent used for the carbon fibers is not particularly limited, and any known agent can be used. Specifically, for example, the agent described in JP 2015-101794 A can be used.

[0048] 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.

[0049] - Shape of continuous reinforcing fiber - The continuous reinforcing fiber is a multifilament consisting of multiple filaments, and from the viewpoint of handleability, the number of single filaments is preferably 30 to 15,000. From the viewpoints of strength and handleability, the single filament diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, even more preferably 6 to 20 μm, and most preferably 8 to 18 μm. 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.

[0050] The density D can be measured using 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

[0051] 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.

[0052] Continuous reinforcing fibers, such as 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, and passing the filaments through a spinning machine before being wound into a direct wound roving (DWR), cake, twisted yarn, or other wound form. While any form of continuous reinforcing fiber is acceptable, winding into a yarn, cake, or DWR is preferred because it increases productivity and production stability in the resin coating process. From the viewpoint of productivity, DWR is most preferred.

[0053] The form of the continuous reinforcing fibers is not particularly limited, and various forms can be mentioned, such as woven fabrics, knitted fabrics, braided cords, pipe-shaped products, non-crimp fabrics, unidirectional materials, etc. Among these, woven fabrics, non-crimp fabrics, and unidirectional materials are preferably used.

[0054] (thermoplastic resin) The thermoplastic resin constituting the continuous fiber reinforced resin composite material of this embodiment is 1 In H-NMR measurement, peak a with a peak top at 2.6 to 2.8 ppm 2.6~2.8 and peak b with a peak top at 5.2 to 5.8 ppm. 5.2~5.8 and peak a 2.6~2.8 When the integrated intensity of peak b is set to 1, 5.2~5.8 It is preferable that the integrated intensity is 0.5 to 3.0 and that there is one or less peaks having a peak top at 1.7 to 2.0 ppm. Above peak a 2.6~2.8 Peak b when the integrated intensity of is set to 1 5.2~5.8 The integrated intensity is more preferably 1.0 to 2.0, and further preferably 1.1 to 1.4. Peak a 2.6~2.8 Peak b when the integrated intensity of is set to 1 5.2~5.8 When the integrated intensity and the number of peaks having peak tops at 1.7 to 2.0 ppm are within the above ranges, the balance between the water absorption property and the fluidity of the continuous fiber reinforced resin composite material can be improved.

[0055] Peak a 2.6~2.8 Peak b when the integrated intensity of is set to 15.2~5.8 The integrated intensity of the thermoplastic resin may be adjusted to fall within the above range by, for example, adjusting the amide group concentration of the thermoplastic resin. Specifically, the amide group concentration per 1 mol of the thermoplastic resin is preferably 80 to 300 / mol, more preferably 90 to 200 / mol, or the amide group concentration per 1 g of the thermoplastic resin is preferably 5.5 to 9.9 mmol / g, more preferably 6.5 to 9.0 mmol / g. Another example is a method of adjusting the ratio of the amide group concentration to the amino terminal group concentration of the thermoplastic resin. The amide group concentration is preferably 100 to 500 times, more preferably 150 to 300 times, the amino terminal group concentration. In addition, examples of a method for adjusting the number of peaks having a peak top at 1.7 to 2.0 ppm to one or less include a method of purifying a thermoplastic resin to remove impurities.

[0056] The thermoplastic resin constituting the continuous fiber reinforced resin composite material of this embodiment is 1 Peak a in H-NMR measurement 2.6~2.8 Peak b when the integrated intensity of is set to 1 5.2~5.8 The integral strength of the continuous fiber reinforced resin composite material 1 Peak A in H-NMR measurement 2.6~2.8 Peak B when the integrated intensity of 5.2~5.8 The integrated intensity is preferably 0.8 to 1.2 times, more preferably 0.8 to 1.0 times, and even more preferably 0.9 to 1.0 times the integrated intensity of the sample. Peak a 2.6~2.8 Peak b when the integrated intensity of is set to 1 5.2~5.8 The integrated intensity of peak A 2.6~2.8 Peak B when the integrated intensity of 5.2~5.8 When the integrated intensity of Peak a is within the above range, there is little change in the amino terminals of the thermoplastic resin caused by the reaction between the continuous reinforcing fibers and the thermoplastic resin during the production of the composite material, and the resulting continuous fiber reinforced resin composite material tends to have an excellent balance between water absorption properties and fluidity. 2.6~2.8 Peak b when the integrated intensity of is set to 1 5.2~5.8 The integrated intensity of peak A 2.6~2.8 Peak B when the integrated intensity of5.2~5.8 As the integrated intensity increases, the molecular weight of the thermoplastic resin decreases, the fluidity changes, and the composite material tends to have increased water absorption. Above Peak A 2.6~2.8 Peak B when the integrated intensity of 5.2~5.8 Peak a versus integrated intensity 2.6~2.8 Peak b when the integrated intensity of is set to 1 5.2~5.8 As a method for adjusting the integrated intensity to fall within the above range, for example, a method of using a coupling agent having an amino group can be mentioned.

[0057] The thermoplastic resin constituting the continuous fiber reinforced resin composite material of this embodiment is 1 In H-NMR measurement, peak d has a peak top at 8.0 to 8.1 ppm. 8.0~8.1 and peak e having a peak top between 2.4 ppm and 2.6 ppm. 2.4以上2.6未満 and the peak d 8.0~8.1 and the integrated intensity of the peak e 2.4以上2.6未満 When the sum of the integrated intensity of the peak and the peak is set to 1, the peak b 5.2~5.8 The integrated intensity of the peak D of the continuous fiber reinforced resin composite material 8.0~8.1 and the integrated intensity of the peak E 2.4以上2.6未満 When the sum of the integrated intensity of the peak and the peak is set to 1, 5.2~5.8 The integrated intensity is preferably 0.2 to 0.9 times, more preferably 0.7 to 0.9 times, and even more preferably 0.8 to 0.9 times the integrated intensity of the sample. Peak d 8.0~8.1 Integrated intensity and peak e 2.4以上2.6未満 Peak b when the sum of the integrated intensity of 5.2~5.8 The integrated intensity of peak D 8.0~8.1 Integrated intensity and peak E 2.4以上2.6未満 Peak B when the sum of the integrated intensity of 5.2~5.8 When the integral strength is within the above range, the continuous reinforcing fibers and the thermoplastic resin are well bonded together during the production of the composite material, improving the strength, and the gaps between the continuous reinforcing fibers and the thermoplastic resin are reduced, tending to improve the water absorption properties. Peak D 8.0~8.1 Integrated intensity and peak E2.4以上2.6未満 Peak B when the sum of the integrated intensity of 5.2~5.8 Peak d for the integrated intensity of 8.0~8.1 Integrated intensity and peak e 2.4以上2.6未満 Peak b when the sum of the integrated intensity of 5.2~5.8 The method for adjusting the integrated intensity of peak D to the above range includes, for example, using a coupling agent having an amino group, adjusting the amide group concentration of the thermoplastic resin contained in the continuous fiber reinforced resin composite material and the balance between the amide group concentration and the amino group concentration, and adjusting the molecular weight of the thermoplastic resin. The higher the amide group concentration of the thermoplastic resin or the higher the molecular weight of the thermoplastic resin, the higher the integrated intensity of peak D 8.0~8.1 Integrated intensity and peak E 2.4以上2.6未満 Peak B when the sum of the integrated intensity of 5.2~5.8 Peak d for the integrated intensity of 8.0~8.1 Integrated intensity and peak e 2.4以上2.6未満 Peak b when the sum of the integrated intensity of 5.2~5.8 The integrated intensity of tends to be large.

[0058] In the present disclosure, the thermoplastic resin 1 For H-NMR measurements, the thermoplastic resin was dissolved in a solvent consisting of a 1:1 mixture of deuterated sulfuric acid and deuterated trifluoroacetic acid by mass ratio, and the resulting solution was analyzed by nuclear magnetic resonance spectroscopy. 1 It can be obtained by H-NMR measurement (see JP 2020-56773 A), and specifically, it can be measured by the method described in the examples below. As for the nuclear magnetic resonance apparatus and the number of accumulations, it is preferable to use a high-resolution nuclear magnetic resonance apparatus with an accumulation number of 512, and it is more preferable to use a superconducting pulse Fourier transform type with a frequency of 500 MHz with an accumulation number of 512. In addition, the above peak a 2.6~2.8 , peak b 5.2~5.8 , peak d 8.0~8.1 , peak e 2.4以上2.6未満For each of the above, if there are multiple peaks (for example, if there are two peaks with peak tops at 2.6 to 2.8 ppm), it is possible that there are peaks derived from the thermoplastic resin and peaks derived from impurities contained in the thermoplastic resin. Therefore, the peak derived from the thermoplastic resin can be identified from the integrated intensity ratio with other peaks (for example, peaks derived from the main chain skeleton of the thermoplastic resin), or the thermoplastic resin can be purified to remove impurities so that only the peak derived from the thermoplastic resin can be seen, thereby identifying the peak derived from the thermoplastic resin as peak a. 2.6~2.8 , peak b 5.2~5.8 , peak d 8.0~8.1 , peak e 2.4以上2.6未満 It is assumed that the peaks are

[0059] The thermoplastic resin preferably has a number average molecular weight (Mn) of 10,000 to 35,000, more preferably 10,000 to 25,000, and even more preferably 12,000 to 23,000. When the number average molecular weight (Mn) is in the above range, Peak A 2.6~2.8 When the integrated intensity of peak B is set to 1, 5.2~5.8 The integrated intensity tends to be adjusted to be 0.5 to 3.0. The number average molecular weight (Mn) of the thermoplastic resin can be measured by GPC (gel permeation chromatography), specifically by the method described in the examples below.

[0060] 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.

[0061] 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.

[0062] -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.

[0063] -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.

[0064] 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.

[0065] Examples of polyamide-based 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, and polyamide 612; semi-aromatic polyamides such as polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide); 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.

[0066] [Additives] The continuous fiber-reinforced resin composite material of this embodiment may contain additives as needed, such as colorants, antidegradants, 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 content of the additive may be 3% by mass or less relative to 100% by mass of the composite material.

[0067] (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.

[0068] (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, it can be used for, but is 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.

[0069] [Composite material molding] The continuous fiber reinforced resin composite material of this embodiment can be further molded by, for example, cutting the continuous fiber reinforced resin composite material of this embodiment to a predetermined size, heating it with an infrared heater, and then hot-compressing and pressing it with a press molding machine. [Example]

[0070] 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 in various modified forms within the scope of the gist of the present invention.

[0071] First, the measurement methods used in the examples and comparative examples will be described.

[0072] [ 1 H-NMR measurement] The thermoplastic resins and continuous fiber reinforced resin composite materials used in each example and comparative example were as follows: 1 H-NMR measurements were carried out. <Preparation of mixed solvent> Mixed solvent 1 was obtained by mixing 5 g of deuterated sulfuric acid (manufactured by Tokyo Chemical Industry Co., Ltd., Sulfuric Acid-d2, 98 atom% D) and 5 g of deuterated trifluoroacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., Trifluoroacetic acid-d; TFA-d, 99.5 atom% D) in a glass container. <Dissolution process> 20 mg of sample and 1:1 g of mixed solvent were added to a 10 mL glass container, and the mixture was stirred by shaking for 30 minutes to prepare a solution with no insoluble matter. < 1 H-NMR measurement> The solution in the glass container prepared in the dissolution process was transferred to a 5 mm diameter tube for nuclear magnetic resonance spectroscopy, and the solution was analyzed using a 500 MHz NMR device (JEOL-ECZ500+Super Cool, manufactured by JEOL). 1 H-NMR spectrum was measured under the following conditions. (Measurement conditions) Resonance frequency: 500MHz Pulse width: 3.9 μsec Wait time: 10.0 seconds Accumulation count: 512 times Criteria: Methylene group protons of main chain amine at 3.04 ppm. If no methylene group protons of main chain amine at 3.04 ppm are detected, the methylene group protons of main chain amine at 3.30 ppm Temperature: room temperature

[0073] [Number average molecular weight] The number-average molecular weight (Mn) of the thermoplastic resins used in each Example and Comparative Example was measured by GPC (gel permeation chromatography, HLC-8020; Tosoh Corporation) using hexafluoroisopropanol as a solvent and a polymethyl methacrylate molecular weight conversion standard sample (Polymer Laboratory Co., Ltd.). The GPC columns used were TSK-GEL, GMHHR-M, and G1000HHR.

[0074] [Amino end group concentration] For the thermoplastic resins used in each of the Examples and Comparative Examples, the amount of amino terminals bound to the polymer terminals was measured by neutralization titration as follows. 4.0 g of thermoplastic resin was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1 N NaOH to determine the amount of amino terminals (μequivalents / g). The endpoint was determined from the color change of the phenolphthalein indicator.

[0075] [Amide group concentration] The number of amide groups per unit of the main chain skeleton of the thermoplastic resin used in each Example and Comparative Example was defined as A, and the formula weight was defined as B. The amide group concentration per 1 mol of thermoplastic resin ( / mol) and the amide group concentration per 1 g of thermoplastic resin (mol / g) were calculated using the following formulas, where the atomic weight of carbon was 12, the atomic weight of oxygen was 18, the atomic weight of hydrogen was 1, and the atomic weight of nitrogen was 14. (Amide group concentration per 1 mol of thermoplastic resin) = A × Mn / B (Amide group concentration per 1g of thermoplastic resin) = A / B

[0076] [Water absorption properties] A rectangular test piece measuring 100 mm in length, 10 mm in width, and 2 mm in thickness was cut out from the continuous fiber reinforced resin composite material, and the test piece was dried in a vacuum dryer at 80°C for 18 hours or more to obtain the dry test piece. In addition, strip-shaped test pieces measuring 100 mm in length, 10 mm in width, and 2 mm in thickness were cut out from the continuous fiber reinforced resin composite material, and immersed in a constant temperature water bath at 80°C for 18 hours. The test pieces were then placed in a constant temperature and humidity bath at 80°C and 70% RH for 150 hours to obtain the test pieces after water absorption. For the test pieces in the dry and water-absorbed state, the bending strength (MPa) was measured using an Instron universal testing machine with a three-point bending jig, with the span set to thickness x 16 (mm), at a speed of 1 mm / min, under an environment of 23°C and 50% RH, and the bending strength retention (%) upon water absorption was calculated using the following formula. Bending strength retention rate when absorbing water = (bending strength when absorbing water / bending strength when dry) x 100

[0077] [Liquidity] A rectangular test piece 100 mm long, 100 mm wide, and 2 mm thick was cut out from the continuous fiber reinforced resin composite material and placed in the center of a mold 150 mm square with a 1 mm clearance and equipped with a temperature sensor.The test piece was then placed in a heating press molding machine set to the melting temperature of the thermoplastic resin + 65°C of a hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons, and pressed at a pressure of 5 MPa while monitoring the temperature.The test piece was then removed from the heating press molding machine 30 seconds after the temperature reached the melting point of the thermoplastic resin, placed in a cooling press, and cooled with water at a pressure of 5 MPa. The average length and width of the test pieces after pressing were evaluated as follows: ◎ (excellent): 130 mm or more, ○ (good): 120 mm or more and less than 130 mm, △ (fair): 110 mm or more and less than 120 mm, × (unfair): less than 110 mm. When the bending strength retention rate upon water absorption was 50% or more and the fluidity was rated as ⊚ or ◯, the balance of water absorption characteristics and fluidity was judged to be excellent.

[0078] The materials used in the examples and comparative examples are as follows. [Continuous reinforcing fiber] (glass fiber) GF1: A 100% by mass glass fiber with a fineness of 1.15 g / m and 2,000 single fibers was produced by attaching 0.5% by mass of a sizing agent to the fiber. The winding method was DWR, and the average single fiber diameter was approximately 16 μm. The sizing agent was prepared by mixing 1.9% by mass of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 4.0% by mass of caranauba wax, and 0.9% by mass of a copolymer compound (a copolymer compound with a weight-average molecular weight of 17,000, obtained by copolymerizing 10% by mass of maleic anhydride and 90% by mass of methyl methacrylate) with deionized water. The coupling agent, γ-aminopropyltrimethoxysilane, had an amino terminal group that was poorly reactive with amino groups. GF2: 100% by mass of glass fiber with a fineness of 1.15 g / m and 2,000 single fibers was produced by attaching 0.5% by mass of a sizing agent. The winding method was DWR, and the average single fiber diameter was approximately 16 μm. The sizing agent was prepared by mixing 1.9% by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 4.0% by mass of caranauba wax, and 0.9% by mass of a copolymer compound (a copolymer compound with a weight-average molecular weight of 17,000, obtained by copolymerizing 10% by mass of maleic anhydride and 90% by mass of methyl methacrylate) with deionized water. The coupling agent, 3-glycidoxypropyltrimethoxysilane, had an epoxy group reactive with an amino group as a reactive terminal group. [Manufacturing method of fiber cloth] A glass cloth was produced by weaving the glass fibers as warp and weft using a rapier loom (weaving width 1 m). The weaving form of the obtained glass cloth was plain weave, with a weave density of 6.5 threads / 25 mm and a basis weight of 600 g / m. 2 It was.

[0079] [Thermoplastic resin] Resin 1: Polyamide 66 (number average molecular weight: 22,000, amino terminal group concentration: 30 μmol / g, amide group concentration per gram: 8.8 mmol / g, amide group concentration per mole: 195 / mol) Resin 2: Polyamide 6I (number average molecular weight: 11,000, amino terminal group concentration: 56 μmol / g, amide group concentration per 1 g: 8.7 mmol / g, amide group concentration per 1 mol: 98 / mol) Resin 3: Polyamide 6 (number average molecular weight: 19,000, amino terminal group concentration: 26 μmol / g, amide group concentration per gram: 8.8 mmol / g, amide group concentration per mole: 168 / mol) Resin 4: Resin 1 and Resin 2 were blended in a 2:1 mass ratio (number average molecular weight: 13,000, amino terminal group concentration: 40 μmol / g, amide group concentration per gram: 8.7 mmol / g, amide group concentration per mole: 163 / mol). Resin 5: Polyamide 612 (number average molecular weight: 15,000, amino terminal group concentration: 0 μmol / g, amide group concentration per gram: 8.8 mmol / g, amide group concentration per mole: 168 / mol) Resin 6: Polyamide 12 (number average molecular weight: 12,000, amino terminal group concentration: 60 μmol / g, amide group concentration per gram: 10.2 mmol / g, amide group concentration per mole: 125 / mol) Resin 7: Polyamide 1010 (number average molecular weight: 20,000, amino terminal group concentration: 10 μmol / g, amide group concentration per gram: 5.3 mmol / g, amide group concentration per mole: 105 / mol) Resin 8: Polyamide 66 (number average molecular weight: 34,000, amino terminal group concentration: 17 μmol / g, amide group concentration per gram: 8.8 mmol / g, amide group concentration per mole: 298 / mol)

[0080] [Method of manufacturing 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 film was 180 μm.

[0081] [Example 1] Using Resin 1, a thermoplastic resin film 1 was obtained by the above method. Also, using GF1, a glass cloth 1 was obtained by the above method. 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 continuous compression molding machine was used as the molding machine. The glass cloth 1 and the thermoplastic resin film 1 were placed on top of each other as described above and placed in the molding machine. The temperature of the heating zone in the molding machine was adjusted to 340°C, and the temperature of the cooling zone was adjusted by water cooling, and compression molding was performed at a pressure of 5 MPa and a belt speed of 0.5 m / min. The physical properties of the obtained continuous fiber reinforced resin composite material and 1 The results of H-NMR peak measurements are shown in Table 1.

[0082] [Examples 2 to 6] Continuous fiber reinforced resin composite materials were obtained in the same manner as in Example 1, except that the resins shown in Table 1 were used as the thermoplastic resins. The physical properties of the obtained continuous fiber reinforced resin composite material and 1 The results of H-NMR peak measurements are shown in Table 1. [Comparative Examples 1 and 2] Continuous fiber reinforced resin composite materials were obtained in the same manner as in Example 1, except that the resins shown in Table 1 were used as the thermoplastic resins. The physical properties of the obtained continuous fiber reinforced resin composite material and 1 The results of H-NMR peak measurements are shown in Table 1. Comparative Example 3 A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1, except that GF2 was used as the glass fiber. The physical properties of the obtained continuous fiber reinforced resin composite material and 1 The results of H-NMR peak measurements are shown in Table 1. Comparative Example 4 The same evaluation as in Example 1 was carried out for "Tepex dynalite 101" manufactured by Bond Laminate, which is a glass cloth impregnated with polyamide 66. Each physical property and each 1 The results of H-NMR peak measurements are shown in Table 1.

[0083] [Table 1] [Industrial Applicability]

[0084] 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.

Claims

1. A continuous fiber reinforced resin composite material containing continuous reinforcing fibers and a thermoplastic resin, the continuous reinforcing fibers are glass fibers, the thermoplastic resin is a polyamide-based resin, The continuous fiber reinforced resin composite material １ In the H-NMR measurement, Peak A having a peak top at 2.6 to 2.8 ppm ２．６～２．８ and peak B having a peak top at 5.2 to 5.8 ppm. ５．２～５．８ and the peak A ２．６～２．８ When the integrated intensity of the peak B is set to 1, ５．２～５．８ The integrated intensity of is 0.5 to 3.0, There is one or less peak with a peak top between 1.7 and 2.0 ppm. A continuous fiber reinforced resin composite material.

2. The peak having a peak top at 1.7 to 2.0 ppm is a peak C having a peak top at 1.9 to 2.0 ppm. １．９～２．０ and Peak C １．９～２．０ When the integrated intensity of the peak A is set to 1, ２．６～２．８ The continuous fiber reinforced resin composite material according to claim 1, wherein the integrated intensity is 1.0 to 3.

0.

3. The continuous fiber reinforced resin composite material １ In H-NMR measurement, peak D having a peak top at 8.0 to 8.1 ppm ８．０～８．１ and peak E having a peak top at 2.4 ppm or more and less than 2.6 ppm. ２．４以上２．６未満 and the peak A ２．６～２．８ When the integrated intensity of the peak D is set to 1, ８．０～８．１ and the integrated intensity of the peak E ２．４以上２．６未満 The continuous fiber reinforced resin composite material according to claim 1 or 2, wherein the sum of the integrated intensity and the integral intensity is 1.0 to 3.

0.

4. Peak A ２．６～２．８ When the integrated intensity of the peak E is set to 1, ２．４以上２．６未満 The continuous fiber reinforced resin composite material according to claim 3, wherein the integrated intensity is 1.5 to 3.

0.

5. A continuous fiber reinforced resin composite material described in any one of claims 1 to 4, wherein the glass fibers are glass fibers having a bundling agent attached thereto.

6. A continuous fiber reinforced resin composite material as described in claim 5, wherein the sizing agent includes a silane coupling agent of an aminosilane type.

7. The continuous fiber reinforced resin composite material of claim 5, wherein the sizing agent comprises γ-aminopropyltrimethoxysilane.

8. A method for producing a continuous fiber reinforced resin composite material according to any one of claims 1 to 7, The thermoplastic resin １ In the H-NMR measurement, Peak a having a peak top at 2.6 to 2.8 ppm ２．６～２．８ and peak b having a peak top at 5.2 to 5.8 ppm. ５．２～５．８ and the peak a ２．６～２．８ When the integrated intensity of the peak b is set to 1, ５．２～５．８ The integrated intensity is 0.5 to 3.0, There is one or less peak with a peak top between 1.7 and 2.0 ppm. A method for producing a continuous fiber reinforced resin composite material, comprising:

9. The peak a of the thermoplastic resin ２．６～２．８ The integrated intensity of the peak b when the integrated intensity of the peak b is set to 1 ５．２～５．８ The integrated intensity of the peak A of the continuous fiber reinforced resin composite material ２．６～２．８ The integrated intensity of the peak B is set to 1. ５．２～５．８ The method for producing a continuous fiber reinforced resin composite material according to claim 8, wherein the integrated intensity is 0.8 to 1.2 times the integrated intensity.

10. The continuous fiber reinforced resin composite material １ In H-NMR measurement, peak D having a peak top at 8.0 to 8.1 ppm ８．０～８．１ and peak E having a peak top at 2.4 ppm or more and less than 2.6 ppm. ２．４以上２．６未満 There are some things that The thermoplastic resin １ In H-NMR measurement, peak d having a peak top at 8.0 to 8.1 ppm ８．０～８．１ and a peak e having a peak top at 2.4 ppm or more and less than 2.6 ppm. ２．４以上２．６未満 There are some things that The peak d of the thermoplastic resin ８．０～８．１ and the integrated intensity of the peak e ２．４以上２．６未満 The sum of the integrated intensity of peak b and the integrated intensity of peak b is set to 1. ５．２～５．８ The integrated intensity of the peak D of the continuous fiber reinforced resin composite material ８．０～８．１ and the integrated intensity of the peak E ２．４以上２．６未満 The sum of the integrated intensity of peak B and the integrated intensity of peak B is set to 1. ５．２～５．８ The method for producing a continuous fiber reinforced resin composite material according to claim 8 or 9, wherein the integrated intensity is 0.2 to 0.9 times the integrated intensity.

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