Continuous fiber-reinforced resin composite material and method for producing same

Abstract

The present invention relates to a continuous fiber-reinforced resin composite material and a method for manufacturing the same, and aims to provide a continuous fiber-reinforced resin composite material having good acoustic emission signals and high strength, elastic modulus and water absorption characteristics, and a method for manufacturing the same. The continuous fiber-reinforced resin composite material is characterized in that the continuous fiber-reinforced resin composite material contains continuous reinforcing fibers and a thermoplastic resin, and the acoustic emission (AE) count A, as determined by the following formula, is 0.30 or less. (AE Count A) = (number of AE signals with amplitude of 40 dB or more and duration of 3500 microseconds or less) / (total number of AE signals)

Description

[0001] This application is a divisional application. The international application number of the original application is PCT / JP2021 / 041408, the international application date is November 10, 2021, the Chinese national application number is 202180074948.X, the entry date into China is May 5, 2023, and the invention title is "Continuous fiber reinforced resin composite material and manufacturing method thereof". Technical Field

[0002] This invention relates to continuous fiber reinforced resin composite materials and methods for manufacturing the same. Background Technology

[0003] Composite molded bodies in which reinforcing materials such as glass fibers are added to the matrix resin material are used in structural components of various machines, automobiles, pressure vessels, and tubular structures. In particular, from the perspective of strength, continuous fiber reinforced resin composites with continuous reinforcing fibers are desirable. As such continuous fiber reinforced resin composites, solutions have been proposed for taking measures on the bundler added to the reinforcing fibers (see, for example, Patent Document 1 below), solutions for taking measures on the difference between melting point and crystallization temperature (see, for example, Patent Document 2 below), solutions for adding organic salts to the resin material (see, for example, Patent Document 3 below), solutions for laminating the fabric of the molding precursor with a thermoplastic resin (see, for example, Patent Document 4 below), and solutions for optimizing the adhesion and affinity at the interface between the continuous reinforcing fibers and the resin (see, for example, Patent Document 5 below).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2003-238213

[0007] Patent Document 2: Japanese Patent No. 5987335

[0008] Patent Document 3: Japanese Patent Application Publication No. 2017-222859

[0009] Patent Document 4: Japanese Patent Application Publication No. 2009-19202

[0010] Patent Document 5: International Publication No. 2019 / 208586 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, existing continuous fiber reinforced resin composites have room for improvement in the following aspects: poor acoustic emission (AE) signals emitted during physical property testing; insufficient physical properties such as strength and elastic modulus, and inadequate water absorption characteristics.

[0013] In view of the level of the prior art, the problem to be solved by the present invention is to provide a continuous fiber reinforced resin composite material with good acoustic emission signal, high strength, elastic modulus and water absorption properties, and a method for manufacturing the same.

[0014] Methods for solving problems

[0015] In order to solve this problem, the inventors conducted in-depth research and repeated experiments. Unexpectedly, they found that by adjusting the interface amount, heating rate, cooling rate, and compatibility between the continuous fiber reinforced resin composite material and the thermoplastic resin, and by taking measures to address the acoustic emission signal of the continuous fiber reinforced resin composite material, the above-mentioned problem can be solved, thus completing this invention.

[0016] That is, the present invention is as follows. [1]

[0018] A continuous fiber reinforced resin composite material, characterized in that,

[0019] It contains continuous reinforcing fibers and thermoplastic resin.

[0020] The acoustic emission (AE) count A, calculated by the following formula, is less than 0.30.

[0021] (AE count A) = (Number of AE signals with amplitude above 40dB and duration below 3500 microseconds) / (Total number of AE signals) [2]

[0023] As described in [1], the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 microseconds or less is 600 or less. [3]

[0025] The continuous fiber reinforced resin composite material as described in [1] or [2], wherein the number of AE signals with an amplitude of 25 to 30 dB and a duration of less than 1000 microseconds is 200 or more. [4]

[0027] The continuous fiber reinforced resin composite material as described in any one of [1] to [3], wherein the AE count B calculated by the following formula is 0.12 or more.

[0028] (AE count B) = (Number of AE signals with amplitude of 25-30dB and duration of less than 1000 microseconds) / (Total number of AE signals) [5]

[0030] The continuous fiber reinforced resin composite material as described in any one of [1] to [4], wherein the total number of AE signals is 2000 or more. [6]

[0032] A method for manufacturing a continuous fiber reinforced resin composite material, which is the method for manufacturing a continuous fiber reinforced resin composite material as described in any one of [1] to [5], characterized in that the interfacial amount of the continuous fiber reinforced resin composite material is 100,000 m. -1 The heating rate is 200–330℃ / minute, and the cooling rate is 10–120℃ / minute.

[0033] Here, fiber-reinforced resin composites, in which reinforcing materials such as glass fibers are added to the matrix resin material, are used in various structural components of machinery, automobiles, pressure vessels, and tubular structures. As such fiber-reinforced resin composites, there are schemes that take measures on the resin at the interface layer between the reinforcing fiber surface and the resin (for example, see Japanese Patent Application Laid-Open No. 2007-269914), schemes that take measures on the porosity of the interface (for example, see International Patent Application Laid-Open No. 2019 / 208586), and schemes that increase the GF coverage at the interface (for example, see Polymer, 2002, No. 43, pp. 4055-4062 and Science and Technology Research, 2016, Vol. 5, No. 2, pp. 163-168).

[0034] However, existing fiber-reinforced resin composites have room for improvement in the following aspects: due to the large amount of resin coated on the reinforcing fibers and the thick layer of interfacial resin, the flexural fatigue characteristics are insufficient.

[0035] Given the level of the prior art, by further possessing the features described below [7], it is possible to provide fiber-reinforced resin composite materials and methods for manufacturing thereof that can sufficiently reduce the thickness of the interfacial resin, have high flexural fatigue characteristics and physical property recovery characteristics. [7]

[0037] The continuous fiber reinforced resin composite material as described in any one of [1] to [5] is a continuous fiber reinforced resin composite material comprising continuous reinforcing fibers and thermoplastic resin, wherein the coverage of the interfacial resin on the continuous reinforcing fibers after resin dissolution is less than 44%. [8]

[0039] As described in [7], the continuous fiber reinforced resin composite material has an exposure of more than 55% of the continuous reinforcing fibers after the resin is dissolved. [9]

[0041] As described in [7] or [8], in a continuous fiber reinforced resin composite material, wherein the relative elemental concentration of interfacial nitrogen in the continuous reinforcing fibers after the resin is dissolved is 6.70 or less.

[10]

[0043] The continuous fiber reinforced resin composite material as described in any one of [7] to [9], wherein the relative elemental concentration of interfacial carbon in the continuous reinforcing fibers after the resin is dissolved is 46.7 or less.

[11]

[0045] The continuous fiber reinforced resin composite material as described in any one of [7] to

[10] , wherein the relative elemental concentration of interfacial aluminum in the continuous reinforcing fibers after the resin is dissolved is 1.80 or more.

[12]

[0047] The continuous fiber reinforced resin composite material as described in any one of [7] to

[11] , wherein the relative elemental concentration of interfacial silicon in the continuous reinforcing fibers after the resin is dissolved is 8.30 or more.

[13]

[0049] The continuous fiber reinforced resin composite material as described in any one of [7] to

[12] , wherein the relative elemental concentration of interfacial calcium in the continuous reinforcing fibers after the resin is dissolved is 2.60 or more.

[14]

[0051] The continuous fiber reinforced resin composite material as described in any one of [7] to

[13] , wherein the relative elemental concentration of interfacial oxygen in the continuous reinforcing fibers after the resin is dissolved is 33.1 or more.

[15]

[0053] A method for manufacturing a continuous fiber reinforced resin composite material, which is the method for manufacturing a continuous fiber reinforced resin composite material according to any one of [7] to

[14] , wherein the contact angle between the continuous reinforcing fiber after the resin is dissolved and the thermoplastic resin based on a static wetting test is 70 to 130% of the contact angle between the continuous reinforcing fiber and the thermoplastic resin based on a static wetting test, which is a material treated only with a coupling agent, and the impregnation rate of the thermoplastic resin on the continuous reinforcing fiber is 32% / min or more.

[0054] Here, composite molded bodies in which reinforcing materials such as glass fibers are added to the matrix resin material are used in various structural components of machinery, automobiles, pressure vessels, and tubular structures. In particular, from the perspective of strength, continuous fiber reinforced resin composites with continuous reinforcing fibers are needed. As such continuous fiber reinforced resin composites, solutions have been proposed for taking measures on the bundler added to the reinforcing fibers (for example, see Japanese Patent Application Laid-Open No. 2003-238213), solutions for taking measures on the difference between melting point and crystallization temperature (for example, see Japanese Patent Application Laid-Open No. 5987335), solutions for adding organic salts to the resin material (for example, see Japanese Patent Application Laid-Open No. 2017-222859), solutions for laminating the fabric of the molding precursor with a thermoplastic resin (for example, see Japanese Patent Application Laid-Open No. 2009-19202), and solutions for optimizing the adhesion and affinity at the interface between the continuous reinforcing fibers and the resin (for example, see International Publication No. 2019 / 208586).

[0055] However, in existing continuous fiber reinforced resin composites, the crystallization behavior is not optimal, and therefore they do not exhibit sufficient warpage characteristics and shape following properties, leaving room for improvement in this regard.

[0056] Given the level of the prior art, by further possessing the features described below

[16] , it is possible to provide continuous fiber reinforced resin composite materials with good crystallization behavior, warpage characteristics, and shape following properties, as well as methods for manufacturing the same.

[16]

[0058] The continuous fiber reinforced resin composite material as described in any one of [1] to [5] comprises continuous reinforcing fibers and thermoplastic resin.

[0059] The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer is greater than or equal to 1.00, and the intensity of the (010) plane is less than or equal to 40,000.

[17]

[0061] As described in

[16] , in a continuous fiber-reinforced resin composite material, the full width at half maximum (WHM) of the (010) plane of the crystalline phase in the inner layer is 1.15 or less.

[18]

[0063] As described in

[16] or

[17] , the continuous fiber reinforced resin composite material wherein the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer is less than 1.25.

[19]

[0065] The continuous fiber reinforced resin composite material as described in any one of

[16] to

[18] , wherein the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer is 0.85 or more.

[20]

[0067] The continuous fiber reinforced resin composite material as described in any one of

[16] to

[19] , wherein the lattice plane spacing of the (010) plane of the crystalline phase in the inner layer is 0.30 to 1.2. [twenty one]

[0069] The continuous fiber reinforced resin composite material as described in any one of

[16] to

[20] , wherein the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer is 0.85 or more. [twenty two]

[0071] The continuous fiber reinforced resin composite material as described in any one of

[16] to

[21] , wherein the 2θ of the peak of the (100) plane of the crystalline phase in the surface layer is 20.34° or higher. [twenty three]

[0073] A method for manufacturing a continuous fiber reinforced resin composite material, which is the method for manufacturing a continuous fiber reinforced resin composite material as described in any one of

[16] to

[22] , characterized in that,

[0074] The manufacturing method includes the step of molding a raw material laminate containing continuous reinforcing fibers and thermoplastic resin under heating.

[0075] The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite satisfies the following relationship.

[0076] (Full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite) < 0.0037 × (maximum temperature during molding) + 0.15 [twenty four]

[0078] The method for manufacturing a continuous fiber reinforced resin composite material as described in

[23] , wherein the ratio of the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material to the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer satisfies the following relationship.

[0079] (Full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite) / (Full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite) ≥ -0.0034 × (maximum temperature during molding) + 2.02

[25]

[0081] The method for manufacturing continuous fiber reinforced resin composites as described in

[23] or

[24] , wherein,

[0082] The manufacturing method includes a step of cooling after molding under heat.

[0083] The ratio of the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite to the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer satisfies the following relationship.

[0084] (Full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite) / (Full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite) ≥ 0.0125 × (cooling rate during molding) + 0.318

[0085] Here, composite molded bodies in which reinforcing materials such as glass fibers are added to the matrix resin material are used in various structural components of machinery, automobiles, pressure vessels, and tubular structures. In particular, from the perspective of strength, continuous fiber reinforced resin composites with continuous reinforcing fibers are desired. As such continuous fiber reinforced resin composites, solutions have been proposed for taking measures on the bundler added to the reinforcing fibers (for example, see Japanese Patent Application Publication No. 2003-238213), solutions for taking measures on the difference between melting point and crystallization temperature (for example, see Japanese Patent Application Publication No. 5987335), solutions for adding organic salts to the resin material (for example, see Japanese Patent Application Publication No. 2017-222859), solutions for laminating the fabric of the molding precursor with a thermoplastic resin (for example, see Japanese Patent Application Publication No. 2009-19202), and solutions for optimizing the adhesion and affinity at the interface between the continuous reinforcing fibers and the resin (for example, see International Publication No. 2019 / 208586).

[0086] However, existing continuous fiber reinforced resin composites all have room for improvement in the following aspects: interfacial abrasion value (the maximum abrasion pressure P (g / cm²) at which no voids are observed between the continuous reinforcing fibers and the thermoplastic resin when the cross-section of the continuous fiber reinforced resin composite is abraded orthogonal to the length direction of the continuous reinforcing fibers and observed using a field emission scanning electron microscope (FESEM)). 2 The value (P / Vf) obtained by dividing the continuous fiber reinforced resin composite by the volume ratio Vf (%) of the continuous fiber reinforced resin composite is not good; the strength, elastic modulus, impact and other physical properties, water absorption characteristics and interfacial recovery characteristics are insufficient.

[0087] Given the level of the prior art, by further possessing the features described below

[26] , it is possible to provide a continuous fiber reinforced resin composite material with good interfacial abrasion value, high strength, elastic modulus, impact properties, high temperature properties, water absorption properties and interfacial recovery properties, and a method for manufacturing the same.

[26]

[0089] The continuous fiber reinforced resin composite material as described in any one of [1] to [5] comprises continuous reinforcing fibers and thermoplastic resin.

[0090] The cross-section of the above-mentioned continuous fiber reinforced resin composite material, orthogonal to the longitudinal direction of the continuous reinforcing fibers, was ground. When the ground cross-section was observed using a field emission scanning electron microscope (FESEM), the interfacial grinding value P / Vf was 10 g / cm. 2 •% or more, this interfacial abrasion value is the maximum abrasion pressure P (g / cm²) at which no voids are observed between the aforementioned continuous reinforcing fibers and the aforementioned thermoplastic resin. 2 The value is obtained by dividing the continuous fiber reinforced resin composite by the volume ratio Vf (%) of the continuous fiber reinforced resin composite.

[27]

[0092] A method for manufacturing a continuous fiber reinforced resin composite material, which is the method for manufacturing a continuous fiber reinforced resin composite material described in

[26] , characterized in that,

[0093] The manufacturing method includes the step of obtaining continuous reinforcing fibers containing a surface treatment agent by treating the continuous reinforcing fibers with a surface treatment agent.

[0094] The interfacial shear strength between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin, calculated by the microdroplet method using equation (1), is 0.8 to 1.2 times that of the interfacial shear strength between the continuous reinforcing fiber treated with coupling agent and the thermoplastic resin, which was treated only with coupling agent instead of the surface treatment agent.

[0095] The droplet contact angle between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin, as determined by the droplet method, is 0.4 to 0.7 times that between the continuous reinforcing fiber without the surface treatment agent and the thermoplastic resin.

[0096] τ=F / πdL ···(1)

[0097] (In the formula, τ represents the interfacial shear strength (MPa), d represents the fiber diameter of the continuous reinforcing fiber (μm), L represents the length of the resin ball (microdroplet) of the thermoplastic resin attached to the single fiber of the continuous reinforcing fiber in the direction of the fiber axis of the continuous reinforcing fiber (μm), and F represents the shear load (N) when the resin ball is pulled away from the continuous reinforcing fiber.)

[28]

[0099] The method for manufacturing a continuous fiber reinforced resin composite material as described in

[27] , wherein the interfacial shear strength between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin is 1.8 to 10 times that between the continuous reinforcing fiber without the surface treatment agent and the thermoplastic resin.

[29]

[0101] The method for manufacturing a continuous fiber reinforced resin composite material as described in

[27] or

[28] , wherein the contact angle between the continuous reinforcing fiber containing the surface treatment agent and the droplet of the thermoplastic resin is 0.8 to 1.6 times that of the contact angle between the continuous reinforcing fiber treated with the coupling agent and the droplet of the thermoplastic resin.

[0102] Here, composite molded bodies in which reinforcing materials such as glass fibers are added to the matrix resin material are used in various structural components of machinery, automobiles, pressure vessels, and tubular structures. In particular, from the perspective of strength, continuous fiber reinforced resin composites with continuous reinforcing fibers are needed. As such continuous fiber reinforced resin composites, solutions have been proposed for taking measures on the bundler added to the reinforcing fibers (for example, see Japanese Patent Application Publication No. 2003-238213), solutions for taking measures on the difference between melting point and crystallization temperature (for example, see Japanese Patent Application Publication No. 5987335), solutions for adding organic salts to the resin material (for example, see Japanese Patent Application Publication No. 2017-222859), solutions for laminating the fabric of the molding precursor with a thermoplastic resin (for example, see Japanese Patent Application Publication No. 2009-19202), and solutions for optimizing the adhesion and affinity at the interface between the continuous reinforcing fibers and the resin (for example, see International Publication No. 2019 / 208586).

[0103] However, existing continuous fiber reinforced resin composites all exhibit interface thickness changes before and after destructive testing, resulting in insufficient interface recovery characteristics and strength stability, leaving room for improvement in these aspects.

[0104] Given the level of the prior art, by further possessing the features described below

[30] , it is possible to provide fiber-reinforced resin composite materials with high vibration fatigue recovery characteristics and strength stability, as well as a method for manufacturing the same.

[30]

[0106] The continuous fiber reinforced resin composite material as described in any one of [1] to [5] comprises continuous reinforcing fibers and thermoplastic resin, wherein the interface coverage variation index of the above-mentioned continuous fiber reinforced resin composite material is expressed by the following formula as 0.8 to 1.2.

[0107] (Interface Coverage Change Index) = (Interface Coverage of Continuous Fiber Reinforced Resin Composite Material Before Destructive Test) / (Interface Coverage of Continuous Fiber Reinforced Resin Composite Material After Destructive Test)

[31]

[0109] As described in

[30] , the continuous fiber reinforced resin composite material has a fiber exposure variation index of 0.8 to 1.2, as expressed by the following formula.

[0110] (Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite before destructive test) / (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite after destructive test)

[32]

[0112] As described in

[30] or

[31] , the continuous fiber reinforced resin composite material has a relative elemental variation index of 0.8 to 1.2 for interfacial nitrogen.

[33]

[0114] The continuous fiber reinforced resin composite material as described in any one of

[30] to

[32] , wherein the relative elemental variation index of interfacial carbon is 0.8 to 1.2.

[34]

[0116] The continuous fiber reinforced resin composite material as described in any one of

[30] to

[33] , wherein the relative elemental variation index of aluminum at the interface is 0.8 to 1.2.

[35]

[0118] The continuous fiber reinforced resin composite material as described in any one of

[30] to

[34] , wherein the relative elemental variation index of interfacial silicon is 0.8 to 1.2.

[36]

[0120] The continuous fiber reinforced resin composite material as described in any one of

[30] to

[35] , wherein the relative elemental variation index of interfacial calcium is 0.8 to 1.2.

[37]

[0122] The continuous fiber reinforced resin composite material as described in any one of

[30] to

[36] , wherein the relative elemental variation index of interfacial oxygen is 0.8 to 1.2.

[38]

[0124] A method for manufacturing a continuous fiber reinforced resin composite material, which is the method for manufacturing a continuous fiber reinforced resin composite material as described in any one of

[30] to

[37] , characterized in that,

[0125] The rate at which thermoplastic resin is impregnated into continuous reinforcing fibers is 0.8 to 1.2 times that of the aforementioned thermoplastic resin impregnated into coupled continuous reinforcing fibers treated only with coupling agents.

[0126] The flexural strength of the coupled continuous fiber reinforced resin composite material composed of the above-mentioned coupled continuous reinforcing fibers and the above-mentioned thermoplastic resin is more than 0.6 times that of the above-mentioned continuous fiber reinforced resin composite material.

[0127] The effects of the invention

[0128] The continuous fiber reinforced resin composite material of the present invention exhibits good acoustic emission signal and demonstrates high strength, elastic modulus, and water absorption properties. Furthermore, it preferably also possesses fatigue properties, physical stability, warpage characteristics, and shape following properties.

[0129] Furthermore, the continuous fiber reinforced resin composite material of the present invention, by having feature (II) described later, has sufficiently thinned interfacial resin in the continuous fiber reinforced resin composite material, and thus can further exhibit higher flexural fatigue characteristics.

[0130] Furthermore, the continuous fiber reinforced resin composite material of the present invention possesses the following feature (III), which exhibits excellent crystallization behavior in both the surface and inner layers, thereby further improving warpage characteristics and shape following properties.

[0131] Furthermore, the continuous fiber reinforced resin composite material of the present invention, by possessing the features (IV) described later, exhibits good interfacial abrasion value and can further demonstrate higher strength, elastic modulus, impact characteristics, high temperature characteristics, water absorption characteristics, and interfacial recovery characteristics.

[0132] Furthermore, the continuous fiber reinforced resin composite material of the present invention possesses the features (V) described later, thereby exhibiting high vibration fatigue recovery characteristics and excellent strength stability. Attached Figure Description

[0133] Figure 1 This is a schematic diagram showing a single fiber of continuous reinforcing fibers and resin balls (microdroplets) of thermoplastic resin attached to the single fiber of continuous reinforcing fibers.

[0134] Explanation of symbols

[0135] 1: Single fiber of continuously reinforced fiber

[0136] 2: Resin spheres (microdroplets) made of thermoplastic resin

[0137] α: Droplet contact angle

[0138] d: Fiber diameter of a single fiber in a continuously reinforced fiber

[0139] L: Length of the resin ball (microdroplet) along the fiber axis of the continuous reinforcing fiber. Detailed Implementation

[0140] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of its key points.

[0141] [Continuous fiber reinforced resin composites]

[0142] The continuous fiber reinforced resin composite material of this embodiment (hereinafter also referred to as "composite material") comprises continuous reinforcing fibers and resin, and the acoustic emission count A, calculated by the following formula, in the bending test is 0.30 or less. The continuous reinforcing fibers preferably contain a surface treatment agent.

[0143] (AE count A) = (Number of AE signals with amplitude above 40dB and duration below 3,500 microseconds) / (Total number of AE signals)

[0144] The aforementioned AE count A is preferably 0.25 or less, more preferably 0.21 or less. When the aforementioned AE count A is within this range, the bundle-forming agent diffuses into the thermoplastic resin in the surface treatment agent of the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material, promoting the bonding between the thermoplastic resin and the aminosilane, and increasing the concentration of active sites of the surface treatment agent, resulting in good adhesion between the continuous reinforcing fibers and the thermoplastic resin, making it less prone to damage to both, and exhibiting excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, warpage characteristics, physical property stability, and shape following properties.

[0145] As a method for adjusting the above signal number to the above range, for example, the following method can be used: In the manufacturing method of continuous fiber reinforced resin composite material, the interface amount of the continuous fiber reinforced resin composite material is made to be 100,000 m. -1 The heating rate is set to 200–330°C / min, the cooling rate to 10–120°C / min, and the SP value difference between the tufting agent contained in the continuous reinforcing fiber and the thermoplastic resin is set to 0.01–5. It should be noted that the SP value difference can be the absolute value of the difference between the SP value of the tufting agent of the continuous reinforcing fiber and the SP value of the thermoplastic resin. The SP value can be measured using the method described in the examples below.

[0146] It should be noted that, in this disclosure, an acoustic emission sensor can be mounted on a fixture for a bending test. During the bending test, the sensor is used to sense the sound emitted by the continuous fiber reinforced resin composite material, thereby obtaining the acoustic emission signal of the continuous fiber reinforced resin composite material. The AE count A is obtained by measuring the number of acoustic emission signals generated in the range of amplitude above 40 dB and duration below 3,500 microseconds and the total number of AE signals. Specifically, it can be calculated using the method described in the embodiments described later.

[0147] In the continuous fiber reinforced resin composite material of this embodiment, the number of acoustic emission signals with an amplitude of 40 dB or more and a duration of 3,500 microseconds or less in the bending test is preferably 600 or less, more preferably 550 or less, and even more preferably 500 or less.

[0148] When the above signal number is within this range, the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material have good adhesion to the resin and are not easily damaged. It can exhibit excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics.

[0149] As a method for adjusting the above signal number to the above range, for example, the interfacial amount of the continuous fiber reinforced resin composite material can be set to 100,000 m. -1 The above results in a basis weight of 637 g / m² for the continuously reinforced fiber substrate. 2 The above method involves making the volume ratio of thermoplastic resin at 45% or more, the heating rate at 200–330°C / min, the cooling rate at 10–120°C / min, the concentration of terminal groups in the thermoplastic resin at 70 μmol / g or more, and ensuring that 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 that of the interfacial shear strength between the continuous reinforcing fiber treated with a coupling agent and the thermoplastic resin, where the coupling agent is used instead of the surface treatment agent.

[0150] In the continuous fiber reinforced resin composite material of this embodiment, the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of less than 1,000 microseconds in the bending test is preferably 200 or more, more preferably 300 or more, and even more preferably 350 or more.

[0151] When the above signal number is within this range, the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material have good adhesion to the resin and are not easily damaged. It can exhibit excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics.

[0152] As a method for adjusting the above signal number to the above range, for example, the cooling rate of the continuous fiber reinforced resin composite material during manufacturing 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 proportion of thermoplastic resin by volume is 45% or more, and the cooling compression time is 1 to 10 minutes.

[0153] In the continuous fiber reinforced resin composite material of this embodiment, the total number of acoustic emission (AE) signals in the bending test is preferably 2000 or more, more preferably 2500 or more, and even more preferably 3000 or more. The aforementioned total AE signal number is preferably 25000 or less, more preferably 20000 or less, even more preferably 10000 or less, and even more preferably 5000 or less.

[0154] When the above signal number is within this range, the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material have good adhesion to the resin and are not easily damaged. It can exhibit excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics.

[0155] As a method for adjusting the above signal number to the above range, for example, setting the interface content of the continuous fiber reinforced resin composite material to 100,000 m -1 The above describes a method in which the crystallinity of the resin contained in the continuous fiber reinforced resin composite material is 20-40%, the cooling compression time is 1-10 minutes, the droplet contact angle between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin, as measured by the droplet method, is 0.4-0.7 times that of the droplet contact angle between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin without the surface treatment agent, and the concentration of the terminal groups of the thermoplastic resin is 70 μmol / g or more.

[0156] In the continuous fiber reinforced resin composite material of this embodiment, the acoustic emission signal in the bending test, calculated by the following formula, preferably has an AE count B of 0.12 or more, more preferably 0.15 or more, and even more preferably 0.20 or more.

[0157] (AE count B) = (Number of AE signals with amplitude of 25-30dB and duration of less than 1000 microseconds) / (Total number of AE signals)

[0158] When the above signal number is within this range, the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material have good adhesion to the resin and are not easily damaged. It can exhibit excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics.

[0159] As a method for adjusting the above signal number to the above range, for example, setting the interface content of the continuous fiber reinforced resin composite material to 100,000 m -1 The above method involves heating at a rate of 200–330 °C / min, cooling at a rate of 10–120 °C / min, and ensuring that the concentration of terminal groups in the thermoplastic resin is 70 μmol / g or higher.

[0160] The atmospheric equilibrium water absorption rate of the continuous fiber reinforced resin composite material in this embodiment is preferably 0.75% by mass or less, and more preferably 0.70% by mass or less.

[0161] It should be noted that atmospheric equilibrium water absorption rate refers to the water absorption rate under conditions of 23℃ and 50% humidity.

[0162] When the atmospheric equilibrium water absorption rate is within this range, it can exhibit excellent strength, elastic modulus, water absorption characteristics, high temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics.

[0163] [Morphology of continuous fiber reinforced resin composites]

[0164] There are no particular limitations on the form of continuous fiber reinforced resin composites, and various forms can be cited as follows. For example, forms can be formed by combining woven or knitted fabrics, non-crimped fabrics, braids, and tubular structures of continuous reinforcing fibers with thermoplastic resin; forms can be formed by combining continuous reinforcing fibers stretched in one direction with thermoplastic resin; forms can be formed by stretching filaments composed of continuous reinforcing fibers and thermoplastic resin in one direction; and forms can be formed by shaping filaments composed of continuous reinforcing fibers and thermoplastic resin into woven fabrics, knitted fabrics, braids, and tubular structures, etc.

[0165] The continuous fiber reinforced resin composite material of this embodiment can be a flat sheet or a laminate containing layers of continuous reinforcing fibers and layers of thermoplastic resin. For example, the longitudinal direction of the continuous reinforcing fibers can be arranged substantially parallel to the surface of the flat sheet. It should be noted that the layer of continuous reinforcing fibers refers to a layer containing continuous reinforcing fibers (e.g., a continuous reinforcing fiber substrate), which can be a layer in which thermoplastic resin is impregnated into the interior of the continuous reinforcing fibers.

[0166] There are no particular limitations on the form of intermediate materials used before molding continuous fiber reinforced resin composites. Examples include: mixed filaments of continuous reinforcing fibers and resin fibers; coated filaments formed by coating the bundles of continuous reinforcing fibers with resin; strips formed by pre-impregnating continuous reinforcing fibers with resin; continuous reinforcing fibers sandwiched in a resin film; resin powder attached to continuous reinforcing fibers; a bundle of continuous reinforcing fibers used as a core material and surrounded by resin fibers to form a braided strip; resin pre-impregnated between the reinforcing fibers; and continuous reinforcing fibers in contact with molten resin.

[0167] [Manufacturing method of continuous fiber reinforced resin composites]

[0168] The method for manufacturing the continuous fiber reinforced resin composite material of this embodiment is not particularly limited, and various methods can be cited below.

[0169] In one method, for example, a substrate constituting a continuous fiber reinforced resin composite material (e.g., a substrate composed of continuous reinforcing fibers, a substrate composed of thermoplastic resin) is cut or shaped according to the desired composite material, and the required number of overlaps or layers are performed taking into account the thickness of the target product, and then placed in a mold according to the mold shape.

[0170] It should be noted that, in this specification, the laminate formed by overlapping substrates constituting a continuous fiber reinforced resin composite material and placed in a mold (the laminate placed in the mold before heating and molding) is sometimes referred to as a raw material laminate.

[0171] The substrate can be cut piece by piece or by overlapping the desired number of pieces. From a productivity standpoint, cutting in an overlapping state is preferred. Any cutting method can be used, such as water jet cutting, blade pressing, hot blade pressing, laser cutting, or slicing. Among these, a hot blade pressing machine is preferred because it provides excellent cross-sectional shape and, when cutting multiple overlapping pieces, facilitates end-face welding for good processability. The appropriate cutting shape can be adjusted through trial and error, but it is preferable to set it through CAE (Computer-Aided Engineering) simulation based on the shape of the mold.

[0172] The substrate can be shaped using any method, for example, it can be shaped into a sheet-like shape.

[0173] After placing the substrate (e.g., raw material laminate) in the mold, the mold is closed and compression is performed. Then, the mold temperature is adjusted to a temperature above the melting point of the thermoplastic resin constituting the continuous fiber-reinforced resin composite, causing the thermoplastic resin to melt and form the composite. The mold closing pressure is not particularly limited, but is preferably 1 MPa or more, more preferably 3 MPa or more. Alternatively, the mold can be temporarily closed for venting or other purposes, and the mold closing pressure can be temporarily released after compression molding. From the perspective of strength performance, the compression molding time is preferably a relatively long time within the range where the thermoplastic resin used will not undergo thermal degradation; from the perspective of productivity, a suitable time is preferably within 2 minutes, more preferably within 1 minute.

[0174] In the method for manufacturing the continuous fiber reinforced resin composite material of this embodiment, the interface content of the continuous fiber reinforced composite material is preferably 100,000 m. -1 The heating rate is 200–330°C / min, and the cooling rate is 10–120°C / min. Furthermore, it is even more preferable that the crystallinity of the resin included in the continuous fiber reinforced resin composite material is 20–40%, and the basis weight of the continuous reinforcing fiber matrix is ​​637 g / m³. 2 The above-mentioned thermoplastic resin has a volume ratio of more than 45% of the total raw material, a cooling and compression time of 1 to 10 minutes, and a terminal group concentration of more than 70 μmol / g.

[0175] The interfacial amount of a continuous fiber reinforced composite material is the amount of the interface between the continuous reinforcing fiber and the matrix resin, which is calculated by the following formula.

[0176] Interface quantity (m) -1 The volume of reinforcing fibers in a continuous fiber-reinforced resin composite (m³) 3 ))×(density of reinforcing fiber (g / m³) 3 ))×(number of single filaments of reinforcing fiber)×(diameter of reinforcing fiber (m))×π / (fineness of reinforcing fiber (g / m)) / (volume of continuous fiber reinforced resin composite (m³)) 3 ))

[0177] The preferred interface size is 100,000m. -1 The above, and more preferably 120,000m -1 The above, and more preferably 130,000m -1 That's all. Additionally, the upper limit is not specifically set, but is preferably 1,000,000m. -1 The following, and more preferably, is 500,000m -1 the following.

[0178] The greater the interface content of continuous fiber reinforced composite materials, the fewer AE signals with amplitudes above 40 dB and durations below 3500 microseconds tend to be, while the more AE signals with amplitudes between 25 and 30 dB and durations below 1000 microseconds tend to be, and the greater the total AE count tends to be.

[0179] The heating rate of continuous fiber reinforced composite materials refers to the rate at which the substrate constituting the continuous fiber reinforced composite material is heated after being placed in the molding machine.

[0180] The heating rate is preferably 200-330℃ / min, more preferably 230-300℃ / min, and even more preferably 250-280℃ / min.

[0181] The slower the heating rate, the lower the AE count A tends to be, the lower the number of acoustic emission signals with an amplitude of 40 dB or more and a duration of less than 3,500 microseconds, and the higher the AE count B tends to be.

[0182] The cooling rate of continuous fiber reinforced composites refers to the rate at which the substrate constituting the continuous fiber reinforced composite is placed in a molding machine, melted, compressed, and then cooled by water cooling or other methods.

[0183] The cooling rate is preferably 10-120°C / min, more preferably 20-100°C / min, and even more preferably 30-90°C / min.

[0184] The smaller the cooling rate, the lower the AE count A tends to be, the lower the number of acoustic emission signals with an amplitude of 40 dB or more and a duration of less than 3,500 microseconds tends to be, the higher the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of less than 1,000 microseconds tends to be, and the higher the AE count B tends to be.

[0185] The crystallinity of the resin contained in a continuous fiber reinforced resin composite refers to the crystallinity when it is in the state of a continuous fiber reinforced composite, which is the proportion of crystalline regions in the resin as a whole.

[0186] The crystallinity is preferably 20-40%, more preferably 25-35%, and even more preferably 28-33%.

[0187] The lower the crystallinity, the more acoustic emission signals with an amplitude of 25–30 dB and a duration of less than 1,000 microseconds tend to increase, and the more total AE signals tend to increase.

[0188] The crystallinity of the resin contained in the continuous fiber reinforced resin composite material can be determined using a differential scanning calorimeter, specifically by the method described in the examples below.

[0189] The basis weight of a continuous fiber-reinforced matrix refers to the weight per 1m³ of the continuous fiber-reinforced matrix (fiber cloth, etc.) used in the manufacture of continuous fiber-reinforced resin composites. 2 The quality.

[0190] The basis weight of the continuously reinforced fiber substrate is preferably 637 g / m³. 2 The above, and more preferably, is 640–700 g / m 2 A further preferred value is 650–690 g / m³. 2 .

[0191] The greater the basis weight of the continuous fiber reinforced matrix, the fewer the number of AE signals with an amplitude of 40 dB or more and a duration of less than 3500 microseconds tend to be, while the more the number of AE signals with an amplitude of 25–30 dB and a duration of less than 1000 microseconds tends to be, and the greater the total number of AE counts tends to be.

[0192] The proportion of thermoplastic resin by volume refers to the volume ratio of the raw material thermoplastic resin relative to the total volume of raw materials used in the manufacture of continuous fiber reinforced resin composites.

[0193] The volume percentage of thermoplastic resin added is preferably 45% or more, more preferably 50% or more. Furthermore, no upper limit is specifically set, but it is preferably 75% or less, more preferably 65% ​​or less.

[0194] The larger the proportion of thermoplastic resin in the feed volume, the fewer AE signals with an amplitude of 40 dB or more and a duration of less than 3500 microseconds tend to be in the continuous fiber reinforced composite material, the more AE signals with an amplitude of 25 to 30 dB and a duration of less than 1000 microseconds tend to be in the continuous fiber reinforced composite material, and the more the total AE count tends to be in the continuous fiber reinforced composite material.

[0195] Cooling and compression time refers to the time required after the substrate constituting the continuous fiber reinforced composite material is placed in a molding machine to melt and compress, and then cooled and compressed again by water cooling or other methods.

[0196] The cooling compression time is preferably 1 to 10 minutes, more preferably 2 to 9 minutes, and even more preferably 3 to 8 minutes.

[0197] The shorter the cooling and compression time, the fewer AE signals with an amplitude of 40 dB or more and a duration of less than 3500 microseconds tend to be, while the more AE signals with an amplitude of 25–30 dB and a duration of less than 1000 microseconds tend to be, and the more the total AE count tends to be.

[0198] The concentration of terminal groups in thermoplastic resins refers to the amount of terminal groups present in 1g of resin.

[0199] The concentration of terminal groups in the thermoplastic resin is preferably 70 μmol / g or more, preferably 100 to 300 μmol / g, and more preferably 120 to 270 μmol / g.

[0200] The higher the concentration of terminal groups in thermoplastic resins, the greater the number of AE signals with an amplitude of 25–30 dB and a duration of less than 1000 microseconds, and the greater the total number of AE counts.

[0201] The concentration of end groups in thermoplastic resins can be determined using... 1 The H-NMR measurements are performed, specifically, by the methods described in the examples below.

[0202] The SP values ​​of the continuously reinforcing fiber tufting agent and the aforementioned thermoplastic resin are values ​​related to the solubility of each substance. The difference between the SP values ​​of the continuously reinforcing fiber tufting agent and the aforementioned thermoplastic resin is preferably 0.01 to 5, more preferably 0.01 to 4, further preferably 0.01 to 3, and even more preferably 0.01 to 2.

[0203] The smaller the difference between the SP value of the tufting agent of the continuous reinforcing fiber and the above-mentioned thermoplastic resin, the lower the AE count A tends to be.

[0204] Continuous fiber reinforced resin composites can also be further injection-filled with a hybrid thermoplastic resin composition to produce hybrid composites. In the manufacturing process of hybrid composites, the above-mentioned substrate can be placed in a mold, the mold closed, pressure applied, and after a specified time, a specified hybrid thermoplastic resin composition can be injected and filled for molding, so that the thermoplastic resin of the substrate is bonded to the specified hybrid thermoplastic resin composition, thereby manufacturing a hybrid composite.

[0205] The timing of injection filling of the specified hybrid thermoplastic resin composition has a significant impact on the interfacial strength between the thermoplastic resin and the substrate. Regarding the timing of injection filling of the specified hybrid thermoplastic resin composition, it is preferably within 30 seconds after placing the substrate in the mold and closing the mold, and then raising the mold temperature to above the melting point or glass transition temperature of the thermoplastic resin constituting the substrate.

[0206] When injecting the specified hybrid thermoplastic resin composition, the mold temperature is preferably above the melting point or glass transition temperature of the thermoplastic resin constituting the substrate that is bonded to the hybrid thermoplastic resin composition. More preferably, it is above the melting point +10°C or the glass transition temperature +10°C of the thermoplastic resin constituting the substrate that is bonded to the hybrid thermoplastic resin composition. Even more preferably, it is above the melting point +20°C or the glass transition temperature +20°C. Even more preferably, it is above the melting point +30°C or the glass transition temperature +30°C.

[0207] In hybrid composite materials, the bonding portion between the thermoplastic resin constituting the substrate and the hybrid thermoplastic resin composition formed by injection molding preferably constitutes a mixed uneven structure.

[0208] Maintaining the mold temperature above the melting point of the injected hybrid thermoplastic resin composition and increasing the resin holding pressure during injection molding (e.g., to 1 MPa or more) are effective in improving interfacial strength. To improve interfacial strength, the aforementioned holding pressure is preferably 5 MPa or more, and more preferably 10 MPa or more.

[0209] In addition, from the perspective of improving interface strength, it is preferable to extend the time of holding the pressure, for example, 5 seconds or more, preferably 10 seconds or more, and more preferably the time of holding the pressure until the mold temperature reaches below the melting point of the thermoplastic resin composition.

[0210] (Hybrid thermoplastic resin composition)

[0211] As for the thermoplastic resin composition for injection molding used in manufacturing hybrid composite materials, there are no particular limitations as long as it is a common thermoplastic resin composition used in injection molding.

[0212] Examples of thermoplastic resins included in a hybrid thermoplastic resin composition include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, acrylic resins, styrene resins, polyethylene terephthalate, polybutylene terephthalate, polyarylates, polyphenylene ether, modified polyphenylene ether resins, fully aromatic polyesters, polyacetals, polycarbonates, polyetherimides, polyethersulfones, polyamide resins, polysulfones, polyetheretherketones, polyetherketones, etc., or mixtures of two or more of these thermoplastic resins.

[0213] Various filler materials can be blended into hybrid thermoplastic resin compositions. Hybrid thermoplastic resin compositions can be black resin compositions containing colorants.

[0214] Examples of various filler materials include short fiber and long fiber materials, which are discontinuous reinforcing materials that are the same type of material as the continuous reinforcing fibers mentioned above.

[0215] When using short or long glass fibers in discontinuous reinforcing materials, the same substance as the bundling agent coated on the continuous reinforcing fibers constituting the continuous fiber reinforced resin composite material of this embodiment can be used. The bundling agent (adhesive) is preferably at least one selected from the group consisting of silane coupling agents, lubricants, and bundling agents. Regarding the types of silane coupling agents, lubricants, and bundling agents, the same substance as the bundling agent used for the continuous reinforcing fibers can be used.

[0216] From the perspective of interfacial strength with the thermoplastic resin to which it is bonded, the thermoplastic resin included in the hybrid thermoplastic resin composition used in injection molding is preferably a substance similar to the thermoplastic resin constituting the bonding surface of the continuous fiber-reinforced resin composite, and more preferably the same substance. Specifically, when polyamide 66 is used in the thermoplastic resin of the bonding surface, the resin material of the hybrid thermoplastic resin composition used for injection molding is preferably polyamide 66.

[0217] Other methods include: a molding method in which a substrate is placed in a mold and compressed using a double-belt press; a molding method in which a mold frame is set to surround the substrate and then pressed using a double-belt press; a molding method in which a compression molding machine for heating and cooling, both set at one or more temperatures, is prepared, and a mold containing the substrate is sequentially fed into the compression molding machine for molding; or a molding method in which a continuous compression molding machine is used for pressing.

[0218] In molding methods using a dual-belt press or a continuous compression molding machine, the materials of the belts and molds are different from those of the continuous fiber-reinforced resin composite material being molded; from a durability perspective, metal or ceramic is preferred. The continuously reinforcing fiber substrate and the thermoplastic resin can be laminated.

[0219] (Continuous reinforcing fiber)

[0220] As a continuous reinforcing fiber, it can be used in materials commonly used in continuous fiber reinforced resin composites.

[0221] Examples of reinforcing fibers include, but are not limited to, glass fiber, carbon fiber, plant fiber, aramid fiber, ultra-high strength polyethylene fiber, polybenzopyrrole fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber.

[0222] From the perspectives of mechanical properties, thermal properties, and versatility, glass fiber, carbon fiber, plant fiber, and aramid fiber are preferred; from the perspective of productivity, glass fiber is preferred.

[0223] The aforementioned continuous reinforcing fibers can be used alone or in combination of two or more types.

[0224] The aforementioned continuous reinforcing fibers may have been treated with a surface treatment agent (preferably a bundling agent described later).

[0225] -Clustering Agent-

[0226] The continuous reinforcing fibers are preferably coated with a bundling agent.

[0227] When glass fiber is chosen as the continuous reinforcing fiber, a slugging agent can be used as a surface treatment agent.

[0228] The sizing agent (adhesive) may contain one or more selected from the group consisting of coupling agents (e.g., silane coupling agents), lubricants, and sizing agents, preferably containing at least a sizing agent or a silane coupling agent. In continuous fiber reinforced resin composites possessing characteristic (V), it is more preferable that the composite is composed of only one or more selected from the group consisting of coupling agents, lubricants, and sizing agents.

[0229] However, cases consisting solely of silane coupling agents are excluded.

[0230] In addition, the bundler can be composed of silane coupling agent and bundler, or it can be composed of silane coupling agent, lubricant and bundler.

[0231] By using a bundler that enables a strong bond between continuous reinforcing fibers (e.g., glass fibers) and the resin that forms a coating around them, it is possible to obtain continuous fiber reinforced resin composites with low porosity.

[0232] Bundling agents can be added to or contained within the material being used. For example, lubricants are sometimes included in commercially available thermoplastic resins.

[0233] Coupling agents are compounds that combine materials with different properties, primarily 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 perspective of compatibility between thermoplastic resins and continuous reinforcing fibers, silane coupling agents are preferred.

[0234] --Silane coupling agent--

[0235] Silane coupling agents are commonly used as surface treatment agents for continuous reinforcing fibers (such as glass fibers and carbon fibers) to help improve interfacial bond strength.

[0236] 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; and maleic acid derivatives. When polyamide is used as a thermoplastic resin, it is preferable to select a substance that readily binds to the carboxyl or amino group, which is the terminal group of the polyamide resin, and aminosilanes are preferred.

[0237] Examples of polymer coupling agents include, but are not limited to, diamines, polycarboxylic acids, and epoxy resins. From the perspective of compatibility with thermoplastic resins, diamines and polycarboxylic acids are preferred.

[0238] Examples of polymerizable coupling agents include, but are not limited to, epoxy resins, phenolic resins, ethers, and lactones. From the perspective of compatibility with thermoplastic resins, phenolic resins and lactones are preferred.

[0239] --Lubricant--

[0240] Lubricants help improve the fiber opening properties of continuous reinforcing fibers (such as glass fibers).

[0241] As a lubricant, any ordinary liquid or solid lubricating material appropriate to the purpose can be used, as long as it does not interfere with silane coupling agents and bundlers. Examples include, but are not limited to, animal, plant or mineral waxes such as carnauba wax and lanolin wax; and surfactants such as fatty amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

[0242] --Bundling Agent--

[0243] Bundling agents help improve the bundle properties of continuous reinforcing fibers (such as glass fibers) and enhance interfacial bond strength.

[0244] As a bundle-forming agent, polymers appropriate to the purpose can be used, and thermoplastic resins other than thermoplastic resins used as the main material for continuous fiber reinforced resin composites.

[0245] Polymers that can be used as bundle-forming agents include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid with other comonomers, copolymers of acrylates and / or methacrylates with comonomers, and their salts with primary, secondary, and tertiary amines. Additionally, polyurethane resins synthesized from isocyanates and polyester or polyether diols, such as m-xylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate, are also suitable.

[0246] As a homopolymer of acrylic acid, the weight-average molecular weight is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.

[0247] As the comonomer constituting the copolymer of acrylic acid and other comonomers, examples include, but are not limited to, monomers having hydroxyl and / or carboxyl groups 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 mesoconic acid (excluding cases where only acrylic acid is used). As the comonomer, it is preferable to have one or more ester-based monomers.

[0248] In the continuous fiber-reinforced resin composite material possessing characteristic (III), examples of acrylates, such as methyl acrylate, can be used as copolymers of acrylates and / or methacrylates with comonomers. Examples of methacrylates, such as methyl methacrylate, can be used as comonomers. Examples of comonomers include one or more monomers selected from the group consisting of acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesoconic acid (maleic anhydride is preferred). Copolymers of one acrylate, one methacrylate, and one comonomer are preferred. The weight-average molecular weight of the copolymer is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.

[0249] In the continuous fiber-reinforced resin composite material possessing characteristic (V), the copolymer of methacrylate and comonomer is preferably a copolymer of methyl methacrylate or ethyl methacrylate (preferably methyl methacrylate) and one or more comonomers selected from the group consisting of acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, trimellitic anhydride, dipyridyl dianhydride, and mesoconic acid (preferably maleic anhydride). For example, it can be a copolymer of one methacrylate and one comonomer. The mass ratio of structural units derived from methacrylate relative to 100% mass of the copolymer of methacrylate and comonomer is preferably 30–98% by mass, more preferably 60–95% by mass. The mass ratio of structural units derived from comonomer relative to 100% mass of the copolymer of methacrylate and comonomer is preferably 2–70% by mass, more preferably 5–40% by mass. The weight-average molecular weight of the copolymer of methacrylate and comonomer is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.

[0250] Examples of homopolymers and copolymers of acrylic acid with salts of primary, secondary, and tertiary amines include, but are not limited to, triethylamine salts, triethanolamine salts, and glycine salts. From the perspective of improving the stability of mixed solutions with other compatible chemical reagents (such as silane coupling agents) and reducing amine odor, the degree of neutralization is preferably 20–90%, more preferably 40–60%.

[0251] 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 perspective of improving the bundle properties of continuous reinforcing fibers (e.g., glass fibers), it is preferably 3,000 or more, and from the perspective of improving the properties when forming a composite molded article, it is preferably 50,000 or less.

[0252] When polyamide is used as a thermoplastic resin, a resin with good wettability or similar surface tension to the polyamide resin is preferably used as a bundle-forming agent. Specifically, for example, polyurethane resin emulsions, polyamide resin emulsions, or their modifiers can be selected.

[0253] Examples of thermoplastic resins used as bundle-forming agents include, but are not limited to, polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, polyetherketone, polyetheretherketone, polyethersulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluoropolymers, and modified thermoplastic resins derived from these. When the thermoplastic resin used as a bundle-forming agent is the same thermoplastic resin and / or a modified thermoplastic resin as the resin surrounding the continuously reinforcing fibers, improved adhesion between the glass fiber and the thermoplastic resin is preferred after the composite material is formed.

[0254] Furthermore, when the adhesion between the continuous reinforcing fibers and the thermoplastic resin covering them is further improved, and the bridging agent is attached to the continuous reinforcing fibers (e.g., glass fibers) in the form of an aqueous dispersion, the thermoplastic resin used as the bridging agent is preferably a modified thermoplastic resin, considering factors such as reducing the proportion of emulsifier components or eliminating the need for emulsifiers.

[0255] Here, modified thermoplastic resin refers to a substance that, in addition to the monomer components that can form the main chain of a thermoplastic resin, modifies the properties of the thermoplastic resin by copolymerizing different monomer components to alter its hydrophilicity, crystallinity, thermodynamic properties, etc.

[0256] Modified thermoplastic resins used as bundle-forming agents include, but are not limited to, modified polyolefin resins, modified polyamide resins, and modified polyester resins.

[0257] Modified polyolefin resins used as binding agents are copolymers of olefin monomers such as ethylene and propylene with monomers such as unsaturated carboxylic acids and / or their esters that can copolymerize with olefin monomers, or homopolymers of monomers such as unsaturated carboxylic acids and / or their esters that can copolymerize with olefin monomers, and can be manufactured by known methods. They can be random copolymers formed by copolymerizing olefin monomers with unsaturated carboxylic acids and / or their esters, or graft copolymers formed by grafting unsaturated carboxylic acids onto olefins.

[0258] Examples of olefin monomers include, but are not limited to, ethylene, propylene, and 1-butene. They can be used alone or in combination of two or more.

[0259] Monomers that can copolymerize with olefin monomers include, for example, 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, mesocarboxylic acid, and their esters (methyl esters, ethyl esters, etc.). They can be used alone or in combination of two or more.

[0260] When the modified polyolefin resin is a copolymer of an olefin monomer and a monomer capable of copolymerizing with the olefin monomer, as a monomer ratio, assuming the total mass of the copolymer is 100% by mass, preferably the olefin monomer is 60-95% by mass and the monomer capable of copolymerizing with the olefin monomer is 5-40% by mass, more preferably the olefin monomer is 70-85% by mass and the monomer capable of copolymerizing with the olefin monomer is 15-30% by mass. When the olefin monomer content is 60% by mass or more, the affinity with the matrix is ​​good; furthermore, when the olefin monomer content is 95% by mass or less, the modified polyolefin resin has good water dispersibility and is easy to uniformly impart to continuous reinforcing fibers.

[0261] In modified polyolefin resins used as bundle-forming agents, modified groups such as carboxyl groups introduced through copolymerization can be neutralized by alkaline compounds. Examples of alkaline 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 bundle-forming agent is not particularly limited, but is preferably 5,000 to 200,000, more preferably 50,000 to 150,000. From the perspective of improving the bundle-forming properties of continuous reinforcing fibers (e.g., glass fibers), a weight-average molecular weight of 5,000 or more is preferred, and from the perspective of improving emulsification stability when forming an aqueous dispersion, a weight-average molecular weight of 200,000 or less is preferred.

[0262] Modified polyamide resins used as bundle-forming agents are modified polyamide compounds with hydrophilic groups such as polyepoxide chains and tertiary amine components introduced into their molecular chains, and can be manufactured by known methods.

[0263] When a polyepoxide chain is introduced into the molecular chain, it can be manufactured by partially or wholly modifying polyethylene glycol or polypropylene glycol into a diamine or dicarboxylic acid and then copolymerizing the resulting modified product. When a tertiary amine component is introduced, it can be manufactured by copolymerizing aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam, etc.

[0264] The modified polyester resin used as a bundle-forming agent is a copolymer of a polycarboxylic acid or its anhydride and a polyol, and has hydrophilic groups in the molecular backbone containing the ends. This resin can be manufactured by known methods.

[0265] Examples of hydrophilic groups include polyepoxyalkyl groups, sulfonates, carboxyl groups, and their neutralized salts. Examples of polycarboxylic acids or their anhydrides include aromatic dicarboxylic acids, aromatic dicarboxylic acids containing sulfonates, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and polycarboxylic acids with three or more functions.

[0266] Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.

[0267] Examples of aromatic dicarboxylic acids containing sulfonates include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfophthalate.

[0268] Examples of aliphatic or alicyclic dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, and maleic anhydride.

[0269] Examples of polycarboxylic acids with three or more functions include, but are not limited to, trimellitic acid, benzopyrene, trimellitic anhydride, and pyromellitic dianhydride.

[0270] Among these, from the perspective of improving the heat resistance of modified polyester resins, it is preferable that 40 to 99 mol% of the total polycarboxylic acid components are aromatic dicarboxylic acids. Furthermore, from the perspective of improving the emulsification stability when the modified polyester resin is formulated into an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid components are sulfonate-containing aromatic dicarboxylic acids.

[0271] Examples of polyols that constitute modified polyester resins include diols and polyols with three or more functions.

[0272] Examples of diols include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, bisphenol A or its epoxide adducts, etc. Examples of polyols with three or more functions include trimethylolpropane, glycerol, pentaerythritol, etc.

[0273] As the copolymerization ratio of polycarboxylic acid or its anhydride to polyol constituting the modified polyester resin, the total mass of the copolymer components is set to 100% by mass. Preferably, the polycarboxylic acid or its anhydride is 40-60% by mass and the polyol is 40-60% by mass. More preferably, the polycarboxylic acid or its anhydride is 45-55% by mass and the polyol is 45-55% by mass.

[0274] The weight-average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, more preferably 10,000 to 30,000. From the perspective of improving the bundle properties of continuous reinforcing fibers (e.g., glass fibers), it is preferably 3,000 or more, and from the perspective of emulsification stability when the aqueous dispersion is prepared, it is preferably 100,000 or less.

[0275] The polymers and thermoplastic resins used as bundle-forming agents can be used alone or in combination.

[0276] Assuming the total amount of the binding agent is 100% by mass, preferably 50% or more, more preferably 60% or more, of one or more polymers selected from homopolymers of acrylic acid, copolymers of acrylic acid with other comonomers, copolymers of acrylates and / or methacrylates with comonomers, and salts of these with primary, secondary, and tertiary amines.

[0277] When the bundling agent is composed of a silane coupling agent and a bundling agent, the amount of bundling agent applied and attached is 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, relative to 100% by mass of the continuous reinforcing fiber (e.g., glass fiber), based on the total attached mass of the silane coupling agent and the bundling agent. From the perspective of controlling the bundling of the continuous reinforcing fiber (e.g., glass fiber) and improving the interfacial bonding strength, the amount of bundling agent attached is preferably 0.1% by mass or more relative to 100% by mass of the continuous reinforcing fiber (e.g., glass fiber), based on the total mass of the silane coupling agent and the bundling agent, and preferably 3% by mass or less from the perspective of fiber processability.

[0278] Furthermore, when the bundler is composed of a silane coupling agent, a lubricant, and a bundler, the amount of bundler preferably applied and attached is 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and even more preferably 0.2 to 1% by mass, relative to 100% by mass of the continuous reinforcing fiber (e.g., glass fiber), based on the total mass of the silane coupling agent, lubricant, and bundler (total attached mass ratio). Additionally, the aforementioned 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.

[0279] From the perspective of controlling the bundled properties of continuous reinforcing fibers (e.g., glass fibers) and improving interfacial bonding strength, the amount of the bundled agent attached is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, relative to 100% by mass of the continuous reinforcing fibers (e.g., glass fibers) and the total mass of the silane coupling agent, lubricant, and bundled agent. From the perspective of the processability of the fibers, it is preferably 3% by mass or less, more preferably 0.3% by mass or less.

[0280] In addition, the attachment mass of the coupling agent relative to 100% by mass of the continuous reinforcing fiber is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.9% by mass.

[0281] --Composition of fiber optic bundlers--

[0282] From the perspective of improving the bundle properties of glass fibers, improving interfacial bonding strength, and improving the mechanical strength of composite molded articles, the mixing amount of silane coupling agent in the bundle agent for glass fibers is preferably 0.1 to 2% by mass, more preferably 0.1 to 1% by mass, and even more preferably 0.2 to 0.5% by mass relative to 100% by mass of the bundle agent.

[0283] Regarding the amount of lubricant mixed in the fiber optic bundler, from the perspective of providing sufficient lubricity, it is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and from the perspective of improving interfacial bonding strength and improving the mechanical strength of the composite molded body, it 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.

[0284] Regarding the mixing amount of the bundle-forming agent in the bundle-forming agent for glass fibers, from the perspective of controlling the bundle-forming properties of glass fibers and improving the interfacial bonding strength and the mechanical strength of the composite molded body, it is preferably 1 to 25% by mass, more preferably 3 to 15% by mass, and even more preferably 3 to 10% by mass.

[0285] When glass fiber is used as a continuous reinforcing fiber, and the bundler is composed of a silane coupling agent, a lubricant, and a bundler, the bundler of the glass fiber preferably contains 0.1 to 2% by mass of a silane coupling agent, 0.01 to 1.5% by mass of a lubricant, and 1 to 25% by mass of a bundler, more preferably 0.1 to 2% by mass of a silane coupling agent, 0.01 to 1% by mass of a lubricant, and 1 to 25% by mass of a bundler. Preferably, these components are diluted with water to adjust the total mass to 100% by mass.

[0286] --How to use fiber optic bubbling agents--

[0287] Depending on the application method, the bridging agent for glass fiber can be prepared in any form, such as an aqueous solution, a colloidal dispersion, or an emulsion containing an emulsifier. From the perspective of improving the dispersion stability and heat resistance of the bridging agent, the aqueous solution form is preferred.

[0288] Regarding the glass fiber, which is the continuous reinforcing fiber constituting the continuous fiber reinforced resin composite material of this embodiment, the aforementioned slugging agent is applied to the glass fiber using a known method such as a roller coater in a known glass fiber manufacturing process, and the manufactured glass fiber is dried, thereby continuously obtaining the glass fiber.

[0289] In addition, other methods of using a fiber optic bubbling agent include immersing fiber optics in a liquid containing the bubbling agent and immersing a fiber optic substrate in a liquid containing the bubbling agent.

[0290] Furthermore, when carbon fiber is selected as the continuous reinforcing fiber, a bundling agent can also be used. The bundling agent is preferably composed of a coupling agent (e.g., a silane coupling agent), a lubricant, and a bundling agent. As the coupling agent, a substance with good compatibility with the hydroxyl groups present on the surface of the carbon fiber can be selected. As the bundling agent, a substance with good wettability or similar surface tension to the selected thermoplastic resin can be selected. As the lubricant, a substance that does not hinder the coupling agent and the bundling agent can be selected. Suitable coupling agents for carbon fiber include diamines such as 1,6-hexanediamine and polycarboxylic acids.

[0291] As a lubricant, one can choose a substance that will not hinder coupling agents and bundlers.

[0292] There are no particular restrictions on the type of slugging agent used in carbon fiber; any known material can be used. Specifically, for example, the material described in Japanese Patent Application Publication No. 2015-101794 can be used.

[0293] When using other continuous reinforcing fibers, the type and amount of slugging agent that can be used in glass fiber or carbon fiber can be appropriately selected according to the characteristics of the continuous reinforcing fiber. It is preferable to use the type and amount of slugging agent based on the slugging agent used in carbon fiber.

[0294] (Shape of continuous reinforcing fibers)

[0295] The continuous reinforcing fiber is a multifilament composed of multiple filaments. From a processability perspective, the number of monofilaments is preferably 30 to 15,000.

[0296] From the perspectives of strength and processability, the monofilament diameter R of the continuous reinforcing fiber is preferably 2-30 μm, more preferably 4-25 μm, further preferably 6-20 μm, and most preferably 8-18 μm.

[0297] From the perspectives of the processability of continuously reinforced fibers and the strength of composite materials, the monofilament diameter R (μm) and density D (g / cm³) of continuously reinforced fibers are related. 3 The product RD is preferably 5–100 μm·g / cm³. 3 More preferably, it is 10–50 μm·g / cm 3 A further preferred value is 15–45 μm·g / cm³. 3 More preferably, it is 20–45 μm·g / cm 3 .

[0298] Density D can be measured using a hydrometer.

[0299] On the other hand, the diameter of a single filament R (μm) can be determined based on the density D (g / cm³). 3 The fineness (dtex) and the number of single filaments are calculated by the following formula.

[0300] [Number 1]

[0301]

[0302] In addition, the diameter of a single filament, R (μm), can be determined, for example, by SEM observation of continuously reinforced fiber filaments.

[0303] To ensure that the product RD of the continuous reinforcing fiber falls within a specified range, the fineness (dtex) and the number of filaments can be appropriately selected based on the density of the commercially available continuous reinforcing fiber. For example, when glass fiber is used as the continuous reinforcing fiber, since its density is approximately 2.5 g / cm³... 3 Therefore, fibers with a single filament diameter of 2–40 μm can be selected. Specifically, when the glass fiber single filament diameter is 9 μm, by selecting glass fibers with a fineness of 660 dtex and 400 single filaments, the product RD is 23. Furthermore, when the glass fiber single filament diameter is 17 μm, by selecting glass fibers with a fineness of 11,500 dtex and 2,000 single filaments, the product RD is 43. When carbon fiber is used as a continuous reinforcing fiber, since the density is approximately 1.8 g / cm³... 3 Therefore, fibers with a single filament diameter of 2.8–55 μm can be selected. Specifically, when the carbon fiber has a single filament diameter of 7 μm, by selecting carbon fibers with a fineness of 2,000 dtex and 3,000 single filaments, the product RD is 13. When aramid fibers are used as continuous reinforcing fibers, the density is approximately 1.45 g / cm³. 3 Therefore, fibers with a single filament diameter of 3.4–68 μm can be selected. Specifically, when the single filament diameter of aramid fiber is 12 μm, by selecting aramid fiber with a fineness of 1,670 dtex and a single filament count of 1,000, the product RD is 17.

[0304] Continuous reinforcing fibers (such as glass fibers) are manufactured as follows: raw glass is metered and mixed, molten glass is produced using a melting furnace, it is spun into glass fibers, coated with a sizing agent, and then wound into the form of direct untwisted roving (DWR), yarn cake, twisted yarn, etc., using a spinning machine.

[0305] Continuous reinforcing fibers can be in any form, but if they are wound into yarn, yarn cake, or DWR, the productivity and production stability in the resin coating process are improved, making it preferable. From a productivity perspective, DWR is the most preferred.

[0306] There are no particular restrictions on the form of continuous reinforcing fibers. Various forms can be included, such as woven fabrics, knitted fabrics, braided tapes, tubular materials, non-crimped fabrics, and unidirectional materials. The preferred forms are woven fabrics, non-crimped fabrics, and unidirectional materials.

[0307] (Thermoplastic resin)

[0308] In the thermoplastic resin constituting the continuous fiber reinforced resin composite material of this embodiment, the peak temperature of the loss tangent tanδ is preferably 80°C or higher, more preferably 85°C or higher, further preferably 90°C or higher, and even more preferably 100°C or higher. When the peak temperature of the thermoplastic resin tanδ is within the above range, the number of AE signals with an amplitude of 40 dB or higher and a duration of 3500 microseconds or less tends to decrease, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 microseconds or less tends to increase, and the total AE count tends to increase.

[0309] The peak temperature of the loss tangent tanδ of a thermoplastic resin refers to the temperature at which the value of tanδ is maximized when tanδ is measured at various temperatures while the temperature is changed. The peak temperature of tanδ can be determined, for example, by applying a nanoindenter to a single filament of a continuous reinforcing fiber in a cross-section orthogonal to its length direction and performing nanoindentation (nanoDMA) on a nanoindenter. Specifically, it can be measured using the method described in the examples below.

[0310] As a method to adjust the tanδ of thermoplastic resin to the above range, for example, a method to adjust the concentration of aromatic rings in the resin can be given. If the concentration of aromatic rings in the resin increases, the peak temperature of tanδ tends to increase.

[0311] In this embodiment, the thermoplastic resin is preferably in the range of 950–1050 cm⁻¹. -1 It has a Raman peak (a peak in the Raman spectrum), more preferably in the range of 970–1030 cm⁻¹. -1 It has this Raman peak. When the Raman peak of the thermoplastic resin is within the above range, the number of AE signals with an amplitude of 40 dB or more and a duration of 3500 microseconds or less in the continuous fiber reinforced composite material tends to decrease, the number of AE signals with an amplitude of 25 to 30 dB and a duration of 1000 microseconds or less tends to increase, and the total number of AE counts tends to increase.

[0312] The Raman peak of the thermoplastic resin in this embodiment can be determined, for example, by measuring the Raman spectrum of the resin region in a cross section orthogonal to the length direction of the continuous reinforcing fibers contained in the thermoplastic resin film using a laser Raman microscope. Specifically, it can be measured by the method described in the embodiments described later.

[0313] In this embodiment, the thermoplastic resin can be two or more types. The difference in saturated water absorption rate between the two or more thermoplastic resins with the highest and lowest saturated water absorption rates is preferably 2.0% by mass or more, more preferably 2.5% by mass or more, and even more preferably 2.8% by mass or more. When the saturated water absorption rate is within this range, the continuous fiber reinforced resin composite material exhibits excellent strength, elastic modulus, water absorption characteristics, high-temperature characteristics, fatigue characteristics, impact characteristics, and warpage characteristics.

[0314] When there are two or more thermoplastic resins, from the perspective of high-temperature properties and water absorption properties, the mass ratio of the resin with the largest mass ratio is preferably 5 times or less than that of the resin with the second largest mass ratio, more preferably 4 times or less, and even more preferably 3 times or less. When the mass ratio of thermoplastic resins is within the above range, the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) of the continuous fiber reinforced resin composite material tend to be improved.

[0315] Thermoplastic resins may 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 polypropylene terephthalate; polyacetal resins such as polyoxymethylene; polycarbonate resins; polyether ketone, polyetheretherketone, polyether glycol, polypropylene glycol, and polytetramethylene ether glycol; polyethersulfone; polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluoropolymers such as tetrafluoroethylene-ethylene copolymer; polyurethane resins; acrylic resins; and modified thermoplastic resins derived from them.

[0316] As a thermoplastic resin used in continuous fiber reinforced resin composites possessing characteristic (II), polyamide 6T, polyamide 6I / 6T, polyamide MXD6, polyamide 11, polyamide 12, polyamide 610, and polyamide 1010 can be used.

[0317] In addition, as a thermoplastic resin used in a continuous fiber reinforced resin composite material having characteristic (III), polyamide 1010, polyamide 12, polyamide 610, and polyamide 410 can be used.

[0318] In addition, polyamide 1010 and polyamide 12 can be used as thermoplastic resins in continuous fiber reinforced resin composites with characteristic (IV).

[0319] Furthermore, as the thermoplastic resin used in the continuous fiber reinforced resin composite material possessing characteristic (V), polyamide resins such as polyamide 6T, polyamide 6I / 6T, polyamide MXD6, polyamide 11, polyamide 12, polyamide 610, and polyamide 1010, as well as polyphenylene ether, can be used. Polyphenylene ether is also a preferred example of the thermoplastic resin used in the continuous fiber reinforced resin composite material possessing characteristic (V).

[0320] Thermoplastic resins can be used alone or in mixtures of two or more.

[0321] Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyethersulfone, polyphenylene sulfide, thermoplastic polyetherimide, and thermoplastic fluoropolymers are preferred. From the perspective of mechanical properties and versatility, polyolefin resins, modified polyolefin resins, polyamide resins, polyester resins, polyurethane resins, and acrylic resins are more preferred. Considering thermal properties, polyamide resins and polyester resins are further preferred. Furthermore, from the perspective of durability against repeated heavy loads, polyamide resins are even more preferred.

[0322] -Polyester-based resins-

[0323] Polyester resins are polymeric compounds with -CO-O- (ester) bonds in their main chain.

[0324] Examples of polyester resins include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexyldimethyl terephthalate, and polyethylene 2,6-naphthalenedicarboxylate.

[0325] Polyester resins can be homopolymer polyesters or copolymer polyesters.

[0326] In the case of copolyester, it is preferable to copolymerize the third component with the homopolymer polyester. Examples of the third component include, but are not limited to, diols such as diethylene glycol, neopentyl glycol, polyalkylene glycol, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and dicarboxylic acid such as 5-(sodium sulfonyl) isophthalic acid.

[0327] Alternatively, polyester resins made from biomaterials can be used, including but not limited to aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and aromatic polyester resins such as polybutylene terephthalate adipate.

[0328] -Polyamide resins-

[0329] Polyamide resins are polymeric compounds with -CO-NH- (amide) bonds in their main chain. Examples include aliphatic polyamides, aromatic polyamides, and fully aromatic polyamides.

[0330] Examples of polyamide resins include, but are not limited to, polyamides obtained by ring-opening polymerization of lactams, polyamides obtained by self-condensation of ω-aminocarboxylic acids, polyamides obtained by condensation of diamines and dicarboxylic acids, and copolymers thereof.

[0331] Polyamide resins can be used alone or in a mixture of two or more types.

[0332] Examples of lactams include, but are not limited to, pyrrolidone, caprolactam, undecylactam, and dodecalactam.

[0333] Examples of ω-aminocarboxylic acids include, but are not limited to, water-based open-ring compounds such as lactams, i.e., ω-amino fatty acids. Lactams or ω-aminocarboxylic acids can be condensed by combining two or more monomers.

[0334] Examples of diamines (monomers) include, but are not limited to, straight-chain 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.

[0335] Examples of dicarboxylic acids (monomers) include, but are not limited to, aliphatic dicarboxylic acids such as adipic acid, pimelic acid, and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Diamines and dicarboxylic acids, as monomers, can be condensed by using one or more of them individually.

[0336] Examples of polyamide resins include, but are not limited to, aliphatic polyamides such as polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaprolactam), polyamide 11 (polyundecanoamide), polyamide 12 (polydodecanoamide), polyamide 46 (polyhexamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, etc., semi-aromatic polyamides such as polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonyl terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide), as well as copolymer polyamides containing them as constituent components.

[0337] Examples of copolyamides include, but are not limited to, copolymers of adipamide and terephthalamide, copolymers of adipamide and isophthalamide, and copolymers of terephthalamide and 2-methylpentanediamine terephthalamide.

[0338] As the thermoplastic resin used in continuous fiber reinforced resin composites with characteristic (II), aliphatic polyamides such as polyamide 1010, semi-aromatic polyamides such as polyamide MXD6 and polyamide 6I / 6T can be used.

[0339] As a thermoplastic resin used in continuous fiber reinforced resin composites with characteristic (V), aliphatic polyamides such as polyamide 1010, semi-aromatic polyamides such as polyamide MXD6 and polyamide 6I / 6T can be used.

[0340] When using polyamide resin, the thermoplastic resin preferably contains 50 to 99 parts by weight of (A) aliphatic polyamide and 1 to 50 parts by weight of (B) semi-aromatic polyamide, wherein the (B) semi-aromatic polyamide contains dicarboxylic acid units (which contain at least 75 mol% of isophthalic acid units) and diamine units (which contain at least 50 mol% of diamine units having 4 to 10 carbon atoms).

[0341] When a thermoplastic resin contains (A) aliphatic polyamide and (B) semi-aromatic polyamide within the above range, the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) of the continuous fiber reinforced resin composite material tend to be improved compared to the case where the polyamide contains only (A) aliphatic polyamide.

[0342] The total content of (A) aliphatic polyamide and (B) semi-aromatic polyamide relative to 100% by mass of thermoplastic resin is preferably 70-100% by mass, more preferably 80-100% by mass, and even more preferably 90-100% by mass.

[0343] The weight-average molecular weight (Mw) of the thermoplastic resin comprising (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably 15,000 to 35,000, more preferably 17,000 to 35,000, further preferably 20,000 to 35,000, even more preferably 22,000 to 34,000, particularly preferably 24,000 to 33,000, and most preferably 25,000 to 32,000. When the weight-average molecular weight (Mw) of the above-mentioned thermoplastic resin is within the above range, it tends to have increased strength and rigidity.

[0344] In addition, among the above-mentioned thermoplastic resins, (A) aliphatic polyamide has a weight-average molecular weight Mw A Preferably, the weight-average molecular weight Mw of (B) semi-aromatic polyamide is... B More than 1.5 times, more preferably more than 2 times. A For Mw B When the strength is more than 1.5 times that of the material, the strength and rigidity tend to increase.

[0345] It should be noted that the weight-average molecular weight (Mw) of the thermoplastic resin, (A) aliphatic polyamide, and (B) semi-aromatic polyamide can be determined by gel permeation chromatography (GPC), specifically by the method described in the examples below.

[0346] Examples of aliphatic polyamides (A) mentioned above include, but are not limited to, polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, etc.

[0347] The content of (A) aliphatic polyamide in 100% by mass of polyamide in the thermoplastic resin is preferably 50-99% by mass, more preferably 60-90% by mass, and even more preferably 70-80% by mass.

[0348] Examples of the above-mentioned (B) semi-aromatic polyamides include, but are not limited to, polyamide 6I, polyamide 9I, and polyamide 10I.

[0349] The total amount of the isophthalic acid unit and the diamine unit with 4 to 10 carbon atoms is preferably 80 to 100 mol% relative to 100 mol% of all structural units of (B) semi-aromatic polyamide, more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%.

[0350] It should be noted that the proportion of monomer units constituting (B) semi-aromatic polyamide can be, for example, determined by... 13 The determination was performed using nuclear magnetic resonance (NMR) spectrophotometry.

[0351] (B) In the semi-aromatic polyamide, the proportion of isophthalic acid units in the dicarboxylic acid units is at least 75 mol%, preferably 85 mol% or more, and more preferably 90 mol% or more. When the proportion of isophthalic acid units in the dicarboxylic acid units is within the above range, the high-temperature properties and water absorption properties tend to be improved.

[0352] (B) In the semi-aromatic polyamide, the proportion of diamine units with 4 to 10 carbon atoms in the diamine unit is at least 50 mol%, preferably 60 mol% or more, and more preferably 70 mol% or more. When the proportion of diamine units with 4 to 10 carbon atoms in the diamine unit is within the above range, the high-temperature properties and water absorption properties tend to be improved.

[0353] The content of (B) semi-aromatic polyamide in 100% by mass of polyamide in the thermoplastic resin is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 20 to 30% by mass.

[0354] The aforementioned (A) aliphatic polyamide and (B) semi-aromatic polyamide can be end-capped using a known end-capping agent. The total amount of end-capped (A) aliphatic polyamide and (B) semi-aromatic polyamide, expressed as the equivalent of 1 g of polyamide combined with (A) aliphatic polyamide and (B) semi-aromatic polyamide, is preferably 5–180 microequivalents (μequivalents) / g, more preferably 10–170 microequivalents / g, further preferably 20–160 microequivalents / g, particularly preferably 30–140 microequivalents / g, and most preferably 40–140 microequivalents / g. When the amount of end-capped (A) is within the above range, physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, and appearance, etc.) tend to improve.

[0355] Here, the amount of terminated ends refers to the total amount of amino and carboxyl terms terminated using a terminating agent. The amount of terminated ends can be determined using... 1 The H-NMR measurements are performed, specifically, by the methods described in the examples below.

[0356] (A) The terminal group concentration of aliphatic polyamide is preferably less than 1 / 2 of the terminal group concentration of (B) semi-aromatic polyamide, more preferably less than 2 / 5 of it. When the terminal group concentration of aliphatic polyamide is less than 1 / 2 of the terminal group concentration of (B) semi-aromatic polyamide, the physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, and appearance, etc.) tend to improve.

[0357] The concentration of the end groups of (A) aliphatic polyamides and (B) semi-aromatic polyamides can be used... 1 The H-NMR measurements are performed, specifically, by the methods described in the examples below.

[0358] The difference in tanδ peak temperature between (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably 45–100°C, more preferably 50–90°C, and even more preferably 60–90°C. When the difference in tanδ peak temperature between (A) aliphatic polyamide and (B) semi-aromatic polyamide is within the above range, the high-temperature properties and water absorption properties tend to be improved.

[0359] The peak temperature of the loss tangent tanδ refers to the temperature at which the value of tanδ is the largest when tanδ is measured at various temperatures while the temperature is changed. The peak temperatures of tanδ for (A) aliphatic polyamides and (B) semi-aromatic polyamides can be measured, for example, using a viscoelasticity measuring and analyzing apparatus, and more specifically, by the methods described in the examples below.

[0360] From the perspectives of strength, rigidity, formability, and appearance, the viscosity difference between (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably more than 3 times, and more preferably more than 4 times.

[0361] The viscosity of thermoplastic resins can be determined by MFR measurement (according to ISO 1133), and more specifically, by observation using the methods described in the examples below.

[0362] [additive]

[0363] The continuous fiber reinforced resin composite material of this embodiment may contain additives as needed. The composite material of this embodiment may contain, for example, colorants, anti-aging agents, antioxidants, weathering agents, metal passivators, light stabilizers, heat stabilizers, ultraviolet absorbers, antibacterial / mildew inhibitors, deodorizers, conductivity imparting agents, dispersants, softeners, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanization aids, foaming agents, foaming aids, flame retardants, shock absorbers, nucleating agents, neutralizing agents, lubricants, anti-blocking agents, dispersants, flowability improvers, release agents, and other additives. It should be noted that the above-mentioned additives refer to substances other than the above-mentioned components (e.g., components contained in the above-mentioned thermoplastic resin, the above-mentioned continuous reinforcing fiber, the above-mentioned hybrid thermoplastic resin composition, and components contained in the bundler).

[0364] The content of additives can be less than 3% by mass relative to 100% of the composite material.

[0365] (Coloring agent)

[0366] Examples of colorants include carbon black, nigroscin, aluminum pigments, titanium dioxide, ultramarine, anthocyanin, anthocyanin green, quinacridone, diatomaceous earth, monoazo salts, perylene, diazo, condensed azo, isoindoline, iron oxide red, nickel titanium yellow, diketopyrrolopyrrole, metal salts, perylene red, metal oxides, bismuth vanadate, cobalt green, cobalt blue, anthraquinone, phthalocyanine green, and phthalocyanine blue. Black colorants are preferred, with carbon black and nigroscin being more preferred.

[0367] In the continuous fiber reinforced resin composite material of this embodiment, it is preferable that the content of continuous reinforcing fiber is 90 to 525 parts by weight relative to 100 parts by weight of thermoplastic resin, and the content of other components is 0 to 2 parts by weight. More preferably, the content of continuous reinforcing fiber is 150 to 340 parts by weight relative to 100 parts by weight of thermoplastic resin, and the content of other components is 0 to 1 part by weight.

[0368] In the continuous fiber reinforced resin composite material of this embodiment with feature (IV), the volume ratio Vf (%) of the continuous reinforcing fibers in the continuous fiber reinforced resin composite material is preferably 20-80%, more preferably 30-70%, and even more preferably 40-60%.

[0369] In the continuous fiber reinforced resin composite material of this embodiment, which has feature (IV), the continuous fiber reinforced resin composite material can be a composite material consisting only of thermoplastic resin and continuous reinforcing fibers.

[0370] Applications of continuous fiber reinforced resin composites

[0371] The continuous fiber reinforced resin composite material of this embodiment can be suitable for use as a structural material in aircraft, vehicles, construction materials, robots, etc.

[0372] In vehicle applications, it can be used in, but is not limited to, chassis / frames, underframes, drive system components, interior components, exterior components, functional components, and other components.

[0373] Specifically, it can be suitably used for the following components: steering shaft, bracket, sunroof, pedal, roof panel, door panel, trunk, tailgate, hood, seat frame, seat back, seatbelt retractor, seatbelt retractor support, clutch, gear, pulley, cam shaft, AG shaft, elastic beam, shock absorber, light, reflector, window, front module, rear door inner panel, brake pedal, steering wheel, electrical components, sound-absorbing materials, door exterior, interior panels, dashboard, tailgate, roof beam, seat, seat frame, wiper linkage, EPS (Electric Power Steering), small motor, radiator, ECU (Engine Control Unit) box, ECU cover, steering gearbox cover, plastic cover, EV (Electric Vehicle) Vehicle components include: motor housings, wiring harnesses, vehicle instruments, combination switches, small motors, springs, shock absorbers, wheels, wheel covers, chassis, subframes, side frames, two-wheeled vehicle frames, fuel tanks, oil pans, intake manifolds, drive shafts, drive motors, single-unit cabins, hydrogen tanks, fuel cell electrodes, panels, floor panels, outer panels, doors, passenger compartments, roofs, covers, valves, and EGR (Exhaust Gas Recirculation). Recirculation valve, variable valve timing unit, connecting rod, cylinder bore, beams (engine mounts, front floor crossbeam, footrest crossbeam, seat crossbeam, inner side beam, rear crossbeam, suspension beam, pillar reinforcement beam, front side beam, front panel beam, upper panel beam, front bulkhead crossbeam, steering column), channels, locking inserts, gearbox, transmission rail, axle housing, roof rail, upper body, side rails, trim strips, door surround assemblies, airbag components, pillars, front bulkhead to pillar support, suspension towers, bumpers, lower body pillars, front pillars, reinforcements (instrument panel, rails, roof, front pillars, roof rails, roof side rails, storage compartments, door waistlines, lower front floor, upper front body pillar, lower front body pillar, center pillar, center pillar hinge, outer door panel), side panels, front door window frames, MICS (Minimum Intrusion Container System).Minimum Intrusion Cabin System components, torque converter, radiator bracket, radiator fan, water pump, fuel pump, electronic throttle, engine control ECU, starter, alternator, manifold, transmission, clutch, front bulkhead, front bulkhead insulation pad, door side impact beams, bumper beams, door beams, partitions, outer side pads, inner side pads, rear seat poles, door panels, door trim sub-assemblies, energy absorption components (bumpers, shock absorbers), shock absorber bodies, shock absorber trim strips, pillar trim strips, inner roof trim strips, resin ribs, side rail front spacer. Components include: side rail rear spacer, seat belt pretensioners, airbag sensors, arms (suspension, lower arm, hood hinges), suspension links, shock absorber brackets, mudguard brackets, inverter brackets, inverter modules, inner hood panel, hood plate, front hood vents, outer front top panel of the front hood, outer top panel of the front hood, floor muffler, shock-absorbing seat, hood insulation, mudguard side panel protectors, front hood insulation, top hood vents, cylinder head cover, tire deflectors, mudguard support brackets, strut towerbar, mission center tunnel, floor tunnel, radiator core supports, trunk trim, trunk floor, accelerator pedal, accelerator pedal base, etc.

[0374] [Molding of composite materials]

[0375] The continuous fiber reinforced resin composite material of this embodiment can be further molded. Examples of the above methods include: cutting the continuous fiber reinforced resin composite material of this embodiment into a predetermined size, heating it with an infrared heater, and then compressing and pressing it using a compression molding machine; or injection molding, where the resin is heated with an infrared heater, compressed and pressed using a compression molding machine, and then injection molded.

[0376] (Feature (II))

[0377] The continuous fiber reinforced resin composite material of this embodiment preferably further possesses the following feature (II).

[0378] [Continuous fiber reinforced resin composites]

[0379] The continuous fiber reinforced resin composite material of this embodiment, possessing feature (II), preferably comprises continuous reinforcing fibers and resin, wherein the AE count A is 0.16 or less, and the coverage of the interfacial resin on the continuous reinforcing fibers after resin dissolution is 44% or less. In this specification, the coverage of the interfacial resin on the continuous reinforcing fibers after resin dissolution is sometimes referred to as "feature (II)".

[0380] The coverage rate is preferably 40% or less, more preferably 37% or less, and even more preferably 35% or less.

[0381] The coverage rate is preferably 3% or more, more preferably 10% or more, and even more preferably 20% or more.

[0382] The resin coating rate of the continuous reinforcing fiber interface after resin dissolution can be determined as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with the above-mentioned fresh solvent to remove components other than the resin bonded to the continuous reinforcing fiber. After drying, the coating rate is determined by X-ray photoelectron spectroscopy (XPS). The coating rate is determined based on the proportion of thermoplastic resin component in the thermoplastic resin component and the continuous reinforcing component at this time.

[0383] The thermoplastic resin contained in the continuous fiber reinforced resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fibers are washed with the above-mentioned fresh solvent to remove components other than the resin bound to the continuous reinforcing fibers. There are no particular limitations on the method of drying, and the following processing methods can be cited.

[0384] (a) Cut the above continuous fiber reinforced resin composite material into thin slices.

[0385] (b) Add 100 mg of the above continuous fiber reinforced resin composite sheet and 20 mL of solvent selected according to the resin into a mixer and stir for 5 hours.

[0386] (c) Remove the solvent by filtration, spray 40 mL of the above-mentioned fresh solvent onto the filter, wash the continuous reinforcing fibers and then air dry them.

[0387] (d) Add the continuous reinforcing fiber obtained in (c) and 20 mL of the fresh solvent mentioned above into a mixer and stir for 2 hours.

[0388] (e) Remove the solvent by filtration, spray 40 mL of the above-mentioned fresh solvent onto the filter, wash the continuous reinforcing fiber, and dry it with a nitrogen stream.

[0389] (f) Add the continuous reinforcing fiber obtained in (e) and 20 mL of the fresh solvent mentioned above into a mixer and stir for 2 hours.

[0390] (g) Remove the solvent by filtration, spray 40 mL of the above-mentioned fresh solvent onto the filter, wash the continuous reinforcing fiber and then air dry it.

[0391] (h) Dry overnight using a vacuum dryer set to room temperature.

[0392] In the above processing method, the solvent selected according to the resin can be a solvent that dissolves the thermoplastic resin contained in the composite material with high solubility (preferably 0.10 g / mL or more, more preferably 0.15 g / mL or more).

[0393] For example, in the case of polyamide, hexafluoroisopropanol (HFIP) can be selected; in the case of polypropylene, hot xylene can be selected; and in the case of polyphenylene ether, chloroform can be selected.

[0394] Regardless of whether the continuous reinforcing fiber is glass fiber or carbon fiber, as long as the continuous reinforcing fiber used is substantially insoluble (solubility less than 0.1 mg / mL) in the solvent selected according to the resin, the above-described processing method can be operated without change.

[0395] When the thermoplastic resin contained in the composite material is different, the solvent can be changed according to the resin, otherwise the same treatment method as described above can be implemented.

[0396] Furthermore, for example, when the resin is polyamide and the continuous reinforcing fiber is glass fiber, the coating ratio can be calculated using (coating ratio) = [N] / ([N] + [Si]). Here, [N] is the relative elemental concentration of nitrogen determined by XPS measurement for the continuous reinforcing fiber after resin dissolution, and [Si] is the relative elemental concentration of silicon determined similarly.

[0397] For example, when the resin is polyamide and the continuous reinforcing fiber is carbon fiber, the coating ratio can be calculated using (coating ratio) = [N] / ([N] + [O]). Here, [N] is the relative elemental concentration of nitrogen determined by XPS for the continuous reinforcing fiber after resin dissolution, and [O] is the relative elemental concentration of oxygen determined by XPS in the same way.

[0398] For example, when the resin is polypropylene and the continuous reinforcing fiber is glass fiber, the coating ratio can be calculated using (coating ratio) = ([C] - [C0]) / ([C] - [C0] + [Si]). Here, [C] is the relative elemental concentration of carbon determined by XPS measurement of the continuous reinforcing fiber after resin dissolution. [C0] is the relative elemental concentration of carbon determined by XPS measurement of the treated continuous reinforcing fiber, which is a raw material without a binding agent (sizing agent). [Si] is the relative elemental concentration of silicon determined by XPS measurement of the continuous reinforcing fiber after resin dissolution. Here, the continuous reinforcing fiber as a material refers to the continuous reinforcing fiber itself as a raw material.

[0399] It should be noted that, regarding XPS measurements, specifically, the measurements were performed as described in the examples.

[0400] When the resin coverage of the continuous reinforcing fiber interface after resin dissolution is within the above range, it can exhibit higher bending vibration fatigue characteristics.

[0401] To adjust the coverage rate to the aforementioned range, for example, a method can be used whereby the contact angle between the continuous reinforcing fiber and the thermoplastic resin, after the resin has been dissolved, and the contact angle between the continuous reinforcing fiber and the thermoplastic resin, as a material treated only with a coupling agent, is 70% to 130% of the contact angle between the continuous reinforcing fiber and the thermoplastic resin, as determined by a static wetting test, and the impregnation rate of the thermoplastic resin onto the continuous reinforcing fiber is 32% / min or higher. Here, the continuous reinforcing fiber as a material refers to the continuous reinforcing fiber itself as a raw material.

[0402] The contact angle is preferably 80-120%, and more preferably 90-110%.

[0403] When the contact angle is within the above range, the thermoplastic resin and the coupling agent are well compatible, and can remove the excess components contained in the sizing agent (applying agent) that do not play a role in interface formation, and the interface thickness is sufficiently reduced.

[0404] It should be noted that the contact angle based on the static wettability test can be measured, for example, as follows: a monofilament of continuous reinforcing fiber and a film of thermoplastic resin are sandwiched between a coverslip, the temperature is raised above the melting point of the thermoplastic resin, and the contact angle between the continuous reinforcing fiber and the thermoplastic resin is observed using an optical microscope just before cooling begins. In detail, the measurement can be performed by the method described in the examples.

[0405] The impregnation rate is preferably 48% / min or more, and more preferably 64% / min or more.

[0406] It should be noted that the impregnation rate can be measured by the following method, specifically, by the method described in the examples. That is, a continuous reinforcing fiber substrate and a thermoplastic resin substrate are laminated. Heating and cooling are performed, with the time required for the thermoplastic resin to reach above its melting point being 60 seconds. Specifically, the mold temperature is set to a suitable temperature, with the highest temperature inside the mold being between the melting point of the thermoplastic resin and 6°C to 25°C. The molding pressure is set to 5 MPa. After heating and pressing, cooling and pressing are performed under water cooling at a pressure of 5 MPa. Subsequently, the obtained continuous reinforcing fiber composite material is cut using a band saw, ground, and the impregnation rate (%) is calculated for the cross-section (described later). This percentage is divided by the time (in minutes) during heating and pressing to reach above the melting point of the thermoplastic resin, thereby determining the impregnation rate.

[0407] Here, the impregnation rate (%) can be determined by the proportion of voids in the continuous reinforcing fibers in a cross-section of the continuous fiber reinforced resin composite material observed by SEM. Specifically, for example, the continuous fiber reinforced resin composite material is cut at an arbitrary location, ground, and then observed by SEM. The resulting cross-sectional image is analyzed using analysis software to calculate the area of ​​the region surrounded by the outer contour line of the continuous reinforcing fibers, which are bundles of monofilaments (filaments), and the area of ​​voids contained in the region surrounded by the outer contour line of the continuous reinforcing fibers.

[0408] Regarding the impregnation rate (%), when the specified area is set to 100%, it is calculated by the following formula.

[0409] Impregnation rate (%) = [1 - {void area / (area of ​​the region surrounded by the outer contour line of the continuous reinforcing fiber)} × 100

[0410] Furthermore, the impregnation rate of each of the 10 continuous reinforcing fibers in the obtained cross-sectional image is calculated, and the average value is taken as the impregnation rate.

[0411] The exposure of the continuously reinforcing resin (hereinafter also referred to as "interface exposed reinforcing fiber") after the above-mentioned resin is dissolved is preferably 55% or more, more preferably 62% or more, further preferably 66% or more, and even more preferably 72% or more.

[0412] The exposure of the reinforcing fiber at the interface is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, and even more preferably 80% or less.

[0413] The exposure degree of the aforementioned interface-exposed reinforcing fiber can be determined, for example, as follows: using the same method as in the determination of the coating rate of the interface resin of the continuous reinforcing fiber after resin dissolution, the thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh of the aforementioned solvent to remove components other than the resin bonded to the continuous reinforcing fiber. After drying, the exposure degree is determined by X-ray photoelectron spectroscopy (XPS). The relative elemental concentration of the elements from the obtained continuous reinforcing fiber is divided by the relative elemental concentration of the elements from the unprocessed continuous reinforcing fiber that has not undergone sizing treatment.

[0414] More specifically, regarding the exposure degree of the continuously reinforcing resin after resin dissolution (exposing the reinforcing fibers at the interface), in the case where the continuously reinforcing fibers are glass fibers, it can be calculated, for example, by (the proportion of reinforcing fibers exposed at the interface) = [Al] / [Al0]. [Al] is the relative elemental concentration of aluminum determined by XPS measurement of the continuously reinforcing fibers after resin dissolution as described above. [Al0] is the relative elemental concentration of aluminum determined by XPS measurement of the treated continuously reinforcing fibers, which are treated similarly as raw materials without a binding agent (adhesive).

[0415] When the continuous reinforcing fiber is carbon fiber, it can be calculated, for example, by (the proportion of reinforcing fiber exposed at the interface) = [O] / [O0]. [O] is the relative elemental concentration of oxygen determined by XPS measurement of the continuous reinforcing fiber after resin dissolution as described above. [O0] is the relative elemental concentration of oxygen determined by XPS measurement of the treated continuous reinforcing fiber after similar treatment using a raw material that does not contain a sizing agent (adhesive).

[0416] When the exposed area of ​​the reinforcing fiber at the interface is within the range described above, it can exhibit high strength under high temperature conditions.

[0417] To adjust the exposure to the aforementioned range, for example, a method can be used to make the contact angle between the continuous reinforcing fiber and the thermoplastic resin based on a static wettability test 70% to 130% of the contact angle between the continuous reinforcing fiber treated only with a coupling agent and the thermoplastic resin based on a static wettability test, and to make the impregnation rate of the thermoplastic resin for the continuous reinforcing fiber 32% / min or more.

[0418] Regarding continuous reinforcing fibers that do not contain sizing agents (hereinafter also referred to as "continuous reinforcing fibers without sizing agents"), "without sizing agents" means that when the total mass of the continuous reinforcing fibers without sizing agents is set at 100%, the content of the sizing agent (hereinafter referred to as "sizing agent") is less than 0.45% by mass. In zeta potential measurement, the isoelectric point is less than pH=3, and the value is negative at pH 3 to 8. It should be noted that the zeta potential can be determined, for example, by using a solid-state dedicated zeta potential meter and adjusting the pH with hydrochloric acid or potassium hydroxide.

[0419] Methods for obtaining continuous reinforcing fibers without sizing agents include: methods that do not use sizing agents (adhesives) during the manufacture of continuous reinforcing fibers; and methods that remove the sizing agents (adhesives) from continuous reinforcing fibers containing sizing agents (adhesives) using an electric furnace or the like.

[0420] In the above-mentioned composite material, the relative elemental concentration of interfacial nitrogen after resin dissolution is preferably 6.70 or less, more preferably 5.70 or less, further preferably 5.20 or less, and even more preferably 5.00 or less.

[0421] The relative elemental concentration of nitrogen at the interface after resin dissolution is preferably 2.90 or more, more preferably 3.50 or more, and even more preferably 4.00 or more.

[0422] In the above-mentioned composite material, the relative elemental concentration of interfacial carbon after resin dissolution is preferably 46.7 or less, more preferably 45.0 or less, further preferably 42.0 or less, and even more preferably 40.0 or less.

[0423] The relative elemental concentration of interfacial carbon after resin dissolution is preferably 30.0 or higher, more preferably 35.0 or higher.

[0424] In the above-mentioned composite material, the relative elemental concentration of aluminum at the interface after resin dissolution is preferably 1.80 or more, more preferably 2.00 or more, further preferably 2.10 or more, and even more preferably 2.30 or more.

[0425] The relative elemental concentration of aluminum at the interface after resin dissolution is preferably 3.00 or less, more preferably 2.90 or less, and even more preferably 2.80 or less.

[0426] In the above-mentioned composite material, the relative elemental concentration of interfacial silicon after resin dissolution is preferably 8.30 or more, more preferably 9.00 or more, and even more preferably 9.30 or more.

[0427] The relative elemental concentration of interfacial silicon after resin dissolution is preferably 12.0 or less, more preferably 11.5 or less, even more preferably 11.0 or less, and even more preferably 10.5 or less.

[0428] In the above-mentioned composite material, the relative elemental concentration of calcium at the interface after resin dissolution is preferably 2.60 or more, more preferably 2.70 or more, further preferably 2.90 or more, even more preferably 3.00 or more, and particularly preferably 3.20 or more.

[0429] The relative elemental concentration of calcium at the interface after resin dissolution is preferably 3.40 or less, more preferably 3.35 or less.

[0430] In the above-mentioned composite material, the relative elemental concentration of interfacial oxygen after resin dissolution is preferably 33.1 or more, more preferably 35.0 or more, further preferably 37.0 or more, even more preferably 38.0 or more, and particularly preferably 39.0 or more.

[0431] The relative elemental concentration of interfacial oxygen after resin dissolution is preferably 47.0 or less, more preferably 45.0 or less.

[0432] In the above-mentioned composite materials, when the relative element concentrations of each element in the continuous reinforcing fibers after resin dissolution are within the above-mentioned range, they can exhibit higher strength and elastic modulus.

[0433] In order to adjust the relative element concentrations of each element in the continuous reinforcing fiber after the resin is dissolved to the above range, for example, the following methods can be used: making the contact angle between the continuous fiber and the thermoplastic resin based on the static wetting test 70 to 130% of the contact angle between the continuous fiber treated with the coupling agent and the thermoplastic resin based on the static wetting test; making the impregnation rate of the thermoplastic resin for the continuous fiber 32% / min or more; and using a silane coupling agent as the coupling agent.

[0434] More specifically, if the contact angle between the aforementioned continuous fiber and the thermoplastic resin based on the static wettability test is increased, and the difference between the contact angle between the continuous fiber treated with only a coupling agent and the aforementioned thermoplastic resin based on the static wettability test is increased, the relative elemental concentration of nitrogen at the interface tends to increase.

[0435] If the difference between the contact angle of the continuous fiber and the thermoplastic resin based on the static wettability test and the contact angle of the continuous fiber treated with only the coupling agent and the thermoplastic resin based on the static wettability test is increased, and the impregnation rate of the thermoplastic resin against the continuous fiber is decreased, then the relative elemental concentration of interfacial carbon tends to increase.

[0436] If the difference between the contact angle of the continuous fiber and the thermoplastic resin based on the static wettability test and the contact angle of the continuous fiber treated with only the coupling agent and the thermoplastic resin based on the static wettability test is reduced, the impregnation rate of the thermoplastic resin for the continuous fiber is increased, and a silane coupling agent is used as the coupling agent, then the relative elemental concentration of aluminum at the interface tends to increase.

[0437] When silane coupling agents are used as coupling agents, the relative elemental concentration of silicon at the interface tends to increase.

[0438] If the difference between the contact angle of the continuous fiber and the thermoplastic resin based on the static wettability test and the contact angle of the continuous fiber treated with only the coupling agent and the thermoplastic resin based on the static wettability test is reduced, the impregnation rate of the thermoplastic resin for the continuous fiber is increased, and a silane coupling agent is used as the coupling agent, then the relative elemental concentration of calcium at the interface tends to increase.

[0439] If the difference between the contact angle of the continuous fiber and the thermoplastic resin based on the static wettability test and the contact angle of the continuous fiber treated with only the coupling agent and the thermoplastic resin based on the static wettability test is reduced, the impregnation rate of the thermoplastic resin for the continuous fiber is increased, and a silane coupling agent is used as the coupling agent, then the relative elemental concentration of oxygen at the interface tends to increase.

[0440] [Manufacturing method of continuous fiber reinforced resin composites]

[0441] There are no particular limitations on the manufacturing method of the continuous fiber reinforced resin composite material having characteristic (II), and the above-described method or the following method can be cited.

[0442] In the manufacture of the continuous fiber reinforced resin composite material possessing the above-described characteristic (II), as described above, in order to obtain the desired composite material, it is preferable that the contact angle between the continuous reinforcing fibers after the resin is dissolved and the thermoplastic resin, based on a static wetting test, is 70% to 130% of the contact angle between the continuous reinforcing fibers (which are treated only with a coupling agent) and the thermoplastic resin, based on a static wetting test, and that the impregnation rate of the thermoplastic resin onto the continuous reinforcing fibers is 32% / min or higher. Here, the continuous reinforcing fibers as materials refer to the continuous reinforcing fibers themselves as raw materials.

[0443] (Feature (III))

[0444] The continuous fiber reinforced resin composite material of this embodiment preferably further possesses the following feature (III).

[0445] [Continuous fiber reinforced resin composites]

[0446] The continuous fiber reinforced resin composite material of this embodiment, possessing feature (III), preferably comprises continuous reinforcing fibers and a thermoplastic resin, wherein the AE count A is 0.16 or less, the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer is 1.00 or more, and the strength of the (010) plane is 40,000 or less. In this specification, the full WHM of the (010) plane of the crystalline phase in the inner layer being 1.00 or more and the strength of the (010) plane being 40,000 or less are sometimes referred to as "feature (III)".

[0447] The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer is preferably 1.03 or more, more preferably 1.05 or more. The full WHM of the (010) plane of the crystalline phase in the inner layer is preferably 1.20 or less, more preferably 1.17 or less, even more preferably 1.15 or less, even more preferably 1.14 or less, and particularly preferably 1.13 or less.

[0448] The strength of the (010) facet of the crystalline phase in the inner layer is preferably 37,000 or less. The strength of the (010) facet of the crystalline phase in the inner layer is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more.

[0449] When the full width at half maximum (FWHM) and intensity of the (010) plane of the crystalline phase in the inner layer are within the above range, the microcrystal size and crystal continuity of the thermoplastic resin contained in the continuous fiber reinforced resin composite material are well balanced, and the warpage characteristics and shape following properties are good.

[0450] As a method to adjust the full width at half maximum (FWHM) and intensity of the (010) plane of the crystalline phase in the inner layer to the aforementioned range, examples include: adjusting the maximum temperature during molding of the continuous fiber reinforced resin composite material during the manufacture of the continuous fiber reinforced resin composite material having heating and cooling processes, and adjusting the temperature difference between the continuous fiber reinforced resin composite material and the dissimilar material in contact with the continuous fiber reinforced resin composite material at the start of the cooling process; and adjusting the contact angle between the continuous reinforcing fiber and the thermoplastic resin at high temperature and room temperature. By increasing the maximum temperature during molding of the continuous fiber reinforced resin composite material and increasing the temperature difference between the continuous fiber reinforced resin composite material and the dissimilar material in contact with the continuous fiber reinforced resin composite material at the start of the cooling process, the contact angle between the continuous reinforcing fiber and the thermoplastic resin at high temperature decreases, and the mobility of the thermoplastic resin molecular chains during crystallization of the thermoplastic resin contained in the continuous reinforcing fiber decreases. Therefore, there is a tendency for the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer to increase, and for the intensity of the (010) plane of the crystalline phase in the inner layer to decrease.

[0451] Regarding the temperature during molding of continuous fiber reinforced resin composites, one method is to measure it by clamping a thermocouple within the inner layer of the composite material. Dissimilar materials are those used in heating, cooling, and shaping processes during manufacturing. Examples include materials composed of metals, ceramics, resins, water, and oil, and examples include molds, castings, and strips. Regarding the temperature of dissimilar materials, one method is to measure the temperature at the interface between the dissimilar material and the continuous fiber reinforced resin composite material using thermocouples, non-contact thermometers, or contact thermometers.

[0452] In addition, the full width at half maximum (FWHM) and intensity of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material can be determined by XRD measurement using the focusing method. Specifically, the determination can be performed by the method described in the examples.

[0453] The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is preferably 1.25 or less, more preferably 1.24 or less. The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is preferably 0.90 or more, more preferably 1.00 or more.

[0454] When the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is within the above-mentioned range, it tends to have good warping characteristics and shape following properties.

[0455] In addition, the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite material can be determined by XRD measurement of the continuous fiber reinforced resin composite material by grazing incidence method. Specifically, the measurement can be performed by the method of the example.

[0456] The full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer of the above-mentioned continuous fiber reinforced resin composite material is preferably 0.85 or more, more preferably 0.85 to 1.1, and even more preferably 0.87 to 1.0.

[0457] When the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer of the above-mentioned continuous fiber reinforced resin composite material is within the above-mentioned range, it tends to have warping characteristics and good shape following properties.

[0458] In addition, the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material can be measured by XRD analysis using a focusing method. Specifically, the measurement can be performed using the method described in the examples.

[0459] The lattice spacing of the (010) facet of the crystalline phase in the inner layer of the above-mentioned continuous fiber reinforced resin composite material is preferably 0.30 to 1.2, more preferably 0.6 to 1.1.

[0460] When the lattice plane spacing of the (010) plane of the crystalline phase in the inner layer of the above-mentioned continuous fiber reinforced resin composite material is within the above-mentioned range, it tends to have warping characteristics and good shape following properties.

[0461] In addition, the lattice spacing of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material can be determined by XRD measurement of the continuous fiber reinforced resin composite material by focusing method. Specifically, the measurement can be performed by the method of the example.

[0462] The full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is preferably 0.85 or more, and more preferably 0.86 or more.

[0463] When the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is within the above-mentioned range, it tends to have warping characteristics and good shape following properties.

[0464] In addition, the full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite material can be determined by XRD measurement of the continuous fiber reinforced resin composite material by grazing incidence method. Specifically, the measurement can be performed by the method of the example.

[0465] The 2θ of the peak of the (100) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is preferably 20.34° or more, more preferably 20.34° to 20.45°, even more preferably 20.35° to 20.40°, and particularly preferably 20.36° to 20.39°.

[0466] When the 2θ of the peak of the (100) plane of the crystalline phase in the surface layer of the above-mentioned continuous fiber reinforced resin composite material is within the above-mentioned range, it tends to have warping characteristics and good shape following properties.

[0467] In addition, the 2θ of the peak of the (100) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite material can be determined by XRD measurement of the continuous fiber reinforced resin composite material by grazing incidence method. Specifically, the determination can be performed by the method of the example.

[0468] [Manufacturing method of continuous fiber reinforced resin composites]

[0469] There are no particular limitations on the manufacturing method of the continuous fiber reinforced resin composite material having characteristic (III), and the above-described method or the following method can be cited.

[0470] As a method for manufacturing a continuous fiber reinforced resin composite material having characteristic (III), the following methods can be cited as an example.

[0471] After placing the substrate (e.g., raw material laminate) into the mold, the mold is closed and compression is performed. Then, the mold temperature is adjusted to a temperature above the melting point of the thermoplastic resin constituting the continuous fiber-reinforced resin composite, causing the thermoplastic resin to melt and form the composite. The mold closing pressure is not particularly limited, but is preferably 1 MPa or more, more preferably 3 MPa or more. Alternatively, the mold can be temporarily closed for venting or other purposes, and the mold closing pressure can be temporarily released after compression molding. From the perspective of strength performance, the compression molding time is preferably a relatively long time within the range where the thermoplastic resin used will not undergo thermal degradation; from the perspective of productivity, a suitable time is preferably within 2 minutes, more preferably within 1 minute.

[0472] As another method, the following method can be cited: using a double-belt press or a continuous compression molding device, the substrate constituting the continuous fiber reinforced resin composite is continuously supplied and heated to above the melting point of the thermoplastic resin, compressed and molded under arbitrary pressure, and then cooled to below the crystallization temperature or glass transition temperature of the thermoplastic resin to manufacture it.

[0473] In the above-described method for manufacturing continuous fiber reinforced resin composite materials, the following method is preferred: the highest temperature during the manufacturing of the continuous fiber reinforced resin composite material (e.g., the highest temperature during molding) is set to a temperature ranging from the melting point of the thermoplastic resin with the highest melting point among the thermoplastic resins contained in the continuous fiber reinforced resin composite material to a temperature of +10°C to +75°C (preferably from the melting point to +12°C to +60°C), such that the temperature difference between the continuous fiber reinforced resin composite material and the dissimilar material in contact with the continuous fiber reinforced resin composite material at the start of the cooling process after reaching the above-described highest temperature is 60°C or more, preferably 80°C or more, more preferably 100°C or more, and even more preferably 120°C or more. Regarding the temperature of the continuous fiber reinforced resin composite material, for example, a method of measuring it by clamping a thermocouple in the inner layer of the continuous fiber reinforced resin composite material can be cited. The dissimilar material is a material used in the above-described cooling process (preferably a material that cools the composite material by contact with it after heat molding in the cooling process), and examples include metals, ceramics, resin materials, water, and oil. Regarding the temperature of dissimilar materials, methods such as using thermocouples, non-contact thermometers, and contact thermometers to measure the temperature at the interface between the dissimilar material and the continuous fiber-reinforced resin composite material can be cited. It should be noted that "the start of the cooling process" refers to the initial moment of the cooling process during manufacturing (e.g., the moment when the dissimilar material comes into contact with the composite material during the cooling process after heat molding).

[0474] When the maximum temperature and the temperature difference between the continuous fiber reinforced resin composite material and the dissimilar material in contact with the continuous fiber reinforced resin composite material at the start of the cooling process are within the above range, there is a tendency for the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material to increase and the strength of the (010) plane of the crystalline phase in the inner layer to decrease.

[0475] In the above-mentioned method for manufacturing continuous fiber reinforced resin composite material, it is preferable to include a step of molding a raw material laminate containing continuous reinforcing fibers and thermoplastic resin under heating, wherein the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material is related to the highest temperature during molding by the following formula.

[0476] (Full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite) < 0.0037 × (maximum temperature during molding) + 0.15

[0477] When the maximum temperature during molding and the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material satisfy the above relationship, there is a tendency to improve the productivity of the continuous fiber reinforced resin composite material.

[0478] In the above-mentioned method for manufacturing continuous fiber reinforced resin composite material, it is preferable that the ratio of the full width at half maximum (WHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material to the full width at half maximum (WHM) of the (010) plane of the crystalline phase in the surface layer is related to the highest temperature during molding by the following formula.

[0479] (Full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite) / (Full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite) ≥ -0.0034 × (maximum temperature during molding) + 2.02

[0480] When the ratio of the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer to that of the (010) plane of the crystalline phase in the surface layer is in the relationship described above with the highest temperature during molding, it tends to have good warpage characteristics.

[0481] The preferred method for manufacturing the above-mentioned continuous fiber reinforced resin composite material includes the steps of loading the raw material laminate into a molding die, molding under heating and then cooling. The ratio of the full width at half maximum (WHM) of the (100) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material to the full width at half maximum (WHM) of the (100) plane of the crystalline phase in the surface layer and the cooling rate during molding are related by the following formula.

[0482] (Full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite) / (Full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite) ≥ 0.0125 × (cooling rate during molding) + 0.318

[0483] When the ratio of the full width at half maximum (WHM) of the (100) plane of the crystalline phase in the inner layer to that of the (100) plane of the crystalline phase in the outer layer, and the cooling rate during molding are in the above-mentioned relationship, the composite material tends to have good warpage characteristics.

[0484] It should be noted that the cooling rate (°C / second) during molding can be determined based on the temperature difference between the highest temperature of the continuous fiber reinforced resin composite and the melting point of the thermoplastic resin contained in the continuous fiber reinforced resin composite at -65°C, and the time required to lower the continuous fiber reinforced resin composite from the highest temperature to the melting point of the thermoplastic resin contained in the continuous fiber reinforced resin composite at -65°C. It should also be noted that the cooling conditions for measuring the cooling rate are the same as the conditions of the cooling process during the manufacture of the continuous fiber reinforced resin composite.

[0485] In the above-mentioned method for manufacturing continuous fiber reinforced resin composite material, the contact angle between the continuous reinforcing fiber and the thermoplastic resin at 280°C is preferably 1.3 to 7.0 times that of the contact angle at 23°C, more preferably 1.4 to 6.0 times, and even more preferably 1.5 to 5.5 times.

[0486] The contact angle between the continuous reinforcing fiber and the thermoplastic resin can be measured as follows: a monofilament of the continuous reinforcing fiber and a film of the thermoplastic resin are sandwiched between a coverslip, the temperature is raised above the melting point of the thermoplastic resin, and the contact angle between the continuous reinforcing fiber and the thermoplastic resin is observed using an optical microscope just before cooling begins. This determines the contact angle at high temperature. After cooling, the contact angle between the continuous reinforcing fiber and the thermoplastic resin at room temperature is observed using an optical microscope. This determines the contact angle at room temperature. In detail, the method described in the examples can be used for measurement.

[0487] When the contact angle between the continuous reinforcing fiber and the thermoplastic resin at high temperature and room temperature is as described above, it tends to have good warp characteristics and shape following properties.

[0488] (Characteristic (IV))

[0489] The continuous fiber reinforced resin composite material of this embodiment preferably further possesses the features described below (IV).

[0490] [Continuous fiber reinforced resin composites]

[0491] The continuous fiber reinforced resin composite material of this embodiment, possessing feature (IV), preferably comprises: continuous reinforcing fibers and thermoplastic resin, wherein the AE count A is 0.16 or less, and when a section of the continuous fiber reinforced resin composite material orthogonal to the length direction of the continuous reinforcing fibers is ground, and the ground section is observed using a field emission scanning electron microscope (FESEM), the maximum grinding pressure P (g / cm²) at which no voids are observed between the continuous reinforcing fibers and the thermoplastic resin is measured. 2The value obtained by dividing the interfacial abrasion value P / Vf by the volume ratio Vf (%) of the continuous fiber reinforced resin composite material is 10 g / cm³. 2 •% or higher. In this specification, when the cross-section of the above-mentioned continuous fiber reinforced resin composite material orthogonal to the length direction of the continuous reinforcing fiber is ground, and the ground cross-section is observed using a field emission scanning electron microscope (FESEM), the interfacial grinding value P / Vf (which is the maximum grinding pressure P (g / cm) at which no voids are observed between the continuous reinforcing fiber and the thermoplastic resin) is determined. 2 The value obtained by dividing the continuous fiber reinforced resin composite by the volume ratio Vf (%) of the continuous fiber reinforced resin composite is 10 g / cm³. 2 Cases exceeding 60% are sometimes referred to as "characteristic (IV)".

[0492] The preferred interfacial abrasion value is 12 g / cm³. 2 •% or more, preferably 17g / cm 2 •% or higher, more preferably 21g / cm 2 •% or higher, and more preferably 25g / cm 2 •% or higher, with a particularly preferred value of 32g / cm³ 2 •% or higher, with the optimal value being 42g / cm³ 2 •% or higher. When the above-mentioned interfacial abrasion value is within this range, the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material have good adhesion to the thermoplastic resin, and are not prone to damage to either of them. It can exhibit excellent strength, elastic modulus, impact characteristics, high temperature characteristics, water absorption characteristics, and interfacial recovery characteristics.

[0493] It should be noted that, in this disclosure, "void" refers to a region in which thermoplastic resin is absent in a width of more than one-twentieth of the diameter of the continuous reinforcing fiber in the radial direction from the outer periphery of the continuous reinforcing fiber.

[0494] In addition, "no voids were observed between the continuous reinforcing fiber and the thermoplastic resin" means that when observing the cross-section after grinding using FESEM, the entire circumference of a single fiber of the continuous reinforcing fiber is set to 100%, and the circumference of the part that produces voids is less than 10%.

[0495] As a method for adjusting the aforementioned interfacial abrasion value to the aforementioned range, for example, the following method can be used: A continuous reinforcing fiber containing a surface treatment agent is produced by treating the continuous reinforcing fiber with the surface treatment agent, such that the interfacial shear strength between the obtained continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin (described later) is 0.8 to 1.2 times that of the interfacial shear strength between the coupling agent-treated continuous reinforcing fiber and the thermoplastic resin, which is treated only with a coupling agent instead of the surface treatment agent; and the droplet contact angle between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin (described later) is 0.4 to 0.7 times that of the droplet contact angle between the continuous reinforcing fiber without the surface treatment agent and the thermoplastic resin (described later). Furthermore, adjustments can be made by methods such as making the interfacial shear strength between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin 1.8 to 10 times that of the interfacial shear strength between the continuous reinforcing fiber without the surface treatment agent and the thermoplastic resin, and by making the droplet contact angle between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin 0.8 to 1.6 times that of the droplet contact angle between the continuous reinforcing fiber treated with the coupling agent and the thermoplastic resin.

[0496] It should be noted that, in this disclosure, the interfacial grinding value P / Vf of the continuous fiber reinforced resin composite material can be calculated as follows: The continuous fiber reinforced resin material is cut using a band saw to obtain a cross-section (grinding surface) orthogonal to the length direction of the continuous reinforcing fibers. After grinding the grinding surface using a grinding machine by varying the grinding pressure applied to it, the grinding surface is observed using FESEM. The maximum grinding pressure P (g / cm²) at which no voids are observed between the resin fibers when observing any 10 individual fibers of the continuous reinforcing fibers is determined. 2 The interfacial abrasion value can be determined by dividing the interfacial abrasion value by the volume ratio Vf (%) of the continuous reinforcing fibers in the continuous fiber reinforced resin composite material. Specifically, it can be determined by the method described in the examples below.

[0497] [Manufacturing method of continuous fiber reinforced resin composites]

[0498] There are no particular limitations on the manufacturing method of the continuous fiber reinforced resin composite material having characteristic (IV), and the above-mentioned method or the following method can be cited.

[0499] As a method for manufacturing a continuous fiber reinforced resin composite material having the above-mentioned feature (II), the following method can be cited: using a double-belt press or a continuous compression molding device, a substrate constituting the continuous fiber reinforced resin composite material is continuously supplied, heated to above the melting point of the thermoplastic resin and compressed under arbitrary pressure, and then cooled to below the crystallization temperature or glass transition temperature of the thermoplastic resin to manufacture it.

[0500] In the above-mentioned method for manufacturing continuous fiber reinforced resin composite material, it is preferable to prepare continuous reinforcing fibers containing a surface treatment agent by treating the continuous reinforcing fibers with a surface treatment agent, such that the interfacial shear strength between the continuous reinforcing fibers containing the surface treatment agent and the thermoplastic resin, calculated by the microdroplet method using the following formula (1), is 0.8 to 1.2 times that of the interfacial shear strength between the continuous reinforcing fibers containing the surface treatment agent and the thermoplastic resin treated only with a coupling agent instead of the surface treatment agent, and the microdroplet contact angle between the continuous reinforcing fibers containing the surface treatment agent and the thermoplastic resin, measured by the microdroplet method, is 0.4 to 0.7 times that of the microdroplet contact angle between the continuous reinforcing fibers without the surface treatment agent and the thermoplastic resin.

[0501] τ=F / πdL ···(1)

[0502] (In the formula, τ represents the interfacial shear strength (MPa), d represents the fiber diameter of the continuous reinforcing fiber (μm), L represents the length of the resin ball (microdroplet) of the thermoplastic resin attached to the single fiber of the continuous reinforcing fiber in the direction of the fiber axis of the continuous reinforcing fiber (μm), and F represents the shear load (N) when the resin ball is pulled away from the continuous reinforcing fiber.)

[0503] The interfacial shear strength between the continuous reinforcing fibers containing the surface treatment agent and the thermoplastic resin is more preferably 0.85 to 1.17 times, more preferably 0.90 to 1.15 times, and even more preferably 1.0 to 1.1 times, that of the continuous reinforcing fibers treated with the coupling agent. When the interfacial shear strength is within the above range, the interfacial abrasion value of the continuous fiber reinforced resin composite material tends to increase.

[0504] It should be noted that the above-mentioned shear load F can be measured using a composite material interface property evaluation device for the portion of a resin ball (microdroplet) on which thermoplastic resin is attached to a single fiber of a continuous reinforcing fiber. In detail, it can be determined by the method described in the following examples.

[0505] Figure 1 This is a schematic diagram showing a single fiber 1 of continuous reinforcing fibers and resin balls (microdroplets) 2 of thermoplastic resin attached to the single fiber 1. d represents the fiber diameter of the single fiber 1, and L represents the length of the resin ball 2 in the direction of the fiber axis of the single fiber 1.

[0506] The interfacial shear strength can be adjusted by changing the type of continuous reinforcing fiber, surface treatment agent, thermoplastic resin, etc.

[0507] Examples of methods for manufacturing continuous reinforcing fibers treated with coupling agents include methods that treat the continuous reinforcing fibers using only coupling agents during manufacturing, and methods that remove the surface treatment agent from the continuous reinforcing fibers containing the surface treatment agent using an electric furnace or similar means, and then treat the fibers using only coupling agents.

[0508] Furthermore, the droplet contact angle between the continuous reinforcing fibers containing the surface treatment agent and the thermoplastic resin is more preferably 0.45 to 0.65 times, and more preferably 0.50 to 0.60 times, that of the continuous reinforcing fibers without the surface treatment agent. When the droplet contact angle is within the above range, the interfacial abrasion value of the continuous fiber reinforced resin composite material tends to increase.

[0509] It should be noted that the contact angle of microdroplets can be measured using a composite material interface property evaluation device for the portion of a resin ball (microdroplet) on which thermoplastic resin is attached to a single fiber of a continuous reinforcing fiber. Specifically, it can be determined by the method described in the examples below.

[0510] Figure 1 This is a schematic diagram showing a single fiber 1 of continuously reinforcing fibers and resin balls (microdroplets) 2 of thermoplastic resin attached to the single fiber 1, where α represents the microdroplet contact angle.

[0511] The aforementioned droplet contact angle can be adjusted by changing the type of continuous reinforcing fiber, surface treatment agent, thermoplastic resin, etc.

[0512] Regarding continuous reinforcing fibers without surface treatment agents, "without surface treatment agents" means that when the total mass of the continuous reinforcing fibers without surface treatment agents is set as 100%, the content of surface treatment agents is less than 0.45% by mass, and in the zeta potential measurement, the isoelectric point is less than pH=3, and the value is negative when the pH is 3 to 8.

[0513] The zeta potential can be determined, for example, by using a solid-state zeta potential meter and adjusting the pH with hydrochloric acid or potassium hydroxide.

[0514] Examples of methods for obtaining continuous reinforcing fibers without surface treatment agents include: methods that do not use surface treatment agents during the manufacture of continuous reinforcing fibers; and methods that remove the surface treatment agent from continuous reinforcing fibers containing surface treatment agents using an electric furnace or the like.

[0515] Furthermore, in the above-described method for manufacturing the continuous fiber reinforced resin composite material, it is preferable that the interfacial shear strength between the continuous reinforcing fiber containing the surface treatment agent and the thermoplastic resin is 1.8 to 10 times, more preferably 2.0 to 8.0 times, further preferably 3.0 to 6.0 times, and even more preferably 3.5 to 5.0 times, that of the continuous reinforcing fiber without the surface treatment agent and the thermoplastic resin. When the interfacial shear strength is within the above range, the interfacial abrasion value of the continuous fiber reinforced resin composite material tends to increase.

[0516] The interfacial shear strength can be adjusted by changing the type of continuous reinforcing fiber, surface treatment agent, thermoplastic resin, etc.

[0517] Furthermore, in the method for manufacturing the aforementioned continuous fiber reinforced resin composite material, it is preferable that the contact angle between the continuous reinforcing fiber containing the surface treatment agent and the microdroplets of the thermoplastic resin is 0.8 to 1.6 times, more preferably 0.85 to 1.4 times, and even more preferably 0.90 to 1.2 times, that of the continuous reinforcing fiber treated with the coupling agent and the microdroplets of the thermoplastic resin. When the microdroplet contact angle is within the above range, the interfacial abrasion value of the continuous fiber reinforced resin composite material tends to increase.

[0518] The aforementioned droplet contact angle can be adjusted by changing the type of continuous reinforcing fiber, surface treatment agent, thermoplastic resin, etc.

[0519] (Feature (V))

[0520] The continuous fiber reinforced resin composite material of this embodiment preferably further possesses the features (V) described below.

[0521] [Continuous fiber reinforced resin composites]

[0522] The continuous fiber reinforced resin composite material of this embodiment, possessing characteristic (V), preferably comprises continuous reinforcing fibers and a thermoplastic resin, wherein the aforementioned AE count A is 0.16 or less, and the interface coverage change index shown in the following formula before and after the destructive test is 0.8 to 1.2. In this specification, the case where the interface coverage change index shown in the following formula before and after the destructive test is 0.8 to 1.2 is sometimes referred to as "characteristic (V)".

[0523] (Interfacial Coverage Change Index) = (Interfacial Coverage of Continuous Fiber Reinforced Resin Composite Before Destructive Test) / (Interfacial Coverage of Composite After Destructive Test)

[0524] The interface coverage change index is preferably 0.9 to 1.2, and more preferably 0.95 to 1.15.

[0525] The interfacial coverage (%) of the above-mentioned continuous fiber reinforced resin composite material can be calculated as follows: X-ray photoelectron spectroscopy (XPS) is used to measure the continuous reinforcing fibers after the thermoplastic resin is dissolved from the continuous fiber reinforced resin composite material into the solvent. The interfacial coverage is calculated based on the relative element concentration of the thermoplastic resin-derived components remaining on the surface of the continuous reinforcing fibers at this time, and the proportion of the relative element concentration of the thermoplastic resin-derived components remaining on the surface of the continuous reinforcing fibers to the total relative element concentration of the components derived from the continuous reinforcing fibers.

[0526] The interface coverage rate (interface coverage rate of the composite material before the destructive test) of the above-mentioned continuous fiber reinforced resin composite material is preferably 3-44%, more preferably 10-40%, and even more preferably 20-37%.

[0527] The coverage of the thermoplastic resin remaining on the surface of the continuous reinforcing fibers after the thermoplastic resin is dissolved in the solvent (interfacial coverage of the continuous reinforcing fiber resin composite material) can be determined, for example, by the following method.

[0528] The continuous fiber reinforced resin composite material is immersed in a solvent to dissolve the thermoplastic resin contained in the composite material. After removing the solvent, the remaining composite material is washed again with fresh solvent to remove the thermoplastic resin from the surface of the continuous reinforcing fibers. At this point, the thermoplastic resin firmly bonded to the bundler (preferably coupling agent) on the surface of the continuous reinforcing fibers remains on the surface of the continuous reinforcing fibers. The solvent is used to remove only the thermoplastic resin that is not bonded to the bundler. After drying, the composite material is measured using X-ray photoelectron spectroscopy (XPS). The interfacial coverage (%) of the continuous fiber reinforced resin composite material can be determined based on the proportion of the relative element concentration of the thermoplastic resin-derived component elements remaining on the surface of the continuous reinforcing fibers to the total relative element concentration of the thermoplastic resin-derived component elements remaining on the surface of the continuous reinforcing fibers and the relative element concentration of the component elements derived from the continuous reinforcing fibers.

[0529] For example, when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, the following processing methods can be cited.

[0530] (a) Cut the above continuous fiber reinforced resin composite material into thin slices.

[0531] (b) 100 mg of the above-mentioned continuous fiber reinforced resin composite sheet and 20 mL of hexafluoroisopropanol (HFIP) as solvent were added to a mixer and stirred at 23°C for 5 hours.

[0532] (c) Remove the solvent by filtration, spray 40 mL of fresh HFIP onto the filter, clean the composite material, and then air dry it.

[0533] (d) Add the composite material obtained in (c) and 20 mL of fresh HFIP into a mixer and stir at 23°C for 2 hours.

[0534] (e) Remove the solvent by filtration, spray 40 mL of fresh HFIP onto the filter, clean the composite material, and dry it with a nitrogen stream at 23°C.

[0535] (f) Add the continuous reinforcing fiber obtained in (e) and 20 mL of fresh HFIP into a mixer and stir at 23°C for 2 hours.

[0536] (g) Remove the solvent by vacuum filtration, spray 40 mL of fresh HFIP onto the filter, clean the composite material, and then air dry it.

[0537] (h) Dry overnight using a vacuum dryer set to 23°C.

[0538] The interface coverage rate can be calculated using the following formula.

[0539] (Interface Coverage Rate) (%) = [N] / ([N]+[Si])×100

[0540] Here, [N] is the relative elemental concentration of nitrogen determined by XPS, and [Si] is the relative elemental concentration of silicon.

[0541] For example, when the thermoplastic resin is polyamide and the continuous reinforcing fiber is carbon fiber, HFIP is used as the solvent, and the sample is prepared by the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber. The interface coverage can be calculated by the following formula.

[0542] (Interface Coverage Rate) (%) = [N] / ([N]+[O])×100

[0543] Here, [O] represents the relative elemental concentration of oxygen determined by XPS.

[0544] For example, when the thermoplastic resin is polypropylene and the continuous reinforcing fiber is glass fiber, xylene is used as the solvent to prepare the sample. In this case, the temperature for stirring the composite material and solvent is 90°C, the drying temperature and the nitrogen gas flow temperature are 120°C, and the vacuum drying temperature is 120°C. Otherwise, the sample is prepared using the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber. The interface coverage can be calculated using the following formula.

[0545] (Interface Coverage Rate) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100

[0546] [C] represents the relative elemental concentration of carbon determined by XPS measurement. [C0] represents the relative elemental concentration of carbon determined by XPS measurement when composite materials and samples were prepared using untreated continuous reinforcing fibers after surface treatment agents such as sizing agents were removed from the continuous reinforcing fibers through incineration, etc. It should be noted that, regarding the interfacial coverage in the case of polypropylene and glass fiber combinations, since carbon is detected even when measuring samples considered to be free of carbon in XPS measurements, the relative elemental concentration of carbon after treatment with untreated continuous reinforcing fibers is used for calculation.

[0547] When the thermoplastic resin is polyphenylene ether, regardless of the type of continuous reinforcing fiber, chloroform can be used as the solvent to prepare the sample using the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, and the interfacial coverage ratio can be determined. Furthermore, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage ratio is as follows.

[0548] (Interface Coverage Rate) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100

[0549] When the thermoplastic resin is polyvinyl alcohol, water can be used as a solvent for preparation regardless of the type of continuous reinforcing fiber. In this case, the temperature for stirring the composite material and solvent can be 95°C, the drying temperature and nitrogen gas flow temperature can be 120°C, and the vacuum drying temperature can be 120°C. Otherwise, the sample is prepared using the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, and the interfacial coverage ratio is calculated. Furthermore, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage ratio is as follows.

[0550] (Interface Coverage Rate) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100

[0551] When the thermoplastic resin is polyvinyl acetate, regardless of the type of continuous reinforcing fiber, acetone can be used as the solvent to prepare the sample using the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, and the interfacial coverage ratio can be determined. Furthermore, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage ratio is as follows.

[0552] (Interface Coverage Rate) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100

[0553] When the thermoplastic resin is polylactic acid, regardless of the type of continuous reinforcing fiber, chloroform can be used as the solvent to prepare the sample using the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, and the interfacial coverage ratio can be determined. Furthermore, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage ratio is as follows.

[0554] (Interface Coverage Rate) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100

[0555] When the thermoplastic resin is polyvinyl chloride, regardless of the type of continuous reinforcing fiber, acetone can be used as the solvent to prepare the sample using the same method as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, and the interfacial coverage ratio can be determined. Furthermore, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage ratio is as follows.

[0556] (Interface Coverage Rate) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100

[0557] The interface coverage change index can be obtained by dividing the interface coverage of the continuous fiber reinforced resin composite (interface coverage of the continuous fiber reinforced resin composite without destructive testing) by the interface coverage of the continuous fiber reinforced resin composite after destructive testing (e.g., after cantilever bending fatigue testing as described in the examples below).

[0558] When the interface coverage change index is within the above range, it exhibits high interface recovery characteristics and can reduce deviations in physical properties (such as strength).

[0559] To adjust the interface coverage change index to the aforementioned range, the following methods can be used, for example: a method in which the rate at which thermoplastic resin is impregnated into continuous reinforcing fibers is 0.8 to 1.2 times, preferably 0.85 to 1.15 times, and more preferably 0.9 to 1.1 times, that of thermoplastic resin impregnated into coupled continuous reinforcing fibers treated only with coupling agents; a method in which the flexural strength of the coupled continuous fiber reinforced resin composite material composed of coupled continuous reinforcing fibers treated only with the aforementioned coupling agent and the aforementioned thermoplastic resin is 0.6 times or more, preferably 0.6 to 1.2 times, that of the flexural strength of the aforementioned continuous fiber reinforced resin composite material; and a method in which glass fibers with a surface treatment agent added using the method described in the examples are combined with PA66 manufactured using the method described in the examples.

[0560] The combination of continuous reinforcing fibers and thermoplastic resins with the aforementioned flexural strength within the aforementioned range is preferably a combination of polyamide resins (preferably polyamide 66, polyamide 6I, polyamide 6, polyamide 610, polyamide 410) and glass fibers or carbon fibers; or a combination of polyolefin resins (preferably polypropylene, modified polypropylene, polyethylene, modified polyethylene) and glass fibers or carbon fibers.

[0561] If the impregnation rate and / or flexural strength are within the above range, the thermoplastic resin is well compatible with the bridging agent (e.g., coupling agent in the bridging agent) on the surface of the continuous reinforcing fiber.

[0562] Here, the impregnation rate can be calculated as follows: The continuous reinforcing fiber substrate and the thermoplastic resin substrate are laminated. The substrate is heated and pressed at a temperature where the highest temperature of the continuous fiber reinforced resin composite is 15°C above the melt temperature of the thermoplastic resin, and the molding pressure is 5 MPa. Then, it is cooled and pressed to room temperature using water cooling (water temperature 20°C) and a pressure of 5 MPa. The resulting continuous reinforcing fiber composite is then cut using a band saw, and the cross-section is ground and observed using SEM. Based on the obtained images, the areas occupied by the continuous reinforcing fiber bundles, thermoplastic resin, and voids are determined. The ratio of the void area to the area of ​​the continuous reinforcing fiber bundle (overall) is calculated, and the impregnation rate (%) is calculated using the following formula:

[0563] Impregnation rate (%) = {1 - (void area / area of ​​continuous reinforcing fiber bundle)} × 100

[0564] The impregnation rate is obtained by dividing the calculated impregnation rate (%) by the time during heating and pressing and cooling pressing when the temperature of the thermoplastic resin is above the melting point (for thermoplastic resins with a melting point) and the time during cooling and pressing when the temperature is above the glass transition temperature (for resins without a melting point) (minutes).

[0565] Regarding the flexural strength of continuous fiber reinforced resin composites, for example, a strip-shaped test piece is cut from the continuous fiber reinforced resin composite and subjected to a three-point bending test at 23°C and 50%RH, thereby determining the flexural strength.

[0566] In the aforementioned composite material, if the thermoplastic resin and the bridging agent (e.g., coupling agent) on the surface of the continuous reinforcing fibers are well compatible, the bridging agent on the surface of the continuous reinforcing fibers will bond or adhere to the thermoplastic resin surrounding the bridging agent. Here, in the sample where the thermoplastic resin has been removed using a solvent by the above method, only the thermoplastic resin bonded or adhered to the bridging agent remains around the continuous reinforcing fibers, while the thermoplastic resin not bonded to the bridging agent is removed. That is, by using this sample, the proportion of thermoplastic resin bonded or adhered to the bridging agent present on the surface of the continuous reinforcing fibers can be determined.

[0567] If a destructive test is performed, the thermoplastic resin that is not bonded or adhered to the bubbling agent, as well as the thermoplastic resin with weak bonding or adhesion to the bubbling agent, will detach from the surface of the continuous reinforcing fibers through impact. If a large amount of thermoplastic resin that is firmly bonded or adhered to the bubbling agent exists on the surface of the continuous reinforcing fibers, the thermoplastic resin is less likely to detach through the destructive test, and the coating ratio of thermoplastic resin on the continuous reinforcing fibers after the destructive test is less likely to decrease. Furthermore, even after the destructive test, a large amount of thermoplastic resin remains on the surface of the continuous reinforcing fibers, and the change in the interfacial coating ratio of the continuous fiber reinforced resin composite material before and after the destructive test is reduced.

[0568] It should be noted that the above example uses an example with a slugging agent on the surface of the continuous reinforcing fiber, but the same evaluation can be performed even when the thermoplastic resin is directly bonded or adhered to the continuous reinforcing fiber without using a slugging agent.

[0569] The fiber exposure variation index of the above-mentioned continuous fiber reinforced resin composite material, expressed by the following formula, is preferably 0.8 to 1.2.

[0570] (Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite before destructive test) / (Reinforcing fiber exposure ratio of composite after destructive test)

[0571] The aforementioned reinforcing fiber exposure variation index is more preferably 0.85 to 1.15, and even more preferably 0.90 to 1.10. When the reinforcing fiber exposure variation index is within the above range, it can exhibit higher interface recovery characteristics and further reduce the deviation of physical properties.

[0572] The fiber exposure variation index can be obtained by dividing the exposed proportion of continuous reinforcing fibers after the thermoplastic resin of the continuous fiber reinforced resin composite is dissolved by the exposed proportion of continuous reinforcing fibers after the thermoplastic resin of the continuous fiber reinforced resin composite is dissolved after a destructive test (e.g., after the cantilever bending fatigue test described in the following examples).

[0573] The exposure ratio of continuous reinforcing fibers after dissolving thermoplastic resin can be determined as follows: The thermoplastic resin contained in the continuous fiber reinforced resin composite is dissolved in a solvent using the above method. After removing the solvent, the remaining continuous reinforcing fibers are cleaned with fresh solvent to remove thermoplastic resin other than that bonded to the continuous reinforcing fibers. After drying, X-ray photoelectron spectroscopy (XPS) is used to determine the exposure ratio. The relative elemental concentration of the elements derived from the obtained continuous reinforcing fibers is divided by the relative elemental concentration of the elements derived from the continuous reinforcing fiber raw material that has not undergone bundle agent treatment.

[0574] Regarding the exposed ratio of reinforcing fibers in composite materials, when the continuous reinforcing fibers are glass fibers, it can be calculated, for example, by the following formula.

[0575] (Exposed reinforcing fiber ratio of composite material) = [Al] / [Al0]

[0576] [Al] represents the relative elemental concentration of aluminum determined by XPS. [Al0] represents the relative elemental concentration of aluminum determined by XPS when continuous reinforcing fibers without sizing agents or other binding agents are treated in the same way.

[0577] When the continuous reinforcing fiber is carbon fiber, it can be calculated, for example, by the following formula.

[0578] (Exposed reinforcing fiber ratio of composite material) = [O] / [O0]

[0579] [O] represents the relative elemental concentration of oxygen determined by XPS measurement. [O0] represents the relative elemental concentration of oxygen determined by XPS measurement when continuous reinforcing fibers without surface treatment agents such as sizing agents are treated in the same way.

[0580] The exposed reinforcing fiber ratio is the proportion of the continuous reinforcing fiber surface exposed after the above treatment. By minimizing the change in the exposed reinforcing fiber ratio before and after the destructive test, a composite material with stable strength can be obtained even when subjected to vibration, impact, etc.

[0581] The relative elemental variation index of interfacial nitrogen in the above-mentioned continuous fiber reinforced resin composite material is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.

[0582] The relative elemental variation index of interfacial carbon in the above-mentioned continuous fiber reinforced resin composite material is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

[0583] The relative elemental variation index of interfacial aluminum in the above-mentioned continuous fiber reinforced resin composite material is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

[0584] The relative elemental variation index of interfacial silicon in the above-mentioned continuous fiber reinforced resin composite material is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.

[0585] The relative elemental variation index of interfacial calcium in the above-mentioned continuous fiber reinforced resin composite material is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

[0586] The relative elemental variation index of interfacial oxygen in the above-mentioned continuous fiber reinforced resin composite material is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

[0587] When the relative elemental change index is within the above range, it can exhibit high interface recovery characteristics and reduce the deviation of physical properties.

[0588] The relative elemental change index can be obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite after dissolution by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite after a destructive test (e.g., the cantilever bending fatigue test described in the later examples). The dissolution of the thermoplastic resin of the continuous fiber reinforced resin composite can be carried out by the method described above.

[0589] To adjust the relative elemental variation index to the aforementioned range, for example, the following methods can be employed: a method in which the rate at which thermoplastic resin is impregnated into continuous reinforcing fibers is 0.8 to 1.2 times, preferably 0.85 to 1.15 times, and more preferably 0.9 to 1.1 times, the rate at which thermoplastic resin is impregnated into coupled continuous reinforcing fibers treated only with coupling agents; and a method in which the flexural strength of a coupled continuous fiber reinforced resin composite material composed of coupled continuous reinforcing fibers treated only with the aforementioned coupling agent and the aforementioned thermoplastic resin is 0.6 to 1.2 times the flexural strength of the aforementioned continuous fiber reinforced resin composite material, using a combination of continuous reinforcing fibers and thermoplastic resin.

[0590] [Manufacturing method of continuous fiber reinforced resin composites]

[0591] In the method for manufacturing a continuous fiber reinforced resin composite material having characteristic (V), it is preferable that the rate at which the thermoplastic resin is impregnated into the continuous reinforcing fibers is 0.8 to 1.2 times the rate at which the thermoplastic resin is impregnated into the coupled continuous reinforcing fibers treated only with a coupling agent. Here, coupled continuous reinforcing fibers refer to continuous reinforcing fibers manufactured using the same method as continuous reinforcing fibers, except that the bundling agent is changed to a coupling agent only. It is preferable to use a bundling agent comprising a coupling agent, a lubricant, and / or a bundling agent in the continuous reinforcing fibers, and to use the coupling agent in the coupled continuous reinforcing fibers.

[0592] In the above-described method for manufacturing the composite material, it is preferable that the flexural strength of the coupling continuous fiber reinforced resin composite material, composed of the above-described coupling continuous reinforcing fibers and the above-described thermoplastic resin, is at least 0.6 times that of the continuous fiber reinforced resin composite material. Here, the coupling continuous fiber reinforced resin composite material refers to a composite material manufactured using the same method as the continuous fiber reinforced resin composite material, except that coupling continuous reinforcing fibers are used as the continuous reinforcing fibers. Preferably, a bundling agent comprising a coupling agent, a lubricant, and / or a bundling agent is used in the continuous reinforcing fibers, and the coupling agent is used in the coupling continuous reinforcing fibers.

[0593] [Morphology of continuous fiber reinforced resin composites]

[0594] Examples of continuous fiber reinforced resin composite materials that possess at least one of the group consisting of features (II), (III), (IV) and (V) described above include the above-described forms, with the same forms as described above being preferred.

[0595] (Continuous reinforcing fiber)

[0596] Examples of continuous reinforcing fibers used in continuous fiber reinforced resin composites having at least one of the group consisting of features (II), (III), (IV) and (V) described above include the aforementioned substances, with the same substances as described above being preferred.

[0597] (Shape of continuous reinforcing fibers)

[0598] As for the shape of the continuous reinforcing fiber used in a continuous fiber reinforced resin composite material having at least one of the group consisting of features (II), (III), (IV) and (V) described above, the shapes described above can be cited, and the same shape as described above is preferred.

[0599] (Thermoplastic resin)

[0600] Examples of thermoplastic resins used in continuous fiber reinforced resin composites that possess at least one of the group consisting of features (II), (III), (IV) and (V) described above include the substances described above, and the same substances as described above are preferred.

[0601] [additive]

[0602] Continuous fiber reinforced resin composites comprising at least one of the group consisting of features (II), (III), (IV), and (V) described above may also contain additives as needed. Examples of such additives include substances identical to those described above, and preferably substances identical to those described above.

[0603] Applications of continuous fiber reinforced resin composites

[0604] As for the use of a continuous fiber reinforced resin composite material having at least one of the group consisting of features (II), (III), (IV) and (V) described above, examples of uses similar to those described above are given, and uses similar to those described above are preferred.

[0605] [Molding of composite materials]

[0606] Continuous fiber reinforced resin composites having at least one selected from the group consisting of features (II), (III), (IV), and (V) can also be further molded. The methods listed above can be cited as examples of the aforementioned methods.

[0607] Example

[0608] The present invention will now be described in detail through examples and comparative examples, but the present invention is not limited to these examples. Of course, various modifications can be made within the scope of the essential points of the present invention.

[0609] [Interface Size]

[0610] The interfacial content (m) of continuous fiber reinforced resin composites is calculated using the following formula. -1 ).

[0611] Interface quantity (m) -1 The volume of reinforcing fibers in a continuous fiber-reinforced resin composite (m³) 3 ))×(density of reinforcing fiber (g / m³) 3 ))×(number of single filaments of reinforcing fiber)×(diameter of reinforcing fiber (m))×π / (fineness of reinforcing fiber (g / m)) / (volume of continuous fiber reinforced resin composite (m³)) 3 ))

[0612] [Tensile strength, tensile strength retention rate]

[0613] Long strips measuring 70 mm in length, 10 mm in width, and 2 mm in thickness were cut from continuous fiber-reinforced resin composites and dried in a vacuum dryer at 80°C for at least 18 hours. Subsequently, using an INSTRON universal testing machine, the test strips were clamped at 30 mm intervals along their length, and the tensile strength (MPa) was measured at a speed of 5 mm / min at 23°C and 50%RH, and at 80°C and 50%RH. The average value of the five samples was calculated.

[0614] The tensile strength retention rate (%) at 80℃ can be calculated using the following formula.

[0615] Tensile strength retention rate at 80℃ = (Tensile strength at 80℃ and 50%RH / Tensile strength at 23℃ and 50%RH) × 100

[0616] [Flexural strength, flexural modulus, flexural strength retention rate, flexural modulus retention rate]

[0617] Strip-shaped test pieces with a length of 100 mm, a width of 10 mm, and a thickness of 2 mm were cut from continuous fiber-reinforced resin composites and dried in a vacuum dryer at 80°C for more than 18 hours. Subsequently, using an INSTRON universal testing machine with a three-point bending fixture, the span was set to thickness × 16 (mm), and the flexural strength (MPa) and flexural modulus (GPa) were measured at a speed of 1 mm / min in environments of 23°C and 50%RH, and in environments of 80°C and 50%RH, respectively. The average value of 5 samples was calculated.

[0618] The flexural strength retention rate (%) and flexural modulus retention rate (%) at 80℃ can be calculated using the following formulas.

[0619] Bending strength retention rate at 80℃ = (Bending strength at 80℃ and 50%RH / Bending strength at 23℃ and 50%RH) × 100

[0620] Flexural modulus retention rate at 80℃ = (Flexural modulus at 80℃ and 50%RH / Flexural modulus at 23℃ and 50%RH) × 100

[0621] [Water absorption characteristics]

[0622] Strip-shaped test pieces, 100 mm in length, 10 mm in width, and 2 mm in thickness, were cut from continuous fiber-reinforced resin composite materials. These pieces were immersed in a constant-temperature water bath at 80°C for 18 hours, and then placed in a constant-temperature and humidity bath at 80°C and 57%RH for at least 150 hours. The test pieces whose humidity was adjusted until their mass stabilized were used as the water-absorbing test pieces. The tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the dry and water-absorbing test pieces were measured using the methods described above at 23°C and 50%RH.

[0623] The following formulas can be used to calculate the retention rates of tensile strength (%), flexural strength (%), and flexural modulus (%) during water absorption.

[0624] Tensile strength retention rate during water absorption = (Tensile strength during water absorption / Tensile strength during drying) × 100

[0625] Flexural strength retention rate during water absorption = (Flexural strength during water absorption / Flexural strength during drying) × 100

[0626] Flexural modulus retention rate during water absorption = (Flexural modulus during water absorption / Flexural modulus during drying) × 100

[0627] Impact strength

[0628] Test pieces measuring 60 mm in length, 60 mm in width, and 2 mm in thickness were cut from continuous fiber-reinforced resin composite materials. Tests were conducted using a high-speed impact testing machine (Shimadzu HYDRO SHOT HITS-P10, Shimadzu Corporation) according to JIS K7211-2:2006, under the following conditions: impact pin diameter 20 mm Ф, support diameter 40 mm Ф, test speed 4.4 m / s, test temperature 23℃, and test number n=5. A curve of test force versus displacement was plotted. The maximum impact strength (kN) was determined from this curve, divided by the thickness of the test piece, and the average value (kN / mm) of the five samples was used to calculate the final impact strength.

[0629] [Acoustic emission measurement]

[0630] Using an acoustic emission measurement system (USB AE NODE AE measurement system 1ch, manufactured by PAC Corporation), an acoustic emission sensor (R6a) was mounted in the center of the three-point bending fixture used in the bending strength test, using silicone grease (Shinetsu Silicone HIVAC-G, Shin-Etsu Chemical Co., Ltd.), and fixed with PVC tape. Acoustic emission signals were acquired simultaneously with the start of the bending test at 23°C and 50% RH. The test was stopped when the test piece failed and reached 80% of its maximum load.

[0631] The number of acoustic emission signals with an amplitude of 40 dB or more and a duration of less than 3500 microseconds is taken as count 1, and the number of acoustic emission signals with an amplitude of 25 to 30 dB and a duration of less than 1000 microseconds is taken as count 2. Count 1, count 2 and the total number of signals are measured, and AE count A and AE count B are calculated by the following formula.

[0632] (AE count A) = (Number of AE signals with amplitude above 40dB and duration below 3500 microseconds) / (Total number of AE signals)

[0633] (AE count B) = (Number of AE signals with amplitude of 25-30dB and duration of less than 1000 microseconds) / (Total number of AE signals)

[0634] The N5 was used for measurement, and its average value was taken as the value.

[0635] [Vibration Fatigue Test]

[0636] ASTM-D1822 tensile impact dumbbell-shaped S-shaped test specimens were prepared from continuous fiber reinforced resin composites. Vibration fatigue tests were conducted using an EHF-EB50kN-40L(RV) (Shimadzu Corporation), with the test temperature set at 23°C, frequency at 20Hz, waveform as a sine wave, and clamp spacing at 35mm. Cases with more than 20,000 fracture cycles at 250MPa were recorded as "0 (Good)," and cases with fewer than 20,000 cycles were recorded as "× (Poor)."

[0637] [Crystallization degree]

[0638] Using a differential scanning calorimeter (Shimadzu DSC-60), the sample amount was approximately 5 mg, based on the amount of resin contained in the continuous fiber-reinforced resin composite. Under an atmosphere flow rate of 30 mL / min and a heating rate of 10 °C / min, the sample was heated from room temperature (25 °C) to a temperature above the predicted melting point until it melted. The heat of fusion measured at this point was divided by the heat of complete fusion, and the crystallinity (%) was calculated from the resulting value. The heat of complete fusion was assumed to be 188 J / g.

[0639] [Microdroplet contact angle, interfacial shear strength]

[0640] Thermoplastic resin was placed in the heating furnace section of a composite material interface property evaluation device (HM410, Toei Sangyo Co., Ltd.). The furnace temperature was set to the melting point of the thermoplastic resin +15°C, allowing the resin to adhere to a single filament of a continuous reinforcing fiber, thus creating microdroplets. The created microdroplets were ellipsoidal in shape, centered on the reinforcing fiber and extending along its length. After cooling to room temperature, the contact angle between the continuous reinforcing fiber and the thermoplastic resin microdroplets was measured (refer to...). Figure 1 The contact angle (α) is obtained from 100 microdroplets with a length L of 95-105 μm along the fiber axis of the continuous reinforcing fiber of the microdroplet. The contact angle (°) of the microdroplet is then calculated based on the central value of the contact angle.

[0641] In addition, after measuring the diameter d (μm) of the continuous reinforcing fiber and the length L (μm) of the continuous reinforcing fiber in the direction of the fiber axis of the microdroplet, shear tests were conducted on microdroplets of 95–105 μm. The shear load F (N) when the resin ball was scraped off with a scraper was measured, and the interfacial shear strength τ (MPa) was calculated using the following formula (1). Assuming that the number of measurements was 100, the median value of the 100 measurements was calculated.

[0642] τ=F / πdL ···(1)

[0643] The continuous reinforcing fibers with surface treatment agents used in each embodiment, the glass fibers without surface treatment agents that were treated in an electric furnace at 650°C for 3 hours, and the continuous reinforcing fibers treated with a coupling agent (made by adjusting γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) to 0.5% by mass with deionized water) were measured, and the interfacial strength ratio and contact angle ratio were determined.

[0644] (Interfacial strength ratio) = (Interfacial strength measured using continuous reinforcing fibers with surface treatment agent) / (Interfacial strength measured using reinforcing fibers treated with coupling agent)

[0645] (Contact angle ratio) = (Contact angle measured using continuous reinforcing fibers with surface treatment agent) / (Contact angle measured using glass fibers without surface treatment agent)

[0646] [Physical stability]

[0647] For 50 test pieces, the bending strength was tested and measured. Let the average bending strength be A, and let the bending strength in the i-th measurement (i=1 to 50) be Ai. The coefficient of variation was calculated according to the following formula and used as the deviation.

[0648] [Number 2]

[0649]

[0650] [Warpage Characteristics]

[0651] The direct-reading micrometer is fixed to the arm, and the continuous fiber-reinforced resin composite plate obtained in each example is plotted, and the difference between the maximum and minimum values ​​is read.

[0652] [Shape Following]

[0653] Test pieces of 150mm × 150mm were cut from the continuous fiber-reinforced resin composite material obtained in each example using a band saw. These pieces were heated to the melting temperature of the resin used in each example +25°C using an infrared heater (INFRASTAIN H7GS-71298NGK, Japanese insulator, wavelength 3–7μm). The pieces were placed in a mold with a flat section of 100mm × 100mm, a wall section of 25mm × 100mm, a wall section radius of 10°, and heated to 180°C, and pressed under a pressure of 10MPa. The maximum gap between the wall section and the mold of the resulting box-shaped molded body was rated as "〇" (Excellent) if it was 0mm or more and less than 1mm, "△" (Good) if it was 1mm or more and less than 3mm, and "×" (Poor) if it was 3mm or more.

[0654] [Determination of SP value]

[0655] The SP value is calculated using the following formula based on the structure of the resin and the bundle-forming agent components of the continuous reinforcing fibers used in each example. Evaporation energy and molar volume are referenced to values ​​based on the Fedors method. In cases with two or more components, the SP value is calculated by summing the values ​​obtained by multiplying the mass percentage of each component by its SP value.

[0656] (SP value) = {(sum of the evaporation energies of atoms or groups of atoms contained in each component) / (molar volume of atoms or groups of atoms contained in each component)}^(1 / 2)

[0657] The materials used in the examples and comparative examples are described below.

[0658] [Continuous Reinforced Fiber]

[0659] (glass fiber)

[0660] Glass Fiber 1: A fiber manufactured by attaching 0.45% by mass of a bundling agent to glass fibers with a fineness of 1.15 g / m and a number of 1500 filaments per 100% by mass. The winding form is DWR, and the average filament diameter is approximately 17 μm. The bundling agent is prepared by adjusting the amount of deionized water to achieve the following proportions: 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 Co., Ltd.) as a bundling agent, and 3% by mass of a copolymer compound (a copolymer compound with a weight average molecular weight of 20000, formed by copolymerizing 40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate). The SP value of the bundling agent is 14.0.

[0661] Glass fiber 2: A fiber manufactured by attaching 0.45% by mass of a bundling agent to glass fibers with a fineness of 1.15 g / m and 1500 monofilaments per 100% by mass. The winding form is DWR, and the average monofilament diameter is approximately 17 μm. The bundling agent is prepared by adjusting the content of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent (0.5% by mass), carnauba wax as a lubricant (0.5% by mass), polyurethane resin (Y65-55, manufactured by ADEKA Co., Ltd.) as a bundling agent (1.8% by mass), and a copolymer compound (a copolymer compound with a weight average molecular weight of 20000, formed by copolymerizing 51% by mass of maleic anhydride, 39% by mass of methyl acrylate, and 10% by mass of methyl methacrylate). The SP value of the bundling agent is 15.5.

[0662] Glass fiber 3: A fiber manufactured by attaching 0.45% by mass of a bundling agent to glass fibers with a fineness of 1.15 g / m and 1500 monofilaments per 100% by mass. The winding form is DWR, and the average monofilament diameter is approximately 17 μm. The bundling agent is prepared by adjusting the content of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent (0.5% by mass), carnauba wax as a lubricant (0.5% by mass), maleic anhydride-modified polypropylene resin as a bundling agent (4% by mass), and a copolymer compound (a copolymer of 71% by mass of methyl acrylate and 29% by mass of methyl methacrylate, with a weight average molecular weight of 20000) (1.4% by mass). The SP value of the bundling agent is 11.1.

[0663] (Carbon fiber)

[0664] Fibers were manufactured by attaching 0.45% by mass of a bundling agent to carbon fibers with 12,000 monofilaments, 9 μm diameter, and 2.58 g / m fineness per 100% by mass. The bundling agent was prepared using deionized water to achieve the following proportions: 1% by mass of carnauba wax, 2% by mass of polyurethane resin (Y65-55, manufactured by ADEKA Co., Ltd.), and 3% by mass of a copolymer compound (a copolymer of 40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate, with a weight average molecular weight of 20,000). The SP value of the bundling agent was 14.0.

[0665] Fabrication of Continuously Reinforced Fiber Substrates

[0666] Glass cloth 1 and glass cloth 2: Glass cloth is manufactured by weaving using a rapier loom (1m width) with the aforementioned glass fiber 1 as both warp and weft yarns. The resulting glass cloth has the following weave: Glass cloth 1 (plain weave, weave density 6.5 threads / 25mm, basis weight 640g / m²). 2 ), Fiberglass cloth 2 (plain weave, weave density 6.5 threads / 25mm, basis weight 660g / m²) 2 ).

[0667] Glass cloth 3: Glass cloth is manufactured by weaving using a rapier loom (1m width) with the aforementioned glass fiber 2 as both warp and weft yarns. The resulting glass cloth is woven as glass cloth 3 (plain weave, weave density 6.5 threads / 25mm, basis weight 640g / m²). 2 ).

[0668] Glass cloth 4: Glass cloth is manufactured by weaving using the aforementioned glass fiber 3 as warp and weft yarns. The resulting glass cloth has the following weave pattern: Glass cloth 4 (plain weave, weave density of 6.5 threads / 25mm, basis weight of 640g / m²). 2 ).

[0669] Carbon fiber fabric: Carbon fiber fabric is manufactured by weaving using the aforementioned carbon fibers as both warp and weft yarns on a rapier loom (1m width). The resulting carbon fiber fabric is woven in a plain weave with a weave density of 6.5 threads / 25mm and a basis weight of 425g / m². 2 .

[0670] [Thermoplastic resin]

[0671] Resin 1: PA66 (carboxyl-terminal group concentration 70 μmol / g, amino-terminal group concentration 30 μmol / g, tanδ peak temperature: 50℃, SP value: 12.4, melting point: 265℃)

[0672] Resin 2: A dry mixture of Resin 1 and PA6I (PA66:PA6I=2:1) ​​(Carboxyl-terminal group concentration 120 μmol / g, amino-terminal group concentration 40 μmol / g, tanδ peak temperature: 110℃, SP value: 12.6, melting point: 260℃)

[0673] Resin 3: Polypropylene (peak temperature of tanδ at 0 μmol / g terminal group concentration: 0℃, SP value: 8.4, melting point: 180℃)

[0674] Resin 4: Maleic acid modified polypropylene (terminal group concentration 21 μmol / g, tanδ peak temperature: 0℃, SP value: 10.1, melting point: 180℃)

[0675] Resin 5: PA6 (carboxyl-terminal group concentration 60 μmol / g, amino-terminal group concentration 30 μmol / g, tanδ peak temperature: 50℃, SP value: 12.3, melting point: 225℃)

[0676] Resin 6: PA6I (carboxyl-terminal group concentration 200 μmol / g, amino-terminal group concentration 60 μmol / g, tanδ peak temperature: 130℃, SP value: 12.9, glass transition temperature: 135℃)

[0677] Resin 7: PPS (Toray Industries, Inc.) (Tanδ peak temperature: 90℃, SP value: 11.7, melting point: 280℃)

[0678] Resin 8: PA610 (carboxyl-terminal group concentration 70 μmol / g, amino-terminal group concentration 30 μmol / g, tanδ peak temperature: 50℃, SP value: 11.5, melting point: 222℃)

[0679] Resin 9: A dry mixture of Resin 3 and Resin 4 (Resin 3: Resin 4 = 90:10) (Terminal group concentration 2 μmol / g, peak temperature of tanδ: 0℃, SP value: 8.6, melting point: 180℃)

[0680] Resin 10: PA12 (Carboxyl-terminal group concentration 60 μmol / g, amino-terminal group concentration 60 μmol / g, tanδ peak temperature: 50℃, SP value: 10.5, melting point: 179℃)

[0681] (Concentration of terminal groups in thermoplastic resins)

[0682] use 1 H-NMR was used to determine the concentration of terminal groups in various thermoplastic resins under the following conditions.

[0683] 1 H-NMR measurement conditions

[0684] Device: JEOL-ECA500 (Nippon Electronics Corporation)

[0685] Observation kernel: 1 H

[0686] Observation frequency: 500MHz

[0687] Measurement method: Single-Plus

[0688] Pulse width: 30°

[0689] Waiting time: 10 seconds

[0690] Points earned: 256 times

[0691] Solvent: D2SO4

[0692] Sample concentration: 1.25% by mass

[0693] [Preparation of thermoplastic resin films]

[0694] Thermoplastic resin film was obtained by molding using a T-die extrusion molding machine (developed by Sou Corporation). The thickness of the thermoplastic resin film was 200 μm.

[0695] [Creating Hybrid Molded Objects]

[0696] The continuous fiber reinforced resin composite material obtained in each embodiment was cut into a rectangle of 200×300mm. The resin used in each embodiment was mixed and molded by compression molding to obtain a box-shaped continuous fiber reinforced resin composite material with a short side of 192mm, a long side of 292mm, a vertical wall of 4mm height formed of polypropylene A on each side, and a cross-shaped rib that connects half of each short side and long side in a direction parallel to the long side.

[0697] In the molding of the hybrid molded body, an infrared heater (INFRASTAIN H7GS-71298NGK, Japanese insulator, wavelength 3-7μm) is used to heat the resin of each embodiment to a temperature of 35°C above the melting point (or glass transition temperature for resins without a melting point). The continuous fiber-reinforced resin composite material, which has been preheated for 60 seconds, is inserted into a mold maintained at 150°C. After pressing at a pressure of 10MPa, the injection pressure is set to 120MPa and the injection temperature is 35°C above the melting point (or glass transition temperature for resins without a melting point). The resin used in each embodiment is injection molded.

[0698] [Example 1]

[0699] Using resin 1, a thermoplastic resin film 1 is obtained by the above method.

[0700] Prepare 5 sheets of glass cloth 1 and 6 sheets of thermoplastic resin film 1. Alternately overlap the glass cloth 1 and thermoplastic resin film 1 with the thermoplastic resin film 1 as the surface to form a continuous fiber-reinforced resin composite material. At this point, the volume ratio of the thermoplastic resin is 50%.

[0701] A double-belt press is used as the molding machine. The glass cloth and the thermoplastic resin film 1 are overlapped as described above and placed in the molding machine. The film is compressed at a heating rate of 280°C / min, a pressure of 3MPa, and a belt speed of 0.5m / min. Then, the film is cooled at a cooling rate of 80°C / min and compressed at 3MPa for 3 minutes to complete the molding process.

[0702] The obtained continuous fiber reinforced resin composite material was used to make a hybrid molded body using the above method. The body was cut into sections with a length of 100 mm and a width of 10 mm. The ribs were removed using abrasive paper in a manner that would not damage the continuous fiber reinforced resin composite material. Acoustic emission measurements were then performed using the above method.

[0703] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0704] [Example 2]

[0705] Resin 2 was used as the thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1.

[0706] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0707] [Example 3]

[0708] Resin 9 was used as the thermoplastic resin, and glass cloth 4 was used as the glass cloth. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1.

[0709] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0710] [Example 4]

[0711] Carbon fiber cloth was used as the continuous reinforcing fiber substrate, and otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Example 2. It should be noted that the volume ratio of the thermoplastic resin was 50%.

[0712] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0713] [Example 5]

[0714] Glass cloth 2 was used as the continuous reinforcing fiber substrate, and otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1. It should be noted that the volume ratio of the thermoplastic resin was 50%.

[0715] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0716] [Example 6]

[0717] Resin 4 was used as a thermoplastic resin, and glass cloth 4 was used as a glass cloth. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1.

[0718] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0719] [Example 7]

[0720] Resin 5 was used as the thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1.

[0721] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0722] [Example 8]

[0723] Resin 6 was used as a thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1.

[0724] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0725] [Example 9]

[0726] Relative to the aforementioned glass fiber 1 (100% by mass), a mixture of 0.3% by mass of 3-epoxypropoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.) as a binding agent, 1.5% by mass of epoxy resin emulsion, and 0.2% by mass of carnauba wax was attached. Using the obtained glass fiber, a plain weave with a weave density of 6.5 strands / 25mm and a basis weight of 640g / m² was manufactured. 2 Five sheets of the glass cloth were laminated and placed in a mold. A mixture of 16g ​​of bisphenol A type liquid epoxy resin (jER828, Mitsubishi Chemical Corporation) and 1.6g of bisphenol A (4,4'-(propane-2,2-diyl)biphenol) was added. The temperature inside the molding machine was set to 40°C, and compression molding was performed for 3 days with a clamping force of 5MPa. The mixture was then cooled for 8 minutes at a cooling rate of 80°C / min and a clamping force of 5MPa to obtain a continuous fiber-reinforced resin composite material. It should be noted that the volume ratio of thermoplastic resin was 50%.

[0727] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0728] [Example 10]

[0729] Resin 7 was used as a thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1.

[0730] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0731] [Example 11]

[0732] Resin 2 is used as a thermoplastic resin, and glass fiber 1 is used as a continuous reinforcing fiber matrix at a basis weight of 640 g / m².2 The substrate was obtained by aligning the fibers, and otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1. It should be noted that the volume ratio of the thermoplastic resin was 50%.

[0733] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0734] [Example 12]

[0735] Glass cloth 3 was used as the glass cloth, and otherwise a continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1.

[0736] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0737] [Example 13]

[0738] Resin 8 was used as a thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1.

[0739] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0740] [Example 14]

[0741] Resin 10 was used as a thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1.

[0742] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0743] [Comparative Example 1]

[0744] Relative to the aforementioned glass fiber 1 (100% by mass), a mixture of 0.3% by mass of 3-epoxypropoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.) as a binding agent, 1.5% by mass of epoxy resin emulsion, and 0.2% by mass of carnauba wax was attached. Using the obtained glass fiber, a plain weave was manufactured with a weave density of 6.5 strands / 25mm and a basis weight of 600g / m². 2 The glass cloth was used, and otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Example 1. It should be noted that the volume ratio of the thermoplastic resin was 50%.

[0745] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0746] [Comparative Example 2]

[0747] The same evaluation as in Example 1 was performed using Bond Laminate, which is made by impregnating polyamide 66 in glass cloth to produce "Tepex dynalite 101".

[0748] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0749] [Comparative Example 3]

[0750] Resin 3 was used as a thermoplastic resin, and glass cloth 3 was used as a glass cloth. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1.

[0751] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 1.

[0752] [Table 1]

[0753]

[0754] The following are examples of continuous fiber reinforced resin composites with feature (II).

[0755] [The coating ratio of the interfacial resin of the continuous reinforcing fiber, the exposure degree of the reinforcing fiber at the interface, and the relative element concentration]

[0756] 100 mg of continuous fiber-reinforced resin composite material cut into thin sheets and 20 mL of solvent selected according to the resin used in each example were added to a homogenizer and stirred for 5 hours. The solvent was removed by vacuum filtration, and 40 mL of fresh solvent was sprayed onto the filter. The continuous reinforcing fibers were then washed and air-dried. The resulting continuous reinforcing fibers and 20 mL of fresh solvent were added to a homogenizer and stirred for 2 hours. The solvent was removed by vacuum filtration, and 40 mL of fresh solvent was sprayed onto the filter. The continuous reinforcing fibers were then washed and dried with a nitrogen stream. The resulting continuous reinforcing fibers and 20 mL of fresh solvent were added to a homogenizer and stirred for 2 hours. The solvent was removed by vacuum filtration, and 40 mL of fresh solvent was sprayed onto the filter. The continuous reinforcing fibers were then washed and air-dried, and finally dried overnight in a vacuum dryer set to room temperature. The obtained continuous reinforcing fibers were pressed into a flat plate, and a 2 mm piece was taken out. The relative elemental concentrations of carbon, oxygen, nitrogen, silicon, aluminum, and calcium were determined using XPS (Versa probe II, ULVAC-PHI Corporation) under the following conditions: excitation source mono.AlKα 20kV×5mA 100W, analysis size 100μm×1.4mm, photoelectron extraction angle 45°, capture range (full scan): 117.4eV, (narrow scan): C1s, O1s, N1s, Si2p, Ca2p, Al2p, pass energy (full scan): 117.4eV, (narrow scan): 46.95eV.

[0757] The coating ratio of the interfacial resin for continuous reinforcing fibers is calculated as follows: When polyamide is used as the resin and glass fiber is used as the continuous reinforcing fiber, the coating ratio is calculated by formula (1); when polyamide is used as the resin and carbon fiber is used as the continuous reinforcing fiber, the coating ratio is calculated by formula (2); when polypropylene is used as the resin and glass fiber is used as the continuous reinforcing fiber, the coating ratio is calculated by formula (3). The details of the formulas are as described above.

[0758] (Cover rate)=[N] / ([N]+[Si]) (1)

[0759] (Cover rate)=[N] / ([N]+[O]) (2)

[0760] (Coverage rate) = ([C] - [C0]) / ([C] - [C0] + [Si])

[0761] Regarding the exposure degree of the reinforcing fiber at the interface, when glass fiber is used as the continuous reinforcing fiber, it is calculated by the following formula (4); when carbon fiber is used as the continuous reinforcing fiber, it is calculated by the following formula (5). The details of the formulas are as described above.

[0762] (Exposure of the reinforcing fiber at the interface) = [Al] / [Al0] (4)

[0763] (Exposure of the reinforcing fiber at the interface) = [O] / [O0] (5)

[0764] [Static Wettability]

[0765] A thermoplastic resin film and a reinforcing fiber are sandwiched between coverslips. The temperature is increased to 280°C at 100°C / min on a heating plate. After 5 minutes, the angle (contact angle) (°) formed between the surface of the reinforcing fiber and the thermoplastic resin is observed using an optical microscope. Four measurements are performed, and the average value is calculated. The smaller the angle, the better the static wettability.

[0766] [Impregnation speed]

[0767] A hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons was used as the molding machine. Five sheets of continuous reinforcing fiber woven fabric were laminated with a thermoplastic resin film. The laminate was placed inside a mold equipped with a temperature sensor and then placed in a heated pressing molding machine with the mold temperature set to the melting point of the thermoplastic resin + 65°C. Heated pressing was performed at 5 MPa pressure while monitoring the temperature. After the temperature inside the mold reached the melting point of the thermoplastic resin for 30 seconds, the laminate was removed from the heated pressing molding machine and placed in a cooling pressing machine for cooling and pressing at 5 MPa pressure with water cooling. The resulting continuous reinforcing fiber composite material was cut with a band saw, ground, and the impregnation content (%) was calculated for the cross-section (described later). The impregnation content was divided by the time (in minutes) during heated pressing when the thermoplastic resin reached above its melting point to calculate the impregnation rate (% / min). It should be noted that the time for the thermoplastic resin to reach above its melting point in the above operation was 60 seconds.

[0768] The impregnation rate (%) was calculated using the following method. The obtained continuous fiber reinforced resin composite was cut at any point and carefully ground in a manner that would not damage the continuous reinforcing fibers. The cross-section was observed using SEM, and the obtained image was analyzed using analysis software (product name: ImageJ). From this, the area of ​​the region surrounded by the outer contour line of the continuous reinforcing fibers, which are bundles of monofilaments (filaments), and the area of ​​the voids contained in the region surrounded by the outer contour line of the continuous reinforcing fibers were calculated.

[0769] And it is calculated using the following formula.

[0770] Impregnation rate (%) = [1 - {void area / (area of ​​the region surrounded by the outer contour line of the continuous reinforcing fiber)} × 100

[0771] For the 10 continuous reinforcing fibers in the obtained cross-sectional image, the impregnation rate was calculated and the average value was calculated as the impregnation rate.

[0772] [Bending fatigue test]

[0773] ASTM-D671 Type A test specimens were prepared from continuous fiber reinforced resin composites. Vibration fatigue tests were conducted using a repetitive vibration fatigue testing machine (B-70, Toyo Seiki Co., Ltd.) at a test temperature of 23°C and a frequency of 20Hz, with the waveform being a sine wave. The number of fractures of each continuous fiber reinforced resin composite under vibration fatigue test at a stress equivalent to 35% of the flexural strength was determined.

[0774] [Bending strength at 23℃, bending strength at 120℃]

[0775] Long strips measuring 100 mm in length, 10 mm in width, and 2 mm in thickness were cut from continuous fiber reinforced resin composite materials. Using an INSTRON universal testing machine with a three-point bending fixture, the span was set to 32 mm. The bending strength (MPa) was measured at a speed of 1 mm / min under conditions of 23°C and 50%RH, and at 120°C and 50%RH.

[0776] The materials used in an example of a continuous fiber reinforced resin composite with characteristic (II) are shown below.

[0777] [Continuous Reinforced Fiber]

[0778] (glass fiber)

[0779] Glass fiber 1 (GF1): A fiber manufactured by attaching 0.10% by mass of a condensing agent to glass fibers with a fineness of 1.15 g / m and a number of 2000 filaments per 100% by mass. The winding form is DWR, and the average filament diameter is approximately 18 μm. The condensing agent is prepared by adjusting the amount of deionized water to achieve 1.5% by mass of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 1% by mass of carnauba wax, and 3% by mass of a copolymer compound with a weight average molecular weight of 10000, formed by copolymerizing 50% by mass of maleic anhydride and 50% by mass of methyl methacrylate.

[0780] Glass fiber 2 (GF2): GF1 was treated in an electric furnace at 650°C for 3 hours, and the resulting glass fiber was immersed in a 1.5% by mass aqueous solution of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) for 30 minutes and dried at 110°C for 3 hours.

[0781] Glass fiber 3 (GF3): GF1 is treated in an electric furnace at 650°C for 3 hours to obtain GF without bundle agent (adhesive).

[0782] Glass fiber 4 (GF4): A fiber manufactured by attaching 0.10% by mass of a sizing agent to glass fibers with a fineness of 1.15 g / m and a number of 2000 filaments per 100% by mass. The winding form is DWR, and the average filament diameter is approximately 18 μm. The sizing agent is prepared by adjusting the content of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) to 1.5% by mass, carnauba wax to 1% by mass, and a copolymer compound with a weight average molecular weight of 13000, formed by copolymerizing 50% by mass of maleic anhydride and 50% by mass of styrene, to 3% by mass.

[0783] Glass fiber 5 (GF5): Glass fiber with a fineness of 1.15 g / m and a single filament count of 2000 per 100% by weight, consisting of glass fibers with a binding agent of 0.3% by weight of 3-epoxypropoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.), 1.5% by weight of epoxy resin emulsion, and 0.2% by weight of carnauba wax.

[0784] (Carbon fiber)

[0785] Carbon fiber 1: A fiber manufactured by attaching 0.1% by mass of a bubbling agent to PAN-based carbon fibers with a single filament count of 12,000. The bubbling agent is prepared by adjusting the composition of 1,6-hexanediamine (1.5% by mass), diphenyl azidophosphate (1.5% by mass), carnauba wax (1% by mass), and a copolymer compound with a weight average molecular weight of 10,000, formed by copolymerizing 50% by mass of maleic anhydride and 50% by mass of methyl methacrylate (3% by mass).

[0786] Carbon fiber 2: PAN-based carbon fibers with a single filament number of 12,000 were impregnated in an aqueous solution containing 1.5% by mass of 1,6-hexanediamine and 1.5% by mass of diphenyl azidophosphate at 60°C for 12 hours and dried at 110°C for 6 hours.

[0787] Carbon fiber 3: PAN-based carbon fiber with a single filament count of 12,000 (excluding bundle binder (sizing agent))

[0788] Fabrication of Continuously Reinforced Fiber Substrates

[0789] Fiberglass cloth: Fiberglass cloth is manufactured using a rapier loom (1m width) and the aforementioned glass fiber 1 as both warp and weft yarns. The resulting fiberglass cloth has a plain weave, a weave density of 6.5 threads / 25mm, and a basis weight of 640g / m². 2 ).

[0790] Carbon fiber fabric: Carbon fiber fabric is manufactured by weaving using a rapier loom (1m width) with the aforementioned carbon fiber 1 as both warp and weft yarns. The resulting carbon fiber fabric is woven in a plain weave with a weave density of 6.5 threads / 25mm and a basis weight of 425g / m². 2 .

[0791] [Thermoplastic resin]

[0792] Resin 1: Polyamide 66

[0793] The polymerization reaction of polyamide is carried out by the "thermal melt polymerization method" as follows.

[0794] 1500g of a mixture containing adipic acid (Wako Pure Chemical Industries) and hexamethylenediamine (Tokyo Chemical Industries) salts in a 55:45 molar ratio, along with 150g of adipic acid, was dissolved in 1500g of distilled water to prepare a 52% by mass homogeneous aqueous solution of the raw material monomers. This aqueous solution was then transferred to a 6.2L autoclave and purged with nitrogen. The mixture was concentrated by slowly venting water vapor while stirring at a temperature between 110°C and 140°C until the solution concentration reached 69% by mass. The internal temperature was then raised to 225°C. At this point, the autoclave was pressurized to 1.9 MPa. This pressure was maintained for 2 hours until the internal temperature reached 245°C. Water vapor was then slowly vented, and the pressure was maintained at 1.9 MPa for 50 minutes. The pressure was then reduced over 1.5 hours. Subsequently, the autoclave was maintained under vacuum at 650 torr for 11 minutes. At this point, the final internal temperature of the polymerization was 265°C. Subsequently, nitrogen gas was used to pressurize the material, forming it into a filament from the lower spinneret (nozzle). This filament was then water-cooled, cut, and discharged as granules. After drying at 100°C under a nitrogen atmosphere for 12 hours, resin 1 (polyamide 66) was obtained. Mw=31000, Mw / Mn=1.95, melting point (Tm)=265°C, glass transition temperature (Tg)=50°C.

[0795] Resin 2: Relative to 100% by mass of Resin 1, 0.05% by mass of copper iodide and 0.2% by mass of potassium iodide were dry-mixed and mixed in a twin-screw mixer (TEM26SS, TOSHIBA MACHINE) set to 280°C. The mixture was then water-cooled, cut, and discharged as granules. It was then dried at 100°C under a nitrogen atmosphere for 12 hours to obtain Resin 2.

[0796] Resin 3: Polyamide 6I

[0797] The polymerization reaction of polyamide is carried out by the "thermal melt polymerization method" as follows.

[0798] 1500g of an equimolar salt containing isophthalic acid (Wako Pure Chemical Industries) and hexamethylenediamine in a 55:45 molar ratio, along with 100g of isophthalic acid, was dissolved in 1500g of distilled water to prepare a homogeneous aqueous solution. The solution was concentrated by slowly venting water vapor while stirring at a temperature between 110°C and 140°C until the concentration reached 68% by mass. The internal temperature was then raised to 235°C. This temperature was maintained for 50 minutes until the internal temperature reached 245°C, while slowly venting water vapor to maintain a constant pressure for another 50 minutes. The pressure was then reduced for 60 minutes. Subsequently, the autoclave was maintained under vacuum at 650 torr for 10 minutes. At this point, the final internal temperature of the polymerization was 265°C. The mixture was then pressurized with nitrogen and formed into a filament from a lower spinneret (nozzle), water-cooled, cut, and discharged as granules. The granules were dried at 100°C under a nitrogen atmosphere for 12 hours to obtain resin 3 (polyamide 6I). The obtained resin 3 (polyamide 6I) has Mw=22000 and Mw / Mn=1.9.

[0799] Resin 4: It is made by dry mixing resin 1 and resin 3 at a mass ratio of 7:3.

[0800] Resin 5: Maleated PP (Mw=42000, acid value: 40eq / g)

[0801] [Preparation of thermoplastic resin films]

[0802] Thermoplastic resin film was obtained by molding using a T-die extrusion molding machine (developed by Sou Corporation). The thickness of the thermoplastic resin film was 180 μm.

[0803] [Refer to Example 2-1]

[0804] Using resin 1, a thermoplastic resin film 1 is obtained by the above method.

[0805] Prepare 5 sheets of glass cloth 1 and 6 sheets of thermoplastic resin film 1. Alternately overlap the glass cloth 1 and thermoplastic resin film 1 with the thermoplastic resin film 1 as the surface to form a continuous fiber-reinforced resin composite material. A continuous compression molding machine is used as the molding machine. The glass cloth and thermoplastic resin film 1 are stacked as described above in the molding machine. The temperature of the heating zone inside the molding machine is set to 350°C, and the temperature of the cooling zone is adjusted using oil cooling. Compression molding is performed under a pressure of 5 MPa and a belt speed of 0.5 m / min.

[0806] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests of GF2, GF3 and resin 1, and the results of impregnation rate tests are shown in Table 2.

[0807] [Refer to Example 2-2]

[0808] Resin 2 is used as a thermoplastic resin, and otherwise a continuous fiber reinforced resin composite material is obtained in the same manner as in Reference Example 2-1.

[0809] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of GF2, GF3 and resin 2, are shown in Table 2.

[0810] [Refer to Example 2-3]

[0811] Resin 3 was used as a thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 2-1.

[0812] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of GF2, GF3 and resin 3, are shown in Table 2.

[0813] [Refer to Example 2-4]

[0814] Resin 4 was used as a thermoplastic resin, and otherwise a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 2-1.

[0815] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of GF2, GF3 and resin 4, are shown in Table 2.

[0816] [Refer to Example 2-5]

[0817] Carbon fiber cloth was used as the continuous reinforcing fiber substrate, and otherwise a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 2-1. It should be noted that a film with a thickness of 118 μm was used as the thermoplastic resin film.

[0818] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of CF2, CF3 and resin 1, are shown in Table 2.

[0819] [Refer to Example 2-6]

[0820] Resin 5 was used as the thermoplastic resin, and GF4 was used as the continuous reinforcing fiber. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 2-1.

[0821] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of GF2, GF3 and resin 5, are shown in Table 2.

[0822] [Compare with Example 2-1]

[0823] Using GF5, a plain weave was manufactured with a weave density of 6.5 threads / 25mm and a basis weight of 600g / m². 2 The glass cloth is used to obtain a continuous fiber reinforced resin composite material in the same manner as in Reference Example 2-1.

[0824] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of GF2, GF3 and resin 1, are shown in Table 2.

[0825] [Compare with Example 2]

[0826] In addition to using GF3, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 2-1.

[0827] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the results of static wettability tests and impregnation rate tests of GF2, GF3 and resin 1, are shown in Table 2.

[0828] [Compare with Example 3]

[0829] The same evaluation as in Reference Example 2-1 was performed using Bond Laminate, which is made by impregnating polyamide 66 in glass cloth, to produce "Tepex dynalite 101".

[0830] The properties of the obtained continuous fiber reinforced resin composites are shown in Table 2.

[0831] [Table 2]

[0832]

[0833] The following are examples of continuous fiber reinforced resin composites with feature (III).

[0834] [Determination of the crystalline phases of the inner and outer layers of continuous fiber-reinforced resin composites]

[0835] Continuous fiber-reinforced resin composite material was cut into 1 cm square pieces using a band saw. X-ray diffraction (XRD) was performed using a SmartLab 9kW apparatus. The inner layer was measured using a focusing optical system, and the surface layer was measured using a parallel optical system with grazing incidence. The full width at half maximum (FWHM), intensity, and lattice spacing of the (010) plane, the FWHM of the (100) plane, and the 2θ of the peaks on each crystal plane were determined. The identification of each crystal plane was determined through simulation.

[0836] Output power: 9kW (45kV / 200mA), 2θ=5~40°, ω=0.3° (parallel optical system), measurement interval: 0.1deg / min, detector: semiconductor detector, divergence slit: 1 / 2°, divergence longitudinal limiting slit: 5mm, scattering slit: 0.5°, light receiving slit: 2mm, Kβ filter.

[0837] The measurement was performed five times, and the result was calculated based on the average value. Furthermore, to ensure that the statistical variation was below 1%, the measurement was conducted with an intensity of at least 10,000 within the measurement range.

[0838] [Determination of the contact angle between continuous reinforcing fibers and thermoplastic resin]

[0839] A thermoplastic resin film and a single filament of a reinforcing fiber are sandwiched between coverslips. The temperature is increased to 280°C at 100°C / min on a heating plate, and after standing for 5 minutes, it is cooled to room temperature at 100°C / min. Images are taken before cooling begins and at room temperature. The angle (contact angle) (°) formed between the surface of the reinforcing fiber and the thermoplastic resin is calculated using ImageJ. The average value at 50° is taken as the contact angle. The contact angle before cooling begins is taken as the contact angle at high temperature, and the contact angle at room temperature is taken as the contact angle at room temperature. The ratio of (contact angle at high temperature) to (contact angle at room temperature) is calculated.

[0840] [Warpage Characteristics]

[0841] The direct-reading micrometer is fixed to the arm, and the continuous fiber-reinforced resin composite plate obtained in each example is plotted, and the difference between the maximum and minimum values ​​is read.

[0842] [Shape Following]

[0843] Test pieces of 150mm × 150mm were cut from the continuous fiber-reinforced resin composite material obtained in each example using a band saw. These pieces were heated to the melting temperature of the resin used in each example +25°C using an infrared heater (INFRASTAIN H7GS-71298NGK, Japanese insulator, wavelength 3–7μm). The pieces were placed in a mold with a flat section of 100mm × 100mm, a wall section of 25mm × 100mm, a wall section radius of 10°, and heated to 180°C, and pressed under a pressure of 10MPa. The maximum gap between the wall section and the mold of the resulting box-shaped molded body was rated as "〇" (Excellent) if it was 0mm or more and less than 1mm, "△" (Good) if it was 1mm or more and less than 3mm, and "×" (Poor) if it was 3mm or more.

[0844] The materials used in an example of a continuous fiber reinforced resin composite with characteristic (III) are shown below.

[0845] [Continuous Reinforced Fiber]

[0846] (glass fiber)

[0847] Glass fiber 1 (GF1): A glass fiber with a fineness of 11500 dtex and 2000 monofilaments, coated with 0.45% by mass of a bundling agent. The winding form is DWR, and the average monofilament diameter is 17 μm.

[0848] The fiberglass slub is applied using an aqueous slub solution, which is prepared by adjusting the composition of γ-aminopropyltriethoxysilane (hereinafter, aminosilane) KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) to 0.5% by mass, carnauba wax to 1% by mass, polyurethane resin Y65-55 (manufactured by ADEKA Co., Ltd.) to 2% by mass, a copolymer compound with a weight average molecular weight of 20,000, which is copolymerized from maleic anhydride to 40% by mass, methyl acrylate to 50% by mass, and methyl methacrylate to 10% by mass, to 3% by mass, and an aqueous solution of the copolymer compound to 3% by mass.

[0849] Regarding the components attached to the glass fiber, relative to 100% mass of the glass fiber, γ-aminopropyltriethoxysilane is 0.034% by mass, polyurethane resin is 0.14% by mass, carnauba wax is 0.069% by mass, and copolymer compound is 0.21% by mass.

[0850] Fabrication of Continuously Reinforced Fiber Substrates

[0851] Fiberglass cloth: A continuous fiber-reinforced substrate is manufactured by weaving the aforementioned fiberglass as both warp and weft yarns using a rapier loom (1m width). The resulting fiberglass cloth has a plain weave, a weave density of 6.5 threads / 25mm, and a basis weight of 640g / m². 2 ).

[0852] [Thermoplastic resin]

[0853] Resin 1: Polyamide 66 (Leona 1300S, Asahi Kasei), Melting point: 265℃

[0854] Resin 2: Polyamide 6 (1011FB, Ube Industries), melting point 225℃

[0855] [Preparation of thermoplastic resin films]

[0856] A thermoplastic resin film is obtained by molding using a T-die extrusion molding machine (developed by Sosho Corporation). The thickness of the thermoplastic resin film is 180 μm.

[0857] [Refer to Example 3-1]

[0858] Using resin 1, a thermoplastic resin film 1 is obtained by the above method.

[0859] Prepare 5 sheets of glass cloth 1 and 6 sheets of thermoplastic resin film 1. Alternately overlap the glass cloth 1 and thermoplastic resin film 1 with the thermoplastic resin film 1 as the surface. Use the resulting raw material laminate to form a continuous fiber-reinforced resin composite material. At this time, the volume ratio of thermoplastic resin is 50%.

[0860] A continuous compression molding machine was used as the molding machine. The glass cloth and the thermoplastic resin film 1 were overlapped as described above and placed in the molding machine. The temperature of the heating zone inside the molding machine was set to 330°C, and the temperature of the cooling zone was adjusted using oil at 180°C. Compression molding was performed under a pressure of 3 MPa and a belt speed of 0.5 m / min. At this time, the highest temperature of the continuous fiber reinforced resin composite material was 313°C, the cooling rate was 15°C / second, and a carbon steel mold was used. It should be noted that in Reference Example 3-1, since the temperature of the cooling zone in the molding machine was adjusted to 180°C, the temperature difference between the temperature of the dissimilar material (carbon steel mold) at the beginning of the cooling process (180°C) and the temperature of the continuous fiber reinforced resin composite material (313°C) was 133°C.

[0861] [Refer to Example 3-2]

[0862] Except that the temperature of the heating zone in the molding machine was set to 345°C and the temperature of the cooling zone was set to 130°C, a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 3-1 and evaluated. At this time, the highest temperature of the continuous fiber reinforced resin composite material was 320°C and the cooling rate was 24°C / second.

[0863] [Refer to Example 3-3]

[0864] A dual-belt press was used as the molding machine, and the temperature of the cooling zone was set to 50°C. Otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 3-1, and then evaluated. At this time, the highest temperature of the continuous fiber-reinforced resin composite material was 306°C, the cooling rate was 60°C / second, and carbon steel was used for the belts.

[0865] [Refer to Example 3-4]

[0866] The temperature of the heating zone in the molding machine was set to 300°C, and the temperature of the cooling zone was set to 180°C. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 3-1, and then evaluated. At this time, the highest temperature of the continuous fiber reinforced resin composite material was 279°C, and the cooling rate was 7°C / second.

[0867] [Refer to Example 3-5]

[0868] The temperature of the heating zone in the molding machine was set to 315°C and the temperature of the cooling zone was set to 180°C. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 3-1, and then evaluated. At this time, the highest temperature of the continuous fiber reinforced resin composite material was 290°C, and the cooling rate was 11°C / second.

[0869] [Refer to Example 3-6]

[0870] Resin 2 was used as the thermoplastic resin, and the temperature of the cooling zone was set to 140°C. Otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 3-1, and an evaluation was conducted. At this time, the highest temperature of the continuous fiber-reinforced resin composite material was 313°C, and the cooling rate was 18°C / second.

[0871] [Compare with Example 3-1]

[0872] A hydraulic molding machine with a maximum clamping force of 50 tons was used as the molding machine, and a carbon steel mold was used as the mold. The temperature inside the molding machine was heated to 330°C, and then the mold was clamped with a clamping force of 5 MPa for 5 minutes. After compression molding, the mold was transferred to a cooling press for water cooling, the mold was opened, and the molded body was removed. Otherwise, the continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 3-1 and evaluated. At this time, the highest temperature of the continuous fiber reinforced resin composite material was 266°C, and the cooling rate was 42°C / second.

[0873] [Compare with Example 3-2]

[0874] The same evaluation was performed using Bond Laminate, which is made by impregnating polyamide 66 in glass cloth, to produce "Tepex dynalite 101".

[0875] [Compare with Example 3-3]

[0876] Instead of GF1, a continuous reinforcing fiber without a binding agent (sizing agent) was used, in which GF1 was treated in an electric furnace at 650°C for 3 hours. Otherwise, a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 3-1 and evaluated. At this time, the highest temperature of the continuous fiber reinforced resin composite material was 313°C, the cooling rate was 15°C / second, and a carbon steel mold was used for cooling.

[0877] [Table 3]

[0878]

[0879] In Reference Examples 3-1 to 3-6, the full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer of the above-mentioned continuous fiber reinforced resin composite material is 1.00 or more, and the strength of the (010) plane of the crystalline phase in the inner layer is 40,000 or less, thus exhibiting high warpage characteristics and shape following properties.

[0880] The following are examples of continuous fiber reinforced resin composites with characteristic (IV).

[0881] The determination and evaluation methods used in examples of continuous fiber reinforced resin composites with characteristic (IV) are shown below.

[0882] [Volume percentage (Vf) of continuous reinforcing fibers in continuous fiber-reinforced resin composites]

[0883] A 2g sample of continuous fiber reinforced resin composite material was cut and placed in an electric furnace, heated at 650℃ for 3 hours to burn off the resin. Afterward, it was allowed to cool naturally to room temperature, and the mass of the remaining continuous reinforcing fibers was measured. The mass ratio of continuous reinforcing fibers to resin in the continuous fiber reinforced resin composite material was then determined. Next, the volume percentage (Vf) of the continuous reinforcing fibers in the continuous fiber reinforced resin composite material was calculated based on the determined mass ratio and density.

[0884] [Interface Polishing Value]

[0885] The continuous fiber reinforced resin composite material was cut using a band saw to obtain a cross-section (grinding surface) orthogonal to the length direction of the continuous reinforcing fibers. A grinding machine (IS-POLISHERISPP-1000 small precision sample preparation system, Ikegami Seiki Co., Ltd.) was used to apply a grinding pressure of 200 g / cm² to the grinding surface. 2 Starting with 20g / cm each time 2 The test pieces were gradually increased in height and then ground. The ground surface was observed using a FESEM (S-4700, Hitachi High Technology Co., Ltd.) (magnification: 4500x). The maximum grinding pressure P (g / cm²) was determined when no voids were observed between any 10 continuous reinforcing fibers. 2 Divide this value by the previously calculated Vf (%) to obtain the interfacial grinding value P / Vf (g / cm³). 2 ·%)

[0886] The grinding was performed in the following order: 10 minutes with #2000 water-resistant sandpaper, 5 minutes with a 9μm silicon carbide film, 5 minutes with a 5μm alumina film, 5 minutes with a 3μm alumina film, 5 minutes with a 1μm alumina film, and 5 minutes with colloidal silica (Baikalox 0.1CR) with a 0.1μm particle size and polishing paper foamed with polyurethane, while adding water at approximately 7mL / min.

[0887] [Tensile strength, tensile strength retention rate]

[0888] Long strips measuring 70 mm in length, 10 mm in width, and 2 mm in thickness were cut from continuous fiber-reinforced resin composite materials and dried in a vacuum dryer at 80°C for at least 18 hours. Subsequently, the test strips were clamped along their length at 30 mm intervals using an INSTRON universal testing machine, and their tensile strength (MPa) was measured at a speed of 5 mm / min at 23°C and 50% RH, and at 100°C and 50% RH.

[0889] The tensile strength retention rate (%) at 80℃ can be calculated using the following formula.

[0890] Tensile strength retention rate at 100℃ = (Tensile strength at 100℃ and 50%RH / Tensile strength at 23℃ and 50%RH) × 100

[0891] [Flexural strength, flexural modulus, flexural strength retention rate, flexural modulus retention rate]

[0892] Strip-shaped test pieces with a length of 100 mm, a width of 10 mm, and a thickness of 2 mm were cut from continuous fiber-reinforced resin composite materials and dried in a vacuum dryer at 80°C for more than 18 hours. Subsequently, using an INSTRON universal testing machine with a three-point bending fixture, the span was set to thickness × 16 (mm), and the flexural strength (MPa) and flexural modulus (GPa) were measured at a speed of 1 mm / min in environments of 23°C and 50%RH, and in environments of 100°C and 50%RH.

[0893] The flexural strength retention rate (%) and flexural modulus retention rate (%) at 100℃ can be calculated using the following formulas.

[0894] Bending strength retention rate at 100℃ = (Bending strength at 100℃ and 50%RH / Bending strength at 23℃ and 50%RH) × 100

[0895] Flexural modulus retention rate at 80℃ = (Flexural modulus at 100℃ and 50%RH / Flexural modulus at 23℃ and 50%RH) × 100

[0896] [Water absorption characteristics]

[0897] Strip-shaped test pieces with a length of 100 mm, a width of 10 mm, and a thickness of 2 mm were cut from continuous fiber-reinforced resin composite materials and immersed in a constant temperature water bath at 80°C for 18 hours to serve as test pieces for water absorption. The tensile strength (MPa), flexural strength (MPa), and flexural modulus (GPa) of the dry and water-absorbed test pieces were measured using the methods described above at 23°C and 50%RH.

[0898] The following formulas can be used to calculate the retention rates of tensile strength (%), flexural strength (%), and flexural modulus (%) during water absorption.

[0899] Tensile strength retention rate during water absorption = (Tensile strength during water absorption / Tensile strength during drying) × 100

[0900] Flexural strength retention rate during water absorption = (Flexural strength during water absorption / Flexural strength during drying) × 100

[0901] Flexural modulus retention rate during water absorption = (Flexural modulus during water absorption / Flexural modulus during drying) × 100

[0902] Impact strength

[0903] Test pieces measuring 60 mm in length, 60 mm in width, and 2 mm in thickness were cut from continuous fiber-reinforced resin composite materials. Tests were conducted using a high-speed impact testing machine (Shimadzu HYDRO SHOT HITS-P10, Shimadzu Corporation) according to JIS K7211-2;2006, under the following conditions: impact pin diameter 20 mm Ф, support diameter 40 mm Ф, test speed 4.4 m / s, test temperature 23℃, and test number n=5. A curve of test force versus displacement was plotted. The maximum impact strength (kN) was determined from this curve, divided by the thickness of the test piece, and the average value (kN / mm) of the five samples was used to calculate the final impact strength.

[0904] [Vibration Fatigue Test]

[0905] ASTM-D1822 tensile impact dumbbell-shaped S-shaped test specimens were prepared from continuous fiber reinforced resin composites. Vibration fatigue tests were conducted using an EHF-EB50kN-40L(RV) (Shimadzu Corporation), with the test temperature set at 23°C, frequency at 20Hz, waveform as a sine wave, and clamp spacing at 35mm. Cases with more than 20,000 fracture cycles at 250MPa were recorded as "0 (Good)," and cases with fewer than 20,000 cycles were recorded as "× (Poor)."

[0906] [Interface Restore Feature]

[0907] After the bending test, the continuous fiber reinforced resin composite material was pressed for 15 minutes at a temperature of 5 MPa at 100°C above the glass transition temperature of the thermoplastic resin contained in the continuous fiber reinforced resin composite material. Subsequently, a bending test section was cut out using a band saw to obtain a cross-section (grinding surface) orthogonal to the length direction of the continuous reinforcing fibers. A grinding machine (IS-POLISHER ISPP-1000 small precision sample preparation system, Ikegami Seiki Co., Ltd.) was used to grind the surface at a grinding pressure of 125 g / cm². 2 The cut bending test section was ground using a specific method. Using a FESEM (S-4700, Hitachi High Technology Co., Ltd.) (magnification: 4500x), any 50 continuous reinforcing fibers on the ground surface were observed. A rating of "1" was given if the proportion of continuous reinforcing fibers with no visible gaps between resins was 0% or more but less than 20% of the proportion of continuous reinforcing fibers with no visible gaps between resins, as calculated similarly in the continuous reinforcing fiber resin composite before the bending test; "2" if it was 20% or more but less than 40%; "3" if it was 40% or more but less than 60%; "4" if it was 60% or more but less than 80%; and "5" if it was 80% or more but less than 100%.

[0908] The grinding was performed in the following order: 10 minutes with #2000 water-resistant sandpaper, 5 minutes with a 9μm silicon carbide film, 5 minutes with a 5μm alumina film, 5 minutes with a 3μm alumina film, and 5 minutes with a 1μm alumina film, while adding water at a rate of approximately 7 mL / min.

[0909] [Microdroplet contact angle, interfacial shear strength]

[0910] Thermoplastic resin was placed in the heating furnace section of a composite material interface property evaluation device (HM410, Toei Sangyo Co., Ltd.). The furnace temperature was set to the melting point of the thermoplastic resin +15°C, allowing the resin to adhere to a single filament of a continuous reinforcing fiber, thus creating microdroplets. The created microdroplets were ellipsoidal in shape, centered on the reinforcing fiber and extending along its length. After cooling to room temperature, the contact angle between the continuous reinforcing fiber and the thermoplastic resin microdroplets was measured (refer to...). Figure 1 The contact angle (α) is obtained from 100 microdroplets with a length L of 95-105 μm along the fiber axis of the continuous reinforcing fiber of the microdroplet. The contact angle (°) of the microdroplet is then calculated based on the central value of the contact angle.

[0911] In addition, after measuring the diameter d (μm) of the continuous reinforcing fiber and the length L (μm) of the continuous reinforcing fiber in the direction of the fiber axis of the microdroplet, a shear test was conducted on microdroplets of 95-105 μm. The shear load F (N) when the resin ball was scraped off with a scraper was measured, and the interfacial shear strength τ (MPa) was calculated by the following formula (1). Assuming that the number of measurements is 100, the median value of the 100 measurements was calculated.

[0912] τ=F / πdL ···(1)

[0913] The materials used in an example of a continuous fiber reinforced resin composite with characteristic (IV) are shown below.

[0914] [Continuous Reinforced Fiber]

[0915] (glass fiber)

[0916] Glass fiber 1 (GF1): A fiber manufactured by attaching 0.45% by mass of a condensing agent to glass fibers with a fineness of 1.15 g / m and a number of 2000 filaments per 100% by mass. The winding form is DWR, and the average filament diameter is approximately 17 μm. The condensing agent is prepared by adjusting the amount of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) to 0.5% by mass, carnauba wax to 1% by mass, polyurethane resin (Y65-55, manufactured by ADEKA Co., Ltd.) to 2% by mass, and a copolymer compound (a copolymer compound with a weight average molecular weight of 20000 formed by copolymerizing 40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate) to 3% by mass.

[0917] Glass fiber 2 (GF2): GF1 was treated in an electric furnace at 650°C for 3 hours to obtain GF2 without surface treatment agent. (Regarding GF2, the content of surface treatment agent in GF2 is less than 0.45% by mass. In addition, the isoelectric point was confirmed to be less than pH=3 and negative in the pH=3 to 8 range by zeta potential measurement.)

[0918] Glass fiber 3 (GF3): Glass fiber 2 was immersed in a 0.5% by mass aqueous solution of γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) for 30 minutes and dried at 110°C for 3 hours.

[0919] Fabrication of Continuously Reinforced Fiber Substrates

[0920] Fiberglass cloth: Fiberglass cloth is manufactured using a rapier loom (1m width) and the aforementioned fiberglass as both warp and weft yarns. The resulting fiberglass cloth has a plain weave, a weave density of 6.5 threads / 25mm, and a basis weight of 640g / m². 2).

[0921] [Thermoplastic resin]

[0922] Resin 1: Polyamide 66

[0923] The polymerization reaction of polyamide is carried out by the "thermal melt polymerization method" as follows.

[0924] An equimolar salt of adipic acid (Wako Pure Chemical Industries) and hexamethylenediamine (Tokyo Chemical Industries) was dissolved in 1500g of distilled water to prepare an equimolar 50% by mass homogeneous aqueous solution of the raw material monomers. This aqueous solution was placed in a 5.4L autoclave and purged with nitrogen. While stirring, water vapor was slowly released to concentrate the solution to a concentration of 70% by mass at a temperature between 110°C and 150°C. The internal temperature was then raised to 220°C. At this point, the autoclave was pressurized to 1.8 MPa. This pressure was maintained for 1 hour until the internal temperature reached 245°C, and water vapor was slowly released while maintaining the pressure at 1.8 MPa for 1 hour. The pressure was then reduced for 1 hour. The autoclave was then maintained under vacuum at 650 torr for 10 minutes. At this point, the final internal temperature of the polymerization was 265°C. Subsequently, nitrogen gas was used to pressurize the material, forming it into a filament from the lower spinneret (nozzle). This filament was then water-cooled, cut, and discharged as granules. The granules were dried at 100°C under a nitrogen atmosphere for 12 hours to obtain resin 1 (polyamide 66). The obtained resin 1 (polyamide 66) had a weight-average molecular weight Mw = 35000 and a molecular weight distribution Mw / Mn = 2.0 (Mn being the number-average molecular weight).

[0925] Resin 2: Polyamide 6I

[0926] The polymerization reaction of polyamide is carried out by the "thermal melt polymerization method" as follows.

[0927] 1500g of isophthalic acid (Wako Pure Chemical Industries) and an equimolar salt of hexamethylenediamine, along with 4.0 mol% acetic acid relative to the total equimolar salt composition, were dissolved in 1500g of distilled water to prepare a homogeneous aqueous solution of the raw material monomers at 50% by mass. The solution was concentrated by slowly venting water vapor while stirring at a temperature between 110°C and 150°C until the concentration reached 70% by mass. The internal temperature was then raised to 220°C. The autoclave was pressurized to 1.8 MPa. This pressure was maintained for 1 hour until the internal temperature reached 245°C, while slowly venting water vapor to maintain the pressure at 1.8 MPa for another hour. The pressure was then reduced over 30 minutes. The autoclave was then maintained under vacuum at 650 torr for 10 minutes. At this point, the final internal temperature of the polymerization was 265°C. The mixture was then pressurized with nitrogen and formed into a filament from a lower spinneret (nozzle), water-cooled, cut, and discharged as granules. The granules were dried at 100°C under a nitrogen atmosphere for 12 hours to obtain resin 2 (polyamide 6I). The obtained resin 2 (polyamide 6I) has Mw=20000 and Mw / Mn=2.0.

[0928] Resin 3: A dry blend of Resin 1 and Resin 2 (mass ratio of Resin 1 (PA66): Resin 2 (PA6I) = 2:1)

[0929] Resin 4: Polyamide 12 (3014U, Ube Industries, Ltd.)

[0930] Resin 5: Polyamide 1010 (Vestamid DS16, Daicel Evonik Co., Ltd.)

[0931] Resin 6: Polyamide 612 (Vestamid D16, Daicel Evonik Co., Ltd.)

[0932] Resin 7: Polyamide 6 (1010X1, Ube Industries, Ltd.)

[0933] Resin 8: Polyamide 9T (Genestar N1000A, KURARAY Co., Ltd.)

[0934] Resin 9: Polypropylene (Prime Polypro J707EG, PRIME POLYMER Co., Ltd.)

[0935] Resin 10: Polyethylene (Suntec J240, Asahi Kasei Corporation)

[0936] [Preparation of thermoplastic resin films]

[0937] A thermoplastic resin film is obtained by molding using a T-die extrusion molding machine (developed by Sosho Corporation). The thickness of the thermoplastic resin film is 200 μm.

[0938] [Refer to Example 4-1]

[0939] Using resin 1, a thermoplastic resin film 1 is obtained by the above method.

[0940] Prepare 5 sheets of glass cloth 1 made of GF1 and 6 sheets of thermoplastic resin film 1. Alternately overlap the glass cloth 1 and thermoplastic resin film 1 with the thermoplastic resin film 1 as the surface to form a continuous fiber-reinforced resin composite material. At this point, the volume ratio of the thermoplastic resin is 50%.

[0941] A continuous compression molding machine is used as the molding machine. The glass cloth and the thermoplastic resin film 1 are overlapped as described above and placed in the molding machine. The temperature of the heating zone in the molding machine is set to 330°C, and the temperature of the cooling zone is adjusted by water cooling. Compression molding is performed under a pressure of 3MPa and a belt speed of 0.5m / min.

[0942] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the interfacial shear strength and droplet contact angle between GF1, GF2, GF3 and resin 1, are shown in Table 4.

[0943] [Refer to Examples 4-2 to 4-6]

[0944] The resins shown in Table 4 were used as thermoplastic resins, and otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 4-1.

[0945] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the interfacial shear strength and droplet contact angle of GF1, GF2, GF3 and the resins used in each example, are shown in Table 4.

[0946] [Refer to Example 4-7]

[0947] A dual-belt press was used as the molding machine, and otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 4-1.

[0948] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the interfacial shear strength and droplet contact angle between GF1, GF2, GF3 and resin 1, are shown in Table 4.

[0949] [Compare with Examples 4-1, 4-2, 4-5, and 4-6]

[0950] The resins shown in Table 4 were used as thermoplastic resins, and otherwise, a continuous fiber-reinforced resin composite material was obtained in the same manner as in Reference Example 4-1.

[0951] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the interfacial shear strength and droplet contact angle of GF1, GF2, GF3 and the resins used in each example, are shown in Table 4.

[0952] [Compare with Example 4-3]

[0953] The Bond Laminate "Tepex dynalite 101", which is made by impregnating polyamide 66 in glass cloth, was evaluated in the same way as in Reference Example 4-1.

[0954] The properties of each material are shown in Table 4.

[0955] [Compare with Example 4-4]

[0956] Glass fiber (GF4) with a mixture of 0.3% by mass of 3-epoxypropoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.) as a binding agent, 1.5% by mass of epoxy resin emulsion, and 0.2% by mass of carnauba wax (100% by mass) relative to the above-mentioned GF2 was used to manufacture a plain weave with a weave density of 6.5 threads / 25mm and a basis weight of 600g / m. 2 The glass cloth was used, and otherwise a continuous fiber reinforced resin composite material was obtained in the same manner as in Reference Example 4-1. It should be noted that the volume ratio of the thermoplastic resin was 50%.

[0957] The physical properties of the obtained continuous fiber reinforced resin composites, as well as the interfacial shear strength and droplet contact angle between GF4, GF2, GF3 and resin 1, are shown in Table 4.

[0958] [Table 4]

[0959]

[0960] The following shows an example of a continuous fiber reinforced resin composite material with characteristic (V).

[0961] [Interfacial coverage change index, reinforcing fiber exposure change index, and relative element concentration change index of continuous fiber reinforced resin composites]

[0962] 100 mg of continuous fiber-reinforced resin composite material cut into thin sheets was added to a mixer along with HFIP (when using resins 1-4) and 20 mL of xylene (when using resin 5). The mixture was stirred at 23°C for 5 hours with HFIP and at 90°C for 5 hours with xylene. The solvent was then removed by filtration, and 40 mL of fresh solvent was sprayed onto the filter. The continuous reinforcing fibers were then washed and air-dried using HFIP and hot-air dried at 120°C using xylene. Alternatively, the obtained continuous reinforcing fibers and 20 mL of fresh solvent were added to a mixer. The mixture was stirred at 23°C for 2 hours with HFIP and at 90°C for 2 hours with xylene. The solvent was then removed by filtration, and 40 mL of fresh solvent was sprayed onto the filter. The continuous reinforcing fibers were then washed and dried using nitrogen at 23°C with HFIP and at 120°C using xylene. The obtained continuous reinforcing fiber and 20 mL of fresh solvent were added to a mixer. When using HFIP, the mixture was stirred at 23°C for 2 hours. When using xylene, the mixture was stirred at 90°C for 2 hours. The solvent was removed by filtration. 40 mL of fresh solvent was sprayed onto the filter. After washing the continuous reinforcing fiber, it was air-dried when using HFIP, and then hot-dried at 120°C when using xylene. It was then dried overnight in a vacuum dryer set to 23°C when using HFIP, and then dried overnight in a vacuum dryer set to 120°C when using xylene. The obtained continuous reinforcing fibers were pressed into a flat plate, and a 2 mm piece was taken out. The relative elemental concentrations of carbon, oxygen, nitrogen, silicon, aluminum, and calcium were determined using XPS (Versa probeII, ULVAC-PHI Corporation) under the following conditions: excitation source mono.AlKα 20 kV × 5 mA 100 W, analysis size 100 μm × 1.4 mm, photoelectron extraction angle 45°, capture range (full scan): 117.4 eV, (narrow scan): C1s, O1s, N1s, Si2p, Ca2p, Al2p, pass energy (full scan): 117.4 eV, (narrow scan): 46.95 eV.

[0963] Regarding the interfacial coverage of continuous fiber reinforced resin composites, it is determined by Equation 1 below in Reference Examples 5-1 to 5-4, 5-6, and Comparative Reference Examples 5-1 to 5-3, by Equation 2 below in Reference Example 5-5, and by Equation 3 below in Reference Example 5-7.

[0964] (Interface coverage) = [N] / ([N] + [Si]) × 100 (1)

[0965] (Interface coverage rate) = [N] / ([N] + [O]) × 100 (2)

[0966] (Interface coverage rate) = ([C] - [C0]) / ([C] - [C0] + [Si]) × 100 (3)

[0967] Regarding the exposed ratio of reinforcing fibers in composite materials, it is determined by the following four equations in Reference Examples 5-1 to 5-4, 5-6, 5-7 and Comparative Reference Examples 5-1 to 5-3, and by the following five equations in Reference Example 5-5.

[0968] (Exposed fiber ratio of continuous fiber reinforced resin composite) = [Al] / [Al0] (4)

[0969] (Exposed fiber ratio of continuous fiber reinforced resin composite) = [O] / [O0] (5)

[0970] [Al0] represents the relative elemental concentration of aluminum when using GF0, and [C0] represents the relative elemental concentration of aluminum when using CF0.

[0971] The following formulas are used to calculate the interface coverage change index, the reinforcing fiber exposure change index, and the relative element change index of each element.

[0972] (Interfacial Coverage Change Index) = (Interfacial Coverage of Continuous Fiber Reinforced Resin Composite Before Destructive Test) / (Interfacial Coverage of Composite After Destructive Test)

[0973] (Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite before destructive test) / (Reinforcing fiber exposure ratio of composite after destructive test)

[0974] (Relative elemental change index of interfacial nitrogen) = (Relative elemental index of interfacial nitrogen in continuous fiber reinforced resin composite before destructive test) / (Relative elemental index of interfacial nitrogen in composite after destructive test)

[0975] (Relative elemental change index of interfacial oxygen) = (Relative elemental index of interfacial oxygen in the continuous fiber reinforced resin composite before the destructive test) / (Relative elemental index of interfacial oxygen in the composite after the destructive test)

[0976] (Relative elemental change index of interfacial carbon) = (Relative elemental index of interfacial carbon in continuous fiber reinforced resin composite before destructive test) / (Relative elemental index of interfacial carbon in composite after destructive test)

[0977] (Relative elemental change index of interfacial silicon) = (Relative elemental index of interfacial silicon in the continuous fiber reinforced resin composite before the destructive test) / (Relative elemental index of interfacial silicon in the composite after the destructive test)

[0978] (Relative elemental change index of interfacial aluminum) = (Relative elemental index of interfacial aluminum in continuous fiber reinforced resin composite before destructive test) / (Relative elemental index of interfacial aluminum in composite after destructive test)

[0979] (Relative elemental change index of interfacial calcium) = (Relative elemental index of interfacial calcium in continuous fiber reinforced resin composite before destructive test) / (Relative elemental index of interfacial calcium in composite after destructive test)

[0980] The aforementioned destructive test is the cantilever bending vibration fatigue test described later.

[0981] [Impregnation speed]

[0982] A hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons was used as the molding machine. Five sheets of continuous fiber-reinforced resin substrate and six sheets of thermoplastic resin film were alternately laminated and placed in a mold equipped with a temperature sensor. The laminations were then placed in a heated pressing molding machine set to the melt temperature of the thermoplastic resin +65°C. While monitoring the temperature, the laminations were pressed at a pressure of 5 MPa. After reaching the melt temperature of the thermoplastic resin for 30 seconds, the laminations were removed from the heated pressing molding machine and placed in a cooling pressing machine for water cooling at a pressure of 5 MPa. At this point, the highest temperature of the continuous fiber-reinforced resin composite material was the melting point of the thermoplastic resin +15°C, and the time above the melt temperature was 1 minute. The obtained continuous fiber reinforced composite material was cut with a band saw, and the cross-section was ground in a manner that did not damage the continuous reinforcing fibers. The image was then observed using FE-SEM at 50x magnification. Using ImageJ, the area occupied by the continuous reinforcing fiber bundle, thermoplastic resin, and voids was determined from the obtained image. The ratio of the void area to the area of ​​the continuous reinforcing fiber bundle (whole) was calculated, and the impregnation content (%) was calculated using the following formula:

[0983] Impregnation rate (%) = {1 - (void area / area of ​​continuous reinforcing fiber bundle)} × 100

[0984] Divide the calculated impregnation rate by the time (in minutes) during heating and cooling the thermoplastic resin at or above its melt temperature during both heating and cooling pressing to obtain the impregnation rate (% / min). Here, the continuous reinforcing fiber bundle is the area of ​​dense fiber (bundle of monofilaments) in the cross-section of the injection molded article, for example, it can be the area where the outer periphery of the dense fibers is connected.

[0985] Here, the melting temperature mentioned above refers to the melting point if the thermoplastic resin has a melting point, and the glass transition temperature if it does not have a melting point.

[0986] [Bending strength]

[0987] Strip-shaped test pieces with a length of 100 mm, a width of 10 mm, and a thickness of 2 mm were cut from continuous fiber-reinforced resin composite materials. Using an INSTRON universal testing machine with a three-point bending fixture, the span was set to 32 mm, and the flexural strength (MPa) was measured at 1 mm / min in an environment of 23°C and 50% RH. Fifty tests were performed, and the median value was taken as the flexural strength.

[0988] [Bending vibration fatigue recovery characteristics]

[0989] ASTM-D671 Type A test pieces were prepared from continuous fiber reinforced resin composites. Using a repetitive vibration fatigue testing machine (B-70, Toyo Seiki Co., Ltd.), cantilever bending vibration fatigue tests were conducted at a test temperature of 23°C and a frequency of 20Hz, with a sinusoidal waveform. The number of fractures (A) of each continuous fiber reinforced resin composite under vibration fatigue testing at a stress equivalent to 35% of the flexural strength was determined. Similarly, vibration fatigue tests were conducted at a stress equivalent to 35% of the flexural strength, and the test was stopped when half of (A) was reached, resulting in a failed test piece. The failed test piece was placed in a mold with a concave structure and heated to 200°C using a hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons. The mold was then closed with a clamping force of 5 MPa for 15 minutes to obtain a recovered test piece. A bending vibration fatigue test was then conducted on the recovered test piece under the same conditions, and the number of fractures (B) was determined.

[0990] The fatigue recovery characteristics of bending vibration can be obtained from the following formula.

[0991] (Bending vibration fatigue characteristics) = (B) / (A)

[0992] [Measurement of Deviation]

[0993] For 50 test pieces, the bending strength was tested and measured. Let the average bending strength be A, and let the bending strength in the i-th measurement (i=1 to 50) be Ai. The coefficient of variation was calculated according to the following formula and used as the deviation.

[0994] [Number 3]

[0995]

[0996] The materials used in an example of a continuous fiber reinforced resin composite with characteristic (V) are shown below.

[0997] [Continuous Reinforced Fiber]

[0998] (glass fiber)

[0999] Glass fiber 1 (GF1):

[1000] This fiber is manufactured by attaching 0.8% by mass of a condensing agent to glass fibers with a fineness of 1.15 g / m and 2000 monofilaments per 100% by mass. The winding configuration is DWR, with an average monofilament diameter of approximately 16 μm. The condensing agent is applied using an aqueous solution, which is prepared by adjusting the concentration of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) to 0.8% by mass, carnauba wax to 1.2% by mass, and a copolymer compound with a weight average molecular weight of 15000, formed by copolymerizing 10% by mass of maleic anhydride and 90% by mass of methyl methacrylate, to 2% by mass. Regarding the components attached to the glass fiber, relative to 100% by mass of the glass fiber, the concentrations are: γ-aminopropyltrimethoxysilane 0.16% by mass, carnauba wax 0.40% by mass, and copolymer compound 0.24% by mass.

[1001] Glass fiber 2 (GF2):

[1002] GF1 was treated in an electric furnace at 650°C for 3 hours. The resulting glass fibers were then immersed in a 0.2% (w / w) aqueous solution of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent for 30 minutes, and dried at 110°C for 3 hours. The amount of γ-aminopropyltrimethoxysilane adhering to the glass fibers was 0.16% (w / w) relative to 100% (w / w) of the glass fibers.

[1003] Glass fiber 0 (GF0):

[1004] GF1 was treated in an electric furnace at 650°C for 3 hours to obtain GF0 without the cleaving agent.

[1005] (Carbon fiber)

[1006] Carbon fiber 1 (CF1):

[1007] Fibers are manufactured by attaching 1.0% by mass of a bundle binder to 100% by mass of PAN-based carbon fibers with 12,000 monofilaments. The bundle binder is applied using an aqueous solution, which is prepared by adjusting the composition with deionized water to achieve 0.8% by mass of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3% by mass of carnauba wax, and 1% by mass of a copolymer compound with a weight average molecular weight of 20,000, formed by copolymerizing 10% by mass of maleic anhydride and 90% by mass of methyl methacrylate. Regarding the components attached to the carbon fibers, relative to 100% by mass of the carbon fibers, γ-aminopropyltrimethoxysilane is 0.38% by mass, carnauba wax is 0.48% by mass, and the copolymer compound is 0.14% by mass.

[1008] Carbon fiber 2 (CF2):

[1009] PAN-based carbon fibers with a monofilament count of 12000 were immersed in an aqueous solution containing 0.38% by mass of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent at 60°C for 12 hours, and then dried at 110°C for 6 hours. The amount of γ-aminopropyltrimethoxysilane adhering to the carbon fibers was 0.38% by mass relative to 100% by mass of the carbon fibers.

[1010] Carbon fiber 0 (CF0): PAN-based carbon fiber with a single filament count of 12,000.

[1011] Fabrication of Continuously Reinforced Fiber Substrates

[1012] Fiberglass cloth:

[1013] Glass cloth 1 (GC1) was manufactured using a rapier loom (1m width) and GF1 as both warp and weft yarns. The resulting glass cloth was woven in a plain weave with a weave density of 6.5 yarns / 25mm and a basis weight of 640g / m². 2 .

[1014] Alternatively, GC2 can be obtained using GF2 in the same way.

[1015] Carbon fiber cloth:

[1016] Carbon fiber fabric 1 (CC1) was manufactured using a rapier loom (1m width) and the aforementioned carbon fiber 1 as both warp and weft yarns. The resulting carbon fiber fabric was woven in a plain weave with a weave density of 6.5 yarns / 25mm and a basis weight of 425g / m². 2 .

[1017] Alternatively, CC2 can be obtained by using carbon fiber 2 in the same way.

[1018] [Thermoplastic resin]

[1019] Resin 1: Polyamide 66

[1020] The polymerization reaction of polyamide is carried out by the "thermal melt polymerization method" as follows.

[1021] 1500g of a mixture containing adipic acid (Wako Pure Chemical Industries) and hexamethylenediamine (Tokyo Chemical Industries) salts in a 45:55 molar ratio, along with 300g of adipic acid, was dissolved in 1500g of distilled water to prepare a 55% by mass homogeneous aqueous solution of the raw material monomers. This aqueous solution was then transferred to a 7.0L autoclave and purged with nitrogen. While stirring at a temperature between 130°C and 150°C, water vapor was slowly released to concentrate the solution until a concentration of 70% by mass was reached. The internal temperature was then raised to 225°C. The autoclave was pressurized to 1.7 MPa. This pressure was maintained for 2 hours until the internal temperature reached 255°C. Water vapor was then slowly released, and the pressure was maintained at 1.7 MPa for 70 minutes. The pressure was then reduced over 1.7 hours. The autoclave was then maintained under vacuum at 650 torr for 15 minutes. At this point, the final internal temperature of the polymerization was 265°C. Subsequently, nitrogen pressure was applied to form a filament from the lower spinneret (nozzle), which was then water-cooled, cut, and discharged as granules. The granules were dried at 100°C under a nitrogen atmosphere for 12 hours. The resulting granules and lubricant (PEG400, Tokyo Chemical Industry) were then extruded using a single-shaft extruder, water-cooled, cut, and discharged as granules. The granules were dried at 100°C under a nitrogen atmosphere for 12 hours to obtain resin 1 (polyamide 66). Mw=42000, Mw / Mn=2.08, melting point (Tm)=264°C, glass transition temperature (Tg)=50°C.

[1022] Resin 2:

[1023] Relative to 100% by mass of resin 1, 0.03% by mass of dry-mixed copper iodide and 0.2% by mass of potassium iodide were mixed using a twin-screw mixer (TEM26SS, TOSHIBA MACHINE) set to 280°C, water-cooled, cut, discharged as granules, and dried at 100°C under a nitrogen atmosphere for 12 hours to obtain resin 2 with a melt temperature of 264°C.

[1024] Resin 3: Polyamide 6I

[1025] The polymerization reaction of polyamide is carried out by the "thermal melt polymerization method" as follows.

[1026] 1500g of an equimolar salt containing isophthalic acid (Wako Pure Chemical Industries) and hexamethylenediamine in a 45:55 molar ratio, along with 300g of isophthalic acid, was dissolved in 1500g of distilled water to prepare a homogeneous aqueous solution. The solution was concentrated by slowly venting water vapor while stirring at a temperature between 110°C and 140°C until the concentration reached 70% by mass. The internal temperature was then raised to 235°C. This temperature was maintained for 70 minutes until the internal temperature reached 245°C, during which water vapor was slowly vented, and the pressure was kept constant while the reaction proceeded for 2 hours. The pressure was then reduced over 90 minutes. The autoclave was then maintained under vacuum at 650 torr for 10 minutes. At this point, the final internal temperature of the polymerization was 265°C. The mixture was then pressurized with nitrogen and formed into a filament from a lower spinneret (nozzle), water-cooled, and cut into granules. The granules were dried at 100°C under a nitrogen atmosphere for 12 hours. The obtained granules and lubricant (PEG400, Tokyo Chemical Industry) were shaped using a single-shaft extruder, water-cooled, and cut, discharged as granules, and dried at 100°C under a nitrogen atmosphere for 12 hours to obtain resin 3 (polyamide 6I). The obtained resin 3 (polyamide 6I) has Mw=18000, Mw / Mn=1.94, and melting temperature (glass transition temperature (Tg))=130°C.

[1027] It should be noted that, in the case of amorphous resins that do not have a crystallization melting point, the glass transition temperature is taken as the melting temperature.

[1028] Resin 4:

[1029] Resin 1 and Resin 3 were dry-mixed at a mass ratio of 2:1 to obtain Resin 4 with a melting temperature of 259℃.

[1030] Resin 5:

[1031] Maleic acid modified polypropylene (Sanyo Chemical Industry Co., Ltd., melting temperature (melting point) = 160°C)

[1032] [Preparation of thermoplastic resin films]

[1033] A thermoplastic resin film is obtained by molding using a T-die extrusion molding machine (developed by Sosho Corporation). The thickness of the thermoplastic resin film is 180 μm.

[1034] [Refer to Example 5-1]

[1035] Using resin 1, a thermoplastic resin film 1 is obtained by the above method.

[1036] Prepare 4 sheets of glass cloth 1 (GC1) and 5 sheets of thermoplastic resin film 1. Alternately overlap the glass cloth 1 and thermoplastic resin film 1 with the thermoplastic resin film 1 as the surface to form a continuous fiber-reinforced resin composite material with a thickness of 2 mm. A continuous compression molding machine is used as the molding machine. The glass cloth and thermoplastic resin film 1 are overlapped as described above and placed in the molding machine. The temperature of the heating zone inside the molding machine is set to 350°C, and the temperature of the cooling zone is adjusted by oil cooling. Compression molding is performed under a pressure of 5 MPa and a belt speed of 0.6 m / min.

[1037] In addition, to compare bending strength, glass cloth 2 (coupling continuous reinforcing fiber) treated only with coupling agent was used to obtain a bending test material (coupling continuous fiber reinforced resin composite material) with a thickness of 2 mm.

[1038] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 5.

[1039] [Refer to Example 5-2]

[1040] Resin 2 was used as the thermoplastic resin, and otherwise, a continuous fiber reinforced resin composite material with a thickness of 2 mm and a material for bending tests (coupled continuous fiber reinforced resin composite material) were obtained in the same manner as in Reference Example 5-1.

[1041] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 5.

[1042] [Refer to Example 5-3]

[1043] Resin 3 was used as a thermoplastic resin, and otherwise, a continuous fiber reinforced resin composite material with a thickness of 2 mm and a material for bending tests (coupled continuous fiber reinforced resin composite material) were obtained in the same manner as in Reference Example 5-1.

[1044] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 5.

[1045] [Refer to Example 5-4]

[1046] Resin 4 was used as the thermoplastic resin. Otherwise, a continuous fiber reinforced resin composite material with a thickness of 2 mm and a material for bending tests (coupled continuous fiber reinforced resin composite material) were obtained in the same manner as in Reference Example 5-1.

[1047] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 5.

[1048] [Refer to Example 5-5]

[1049] Carbon fiber cloth 1 was used as the continuous reinforcing fiber substrate to produce a composite material consisting of carbon fiber cloth 1 and thermoplastic resin film 1. Otherwise, a continuous fiber reinforced resin composite material with a thickness of 2 mm was obtained in the same manner as in Reference Example 5-1. It should be noted that the thermoplastic resin film was made in the same manner as the thermoplastic resin film described above, except that the thickness was 118 μm.

[1050] In addition, to compare bending strength, carbon fiber cloth 2, which was treated with only coupling agent, was used to obtain a bending test material (coupling continuous fiber reinforced resin composite) with a thickness of 2 mm.

[1051] The physical properties of the obtained continuous fiber reinforced resin composites are shown in Table 5.

[1052] [Refer to Examples 5-6]

[1053] Instead of using GF1, GF1 was treated with a 20wt% sodium aluminate aqueous solution as an additive to adjust the aluminum concentration for 1 hour, and then dried at 110°C for 2 hours. The resulting g...

Claims

1. A continuous fiber-reinforced resin composite material, characterized in that, It contains continuous reinforcing fibers and thermoplastic resin. The continuous fiber reinforced resin composite material has an acoustic emission (AE) count A of less than 0.30, calculated by the following formula. (AE count A) = (Number of AE signals with amplitude above 40dB and duration below 3500 microseconds) / (Total number of AE signals) The acoustic emission (AE) signal of the continuous fiber reinforced resin composite material is obtained by mounting an acoustic emission sensor to the fixture of the bending test, and by using the sensor to detect the sound emitted by the continuous fiber reinforced resin composite material during the bending test. The interfacial amount of the continuous fiber reinforced resin composite material is 100,000 m. -1 The interfacial amount of the continuous fiber reinforced resin composite material is the amount of the interface between the continuous reinforcing fiber and the matrix resin, which is calculated by the following formula: Interface quantity (m) -1 The volume of reinforcing fibers in a continuous fiber-reinforced resin composite (m³) 3 ))×(density of reinforcing fiber (g / m³) 3 ))×(number of single filaments of reinforcing fiber)×(diameter of reinforcing fiber (m))×π / (fineness of reinforcing fiber (g / m)) / (volume of continuous fiber reinforced resin composite (m³)) 3 )).

2. The continuous fiber reinforced resin composite material as described in claim 1, wherein, The number of AE signals with an amplitude of 40dB or more and a duration of 3500 microseconds or less is less than 600.

3. The continuous fiber reinforced resin composite material as described in claim 1 or 2, wherein, The number of AE signals with an amplitude of 25dB to 30dB and a duration of less than 1000 microseconds is 200 or more.

4. The continuous fiber reinforced resin composite material according to any one of claims 1 to 3, wherein, The continuous fiber reinforced resin composite material has an AE count B of 0.12 or higher, calculated by the following formula. (AE count B) = (number of AE signals with amplitude of 25-30dB and duration of less than 1000 microseconds) / (total number of AE signals).

5. The continuous fiber reinforced resin composite material according to any one of claims 1 to 4, wherein, The total number of AE signals is over 2000.

6. A method for manufacturing a continuous fiber reinforced resin composite material, which is the method for manufacturing the continuous fiber reinforced resin composite material according to any one of claims 1 to 5, characterized in that, The method includes: placing a substrate constituting a continuous fiber reinforced composite material in a molding machine to melt and compress it. The interfacial amount of the continuous fiber reinforced resin composite material is 100,000 m. -1 The heating rate after placing the substrate in the molding machine is 200℃ / min to 330℃ / min. The cooling rate after placing the substrate in the molding machine to melt and compress it, followed by water cooling or other methods, is 10℃ / min to 120℃ / min. The interfacial amount of the continuous fiber reinforced resin composite material is the amount of the interface between the continuous reinforcing fibers and the matrix resin, which is calculated by the following formula: Interface quantity (m) -1 The volume of reinforcing fibers in a continuous fiber-reinforced resin composite (m³) 3 ))×(density of reinforcing fiber (g / m³) 3 ))×(number of single filaments of reinforcing fiber)×(diameter of reinforcing fiber (m))×π / (fineness of reinforcing fiber (g / m)) / (volume of continuous fiber reinforced resin composite (m³)) 3 )).

7. The continuous fiber reinforced resin composite material according to any one of claims 1 to 5, wherein it is a continuous fiber reinforced resin composite material comprising continuous reinforcing fibers and thermoplastic resin, characterized in that, The coating rate of the interfacial resin on the continuous reinforcing fiber after resin dissolution is less than 44%. The coating rate of the interfacial resin on the continuous reinforcing fiber after resin dissolution is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bonded to the continuous reinforcing fiber. After drying, the coating rate is determined by X-ray photoelectron spectroscopy (XPS). The coating rate is calculated based on the proportion of thermoplastic resin components in the continuous reinforcing components at this time.

8. The continuous fiber reinforced resin composite material as described in claim 7, wherein, The exposure of the continuous reinforcing fibers after resin dissolution is 55% or more. The exposure of the continuous reinforcing fibers is determined as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fibers are washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fibers. After drying, the exposure is determined by X-ray photoelectron spectroscopy (XPS). The relative elemental concentration of the elements from the obtained continuous reinforcing fibers is divided by the relative elemental concentration of the elements from the unprocessed continuous reinforcing fibers that have not undergone sizing treatment.

9. The continuous fiber reinforced resin composite material as described in claim 7 or 8, wherein, The relative elemental concentration of interfacial nitrogen in the continuous reinforcing fiber after resin dissolution is below 6.

70. The relative elemental concentration of interfacial nitrogen is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fiber. After drying, the continuous reinforcing fiber is measured by X-ray photoelectron spectroscopy (XPS).

10. The continuous fiber reinforced resin composite material according to any one of claims 7 to 9, wherein, The relative elemental concentration of interfacial carbon in the continuous reinforcing fiber after resin dissolution is below 46.

7. The relative elemental concentration of interfacial carbon is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fiber. After drying, the continuous reinforcing fiber is measured by X-ray photoelectron spectroscopy (XPS).

11. The continuous fiber reinforced resin composite material according to any one of claims 7 to 10, wherein, The relative elemental concentration of interfacial aluminum in the continuous reinforcing fiber after resin dissolution is above 1.

80. The relative elemental concentration of interfacial aluminum is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fiber. After drying, the continuous reinforcing fiber is measured by X-ray photoelectron spectroscopy (XPS).

12. The continuous fiber reinforced resin composite material according to any one of claims 7 to 11, wherein, The relative elemental concentration of interfacial silicon in the continuous reinforcing fiber after resin dissolution is above 8.

30. The relative elemental concentration of interfacial silicon is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fiber. After drying, the continuous reinforcing fiber is measured by X-ray photoelectron spectroscopy (XPS).

13. The continuous fiber reinforced resin composite material according to any one of claims 7 to 12, wherein, The relative elemental concentration of interfacial calcium in the continuous reinforcing fiber after resin dissolution is above 2.

60. The relative elemental concentration of interfacial calcium is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fiber. After drying, the continuous reinforcing fiber is measured by X-ray photoelectron spectroscopy (XPS).

14. The continuous fiber reinforced resin composite material according to any one of claims 7 to 13, wherein, The relative elemental concentration of interfacial oxygen in the continuous reinforcing fiber after resin dissolution is 33.1 or higher. The relative elemental concentration of interfacial oxygen is calculated as follows: The thermoplastic resin contained in the continuous fiber reinforcing resin is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fiber is washed with fresh solvent to remove components other than the resin bound to the continuous reinforcing fiber. After drying, the continuous reinforcing fiber is measured by X-ray photoelectron spectroscopy (XPS).

15. The continuous fiber reinforced resin composite material according to any one of claims 1 to 5, wherein, It contains continuous reinforcing fibers and thermoplastic resin. The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer is 1.00 or more, and the intensity of the (010) plane is 40,000 or less. The full WHM and the intensity of the (010) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material are measured by X-ray diffraction (XRD) of the continuous fiber reinforced resin composite material using the focusing method described in the embodiments of the specification.

16. The continuous fiber reinforced resin composite material as described in claim 15, wherein, The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the inner layer is less than 1.

15.

17. The continuous fiber reinforced resin composite material as described in claim 15 or 16, wherein, The full width at half maximum (FWHM) of the (010) plane of the crystalline phase in the surface layer is less than 1.

25. The full WHM of the (010) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite material is measured by XRD determination of the continuous fiber reinforced resin composite material using the grazing incidence method described in the embodiments of the specification.

18. The continuous fiber reinforced resin composite material according to any one of claims 15 to 17, wherein, The full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the inner layer is 0.85 or greater. The full WHM of the (100) plane of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material is measured by XRD determination of the continuous fiber reinforced resin composite material using the focusing method described in the embodiments of the specification.

19. The continuous fiber-reinforced resin composite material according to any one of claims 15 to 18, wherein, The lattice plane spacing of the (010) facet of the crystalline phase in the inner layer is 0.30 to 1.

2. The lattice plane spacing of the (010) facet of the crystalline phase in the inner layer of the continuous fiber reinforced resin composite material is measured by XRD determination of the continuous fiber reinforced resin composite material using the focusing method described in the embodiments of the specification.

20. The continuous fiber reinforced resin composite material according to any one of claims 15 to 19, wherein, The full width at half maximum (FWHM) of the (100) plane of the crystalline phase in the surface layer is 0.85 or greater. The full WHM of the (100) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite material is measured by XRD determination of the continuous fiber reinforced resin composite material using the grazing incidence method described in the embodiments of the specification.

21. The continuous fiber reinforced resin composite material according to any one of claims 15 to 20, wherein, The 2θ of the peak of the (100) plane of the crystalline phase in the surface layer is 20.34° or higher. The 2θ of the peak of the (100) plane of the crystalline phase in the surface layer of the continuous fiber reinforced resin composite material is measured by XRD determination of the continuous fiber reinforced resin composite material using the grazing incidence method described in the embodiments of the specification.

22. The continuous fiber reinforced resin composite material according to any one of claims 1 to 5, comprising continuous reinforcing fibers and thermoplastic resin, A section of the continuous fiber-reinforced resin composite material orthogonal to the longitudinal direction of the continuous reinforcing fibers was ground. When the ground section was observed using a field emission scanning electron microscope (FESEM), the interfacial grinding value P / Vf was 10 g / cm. 2 •% or higher, this interfacial abrasion value is the maximum abrasion pressure P (g / cm²) at which no voids are observed between the continuous reinforcing fibers and the thermoplastic resin. 2 The value is obtained by dividing the continuous fiber reinforced resin composite by the volume ratio Vf (%) of the continuous fiber reinforced resin composite.

23. The continuous fiber reinforced resin composite material according to any one of claims 1 to 5, comprising continuous reinforcing fibers and thermoplastic resin, wherein, The interfacial coverage variation index of the continuous fiber reinforced resin composite material, expressed by the following formula, is 0.8–1.

2. (Interface Coverage Change Index) = (Interface Coverage of Continuous Fiber Reinforced Resin Composite Material Before Destructive Test) / (Interface Coverage of Continuous Fiber Reinforced Resin Composite Material After Destructive Test) The interfacial coverage of the continuous fiber reinforced resin composite material is determined as follows: X-ray photoelectron spectroscopy (XPS) is used to measure the continuous reinforcing fibers after the thermoplastic resin has been dissolved from the continuous fiber reinforced resin composite material into a solvent. The interfacial coverage is determined by the proportion of the relative element concentration of the thermoplastic resin-derived components remaining on the surface of the continuous reinforcing fibers at this time to the total relative element concentration of the thermoplastic resin-derived components remaining on the surface of the continuous reinforcing fibers and the relative element concentration of the components derived from the continuous reinforcing fibers.

24. The continuous fiber reinforced resin composite material as described in claim 23, wherein, The reinforcing fiber exposure variation index, expressed by the following formula, is 0.8–1.

2. (Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composites before destructive test and after thermoplastic resin dissolution) / (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composites after destructive test and after thermoplastic resin dissolution) The exposed ratio of the reinforcing fibers in the continuous fiber reinforced resin composite material after the thermoplastic resin is dissolved is determined as follows: The thermoplastic resin contained in the continuous fiber reinforced resin composite material is dissolved in a solvent. After removing the solvent, the remaining continuous reinforcing fibers are cleaned with fresh solvent to remove the thermoplastic resin other than the thermoplastic resin bonded to the continuous reinforcing fibers. After drying, the mixture is measured by X-ray photoelectron spectroscopy (XPS). The relative element concentration of the elements derived from the obtained continuous reinforcing fibers is divided by the relative element concentration of the elements derived from the continuous reinforcing fiber raw material that has not undergone bundle agent treatment, thereby determining the exposed ratio.

25. The continuous fiber reinforced resin composite material as described in claim 23 or 24, wherein, The relative elemental variation index of interfacial nitrogen is 0.8 to 1.

2. The relative elemental variation index is obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite material before the destructive test by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite material after the destructive test.

26. The continuous fiber reinforced resin composite material according to any one of claims 23 to 25, wherein, The relative elemental variation index of interfacial carbon is 0.8 to 1.

2. The relative elemental variation index is obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite material before the destructive test by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite material after the destructive test.

27. The continuous fiber reinforced resin composite material according to any one of claims 23 to 26, wherein, The relative elemental variation index of the interface aluminum is 0.8 to 1.

2. The relative elemental variation index is obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite material before the destructive test by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite material after the destructive test.

28. The continuous fiber reinforced resin composite material according to any one of claims 23 to 27, wherein, The relative elemental variation index of interfacial silicon is 0.8 to 1.

2. The relative elemental variation index is obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite material before the destructive test by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite material after the destructive test.

29. The continuous fiber reinforced resin composite material according to any one of claims 23 to 28, wherein, The relative elemental variation index of interfacial calcium is 0.8 to 1.

2. The relative elemental variation index is obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite material before the destructive test by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite material after the destructive test.

30. The continuous fiber reinforced resin composite material according to any one of claims 23 to 29, wherein, The relative elemental variation index of interfacial oxygen is 0.8 to 1.

2. The relative elemental variation index is obtained by dividing the relative elemental concentration of the thermoplastic resin of the continuous fiber reinforced resin composite material after the destructive test is performed by the relative elemental concentration of the resin of the continuous fiber reinforced resin composite material after the destructive test is performed by dissolving the resin.

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