Composite material member, composite material, mobile body, and film manufacturing method

Abstract

To provide a member for composite materials having excellent durability, impact resistance, and productivity, and provide a composite material, a moving body and a method for producing a film each of which uses the member for composite materials.SOLUTION: A member for composite materials is characterized by containing a resin component including a polyaryletherketone as a main component, wherein: the resin component has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 63,000 or more; and the composite material includes a resin and reinforcing fibers having a number average fiber length of 5 mm or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite material member made of polyaryl ether ketone that can be applied to composite materials in electric and electronic devices, automobiles, aircraft, etc., and to a composite material and a mobile body that use this composite material member. The present invention also relates to a method for producing a film. [Background technology]

[0002] In recent years, super engineering plastics such as polyether ether ketone (PEEK), polyetherimide sulfone (PEI), polyethersulfone (PES), polyether ketone (PEK), polyether ketone ketone (PEKK), and polyether ketone ether ketone ketone (PEKEKK) have been widely adopted as films for applications in electrical and electronic equipment, automobiles, aircraft, and other applications due to their excellent heat resistance, mechanical properties, chemical resistance, and durability.

[0003] Among these, polyether ether ketone is used as a matrix material for fiber-reinforced materials due to its excellent heat resistance, mechanical properties, chemical resistance, etc. To fully utilize these properties, the resin needs to be crystallized, but if the degree of crystallization is too high, there is a problem that durability and impact resistance decrease, and further improvement in these physical properties when used as a fiber-reinforced material has been desired.

[0004] Patent Document 1 discloses a composite material having a polyetheretherketone matrix and fibers sized with polyethersulfone as a reinforcement material, while Patent Document 2 discloses a fiber-reinforced thermoplastic resin prepreg using a polyarylketone resin composition having a specific intrinsic viscosity. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 115033 / 1983 [Patent Document 2] Japanese Patent Application Publication No. 2019-147876 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the inventors' studies have revealed that the polyether ether ketone described in Patent Document 1 has a low molecular weight, and therefore does not have sufficient durability and impact resistance for use as a reinforced fiber composite material. Furthermore, the inventors' studies have also revealed that the polyaryl ketone described in Patent Document 2 has an excessively broad molecular weight distribution, which can cause productivity problems when producing composite material members, and the resulting composite material members can have excessively high crystallinity, resulting in problems with durability and impact resistance depending on the method of use. In particular, the inventors' studies have also revealed that in order to obtain a composite material with excellent durability, increasing the folding endurance (number of foldings) of members such as films used in the composite material can make the material suitable for use in applications requiring high durability, such as those where repeated stress is applied.

[0007] The present invention was made under these circumstances, and aims to provide a composite material member or the like that has excellent durability and impact resistance and is also highly producible while maintaining the heat resistance that is inherent to polyaryl ether ketone. [Means for solving the problem]

[0008] The present invention provides a composite material member or the like using a polyaryl ether ketone having a specific molecular weight distribution and molecular weight, as a means for solving the above-mentioned problems of the prior art.

[0009] That is, the present invention provides the following [1] to

[25] .

[0010] [1] A composite material member containing a resin component containing polyaryl ether ketone as a main component, characterized in that the molecular weight distribution of the resin component is 2 or more but less than 4, the mass average molecular weight is 63,000 or more, and the composite material is a composite material containing a resin and reinforcing fibers with a number average fiber length of 5 mm or more.

[0011] [2] The composite material member according to [1], wherein the polyaryletherketone is polyetheretherketone.

[0012] [3] The composite material member according to [1] or [2], wherein the content of polyaryl ether ketone in the resin component is more than 90 mass%.

[0013] [4] The composite material member according to any one of [1] to [3], wherein the resin component has a mass average molecular weight of 150,000 or less.

[0014] [5] The composite material member according to any one of [1] to [4], wherein the polyaryl ether ketone has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 63,000 or more.

[0015] [6] The composite material member according to any one of [1] to [5], wherein the polyaryl ether ketone has a mass average molecular weight of 150,000 or less.

[0016] [7] The composite material member according to any one of [1] to [6], wherein the heat of crystalline fusion is 30 J / g or more and 45 J / g or less.

[0017] [8] A composite material member according to any one of [1] to [7], which has a folding endurance of 5,000 or more times measured under the conditions of a thickness of 100 μm, a bending angle of 135 degrees, a bending speed of 175 cpm, and a load of 9.8 N.

[0018] [9] A composite material member according to any one of [1] to [8], having a puncture impact strength of 0.3 J or more measured under the conditions of a thickness of 100 μm, 23°C, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s.

[0019]

[10] A composite material member according to any one of [1] to [9], having a puncture impact strength of 0.3 J or more measured under the conditions of a thickness of 100 μm, -20°C, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s.

[0020]

[11] The composite material member according to any one of [1] to

[10] , having a thickness precision of 7% or less.

[0021]

[12] A composite material member according to any one of [1] to

[11] , wherein the arithmetic mean height of the surface on at least one side is 0.001 to 1 μm.

[0022]

[13] A composite material member according to any one of [1] to

[12] , wherein the maximum height of the surface on at least one side is 0.1 to 10 μm.

[0023]

[14] A composite material member according to any one of [1] to

[13] , wherein the arithmetic mean roughness of the surface on at least one side is 0.005 to 1 μm.

[0024]

[15] A composite material member according to any one of [1] to

[14] , wherein the maximum height roughness of the surface on at least one side is 0.05 to 5 μm.

[0025]

[16] The composite material member according to any one of [1] to

[15] , which has a relative crystallinity of 50% or more.

[0026]

[17] The composite material member according to any one of [1] to

[16] , which is a film.

[0027]

[18] A composite material obtained by combining the composite material member according to any one of [1] to

[17] with reinforcing fibers.

[0028]

[19] The composite material according to

[18] , which is a prepreg.

[0029]

[20] A mobile body, such as an aircraft, automobile, ship, or railroad vehicle, using the composite material according to

[18] or

[19] .

[0030]

[21] A composite material member containing a resin component containing polyaryl ether ketone as a main component, characterized in that the molecular weight distribution of the resin component is 2 or more but less than 4, the mass average molecular weight is 63,000 or more, and the composite material member is a plate-shaped member.

[0031]

[22] The composite material member according to

[21] , wherein the polyaryletherketone is polyetheretherketone.

[0032]

[23] The composite material member according to

[21] or

[22] , wherein the plate-like member is a film.

[0033]

[24] A method for producing a film containing a resin component containing polyaryl ether ketone as a main component, the method comprising: preparing a resin component having a molecular weight distribution of 2 or more but less than 4 and a mass average molecular weight of 63,000 or more; melt-kneading the resin component in an extruder; extruding the molten resin from a die; and cooling the molten resin with a cast roll to form a film; and ensuring that the cooled film has a folding endurance of 5,000 or more times as measured under conditions of a thickness of 100 μm, a bending angle of 135 degrees, a bending speed of 175 cpm, and a load of 9.8 N; and that the puncture impact strength at 23°C is 0.3 J or more and at -20°C is 0.3 J or more as measured under conditions of a thickness of 100 μm, a fixing frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s.

[0034]

[25] The method for producing a film according to

[24] , wherein the molecular weight distribution of the polyaryl ether ketone is 2 or more but less than 4, and the mass average molecular weight is 63,000 or more. [Effects of the Invention]

[0035] According to the present invention, it is possible to provide a composite material member that is excellent in durability, impact resistance and productivity, as well as a composite material and a mobile body that use the same. [Brief explanation of the drawings]

[0036] [Figure 1] 1A to 1C are explanatory views of a main part, each of which is a schematic view showing an embodiment of a film manufacturing method. DETAILED DESCRIPTION OF THE INVENTION

[0037] An example of an embodiment of the present invention will be described below, but the present invention is not limited to the embodiment described below as long as it does not depart from the gist of the present invention.

[0038] In the present invention, when the expression "X to Y" (X and Y are any numbers) is used, it includes the meaning of "X or more and Y or less", as well as "preferably larger than X" and "preferably smaller than Y", unless otherwise specified. Furthermore, in the present invention, when the expression "X or more" (X is any number) is used, it includes the meaning of "preferably larger than X" unless otherwise specified, and when the expression "Y or less" (Y is any number) is used, it includes the meaning of "preferably smaller than Y" unless otherwise specified.

[0039] In the present invention, the term "major component" refers to the component that accounts for the largest proportion in the target substance, and is preferably 50% by mass or more of the target substance, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.

[0040] One embodiment of the present invention relates to a composite material member, which is a composite material member containing a resin and reinforcing fibers having a number average fiber length of 5 mm or more, and which contains a resin component containing polyaryl ether ketone as a main component, and which has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 63,000 or more. Another embodiment of the composite material member of the present invention is a composite material member containing a resin component containing polyaryl ether ketone as a main component, wherein the resin component has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 63,000 or more, and the composite material member is a plate-shaped member. Preferably, the polyaryl ether ketone has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 63000 or more. This will be explained in detail below.

[0041] <Resin component> The resin component contained in the composite material member of the present invention is not particularly limited as long as it contains polyaryletherketone as a main component, has a molecular weight distribution of 2 or more and less than 4, and has a mass average molecular weight of 63,000 or more.

[0042] The molecular weight distribution of the resin component is 2 or more, preferably 2.1 or more, more preferably 2.2 or more, even more preferably 2.5 or more, particularly preferably 3 or more, particularly preferably 3.2 or more, and most preferably 3.4 or more. When the molecular weight distribution is above the lower limit, the resin component contains an appropriate amount of low-molecular-weight and high-molecular-weight components, thereby achieving both fluidity and mechanical properties. On the other hand, the molecular weight distribution of the resin component is less than 4, preferably 3.9 or less, more preferably 3.8 or less, and even more preferably 3.7 or less. A narrow molecular weight distribution means that the proportion of low-molecular-weight components that can act as crystal nucleating agents is low, and even when crystallized, the degree of crystallization is kept low, resulting in high durability and impact resistance. Furthermore, when producing a film, if the raw material contains a large amount of low-molecular-weight components, the low-molecular-weight components may adhere to the casting roll and be transferred to the film, potentially damaging the film's appearance. A narrow molecular weight distribution and a low proportion of low-molecular-weight components prevent contamination of the casting roll and produce a film with excellent appearance. Furthermore, when a composite material containing reinforcing fibers is produced, there is no problem of contamination of the production equipment due to volatilization of low molecular weight components.

[0043] The mass average molecular weight of the resin component is 63,000 or more, preferably 65,000 or more, more preferably 68,000 or more, even more preferably 70,000 or more, even more preferably 72,000 or more, even more preferably 75,000 or more, even more preferably 78,000 or more, particularly preferably 80,000 or more, especially preferably 83,000 or more, and most preferably 85,000 or more. When the mass average molecular weight is above the lower limit, mechanical properties such as durability and impact resistance are excellent. On the other hand, the mass average molecular weight of the resin component is preferably 150,000 or less, more preferably 140,000 or less, even more preferably 135,000 or less, even more preferably 130,000 or less, particularly preferably 125,000 or less, especially preferably 120,000 or less, and most preferably 115,000 or less. When the mass average molecular weight is below the upper limit, the crystallization degree, crystallization rate, and fluidity during melt molding tend to be excellent.

[0044] The content of polyaryl ether ketone in the resin component, particularly preferably polyether ether ketone, is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably more than 90% by mass. When a resin other than polyaryl ether ketone is contained, as long as the content of polyaryl ether ketone is within this range, it becomes easy to impart the effects required appropriately while maintaining the effects of the present invention.

[0045] When other resin components are blended with polyaryletherketone for the purpose of modifying the polyaryletherketone, the type is not particularly limited, and polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylpentene, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyacetal, aliphatic polyamide, polymethyl methacrylate, polycarbonate, ABS, aromatic polyamide, polyphenylene sulfide, polyarylate, polyetherimide, polyamideimide, polysulfone, polyethersulfone, liquid crystal polymer, copolymers thereof, and mixtures thereof can be used. Among them, polyphenylene sulfide, polyarylate, polyetherimide, polyamideimide, polysulfone, polyethersulfone, and liquid crystal polymer can be preferably used, and polyetherimide can be particularly preferably used, from the viewpoint that they have a molding temperature close to that of polyaryletherketone and are easy to suppress decomposition and crosslinking during melt molding. Polyaryletherketone and polyetherimide are highly compatible and can be mixed at the molecular level, making it easy to improve the glass transition temperature of polyaryletherketone and control the crystallinity.

[0046] Furthermore, when polyether ether ketone is used as the polyaryl ether ketone, other resin components to be blended for the purpose of modifying the polyaryl ether ketone may be the same as the resins used for the purpose of modifying the polyaryl ether ketone. However, it is also preferable to use a polyaryl ether ketone other than polyether ether ketone, such as polyether ketone, polyether ketone ketone, polyether ketone ether ketone ketone, or polyether ether ketone ketone, in combination with polyether ether ketone.

[0047] [Polyaryletherketone] The polyaryl ether ketone will be described below. Polyaryletherketone is a homopolymer or copolymer containing a monomer unit containing one or more aryl groups, one or more ether groups, and one or more ketone groups. Examples include polyetheretherketone, polyetherketoneketone, polyetherketone, polyetherketoneetherketoneketone, polyetheretherketoneketone, polyetherdiphenyletherketone, and copolymers thereof (e.g., polyetherketone-polyetherdiphenyletherketone copolymer). Among these, polyetheretherketone is particularly preferred because of its excellent heat resistance, mechanical properties, chemical resistance, and the like.

[0048] The molecular weight distribution of the polyaryl ether ketone is preferably 2 or more, more preferably 2.1 or more, even more preferably 2.2 or more, even more preferably 2.5 or more, particularly preferably 3 or more, especially preferably 3.2 or more, and most preferably 3.4 or more. When the molecular weight distribution is at or above the lower limit, the polyaryl ether ketone contains an appropriate amount of low-molecular-weight and high-molecular-weight components, making it easy to achieve both good fluidity and good mechanical properties. On the other hand, the molecular weight distribution of the polyaryl ether ketone is preferably less than 4, more preferably 3.9 or less, even more preferably 3.8 or less, and especially preferably 3.7 or less. A narrow molecular weight distribution means that the proportion of low-molecular-weight components that can act as crystal nucleating agents is low, and even when crystallized, the degree of crystallization is kept low, resulting in increased durability and impact resistance. Furthermore, when producing a film, if the raw material contains a large amount of low-molecular-weight components, the low-molecular-weight components may adhere to the casting roll and be transferred to the film, potentially damaging the film's appearance. The narrow molecular weight distribution and low proportion of low molecular weight components have the excellent effect of preventing contamination of the casting roll and facilitating the production of films with excellent appearance.Furthermore, when producing composite materials with reinforcing fibers, there is also the advantage that the problem of contamination of the production equipment due to volatilization of low molecular weight components is unlikely to occur.

[0049] The mass average molecular weight of the polyaryl ether ketone is preferably 63,000 or more, more preferably 65,000 or more, even more preferably 68,000 or more, even more preferably 70,000 or more, even more preferably 72,000 or more, even more preferably 75,000 or more, even more preferably 78,000 or more, particularly preferably 80,000 or more, especially preferably 83,000 or more, and most preferably 85,000 or more. If the mass average molecular weight of the polyaryl ether ketone is above the lower limit, mechanical properties such as durability and impact resistance tend to be excellent. On the other hand, the mass average molecular weight is preferably 150,000 or less, more preferably 140,000 or less, even more preferably 135,000 or less, even more preferably 130,000 or less, particularly preferably 125,000 or less, especially preferably 120,000 or less, and most preferably 115,000 or less. When the mass average molecular weight of the polyaryl ether ketone is equal to or less than the upper limit, the degree of crystallization, the crystallization rate, and the fluidity during melt molding tend to be excellent.

[0050] Hereinafter, polyether ether ketone, which is preferably used among polyaryl ether ketones, will be described. [Polyether ether ketone] The polyether ether ketone may be any resin having at least two ether groups and a ketone group as structural units, but is preferably one having a repeating unit represented by the following general formula (1) because it has excellent thermal stability, melt moldability, rigidity, chemical resistance, impact resistance, and durability.

[0051] [ka]

[0052] (In the above general formula (1), Ar 1 ~Ar 3each independently represents an arylene group having 6 to 24 carbon atoms, and each may have a substituent.

[0053] In the above general formula (1), Ar 1 ~Ar 3 The arylene groups in Ar may be different from each other, but are preferably the same. 1 ~Ar 3 Specific examples of the arylene group include a phenylene group and a biphenylene group, and among these, a phenylene group is preferred, and a p-phenylene group is more preferred.

[0054] Ar 1 ~Ar 3 Examples of the substituent that the arylene group may have include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups, and alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups. 1 ~Ar 3 When has a substituent, there is no particular limitation on the number of the substituents.

[0055] Among these, polyether ether ketones having a repeating unit represented by the following structural formula (2) are preferred from the viewpoints of thermal stability, melt moldability, rigidity, chemical resistance, impact resistance, and durability.

[0056] [ka]

[0057] The molecular weight distribution of polyether ether ketone is preferably 2 or more, more preferably 2.1 or more, even more preferably 2.2 or more, even more preferably 2.5 or more, particularly preferably 3 or more, especially preferably 3.2 or more, and most preferably 3.4 or more. When the molecular weight distribution is at or above the lower limit, the polyether ether ketone contains an appropriate amount of low-molecular-weight and high-molecular-weight components, making it easy to achieve both good fluidity and good mechanical properties. On the other hand, the molecular weight distribution of polyether ether ketone is preferably less than 4, more preferably 3.9 or less, even more preferably 3.8 or less, and especially preferably 3.7 or less. A narrow molecular weight distribution means that the proportion of low-molecular-weight components that can act as crystal nucleating agents is low, and even when crystallized, the degree of crystallization is kept low, resulting in increased durability and impact resistance. Furthermore, when producing a film, if the raw material contains a large amount of low-molecular-weight components, the low-molecular-weight components may adhere to the casting roll and be transferred to the film, potentially damaging the film's appearance. The narrow molecular weight distribution and low proportion of low molecular weight components have the excellent effect of preventing contamination of the casting roll and facilitating the production of films with excellent appearance.Furthermore, when producing composite materials with reinforcing fibers, there is also the advantage that the problem of contamination of the production equipment due to volatilization of low molecular weight components is unlikely to occur.

[0058] The mass average molecular weight of the polyether ether ketone is preferably 63,000 or more, more preferably 65,000 or more, even more preferably 68,000 or more, even more preferably 70,000 or more, even more preferably 72,000 or more, even more preferably 75,000 or more, even more preferably 78,000 or more, particularly preferably 80,000 or more, especially preferably 83,000 or more, and most preferably 85,000 or more. When the mass average molecular weight of the polyether ether ketone is at or above the lower limit, mechanical properties such as durability and impact resistance tend to be excellent. On the other hand, the mass average molecular weight is preferably 150,000 or less, more preferably 140,000 or less, even more preferably 135,000 or less, even more preferably 130,000 or less, particularly preferably 125,000 or less, especially preferably 120,000 or less, and most preferably 115,000 or less. When the mass average molecular weight of the polyether ether ketone is equal to or less than the upper limit, the degree of crystallization, the crystallization rate, and the fluidity during melt molding tend to be excellent.

[0059] The molecular weight and molecular weight distribution can be determined by gel permeation chromatography using an eluent that dissolves the resin component used. For example, a mixture of chlorophenol and a halogenated benzene such as chlorobenzene, chlorotoluene, bromobenzene, bromotoluene, dichlorobenzene, dichlorotoluene, dibromobenzene, or dibromotoluene, or a mixture of pentafluorophenol and chloroform can be used as the eluent. Specifically, it can be measured by the method described in the Examples below, for example, by the following method. (1) Obtain an amorphous film of a resin component such as polyether ether ketone. For example, resin pellets such as polyether ether ketone are pressed at, for example, 350 to 400°C and then rapidly cooled, or, when forming into a film using an extruder, the temperature of a cast roll is lowered, for example, to 20 to 140°C, to obtain an amorphous film. (2) 3 g of pentafluorophenol is added to 9 mg of the film. (3) Using a heat block, heat to 100°C for 60 minutes to dissolve. (4) Next, remove from the heat block, allow to cool, then slowly add 6 g of room temperature (approximately 23°C) chloroform little by little and shake gently to mix. (5) The sample is then filtered through a 0.45 μm PTFE (polytetrafluoroethylene) cartridge filter, and the number average molecular weight (Mn), mass average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are measured using gel permeation chromatography.

[0060] The crystalline melting temperature of polyaryletherketone, particularly polyetheretherketone, is preferably 330°C or higher, more preferably 331°C or higher, even more preferably 332°C or higher, and particularly preferably 333°C or higher. If the crystalline melting temperature of polyaryletherketone is above the lower limit, the resulting composite material member tends to have excellent heat resistance. On the other hand, the crystalline melting temperature of polyaryletherketone, particularly polyetheretherketone, is preferably 370°C or lower, more preferably 365°C or lower, even more preferably 360°C or lower, particularly preferably 355°C or lower, and most preferably 350°C or lower. If the crystalline melting temperature of polyaryletherketone is below the upper limit, the resulting composite material member tends to have excellent fluidity during melt molding, such as during the production of the composite material member.

[0061] The crystalline melting temperature of polyaryl ether ketone, particularly polyether ether ketone, can be determined in accordance with JIS K7121:2012 from the peak-top temperature of the melting peak of the detected DSC curve using a differential scanning calorimeter (for example, "Pyris1 DSC" manufactured by PerkinElmer) in a temperature range of 25 to 400°C at a heating rate of 10°C / min.

[0062] The heat of crystalline fusion of polyaryl ether ketone, particularly polyether ether ketone, is preferably 30 J / g or more, more preferably 31 J / g or more, even more preferably 32 J / g or more, and particularly preferably 33 J / g or more. If the heat of crystalline fusion of polyaryl ether ketone is equal to or greater than the lower limit, the resulting composite material member tends to have sufficient crystallinity and, therefore, excellent heat resistance and rigidity. On the other hand, the heat of crystalline fusion of polyaryl ether ketone, particularly polyether ether ketone, is preferably 45 J / g or less, more preferably 43 J / g or less, and even more preferably 40 J / g or less. If the heat of crystalline fusion of polyaryl ether ketone is equal to or less than the upper limit, the crystallinity is not too high, which tends to result in excellent melt moldability during the production of composite material members, and the resulting composite material member tends to have excellent durability and impact resistance.

[0063] The heat of crystalline fusion of polyaryl ether ketone, particularly polyether ether ketone, can be determined in accordance with JIS K7122:2012 using a differential scanning calorimeter (for example, "Pyris1 DSC" manufactured by PerkinElmer) by raising the temperature in the temperature range of 25 to 400°C at a heating rate of 10°C / min, and from the area of ​​the melting peak of the detected DSC curve.

[0064] The crystallization temperature of polyaryletherketone, particularly polyetheretherketone, during the cooling process is preferably 280°C or higher, more preferably 281°C or higher, even more preferably 282°C or higher, particularly preferably 283°C or higher, and most preferably 284°C or higher. If the crystallization temperature of polyaryletherketone during the cooling process is equal to or higher than the lower limit, the crystallization rate is high and the productivity of composite material components tends to be excellent. Specifically, for example, when producing a film, setting the temperature of the casting roll to be equal to or higher than the glass transition temperature and equal to or lower than the crystalline melting temperature promotes crystallization while the resin is in contact with the casting roll, resulting in a crystallized film. However, if the crystallization temperature during the cooling process is equal to or higher than the lower limit, the crystallization rate is high and crystallization can be completed by the casting roll, resulting in a high elastic modulus, which results in less sticking to the roll and a tendency for the film to have a better appearance.

[0065] On the other hand, the crystallization temperature of polyaryl ether ketone, particularly polyether ether ketone, during the temperature drop process is preferably 310° C. or lower, more preferably 306° C. or lower, even more preferably 304° C. or lower, and particularly preferably 302° C. or lower. If the crystallization temperature during the temperature drop process is equal to or lower than the upper limit, crystallization will not be too fast, reducing uneven cooling during molding of a composite material member such as a film, and tending to produce a uniformly crystallized, high-quality composite material member.

[0066] The crystallization temperature of polyaryl ether ketone, particularly polyether ether ketone, during the temperature decrease process can be determined in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, "Pyris1 DSC" manufactured by PerkinElmer) by decreasing the temperature in the temperature range of 400 to 25°C at a rate of 10°C / min, from the peak top temperature of the crystallization peak on the detected DSC curve.

[0067] The method for producing polyaryl ether ketones, particularly polyether ether ketones, having a molecular weight distribution of 2 or more but less than 4 and a mass average molecular weight of 63,000 or more is not particularly limited, and they can be produced by known production methods. In production, conditions for achieving the desired molecular weight distribution and mass average molecular weight may be appropriately selected and adopted. Specific examples include methods for adjusting the type, amount, and concentration of the monomers, polymerization initiators, catalysts, and chain transfer agents added as needed during polymerization, as well as the method of adding each of them, or adjusting polymerization conditions such as polymerization temperature, polymerization time, and polymerization pressure. Also, so-called multi-stage polymerization, in which polymerization conditions are changed in stages, may be adopted.

[0068] <Composite material components> The resin component containing the above-mentioned polyaryletherketone, preferably polyetheretherketone, as a main component, has a molecular weight distribution of 2 or more but less than 4, and a mass-average molecular weight of 63,000 or more, and is suitable for use as a composite material member (hereinafter sometimes referred to as "this member"), which is a material component for obtaining a composite material containing a resin and fibers (reinforcing fibers) for reinforcing the resin. This component is particularly suitable for use as a composite material member containing a resin and reinforcing fibers with a number-average fiber length of 5 mm or more. By including polyaryletherketone, preferably polyetheretherketone, having the above-mentioned specific molecular weight distribution and mass-average molecular weight, the resulting composite material member tends to be excellent in durability, impact resistance, and productivity. These advantages of including the specific polyaryletherketone, particularly polyetheretherketone, are particularly pronounced when compounded with reinforcing fibers with a number-average fiber length of 5 mm or more.

[0069] The present member may contain various additives such as heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antibacterial and antifungal agents, antistatic agents, lubricants, pigments, dyes, and fillers, as long as the effects of the present invention are not impaired.

[0070] The proportion of the resin component in the member, particularly polyaryletherketone, preferably polyetheretherketone, is preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more. When the proportion of the resin component, particularly polyaryletherketone, preferably polyetheretherketone, in the member is at or above the lower limit, the member is likely to have excellent heat resistance and rigidity. On the other hand, there is no particular upper limit. To fully exhibit properties such as heat resistance and rigidity, the proportion of the resin component, particularly polyaryletherketone, preferably polyetheretherketone, is preferably as high as possible. However, when additives, fillers, etc. are further included to modify the resin component, particularly polyaryletherketone, preferably polyetheretherketone, the proportion is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. When the proportion of the resin component contained in the present member, particularly polyaryletherketone, preferably polyetheretherketone, is not more than the above upper limit, when additives, fillers, etc. are further contained, the effects of those additives, fillers, etc. are likely to be fully exhibited.

[0071] This member may be in a completely uncrystallized state or in a crystallized state. Depending on the purpose, it is possible to adjust the crystallinity appropriately using known methods during the manufacturing process. In general, a material has excellent toughness in an uncrystallized state, and excellent heat resistance and rigidity in a crystallized state. For applications requiring higher functionality such as heat resistance and rigidity, a completely crystallized state is preferable. Note that being completely crystallized means that no exothermic peak associated with crystallization is observed during the temperature rise process in differential scanning calorimetry (DSC).

[0072] [Crystalline melting temperature] The crystalline melting temperature of this member is preferably 330°C or higher, more preferably 331°C or higher, even more preferably 332°C or higher, and particularly preferably 333°C or higher. If the crystalline melting temperature of this member is above the lower limit, it tends to have excellent heat resistance. On the other hand, the crystalline melting temperature is preferably 370°C or lower, more preferably 365°C or lower, even more preferably 360°C or lower, particularly preferably 355°C or lower, and most preferably 350°C or lower. If the crystalline melting temperature of this member is below the upper limit, it tends to have excellent secondary processability, such as fiber impregnation, when using this member to produce a composite material with reinforcing fibers.

[0073] The crystalline melting temperature of the material can be determined in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, PerkinElmer's "Pyris1 DSC"), by raising the temperature in the temperature range of 25 to 400°C at a heating rate of 10°C / min, and from the peak-top temperature of the melting peak of the detected DSC curve.

[0074] [Crystal melting heat] The heat of crystalline fusion of this member is preferably 30 J / g or more, more preferably 31 J / g or more, even more preferably 32 J / g or more, and particularly preferably 33 J / g or more. If the heat of crystalline fusion of this member is above the lower limit, it will have sufficient crystallinity and therefore tend to have excellent heat resistance and rigidity. Furthermore, when it is made into a composite material with reinforcing fibers, it will also tend to have excellent heat resistance and rigidity. On the other hand, the heat of crystalline fusion of this member is preferably 45 J / g or less, more preferably 43 J / g or less, and even more preferably 40 J / g or less. If the heat of crystalline fusion of this member is below the upper limit, the degree of crystallinity will not be too high, and therefore it will tend to have excellent secondary processability, such as impregnation into reinforcing fibers, when producing a composite material with reinforcing fibers.

[0075] The heat of crystalline fusion of this material can be determined in accordance with JIS K7122:2012 using a differential scanning calorimeter (for example, PerkinElmer's "Pyris1 DSC"), by raising the temperature in the temperature range of 25 to 400°C at a heating rate of 10°C / min, and from the area of ​​the melting peak at the time of melting on the detected DSC curve.

[0076] [Crystallization temperature] The crystallization temperature of the present member during the cooling process is preferably 280° C. or higher, more preferably 281° C. or higher, even more preferably 282° C. or higher, particularly preferably 283° C. or higher, and most preferably 284° C. or higher. If the crystallization temperature of the present member during the cooling process is equal to or higher than the lower limit mentioned above, the crystallization rate is high, the cycle for producing a composite material with reinforcing fibers can be shortened, and productivity tends to be excellent.

[0077] On the other hand, the crystallization temperature during the cooling process is preferably 310°C or lower, more preferably 306°C or lower, even more preferably 304°C or lower, and particularly preferably 302°C or lower. If the crystallization temperature during the cooling process of the present component is below the upper limit, crystallization will not be too rapid, reducing uneven cooling during the production of a composite material with reinforcing fibers, and a uniformly crystallized, high-quality composite material will tend to be obtained. In addition, this also has the advantage that it becomes easier to sufficiently impregnate the present component into the reinforcing fibers during the production of a composite material with reinforcing fibers, making it easier for the resulting composite material to be uniformly crystallized and high-quality.

[0078] The crystallization temperature of this material can be determined in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, PerkinElmer's "Pyris1 DSC"), by lowering the temperature in the temperature range of 400 to 25°C at a rate of 10°C / min, and from the peak-top temperature of the crystallization peak on the detected DSC curve.

[0079] [Number of folding times] The folding endurance of this member is preferably 5,000 or more, more preferably 6,000 or more, even more preferably 7,000 or more, particularly preferably 8,000 or more, particularly preferably 9,000 or more, and most preferably 10,000 or more. If the folding endurance is within this range, durability is sufficiently high, and the resulting composite material also has excellent durability and is likely to be resistant to breakage even in applications where repeated stress is applied. The folding endurance can be measured in accordance with JIS P8115:2001 under the conditions of a thickness of 100 μm, a bending angle of 135°, a bending speed of 175 cpm, and a load of 9.8 N.

[0080] [Puncture impact strength] The puncture impact strength of this member, measured under conditions of a thickness of 100 μm, 23°C, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s, is preferably 0.3 J or more, more preferably 0.4 J or more, even more preferably 0.6 J or more, and particularly preferably 0.7 J or more. If the puncture impact strength at 23°C is within this range, the member is likely to have sufficiently high impact resistance and is unlikely to break even when subjected to external impact, and the resulting composite material is also likely to have excellent impact resistance.

[0081] The puncture impact strength of this member, measured under conditions of a thickness of 100 μm, -20°C, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s, is preferably 0.3 J or more, more preferably 0.4 J or more, and even more preferably 0.5 J or more. If the puncture impact strength at -20°C is within this range, the member will have sufficiently high impact resistance, particularly at low temperatures, and will likely be a composite material member that is resistant to destruction even when subjected to external impact, and the resulting composite material will also likely have excellent impact resistance. The puncture impact strength at 23°C and -20°C can be measured with reference to JIS K7124-2:1999 under the conditions of a thickness of 100 μm, an inner diameter of the measurement sample fixing frame of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s. However, if the thickness of the component is 1 mm or more, it can be measured under similar conditions with reference to JIS K7211-2:2006.

[0082] [Thickness precision] When the component is a thin, flat shape such as a film, sheet, or plate, with a thickness that is extremely small compared to its length and width, the thickness precision of the component is preferably 7% or less, more preferably 5% or less, even more preferably 4% or less, particularly preferably 3% or less, especially preferably 2.5% or less, and most preferably 2% or less. When the thickness precision is within this range, when combined with reinforcing fibers, the variation in the reinforcing fiber content in the resulting composite material is likely to be small. In other words, the variation in mechanical properties such as strength between different parts of the composite material is small, making it easier to obtain a composite material with highly uniform mechanical properties. The lower limit of the thickness precision is not particularly limited, and is preferably 0%, but is typically 0.1%, and may be 0.3%, 0.5%, 0.8%, or 1%. The thickness precision can be calculated from the average value and standard deviation of the measured film thickness using the following formula 1, and specifically, can be measured by the method described in the examples below. [Formula 1] Thickness accuracy (%) = standard deviation (μm) / average value (μm) x 100

[0083] [Surface roughness] When the member has a thin, flat shape such as a film, sheet, or plate, where the thickness is extremely small compared to the length and width, it is preferable that the surface roughness of at least one surface (single side) be within a specific range. Specifically, it is preferable that the arithmetic mean height (Sa), maximum height (Sz), arithmetic mean roughness (Ra), and maximum height roughness (Rz) of at least one side of the member be within the specific ranges described below. It is also preferable that the surface roughness of both sides of the member be within the specific ranges described below.

[0084] Arithmetic mean height (Sa) The arithmetic mean height (Sa) of at least one surface of the member is preferably 0.001 μm or more, more preferably 0.005 μm or more, even more preferably 0.007 μm or more, particularly preferably 0.01 μm or more, especially preferably 0.015 μm or more, and most preferably 0.018 μm or more. The arithmetic mean height (Sa) is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.2 μm or less, especially preferably 0.1 μm or less, especially preferably 0.08 μm or less, and most preferably 0.05 μm or less. If the arithmetic mean height (Sa) is equal to or greater than the lower limit, problems such as meandering or skewing of the film due to reduced slipperiness when unwinding the film from a film roll or the like during lamination with a reinforcing fiber sheet or the like during the production of a composite material such as a prepreg are less likely to occur, resulting in a composite material component with excellent processability. Furthermore, problems such as sparks generated by static electricity accumulating on the film roll or the like during unwinding, causing scratches on the surface of the film, or floating dust being attracted by static electricity and adhering to the surface of the film or the like, resulting in the inclusion of foreign matter in the resulting composite material, are less likely to occur. Furthermore, if the arithmetic mean height (Sa) is equal to or less than the upper limit, when combined with reinforcing fibers, the resulting composite material is more likely to have minimal variation in the reinforcing fiber content. This means that the mechanical properties, such as strength, of the composite material vary less depending on the region, making it easier to obtain a composite material with highly uniform mechanical properties. Another advantage is that problems such as slippage, shifting, twisting, and wrinkling of the film on the transport roll during film transport when unwinding the film from the film roll or the like are less likely to occur. The arithmetic mean height (Sa) can be measured using a white light interference microscope, specifically by the method described in the examples below.

[0085] Maximum Height (Sz) The maximum height (Sz) of at least one surface of the member is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, particularly preferably 0.7 μm or more, and most preferably 0.8 μm or more. The maximum height (Sz) is preferably 10 μm or less, more preferably 7 μm or less, even more preferably 5 μm or less, particularly preferably 3 μm or less, particularly preferably 2.5 μm or less, and most preferably 2 μm or less. If the maximum height (Sz) is equal to or greater than the lower limit, problems such as meandering or skewing of the film due to reduced slipperiness when unwinding the film from a film roll or the like during lamination with a reinforcing fiber sheet or the like during the production of a composite material such as a prepreg are less likely to occur, resulting in a composite material component with excellent processability. Furthermore, problems such as sparks generated by static electricity accumulating on the film roll or the like during unwinding, causing scratches on the surface of the film, or floating dust being attracted by static electricity and adhering to the surface of the film or the like, resulting in the inclusion of foreign matter in the resulting composite material, are less likely to occur. Furthermore, if the maximum height (Sz) is equal to or less than the upper limit, when combined with reinforcing fibers, the resulting composite material is more likely to have minimal variation in the reinforcing fiber content. This means that the mechanical properties, such as strength, of the composite material vary little from part to part, making it easier to obtain a composite material with highly uniform mechanical properties. Another advantage is that problems such as slippage, shifting, twisting, and wrinkling of the film on the transport roll during film transport when unwinding the film from the film roll or the like are less likely to occur. The maximum height (Sz) can be measured using a white light interference microscope, specifically by the method described in the examples below.

[0086] [Arithmetic mean roughness (Ra)] The arithmetic mean roughness (Ra) of at least one surface of the member is preferably 0.005 μm or more, more preferably 0.008 μm or more, even more preferably 0.01 μm or more, particularly preferably 0.015 μm or more, and most preferably 0.02 μm or more. The arithmetic mean roughness (Ra) is preferably 1 μm or less, more preferably 0.7 μm or less, even more preferably 0.5 μm or less, even more preferably 0.3 μm or less, particularly preferably 0.2 μm or less, particularly preferably 0.15 μm or less, and most preferably 0.1 μm or less. If the arithmetic mean roughness (Ra) is equal to or greater than the lower limit, problems such as meandering or skewing of the film due to reduced slipperiness when unwinding the film from a film roll or the like during lamination with a reinforcing fiber sheet or the like during the production of a composite material such as a prepreg are less likely to occur, resulting in a composite material component with excellent processability. Furthermore, problems such as sparks generated by static electricity accumulating on the film roll or the like during unwinding, causing scratches on the surface of the film, or floating dust being attracted by static electricity and adhering to the surface of the film or the like, resulting in the inclusion of foreign matter in the resulting composite material, are less likely to occur. Furthermore, if the arithmetic mean roughness (Ra) is equal to or less than the upper limit, when combined with reinforcing fibers, the resulting composite material is more likely to have minimal variation in the reinforcing fiber content. This means that the mechanical properties, such as strength, of the composite material vary less depending on the region, making it easier to obtain a composite material with highly uniform mechanical properties. Another advantage is that problems such as slippage, shifting, twisting, and wrinkling of the film on the transport roll during film transport when unwinding the film from the film roll or the like are less likely to occur. The arithmetic mean roughness (Ra) can be measured using a contact surface roughness meter in accordance with JIS B0601:2013, and specifically, can be measured by the method described in the examples below.

[0087] Maximum height roughness (Rz) The maximum roughness in height (Rz) of at least one surface of the member is preferably 0.05 μm or more, more preferably 0.08 μm or more, even more preferably 0.1 μm or more, particularly preferably 0.15 μm or more, and most preferably 0.2 μm or more. The maximum roughness in height (Rz) is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 2 μm or less, particularly preferably 1 μm or less, and most preferably 0.8 μm or less. If the maximum height roughness (Rz) is equal to or greater than the lower limit, problems such as meandering or skewing of the film due to reduced slipperiness when unwinding the film from a film roll or the like during lamination with a reinforcing fiber sheet or the like during the production of a composite material such as a prepreg are less likely to occur, resulting in a composite material component with excellent processability. Furthermore, problems such as sparks generated by static electricity accumulating on the film roll or the like during unwinding, causing scratches on the surface of the film, or floating dust being attracted by static electricity and adhering to the surface of the film or the like, resulting in the inclusion of foreign matter in the resulting composite material, are less likely to occur. Furthermore, if the maximum height roughness (Rz) is equal to or less than the upper limit, when combined with reinforcing fibers, the resulting composite material is more likely to have minimal variation in the reinforcing fiber content. This means that the mechanical properties, such as strength, of the composite material vary less depending on the region, making it easier to obtain a composite material with highly uniform mechanical properties. Another advantage is that problems such as slippage, shifting, twisting, and wrinkling of the film on the transport roll during film transport when unwinding the film from the film roll or the like are less likely to occur. The maximum height roughness (Rz) can be measured using a contact surface roughness meter in accordance with JIS B0601:2013, and specifically, can be measured by the method described in the examples below.

[0088] [Relative crystallinity] The relative crystallinity of the component is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, particularly preferably 80% or more, particularly preferably 90% or more, and most preferably 95% or more. The upper limit is usually 100%. If the relative crystallinity of the component is equal to or greater than the lower limit, it becomes easier to suppress thermal shrinkage when the component and reinforcing fibers are thermocompressed to form a composite material, and the component can have better heat resistance and rigidity. The relative crystallinity can be calculated using the following formula 2 from the heat quantity (J / g) of the crystal melting peak and the heat quantity (J / g) of the recrystallization peak obtained at this time by using a differential scanning calorimeter (for example, "Pyris1 DSC" manufactured by PerkinElmer) in the temperature range of 25 to 400°C and increasing the temperature at a heating rate of 10°C / min. [Formula 2] Relative crystallinity (%) = {1-(ΔHc / ΔHm)} × 100 ΔHc: Heat quantity (J / g) of the recrystallization peak under the temperature increase condition of 10°C / min ΔHm: Heat of crystal melting peak (J / g) when the temperature of this material is increased at 10°C / min

[0089] When there are multiple recrystallization peaks, the sum of their heat quantities is calculated as ΔHc, and when there are multiple crystal melting peaks, the sum of their heat quantities is calculated as ΔHm. When measured with a differential scanning calorimeter, if no recrystallization peak is observed (ΔHc = 0 J / g), the material can be said to be crystallized, and if a recrystallization peak is observed, the material can be said to be not completely crystallized.

[0090] [specific gravity] The specific gravity of this component is preferably 1.27 or higher, more preferably 1.28 or higher. There is a correlation between relative crystallinity and specific gravity, and typically, the higher the relative crystallinity, the higher the specific gravity. Therefore, if the specific gravity is equal to or higher than the lower limit, shrinkage due to heat tends to be suppressed when this component and reinforcing fibers are bonded together by heat or pressure to form a composite material, and the resulting composite tends to have excellent heat resistance and rigidity. Meanwhile, the specific gravity of this component is preferably 1.35 or lower, more preferably 1.34 or lower. The specific gravity is a value measured at a temperature of 23°C in accordance with the measurement method of JIS K7112:1999 (Method D).

[0091] [Heat shrinkage rate] The heat shrinkage of this member is preferably 2.5% or less, more preferably 2.2% or less, even more preferably 1.8% or less, particularly preferably 1.5% or less, particularly preferably 1.2% or less, especially preferably 0.8% or less, and most preferably 0.7% or less. By setting the heat shrinkage to the above upper limit or less, shrinkage due to heat tends to be suppressed when this member and reinforcing fibers are thermocompression bonded to form a composite material, and the resulting composite material also tends to be less prone to appearance defects such as wrinkles. The lower limit of the heat shrinkage of this member is not particularly limited, and is preferably 0%, but may be 0.1% or 0.2%. The heat shrinkage rate is determined by cutting a 120mm x 120mm test piece from the film or other form of this material, marking lines at 100mm intervals in the direction (TD) perpendicular to the direction of resin flow (MD), and leaving this test piece in a 200°C environment for 10 minutes, and then using the distance between the lines before and after heating, using the following formula 3. [Formula 3] Heat shrinkage rate (%) = [(gauge length before heating - gauge length after heating) / gauge length before heating] x 100

[0092] [Heat shrinkage stress] The heat shrinkage stress of this member is preferably 1.2 mN or less, more preferably 1 mN or less, even more preferably 0.8 mN or less, particularly preferably 0.5 mN or less, and most preferably 0.3 mN or less. By setting the heat shrinkage stress to the above upper limit or less, shrinkage due to heat tends to be suppressed when this member and reinforcing fibers are thermocompression bonded to form a composite material, and the resulting composite material also tends to be less prone to appearance defects such as wrinkles. The lower limit of the heat shrinkage stress of this member is not particularly limited, and is preferably 0 mN. The heat shrinkage stress can be determined by the following method. A rectangular test piece 10 mm long and 3 mm wide is cut from this film-like member, and using a thermomechanical analyzer (for example, a thermomechanical analyzer "TMA7100" manufactured by Hitachi High-Tech Science Corporation), one end of the test piece is set in the chuck of a load detector and the other end is set in a fixed chuck. The test piece is heated from room temperature (23°C) to 340°C at a heating rate of 5°C / min without applying a load, and the stress value at 145°C is measured. Measurements are made in both the resin flow direction (MD) and the direction perpendicular to it (TD), and the larger stress value is taken as the heat shrinkage stress of the present invention.

[0093] The shape of the member is not particularly limited and may be any of a film, plate, fiber, bottle, tube, rod, powder, pellet, etc., but is preferably a film, plate, or fiber, more preferably a film or plate, and even more preferably a film. When the member is a plate-like member, the term "plate-like" refers to a flat shape with any maximum thickness, including not only so-called plates with a thickness of 1 mm or more, but also films with a thickness of less than 1 mm. A thin plate-like member is preferred, with a thickness of 2 mm or less, more preferably less than 1 mm, even more preferably 500 μm or less, particularly preferably 400 μm or less, particularly preferably 300 μm or less, and most preferably 250 μm or less. The lower limit is typically 3 μm. When using a resin in the form of powder, pellets, or the like, the raw material resin may be used as is, or may be processed into a powder, pellet, or the like. When it is in another shape, it can be molded by a general molding method, for example, extrusion molding, injection molding, melt casting, or other casting molding, press molding, or the like, to form various shapes, preferably into components such as films and plates. In each molding method, the apparatus and processing conditions are not particularly limited, and known methods can be employed. In particular, from the viewpoint of processability when forming a composite material with reinforcing fibers, which will be described later, a composite material component formed into a film by extrusion molding, particularly the T-die method, is preferred.

[0094] In the present invention, film encompasses sheets. Generally, a film refers to a thin, flat product whose thickness is extremely small compared to its length and width, with an arbitrarily limited maximum thickness, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900:1994). Generally, a sheet, as defined in JIS, refers to a thin, flat product whose thickness is generally small compared to its length and width. However, since the boundary between sheet and film is unclear, in the present invention, film encompasses sheets. Therefore, "film" may also refer to "sheet."

[0095] <Film manufacturing method> When the present member is a film, the method for producing the film is not particularly limited, but it can be obtained, for example, as an unstretched or stretched film. From the viewpoint of secondary processability when producing a composite material, it is preferable to obtain it as an unstretched film. Note that an unstretched film is a film that is not actively stretched in order to control the orientation of the film, and includes a film that is oriented when taken up by a cast roll in extrusion molding such as a T-die method, and a film that is stretched less than 2 times by a stretching roll.

[0096] In the case of an unstretched film, it can be produced by melt-kneading the constituent materials of the film, followed by extrusion molding and cooling. Melt-kneading can be performed using a known kneader such as a single-screw or twin-screw extruder. The melting temperature is adjusted appropriately depending on the type and mixing ratio of the resin, and the presence and type of additives. From the viewpoint of productivity, it is preferably 320°C or higher, more preferably 340°C or higher, even more preferably 350°C or higher, and particularly preferably 360°C or higher. By setting the resin temperature at or above the lower limit, crystals of raw materials such as pellets are sufficiently melted and are less likely to remain in the film, which tends to improve the number of folding cycles and puncture impact strength. On the other hand, the melting temperature is preferably 450°C or lower, more preferably 430°C or lower, even more preferably 410°C or lower, and particularly preferably 390°C or lower. By setting the resin temperature at or below the upper limit, the resin is less likely to decompose during melt molding and its molecular weight is more likely to be maintained, which tends to improve the number of folding cycles and puncture impact strength of the film.

[0097] Cooling can be carried out, for example, by contacting the molten resin with a cooling device such as a cooled casting roll. The cooling temperature (e.g., the temperature of the casting roll) varies depending on whether a crystallized film or a completely incrystallized film is to be produced. When producing a crystallized film, the cooling temperature can be appropriately selected to achieve the desired crystallinity. The cooling temperature is preferably 30 to 150°C higher than the glass transition temperature of the resin component contained in the present member, more preferably 35 to 140°C higher, and particularly preferably 40 to 135°C higher. By setting the cooling temperature within the above range, the cooling rate of the film can be slowed, which tends to increase the relative crystallinity. For example, when polyether ether ketone is contained as the resin component, the cooling temperature (cast roll temperature) is preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher. To obtain a film with a higher crystallinity, the cooling temperature (cast roll temperature) is particularly preferably 210°C or higher, and most preferably 220°C or higher. On the other hand, the cooling temperature (cast roll temperature) is preferably 300°C or lower, more preferably 280°C or lower, even more preferably 270°C or lower, particularly preferably 260°C or lower, particularly preferably 250°C or lower, and most preferably 240°C or lower.

[0098] The crystallization rate of polymer materials is thought to be maximized in the temperature range between the glass transition temperature and the crystalline melting temperature, due to the balance between the nucleation rate and growth rate of crystals. When producing a film with a high relative crystallinity, if the cooling temperature (cast roll temperature) is within the range between the lower and upper limits, the crystallization rate will be maximized, making it easier to obtain a crystallized film with excellent productivity.

[0099] On the other hand, when producing a film that is not completely crystallized, it is important to rapidly cool the molten state to below the glass transition temperature in one go, reducing the molecular mobility to a range where crystals cannot grow. In this case, the cooling temperature (for example, the cast roll temperature) is preferably 50°C or higher, more preferably 100°C or higher, and even more preferably 120°C or higher. On the other hand, the cooling temperature (cast roll temperature) is preferably 150°C or lower, more preferably 140°C or lower. When producing a film that is not completely crystallized, if the cooling temperature (cast roll temperature) is within this range, a film with a good appearance that is free from wrinkles or sticking due to rapid cooling is likely to be obtained.

[0100] The glass transition temperature refers to a value measured in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, "Pyris1 DSC" manufactured by PerkinElmer) under conditions of a temperature range of 25 to 400°C and a heating rate of 10°C / min. When a mixture of multiple resins has multiple glass transition temperatures, the highest glass transition temperature is regarded as the glass transition temperature of the resin component, and the cooling temperature can be adjusted accordingly.

[0101] To achieve the desired relative crystallinity of the present member, for example, when the present member is a film, it is preferable to employ extrusion molding and appropriately adjust the conditions for extruding the film. However, in the present invention, it is more preferable to employ the following methods (1) to (4). These methods may be used in combination. Of these, method (1) is preferred because it reduces the likelihood of wrinkles occurring in the resulting composite material and consumes less energy.

[0102] (1) A method of adjusting the cooling conditions when cooling the molten resin to form a film. The cooling can be carried out, for example, by using a cast roll as a cooler and bringing the extruded molten resin into contact with the cast roll. Specifically, the following method is preferably employed.

[0103] One example is a method in which the cooling temperature is set to a temperature 30 to 150°C higher than the glass transition temperature of the resin component. The cooling temperature is more preferably 35 to 140°C higher, and particularly preferably 40 to 135°C higher, than the glass transition temperature of the resin component. By setting the cooling temperature within this range, the cooling rate of the film can be slowed, and the relative crystallinity tends to be increased. In particular, when the resin component contains polyether ether ketone as the main component, the cooling temperature is preferably 180°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher, and particularly preferably 210°C or higher. On the other hand, the cooling temperature is preferably 300°C or lower, more preferably 280°C or lower, even more preferably 260°C or lower, particularly preferably 250°C or lower, and most preferably 240°C or lower.

[0104] (2) A method of reheating the film using a heating roll. Specifically, a method of heating using a roll other than the cast roll of a longitudinal stretching machine, etc. The heating temperature is preferably in the same range as the cooling temperature in (1) above.

[0105] (3) Reheating the film in an oven. Specifically, the film is passed through a drying device such as a floating dryer, tenter, or band dryer and heated with hot air. The heating temperature is preferably in the same range as the cooling temperature in (1) above.

[0106] (4) A method of reheating the film with infrared rays. Specifically, a far-infrared heater such as a ceramic heater may be installed between the rolls to heat the film in a roll-to-roll manner, or the film may be heated by passing it through a far-infrared dryer. The temperature during heating is preferably in the same range as the cooling temperature in (1) above.

[0107] The treatments (2) to (4) above may be carried out simultaneously with the film production by providing dedicated equipment within the film production line, or the film may be wound into a roll and then treated on the film roll by these equipment outside the production line.

[0108] The method for adjusting the arithmetic mean height (Sa), maximum height (Sz), arithmetic mean roughness (Ra), and maximum height roughness (Rz) of the present member is not particularly limited. Examples include transfer processes such as embossed roll transfer, embossed belt transfer, and embossed film transfer; sandblasting, shot blasting, etching, engraving, and surface crystallization; and in the casting process in which the present member is obtained by applying a resin component to a support, drying, and heat-treating it, various methods can be used, such as polishing the surface roughness of a metal roll, endless metal belt, polymer film, or other support. Among these, a preferred method is to cast a film of molten resin onto a roll such as a casting roll, because it is easy to continuously and uniformly adjust the surface roughness while extruding the molten resin into a film. In this case, the surface roughness of the resin film can be adjusted by adjusting the surface roughness, such as the arithmetic mean roughness, of the cast roll.

[0109] Furthermore, there are no particular limitations on the method for adjusting the thickness accuracy of the present member to a desired range, but for example, if the present member is a film, extrusion molding may be employed and the conditions for extruding the film may be appropriately adjusted. (1) A method of adjusting the lip opening by mechanically rotating the lip bolt of a die such as a T-die. (2) A method in which heating devices are attached to the die lip at regular intervals and the temperature is adjusted individually to utilize the temperature change in the viscosity of the molten resin to adjust the film thickness. (3) A method of adjusting the distance between the die and the casting roll to minimize the occurrence of film vibration or pulsation of the molten resin extruded into a film. (4) A method of blocking the air flow by installing a plate or cover to prevent pulsation caused by the flow of gas such as surrounding air when the molten resin extruded into a film contacts the casting roll. (5) A method for adjusting the discharge amount so that it does not fluctuate when extruding into a film (6) Method to reduce the rotational fluctuation rate of the cast roll and suppress the unevenness of the roll rotation (7) A method in which a high-voltage electrode is used to apply an electrostatic charge to the molten resin extruded into a film, causing it to adhere to a casting roll by electrostatic force (electrostatic adhesion method). (8) A method in which a curtain of compressed air is blown onto the molten resin extruded into a film, causing it to adhere to a casting roll. (9) A method in which the molten resin extruded into a film is adhered to a casting roll by a nip roll. etc.

[0110] When this member is used as a film, there are no particular restrictions on the film thickness, but it is usually 3 μm or more, preferably 6 μm or more, more preferably 9 μm or more, even more preferably 12 μm or more, even more preferably more than 15 μm, even more preferably 20 μm or more, particularly preferably 35 μm or more, particularly preferably 50 μm or more, and most preferably 60 μm or more. On the other hand, the film thickness is preferably 500 μm or less, more preferably 450 μm or less, even more preferably 400 μm or less, even more preferably 350 μm or less, particularly preferably 300 μm or less, particularly preferably 250 μm or less, and most preferably 200 μm or less. If the film thickness is within this range, it is neither too thin nor too thick, so it tends to have an excellent balance of mechanical properties, film formability, insulation properties, etc., and excellent secondary processability when combined with reinforcing fibers. The thickness of the film specifically refers to the average thickness measured by the method in the examples.

[0111] Furthermore, when the present member is a film, it may be a multilayer film in which other layers are laminated, as long as the effects of the present invention are not impaired. The multilayering method may be a known method such as coextrusion, extrusion lamination, thermal lamination, or dry lamination.

[0112] [Use and usage] Because this member has excellent durability, impact resistance, and productivity, it can be used as a composite material for resin and reinforcing fibers, especially reinforcing fibers with a number average fiber length of 5 mm or more. In particular, when this member is in the form of a film, it can be suitably used as a composite material for resin and reinforcing fibers with a number average fiber length of 5 mm or more.

[0113] The type of reinforcing fiber having a number average fiber length of 5 mm or more is not particularly limited, and examples thereof include inorganic fibers such as carbon fiber, glass fiber, boron fiber, and alumina fiber, organic fibers such as liquid crystal polymer fiber, polyethylene fiber, aramid fiber, and polyparaphenylenebenzoxazole fiber, and metal fibers such as aluminum fiber, magnesium fiber, titanium fiber, SUS fiber, copper fiber, and metal-coated carbon fiber. Among these, carbon fiber is preferred from the viewpoints of rigidity and light weight.

[0114] Carbon fibers include polyacrylonitrile (PAN)-based, petroleum / coal pitch-based, rayon-based, lignin-based, etc., and any of these carbon fibers can be used. In particular, PAN-based carbon fibers made from PAN as a raw material, strands or tows with 12,000 to 48,000 filaments, are preferred because of their excellent productivity and mechanical properties on an industrial scale.

[0115] The number-average fiber length is 5 mm or more, preferably 10 mm or more, more preferably 20 mm or more, more preferably 30 mm or more, particularly preferably 40 mm or more, and most preferably 50 mm or more. It is also preferable that the reinforcing fibers are continuous fibers. By setting the number-average fiber length to the above-mentioned lower limit or more, the mechanical properties of the resulting composite material tend to be sufficient. The upper limit of the number-average fiber length is not particularly limited, but when the reinforcing fibers are discontinuous fibers such as woven fabrics, knitted fabrics, and nonwoven fabrics as described below, the number-average fiber length is preferably 500 mm or less, more preferably 300 mm or less, and even more preferably 150 mm or less. Setting the number-average fiber length to the above-mentioned upper limit or less ensures sufficient filling of the reinforcing fibers into complex-shaped portions when molding final products, particularly final products with complex shapes, using the composite material, and tends to easily suppress the occurrence of a decrease in strength in those portions. The number-average fiber length of reinforcing fibers refers to the average length of the longest portion observed when the reinforcing fibers are observed using an electron microscope such as a scanning electron microscope or an optical microscope. Specifically, it can be determined by observing a cross section of the reinforcing fibers present in a composite material in which the longitudinal direction of the fibers can be observed, and then number-averaging the measured fiber lengths. Another method is to thin-film laminate a dispersion obtained by removing the resin components from reinforcing fibers using a solvent or the like and dispersing the dispersion in an appropriate dispersant, and then to obtain the number average fiber length using image processing software or the like using an image of the reinforcing fibers photographed with a scanner or the like.

[0116] The shape of the reinforcing fibers is not particularly limited, and can be appropriately selected as needed from fiber bundles such as chopped strands and rovings, woven fabrics such as plain weave and twill weave, knitted fabrics, nonwoven fabrics, fiber paper, and reinforcing fiber sheets such as UD materials (unidirectional materials).

[0117] There are no particular limitations on the method for combining the reinforcing fibers with the component, and composite materials such as prepregs in which the component is impregnated or semi-impregnated in a reinforcing fiber bundle or a reinforcing fiber sheet can be produced by employing conventionally known methods such as a resin film impregnation method (film stacking method), a mixed weaving method, a melting method, a solvent method, or a powder method such as a dry powder coating method or a powder suspension method. Among these, the resin film impregnation method (film stacking method) is preferably employed in the present invention.

[0118] Specifically, the component can be laminated on one or both sides of the aforementioned reinforcing fiber sheet and then heated and pressurized to melt and impregnate the resin component of the component into the reinforcing fiber sheet to form a prepreg. By adjusting the heating and pressurization conditions, a prepreg with a controlled amount of voids can be obtained. Prepregs can also be produced by temporarily bonding the component to the reinforcing fiber sheet by thermal fusion, omitting the pressurization step. Prepregs temporarily bonded in this manner, especially those containing a large number of voids, have the advantage of shortening the manufacturing time and reducing manufacturing costs, as well as being flexible and easily deformable to fit the actual shape. The above-mentioned method is particularly suitable for use when the component is a film.

[0119] This prepreg can be subjected to known processes such as autoclave molding, infusion molding, heat and cool press molding, stamping molding, and automated lamination molding using a robot to obtain a composite material product, and the molding conditions can be selected depending on the amount of voids contained. The film and other components used in prepreg production require secondary processability, such as the ability to impregnate reinforcing fiber sheets and heat sealability. This component contains polyaryletherketone, preferably polyetheretherketone, with a specific molecular weight distribution and mass average molecular weight, which provides moderately suppressed crystallinity and therefore excellent secondary processability. The resulting composite material also has excellent durability and impact resistance, making it particularly suitable for use.

[0120] From the viewpoints of elastic modulus and strength, the content of reinforcing fibers in the composite material obtained in this manner is preferably 20% by volume or more, more preferably 30% by volume or more, and even more preferably 40% by volume or more, while the content of reinforcing fibers in the composite material is preferably 90% by volume or less, more preferably 80% by volume or less, and even more preferably 70% by volume or less.

[0121] The composite material obtained by combining this member with reinforcing fibers has heat resistance, light weight, mechanical strength, etc., and can be suitably used in mobile objects such as aircraft, automobiles, ships, and railroad vehicles, as well as in sporting goods, home appliances, building materials, etc., and is particularly useful industrially as a component of mobile objects such as aircraft, automobiles, ships, and railroad vehicles.

[0122] The present invention also discloses a method for producing a film containing polyaryl ether ketone as a main resin component. In particular, when the polyaryl ether ketone is polyether ether ketone, the following production method can be suitably adopted. Specifically, this is a film manufacturing method in which a resin component with a molecular weight distribution of 2 or more but less than 4 and a mass average molecular weight of 63,000 or more is prepared, melt-kneaded in an extruder, the molten resin is extruded from a die, and the molten resin is cooled using a cast roll to form a film.The film after cooling is characterized by having a folding endurance of 5,000 or more times measured under conditions of a thickness of 100 μm, a bending angle of 135 degrees, a bending speed of 175 cpm, and a load of 9.8 N, and a puncture impact strength of 0.3 J or more at 23°C and 0.3 J or more at -20°C, measured under conditions of a thickness of 100 μm, a fixing frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s.

[0123] Furthermore, the present invention also discloses a method for producing a film in which the heat of crystalline fusion of the film after cooling is 30 J / g or more and 45 J / g or less.

[0124] In the above-mentioned production method, it is preferable that the polyaryl ether ketone, preferably the polyether ether ketone, has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 63,000 or more.

[0125] In order to produce a film having the above-mentioned folding endurance number and puncture impact strength, and preferably having a crystalline fusion heat of 30 J / g or more and 45 J / g or less, it is sufficient to appropriately adjust the selection of the polyaryl ether ketone used as the raw material, the conditions for extruding the film, etc., but in the present invention, it is preferable to adopt the following methods (1) to (4).

[0126] (1) The polyaryl ether ketone, preferably polyether ether ketone, used as a raw material has a molecular weight distribution of 2 or more but less than 4 and a mass average molecular weight of 63,000 or more. Other details such as the physical properties of the polyaryl ether ketone, preferably polyether ether ketone, are the same as those of the polyaryl ether ketone and polyether ether ketone used in the composite material member described above, and therefore a description thereof will be omitted here.

[0127] (2) Adjusting the melt-kneading temperature in the extruder. Specifically, the resin temperature at the extruder outlet is preferably 350°C or higher, more preferably 360°C or higher, even more preferably 370°C or higher, and particularly preferably 380°C or higher. By setting the resin temperature at the extruder outlet at or above the lower limit, not only are the pellets sufficiently melted and extrusion stabilized, but the pellet crystals are also sufficiently melted and less likely to remain in the film, which tends to improve the number of folding cycles and puncture impact strength, and also tends to result in an excellent appearance of the resulting film. On the other hand, the resin temperature at the extruder outlet is preferably 450°C or lower, more preferably 430°C or lower, and even more preferably 410°C or lower. By setting the resin temperature at the extruder outlet at or below the upper limit, the resin is less likely to decompose during melt molding and its molecular weight is more likely to be maintained, which tends to improve the number of folding cycles and puncture impact strength of the film.

[0128] (3) Adjusting the cooling conditions when cooling the molten resin to form a film. Cooling can be performed, for example, by using a cast roll as a cooler and bringing the extruded molten resin into contact with the cast roll. Specifically, it is preferable to adopt the following methods (3-1) and (3-2).

[0129] (3-1) Adjusting the temperature of the casting roll. Specifically, the temperature of the casting roll is preferably 30 to 150°C higher than the glass transition temperature of the polyaryletherketone, more preferably 35 to 140°C higher, and particularly preferably 40 to 135°C higher. More specifically, when the polyaryletherketone is polyetheretherketone, the temperature of the casting roll is preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher. On the other hand, the temperature of the casting roll is preferably 280°C or lower, more preferably 270°C or lower, even more preferably 260°C or lower, particularly preferably 250°C or lower, and most preferably 240°C or lower.

[0130] (3-2) Adjusting the time from when the molten resin is extruded from the die to when cooling begins. This time can be adjusted, for example, by the distance from the die to the casting roll. By shortening this distance, the time from when the molten resin is extruded to when cooling begins can be shortened, while by increasing this distance, the start of cooling can be delayed. This distance can be adjusted appropriately taking into account the resin temperature of the extruded molten resin, the temperature of the casting roll, etc., and is preferably 5 mm or more, more preferably 7 mm or more, and even more preferably 10 mm or more, and preferably 100 mm or less, more preferably 70 mm or less, and even more preferably 50 mm or less.

[0131] (4) When using a casting roll, the contact angle θ when the molten resin contacts the casting roll is adjusted. Instead of dropping the molten resin perpendicularly onto the contact point between the casting roll and the pressure roll, as shown in FIG. 1, the molten resin is dropped from the die slightly offset toward the center of the casting roll and contacted with the casting roll. This reduces problems such as waviness and wrinkles when the molten resin is cooled and formed into a film, making it easier to obtain a uniformly crystallized film. The contact angle θ is the angle formed by the line connecting the contact point between the pressure roll 3 and the casting roll 4 and the die, and the vertical line from the contact point (the dotted line in FIG. 1), as shown in FIG. 1. θ is preferably 1° or more, more preferably 2° or more, and even more preferably 3° or more. It is preferably 10° or less, more preferably 8° or less, and even more preferably 5° or less.

[0132] The film obtained by the production method of the present invention has excellent durability, impact resistance, and productivity, making it suitable as a composite material for resins and reinforcing fibers, particularly reinforcing fibers with a number-average fiber length of 5 mm or more. Furthermore, composite materials obtained by combining the film obtained by the production method of the present invention with reinforcing fibers are suitable for use in mobile objects such as aircraft, automobiles, ships, and railroad vehicles, as well as in sporting goods, home appliances, and building materials, due to their heat resistance, light weight, mechanical strength, and the like, and are particularly useful industrially as components for mobile objects such as aircraft, automobiles, ships, and railroad vehicles. Details of these features are common to those for the composite material members and composite materials described above, and therefore will not be described here. [Example]

[0133] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0134] 1. Film manufacturing In the examples and comparative examples, films were produced using polyether ether ketones as raw materials having the number average molecular weight (Mn), mass average molecular weight (Mw), molecular weight distribution (Mw / Mn), crystalline melting temperature (Tm), crystalline heat of fusion (ΔHm), and crystallization temperature (Tc) shown in Table 1.

[0135] (Examples 1 and 2 and Comparative Examples 1 to 6) The raw material pellets of polyether ether ketone listed in Table 1 were fed into a 40 mm diameter single-screw extruder, melted while kneading, extruded through a die, and then contacted and cooled on a casting roll (arithmetic mean roughness (Ra) 0.03 μm, maximum height roughness (Rz) 0.34 μm) to obtain a crystallized film with a thickness of 100 μm. The temperatures of the extruder, conduit, and die (T-die) were set to 380°C, the temperature of the casting roll was 210°C, and the lip clearance of the die lip was adjusted appropriately to produce a film. The resin temperature at the extruder outlet was 400°C. The obtained crystallized film with a thickness of 100 μm was evaluated for crystalline melting temperature, heat of crystalline melting, crystallization temperature, number of folding cycles, puncture impact strength, and roll contamination using the methods described below. In addition, a crystallized film having a thickness of 50 μm was separately prepared under the same conditions except for the thickness being 50 μm, and this film was evaluated for thickness accuracy, surface roughness, relative crystallinity, specific gravity, heat shrinkage rate, and heat shrinkage stress. The evaluation results are shown in Table 1.

[0136] 2. Evaluation of resin raw materials and films The resin raw materials used in the above Examples and Comparative Examples and the films obtained by the above methods were evaluated and measured for various items as follows: The "machine" of the film refers to the direction (MD) in which the film is extruded from the die (T-die), and the direction perpendicular to this in the plane of the film is called the "transverse" (TD).

[0137] (1) Molecular weight distribution (Mw / Mn), mass average molecular weight (Mw), number average molecular weight (Mn) The raw material resin pellets were measured using gel permeation chromatography (HLC-8320GPC (manufactured by Tosoh Corporation)) under the following conditions. Column: TSKgel guard column SuperH-H (4.6 mm I.D. x 3.5 cm) + TSKgel SuperHM-H (6.0 mm I.D. x 15 cm) x 2 (Tosoh Corporation) Eluent: pentafluorophenol / chloroform = 1 / 2 (mass ratio) Detector: differential refractometer, polarity=(+) ·Flow rate: 0.6mL / min Column temperature: 40℃ Sample concentration: 0.1% by mass Sample injection volume: 20 μL Calibration curve: Cubic approximation curve using standard polystyrene (Tosoh Corporation)

[0138] (2) Crystal melting temperature (Tm) The raw material resin pellets and the film obtained by the above-mentioned method were heated in the temperature range of 25 to 400°C at a heating rate of 10°C / min using a PerkinElmer differential scanning calorimeter "Pyris1 DSC" in accordance with JIS K7121:2012, and the melting peak was determined from the peak top temperature of the melting peak detected in the DSC curve.

[0139] (3) Heat of crystal fusion (ΔHm) The raw resin pellets and the film obtained by the above-mentioned method were heated in the temperature range of 25 to 400°C at a heating rate of 10°C / min using a PerkinElmer differential scanning calorimeter "Pyris1 DSC" in accordance with JIS K7122:2012, and the heat of crystalline fusion was calculated from the area of ​​the melting peak of the detected DSC curve.

[0140] (4) Crystallization temperature (Tc) The raw resin pellets and the film obtained by the above-mentioned method were cooled at a rate of 10°C / min in a temperature range of 400 to 25°C using a PerkinElmer differential scanning calorimeter "Pyris1 DSC" in accordance with JIS K7121:2012, and the crystallization peak was determined from the peak top temperature of the crystallization peak detected in the DSC curve.

[0141] (5) Number of folding times The number of folding times of the film obtained by the above method was measured in accordance with JIS P8115:2001 using an MIT folding fatigue tester manufactured by Toyo Seiki Seisaku-Sho, Ltd. under the conditions of a folding angle of 135 degrees, a folding speed of 175 cpm, and a measuring load of 9.8 N. The measurement was completed up to 10,000 times.

[0142] (6) Puncture impact strength The films obtained by the above method were measured using a Shimadzu Corporation high-speed puncture impact tester "Hydroshot HITS-P10" in accordance with JIS K7124-2:1999 under the following conditions: temperature environments of 23°C and -20°C, an inner diameter of the measurement sample fixing frame of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s.

[0143] (7) Roller soiling During film production, the extruder was operated for 1 hour, and then the contamination of the casting roll due to the accumulation of low molecular weight components was visually evaluated.

[0144] (8) Thickness accuracy Using a micrometer with a resolution of 1 μm, the thickness of the film obtained by the above method was measured at 30 points at 10 mm intervals in the longitudinal direction of the film (direction of resin flow: MD) at the center of the width direction. The thickness accuracy was calculated using the following formula 1 from the average and standard deviation of the measurement results obtained. [Formula 1] Thickness accuracy (%) = standard deviation (μm) / average value (μm) x 100

[0145] (9) Surface roughness (9-1) Arithmetic mean height (Sa), maximum height (Sz) The surface that came into contact with the casting roll during film production was measured using a BRUKER white light interference microscope "ContourGT-X" with an eyepiece magnification of 1.0x, an objective lens magnification of 20x, and a measurement area of ​​235 μm length x 313 μm width. After smoothing using a Gaussian function, the arithmetic mean height (Sa) and maximum height (Sz) were calculated.

[0146] (9-2) Arithmetic mean roughness (Ra), maximum height roughness (Rz) The surface that came into contact with the casting roll during film production was measured in the longitudinal direction of the film (direction of resin flow) using a contact surface roughness meter "Surf Coder ET4000A" manufactured by Kosaka Laboratory under the following conditions: stylus tip radius 0.5 mm, measurement length 8.0 mm, reference length 8.0 mm, cutoff value 0.8 mm, and measurement speed 0.2 mm / sec, and the arithmetic mean roughness (Ra) and maximum height roughness (Rz) were calculated.

[0147] (10) Relative crystallinity The film obtained by the above method was heated at a heating rate of 10°C / min using a PerkinElmer differential scanning calorimeter "Pyris1 DSC." The relative crystallinity was calculated from the heat quantity (J / g) of the crystalline melting peak and the heat quantity (J / g) of the recrystallization peak obtained at this time using the following formula 2. [Formula 2] Relative crystallinity (%) = {1-(ΔHc / ΔHm)} × 100 ΔHc: Heat energy (J / g) of the recrystallization peak of the film when the temperature is increased at 10°C / min ΔHm: Heat of crystal melting peak when film is heated at 10°C / min (J / g)

[0148] (11) Specific gravity The specific gravity of the film obtained by the above method was measured at a temperature of 23°C in accordance with JIS K7112:1999 (Method D).

[0149] (12) Heat shrinkage rate A test piece measuring 120 mm x 120 mm was cut out from the film obtained by the above method, and benchmark lines were marked at 100 mm intervals in the horizontal direction of the film. This test piece was left to stand in an environment of 200°C for 10 minutes, and the thickness was calculated from the distance between the benchmark lines before and after heating using the following equation 3. [Formula 3] Heat shrinkage rate (%) = [(gauge length before heating - gauge length after heating) / gauge length before heating] x 100

[0150] (13) Heat shrinkage stress A rectangular test piece 10 mm long and 3 mm wide was cut from the film obtained by the above method, and using a Hitachi High-Tech Science Corporation thermomechanical analyzer "TMA7100," one end of the test piece was set in the chuck of the load detector and the other end in the fixed chuck, and heated from room temperature (23°C) to 340°C at a heating rate of 5°C / min without applying a load, and the stress value at 145°C was measured. Measurements were made in both the longitudinal and transverse directions of the film, and the value in the direction with the largest stress value was taken as the heat shrinkage stress (mN). In this measurement method, a negative value for the heat shrinkage stress means that there is no heat shrinkage.

[0151] [Table 1]

[0152] In Examples 1 and 2, the molecular weight distribution of the resin component used was less than 4 and the mass average molecular weight was 63,000 or more, so even when the resulting film was completely crystallized, the degree of crystallization was kept low, and it was found that the durability (number of folding cycles) and impact resistance (puncture impact strength) were high. In addition, because the molecular weight distribution was narrow and the amount of low-molecular-weight substances contained was small, there was little contamination of the casting roll.

[0153] On the other hand, it was found that the durability (number of folding times) and impact resistance (puncture impact strength) were poor in Comparative Examples 1 to 4 because the mass average molecular weight of the resin component used was less than 63,000. Furthermore, in Comparative Example 4, the casting roll was heavily soiled. Furthermore, in Comparative Example 5, although the mass average molecular weight of the resin component used was 63,000 or more, the molecular weight distribution was broad, and therefore the impact resistance (puncture impact strength) at low temperatures was poor. It was found that Comparative Example 6 contained a large amount of low molecular weight substances with a wide molecular weight distribution, causing a large amount of staining on the casting roll. In the films of the examples and comparative examples, no exothermic peak associated with crystallization was observed during the DSC temperature rise process, and it was confirmed that the films were completely crystallized (relative crystallinity: 100%). [Explanation of symbols]

[0154] 1 die 2 nozzle 3 Crimping roll 4 Cast Roll 5 Film

Claims

1. A composite material member containing a resin component containing polyaryl ether ketone as a main component, characterized in that the resin component has a molecular weight distribution of 2 or more but less than 4 and a mass average molecular weight of 70,000 or more and 120,000 or less, and the composite material is a composite material containing a resin and reinforcing fibers having a number average fiber length of 5 mm or more.

2. 2. The composite material component according to claim 1, wherein the polyaryletherketone is polyetheretherketone.

3. 3. The composite material member according to claim 1, wherein the content of the polyaryl ether ketone in the resin component is more than 90 mass%.

4. The composite material member according to any one of claims 1 to 3, wherein the resin component has a mass average molecular weight of 115,000 or less.

5. The composite material member according to any one of claims 1 to 4, wherein the polyaryl ether ketone has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 70,000 or more and 120,000 or less.

6. The composite material member according to any one of claims 1 to 5, wherein the polyaryl ether ketone has a mass average molecular weight of 115,000 or less.

7. The composite material member according to any one of claims 1 to 6, wherein the heat of crystalline fusion is 30 J / g or more and 45 J / g or less.

8. The composite material member according to any one of claims 1 to 7, having a folding endurance of 5,000 or more times measured under conditions of a thickness of 100 µm, a bending angle of 135 degrees, a bending speed of 175 cpm, and a load of 9.8 N.

9. The composite material member according to any one of claims 1 to 8, wherein the puncture impact strength measured under the conditions of a thickness of 100 µm, 23 ° C, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / sec is 0.3 J or more.

10. The composite material member according to any one of claims 1 to 9, having a puncture impact strength of 0.3 J or more measured under the conditions of a thickness of 100 μm, -20 ° C, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / sec.

11. The composite material member according to any one of claims 1 to 10, having a thickness precision of 7% or less.

12. The composite material member according to any one of claims 1 to 11, wherein the arithmetic mean height of the surface on at least one side is 0.001 to 1 µm.

13. The composite material member according to any one of claims 1 to 12, wherein the maximum height of the surface on at least one side is 0.1 to 10 µm.

14. The composite material member according to any one of claims 1 to 13, wherein the arithmetic mean roughness of the surface on at least one side is 0.005 to 1 µm.

15. The composite material member according to any one of claims 1 to 14, wherein the maximum height roughness of the surface on at least one side is 0.05 to 5 µm.

16. The composite material member according to any one of claims 1 to 15, having a relative crystallinity of 50% or more.

17. The composite material member according to any one of claims 1 to 16, which is a film.

18. A composite material obtained by combining the composite material member according to any one of claims 1 to 17 with reinforcing fibers.

19. 20. The composite material of claim 18, which is a prepreg.

20. A mobile body, which is an aircraft, an automobile, a ship, or a railway vehicle, using the composite material according to claim 18 or 19.

21. A composite material member containing a resin component containing polyaryl ether ketone as a main component, wherein the resin component has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 70,000 or more and 120,000 or less, and the composite material member is a plate-shaped member.

22. 22. The composite component of claim 21, wherein the polyaryletherketone is polyetheretherketone.

23. The composite material member according to claim 21 or 22, wherein the plate-like member is a film.

24. A method for producing a film containing a resin component containing polyaryl ether ketone as a main component, the method comprising: preparing a resin component having a molecular weight distribution of 2 or more but less than 4 and a mass average molecular weight of 70,000 or more and 120,000 or less as the resin component; melt-kneading the resin component in an extruder; extruding the molten resin from a die; and cooling the molten resin with a cast roll to form a film; and ensuring that the cooled film has a folding endurance of 5,000 or more, as measured under conditions of a thickness of 100 μm, a bending angle of 135 degrees, a bending speed of 175 cpm, and a load of 9.8 N; and that the puncture impact strength at 23°C is 0.3 J or more, as measured under conditions of a thickness of 100 μm, a fixing frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m / s, and that the puncture impact strength at -20°C is 0.3 J or more.

25. The method for producing a film according to claim 24, wherein the polyaryl ether ketone has a molecular weight distribution of 2 or more and less than 4, and a mass average molecular weight of 70,000 or more and 120,000 or less.

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