JP7745824B2 - Composite material member, composite material, mobile body, and film manufacturing method - Google Patents

Description

The present invention relates to a composite material member made of polyaryl ether ketone that can be used in composite materials for electrical and electronic devices, automobiles, aircraft, etc., as well as a composite material and a mobile object that use this composite material member. The present invention also relates to a method for producing a film.

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 devices, automobiles, aircraft, and other applications due to their excellent heat resistance, mechanical properties, chemical resistance, and durability.

In particular, polyether ether ketone is used as a matrix material for fiber-reinforced materials due to its excellent heat resistance, mechanical properties, and chemical resistance. To fully utilize these properties, the resin must be crystallized, but if the degree of crystallization is too high, durability and impact resistance decrease, creating the problem of a decrease in these physical properties when used as a fiber-reinforced material.

Patent Document 1 discloses a composite material made of a polyether ether ketone matrix reinforced with fibers sized with polyethersulfone. Furthermore, Patent Document 2 discloses a fiber-reinforced thermoplastic resin prepreg made using a polyaryl ketone resin composition having a specific intrinsic viscosity.

Japanese Unexamined Patent Publication No. 115033/1983 JP 2019-147876 A

However, the inventors' investigations 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' investigations 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 components, and the resulting composite material components can have excessively high crystallinity, which can cause durability and impact resistance problems depending on the method of use. The inventors' investigations also revealed that in order to obtain a composite material with excellent durability, increasing the folding endurance (number of foldings) of components such as films used in the composite material can make it suitable for use in applications requiring high durability, such as those where repeated stress is applied.

The present invention was made under these circumstances, and its purpose is to provide composite material components and the like that have excellent durability and impact resistance, and are also highly manufacturable, while maintaining the inherent heat resistance of polyaryl ether ketone.

The present invention provides a composite material component, etc., that uses a polyaryl ether ketone having a specific molecular weight distribution and molecular weight as a means of solving the problems of the prior art.

That is, the present invention provides the following [1] to [25].

[1] 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 but less than 4, a mass average molecular weight of 63,000 or more, and the composite material contains a resin and reinforcing fibers having a number average fiber length of 5 mm or more.

[2] The composite material member described in [1], wherein the polyaryl ether ketone is polyether ether ketone.

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

[4] A 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.

[5] A 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 but less than 4 and a mass average molecular weight of 63,000 or more.

[6] A 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.

[7] A 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.

[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.

[9] A composite material member according to any one of [1] to [8], having a puncture impact strength of 0.3 J or greater 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.

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

[11] A composite material member according to any one of [1] to [10], having a thickness accuracy of 7% or less.

[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.

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

[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.

[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.

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

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

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

[19] The composite material described in [18], which is a prepreg.

[20] A mobile object such as an aircraft, automobile, ship, or railroad vehicle, using the composite material described in [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 but less than 4 and a mass average molecular weight of 63,000 or more, and the composite material member is a plate-shaped member.

[22] The composite material member according to [21], wherein the polyaryl ether ketone is polyether ether ketone.

[23] The composite material member according to [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, wherein the resin 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 melt-kneaded in an extruder, the molten resin is extruded from a die, and the molten resin is cooled with a cast roll to form a film. The cooled film has 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 fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m/s.

[25] The method for producing a film described in [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.

The present invention makes it possible to provide composite material components that are excellent in durability, impact resistance, and productivity, as well as composite materials and mobile objects that use such components.

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.

An example of an embodiment of the present invention is 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 invention.

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), it includes the meaning of "preferably smaller than Y" unless otherwise specified.

In the present invention, the term "main component" refers to the component that is most abundant in the target substance, and preferably accounts for 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.

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 but 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, 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.

<Resin component>
The resin component contained in the composite material member of the present invention is not particularly limited as long as it contains polyaryl ether ketone 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.

The molecular weight distribution of the resin component is 2 or greater, preferably 2.1 or greater, more preferably 2.2 or greater, even more preferably 2.5 or greater, particularly preferably 3 or greater, especially preferably 3.2 or greater, and most preferably 3.4 or greater. A molecular weight distribution above the lower limit mentioned above ensures a moderate mix of low-molecular-weight and high-molecular-weight components, achieving both excellent 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 a low proportion of low-molecular-weight components that can act as crystal nucleating agents. This keeps the degree of crystallization low even after crystallization, resulting in high durability and impact resistance. Furthermore, when producing films, if the raw materials contain a high content of low-molecular-weight components, they may adhere to the casting roll and transfer to the film, potentially damaging the film's appearance. A narrow molecular weight distribution and a low proportion of low-molecular-weight components prevent casting roll contamination and produce films with excellent appearance. Furthermore, when manufacturing composite materials with reinforcing fibers, there is no problem of contamination of manufacturing equipment due to volatilization of low molecular weight components, which is an advantage.

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. A mass average molecular weight above the lower limit indicated above provides excellent mechanical properties such as durability and impact resistance. 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, especially preferably 125,000 or less, especially preferably 120,000 or less, and most preferably 115,000 or less. If the mass average molecular weight is below the upper limit, the degree of crystallization, crystallization rate, and fluidity during melt molding tend to be excellent.

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 included, so long as the content of polyaryl ether ketone is within this range, it will be easy to impart the desired effects as appropriate while maintaining the effects of the present invention.

When blending other resin components with polyaryletherketone for the purpose of modifying it, the type of resin is not particularly limited, and examples include 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 polymers, and copolymers and mixtures thereof. Among these, polyphenylene sulfide, polyarylate, polyetherimide, polyamideimide, polysulfone, polyethersulfone, and liquid crystal polymers are preferred, with polyetherimide being particularly preferred, due to their similar molding temperatures to polyaryletherketone and their ability to suppress decomposition and crosslinking during melt molding. Polyaryletherketone and polyetherimide are highly compatible and blend at the molecular level, making it easy to improve the glass transition temperature of polyaryletherketone and control its crystallinity.

Furthermore, when polyether ether ketone is used as the polyaryl ether ketone, other resin components that can be blended for the purpose of modifying it can be the same as the resins used for modifying the polyaryl ether ketone described above. However, it is also preferable to use polyaryl ether ketones other than polyether ether ketone, such as polyether ketone, polyether ketone ketone, polyether ketone ether ketone ketone, and polyether ether ketone ketone, in combination with polyether ether ketone.

[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.

The molecular weight distribution of polyaryl ether ketone is preferably 2 or greater, more preferably 2.1 or greater, even more preferably 2.2 or greater, even more preferably 2.5 or greater, particularly preferably 3 or greater, especially preferably 3.2 or greater, and most preferably 3.4 or greater. A molecular weight distribution above the lower limit mentioned above facilitates the balancing of fluidity and mechanical properties due to the appropriate content of low and high molecular weight components. On the other hand, the molecular weight distribution of 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, which reduces the degree of crystallization even after crystallization, 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 making it easier to produce films with excellent appearance. Furthermore, when producing composite materials with reinforcing fibers, there is also the advantage that the problem of contamination of production equipment due to volatilization of low molecular weight components is less likely to occur.

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. When the mass average molecular weight of the polyaryl ether ketone is above the lower limit, it tends to exhibit excellent mechanical properties such as durability and impact resistance. 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, especially 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, crystallization rate, and fluidity during melt molding tend to be excellent.

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.

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

In the general formula (1), the arylene groups of Ar ¹ to Ar ³ may be different from one another, but are preferably the same. Specific examples of the arylene groups of Ar ¹ to Ar ³ include phenylene groups and biphenylene groups. Of these, phenylene groups are preferred, and p-phenylene groups are more preferred.

Examples of substituents that the arylene groups Ar ¹ to Ar ³ may have include alkyl groups having 1 to 20 carbon atoms, such as a methyl group or an ethyl group, and alkoxy groups having 1 to 20 carbon atoms, such as a methoxy group or an ethoxy group. When Ar ¹ to Ar ³ have substituents, there are no particular restrictions on the number of the substituents.

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

The molecular weight distribution of polyether ether ketone is preferably 2 or greater, more preferably 2.1 or greater, even more preferably 2.2 or greater, even more preferably 2.5 or greater, particularly preferably 3 or greater, especially preferably 3.2 or greater, and most preferably 3.4 or greater. A molecular weight distribution above the lower limit mentioned above facilitates achieving both excellent fluidity and mechanical properties due to the appropriate content of low and high molecular weight components. 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, which reduces the degree of crystallization upon crystallization and tends to result in high durability and impact resistance. Furthermore, when producing films, if the raw materials contain a large amount of low molecular weight components, these low molecular weight components may adhere to the casting roll and transfer 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 making it easier to produce films with excellent appearance. Furthermore, when producing composite materials with reinforcing fibers, there is also the advantage that the problem of contamination of production equipment due to volatilization of low molecular weight components is less likely to occur.

The weight 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 weight average molecular weight of the polyether ether ketone is at or above the lower limit, it tends to exhibit excellent mechanical properties such as durability and impact resistance. On the other hand, the weight 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, especially 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, crystallization rate, and fluidity during melt molding tend to be excellent.

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) Obtaining 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 and dissolve at 100°C for 60 minutes.
(4) Next, remove from the heat block, allow to cool, and then slowly add 6 g of room temperature (approximately 23°C) chloroform little by little and shake gently to mix.
(5) Thereafter, the sample obtained by filtering through a 0.45 μm PTFE (polytetrafluoroethylene) cartridge filter is subjected to gel permeation chromatography to measure the number average molecular weight (Mn), mass average molecular weight (Mw), and molecular weight distribution (Mw/Mn).

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 component 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 composite material component tends to have excellent fluidity during melt molding, such as when producing the composite material component.

The crystalline melting temperature of polyaryl ether ketone, particularly polyether ether ketone, can be determined in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, PerkinElmer's "Pyris1 DSC") in a 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 on the detected DSC curve.

The heat of crystalline fusion of polyaryletherketone, particularly polyetheretherketone, 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 polyaryletherketone is above 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 polyaryletherketone, particularly polyetheretherketone, 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 polyaryletherketone is below 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.

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, PerkinElmer's "Pyris1 DSC") in a temperature range of 25 to 400°C at a heating rate of 10°C/min, and from the area of the melting peak on the detected DSC curve.

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 above the above-mentioned 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 above the glass transition temperature and below 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 above the above-mentioned 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 tends to improve the appearance of the film.

On the other hand, the crystallization temperature of polyaryl ether ketone, and particularly polyether ether ketone, 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 is below the upper limit, crystallization will not be too rapid, resulting in less uneven cooling during molding of composite material components such as films, and tending to produce uniformly crystallized, high-quality composite material components.

The crystallization temperature of polyaryl ether ketone, particularly polyether ether ketone, during the cooling process can be determined in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, a "Pyris1 DSC" manufactured by PerkinElmer) 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.

The method for producing polyaryl ether ketones, particularly polyether ether ketones, 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 not particularly limited, and they can be produced by known methods. During production, conditions for achieving the desired molecular weight distribution and mass average molecular weight can be appropriately selected and adopted. Specific examples include adjusting the type, amount, and concentration of the monomers, polymerization initiators, catalysts, and chain transfer agents (if added as needed) charged during polymerization, as well as the method of adding each of these, 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 used.

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

This member may contain various additives such as heat stabilizers, antioxidants, UV 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.

The proportion of the resin component, particularly polyaryletherketone, preferably polyetheretherketone, in the component 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. If the proportion of the resin component, particularly polyaryletherketone, preferably polyetheretherketone, in the component is at or above the lower limit, the component 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, if 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. If the proportion of the resin components contained in this member, particularly polyaryl ether ketone, and preferably polyether ether ketone, is below the upper limit stated above, the effects of additives, fillers, etc., which may also be contained, are more likely to be fully exerted.

This member may be in a completely uncrystallized state or in a crystalline state. Depending on the purpose, the crystallinity can be adjusted appropriately using known techniques during the manufacturing process. Generally, a material has excellent toughness in an uncrystallized state, while a material has excellent heat resistance and rigidity in a crystalline state. For applications requiring higher functionality such as heat resistance and rigidity, a completely crystallized state is preferable. "Completely crystallized" means that no exothermic peak associated with crystallization is observed during the heating process in differential scanning calorimetry (DSC).

[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.

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

[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.

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") at a temperature range of 25 to 400°C and 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.

[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, the crystallization rate is high, the cycle for producing a composite material with reinforcing fibers can be shortened, and productivity tends to be excellent.

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 this component is below the upper limit mentioned above, crystallization will not be too rapid, which will reduce uneven cooling during the production of a composite material with reinforcing fibers and tend to result in a uniformly crystallized, high-quality composite material. In addition, this also makes it easier to fully impregnate the component into the reinforcing fibers during the production of a composite material with reinforcing fibers, which has the advantage that the resulting composite material is more likely to be uniformly crystallized and high-quality.

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 over a 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.

[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 less susceptible 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.

[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.

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 at least 0.3 J, more preferably at least 0.4 J, and even more preferably at least 0.5 J. 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 breakage 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 this member is 1 mm or more, it may be measured under similar conditions with reference to JIS K7211-2:2006.

[Thickness accuracy]
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 accuracy of the component is preferably 7% or less, more preferably 5% or less, even more preferably 4% or less, particularly preferably 3% or less, particularly preferably 2.5% or less, and most preferably 2% or less. When the thickness accuracy 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 accuracy 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) × 100

[Surface roughness]
When the present member has a thin, flat shape such as a film, sheet, or plate, with a thickness that is extremely small compared to its length and width, it is preferable that the surface roughness of at least one surface (single surface) 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 surface of the present member be within the specific ranges described below. It is also preferable that the surface roughness of both surfaces of the present member be within the specific ranges described below.

[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 being generated when the film is unwound due to static electricity accumulated on the film roll or the like, 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 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. 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.

[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, the film is less likely to meander or become skewed during lamination with a reinforcing fiber sheet or the like during the production of a composite material such as a prepreg. This reduces the slipperiness of the film when unwound from a film roll or the like, resulting in a composite material with excellent processability. Furthermore, problems such as sparks being generated when the film is unwound due to static electricity accumulated on the film roll or the like, 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, the variation in the reinforcing fiber content in the resulting composite material when combined with reinforcing fibers is likely to be reduced. 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. Another advantage is that the film is less likely to slip, shift, twist, wrinkle, or other problems when conveyed from the film roll or the like during unwinding.
The maximum height (Sz) can be measured using a white light interference microscope, specifically by the method described in the examples below.

[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 when unwinding the film due to static electricity accumulated on the film roll or the like, 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 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. 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.

[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 variation in the reinforcing fiber content in the resulting composite material is likely to be reduced. In other words, the variation in mechanical properties such as strength between different parts of the composite material is reduced, 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.

[Relative Crystallinity]
The relative crystallinity of the present member 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 present member is equal to or greater than the lower limit, it becomes easier to suppress thermal shrinkage when the present member and reinforcing fibers are thermocompressed to form a composite material, and the heat resistance and rigidity can be improved.
The relative crystallinity can be calculated 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, and the calorific value (J/g) of the crystal melting peak and the calorific value (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 quantity (J/g) of the recrystallization peak of the present material under a temperature increase condition of 10 ° C./min
ΔHm: Heat quantity (J/g) of the crystal melting peak of this material under the temperature rising condition of 10 ° C./min

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

[specific gravity]
The specific gravity of the present member is preferably 1.27 or more, more preferably 1.28 or more. There is a correlation between the relative crystallinity and the specific gravity, and typically, the higher the relative crystallinity, the higher the specific gravity. Therefore, if the specific gravity is equal to or greater than the lower limit, shrinkage due to heat tends to be suppressed when the present member and the 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. On the other hand, the specific gravity of the present member is preferably 1.35 or less, more preferably 1.34 or less.
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).

[Heat shrinkage rate]
The heat shrinkage of the present 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 the present member and the reinforcing fibers are thermocompressed 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 the present 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 120 mm × 120 mm test piece from the film or other form of this member, marking lines at 100 mm intervals in the direction (TD) perpendicular to the direction of resin flow (MD), leaving this test piece at rest in a 200°C environment for 10 minutes, and then using the distance between the marks before and after heating, according to the following formula 3.
[Formula 3]
Heat shrinkage rate (%) = [(gauge line distance before heating - gauge line distance after heating) / gauge line distance before heating] x 100

[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 it 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, and 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 flow direction of the resin (MD) and the direction perpendicular thereto (TD), and the larger stress value is taken as the heat shrinkage stress of the present invention.

The shape of the member is not particularly limited and may be any shape, such as a film, plate, fiber, bottle, tube, rod, powder, or pellet. However, a film, plate, or fiber is preferred, a film or plate is more preferred, and a film is even more preferred. 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, 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.

In the present invention, film is considered to encompass sheets. Generally, a film is a thin, flat product that is extremely thin compared to its length and width, with an arbitrarily limited maximum thickness, and is usually supplied in roll form (Japanese Industrial Standards JIS K6900:1994). Generally, a sheet, as defined in JIS, is 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 is considered to encompass sheets. Therefore, "film" can also be "sheet."

<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 by a stretching roll at a stretching ratio of less than 2 times.

Unstretched films 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 perspective of productivity, however, 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 maintaining the resin temperature at or above the lower limit, crystals from 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 maintaining 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.

Cooling can be performed, 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 degree of 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.

The crystallization rate of polymeric 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 crystal nucleation rate and growth rate. When producing a film with a high relative degree of 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.

On the other hand, when producing a film that is not completely crystallized, it is important to rapidly cool the material from a molten state to below the glass transition temperature in one go, reducing molecular mobility to a range where crystals cannot grow. In this case, the cooling temperature (e.g., 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, and 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, it is easy to obtain a film with a good appearance that is free from wrinkles and sticking due to rapid cooling.

The glass transition temperature is the value measured in accordance with JIS K7121:2012 using a differential scanning calorimeter (for example, PerkinElmer's "Pyris1 DSC") at a temperature range of 25 to 400°C and a heating rate of 10°C/min. Furthermore, if a mixture of multiple resins has multiple glass transition temperatures, the highest glass transition temperature should be considered the glass transition temperature of the resin component, and the cooling temperature should be adjusted accordingly.

To achieve the desired relative crystallinity of the component, for example, if the component is a film, it is preferable to use extrusion molding and appropriately adjust the conditions for extruding the film. However, in the present invention, it is more preferable to use the following methods (1) to (4). These methods may be used in combination. Of these, method (1) is preferred, as it is less likely to cause wrinkles in the resulting composite material and consumes less energy.

(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.

An example of such a method is to set the cooling temperature 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 the above 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 a 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.

(2) A method of reheating the film using a heating roll. Specifically, this method involves heating using a roll separate from the cast roll of a longitudinal stretching machine or the like. The heating temperature is preferably in the same range as the cooling temperature described above in (1).

(3) A method of reheating the film in an oven. Specific examples include a method of passing the film through a drying device such as a floating dryer, tenter, or band dryer and heating it with hot air. The heating temperature is preferably in the same range as the cooling temperature described above in (1).

(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 heating temperature is preferably in the same range as the cooling temperature described above in (1).

The above processes (2) to (4) may be carried out simultaneously with film production by installing dedicated equipment within the film production line, or the film may be wound into a roll and then these processes may be carried out on the film roll using equipment outside the production line.

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 embossing roll transfer, embossing belt transfer, and embossing 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, as this method allows for continuous, uniform adjustment of 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.

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 of attaching heating devices to the die lip at regular intervals and individually adjusting the temperature of these devices to adjust the film thickness by utilizing the temperature change of the viscosity of the molten resin. (3) A method of adjusting the distance between the die and the casting roll to minimize the occurrence of membrane vibration and pulsation of the molten resin extruded into a film. (4) A method of installing a plate or cover to block the air flow so that the molten resin extruded into a film does not pulsate due to the flow of gas such as surrounding air when it contacts the casting roll. (5) A method of adjusting to prevent fluctuations in the discharge volume when extruding into a film. (6) A method of reducing the rotation fluctuation rate of the casting roll to suppress uneven rotation of the roll. (7) A method of applying an electrostatic charge to the molten resin extruded into a film from an electrode to which a high voltage is applied, and adhering it to the 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 to adhere it to a casting roll; (9) A method in which the molten resin extruded into a film is adhered to a casting roll using a nip roll.

When this member is used as a film, there are no particular restrictions on the thickness of the film, 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 thickness of the film 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.

Furthermore, when the member is a film, it can be made into a multilayer film by laminating other layers to the extent that the effects of the present invention are not impaired. Known methods for multilayering, such as coextrusion, extrusion lamination, thermal lamination, and dry lamination, can be used.

[Use and mode of use]
The present member is excellent in durability, impact resistance, and productivity, and can therefore be used as a composite material for resin and reinforcing fiber, particularly reinforcing fiber having a number average fiber length of 5 mm or more. In particular, when the present member is a film, it can be suitably used as a composite material for resin and reinforcing fiber having a number average fiber length of 5 mm or more.

The type of reinforcing fiber having a number average fiber length of 5 mm or more is not particularly limited, but examples 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. Of these, carbon fiber is preferred from the standpoint of rigidity and light weight.

Carbon fibers include polyacrylonitrile (PAN), petroleum/coal pitch, rayon, and lignin-based fibers, and any of these can be used. PAN-based carbon fibers made from PAN, particularly strands or tows with 12,000 to 48,000 filaments, are preferred due to their superior productivity and mechanical properties on an industrial scale.

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 shape of the reinforcing fibers is discontinuous, such as a woven fabric, knitted fabric, or nonwoven fabric, 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 a final product, particularly a final product with a complex shape, 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.

The shape of the reinforcing fibers is not particularly limited, and can be appropriately selected as needed from among fiber bundles such as chopped strands and roving, 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).

There are no particular restrictions on the method for combining the reinforcing fibers with the component. Conventional methods, such as resin film impregnation (film stacking), mixed weaving, melting, solvent coating, and powder methods such as dry powder coating and powder suspension, can be used to produce composite materials such as prepregs in which the component is impregnated or semi-impregnated into reinforcing fiber bundles or reinforcing fiber sheets. Among these, the resin film impregnation (film stacking) method is preferably used in the present invention.

Specifically, the component can be layered 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, producing a prepreg. By adjusting the heating and pressurizing 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 pressurizing step. Prepregs temporarily bonded in this manner, especially those containing many 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.

Composite material products can be obtained by subjecting this prepreg to known processes such as autoclave molding, infusion molding, heat and cool press molding, stamping molding, and automated lamination molding using a robot, with molding conditions 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 seal. This component contains polyaryl ether ketone, preferably polyether ether ketone, with a specific molecular weight distribution and mass average molecular weight, which provides moderately suppressed crystallinity, resulting in excellent secondary processability. The resulting composite material also exhibits excellent durability and impact resistance, making it particularly suitable for use.

From the standpoint 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. On the other hand, 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.

The composite material obtained by combining this member with reinforcing fibers is 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 its heat resistance, light weight, and mechanical strength. It is particularly useful industrially as a component for mobile objects such as aircraft, automobiles, ships, and railroad vehicles.

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 method for producing a film, characterized in that 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 is prepared, melt-kneaded in an extruder, the molten resin is extruded from a die, and the molten resin is cooled with a cast roll to form a film, and 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 a puncture impact strength of 0.3 J or more at 23°C and 0.3 J or more as measured under conditions of a thickness of 100 μm, a fixed frame inner diameter of 50 mm, a punching striker diameter of 12.7 mm, and a test speed of 3 m/s.

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

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

To produce a film that has the above-mentioned folding endurance and puncture impact strength, and preferably has a crystalline heat of fusion of 30 J/g or more and 45 J/g or less, it is sufficient to appropriately select the polyaryl ether ketone used as the raw material and adjust the conditions for extruding the film. However, in the present invention, it is preferable to adopt the following methods (1) to (4).

(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 members described above, and therefore will not be described here.

(2) Adjust 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 for 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.

(3) Adjust 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).

(3-1) Adjust 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.

(3-2) Adjust the time from when the molten resin is extruded from the die until 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 until cooling begins can be shortened, while by increasing this distance, the start of cooling can be delayed. The distance can be adjusted appropriately taking into account the resin temperature of the extruded molten resin, the temperature of the casting roll, etc., but the distance 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.

(4) When using a casting roll, adjust the contact angle θ when the molten resin contacts the casting roll. Instead of dropping the molten resin perpendicularly onto the contact point between the casting roll and the pressure roll, as shown in Figure 1, drop the molten resin from the die slightly offset toward the center of the casting roll and contact 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. Note that the contact angle θ refers to 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 Figure 1), as shown in Figure 1. θ is preferably 1° or more, more preferably 2° or more, even more preferably 3° or more, and preferably 10° or less, more preferably 8° or less, and even more preferably 5° or less.

The film obtained by the manufacturing 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 reinforcing fibers with films obtained by the manufacturing method of the present invention have heat resistance, light weight, mechanical strength, and other properties that make them suitable for use in mobile objects such as aircraft, automobiles, ships, and railroad vehicles, as well as sporting goods, home appliances, and building materials. They are particularly useful industrially as components for mobile objects such as aircraft, automobiles, ships, and railroad vehicles. Details of these points are common to those for the composite material members and composite materials described above, so a detailed explanation will be omitted here.

The present invention will be described in detail below using examples, but the present invention is not limited thereto.

1. Production of Films In the examples and comparative examples, films were produced using polyether ether ketones 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 as raw materials.

(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 Φ40 mm single-screw extruder, melted while kneading, extruded from a die, and adhered to a cast roll (arithmetic mean roughness (Ra) 0.03 μm, maximum height roughness (Rz) 0.34 μm) and cooled to obtain a crystallized film with a thickness of 100 μm. The temperature of the extruder, conduit, and die (T-die) was 380 ° C., the temperature of the cast roll was 210 ° C., and the lip clearance of the die lip was appropriately adjusted 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 endurance 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 that the thickness was 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.

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. Note that the "machine direction" 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 direction" (TD).

(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 Super H-H (4.6 mm ID x 3.5 cm) + TSKgel Super HM-H (6.0 mm ID x 15 cm) x 2 (manufactured by Tosoh Corporation)
Eluent: pentafluorophenol/chloroform = 1/2 (mass ratio)
Detector: differential refractometer, polarity = (+)
Flow rate: 0.6 mL/min Column temperature: 40°C
Sample concentration: 0.1% by mass
Sample injection volume: 20 μL
Calibration curve: Cubic approximation curve using standard polystyrene (manufactured by Tosoh Corporation)

(2) Crystalline 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 differential scanning calorimeter "Pyris1 DSC" manufactured by PerkinElmer in accordance with JIS K7121:2012, and the melting peak was determined from the peak top temperature of the melting peak of the detected DSC curve.

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

(4) Crystallization temperature (Tc)
The raw material resin pellets and the film obtained by the above-mentioned method were cooled in the temperature range of 400 to 25°C at a rate of 10°C/min using a differential scanning calorimeter "Pyris1 DSC" manufactured by PerkinElmer 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.

(5) Folding Endurance Number of Times The film obtained by the above method was measured for folding endurance number of times in accordance with JIS P8115:2001 using an MIT folding endurance 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.

(6) Puncture Impact Strength The film obtained by the above method was measured using a high-speed puncture impact tester "Hydroshot HITS-P10" manufactured by Shimadzu Corporation, in accordance with JIS K7124-2:1999, under conditions of a temperature environment 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.

(7) Roll Contamination 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 and the like was visually evaluated.

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

(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 "Contour GT-X" under the conditions of an eyepiece magnification of 1.0, an objective lens magnification of 20, and a measurement area of 235 μm length × 313 μm width. After smoothing using a Gaussian function, the arithmetic mean height (Sa) and maximum height (Sz) were calculated.

(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.

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

(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).

(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 lateral direction of the film. This test piece was left to stand in an environment of 200°C for 10 minutes, and the heat shrinkage rate was calculated from the distance between the benchmark lines before and after heating using the following formula 3.
[Formula 3]
Heat shrinkage rate (%) = [(gauge line distance before heating - gauge line distance after heating) / gauge line distance before heating] x 100

(13) Heat shrinkage stress A rectangular test piece 10 mm long and 3 mm wide was cut out from the film obtained by the above method, and using a thermomechanical analyzer "TMA7100" manufactured by Hitachi High-Tech Science Corporation, one end of the test piece was set in the chuck of a load detector and the other end in a fixed chuck, and the test piece was 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 larger 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.

In Examples 1 and 2, the molecular weight distribution of the resin components used was less than 4 and the mass average molecular weight was 63,000 or greater. Therefore, even when the resulting film was completely crystallized, the degree of crystallinity was kept low, and it was found to have high durability (number of folding cycles) and impact resistance (puncture impact strength). Furthermore, because the molecular weight distribution was narrow and there was little low molecular weight material, there was little contamination of the casting roll.

On the other hand, in Comparative Examples 1 to 4, the mass average molecular weight of the resin component used was less than 63,000, so it was found that the durability (number of folding times) and impact resistance (puncture impact strength) were poor. Also, in Comparative Example 4, the casting roll was heavily soiled.
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, and therefore the cast roll was heavily soiled.
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%).

1 Die 2 Die 3 Pressing roll 4 Cast roll 5 Film

Claims (25)

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. The composite material component according to claim 1, wherein the polyaryletherketone is polyetheretherketone. The composite material member according to claim 1 or 2, wherein the content of polyaryl ether ketone in the resin component is greater than 90% by mass. 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. 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 . 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. A composite material member according to any one of claims 1 to 6, having a crystalline fusion heat of 30 J/g or more and 45 J/g or less. A composite material member according to any one of claims 1 to 7, having 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. A composite material member according to any one of claims 1 to 8, having a puncture impact strength of 0.3 J or greater when 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. A composite material member according to any one of claims 1 to 9, having a puncture impact strength of 0.3 J or greater when measured under the following conditions: thickness 100 μm, -20°C, fixed frame inner diameter 50 mm, punching striker diameter 12.7 mm, and test speed 3 m/s. A composite material member according to any one of claims 1 to 10, having a thickness accuracy of 7% or less. A 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. A composite material member according to any one of claims 1 to 12, wherein the maximum surface height on at least one side is 0.1 to 10 μm. A 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. A 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. A composite material member according to any one of claims 1 to 15, having a relative crystallinity of 50% or more. The composite material member according to any one of claims 1 to 16, which is a film. A composite material obtained by combining the composite material member according to any one of claims 1 to 17 with reinforcing fibers. The composite material described in claim 18, which is a prepreg. A mobile object such as an aircraft, automobile, ship, or railroad vehicle, using the composite material described in claim 18 or 19. 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 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. The composite material component according to claim 21, wherein the polyaryletherketone is polyetheretherketone. The composite material member according to claim 21 or 22, wherein the plate-like member is a film. 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. 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 .