JP2021191834A - Fiber-reinforced plastic member, composite material, and mobile body - Google Patents

Abstract

To provide a fiber-reinforced plastic member that is excellent in heating dimensional stability, productivity, and rigidity.SOLUTION: A fiber-reinforced plastic member contains, as a resin component, a crystalline resin. The resin component has a molecular weight distribution of 3.3 or more and a mass average molecular weight of less than 87000. The fiber-reinforced plastic member has a relative crystallinity of 50% or more when measured with a differential scanning calorimeter.SELECTED DRAWING: None

Description

The present invention relates to a fiber-reinforced plastic member that can be suitably used for a composite material, a composite material obtained by combining the fiber-reinforced plastic member and the reinforcing fiber, and a moving body using the composite material. ..

Fiber reinforced plastic, which is one of the fiber reinforced composite materials, is lightweight, has high strength, and has high rigidity, so that it is widely used from sports / leisure applications to industrial applications such as automobiles and aircraft.
As a method for producing a fiber reinforced plastic, there is a method of using an intermediate material, that is, a prepreg, in which a reinforcing material made of long fibers (continuous fibers) such as reinforced fibers is impregnated with a matrix resin. According to this method, there is an advantage that the content of the reinforced fiber of the fiber reinforced plastic can be easily controlled and the content can be designed to be high. , A molded product can be obtained.

As the matrix resin, super engineering plastics have been widely adopted because they are excellent in heat resistance, mechanical properties, chemical resistance, durability and the like.

For example, Patent Document 1 discloses a composite material in which a polyetheretherketone is used as a matrix resin and a fiber sized by a polyether sulfone is used as a reinforcing material. Further, Patent Document 2 discloses a fiber-reinforced thermoplastic resin prepreg using a polyarylketone resin composition having a specific intrinsic viscosity.

Japanese Unexamined Patent Publication No. 62-115033 Japanese Unexamined Patent Publication No. 2019-147876

However, in the disclosed techniques of Patent Documents 1 and 2, in the step of heat-pressing a film-shaped matrix resin and a reinforcing fiber by, for example, roll-to-roll to form a composite material, the film undergoes a dimensional change due to heat, depending on the conditions. Wrinkles may occur in the obtained composite material, and further improvement is required. Further, the disclosed techniques of Patent Documents 1 and 2 may have low productivity due to low impregnation of the matrix resin in the reinforcing fibers or a long cycle during the production of the composite material depending on the conditions, and may have low rigidity. It was clarified by the studies by the present inventors that there is room for further improvement in this respect as well.

Therefore, it is an object of the present invention to provide a member for fiber reinforced plastic having excellent thermal dimensional stability, productivity, and rigidity under such a background.

As a result of diligent studies on the above-mentioned problems, the present inventors can solve the above-mentioned problems by increasing the relative crystallinity of the fiber reinforced plastic member by using a resin component having a specific molecular weight distribution and mass average molecular weight. And completed the present invention.

That is, the present invention provides the following [1] to [18].

[1] A member for fiber reinforced plastic containing a crystalline resin as a resin component, wherein the resin component has a molecular weight distribution of 3.3 or more and a mass average molecular weight of less than 87,000, and can be obtained by using a differential scanning calorimeter. A member for fiber reinforced plastic having a relative crystallinity of 50% or more.

[2] The fiber-reinforced plastic member according to [1], wherein the resin component contains a polyaryletherketone.

[3] The fiber-reinforced plastic member according to [2], wherein the polyaryletherketone has a molecular weight distribution of 3.3 or more and a mass average molecular weight of less than 87,000.

[4] The fiber-reinforced plastic member according to any one of [1] to [3], wherein the fiber-reinforced plastic member has a specific gravity of 1.27 or more.

[5] The fiber-reinforced plastic member according to any one of [1] to [4], wherein the fiber-reinforced plastic member has a heat shrinkage rate of 2.2% or less.

[6] The fiber reinforced plastic member according to any one of [1] to [5], wherein the heat shrinkage stress of the fiber reinforced plastic member is 1 mN or less.

[7] The fiber-reinforced plastic member according to any one of [1] to [6], wherein the fiber-reinforced plastic member has a tensile elastic modulus of 3500 MPa or more measured under the condition of a tensile speed of 5 mm / min.

[8] The fiber-reinforced plastic member according to any one of [1] to [7], wherein the fiber-reinforced plastic member has a crystallization temperature of 296 ° C. or higher.

[9] The fiber-reinforced plastic member according to any one of [1] to [8], wherein the fiber-reinforced plastic member has a thickness of 10 to 100 μm.

[10] The fiber-reinforced plastic member according to any one of [1] to [9], wherein the fiber-reinforced plastic member has a thickness accuracy of 7% or less.

[11] The fiber-reinforced plastic member according to any one of [1] to [10], wherein the arithmetic average height of the surface of the fiber-reinforced plastic member on at least one surface is 0.001 to 1 μm.

[12] The fiber-reinforced plastic member according to any one of [1] to [11], wherein the maximum height of the surface of the fiber-reinforced plastic member on at least one surface is 0.1 to 10 μm.

[13] The fiber-reinforced plastic member according to any one of [1] to [12], wherein the arithmetic average roughness of the surface of the fiber-reinforced plastic member on at least one surface is 0.005 to 1 μm.

[14] The fiber-reinforced plastic member according to any one of [1] to [13], wherein the maximum height roughness of the surface of the fiber-reinforced plastic member on at least one surface is 0.05 to 5 μm.

[15] The fiber-reinforced plastic member according to any one of [1] to [14], which is a film.

[16] A composite material obtained by combining the fiber-reinforced plastic member according to any one of [1] to [15] and the reinforcing fiber.

[17] The composite material according to [16], which is a prepreg.

[18] A moving body that is an aircraft, automobile, ship, or railroad vehicle using the composite material according to [16] or [17].

According to the present invention, it is possible to obtain a member for fiber reinforced plastic having excellent heating dimensional stability, productivity and rigidity.

Hereinafter, an example of the embodiment of the present invention will be described, but the present invention is not limited to the embodiment described below as long as the gist thereof is not exceeded.

In the present invention, when expressed as "X to Y" (X and Y are arbitrary numbers), it means "X or more and Y or less", as well as "greater than X" and "less than Y" unless otherwise specified. It includes the meaning of ".

Further, in the present invention, the film includes a sheet. Generally, a film is a thin, flat product whose thickness is extremely small compared to its length and width, and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standards). JIS K6900: 1994), a sheet generally refers to a product that is thin by definition in JIS and whose thickness is generally small for its length and width and is flat. However, since the boundary between the sheet and the film is not clear, the film includes the sheet in the present invention. Therefore, the "film" may be a "sheet".

The resin component contained in the fiber-reinforced plastic member of the present invention (hereinafter, may be referred to as "this member" or "FRP member") contains a crystalline resin and has a specific molecular weight distribution and mass average molecular weight. It is a thing. Hereinafter, the resin component will be described.

<Resin component>
The molecular weight distribution of the resin component is 3.3 or more, more preferably 3.5 or more, particularly preferably 3.6 or more, particularly preferably 3.8 or more, and most preferably 4 or more. That is, the resin component used in the present invention has a relatively wide molecular weight distribution. A wide molecular weight distribution means that the proportion of low molecular weight components is higher than that of a narrow molecular weight distribution. Since the low molecular weight component has low molecular chain entanglement and high motility, the molecular chain is easily folded during crystallization and the crystallization rate is high. Therefore, if there are many low molecular weight components, the low molecular weight components crystallize first when crystallizing, and the crystals act as a crystal nucleating agent, so that the crystal melting temperature, crystallinity, and crystallization rate of the entire resin are improved. It will be easier. When the molecular weight distribution is equal to or higher than the above value, a sufficient amount of low molecular weight components are contained, so that the crystallinity and crystallization rate can be increased, and the heat resistance, productivity, and rigidity can be improved. can. The molecular weight distribution is obtained by dividing the mass average molecular weight by the number average molecular weight.

On the other hand, the molecular weight distribution of the resin component is preferably 8 or less, more preferably 7 or less, further preferably 6.5 or less, still more preferably 6 or less. It is more preferably 5 or less, particularly preferably 5.3 or less, particularly preferably 5.1 or less, particularly preferably 4.9 or less, and 4.7 or less. Is most preferable. When the upper limit of the molecular weight distribution is not more than the above-mentioned numerical value, the ratio of the high molecular weight component and the low molecular weight component is not too large, so that the balance between the crystallinity, the fluidity and the mechanical properties is excellent.

The mass average molecular weight of the resin component is less than 87,000, preferably 83,000 or less, more preferably 80,000 or less, and even more preferably 75,000 or less. When the mass average molecular weight of the resin component is less than the above-mentioned numerical values, the crystallinity, the crystallization rate, and the fluidity at the time of melt molding are excellent.
On the other hand, the mass average molecular weight of the resin component is preferably 10,000 or more, more preferably 30,000 or more, further preferably 40,000 or more, particularly preferably 50,000 or more, and 55,000 or more. Is particularly preferable, and 59000 or more is most preferable. When the mass average molecular weight is equal to or higher than the above value, the mechanical properties such as durability and impact resistance tend to be excellent.

The melt flow rate (MFR) [temperature 380 ° C., load 5 kgf] of the resin component is preferably 15 g / 10 minutes or more, more preferably 20 g / 10 minutes or more, and 30 g / 10 minutes or more. It is more preferably 40 g / 10 minutes or more, particularly preferably 50 g / 10 minutes or more, and most preferably 60 g / 10 minutes or more. When the MFR of the resin component is equal to or higher than the above value, there is a tendency for excellent secondary processability such as impregnation property into fibers and melt moldability when producing a composite material with reinforcing fibers using this member.
On the other hand, the MFR of the resin component is preferably 150 g / 10 minutes or less, more preferably 130 g / 10 minutes or less, particularly preferably 120 g / 10 minutes or less, and 110 g / 10 minutes or less. This is particularly preferable, and 100 g / 10 minutes or less is most preferable. When the MFR of the resin component is not more than the above value, an appropriate impregnation property can be imparted, the processing time is short, and the productivity tends to be excellent.
The MFR can be obtained by measuring by a method according to JIS K7210-1: 2014 (method A).

The method for adjusting the molecular weight distribution, the mass average molecular weight, and the MFR is not particularly limited, and can be adjusted by a known method. For example, in the production (polymerization) of the resin component, the conditions for obtaining the target molecular weight distribution, mass average molecular weight, and MFR may be appropriately selected and adopted. Specifically, for example, the type / amount / concentration of the monomer to be charged at the time of polymerization, the polymerization initiator, the catalyst, the chain transfer agent added as needed, the method of addition thereof, the polymerization temperature, and the polymerization time can be adjusted. , Adopting a method of adjusting polymerization conditions such as polymerization pressure. Further, so-called multi-stage polymerization may be adopted in which the polymerization conditions are changed stepwise to carry out the polymerization.

<Crystalline resin>
The crystalline resin contained in the resin component of the FRP member of the present invention is preferably a thermoplastic resin, for example, polyaryletherketone such as polyetheretherketone and polyetherketoneketone, polyphenylene sulfide, polyimide, liquid crystal. Examples thereof include polyamides such as polymers, fluororesins, polymethylpentene, aliphatic polyamides and semi-aromatic polyamides, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene terephthalate, polypropylene and polyacetal. These may be used alone or in combination of two or more. Of these, polyaryletherketone is preferable, and polyetheretherketone is particularly preferable, because it is excellent in heat resistance, mechanical properties, chemical resistance, and the like.

The content ratio of the crystalline resin in the resin component is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more. Is particularly preferable, more than 90% by mass is most preferable, and 95% by mass or more is particularly preferable. As long as the content ratio of the crystalline resin is within such a range, even when a resin other than the crystalline resin is contained, it becomes easy to appropriately impart a necessary effect while maintaining the effect of the present invention.

When the resin component contains a polyaryletherketone, particularly a polyetheretherketone, the content ratio of the polyaryletherketone, particularly the polyetheretherketone, is preferably 50% by mass or more in the resin component, preferably 60% by mass. % Or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably more than 90% by mass, and more preferably 95% by mass or more. Especially preferred. As long as the content ratio of the polyaryletherketone, particularly the polyetheretherketone is within such a range, even if a resin other than the crystalline resin is contained, the necessary effect is appropriately imparted while maintaining the effect of the present invention. Becomes easier.

Hereinafter, each resin listed as the crystalline resin will be described.

[Polyaryletherketone]
Hereinafter, the polyaryletherketone will be described.
A polyaryl etherketone 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. For example, polyether ether ketone, polyether ketone ketone, polyether ketone, polyether ketone ether ketone ketone, polyether ether ketone ketone, polyether diphenyl ether ketone and the like, and copolymers thereof (for example, polyether ketone-polyether). Diphenyl ether ketone copolymer). Among them, polyetheretherketone is particularly preferable because it is excellent in heat resistance, mechanical properties, chemical resistance and the like.

The molecular weight distribution of the polyaryletherketone is preferably 3.3 or more, more preferably 3.5 or more, particularly preferably 3.6 or more, particularly preferably 3.8 or more, and most preferably 4 or more. A wide molecular weight distribution means that the proportion of low molecular weight components is higher than when the molecular weight distribution is narrow. Since the low molecular weight component has low molecular chain entanglement and high motility, the molecular chain is easily folded during crystallization and the crystallization rate is high. Therefore, if there are many low molecular weight components, the low molecular weight components crystallize first during crystallization, and the crystals act as a crystal nucleating agent, so that the crystal melting temperature, crystallinity, and crystallization rate of the entire resin are improved. It is thought that. When the molecular weight distribution is equal to or higher than the above value, a sufficient amount of the low molecular weight component is contained, so that the crystallinity and the crystallization rate can be increased, which in turn tends to improve heat resistance, rigidity, and productivity.

On the other hand, the molecular weight distribution of the polyaryletherketone is preferably 8 or less, more preferably 7 or less, further preferably 6.5 or less, still more preferably 6 or less. It is more preferably 5 or less, more preferably 5.3 or less, particularly preferably 5.1 or less, particularly preferably 4.9 or less, and 4.7 or less. Most preferably. When the molecular weight distribution is equal to or less than the above value, the ratio of the high molecular weight component to the low molecular weight component is not too large, so that the balance between the crystallinity, the fluidity, and the mechanical properties tends to be excellent.

The mass average molecular weight of the polyaryletherketone is preferably less than 87,000, more preferably 83,000 or less, further preferably 80,000 or less, and even more preferably 75,000 or less. When the mass average molecular weight is less than the above-mentioned numerical values, the crystallinity, the crystallization rate, and the fluidity at the time of melt molding tend to be excellent.
On the other hand, the mass average molecular weight is preferably 10,000 or more, more preferably 30,000 or more, further preferably 40,000 or more, particularly preferably 50,000 or more, and particularly preferably 55,000 or more. Most preferably, it is 59000 or more. When the mass average molecular weight is equal to or higher than the above value, the mechanical properties such as durability and impact resistance tend to be excellent.

Hereinafter, the polyetheretherketone preferably used among the polyaryletherketones will be described.

(Polyetheretherketone)
The polyether ether ketone may be a resin having at least two ether groups and a ketone group as structural units, but is excellent in thermal stability, melt moldability, rigidity, chemical resistance, impact resistance, and durability. Therefore, it preferably has a repeating unit represented by the following general formula (1).

（前記一般式（１）において、Ａｒ¹〜Ａｒ³は、それぞれ独立に、炭素原子数６〜２４のアリーレン基を表し、また、それぞれ置換基を有していてもよい）

(In the above general formula (1), Ar ^{1 to} Ar ³ 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 each other, but are preferably the same. Examples of the arylene group of Ar ^{1 to} Ar ³ include a phenylene group and a biphenylene group. Of these, a phenylene group is preferable, and a p-phenylene group is more preferable.

Examples of the substituent that the arylene groups of Ar ^{1 to} Ar ³ may have include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon atom such as a methoxy group and an ethoxy group. Examples thereof include an alkoxy group having a number of 1 to 20. When Ar ^{1 to} Ar ³ have substituents, the number of the substituents is not particularly limited.

Among them, polyetheretherketone having a repeating unit represented by the following structural formula (2) is preferable from the viewpoint of thermal stability, melt moldability, rigidity, chemical resistance, impact resistance, and durability.

The molecular weight distribution of the polyetheretherketone is preferably 3.3 or more, more preferably 3.5 or more, further preferably 3.6 or more, and particularly preferably 3.8 or more. It is preferably 4 or more, and most preferably 4 or more. When the molecular weight distribution is equal to or higher than the above value, a sufficient amount of low molecular weight components are contained, so that the crystallinity and crystallization rate can be increased, which in turn tends to lead to improvement in heat resistance, rigidity, and productivity. ..
On the other hand, the molecular weight distribution of the polyetheretherketone is preferably 8 or less, more preferably 7 or less, further preferably 6.5 or less, still more preferably 6 or less. It is more preferably 5 or less, more preferably 5.3 or less, particularly preferably 5.1 or less, particularly preferably 4.9 or less, and 4.7 or less. Most preferably. When the upper limit of the molecular weight distribution of the polyetheretherketone is not more than the above-mentioned numerical value, the ratio of the high molecular weight component and the low molecular weight component is not too large, so that the balance between the crystallinity, the fluidity and the mechanical properties tends to be excellent.

The mass average molecular weight of the polyetheretherketone is preferably less than 87,000, more preferably 83,000 or less, further preferably 80,000 or less, and even more preferably 75,000 or less. When the mass average molecular weight of the polyetheretherketone is less than the above-mentioned numerical values, the crystallinity, the crystallization rate, and the fluidity at the time of melt molding tend to be excellent.
On the other hand, the mass average molecular weight is preferably 10,000 or more, more preferably 30,000 or more, further preferably 40,000 or more, particularly preferably 50,000 or more, and particularly preferably 55,000 or more. Most preferably, it is 59000 or more. When the mass average molecular weight is equal to or higher than the above value, the mechanical properties such as durability and impact resistance tend to be excellent.

In the present invention, the molecular weight and the molecular weight distribution can be determined by gel permeation chromatography using an eluent in which the resin component used is dissolved. For example, a mixed solution of chlorophenol as an eluent with halogenated benzenes such as chlorobenzene, chlorotoluene, bromobenzene, bromotoluene, dichlorobenzene, dichlorotoluene, dibromobenzene, and dibromotoluene, and pentafluorophenol as an eluent. A mixed solution of chloroform can be used.
Specifically, it can be measured by the method described in Examples described later, but for example, it can be measured by the following method.
(1) An amorphous film having a resin component such as polyetheretherketone is obtained. For example, resin pellets such as polyetheretherketone are pressed at 350 to 400 ° C. and then rapidly cooled, or when filmed by an extruder, the temperature of the cast roll is lowered, for example, cooled at 20 to 140 ° C. to be amorphous. Obtain a crystalline film.
(2) Add 3 g of pentafluorophenol to 9 mg of the film.
(3) Using a heat block, heat and dissolve at 100 ° C. for 60 minutes.
(4) Then, remove from the heat block, allow to cool, add 6 g of chloroform at room temperature (about 23 ° C) gently little by little, and shake gently.
(5) After that, the sample obtained by filtering with a 0.45 μm PTFE (polytetrafluoroethylene) cartridge filter was subjected to gel permeation chromatography to have a number average molecular weight (Mn), a mass average molecular weight (Mw), and a molecular weight. The distribution (Mw / Mn) is measured.

If the resin component is a mixture of multiple types of resin and multiple peaks are confirmed by gel permeation chromatography measurement, or if multiple peaks are confirmed even for a single type of resin component. Mn, Mw, and Mw / Mn may be calculated by an analysis method in which a plurality of peaks are designated as one peak. Specifically, the peak area is calculated in the range from the retention time of the peak start of the first confirmed peak to the retention time of the peak end of the last confirmed peak, and Mn, Mw, and Mw / Mn are calculated. be able to.

The melt flow rate (MFR) [temperature 380 ° C., load 5 kgf] of the polyaryletherketone, particularly the polyetheretherketone, is preferably 15 g / 10 minutes or more, and more preferably 20 g / 10 minutes or more. It is more preferably 30 g / 10 minutes or more, particularly preferably 40 g / 10 minutes or more, particularly preferably 50 g / 10 minutes or more, and most preferably 60 g / 10 minutes or more. .. When the MFR of the polyaryletherketone is equal to or higher than the above value, the secondary processability such as impregnation property into the fiber and the melt moldability tend to be excellent when the composite material with the reinforcing fiber is manufactured by using this member. be.
On the other hand, the MFR of the polyaryletherketone, particularly the polyetheretherketone, is preferably 150 g / 10 minutes or less, more preferably 130 g / 10 minutes or less, and particularly preferably 120 g / 10 minutes or less. It is particularly preferably 110 g / 10 minutes or less, and most preferably 100 g / 10 minutes or less. When the MFR of the polyaryletherketone is not more than the above value, an appropriate impregnation property can be imparted, the processing time is short, and the productivity tends to be excellent.
The MFR can be obtained by measuring by a method according to JIS K7210-1: 2014 (method A).

The crystal melting temperature (Tm) of the polyaryletherketone, particularly the polyetheretherketone, is preferably 320 ° C. or higher, more preferably 330 ° C. or higher, further preferably 335 ° C. or higher, and 340 ° C. or higher. It is particularly preferable that the temperature is above ° C. When the crystal melting temperature of the polyaryletherketone is equal to or higher than the above temperature, the obtained member tends to have excellent heat resistance.
On the other hand, the crystal melting temperature of the polyaryletherketone, particularly the polyetheretherketone, is preferably 370 ° C. or lower, more preferably 365 ° C. or lower, further preferably 360 ° C. or lower, and 355 ° C. or lower. Is particularly preferable, and the temperature is most preferably 350 ° C. or lower. When the crystal melting temperature of the polyaryletherketone is equal to or lower than the above temperature, the fluidity tends to be excellent at the time of melt molding such as at the time of manufacturing a member for FRP.

The crystal melting temperature in the present invention shall be in the temperature range of 25 to 400 ° C. and the heating rate of 10 ° C./using using a differential scanning calorimeter (for example, “Pyris1 DSC” manufactured by PerkinElmer) in accordance with JIS K7121: 2012. It can be obtained from the peak top temperature of the melting peak of the detected DSC curve by raising the temperature in minutes.

The crystallization temperature (Tc) of the polyaryletherketone, especially the polyetheretherketone in the temperature lowering process, is preferably 296 ° C. or higher, more preferably 300 ° C. or higher, still more preferably 302 ° C. or higher. , 303 ° C. or higher is particularly preferable, and 304 ° C. or higher is most preferable. When the crystallization temperature in the temperature lowering process of the polyaryletherketone is equal to or higher than the above temperature, the crystallization rate is high and the productivity of the FRP member tends to be excellent. Specifically, for example, in the case of producing a film, the resin is in contact with the cast roll by setting the temperature (cooling temperature) of the cast roll to a temperature equal to or higher than the glass transition temperature and lower than the crystal melting temperature. During that time, crystallization is promoted and a crystallized film is obtained. When the crystallization temperature in the temperature lowering process is higher than the above temperature, the crystallization rate is high and the crystallization can be completed with the cast roll, so that the elastic modulus is high, and as a result, sticking to the roll is suppressed. The appearance of the film tends to improve.

On the other hand, the crystallization temperature of the polyaryletherketone, particularly the polyetheretherketone in the temperature lowering process, is preferably 320 ° C. or lower, more preferably 315 ° C. or lower, and even more preferably 312 ° C. or lower. It is particularly preferable that the temperature is 310 ° C. or lower. If the crystallization temperature in the temperature lowering process of the polyetheretherketone is lower than the above temperature, the crystallization is not too fast, so that the cooling unevenness at the time of molding the FRP member such as a film is reduced, and the crystallization is uniform and high quality. A member can be obtained, and the heating dimensional stability of the present member tends to be excellent when it is used as a composite material with a reinforcing fiber described later.

The crystallization temperature in the temperature lowering process in the present invention is in a temperature range of 400 to 25 ° C. and a speed of 10 using a differential scanning calorimeter (for example, “Pyris1 DSC” manufactured by PerkinElmer) according to JIS K7121: 2012. It can be obtained from the peak top temperature of the crystallization peak of the detected DSC curve by lowering the temperature at ° C./min.

The heat of crystal melting of the polyaryletherketone, particularly the polyetheretherketone, is preferably 42 J / g or more, more preferably 44 J / g or more, further preferably 46 J / g or more, and 48 J / g. It is particularly preferably g or more, and most preferably 50 J / g or more. When the amount of heat of crystal melting of the polyaryletherketone is equal to or higher than the above value, the obtained member has a sufficient crystallinity, and thus tends to have excellent heat resistance and rigidity. In addition, the composite material tends to have excellent heating dimensional stability during production, and the obtained composite material tends to have a high crystallinity, and thus has a tendency to have excellent heat resistance and rigidity.
On the other hand, the heat of crystal melting of the polyaryletherketone, particularly the polyetheretherketone, is preferably 60 J / g or less, more preferably 58 J / g or less, still more preferably 56 J / g or less. It is particularly preferable that it is 54 J / g or less. If the amount of heat of crystal melting of the polyaryletherketone is equal to or less than the above value, the crystallinity is not too high, so that the melt formability tends to be excellent at the time of manufacturing FRP members, and the obtained composite material has durability and impact resistance. It tends to be excellent in sex.

The amount of heat of crystal melting in the present invention shall be in the temperature range of 25 to 400 ° C. and the heating rate of 10 ° C./using using a differential scanning calorimeter (for example, "Pyris1 DSC" manufactured by PerkinElmer Co., Ltd.) according to JIS K7122: 2012. It can be obtained from the area of the melting peak of the detected DSC curve by raising the temperature in minutes.

When blending other resin components for the purpose of modifying the polyaryletherketone, the type is not particularly limited, but among them, the molding temperature is close to that of the polyaryletherketone, and decomposition and cross-linking during melt molding occur. From the viewpoint of easy suppression, for example, polyphenylene sulfide, polyarylate, polyetherimide, polyamideimide, polysulfone, polyethersulfone, liquid crystal polymer and the like can be preferably used. These may be used alone or in combination of two or more. Among these, polyetherimide can be particularly preferably used. Since polyaryletherketone and polyetherimide are highly compatible and easy to mix at the molecular level, the characteristics of polyetherimide such as improving the glass transition temperature of polyaryletherketone while maintaining the crystallinity of this member can be obtained. It becomes easy to give.

When the polyetheretherketone is used as the polyetheretherketone, the same resin as the resin used for the modification of the polyetheretherketone is used as the other resin component to be blended for the purpose of modifying the polyetheretherketone. However, polyetheretherketones other than polyetheretherketone, such as polyetherketone, polyetherketoneketone, polyetherketoneetherketoneketone, and polyetheretherketoneketone, may be used in combination with polyetheretherketoneketone. Is also preferable.

(Polyetherketone Ketone)
The polyetherketone The ketone has at least one of a repeating unit (a-1) represented by the following general formula (3) and a repeating unit (a-2) represented by the following general formula (4). Ketone Ketone is preferably a polyetherketone ketone having a repeating unit (a-1) represented by the following general formula (3) and a repeating unit (a-2) represented by the following general formula (4). It is more preferable to have it. Each of these repeating units (a-1) and (a-2) has one ether group and two ketone groups.

（前記一般式（３）、（４）において、Ａｒ⁴〜Ａｒ⁹は、それぞれ独立に、炭素原子数６〜２４のアリーレン基を表し、また、それぞれ置換基を有していてもよい。
一般式（３）中の（１，４）Ａｒ⁶は、ケトン基がＡｒ⁶基の１位と４位に結合しており、一般式（４）中の（１，３）Ａｒ⁹は、ケトン基がＡｒ⁹基の１位と３位に結合している。）

(In the above general formulas (3) and (4), Ar ^{4 to} Ar ⁹ independently represent an arylene group having 6 to 24 carbon atoms, and may each have a substituent.
^{In (1,4) Ar 6} in the general formula (3), the ketone group is bonded to the 1-position and the 4-position of the ^{Ar 6 group, and in (1,3) Ar 9} in the general formula (4), The ketone group is bonded to the 1st and 3rd positions of the ^{Ar 9 group.} )

In the general formulas (3) and (4), ^{the arylene groups of Ar 4 to} Ar ⁹ may be different from each other, but are preferably the same. Examples of the arylene group of Ar ^{4 to Ar 9} represent an arylene group having 6 to 24 carbon atoms, and specific examples thereof include a phenylene group and a biphenylene group. Of these, a phenylene group is preferable, and Ar ⁴ , Ar ⁵ , Ar. ⁷ , Ar ⁸ is preferably a p-phenylene group. Ar ⁶ is a p-allylene group, preferably a p-phenylene group. Ar ⁹ is an m-allylene group, preferably an m-phenylene group.

Examples of the substituent that the arylene group of Ar ^{4 to} Ar ⁹ may have include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon atom number such as a methoxy group and an ethoxy group. Examples thereof include 1 to 20 alkoxy groups. When Ar ^{4 to} Ar ⁹ have substituents, the number of the substituents is not particularly limited.

Polyetherketone The repeating unit (a-1) represented by the general formula (3) constituting the ketone is the repeating unit represented by the following structural formula (1A), according to the general formula (4). As the repeating unit (a-2) represented by, the repeating unit represented by the following structural formula (2A) is preferable from the viewpoint of mechanical properties, thermal stability and melt moldability.

Polyetherketone The unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and the repeating unit (a-2) in the ketone is preferably 1 or more, and 1.1. The above is more preferable, 1.2 or more is further preferable, 1.3 or more is particularly preferable, 1.4 or more is particularly preferable, and 1.5 or more is particularly preferable. Most preferred. When the unit molar ratio is equal to or higher than the above value, the glass transition temperature is unlikely to decrease, and it becomes easy to maintain excellent heat resistance. On the other hand, the unit molar ratio [(a-1) / (a-2)] is preferably 5 or less, more preferably 4 or less, further preferably 3 or less, and 2 or less. It is particularly preferable, and it is most preferable that it is 1.5 or less. When the unit molar ratio is not more than the above numerical value, the glass transition temperature and the crystal melting temperature do not become too high, so that the melt moldability is excellent and the heat fusion property when composited with the reinforcing fiber described later is also excellent and preferable. ..

The crystallinity of the polyetherketone ketone differs depending on the unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and the repeating unit (a-2), and for example, the polyaryletherketone In the case of a resin having a repeating unit represented by the structural formula (1A) and a repeating unit represented by the structural formula (2A), generally, if the unit molar ratio is 1.5 or more, the crystallinity is likely to be exhibited. ..

Polyetherketone The total number (degree of polymerization) of the repeating unit (a-1) and the repeating unit (a-2) in the ketone is preferably 10 or more, more preferably 20 from the viewpoint of ensuring mechanical properties. That is all. Further, from the viewpoint of melt moldability, it is preferably 100 or less, and more preferably 50 or less.

The polyether ketone ketone may have a repeating unit (a-1) and other repeating units other than the repeating unit (a-2), but in that case, the repeating unit (a-) is used as the polyether ketone ketone. In order to surely obtain the above-mentioned effect by having the 1) and the repeating unit (a-2), the total of the repeating unit (a-1), the repeating unit (a-2) and the other repeating units is determined. The ratio of the other repeating units is preferably 20 mol% or less, particularly preferably 10 mol% or less, and most preferably no other repeating units.

The glass transition temperature of the polyetherketone ketone is preferably 125 ° C. or higher, more preferably 128 ° C. or higher, and even more preferably 130 ° C. or higher. When the glass transition temperature is equal to or higher than the above temperature, it is easy to obtain an FRP member having sufficient heat resistance. On the other hand, the glass transition temperature of the polyetheretherketone is preferably 200 ° C. or lower, more preferably 190 ° C. or lower, further preferably 180 ° C. or lower, and particularly preferably 170 ° C. or lower. Most preferably, it is 160 ° C. or lower. When the glass transition temperature is equal to or lower than the above temperature, the melt moldability is excellent, and when composited with the reinforcing fiber, heat fusion is easy at a low temperature, which is preferable.

The crystal melting temperature of the polyetherketone ketone is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, further preferably 290 ° C. or higher, particularly preferably 295 ° C. or higher, and 300 ° C. The above is the most preferable. When the crystal melting temperature is equal to or higher than the above temperature, the heat resistance tends to be excellent. On the other hand, the crystal melting temperature is preferably 370 ° C. or lower, more preferably 360 ° C. or lower, further preferably 350 ° C. or lower, particularly preferably 340 ° C. or lower, and 335 ° C. or lower. Is most preferable. When the crystal melting temperature is equal to or lower than the above temperature, the melt moldability tends to be excellent.

The heat of crystal melting of the polyetherketone ketone is preferably 45 J / g or less, more preferably 40 J / g or less, further preferably 37 J / g or less, and more preferably 35 J / g or less. It is particularly preferable, and most preferably 32 J / g or less. When the amount of heat of crystal melting is equal to or less than the above value, the heat-sealing property tends to be excellent when the fiber is combined with the reinforcing fiber. On the other hand, the amount of heat of crystal melting is preferably 15 J / g or more, more preferably 20 J / g or more, further preferably 23 J / g or more, particularly preferably 25 J / g or more, and 27 J. Most preferably, it is / g or more. When the amount of heat for melting the crystal is equal to or higher than the above value, the heat resistance tends to be easily maintained.

The glass transition temperature of the polyetherketone is set in a temperature range of 25 to 400 ° C. and a heating rate of 10 using a differential scanning calorimeter (for example, “Pyris1 DSC” manufactured by PerkinElmer) according to JIS K7121: 2012. It can be obtained from the detected DSC curve by raising the temperature at ° C./min. The crystal melting temperature and the amount of heat of crystal melting are as described above.

[Polyphenylene sulfide]
Examples of the polyphenylene sulfide include a polymer containing a structural unit represented by the following formula.
-(Ph-S)-
(Ph in the above formula represents a phenylene group such as p-phenylene, m-phenylene, o-phenylene, and S represents a sulfur atom.)

Further, the polyphenylene sulfide that can be used in the present invention may further contain a structural unit derived from a monomer other than the structural unit represented by the above formula. Examples of other monomers include alkyl-substituted phenylene (preferably an alkyl group having 1 to 6 carbon atoms), phenyl-substituted phenylene, halogen-substituted phenylene, amino-substituted phenylene, amide-substituted phenylene, and p, p'-diphenylene sulfone. , P, p'-biphenylene, p, p'-biphenylene ether, p, p'-biphenylene carbonyl, naphthalene and the like. These may be used alone or in combination of two or more.

[Polyimide]
The polyimide is not particularly limited as long as it has an imide bond and is crystalline. For example, in tetracarboxylic acid dianhydride and diamine, a thermally stable functional group or aromatic group other than the imide group is used. Examples thereof include thermoplastic polyimide in which a system atomic group is introduced to reduce the concentration of the produced imide group in the repeating unit.

Examples of the thermoplastic polyimide include thermoplastic polyimide, thermoplastic polyamideimide, thermoplastic polyetherimide, and thermoplastic polyesterimide. Of these, thermoplastic polyimide is preferable, and thermoplastic polyimide obtained by polymerizing tetracarboxylic acid dianhydride with at least one of an aliphatic and alicyclic diamine is more preferable.

Examples of the tetracarboxylic acid dianhydride include cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and cyclohexane-1,2,4,5-tetra. Dianhydride of alicyclic tetracarboxylic acid such as carboxylic acid, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid , Naphthalene-1,4,5,8-tetracarboxylic acid, pyromellitic acid and other aromatic tetracarboxylic acid dianhydrides can be exemplified. Further, these alkyl esters can also be used. These may be used alone or in combination of two or more. Of these, aromatic tetracarboxylic dianhydride is preferable, and pyromellitic dianhydride is more preferable from the viewpoint of heat resistance, secondary processability, and low water absorption.

The aliphatic diamine may be linear or branched, but has amine groups at both ends of the linear hydrocarbon from the viewpoint of impact resistance, moldability, and secondary processability. It is preferably a linear aliphatic diamine. The linear aliphatic diamine is not particularly limited as long as it is a diamine component having amine groups at both ends of the alkyl group, but for example, ethylenediamine, propylenediamine, butanediamine, pentandiamine, hexanediamine, heptanediamine, octane. Diamines, nonanediamines, decanediamines, undecanediamines, dodecanediamines, tridecanediamines, tetradecanediamines, pentadecanediamines, hexadecanediamines, heptadecanediamines, octadecanediamines, nonadecandiamines, eikosan, triacanthans, tetracontanes, pentacontanes, etc. Will be. These may be used alone or in combination of two or more. Among these, linear aliphatic diamines having 4 to 12 carbon atoms are more preferable from the viewpoints of moldability, secondary processability, and low hygroscopicity.

The alicyclic diamine is not particularly limited as long as it is a compound having two amine groups in the cyclic hydrocarbon, and for example, 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl). Cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis (2-methylcyclohexylamine), isophoronediamine, norbornanediamine, bis (aminomethyl) tricyclodecane and the like can be mentioned. These may be used alone or in combination of two or more. Among these, 1,3-bis (aminomethyl) cyclohexane is preferable from the viewpoint of heat resistance, moldability, and secondary processability.

Further, the diamine component may contain a diamine component other than the aliphatic diamine and the alicyclic diamine. Examples of other diamine components include 1,4-phenylenediamine, 1,3-phenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'. -Diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, α, α'-bis ( 4-Aminophenyl) -1,4'-diisopropylbenzene, α, α'-bis (3-aminophenyl) -1,4-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 4,4'-diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,6-diaminonaphthalene, 1,5- Aromatic diamines such as diaminonaphthalene, p-xylylene diamine, m-xylylene diamine, ether diamines such as polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, siloxane diamine and the like. Can be mentioned. These may be used alone or in combination of two or more.

The diamine component preferably contains both an aliphatic diamine and an alicyclic diamine from the viewpoint of excellent balance between heat resistance and moldability, and may contain both a linear aliphatic diamine and an alicyclic diamine. preferable. The content of each is preferably in the range of aliphatic diamine: alicyclic diamine = 99: 1 to 1:99 mol%, more preferably 90:10 to 10:90 mol%, and 80: It is more preferably 20 to 20:80 mol%, particularly preferably 70:30 to 30:70 mol%, and most preferably 60:40 to 40:60 mol%.

[Liquid polymer]
Examples of the liquid crystal polymer include aromatic polyester resins in which p-hydroxybenzoic acid is used as a basic skeleton and acid components such as ethylene terephthalate, 2,6-hydroxynaphthoic acid, phenol and phthalic acid are ester-bonded.

[Fluororesin]
As the fluororesin, it is preferable to use a fluororesin having a glass transition temperature of more than 120 ° C. measured by a differential scanning calorimeter, for example, a tetrafluoroethylene / fluoroalkyl vinyl ether copolymer or a tetrafluoroethylene / hexafluoropropylene copolymer. Examples thereof include coalescing, ethylene / tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene / chlorotrifluoroethylene copolymer and the like. Further, if necessary, it may have a functional group such as a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group.

[Polymethylpentene]
Examples of the polymethylpentene include a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and ethylene or an α-olefin other than 4-methyl-1-pentene.
Among them, a polymer containing 4-methyl-1-pentene is preferably contained in an amount of preferably 85 to 100 mol%, more preferably 90 to 100 mol%.

Examples of the α-olefin other than 4-methyl-1-pentene include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like having 3 to 20 carbon atoms. Α-olefins of. These may be used alone or in combination of two or more. Of these, 1-decene, 1-tetradecene, and 1-octadecene are preferable because they have good copolymerizability with 4-methyl-1-pentene and good toughness can be easily obtained.

[Alphatic polyamide]
As the aliphatic polyamide, those having a glass transition temperature of about 50 to 90 ° C. measured by a differential scanning calorimeter are preferably used, and examples thereof include polyamide 6, polyamide 66, and polyamide 46.

[Semi-aromatic polyamide]
As the semi-aromatic polyamide, it is preferable to use a polyamide having a glass transition temperature of about 80 to 200 ° C. measured by a differential scanning calorimeter. For example, polyamide MXD6 and polyamide 4T obtained from m-xylylenediamine and adipic acid. , Polyamide 6T, Modified Polyamide 6T, Polyamide 9T, Polyamide 10T, Polyamide 11T and the like.

[polyethylene terephthalate]
Examples of the polyethylene terephthalate include crystalline polyethylene terephthalate obtained by polycondensation of ethylene glycol and terephthalic acid having a glass transition temperature of 70 to 80 ° C. measured by a differential scanning calorimeter.

[Polybutylene terephthalate]
The polybutylene terephthalate is obtained, for example, by polycondensation of 1,4-butanediol with at least one of terephthalic acid and dimethyl terephthalate having a glass transition temperature of 35 to 55 ° C. measured by a differential scanning calorimeter. And so on.

[Polyethylene naphthalate]
The polyethylene naphthalate is, for example, bishydroxyethylene-2,6 by transesterifying dimethyl 2,6-naphthalenedicarboxylic acid and ethylene glycol having a glass transition temperature of 100 ° C. or higher as measured by a differential scanning calorimeter. − Examples thereof include those obtained by subjecting to polycondensation reaction after obtaining naphthalate.

[Polycyclohexanedimethylene terephthalate]
As the polycyclohexanedimethylene terephthalate, for example, at least one of terephthalic acid and dimethyl terephthalate having a glass transition temperature of 80 ° C. or higher measured by a differential scanning calorimeter is subjected to a transesterification reaction with 1,4-cyclohexanedimethanol. Examples thereof include those obtained by subjecting poly-1,4-cyclohexanedimethylene terephthalate to a polycondensation reaction.

[polypropylene]
Examples of the polypropylene include a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer, and a propylene-ethylene having a glass transition temperature of less than 100 ° C. measured by a differential scanning calorimeter. -Α-olefin copolymer, propylene block copolymer (propylene homopolymer component or copolymer component mainly composed of propylene, at least one of the monomers selected from ethylene and α-olefin, and propylene are used together. A copolymer composed of a copolymer component obtained by polymerization) and the like can be mentioned.

[Polyacetal]
The polyacetal is not particularly limited as long as it is a crystalline resin having an oximethylene group as a repeating unit. For example, a homopolymer composed of only this oximethylene group or an oxyethylene group coexisting therein as a copolymerization unit. Examples include the copolymers that have been made to.

Further, the resin component may contain a resin other than the crystalline resin. Examples of the resin other than the crystalline resin include polyvinyl chloride, polystyrene, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyphenylene ether, polymethylmethacrylate, polycarbonate, ABS, polyetherimide, and polyamideimide. , Polyallylate, Polysulfone, Polyethersulfone, polymers thereof and mixtures thereof and the like can be used. These may be used alone or in combination of two or more.

The content ratio of the resin component in the present member is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more. It is particularly preferable, and it is most preferably 90% by mass or more, and particularly preferably 100% by mass. As long as the content ratio of the resin component is within such a range, it becomes easy to appropriately impart the necessary effect while maintaining the effect of the present invention.

<Members for fiber reinforced plastics>
The member for fiber reinforced plastic of the present invention is a material member for obtaining fiber reinforced plastic, and the member is composited with a reinforcing fiber which is a fiber for reinforcing a resin such as continuous fiber and discontinuous fiber. A composite material (here, fiber reinforced plastic) can be obtained. The member contains a crystalline resin as a resin component, the molecular weight distribution of the resin component is 3.3 or more, the mass average molecular weight is less than 87,000, and the relative crystallinity of the member is 50% or more. As a result, the obtained fiber-reinforced plastic becomes excellent in heat dimensional stability, productivity, and rigidity.

Further, the present member includes, for example, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antibacterial / antifungal agent, an antistatic agent, a lubricant, a pigment, and a dye, as long as the effects of the present invention are not impaired. It may contain various additives such as fillers other than reinforcing fibers. These may be used alone or in combination of two or more.

The shape of the member is not particularly limited, and may be any shape such as a film, a plate, a fiber, a tube, a rod, etc., but a film or a plate is preferable, and a film is more preferable. ..
When this member is a plate-shaped member, the "plate-shaped" of the plate-shaped member means a flat shape having an arbitrary maximum thickness, and not only a so-called plate having a thickness of 1 mm or more but also a film having a thickness of less than 1 mm. The purpose is to include. As the plate-shaped member, a thin plate-shaped member is preferable, the thickness thereof is preferably 2 mm or less, more preferably less than 1 mm, further 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 usually 3 μm.
Further, this member is molded by a general molding method, for example, extrusion molding, injection molding, casting molding such as solution casting, press molding, etc., and various shapes, preferably films, plates, etc., are more preferable. Can be molded into film members. In each molding method, the apparatus and processing conditions are not particularly limited, and a known method can be adopted. In particular, from the viewpoint of processability when forming a composite material with a reinforcing fiber described later, it is preferable that the member is made into a film by an extrusion molding method, particularly a T-die method.

The thickness of the present member, preferably the thickness of the film, is not particularly limited, but is preferably 3 μm or more, more preferably 6 μm or more, further preferably 9 μm or more, and further preferably 12 μm or more. It is particularly preferable, it is particularly preferably 20 μm or more, and most preferably 50 μm or more. On the other hand, the thickness of the present member is preferably 100 μm or less, more preferably 90 μm or less, further preferably 80 μm or less, particularly preferably 70 μm or less, and most preferably 60 μm or less. .. As long as the thickness of this member is within the range, the thickness is neither too thin nor too thick, so it tends to be excellent in balance of mechanical properties, film forming property, insulating property, etc., and secondary workability when composited with reinforcing fibers. Become.
The thickness of this member specifically means the average thickness measured by the method of the embodiment, and when the shape of this member is a film, a plate, a tube, etc., the average thickness thereof, and the shape of this member is a fiber. , In the case of a rod or the like, the average diameter is referred to, and these average values can be calculated by the method described in the examples.

[Manufacturing method of this member]
When the present member is a film, the film is not particularly limited, and may be, for example, either a non-stretched film or a stretched film. Of these, a non-stretched film is preferable from the viewpoint of secondary processability when producing a composite material. The non-stretched film is a film that is not actively stretched for the purpose of controlling the orientation of the film, and is oriented when taken up by a cast roll in extrusion molding such as the T-die method, or stretched by a stretched roll. It also includes films with a magnification of less than 2x.

The film can be produced by melt-kneading the constituent materials of the present member, extruding and cooling the film.

A known kneader such as a single-screw or twin-screw extruder can be used for melt-kneading. The melting temperature is appropriately adjusted according to the type and mixing ratio of the resin, the presence or absence of additives, and the type, but from the viewpoint of productivity and the like, it is preferably 320 ° C. or higher, and more preferably 340 ° C. or higher. It is preferably 350 ° C. or higher, more preferably 360 ° C. or higher, and particularly preferably 360 ° C. or higher. When the melting temperature is set to the above temperature or higher, the crystals of the raw material such as pellets are sufficiently melted and are less likely to remain on the film, so that the durability such as the number of folding times and the puncture impact strength can be easily improved. On the other hand, the melting temperature is preferably 450 ° C. or lower, more preferably 430 ° C. or lower, further preferably 410 ° C. or lower, and particularly preferably 390 ° C. or lower. By setting the melting temperature to the above temperature or lower, the resin is less likely to decompose during melt molding and the molecular weight is easily maintained, so that the heat resistance and tensile elastic modulus of the film tend to be improved.

Cooling can be performed, for example, by bringing the molten resin into contact with a cooler such as a cooled cast roll. As the cooling temperature (for example, the temperature of the cast roll), the cooling temperature may be appropriately selected so as to have a desired relative crystallization degree.

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 40 to 135 ° C. higher. It is particularly preferable to have. By setting the cooling temperature within the above range, the cooling rate of the film can be slowed down, and the relative crystallinity tends to be increased.
For example, when polyetheretherketone is contained as a resin component, the cooling temperature is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, further preferably 200 ° C. or higher, and 210 ° C. or higher. Is particularly preferred.
On the other hand, the cooling temperature is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, further preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower, and 240 ° C. or lower. Is the most preferable.

In general, the crystallization rate of a polymer material is considered to be maximized in the temperature range between the glass transition temperature and the crystal melting temperature from the balance between the nucleation rate and the growth rate of the crystal. When producing a film with a high degree of relative crystallinity, if the lower and upper limits of the cooling temperature (cast roll temperature) are applied, the crystallization rate is maximized and it is easy to obtain a crystallized film with excellent productivity. ..

The glass transition temperature is defined as a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C./min using a differential scanning calorimeter (for example, “Pyris1 DSC” manufactured by PerkinElmer Co., Ltd.) according to JIS K7121: 2012. The value measured under the conditions of. When a plurality of glass transition temperatures are present in a mixture of a plurality of types of crystalline resins, the highest temperature may be regarded as the glass transition temperature of the resin component, and the cooling temperature may be adjusted.

Further, when the present member is a film, it may be a multilayer film in which other layers are laminated as long as the effect of the present invention is not impaired. As the method of multi-layering, for example, known methods such as coextrusion, extrusion laminating, thermal laminating, and dry laminating can be used.

[Relative crystallinity]
The FRP member of the present invention thus obtained has a relative crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 85%. As mentioned above, it is most preferably 90% or more. The upper limit is usually 100%. When the relative crystallinity of this member is equal to or higher than the above value, shrinkage due to heat can be suppressed when the member and the reinforcing fiber are heat-bonded to form a composite material, and the heat resistance and rigidity are excellent. Can be the same.

The relative crystallinity is determined by heating the FRP member at a heating rate of 10 ° C./min using a differential scanning calorimeter (“Pyris1 DSC” manufactured by PerkinElmer), and the crystal melting peak obtained at this time. It can be obtained by calculating from the calorific value (J / g) and the calorific value of the recrystallization peak (J / g) using the following formula 1.
[Equation 1]
Relative crystallinity (%) = {1- (ΔHc / ΔHm)} × 100
ΔHc: Calorific value (J / g) of the recrystallization peak of the FRP member under a heating condition of 10 ° C./min.
ΔHm: Calorific value (J / g) of the crystal melting peak of the FRP member under a heating condition of 10 ° C./min.

If there are a plurality of recrystallization peaks, the total calorific value is calculated as “ΔHc”, and if there are a plurality of crystal melting peaks, the total calorific value is calculated as “ΔHm”. Those without a recrystallization peak (ΔHc = 0J / g) when measured with a differential scanning calorimeter are “fully crystallized FRP members”, and those with a recrystallization peak are “completely”. It can be said that it is a non-crystallized FRP member.

In order to keep the relative crystallinity within the above range, for example, when the FRP member is a film, the selection of the resin component used as a raw material, the conditions for extruding the film, etc. may be appropriately adjusted. , It is preferable to adopt the following methods (1) to (4). These methods may be used in combination. Among them, the method (1), in which wrinkles are less likely to occur due to the obtained composite material and energy consumption is low, is preferable.

(1) A method of adjusting the cooling conditions when the molten resin is cooled to form a film shape. The 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 method.

A method of setting the cooling temperature to a temperature 30 to 150 ° C. higher than the glass transition temperature of the resin component can be mentioned. The cooling temperature is more preferably 35 to 140 ° C. higher than the glass transition temperature of the resin component, 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 down, and the relative crystallinity tends to be increased.
In particular, when the resin component contains polyetheretherketone as a main component, the cooling temperature is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, further preferably 200 ° C. or higher, and 210 ° C. The above is particularly preferable.
On the other hand, the cooling temperature is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, further preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower, and 240 ° C. or lower. Is the most preferable.
In the present invention, the "main component" refers to the most abundant component in the object, preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70 in the object. It is by mass, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.

(2) A method of reheating a film using a heating roll. Specifically, a method of heating with a roll different from the cast roll such as a longitudinal stretching machine can be mentioned. The temperature at the time of heating is preferably in the same range as the cooling temperature of (1) above.

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

(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 by roll-to-roll, or the film may be passed through a far-infrared dryer to heat the film. The temperature at the time of heating is preferably in the same range as the cooling temperature of (1) above.

The treatments (2) to (4) may be performed at the same time as the film production by providing equipment for that purpose in the film production line, or once the film is wound into a roll, the film roll may be performed. May be carried out by these facilities outside the production line.

[specific gravity]
The specific gravity of this member is preferably 1.27 or more, and more preferably 1.28 or more. There is a correlation between the relative crystallinity and the specific gravity, and usually, the higher the relative crystallinity, the higher the specific gravity. Therefore, when the specific gravity is equal to or higher than the above value, shrinkage due to heat tends to be suppressed when the present member and the reinforcing fiber are heat-bonded to form a composite material, and the material has excellent heat resistance and rigidity. It becomes a tendency that can be.
On the other hand, the specific gravity of this member is preferably 1.35 or less, and more preferably 1.34 or less.
The specific gravity in the present invention is a value measured under the condition of a temperature of 23 ° C. in accordance with the measuring method of JIS K7112: 1999 (method D).

[Heat shrinkage rate]
The heat shrinkage rate of this member is preferably 2.2% or less, more preferably 1.8% or less, further preferably 1.5% or less, and 1.2% or less. It is particularly preferable, 0.8% or less is particularly preferable, and 0.6% or less is most preferable. By setting the heat shrinkage rate to the above value or less, shrinkage due to heat tends to be suppressed when the present member and the reinforcing fiber are heat-bonded to form a composite material, and the obtained composite material also has an appearance such as wrinkles. It tends to be less likely to cause defects. The lower limit of the heat shrinkage rate of the present member is not particularly limited and is preferably 0%, but may be 0.1% or 0.2%.
In the present invention, the heat shrinkage rate is set on a test piece having a size of 120 mm × 120 mm cut out from the present member in the form of a film or the like, and marked lines at intervals of 100 mm in a direction (TD) orthogonal to the resin flow direction (MD). Then, this test piece is allowed to stand in an environment of 200 ° C. for 10 minutes, and is obtained by the following formula 2 from the distance between the marked lines before and after heating.
[Equation 2]
Heat shrinkage rate (%) = [(Distance between marked lines before heating-Distance between marked lines after heating)
/ Distance between marked lines before heating] x 100

[Heat shrinkage stress]
The heat shrinkage stress of this member is preferably 1 mN or less, 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 value or less, shrinkage due to heat tends to be suppressed when the present member and the reinforcing fiber are heat-bonded to form a composite material, and the obtained composite material also has an appearance such as wrinkles. Defects tend to be less likely to occur. The lower limit of the heat shrinkage stress of this member is not particularly limited and is preferably 0 mN.
In the present invention, the heat shrinkage stress can be obtained by the following method.
A strip-shaped test piece with a length of 10 mm and a width of 3 mm is cut out from this member in the form of a film, and one end of the test piece is used as a chuck for a load detector using the thermomechanical analyzer "TMA7100" manufactured by Hitachi High-Tech Science. The other end is set on the fixed chuck, 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 for each of the resin flow direction (MD) and the direction orthogonal to it (TD), and the one with the larger stress value is taken as the heat shrinkage stress of the present invention.

[Tension modulus]
The tensile elastic modulus of this member is preferably 3450 MPa or more, more preferably 3500 MPa or more, further preferably 3550 MPa or more, and particularly preferably 3600 MPa or more. Since this member contains a crystalline resin having a wide molecular weight distribution, it contains a relatively large amount of high molecular weight components, and the proportion of a crystal region having high rigidity is large, so that the tensile elastic modulus tends to be high as a result. If the tensile elastic modulus is equal to or higher than the above value, the rigidity is excellent, and the obtained composite material tends to be excellent in rigidity and strength.
On the other hand, the tensile elastic modulus is preferably 5000 MPa or less, more preferably 4500 MPa or less, further preferably 4000 MPa or less, particularly preferably 3900 MPa or less, and most preferably 3800 MPa or less. When the tensile elastic modulus is equal to or less than the above value, the obtained member does not have too high rigidity and tends to be excellent in secondary workability such as shaping of the composite material.
The tensile elastic modulus in the present invention is as follows: a strip-shaped test piece having a length of 400 mm and a width of 5 mm is prepared from the film-shaped member, and a "tensile compression tester 205 type" manufactured by Intesco is used at a temperature of 23 ° C. and between chucks. It is a value measured under the conditions of a distance of 300 mm and a tensile speed of 5 mm / min. When the FRP member has directionality such as an extruded film, measurements are taken in both the resin extrusion (flow) direction (MD) and the direction orthogonal to it (TD), and the average value is the tensile elastic modulus. And.

[Crystal melting temperature (Tm)]
The crystal melting temperature of this member is preferably 320 ° C. or higher, more preferably 330 ° C. or higher, further preferably 340 ° C. or higher, particularly preferably 341 ° C. or higher, and 342 ° C. or higher. Is most preferable. When the crystal melting temperature of the present member is equal to or higher than the above temperature, the obtained present member tends to have excellent heat resistance. On the other hand, the crystal melting temperature is preferably 370 ° C. or lower, more preferably 365 ° C. or lower, further preferably 360 ° C. or lower, particularly preferably 355 ° C. or lower, and 350 ° C. or lower. Is most preferable. When the crystal melting temperature of this member is equal to or lower than the above temperature, the fluidity tends to be excellent at the time of melt molding such as at the time of manufacturing this member, and to the fiber when manufacturing a composite material with a reinforcing fiber using this member. It tends to be excellent in secondary processability such as impregnation property.

[Crystalization temperature (Tc)]
The crystallization temperature in the temperature lowering process of this member is preferably 296 ° C. or higher, more preferably 300 ° C. or higher, further preferably 302 ° C. or higher, particularly preferably 303 ° C. or higher, 304. Most preferably, it is above ° C. When the crystallization temperature in the temperature lowering process of this member is equal to or higher than the above temperature, the crystallization rate is high, the cycle for producing the composite material with the reinforcing fiber can be shortened, and the productivity tends to be excellent.

On the other hand, the crystallization temperature in the temperature lowering process is preferably 320 ° C. or lower, more preferably 315 ° C. or lower, further preferably 312 ° C. or lower, and particularly preferably 310 ° C. or lower. If the crystallization temperature in the temperature lowering process of this member is lower than the above temperature, the crystallization is not too fast, so that the cooling unevenness during the production of the composite material with the reinforcing fiber is reduced, and the uniformly crystallized high-quality composite material. Will be obtained. In addition, it becomes easy to sufficiently impregnate the reinforcing fiber with this member when manufacturing a composite material with the reinforcing fiber, and there is an advantage that the obtained composite material tends to be uniformly crystallized and of high quality.

[Crystal melting heat (ΔHm)]
The amount of heat of crystal melting of this member is preferably 42 J / g or more, more preferably 44 J / g or more, further preferably 46 J / g or more, and particularly preferably 48 J / g or more. Most preferably, it is 50 J / g or more. When the amount of heat of crystal melting of the present member is equal to or higher than the above value, the obtained present member has a sufficient degree of crystallinity, and thus tends to be excellent in heat resistance and rigidity. Further, the heating dimensional stability tends to be excellent when the composite material is used as a composite material with the reinforcing fiber, and the obtained composite material also tends to be excellent in heat resistance and rigidity.
On the other hand, the amount of heat of crystal melting of this member is preferably 60 J / g or less, more preferably 58 J / g or less, further preferably 56 J / g or less, and particularly preferably 54 J / g or less. preferable. If the amount of heat of crystal melting of this member is equal to or less than the above value, the crystallinity is not too high, so that the secondary processability such as impregnation property into the fiber when producing a composite material with the reinforcing fiber tends to be excellent. Further, the obtained composite material tends to be excellent in durability and impact resistance.

[Thickness accuracy]
When the shape of this member is a thin flat shape whose thickness is extremely small compared to the length and width of a film, sheet, plate, etc., the thickness accuracy of this member is preferably 7% or less, preferably 5%. It is more preferably less than or equal to, further preferably 4% or less, particularly preferably 3% or less, particularly preferably 2.5% or less, and most preferably 2% or less. Within the range where the thickness accuracy is applied, the variation in the content of the reinforcing fiber in the obtained composite material tends to be small when the composite is combined with the reinforcing fiber, that is, the variation in the mechanical property values such as the strength depending on the part of the composite material is likely to be small. It is easy to obtain a composite material that is small and has high uniformity of mechanical properties. The lower limit of the thickness accuracy is not particularly limited and is preferably 0%, but is usually 0.1%, may be 0.3%, may be 0.5%, or is 0. It may be 8.8% or 1%.
The thickness accuracy can be calculated by the following formula 3 from the average value and standard deviation of the measured film thickness, and specifically, it can be measured by the method described in Examples described later.
[Equation 3]
Thickness accuracy (%) = standard deviation (μm) / average value (μm) x 100

The method for adjusting the thickness accuracy of the present member to a desired range is not particularly limited. For example, when the present member is a film, extrusion molding may be adopted and the conditions for extruding the film may be appropriately adjusted. .. Specifically, for example
(1) A method of adjusting the lip opening by mechanically rotating the lip bolt of a die such as a T-die (2) Attaching a heating device to the die lip at regular intervals and adjusting the temperature of each individually to adjust the viscosity of the molten resin. Method of adjusting the film thickness by using the temperature change of (3) Method of adjusting the distance between the die and the cast roll so that the film vibration and pulsation of the molten resin extruded into the film shape are not generated as much as possible (4) Film A method of installing a plate or cover to block the air flow so that the molten resin extruded in the shape does not pulsate due to the flow of gas such as the surrounding air when it comes into contact with the cast roll (5) Extruded into a film shape. A method of adjusting so that the discharge amount does not fluctuate at the time (6) A method of reducing the rotation fluctuation rate of the cast roll to suppress the rotation unevenness of the roll (7) A high voltage is applied to the molten resin extruded into a film shape. A method in which static charge is applied from the electrode and the cast roll is brought into close contact with the cast roll by electrostatic force (electrostatic contact method).
(8) A method in which a curtain-shaped compressed air is blown onto the molten resin extruded into a film to be brought into close contact with the cast roll (9) A method in which the molten resin extruded into a film is brought into close contact with the cast roll by a nip roll and the like can be mentioned. ..

[Surface roughness]
When the shape of this member is a thin flat shape whose thickness is extremely small compared to the length and width of a film, sheet, plate, etc., the surface roughness of at least one surface (one side) may be within a specific range. preferable. Specifically, the arithmetic mean height (Sa), the maximum height (Sz), the arithmetic average roughness (Ra), and the maximum height roughness (Rz) of at least one surface of the present member are specific ranges described later. Is preferable. It is also preferable that the surface roughness of both surfaces of the present member is within a specific range described later.

[Arithmetic Mean Height (Sa)]
The arithmetic mean height (Sa) of at least one side of this member is preferably 0.001 μm or more, more preferably 0.005 μm or more, further preferably 0.01 μm or more, and more preferably 0.015 μm or more. Is particularly preferable, 0.02 μm or more is particularly preferable, 0.025 μm or more is particularly preferable, and 0.03 μm or more is most preferable. The arithmetic mean height (Sa) is preferably 1 μm or less, more preferably 0.5 μm or less, further preferably 0.25 μm or less, and more preferably 0.2 μm or less. Further preferably, it is particularly preferably 0.1 μm or less, particularly preferably 0.08 μm or less, and most preferably 0.06 μm or less.
When the arithmetic mean height (Sa) is equal to or higher than the above value, the slipperiness when feeding the film or the like from the film roll or the like is lowered in the process of laminating with the reinforcing fiber sheet or the like when manufacturing a composite material such as a prepreg. As a result, it is difficult for the film or the like to meander or become slanted, and it is easy to obtain an FRP member having excellent workability. In addition, the static electricity accumulated on the film roll or the like causes sparks when the film is unwound to damage the surface of the film or the like, or the floating dust is attracted by the static electricity and adheres to the surface of the film or the like to obtain the composite material. It is preferable that the problem that foreign matter is mixed in is less likely to occur. Further, when the arithmetic average height (Sa) is equal to or less than the above value, the variation in the content of the reinforcing fiber in the obtained composite material tends to be small when the composite is combined with the reinforcing fiber, that is, the strength depending on the part of the composite material. It becomes easy to obtain a composite material having high uniformity of mechanical properties due to small variation in mechanical property values such as. Further, there is an advantage that the problem that the film or the like slips, shifts, twists, wrinkles or the like occurs on the transport roll during the film transport when the film or the like is unwound from the film roll or the like is unlikely to occur.
The arithmetic mean height (Sa) can be measured using a white interference microscope, and specifically, can be measured by the method described in Examples described later.

[Maximum height (Sz)]
The maximum height (Sz) of at least one surface of the present member is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 0.75 μm or more, and further preferably 1 μm or more. Is particularly preferable, 1.3 μm or more is particularly preferable, and 1.5 μm or more is most preferable. The maximum height (Sz) is preferably 10 μm or less, more preferably 7 μm or less, further preferably 5 μm or less, further preferably 4 μm or less, and 3.5 μm or less. It is particularly preferably present, particularly preferably 3 μm or less, particularly preferably 2.5 μm or less, and most preferably 2.2 μm or less.
When the maximum height (Sz) is equal to or higher than the above value, the slipperiness when feeding the film or the like from the film roll or the like is lowered in the process of laminating with the reinforcing fiber sheet or the like when manufacturing a composite material such as a prepreg. This makes it difficult for the film or the like to meander or tilt, and tends to be an FRP member with excellent workability. In addition, the static electricity accumulated on the film roll or the like causes sparks when the film is unwound to damage the surface of the film or the like, or the floating dust is attracted by the static electricity and adheres to the surface of the film or the like to obtain the composite material. It is preferable that the problem that foreign matter is mixed in is less likely to occur. Further, when the maximum height (Sz) is equal to or less than the above value, the variation in the content of the reinforcing fibers in the obtained composite material tends to be small when the composite is combined with the reinforcing fibers, that is, the strength depending on the part of the composite material, etc. The variation in the mechanical property values of the above is small, and it becomes easy to obtain a composite material having high uniformity of mechanical properties. Further, there is an advantage that the problem that the film or the like slips, shifts, twists, wrinkles or the like occurs on the transport roll during the film transport when the film or the like is unwound from the film roll or the like is unlikely to occur.
The maximum height (Sz) can be measured using a white interference microscope, and specifically, can be measured by the method described in Examples described later.

[Arithmetic Mean Roughness (Ra)]
The arithmetic mean roughness (Ra) of at least one side of this member is preferably 0.005 μm or more, more preferably 0.008 μm or more, further preferably 0.01 μm or more, and more preferably 0.015 μm or more. Is particularly preferable, 0.02 μm or more is particularly preferable, and 0.025 μm or more is most preferable. Further, the arithmetic mean roughness (Ra) is preferably 1 μm or less, more preferably 0.7 μm or less, further preferably 0.5 μm or less, and further preferably 0.3 μm or less. It is preferably 0.2 μm or less, particularly preferably 0.15 μm or less, particularly preferably 0.1 μm or less, and most preferably 0.07 μm or less.
When the arithmetic mean roughness (Ra) is equal to or higher than the above value, the slipperiness when feeding the film or the like from the film roll or the like is lowered in the process of laminating with the reinforcing fiber sheet or the like when manufacturing a composite material such as a prepreg. As a result, it is difficult for the film or the like to meander or become slanted, and it is easy to obtain an FRP member having excellent workability. In addition, the static electricity accumulated on the film roll or the like causes sparks when the film is unwound to damage the surface of the film or the like, or the floating dust is attracted by the static electricity and adheres to the surface of the film or the like to obtain the composite material. It is preferable that the problem that foreign matter is mixed in is less likely to occur. Further, when the arithmetic average roughness (Ra) is equal to or less than the above value, the variation in the content of the reinforcing fibers in the obtained composite material tends to be small when the composite is combined with the reinforcing fibers, that is, the strength depending on the site of the composite material. It becomes easy to obtain a composite material having high uniformity of mechanical properties due to small variation in mechanical property values such as. Further, there is an advantage that the problem that the film or the like slips, shifts, twists, wrinkles or the like occurs on the transport roll during the film transport when the film or the like is unwound from the film roll or the like is unlikely to occur.
The arithmetic average roughness (Ra) can be measured using a contact type surface roughness meter in accordance with JIS B0601: 2013, and specifically, it can be measured by the method described in Examples described later. can.

[Maximum height roughness (Rz)]
The maximum height roughness (Rz) of at least one surface of the present member is preferably 0.05 μm or more, more preferably 0.1 μm or more, particularly preferably 0.15 μm or more, and 0.2 μm. The above is particularly preferable, and 0.25 μm or more is most preferable. The maximum height roughness (Rz) is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, particularly preferably 1 μm or less, and 0.8 μm or less. Is particularly preferable, and 0.5 μm or less is most preferable.
When the maximum height roughness (Rz) is equal to or higher than the above value, the slipperiness when feeding the film or the like from the film roll or the like is lowered in the process of laminating with the reinforcing fiber sheet or the like when manufacturing a composite material such as a prepreg. By doing so, it is difficult for the film or the like to meander or become slanted, and it is easy to obtain an FRP member having excellent workability. In addition, the static electricity accumulated on the film roll or the like causes sparks when the film is unwound to damage the surface of the film or the like, or the floating dust is attracted by the static electricity and adheres to the surface of the film or the like to obtain the composite material. It is preferable that the problem that foreign matter is mixed in is less likely to occur. Further, when the maximum height roughness (Rz) is equal to or less than the above value, the variation in the content of the reinforcing fibers in the obtained composite material tends to be small when the composite is combined with the reinforcing fibers, that is, it depends on the site of the composite material. The variation in mechanical property values such as strength is small, and it becomes easy to obtain a composite material having high uniformity of mechanical property. Further, there is an advantage that the problem that the film or the like slips, shifts, twists, wrinkles or the like occurs on the transport roll during the film transport when the film or the like is unwound from the film roll or the like is unlikely to occur.
The maximum height roughness (Rz) can be measured by using a contact type surface roughness meter in accordance with JIS B0601: 2013, and specifically, it shall be measured by the method described in Examples described later. Can be done.

The method for adjusting the arithmetic average height (Sa), maximum height (Sz), arithmetic average roughness (Ra), and maximum height roughness (Rz) of this member is not particularly limited, but for example. , Embossed roll transfer, embossed belt transfer, embossed film transfer, etc., sandblasting, shotblasting, etching, engraving, surface crystallization, and coating, drying, and heat treatment of resin components on the support. In the casting step of obtaining this member, various methods such as a method of appropriately adjusting the surface roughness of a metal roll, an endless metal belt, a polymer film or the like used as a support by polishing or the like can be used. Above all, since it is easy to continuously and uniformly adjust the surface roughness while extruding the molten resin into a film shape, the desired roughness is adjusted by casting the film-shaped molten resin on a roll such as a cast roll. The method is preferred. In this case, the surface roughness of the resin film can be adjusted by adjusting the surface roughness such as the arithmetic average roughness of the cast roll.

[Usage / Usage]
Since this member is excellent in heat dimensional stability, rigidity, and productivity, it can be used as a material for composite with reinforcing fibers. In particular, when the FRP member of the present invention is a film, it can be suitably used as a material for composite with reinforcing fibers.

The type of the reinforcing fiber is not particularly limited, but for example, carbon fiber, glass fiber, boron fiber, inorganic fiber such as alumina fiber, liquid crystal polymer fiber, polyethylene fiber, aramid fiber, polyparaphenylene benzoxazole fiber and the like. Examples thereof include organic fibers, aluminum fibers, magnesium fibers, titanium fibers, SUS fibers, copper fibers, metal fibers such as carbon fibers coated with metal, and the like. Among these, carbon fiber is preferable from the viewpoint of rigidity and lightness.

Examples of the carbon fiber include polyacrylonitrile (PAN) type, petroleum / coal pitch type, rayon type, lignin type and the like, and any carbon fiber can be used. In particular, PAN-based carbon fibers made from PAN, and strands or tows of 12,000 to 48,000 filaments are preferable because they are excellent in productivity and mechanical properties on an industrial scale.

The number average fiber length of the reinforcing fibers is usually 0.5 mm or more, preferably 1 mm or more, more preferably 3 mm or more, further preferably 5 mm or more, and particularly preferably 10 mm or more. , 30 mm or more is particularly preferable, and 50 mm or more is most preferable. Further, it is also preferable that the reinforcing fiber is a continuous fiber. By setting the number average fiber length to the above value or more, the mechanical properties of the obtained composite material tend to be sufficient. The upper limit of the number average fiber length is not particularly limited, but in the case of discontinuous fibers such as woven fabrics, knits, and non-woven fabrics in which the shape of the reinforcing fiber is described later, the number average fiber length is preferably 500 mm or less, preferably 300 mm or less. It is more preferable that it is 150 mm or less, and it is further preferable that it is 150 mm or less. By setting the number average fiber length to the above-mentioned numerical value or less, the filling property of the reinforcing fiber into the complicated shape portion when molding the final product, particularly the final product having a complicated shape, by using the composite material is made sufficient, and the relevant portion. It tends to be easy to suppress the occurrence of the decrease in strength.

The number average fiber length of the reinforcing fibers refers to the average length of the portion where the length is observed to be the longest when the reinforcing fibers are observed using an electron microscope such as a scanning electron microscope or an optical microscope. Specifically, it can be obtained by observing a cross section in which the length direction of the reinforcing fibers existing in the composite material can be observed and averaging the measured fiber lengths.
As another method, a dispersion liquid in which the reinforcing fibers from which the resin component has been removed with a solvent or the like is dispersed in an appropriate dispersant is laminated in a thin film, and the image of the reinforcing fibers taken by a scanner or the like is used by image processing software or the like. Another method is to obtain the number average fiber length.

The shape of the reinforcing fiber is also not particularly limited, and is not particularly limited, and fiber bundles such as chopped strands and rovings, woven fabrics such as plain weave and twill weave, knitted fabrics, non-woven fabrics, fiber papers, and UD materials (unidirectional materials). From the above-mentioned reinforcing fiber sheets, it can be appropriately selected as needed.

The method of compositing the reinforcing fiber and this member is not particularly limited, and by adopting a conventionally known method such as a resin film impregnation method (film stacking method) or a mixed weaving method, the reinforcing fiber bundle or the reinforcing fiber sheet can be used. It is possible to manufacture a composite material such as a prepreg impregnated or semi-impregnated with this member. Among these, in the present invention, it is preferable to adopt the resin film impregnation method (film stacking method).

Specifically, the resin component of the present member can be melted and impregnated in the reinforcing fiber sheet to form a prepreg by superimposing the present member on one side or both sides of the above-mentioned reinforcing fiber sheet and heating / pressurizing the member. At this time, by adjusting the heating and pressurizing conditions, it is possible to obtain a prepreg in which the amount of voids contained is controlled. The prepreg also includes a form in which the pressurizing step is omitted and the member is temporarily bonded to the reinforcing fiber sheet by heat fusion. In the case of a prepreg temporarily bonded in this way, particularly one containing a large amount of voids, there is an advantage that the time required for manufacturing can be shortened, which leads to a reduction in manufacturing cost, and because it has flexibility, it is easily deformed according to the actual shape. .. The above method can be suitably used when the present member is a film.

By subjecting this prepreg to known processes such as autoclave molding, infusion molding, heat and cool press molding, stamping molding, and automatic laminating molding by a robot, a composite material product can be obtained, and the molding conditions thereof are included. It can be selected according to the amount of voids. This member, such as a film used for producing a prepreg, is required to have excellent molding cycle when composited with a reinforcing fiber, in addition to secondary processability such as impregnation property into a reinforcing fiber sheet and heat fusion property. Since this member contains a resin component with a specific molecular weight distribution and mass average molecular weight and has a high crystallization rate, the molding cycle is short and the productivity is excellent, and the obtained composite material also has excellent rigidity and heat resistance. Can be suitably used.

The content ratio of the reinforcing fibers in the composite material thus obtained is preferably 20% by volume or more, more preferably 30% by volume or more, and more preferably 40% by volume or more from the viewpoint of elastic modulus and strength. Is more preferable. On the other hand, the content ratio of the reinforcing fibers in the composite material is preferably 90% by volume or less, more preferably 80% by volume or less, and further preferably 70% by volume or less.

Due to its heat resistance, light weight, mechanical strength, etc., composite materials made by combining this member and reinforcing fibers are used for moving objects such as aircraft, automobiles, ships, or railroad vehicles, sports equipment, home appliances, building materials, etc. However, it is particularly industrially useful as a component of a moving body such as an aircraft, an automobile, a ship, or a railroad vehicle.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

<Examples 1 to 3 and Comparative Examples 1 to 6>
Number average molecular weight (Mn), mass average molecular weight (Mw), molecular weight distribution (Mw / Mn), melt flow rate (MFR), crystal melting temperature (Tm), crystallization temperature (Tc), crystals shown in Table 1 below. Raw material resin pellets of polyether ether ketone (glass transition temperature 143 ° C.) having a heat of melting (ΔHm) were put into a Φ40 mm single shaft extruder and melted while kneading. Then, it was extruded from a base (T die) and brought into close contact with and cooled to a cast roll to obtain an FRP member (film). The temperature of the extruder, the connecting pipe, and the base (T die) was 380 ° C., and the temperature and film thickness of the cast roll were the temperatures and thicknesses shown in Table 1 below. The resin temperature at the outlet of the extruder was 400 ° C.

<Evaluation of resin raw materials and films>
The raw material resins used in the Examples and Comparative Examples and the films obtained by the above methods were evaluated and measured for various items as follows. The evaluation results are shown in Table 1.
The "vertical" of the film refers to the direction (MD) in which the film is extruded from the base (T die), and the direction orthogonal to this in the film surface is defined as "horizontal" (TD).

(1) Molecular weight distribution (Mw / Mn), mass average molecular weight (Mw), number average molecular weight (Mn)
With respect to the raw material resin pellets, a sample prepared according to the following sample preparation conditions was measured under the following measurement conditions using a gel permeation chromatograph “HLC-8320GPC” manufactured by Tosoh Corporation.
[Sample preparation conditions]
The raw material resin pellets were pressed at 380 ° C. and then rapidly cooled at 100 ° C. to obtain an amorphous raw material resin film. 3 g of pentafluorophenol was added to 9 mg of this amorphous raw material resin film, and the mixture was heated and dissolved at 100 ° C. for 60 minutes using a heat block. Subsequently, it was taken out from the heat block, allowed to cool, and then 6 g of chloroform at room temperature (23 ° C.) was gently added little by little and shaken gently. Then, a sample filtered through a 0.45 μm PTFE cartridge filter was used as a sample.
[Measurement condition]
-Column: TSKgel guardgroup SuperH-H (4.6 mm I.D. x 3.5 cm) x 1 + TSKgel SuperHM-H (6.0 mm I.D. 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 amount: 20 μL
-Calibration curve: A cubic approximation curve using standard polystyrene (manufactured by Tosoh Corporation)

(2) Melt flow rate (MFR)
The MFR of the raw material resin pellets was measured in accordance with JIS K7210-1: 2014 (method A) under the conditions of a temperature of 380 ° C. and a load of 5 kgf.

(3) Crystal melting temperature (Tm)
For the raw material resin pellets and the film obtained by the above method, a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C./ The temperature was raised in minutes, and the crystal melting temperature was determined from the peak top temperature of the melting peak of the detected DSC curve.

(4) Crystallization temperature (Tc)
For the raw material resin pellets and the film obtained by the above method, a temperature range of 400 to 25 ° C. and a speed of 10 ° C./min using a differential scanning calorimeter "Pyris1 DSC" manufactured by PerkinElmer Co., Ltd. according to JIS K7121: 2012. The temperature was lowered in 1 and the crystallization temperature was obtained from the peak top temperature of the crystallization peak of the detected DSC curve.

(5) Heat for melting crystals (ΔHm)
For the raw material resin pellets and the film obtained by the above method, a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C./ The temperature was raised in minutes, and the amount of heat of crystal melting was obtained from the area of the melting peak of the detected DSC curve.

(6) Relative Crystallinity With respect to the film obtained by the above method, the film was heated at a heating rate of 10 ° C./min using a differential scanning calorimeter "Pyris1 DSC" manufactured by PerkinElmer Co., Ltd., at this time. The relative crystallization degree was calculated using the following formula 1 from the calorific value (J / g) of the obtained crystal melting peak and the calorific value (J / g) of the recrystallization peak.
[Equation 1]
Relative crystallinity (%) = {1- (ΔHc / ΔHm)} × 100
ΔHc: Calorific value (J / g) of the recrystallization peak of the film under the heating condition of 10 ° C./min.
ΔHm: Calorific value (J / g) of the crystal melting peak of the film under the heating condition of 10 ° C./min.

(7) Relative Density With respect to the film obtained by the above method, the relative density was measured under the condition of a temperature of 23 ° C. in accordance with JIS K71112: 1999 (Method D).

(8) Tension elastic modulus A strip-shaped test piece having a length of 400 mm and a width of 5 mm was prepared from the film obtained by the above method, and a "tensile compression tester type 205" manufactured by Intesco was used to obtain a chuck distance of 300 mm and tension. The tensile elastic modulus (MPa) at 23 ° C. was measured under the condition of a speed of 5 mm / min and used as an index of rigidity. Measurements were performed in the vertical and horizontal directions of the film, and the average value of the obtained measured values was adopted.

(9) Heat Shrinkage Rate A test piece having a size of 120 mm × 120 mm cut out from the film obtained by the above method is marked with lines at intervals of 100 mm in the lateral direction of the film, and the test piece is placed in an environment of 200 ° C. It was allowed to stand for 10 minutes, and was calculated by the following formula 2 from the distance between the marked lines before and after heating.
[Equation 2]
Heat shrinkage rate (%) = [(Distance between marked lines before heating-Distance between marked lines after heating)
/ Distance between marked lines before heating] x 100

(10) Heat-shrinkage stress A strip-shaped test piece having a length of 10 mm and a width of 3 mm is cut out from the film obtained by the above method, and one end of the test piece is used by Hitachi High-Tech Science's thermomechanical analyzer "TMA7100". Is set on the chuck of the load detector and the other end is set on the fixed chuck, 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. did. Measurements were made in the vertical direction and the horizontal direction of the film, respectively, and the value in the direction in which the stress value was large was defined as the heat shrinkage stress (mN).
In this measurement method, a negative value of heat shrinkage stress means that there is no heat shrinkage.

(11) Thickness accuracy Using a micrometer having a resolution of 1 μm unit, the thickness of the central portion of the film obtained by the above method in the width direction was measured at 30 points at 10 mm intervals in the vertical direction of the film. From the average value and standard deviation of the obtained measurement results, the thickness accuracy was calculated using the following formula 3.
[Equation 3]
Thickness accuracy (%) = standard deviation (μm) / average value (μm) x 100

(12) Surface roughness (12-1) Arithmetic mean height (Sa), maximum height (Sz)
For the surface on the side in contact with the cast roll during film formation, using the BRUKER white interference microscope "FunctionGT-X", the eyepiece magnification was 1.0 times, the objective lens magnification was 20 times, and the measurement area was 235 μm x. The measurement was performed under the condition of horizontal 313 μm, and after performing the smoothing process by the Gaussian function, the arithmetic average height (Sa) and the maximum height (Sz) were calculated.

(12-2) Arithmetic mean roughness (Ra), maximum height roughness (Rz)
For the surface on the side in contact with the cast roll during film formation, a contact type surface roughness meter "Surf Coder ET4000A" manufactured by Kosaka Research Institute was used to measure the tip radius of the stylus of 0.5 mm and the measurement length of 8.0 mm. The arithmetic average roughness (Ra) and the maximum height roughness (Rz) are measured in the vertical direction of the film under the conditions of a reference length of 8.0 mm, a cutoff value of 0.8 mm, and a measurement speed of 0.2 mm / sec. Calculated.

In the FRP members (films) of Examples 1 to 3, the resin component used has a molecular weight distribution of 3.3 or more and a mass average molecular weight of less than 87,000, so that the crystallization temperature during cooling is high, that is, the crystallization rate. Because of the high speed, the film was sufficiently crystallized when the film was separated from the cast roll, and the film productivity was excellent. Further, since the relative crystallinity is 50% or more, the dimensional change is unlikely to occur when the composite is formed by heat-pressing with the reinforcing fiber, and the obtained composite material such as prepreg is wrinkle-free. Further, since the FRP members of Examples 1 to 3 contain a relatively large amount of low molecular weight components due to the small mass average molecular weight of the resin components and the wide molecular weight distribution, the crystallization rate during cooling is fast, that is, they are strengthened. Since the crystallization is fast when the composite is combined with the fiber and the impregnation property into the reinforcing fiber is good, the effect that the cycle at the time of producing the composite material is short can be obtained. In addition, since the obtained film contains a resin component having a wide molecular weight distribution, it can be seen that the content ratio of the high molecular weight resin component is high and the tensile elastic modulus (rigidity) is also high.

On the other hand, since the FRP members of Comparative Examples 1, 2, 4 and 5 have a relative crystallinity of less than 50%, the film is dimensionally changed when it is heat-bonded to the reinforcing fiber to form a composite, and the finished product is completed. The prepreg was wrinkled.
Further, the FRP member of Comparative Example 3 using a resin component having a molecular weight distribution narrower than 3.3 had a low tensile elastic modulus because the content ratio of the high molecular weight resin component was low.
Since the FRP members of Comparative Examples 5 and 6 have a mass average molecular weight of 87,000 or more, the crystallization temperature is low, that is, the crystallization rate is slow, so that the productivity of the FRP members and the composite material is low.

Further, the composite material obtained by combining the films of Examples 1 to 3 with reinforcing fibers such as carbon fibers can be used for moving bodies such as aircraft, automobiles, ships or railroad vehicles, sporting goods, home appliances, building materials and the like. Although it can be suitably used, it can be particularly preferably used as a structure of an aircraft, an automobile, a ship, a railroad vehicle, or the like.

Since the FRP member of the present invention is excellent in heat dimensional stability, rigidity, and productivity, it can be used as a material for composite with reinforcing fibers.

Claims (18)

A member for fiber reinforced plastic containing a crystalline resin as a resin component, wherein the member has a molecular weight distribution of 3.3 or more and a mass average molecular weight of less than 87,000, and is obtained by using a differential scanning calorimeter. A member for fiber reinforced plastic having a relative crystallinity of 50% or more. The fiber-reinforced plastic member according to claim 1, wherein the resin component contains a polyaryletherketone. The fiber-reinforced plastic member according to claim 2, wherein the polyaryletherketone has a molecular weight distribution of 3.3 or more and a mass average molecular weight of less than 87,000. The fiber-reinforced plastic member according to any one of claims 1 to 3, wherein the fiber-reinforced plastic member has a specific gravity of 1.27 or more. The fiber-reinforced plastic member according to any one of claims 1 to 4, wherein the fiber-reinforced plastic member has a heat shrinkage rate of 2.2% or less. The fiber-reinforced plastic member according to any one of claims 1 to 5, wherein the heat shrinkage stress of the fiber-reinforced plastic member is 1 mN or less. The fiber-reinforced plastic member according to any one of claims 1 to 6, wherein the fiber-reinforced plastic member has a tensile elastic modulus of 3500 MPa or more measured under a condition of a tensile speed of 5 mm / min. The fiber-reinforced plastic member according to any one of claims 1 to 7, wherein the fiber-reinforced plastic member has a crystallization temperature of 296 ° C. or higher. The fiber-reinforced plastic member according to any one of claims 1 to 8, wherein the fiber-reinforced plastic member has a thickness of 10 to 100 μm. The fiber-reinforced plastic member according to any one of claims 1 to 9, wherein the thickness accuracy of the fiber-reinforced plastic member is 7% or less. The fiber-reinforced plastic member according to any one of claims 1 to 10, wherein the arithmetic average height of the surface of the fiber-reinforced plastic member on at least one surface is 0.001 to 1 μm. The fiber-reinforced plastic member according to any one of claims 1 to 11, wherein the maximum height of the surface of the fiber-reinforced plastic member on at least one surface is 0.1 to 10 μm. The fiber-reinforced plastic member according to any one of claims 1 to 12, wherein the arithmetic mean roughness of the surface of the fiber-reinforced plastic member on at least one surface is 0.005 to 1 μm. The fiber-reinforced plastic member according to any one of claims 1 to 13, wherein the maximum height roughness of the surface of the fiber-reinforced plastic member on at least one surface is 0.05 to 5 μm. The fiber reinforced plastic member according to any one of claims 1 to 14, which is a film. A composite material obtained by combining the fiber-reinforced plastic member according to any one of claims 1 to 15 and the reinforcing fiber. The composite material of claim 16, which is a prepreg. A moving body that is an aircraft, automobile, ship, or railroad vehicle using the composite material according to claim 16 or 17.