JP5830500B2 - Method for producing graphite film - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a graphite film used as a heat dissipation film and heat spreader material for electronic equipment, precision equipment, and the like, and a method for producing the same, and in particular, a thin graphite film having flexibility and excellent thermal diffusivity, and the production thereof. Regarding the method.

  Cooling problems such as semiconductor elements mounted on various electronic / electrical devices such as computers and other heat generating parts are attracting attention. As a method of cooling such a heat generating component, a fan is attached to the device housing on which the heat generating component is mounted and the device housing is cooled, or heat generation such as a heat pipe, heat spreader, heat sink or fin is applied to the heat generating component. A method of cooling by attaching a body and carrying heat from the element to the outside is common. Examples of the heat conductive material attached to the heat generating component include an aluminum plate and a copper plate. In this case, a heat generating component is attached to a part of an aluminum or copper plate or a heat pipe, and the other part of the plate is radiated to the outside using fins or a fan.

By the way, in recent years, each device on which a heat-generating component such as a semiconductor element is mounted tends to be downsized, and the amount of heat generated by the member tends to increase. Further, since the housing is downsized, the space for inserting components such as fins, heat sinks and fans has been limited. Under such circumstances, in recent years, the use of a graphite film excellent in thermal diffusibility as a heat conductor (heat conductor) has been rapidly increasing. The graphite film has a layered structure of carbon, the in-plane thermal conductivity of the graphite film is very high, the density is as light as 1 to 2 g / cm ³ , and the sheet thickness can be reduced, allowing flexibility. Have Therefore, it is often used as a heat conductor material or a heat spreader material in a narrow place or a place where it is necessary to route around a gap.

  As a generally available graphite film, there is a graphite film produced by a polymer pyrolysis method or an expanding method. In the expanding method manufactured from powder, it is difficult to manufacture a film thinner than 0.1 mm practically and the strength of the film is limited. On the other hand, the polymer pyrolysis method is a polymer film such as polyoxadiazole, polyimide, polyphenylene vinylene, polybenzimidazole, polybenzoxazole, polythiazole, or polyamide as in Patent Documents 1 and 2, such as argon, helium, etc. It is a method of heat-treating in an inert atmosphere or under reduced pressure, and it is possible to obtain a graphite film that is relatively thin, strong, and flexible.

  According to Patent Documents 1 and 2, production of a flexible graphite film by a polymer decomposition method includes three main processes. The first step is a carbonization step in which the polymer film is heat-treated in an inert gas stream and converted to a film containing carbon as a main component. Usually, it is performed up to 1000 ° C., accompanied by gas generation such as carbon dioxide, hydrogen and nitrogen. Moreover, there exists a graphitization process which heat-processes a carbonized polymer film (carbonized film) to 2400 degreeC or more as a 2nd process. In the second step, the graphene layer is oriented in the plane direction and graphitization proceeds. During this graphitization step, nitrogen and other components that remain slightly in the film and do not form a graphene skeleton escape from the film as outgas (foaming gas) at the final stage of graphitization (temperature range of 2400 ° C. or higher). This outgas lifts the graphite layer and foams the film. As a third step, flexibility can be contributed to the film by rolling the expanded graphite film.

In addition, a plurality of carbonized films obtained by heat-treating aromatic polyimide are characterized in that carbonaceous films are pressure-bonded while applying a pressure of 4 kg / cm ² or more in a temperature region of 1600 ° C. or higher. A method for producing graphite (Patent Document 3) is also known. Unlike Patent Documents 1 and 2, this method is not intended to produce a graphite film, but is intended to produce a very thick graphite block by pressing the films together.

  Furthermore, Patent Document 4 discloses that a raw material film is laminated to obtain a graphite film, but only a thick material film is used.

  Currently, a flexible graphite film that has been developed has a thickness of 25 μm (made by Matsushita Electric Industrial Co., Ltd., trade name: PGS). This graphite film is also produced by thermally decomposing a polyimide film by a polymer decomposition method.

  However, while current electronic devices such as mobile phones are becoming more complex, they are becoming smaller and thinner, and enough space can be installed even with thin graphite films developed so far. I can't. Therefore, there is an urgent need to develop a thin and flexible graphite film.

JP 61-275116 A Patent Publication No. 2976481 JP-A 64-56364 JP 2008-285362 A

  Like patent document 2, a thin graphite film can be produced by using a thin raw material (polyimide film). However, when a raw material having a small thickness is used, it is difficult to produce a flexible graphite film, and no film having sufficient flexibility below 25 μm has been produced so far. For example, as shown in Patent Document 2, a graphite film produced by heat-treating a 25 μm thick polyimide film (KAPTON) at a carbonization rate of 10 ° C./min and a graphitization rate of 20 ° C./min is also available from Toyo Seiki Co., Ltd. The number of times of bending in an MIT test using a MIT anti-fatigue fatigue testing machine model D (folding clamp radius of curvature R is 2 mm, right and left bending angle 90 degrees, bending speed 90 times / min, load 0.98 N) is 10 times. However, it was not flexible enough to be mounted on electronic devices.

  In the case of a rigid graphite film that is not flexible, various problems such as cracks, breaks, and powder falling occur when it is attached or a composite film is produced. In addition, since it is difficult to attach to a curved portion, there are many cases where it cannot be used with the current small electronic devices whose space has been reduced. From such a point of view, development of a graphite film having sufficient flexibility and a thin thickness (21 μm or less) has been demanded.

  The following explains briefly why it is difficult to produce a flexible film when the thickness of the raw material film is reduced.

  As described above, in order to contribute flexibility, in the process of heat treatment (graphitization), it is necessary to foam the film with an outgas composed of a component that does not form a graphite layer generated from the inside (FIGS. 1 and 2). 2). As shown in FIG. 2, the foamed graphite film has a slight space between the layers, so that the strain applied at the time of folding can be released, so that it has flexibility as shown in FIG. However, if the film is thin, the amount of outgas generated is small and the distance from the inside to the surface is short, so that the gas is smoothly released from the film and foaming is difficult. Therefore, a hardened graphite film as shown in FIGS.

In addition, the present inventors have discovered the effect of metal impurities as another factor that inhibits foaming of the film in the study of the present invention. The effect of metal impurities on the film is as follows. Insulating materials, containers, heaters, etc. constituting the graphitization furnace are made of graphite. Since natural graphite, which is a raw material of graphite material, contains many metal impurities (such as iron and nickel), these substances are present in large quantities in the furnace. The metal component acts as a graphitization catalyst for the polymer film, and causes graphitization to progress so as to inhibit the development of a graphite layer that would normally proceed in the plane direction (FIGS. 6 and 7). For this reason, outgas easily escapes from the gap between small graphite crystallites that could not be developed in the plane direction, and the film is difficult to foam. In particular, when heat treatment is performed in a large furnace (effective treatment volume is 20000 cm ³ or more), since a metal impurity concentration is high, a hard film is easily obtained.

  Due to the above factors, mass production of a graphite film having a small thickness and flexibility in a large furnace has been very difficult.

Generally, as a method for producing a graphite film with a single sheet, as disclosed in Patent Documents 1 and 2, a method of heat-treating a single raw material film between graphite plates is disclosed. Further, as disclosed in Patent Document 3, a method for producing a graphite block is known, in which a plurality of thin raw material films are laminated and heat-treated while applying a large pressure (4 kg / cm ² or more) in the thickness direction of the film. However, in these methods, since a thin raw material film could not be foamed, a thin and flexible graphite film could not be produced.

  The point of the present invention is how to foam a thin film. To that end, the authors have found that it is important to 1) keep the outgas that causes foaming in the final stage of graphitization in the film, and 2) suppress the action of metal impurities that inhibit foaming, The present invention has been developed.

  That is, the present invention is as follows.

  (1) heat treating a polymer film having a thickness of 5 μm or more and 45 μm or less or a carbonized polymer film having a thickness of 5 μm or more and 45 μm or less at a temperature of 2600 ° C. or more, The method for producing a graphite film is performed in a graphitization furnace having an internal volume of 125 to 17000 L.

(2) at least a portion of 1000 ° C. or higher 2400 ° C. or less of the temperature range, atmospheric pressure - the manufacturing method of the graphite film according to, characterized in that it is heat-treated under reduced pressure to below 0.08 MPa (1).

  (3) The method for producing a graphite film according to any one of (1) to (2), wherein birefringence of the polymer film is 0.12 or more.

  (4) The method for producing a graphite film according to any one of (1) to (3), wherein the polymer film is a polyimide film.

(5) A pressure is applied in the thickness direction of the directly laminated raw material film, and the pressure is 1.0 g / cm ² or more and 200 g / cm ² or less, according to any one of (1) to (4), The manufacturing method of the graphite film of description.

(6) The method for producing a graphite film according to any one of (1) to (5), wherein an area of the raw material film is 100 cm ² or more.

  (7) In the carbonization, the polymer film and the heat conductive sheet directly laminated on the two or more sheets are alternately laminated to be carbonized. (1) to (6) A method for producing a graphite film.

  (8) A graphite film characterized by subjecting a graphite film produced by the production method according to any one of (1) to (7) to a sheet shape at a pressure of 4 MPa to 20 MPa. Manufacturing method.

  (9) The method for producing a graphite film according to any one of (1) to (8), wherein two or more of the raw material films are directly laminated and heat-treated at a temperature of 2600 ° C. or higher.

  (10) A graphite film produced by the production method according to any one of (1) to (9).

  In addition, even if other members are sandwiched between a plurality of raw material films, the members are merely sandwiched formally, and when the manufacturing method sufficiently exhibits the effects of the present invention, It is assumed that “two or more raw material films are directly laminated”.

  Provided is a graphite film that is thin, flexible, and excellent in thermal diffusivity.

Foamed graphite film (surface). The cross-sectional SEM photograph of the expanded graphite film. Bending of graphite film that has been given flexibility. Hardened graphite film (surface). Bending of hardened graphite film. The cross-sectional SEM photograph of the graphite film which the metal impurity acted on. The schematic diagram of the cross section of the graphite film which the metal impurity acted on. One raw film and carbonaceous sheet are laminated alternately. Multiple raw films and carbonaceous sheets are laminated alternately. Polyimide film and wedge-shaped sheet. The perspective view of a wedge-shaped sheet | seat. Wrinkles generated on graphite film.

  The first aspect of the present invention is that a polymer film having a thickness of 5 μm or more and 45 μm or less, or a raw film made of the carbonized polymer film having a thickness of 5 μm or more and 45 μm or less is directly laminated, and 2600 ° C. or more A method for producing a graphite film, comprising a step of heat-treating at a temperature of

<Graphite film>
As a countermeasure against an increase in heat generation density of electronic devices in recent years, a graphite film having an excellent thermal diffusibility has attracted attention. Currently, there is a graphite film produced by a polymer pyrolysis method or an expanding method as a generally available graphite film.

  In general, a graphite film obtained by a polymer pyrolysis method in which a raw material film is heat-treated in an inert atmosphere such as argon or helium or under reduced pressure is excellent in flexibility and thermal diffusivity.

  On the other hand, the graphite film obtained by the expanding method has a flexibility because it is made by compacting powdery and flake-like natural graphite, but it has high flexibility because it has small crystallites and poor crystallinity. Compared to graphite obtained by molecular pyrolysis, it is inferior in thermal diffusibility, and the film is weak and often brittle.

<Polymer film>
The polymer film that can be used in the present invention is not particularly limited, but is polyimide (PI), polyamide (PA), polyoxadiazole (POD), polybenzoxazole (PBO), polybenzobisoxazal (PBBO). ), Polythiazole (PT), polybenzothiazole (PBT), polybenzobisthiazole (PBBT), polyparaphenylene vinylene (PPV), polybenzimidazole (PBI), and polybenzobisimidazole (PBBI). A heat-resistant aromatic polymer film containing at least one selected from the above is preferable because the flexibility and thermal diffusivity of the finally obtained graphite are increased. What is necessary is just to manufacture these films with a well-known manufacturing method. Among these, polyimide is preferable because various materials and structures can be obtained by selecting various raw material monomers. In addition, since a polyimide film is more easily carbonized and graphitized than a polymer film using other organic materials as raw materials, the polyimide film tends to be a graphite film having excellent flexibility and thermal diffusibility.

<Thickness of polymer film>
The thickness of the polymer film that can be used in the present invention is 5 μm to 45 μm, preferably 7 μm to 40 μm, and more preferably 10 μm to 30 μm.

  When the thickness of the raw material polymer film is 5 μm or more and 45 μm or less, a graphite film exhibiting flexibility that is sufficiently thin can be obtained. However, it is difficult to produce a flexible graphite film of a polymer film with a thickness of less than 5 μm by this method. On the other hand, when it is thicker than 45 μm, only a thick graphite film can be produced, so that it may not be mounted on a small electronic device.

<Carbonized polymer film (carbonized film)>
The carbonized polymer film used in the present invention can be obtained by preheating a polymer film as a starting material under reduced pressure or in an inert gas. This preheating is usually performed at a temperature of about 1000 ° C., and for example, when the temperature is raised at a rate of 2 ° C./min, it is desirable to hold the temperature for about 60 minutes in the temperature range of 1000 ° C.

<Raw film>
The raw material film that can be used in the present invention is a polymer film or a carbonized polymer film.

  When using a polymer film as a raw material, it is preferable to carry out a carbonization step in which the polymer film is preheated under reduced pressure or in an inert gas. When using a carbonized film (carbonized polymer film) that has been preheated as a raw material film, it is particularly flexible when a graphitization step (graphitization) is performed in which two or more layers are laminated and heat-treated at a temperature of 2600 ° C or higher. And a graphite film excellent in heat diffusivity can be obtained. Carbonization and graphitization may be performed separately or continuously. In other words, the carbonized film may be taken out from the furnace once and set again in a form suitable for the graphitization process, and the graphitization process may be performed without taking out the carbonized film. May be carried out continuously.

<Carbonization (carbonization) process>
Carbonization is performed by preheating a polymer film as a starting material under reduced pressure or in nitrogen gas. This preheating is usually performed at a temperature of room temperature to 1500 ° C. The heat treatment temperature for carbonization needs to be at least 800 ° C., preferably 900 ° C. or more, more preferably 1000 ° C. or more, in order to obtain graphite having excellent flexibility and thermal diffusibility. .

  In the temperature raising stage, pressure may be applied in the thickness direction of the film to the extent that the film is not damaged so that wrinkles are not generated in the starting polymer film.

<Film setting method for carbonization (carbonization)>
Examples of the film setting method in the carbonization step of the present invention include a method of alternately laminating one or more (that is, a plurality of) polymer films and a heat conductive sheet. Here, “alternately laminating” means that a plurality of polymer films are sandwiched and laminated between thermally conductive sheets.

  Here, if the heat conductive sheet used in this invention is a shape which has a main surface with a large area, there will be no limitation in thickness, A film, a board, etc. are contained.

  Such a heat conductive sheet is not particularly limited, but metal films such as copper, iron and stainless steel (including metal sheets and metal plates; the same shall apply hereinafter), ceramic plates such as alumina, carbonaceous sheets (carbon And the like, and so on). Here, the carbonaceous sheet has high heat resistance as compared with the metal film, and has an advantage that metal impurities are less mixed into the produced graphite film. In addition, the carbonaceous sheet has the advantages of being tougher and having higher heat resistance than the ceramic plate. From this point of view, a carbonaceous sheet is preferable as the heat conductive sheet used in the heat resistant film. In the carbonaceous sheet, a graphite sheet (including a graphite film and a graphite plate, the same applies hereinafter) is more preferable. The graphite sheet has high thermal conductivity in addition to high heat resistance. For this reason, the polymer film in a laminated body can be heat-processed uniformly, and generation | occurrence | production of the wrinkle and distortion in a film can be suppressed. Moreover, since the graphite sheet is soft and has high slidability, it is possible to prevent cracking due to shrinkage of the film in the carbonization step by heat treatment of the polymer film.

  These graphite sheets include isotropic graphite sheets (including isotropic graphite films and isotropic graphite plates), extruded graphite sheets (including extruded graphite films and extruded graphite plates), C /. C composite sheets (including C / C composite films and C / C composite plates), expanded graphite sheets (including expanded graphite films and expanded graphite plates), and the like. Here, the C / C composite refers to a carbon fiber reinforced carbon composite material in which graphite is reinforced with carbon fibers. These graphite sheets can be obtained as commercial products. For example, an isotropic graphite sheet (trade name: IG-11, ISEM-3, etc.) manufactured by Toyo Tanso Co., Ltd., a C / C composite board (trade names: CX-26, CX-) manufactured by Toyo Tanso Co., Ltd. 27), an extruded graphite plate manufactured by SEC Carbon Co., Ltd. (trade names: PSG-12, PSG-332, etc.), an expanded graphite sheet manufactured by Toyo Tanso Co., Ltd. (trade name: PERMA-FOIL (grade name: PF) , PF-R2, PF-UHPL)) and the like.

<Graphitization process>
Next, the graphitization may be performed after the carbonized polymer film is taken out and then transferred to a graphitization furnace, or may be continuously performed from the carbonization. Graphitization is performed under reduced pressure or in an inert gas, and argon and helium are suitable as the inert gas. The heat treatment temperature needs to be at least 2000 ° C. or higher, and finally it is 2600 ° C. or higher, preferably 2800 ° C. or higher, more preferably 2900 ° C. or higher. The higher the maximum temperature, the more excellent the flexibility and thermal diffusivity of the graphite film.

<Film setting method for graphitization process>
A method for producing a graphite block, comprising: bonding a plurality of carbonized films to each other in a temperature range of 1600 ° C. or more while applying a pressure of 4 kg / cm ² or more as in Patent Document 3. However, as described above, a graphite film cannot be obtained by this method.

  Usually, as a method for setting a raw material film in the case of graphitizing in the form of a single wafer, as described in Patent Documents 1 and 2, a single raw material film is replaced with a carbonaceous sheet (carbonaceous film, Including). That is, as shown in FIG. 8, heat treatment is performed in a state in which one raw material film and one carbonaceous sheet are alternately laminated. When a plurality of raw material films are directly laminated and the laminate is sandwiched between carbonaceous sheets, wrinkles or strains are likely to occur in the resulting graphite film. Moreover, the raw material films may be pressure-bonded and graphitized, and the number of raw material films sandwiched between the carbonaceous sheets is one fixed stone. However, in this method, when a polymer film of 45 μm or less (particularly 30 μm or less) is used as a raw material, it is difficult to foam and a flexible graphite film cannot be obtained.

  Therefore, in the present invention, as a raw material film setting method in the graphitization step, it has been proposed to directly laminate two or more raw material films as shown in FIG. More specifically, two or more raw material films are directly laminated, the two or more raw material film laminates are sandwiched and held between carbonaceous sheets, and heat-treated at a temperature of 2600 ° C. or more, so that it is thin and flexible. We succeeded in obtaining a graphite film with excellent heat and heat diffusivity. It was an unexpected effect that hardening was suppressed and flexibility was imparted by laminating two or more raw material films.

  The mechanism is described below. A carbonized polymer film (carbonized film), which is a raw material for the graphite film, is a material having a very low gas permeability. Therefore, by laminating two or more raw material films directly and bringing the surfaces into close contact with each other, 1) outgassing that causes foaming can be retained in the film, and 2) metal impurities from the outside that are a factor in hardening It is presumed that the hardening could be suppressed because the intrusion could be prevented.

  Further, generation of wrinkles or distortion, which has been a problem in direct lamination so far, was not particularly problematic because the raw material used was a thin polymer film (45 μm or less). In addition, the graphite sheet etc. which were enumerated by the item of the carbonization process of a polymer film can be used for the carbonaceous sheet which pinches | interposes a raw material film laminated body.

  The number of raw material films directly laminated in the present invention is 2 or more, preferably 5 or more, and more preferably 10 or more. Moreover, the wrinkles and distortion by direct lamination | stacking can be suppressed by processing, applying a pressure in the thickness direction of a film during heat processing. The pressure can be constantly kept constant during the heat treatment, for example, by placing a weight on a heavy stone. By applying pressure, the number of stacked layers can be further increased. In the presence of a pressure load, the number of stacked layers is 20 or more, preferably 50 or more, more preferably 100 or more. If it is one sheet, it will be hardened.

  In addition, the method for directly laminating the raw material films is not particularly limited, but it is preferable that the raw film is laminated with the ends of the raw material films aligned. If the films are displaced, a graphite film with a lot of wrinkles and distortion can be obtained without applying a uniform load. Moreover, the one where the flatness of the raw material film to be used is higher is preferable. If the flatness of the raw material film is poor, the films cannot be brought into close contact with each other, so that the effect of confining outgas and the suppression of metal impurity entry are insufficient. Therefore, when a carbonized polymer film is used as the raw material film, the point is not to generate wrinkles or strains during carbonization. Therefore, a carbonization process that sufficiently considers suppression of wrinkles and strains, such as the carbonization process setting method described above, is desired.

<Pressure applied in the thickness direction of the raw film>
In the present invention, heat treatment is preferably performed in a state where pressure is applied in the thickness direction of the raw material film. Heat treatment with pressure applied in the thickness direction of the raw material film is preferable because a graphite film excellent in flexibility and thermal diffusivity can be obtained. By applying pressure in the thickness direction of the film, it is possible to suppress wrinkling and distortion, escape out of the gaps between the raw film, keep outgas that causes foaming in the film, Intrusion of metal impurities from some outside can also be prevented. In the present invention, the pressure in the thickness direction of the raw material film is preferably 1.0 g / cm ² or more and 200 g / cm ² or less. When the raw material film is graphitized, the raw material film undergoes a process of expanding and / or shrinking. When heat treatment is performed in a state where the pressure is less than 1.0 g / cm ^2, non-uniform film expansion and / or contraction accompanying the graphitization of the raw material film occurs, film flatness is impaired, and impurities are generated from the gaps in the raw material film. It enters and hardens. On the other hand, when the pressure is higher than 200 g / cm ² , the raw material films are pressed against each other, which is not good. Moreover, foaming is suppressed by a physical pressure in the thickness direction, and a hard film may be obtained. According to the present invention, the pressure in the thickness direction of the raw material film is preferably 1.0 g / cm ² or more and 200 / cm ² or less, more preferably 5.0 g / cm ² or more and 100 / cm ² or less, more preferably 7. It is 0 g / cm ² or more and 80 / cm ² or less. As a method of applying pressure in the film thickness direction of the raw material film, the weight of the jig used to hold the film, the pressure received from the lid when a container is used to hold the film, or the film by heating This is achieved by, but not limited to, the expansion of the surrounding container and the pressure due to the expansion of the jig used to hold the film. In addition, the said pressure is calculated with respect to the area of the raw material film to heat-process.

<Polymer film and birefringence>
In the polymer film that can be used in the present invention, the birefringence Δn related to the in-plane orientation of the molecule is 0.12 or more, preferably 0.13 or more, more preferably 0 in any direction in the film plane. .14 or higher polymer film.

  The authors believe that the higher the birefringence, the better the in-plane orientation of the polymer film itself. Therefore, when this polymer film is carbonized, the degree of crystal orientation of the film after carbonization also increases and becomes more dense. It was clarified that it becomes a carbonized film of structure. In addition, it has been found that when a carbonized film having such a dense structure is graphitized, a polymer film having high birefringence is suitable for producing a thin graphite film that is easy to foam and has flexibility. This is because the outgas generated during graphitization is difficult to escape due to its dense structure and escapes while lifting the graphite layer.

  If the birefringence Δn is 0.12 or more in any direction within the film plane, a flexible graphite film can be obtained. On the other hand, if it is less than 0.12, it is difficult to obtain a flexible graphite film because a carbonized film having a dense structure cannot be obtained unless the carbonization rate is extremely slowed.

<Birefringence>
Birefringence here means the difference between the refractive index in an arbitrary direction in the film plane and the refractive index in the thickness direction, and the birefringence Δnx in the arbitrary direction X in the film plane is given by the following formula (Formula 1). It is done.

  10 and 11, a specific method for measuring birefringence is illustrated. In the plan view of FIG. 10, a thin wedge-shaped sheet 2 is cut out from the film 1 as a measurement sample. The wedge-shaped sheet 2 has an elongated trapezoidal shape having one oblique side, and its base angle is a right angle. At this time, the base of the trapezoid is cut out in a direction parallel to the X direction. FIG. 11 is a perspective view of the measurement sample 2 cut out in this way. When sodium light 4 is irradiated at right angles to the cut-out cross section corresponding to the bottom side of the trapezoidal sample 2 and observed with a polarizing microscope from the cut-out cross section side corresponding to the oblique side of the trapezoidal sample 2, the interference fringes 5 are observed. If the number of interference fringes is n, the birefringence Δnx in the film in-plane X direction is expressed by the following formula (Formula 2).

  Here, λ is the wavelength 589 nm of the sodium D line, and d is the width 3 of the sample corresponding to the trapezoidal height of the sample 2.

  The above-mentioned “arbitrary direction X in the film plane” means, for example, the X direction is the 0 ° direction, 45 ° direction, 90 ° direction, 135 ° direction in the plane with reference to the direction of material flow during film formation. In any direction. The sample measurement location and the number of measurements are preferably as follows. For example, when a sample is cut out from a roll-shaped raw material film (width: 514 mm), six locations are sampled at intervals of 10 cm in the width direction, and birefringence is measured at each portion. The average is defined as birefringence.

<Preparation method of polyimide film>
The polyimide film used in the present invention is prepared by mixing an organic solution of polyamic acid, which is a polyimide precursor, with an imidization accelerator, and then casting it on a support such as an endless belt or a stainless drum, followed by drying and baking. Can be produced by imidization.

  As a method for producing the polyamic acid used in the present invention, a known method can be used. Usually, at least one aromatic dianhydride and at least one diamine are substantially equimolar amounts in an organic solvent. Dissolved in. The obtained organic solution is stirred under controlled temperature conditions until the polymerization of the acid dianhydride and the diamine is completed, whereby a polyamic acid can be produced. Such a polyamic acid solution is usually obtained at a concentration of 5 to 35 wt%, preferably 10 to 30 wt%. When the concentration is in this range, an appropriate molecular weight and solution viscosity can be obtained.

  Any known method can be used as the polymerization method. For example, the following polymerization methods (1) to (5) are preferable.

  (1) A method in which an aromatic diamine is dissolved in an organic polar solvent, and this is reacted with a substantially equimolar amount of an aromatic tetracarboxylic dianhydride for polymerization.

  (2) An aromatic tetracarboxylic dianhydride and a small molar amount of the aromatic diamine compound are reacted with each other in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using an aromatic diamine compound so that it may become substantially equimolar with respect to aromatic tetracarboxylic dianhydride.

  This is the same as the method of synthesizing a polyamic acid by synthesizing a prepolymer having the acid dianhydride at both ends using diamine and acid dianhydride, and reacting the prepolymer with a diamine different from the above.

  (3) An aromatic tetracarboxylic dianhydride is reacted with an excess molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after adding an aromatic diamine compound to the prepolymer, polymerization was performed using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar. how to.

  (4) After dissolving and / or dispersing aromatic tetracarboxylic dianhydride in an organic polar solvent, an aromatic diamine compound is used so as to be substantially equimolar with respect to the acid dianhydride. Polymerization method.

  (5) A method in which a substantially equimolar mixture of aromatic tetracarboxylic dianhydride and aromatic diamine is reacted in an organic polar solvent for polymerization.

  Among these, a method of performing polymerization by performing sequential control (sequence control) (combination of block polymers / control of connection between block polymer molecules) via the prepolymer shown in (2) and (3) is preferable. By using this method, it is easy to obtain a polyimide film having a large birefringence and a small linear expansion coefficient. By heat-treating this polyimide film, the crystallinity is high, and the density and thermal conductivity are excellent. This is because it becomes easier to obtain graphite. Further, it is presumed that, when controlled regularly, the aromatic rings overlap, and graphitization is likely to proceed even at low temperature heat treatment. Also, increasing the imide group content to increase birefringence decreases the carbon ratio in the resin and decreases the carbonization yield after graphite treatment, but the polyimide film synthesized with sequential control is This is preferable because the birefringence can be increased without reducing the carbon ratio. Since the carbon ratio increases, generation of cracked gas can be suppressed, and a graphite film excellent in appearance can be easily obtained. Moreover, rearrangement of the aromatic ring can be suppressed, and a graphite film excellent in thermal conductivity can be obtained.

  Acid dianhydrides that can be used for the synthesis of polyimide in the present invention are pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl. Tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4- Dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2 , 3-Zika Boxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, p-phenylenebis (trimerit Acid monoester acid anhydride), ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid anhydride), and the like, which may be used alone or in any It can be used in a mixture of proportions.

  Examples of diamines that can be used for the synthesis of polyimide in the present invention include 4,4′-oxydianiline, p-phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, benzidine, and 3,3. '-Dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether (4,4'-oxydianiline), 3,3'-diaminodiphenyl ether (3,3'-oxydianiline), 3,4'-diaminodiphenyl ether (3,4'-oxydianiline), 1,5-diaminonaphthalene, 4,4'-diaminodiphenyl Diethylsilane, 4,4'-diaminodiphenylsilane, 4,4 -Diaminodiphenylethylphosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiphenyl N-phenylamine, 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene 1,2-diaminobenzene and their analogs, which can be used alone or in any proportion of the mixture.

  In particular, from the viewpoint of increasing the elastic modulus and increasing the birefringence by reducing the linear expansion coefficient, the acid dianhydride represented by the following formula (1) is used as a raw material in the production of the polyimide film in the present invention. It is preferable.

Here, R ₁ is any one selected from the group of divalent organic groups included in the following formulas (2) to (14),

Here, each of R ₂ , R ₃ , R ₄ , and R ₅ can be any selected from the group of —CH ₃ , —Cl, —Br, —F, or —OCH ₃ .

  By using the above-mentioned acid dianhydride, a polyimide film having a relatively low water absorption can be obtained, which is also preferable from the viewpoint that foaming due to moisture can be prevented in the graphitization process.

In particular, when an organic group containing a benzene nucleus as shown in the formula (2) to the formula (14) is used as R ₁ in the acid dianhydride, the molecular orientation of the obtained polyimide film increases, This is preferable from the viewpoints of low expansion coefficient, high elastic modulus, high birefringence, and low water absorption.

  In order to further reduce the linear expansion coefficient, increase the elastic modulus, increase the birefringence, and decrease the water absorption, an acid dianhydride represented by the following formula (15) is used as a raw material for the synthesis of polyimide in the present invention. That's fine.

In particular, a polyimide film obtained by using an acid dianhydride having a structure in which a benzene ring is linearly bonded by two or more ester bonds as a raw material has a very linear conformation as a whole although it contains a bent chain. It has a relatively rigid property. As a result, by using this raw material, the linear expansion coefficient of the polyimide film can be reduced, for example, 1.5 × 10 ⁻⁵ / ° C. or less. Further, the elastic modulus can be increased to 500 kgf / mm ² or more, and the water absorption can be decreased to 1.5% or less.

  In order to further reduce the linear expansion coefficient, increase the elastic modulus, and increase the birefringence, the polyimide in the present invention is preferably synthesized using p-phenylenediamine as a raw material.

  The most suitable diamines used in the synthesis of the polyimide in the present invention are 4,4′-oxydianiline and p-phenylenediamine, and the total moles of these alone or the two are 40 mol% based on the total diamine. More preferably, it is 50 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. Furthermore, it is preferable that p-phenylenediamine contains 10 mol% or more, further 20 mol% or more, further 30 mol% or more, and further 40 mol% or more. If the content of these diamines is less than the lower limit of these mol% ranges, the resulting polyimide film tends to have a high linear expansion coefficient, a low elastic modulus, and a low birefringence. However, if the total amount of diamine is p-phenylenediamine, it is difficult to obtain a thick polyimide film with less foaming, so 4,4'-oxydianiline is preferably used. In addition, the carbon ratio can be reduced, the amount of cracked gas generated can be reduced, the need for rearrangement of aromatic rings is reduced, and graphite having excellent appearance and thermal conductivity can be obtained.

  The most suitable acid dianhydride used in the synthesis of the polyimide film in the present invention is pyromellitic dianhydride and / or p-phenylenebis represented by the formula (15) (trimellitic acid monoester dianhydride). And the total mole of these alone or the two is 40 mole% or more, further 50 mole% or more, further 70 mole% or more, or even 80 mole% or more based on the total acid dianhydride. Is preferred. If the amount of these acid dianhydrides used is less than 40 mol%, the resulting polyimide film tends to have a large linear expansion coefficient, a small elastic modulus, and a small birefringence.

  Moreover, you may add additives, such as carbon black and a graphite, with respect to a polyimide film, a polyamic acid, and a polyimide resin.

  Preferred solvents for synthesizing the polyamic acid are amide solvents N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like, N, N-dimethylformamide, N, N-dimethylacetamide can be used particularly preferably.

  Next, a polyimide production method includes a heat curing method in which polyamic acid as a precursor is converted to imide by heating, or a polyhydric acid such as acetic anhydride and other dehydrating agents, picoline, quinoline, isoquinoline, Any of the chemical curing methods in which imide conversion is performed using a tertiary amine such as pyridine as an imidization accelerator may be used. Among them, a higher boiling point such as isoquinoline is preferable. This is preferable because it does not evaporate in the initial stage of film production, and the catalytic effect is easily exhibited until the last step of drying. In particular, the resulting film has a low coefficient of linear expansion, high modulus of elasticity, high birefringence, and can be rapidly graphitized at a relatively low temperature to obtain high-quality graphite. Cure is preferred. In particular, the combined use of a dehydrating agent and an imidization accelerator is preferable because the resulting film has a small linear expansion coefficient, a large elastic modulus, and a large birefringence. In addition, the chemical cure method is an industrially advantageous method that is excellent in productivity because the imidization reaction proceeds faster and the imidization reaction can be completed in a short time in the heat treatment.

  In the production of a film by a specific chemical cure, first, an imidization accelerator comprising a dehydrating agent and a catalyst of a stoichiometric amount or more is added to a polyamic acid solution, an organic film such as a support plate, PET, a drum, or an endless belt. A film having self-supporting properties is obtained by casting or coating on a support such as a film to evaporate the organic solvent. Next, the self-supporting film is further heated and dried to be imidized to obtain a polyimide film. The temperature during the heating is preferably in the range of 150 ° C to 550 ° C. There is no particular limitation on the rate of temperature increase at the time of heating, but it is preferable to gradually heat in a continuous or stepwise manner so that the maximum temperature falls within the predetermined temperature range. Although the heating time varies depending on the film thickness and the maximum temperature, it is generally preferably in the range of 10 seconds to 10 minutes after reaching the maximum temperature. Furthermore, if the process of fixing or stretching the film to prevent shrinkage is included in the polyimide film manufacturing process, the resulting film has a low coefficient of linear expansion, a high elastic modulus, and a high birefringence. It is preferable because it tends to be easy.

<Atmosphere of 1000 ° C. or higher and 2400 ° C. or lower>
As a point of the present invention, how to suppress the action of metal impurities on the raw material film is important. As described above, the foaming of the film is hindered by the action of the metal impurities, resulting in a hard film. In particular, when a thin polymer film (45 μm or less) is used as a raw material as in the present invention, this is remarkable. The authors have clarified that the action of this metal impurity on the film occurs in a temperature range of 1000 ° C. or higher and 2400 ° C. or lower where the metal material is vaporized from the examination so far. Therefore, in this temperature region, in order to remove the metal component filled in the furnace as a gas, at least part of the temperature region of 1000 ° C. or higher and 2400 ° C. or lower was reduced in pressure. As a result, it was discovered that the foaming of the film increased dramatically and a flexible film could be obtained. It was an unexpected effect that the metal impurities were suppressed by the treatment under reduced pressure and foaming was possible.

In the heat treatment of the present invention, 1000 2400 ° C. or less of the temperature range over ° C., preferably at 1200 ° C. or higher 2300 ° C. or less, more preferably at least a portion of 1400 ° C. or higher 2200 ° C. or less atmospheric pressure - and the pressure was reduced to below 0.08MPa It is desirable to be processed. Also, most preferably all of the region of the temperature range atmospheric - may be treated under reduced pressure to less than 0.08 MPa.

  In addition, it is not specifically limited about the atmosphere below 1000 degreeC. Further, decompression at a temperature higher than 2400 ° C. is dangerous because it leads to deterioration in the furnace.

<Degree of decompression>
Moreover, as also the degree of reduced pressure, atmospheric pressure - below 0.08 MPa, preferably atmospheric pressure - below 0.09 MPa, more preferably atmospheric pressure - 0.099MPa or less good. If the pressure is lower than atmospheric pressure- 0.08 MPa, the effect of suppressing the action of metal impurities is difficult to obtain.

<Raw material film size>
The size of the raw material film used in the present invention is 100 cm ² or more, preferably 200 cm ² or more, more preferably 400 cm ² or more.

  If the size of the raw film is large, the finished graphite film also has a large area. If a graphite film with a large area can be obtained, the treatment with a large area is desired from the viewpoints of widespread use and increased mass productivity.

  However, when processing with a single wafer, in order to process a large-area raw material film, a large furnace is required. As described at the beginning, in a large furnace, the metal impurity concentration is high, so that the film is easily hardened. The authors faced the challenge of hardening, which was not particularly problematic in the small-scale study in the laboratory, for the first time using a large furnace. As a result of various studies on this problem, an improvement measure like the present invention has been developed.

Therefore, it can be said that the present invention is particularly effective when the raw material film size is 100 cm ² or more.

  In addition, as a graphitization furnace, it is preferable to use a thing with an internal volume of 125-17000L (liter).

<Rear surface pressure process>
In the method for producing a graphite film according to the present invention, it is preferable that the raw material film graphitized through the graphitization step, that is, the graphite film, further includes a “rear surface pressurizing step” for pressurizing in a planar manner. A graphite film having excellent flexibility and thermal diffusivity, no scratches or dents on the surface, no wrinkles, and excellent flatness can be obtained, which is an important process particularly for improving the bending resistance. Such a “rear surface pressing step” can be performed at room temperature. In such a “rear surface pressurizing step”, it is preferable to pressurize in a planar manner together with a film-like medium other than the graphite film.

  In addition, it is preferable to press the sheet in a state where a plurality of the graphite films are laminated and arranged, and the graphite film itself plays a role as a cushioning material, so that the graphite having excellent flatness without scratching the surface. A film can be obtained.

  Such “rear surface pressurization” can be performed by a single plate press, a vacuum press, or the like, but is included in the graphite film in order to perform vacuuming in addition to being able to pressurize uniformly in a surface state. A vacuum press is particularly preferred because the air layer can be compressed.

  More specifically, a graphite film is sandwiched between a plastic plate, a ceramic plate, and a metal plate with a bolt by using a press that can press the graphite film in a plane, such as a press, a hot press, or a single plate press. There is a method of tightening. By using these methods, it becomes possible to pressurize uniformly in a planar shape, the graphite layer is compressed without breakage, does not cause a decrease in thermal diffusivity, high thermal diffusivity, high density, A graphite film having no flaws and no wrinkles on the surface can be obtained. Moreover, in order to perform more uniformly, it is good to heat during pressurization.

  In addition, as a method of vacuum pressing, a press method such as a press machine, a hot press machine, and a single plate press machine is used to press using a vacuum press machine provided with a vacuum drawing function, or on a plastic plate, a ceramic plate, and a metal plate. A method of vacuuming the whole after clamping the graphite film with bolts and a method of pressing the film uniformly by vacuuming the inside and vacuuming the inside like a vacuum rubber press It is done. In these methods, in addition to being able to pressurize uniformly in a plane, the vacuum layer is compressed, the air layer contained in the graphite film is compressed, the graphite layer is compressed without being damaged, and the thermal diffusivity The graphite film having a higher thermal diffusivity, higher density, no scratches on the surface, and no wrinkles can be obtained. Moreover, when performing a vacuum press, it is preferable to evacuate before pressurizing. When the pressure treatment is first performed, soot may be formed, but when the pressure reduction treatment is performed first, the entire graphite film is uniformly pressurized, and a graphite film having excellent quality can be obtained without any wrinkles. Moreover, in this method, in order to carry out more uniformly, it is good to heat during pressurization. Since the graphite film is excellent in thermal diffusivity, heat is transmitted uniformly, and a uniform and smooth graphite film can be obtained in a plane.

  Uniform pressurization in the plane direction can be performed uniformly stronger than the rolling process, so that it becomes a graphite film having extremely excellent bending resistance as compared with the rolling process. In particular, in the case of a thin graphite film, uneven pressing tends to occur, and thus a planar pressing process such as a pressing process capable of performing strong pressing is preferable.

<Pressure in rear surface pressurization process>
The pressure for pressurizing the graphite film in the rear surface pressing step of the present invention in a planar shape is 2 MPa to 40 MPa, preferably 4 MPa to 20 MPa, more preferably 8 MPa to 15 MPa. When the pressure for pressurizing the graphite film in a planar shape is smaller than 2 MPa, the pressure is too small to be sufficiently compressed, resulting in a graphite film with poor bending resistance. On the other hand, if the pressure for pressurizing the graphite film in a planar shape is larger than 40 MPa, the pressure is too great and the graphite film is destroyed during the compression treatment, resulting in a graphite film with poor bending resistance, thermal diffusivity, and poor appearance.

<Film medium>
Examples of the film-like medium other than the graphite film include a graphite film obtained from natural graphite, a resin film, a metal plate, and a metal foil. Specific examples include graphite films obtained from natural graphite, buffer rubber materials, iron plates, Teflon (registered trademark) films, polyimide films, and PET films. Conductive resin composition with kneading so-called conductive polymer with chemical structure that enables electron transfer, surfactant, electrolyte and other compounds, conductive powder such as metal powder, carbon black, etc. The conductive polymer material is particularly suitable from the viewpoint of removing static electricity.

<Flexibility of graphite film>
In the MIT bending resistance test of the graphite film of the present invention, the number of bendings (R is 2 mm, right and left bending angle 90 °) is 500 times or more, preferably 1000 times or more, and more preferably 10,000 times or more. If it is 500 times or more, since it is excellent in bending resistance, it is difficult to be destroyed even if it is used in a bent portion. Specifically, even when it is used at a hinge of a mobile phone or a bent portion of a small electronic device, it can be used without reducing its function. Moreover, since it is excellent in bending resistance, handling property at the time of attachment to an electronic device is also improved. Moreover, it is good also when it combines with composite materials, such as an adhesive material and a protective film, because it is hard to generate | occur | produce a crack, a crease, and powder fall. On the other hand, if it is less than 100 times, since the bending resistance is inferior, the film is easily broken during use at the bent portion. Moreover, the handling property at the time of handling also worsens. In addition, cracks and breaks are likely to occur when a laminator is passed to bond the composite material. In particular, when the bending angle is large, when the bending radius is small, the film tends to deteriorate.

<Bending radius and bending angle of MIT bending test>
The MIT bending resistance test of the graphite film can be measured using an MIT fatigue resistance tester model D manufactured by Toyo Seiki Co., Ltd. In the measurement, a bending radius R, a bending angle, a load, and the like can be selected, and R can be selected to be 2 mm, 1 mm, or the like. Usually, the smaller the bending radius R, the larger the bending angle, and the heavier the load, the more severe the test. In particular, in electronic devices such as mobile phones, game machines, liquid crystal TVs, and PDPs, which have a small space, it is very important that the device has a small folding radius and a large folding angle, which enables space-saving design of the device. is there. The details of the MIT test method are described in the Examples column.

<Thickness of graphite film>
The thickness of the graphite film of the present invention is 1 μm to 21 m, preferably 3 μm to 15 μm, and more preferably 5 μm to 12 μm.

  Since the graphite film having a thickness of less than 1 μm has low strength, handling properties are poor and it is difficult to produce a composite sheet and attach it to an electronic device. Moreover, since the thickness is too thin and the heat transport capability is small, it is difficult to use as a heat dissipation sheet. In addition, it is difficult in the first place to produce a flexible graphite film of less than 1 μm with the method of the present invention.

  Further, since the graphite film thicker than 21 μm is thick, it may not be mounted in a small space of a miniaturized electronic device (in order to mount it, the space for mounting the graphite film must be designed in advance). Moreover, in order to produce a graphite film thicker than 21 μm, a thick raw material film is required, which is not good because the ratio of the raw material cost per unit area increases.

  As a method for measuring the thickness of the graphite film, a film of 50 mm × 50 mm was measured at any 10 points in a constant temperature room at 25 ° C. using a thickness gauge (HEIDENHAIN-CERTO, manufactured by HEIDENHAIN Co., Ltd.). The average value was taken as the measured value.

<Area of graphite film>
The area of the graphite film of the present invention is 25 cm ² or more, preferably 50 cm ² or more, more preferably 100 cm ² or more.

In order to use a graphite film as a heat dissipation sheet, it is sufficient that the area having an area of 25 cm ² or more can diffuse heat over a large area. In addition, if a sheet having a large area of 50 cm ² or more, more preferably 100 cm ² or more can be produced, a plurality of graphite films having a size suitable as a heat radiation sheet of about 30 mm square can be extracted from one sheet, so that mass production is possible. Especially good because it is expensive.

  However, it is very difficult to produce a thin graphite film with a large area. This is because when the thickness is small and the area is large, the film is very weak, so that the film is easily wrinkled by the carbonization treatment as the first step. In the second step of graphitization, cracks due to the wrinkles, thickness unevenness, etc. occur, and it becomes difficult to produce a uniform graphite film. Even if a uniform film can be processed by carbonization, wrinkles and uneven thickness may occur in the graphitization process.

  When the rate of temperature increase is high, the film rapidly contracts and expands, so that wrinkles and cracks are likely to occur. Therefore, in order to produce a large-area graphite film, it is necessary to process at the lowest possible temperature increase rate.

<Thermal diffusivity of graphite film>
The thermal diffusivity in the surface direction of the graphite film used in the present invention is 3.0 × 10 ⁻⁴ m ² / s or more, preferably 5.0 × 10 ⁻⁴ m ² / s or more, and more preferably 8.0. It is good in it being more than ^x10 < ^-4 > m < ² > / s. When the thickness is 3.0 × 10 ⁻⁴ m ² / s or more, the thermal conductivity of the graphite film is improved, and thus sufficient heat transport capability is exhibited even if the thickness is small.

  Such a thermal diffusivity becomes an index of the progress of graphitization, and for example, the higher the thermal diffusivity in the film surface direction, the more remarkable the graphitization. The thermal diffusivity can be measured at 10 Hz in an atmosphere at 20 ° C. using a thermal diffusivity measuring apparatus (trade name “LaserPit” available from ULVAC-RIKO Co., Ltd.) using an optical alternating current method.

<Applications>
Since the graphite film according to the present invention is excellent in thermal conductivity, it can be used for any heat-related applications. Moreover, since it is thin and excellent in flexibility, it is suitable for applications utilizing this feature, for example, for use in a small space portion such as a small electronic device, or for a bending portion. The characteristics of graphite film that excel in heat conduction are that it is necessary for applications that need to transfer heat, escape heat, spread heat, make heat uniform, make heat response faster, warm faster, cool faster. Is suitable. By spreading the heat instantaneously, it is possible to prevent and mitigate sudden temperature changes, or to avoid local heat concentration. On the other hand, it can be used for applications that cause sudden changes or detect slight changes in heat. By relaxing the heat, strength and adhesiveness can be ensured even in a high temperature environment. In addition, by transferring heat uniformly and accurately, characteristics such as high accuracy, high quality, and high image quality can be improved. When used in manufacturing equipment, it is possible to improve productivity by shortening tact time, improving heating / cooling efficiency, improving drying efficiency, speeding up, and shortening waiting time by taking advantage of the ability to transport heat quickly and in large quantities. . In addition, it is possible to reduce defects and enhance the heat retaining function by uniformizing heat and quick transportation. In addition, by adopting it in various devices, it is possible to save space, thin film, reduce weight, simplify the mechanism, improve the degree of freedom of installation, and eliminate unnecessary parts to save power and reduce noise. It becomes possible. In addition, since heat can be released, there is no deterioration in characteristics even in heat cycle environmental tests and annealing treatments, solder heat resistance, adhesive layer adhesion, heat resistance, reliability, durability can be improved, and heat insulation can be improved. It can also be increased and protected from heat-sensitive parts. As a result, maintenance can be reduced, cost can be reduced, and safety can be improved.

  Specific applications include the following. For example, electronic devices such as servers, server personal computers, desktop personal computers, word processors, keyboards, and games, portable electronic devices such as notebook computers, electronic dictionaries, PDAs, mobile phones, portable game devices, and portable music players. Liquid crystal display, transmissive liquid crystal display device, reflective LCD panel, plasma display, SED, LED, organic EL, inorganic EL, liquid crystal projector, rear projector, liquid crystal panel, backlight device (variation prevention, temperature unevenness improvement), TFT substrate , Electron emission devices, electron source substrates and face plates (weight reduction), display panel frame composites, light emitting devices, charge injection light emitting devices, optical and display devices such as watches, and parts thereof. Light emitting / illuminating devices such as lasers, semiconductor lasers, light emitting diodes, fluorescent lamps, incandescent bulbs, light emitting dots, issuing element arrays, lighting units, flat light emitting devices, and document lighting devices. Single or multiple recording heads (heater, heat insulating material, heat storage layer, etc.) for inkjet (spreading ink using thermal energy), line heads, long ink heads, solid ink jet devices, heat dissipation for ink jet heads Ink jet printer (ink head) devices such as plates, ink cartridges, ink jet head silicon substrates, ink jet drive drivers, and heating sources (halogen lamp heaters) for heating ink jet recording paper, and parts thereof. Toner cartridge, device having laser light source, scanning optical device (light emitting unit, deflection scanning polygon mirror, polygon mirror rotation driving motor, optical component leading to photosensitive drum), exposure device, developing device (photosensitive drum, light receiving member, Development roller, development sleeve, cleaning device), transfer device (transfer roll, transfer belt, intermediate transfer belt, etc.), fixing device (fixing roll (core, outer peripheral member, halogen heater, etc.), surf heater, electromagnetic induction heater, ceramic Electrophotographic equipment consisting of heater, fixing film, film heating device, heating roller, pressure roller / heating body, pressure member, belt nip), sheet cooling device, sheet loading device, sheet discharge device, sheet processing device, etc. Image forming apparatus and parts thereof. In the fixing device, the effect of improving the thermal characteristics due to the use of graphite film is remarkable, including uneven image quality in the width direction, image quality defects, image quality variation in continuous paper feeding, rise / fall time, real-time support, high temperature followability, paper feeding The temperature difference, wrinkle, strength, power saving, on-demand heating, high temperature offset and low temperature offset, overheating of the heater peripheral member, and heater cracking can be greatly improved. Other recording devices such as thermal transfer recording devices (ribbons), dot printers, sublimation printers. Semiconductor-related parts such as semiconductor elements, semiconductor packages, semiconductor sealing cases, semiconductor die bonding, liquid crystal display element driving semiconductor chips, CPUs, MPUs, memories, power transistors, and power transistor cases. Printed circuit board, rigid wiring board, flexible wiring board, ceramic wiring board, build-up wiring board, mounting board, high-density mounting printed circuit board, (tape carrier package), TAB, hinge mechanism, sliding mechanism, through hole, resin packaging Wiring boards such as sealing materials, multilayer resin moldings, and multilayer boards. CD, DVD (optical pickup, laser generator, laser receiver), Blu-ray disc, DRAM, flash memory, hard disk drive, optical recording / reproducing device, magnetic recording / reproducing device, magneto-optical recording / reproducing device, information recording medium, optical recording disc , Magneto-optical recording medium (translucent substrate, optical interference layer, domain wall motion layer, intermediate layer, recording layer, protective film layer, heat dissipation layer, information track), light receiving element, light detecting element, optical pickup device, magnetic head, Recording devices such as magnetic heads for magneto-optical recording, semiconductor laser chips, laser diodes, laser drive ICs, recording / reproducing devices, and components thereof. Digital camera, analog camera, digital single-lens reflex camera, analog single-lens reflex camera, digital camera, digital video camera, camera-integrated VTR, camera-integrated VTR IC, video camera light, electronic flash device, imaging device, imaging tube cooling Apparatus, imaging apparatus, imaging element, CCD element, lens barrel, image sensor and information processing apparatus using the same, X-ray absorber pattern, X-ray mask structure, X-ray imaging apparatus, X-ray exposure apparatus, X-ray Flat detector, X-ray digital imaging device, X-ray area sensor substrate, electron microscope sample cooling holder, electron beam drawing device (electron gun, electron gun, electron beam drawing device), radiation detection device and radiation imaging system, scanner, Image reading device, moving image pickup device and still image pickup device, image recording device such as a microscope, and parts thereof. Primary batteries such as alkaline batteries and manganese batteries, secondary batteries such as lithium ion batteries, nickel metal hydride and lead storage batteries, electric double layer capacitors, electrolytic capacitors, assembled batteries, solar cells, solar cell module installation structures, photoelectric conversion substrates, Heat dissipation materials for battery devices such as photovoltaic element arrays, power generation elements, and fuel cells (power generation cells, outside the housing, inside the fuel tank). Power supplies (rectifier diodes, transformers), DC / DC converters, switching power supply devices (forward type), current leads, superconducting device systems, etc. and their components. Motors and parts such as motors, linear motors, planar motors, vibration wave motors, motor coils, circuit units for rotational control drive, motor drivers, inner rotor motors, vibration wave actuators, etc. Vacuum processing equipment, semiconductor manufacturing equipment, vapor deposition equipment, thin film single crystal semiconductor layer manufacturing equipment, plasma CVD, microwave plasma CVD, sputtering equipment, vacuum chambers, vacuum pumps, vacuum pumps, cryotraps, cryopumps, etc., electrostatic chucks , Vacuum vacuum chucks, pin chuck type wafer chucks, sputtering targets, semiconductor exposure devices, lens holding devices and projection exposure devices, photomasks, and other deposited film manufacturing devices (temperature constant, quality stable) and parts thereof. Heat treatment equipment by resistance heating / induction heating / infrared heating, dryer, annealing equipment, laminating equipment, reflow equipment, heat bonding (crimping) equipment, injection molding equipment (nozzles / heating section), resin molding dies, LIM molding, rollers Molding equipment reformed gas production (reforming part, catalyst part, heating part, etc.) stamper, (film, roll, recording medium), bonding tool, catalyst reactor, chiller, color filter substrate coloring device, resist Various manufacturing devices such as heating / cooling devices, welding equipment, magnetic induction heating films, anti-condensation glass, liquid remaining amount detection devices, heat exchange devices, and parts thereof. Heat insulation devices such as heat insulation materials, vacuum heat insulation materials, and radiation heat insulation materials. Chassis, housing, and exterior cover for various electronic and electrical equipment and manufacturing equipment. Heat dissipation components such as radiators, openings, heat pipes, heat sinks, fins, fans, and heat dissipation connectors. Cooling parts such as Peltier elements, electrothermal conversion elements, and water-cooled parts. Temperature control device, temperature control device, temperature detection device and parts. Heating element-related parts such as thermistors, thermoswitches, thermostats, thermal fuses, overvoltage protection elements, thermoprotectors, ceramic heaters, flexible heaters, composites of heaters, heat conduction plates and insulation, heater connectors and electrode terminal parts. Suitable for radiating parts with high emissivity, electromagnetic shielding parts such as electromagnetic shielding and electromagnetic wave absorbers, composites with metals such as aluminum, copper and silicon, and composites with ceramics such as silicon nitride, boron nitride and alumina is there.

  The present invention can also be configured as follows.

  (1) Two or more raw films made of a polymer film having a thickness of 5 μm to 45 μm or a carbonized polymer film having a thickness of 5 μm to 45 μm are directly laminated and heat-treated at a temperature of 2600 ° C. or more. The manufacturing method of the graphite film characterized by including a process.

(2) at least a portion of 1000 ° C. or higher 2400 ° C. or less of the temperature range, atmospheric pressure - the manufacturing method of the graphite film according to, characterized in that it is heat-treated under reduced pressure to below 0.08 MPa (1).

  (3) The method for producing a graphite film according to any one of (1) to (2), wherein birefringence of the polymer film is 0.12 or more.

  (4) The method for producing a graphite film according to any one of (1) to (3), wherein the polymer film is a polyimide film.

(5) A pressure is applied in the thickness direction of the directly laminated raw material film, and the pressure is 1.0 g / cm ² or more and 200 g / cm ² or less, according to any one of (1) to (4), Method for producing graphite film.

(6) The method for producing a graphite film according to any one of (1) to (5), wherein an area of the raw material film is 100 cm ² or more.

  (7) In the carbonization, the polymer film and the heat conductive sheet directly laminated on the two or more sheets are alternately laminated to be carbonized. (1) to (6) A method for producing a graphite film.

  (8) A graphite film characterized by subjecting a graphite film produced by the production method according to any one of (1) to (7) to a sheet shape at a pressure of 4 MPa to 20 MPa. Manufacturing method.

  (9) The method for producing a graphite film according to any one of (1) to (8), which is performed in a graphitization furnace having an internal volume of 125 to 17000 L.

  (10) A graphite film produced by the production method according to any one of (1) to (9).

  Embodiments and effects of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

<Polyimide films A, B, C>
[Production Method of Polyimide Film A]
A solution containing 4 mol of pyromellitic dianhydride in a DMF solution in which 3 equivalents of 4,4′-oxydianiline is dissolved to synthesize a prepolymer having acid anhydrides at both ends, and then containing the prepolymer A solution containing 18.5 wt% of polyamic acid obtained by dissolving 1 equivalent of p-phenylenediamine was obtained.

  While this solution was cooled, an imidation catalyst containing 1 equivalent of acetic anhydride, 1 equivalent of isoquinoline, and DMF was added to the carboxylic acid group contained in the polyamic acid to degas. Next, this mixed solution was applied onto an aluminum foil so as to have a predetermined thickness after drying. The mixed solution layer on the aluminum foil was dried using a hot air oven and a far infrared heater.

  The drying conditions when the finished thickness is 75 μm are shown. The mixed solution layer on the aluminum foil was dried in a hot air oven at 120 ° C. for 240 seconds to form a self-supporting gel film. The gel film was peeled off from the aluminum foil and fixed to the frame. Further, the gel film was stepped in a hot air oven at 120 ° C. for 30 seconds, 275 ° C. for 40 seconds, 400 ° C. for 43 seconds, 450 ° C. for 50 seconds, and a far infrared heater at 460 ° C. for 23 seconds. Heat to dry. For other thicknesses, the firing time was adjusted in proportion to the thickness. For example, in the case of a film having a thickness of 25 μm, the firing time was set to be 1/3 shorter than that in the case of 75 μm.

As described above, three types of polyimide films A having a thickness of 12.5 μm, 25 μm, and 45 μm (elastic modulus 4.4 GPa, water absorption 2.2%, birefringence 0.14, linear expansion coefficient 21.8 × 10 ⁻⁶ / ° C.).

[Production Method of Polyimide Film B]
Polyamic acid obtained by dissolving 4 equivalents of pyromellitic dianhydride in a DMF (dimethylformamide) solution in which 3 equivalents of 4,4′-oxydianiline and 1 equivalent of p-phenylenediamine were dissolved. 25 μm thick polyimide film C (elastic modulus 3.9 GPa, water absorption 3.0%, birefringence 0.12, linear expansion coefficient 23.7 × 10 ⁻⁶ / ° C.) ) Was produced.

[Polyimide film C]
The polyimide film D is “KAPTON H” having a thickness of 25 μm, which is available from Toray DuPont. (Elastic modulus 3.4 GPa, water absorption 3.0%, birefringence 0.10, 27.9 × 10 ⁻⁶ / ° C.)
According to the literature, KAPTON H uses polyamic acid obtained by dissolving 1 equivalent of pyromellitic dianhydride in a DMF (dimethylformamide) solution in which 1 equivalent of 4,4′-oxydianiline is dissolved. It is estimated that

  The production methods and various physical properties of the obtained polyimide film are summarized in Table 1.

Example 1
A polyimide film A having a size of 200 mm × 200 mm and a thickness of 25 μm was sandwiched between graphite sheets having a size of 220 mm × 220 mm, and heated to 1000 ° C. at a rate of 2 ° C./min in a nitrogen atmosphere using an electric furnace. Carbonized by heat treatment at 1000 ° C. for 1 hour.

The obtained carbonized film having a size of 160 mm × 160 mm is directly laminated with two ends aligned, and this laminate is sandwiched between graphite sheets having a size of 220 mm × 220 mm so that the pressure in the thickness direction is 20 g / cm ^2. A graphite plate having a size of 220 mm × 220 mm and a weight of 5.12 kg was placed on top. Using a graphitization furnace, from room temperature to 2200 ° C. or lower is under a reduced pressure of atmospheric pressure −0.0999 Mpa or lower (actually, with a Pirani vacuum gauge, 100 Pa or lower), a temperature range higher than 2200 ° C. is in an argon atmosphere, The temperature was raised to 2900 ° C. (graphitization maximum temperature) at a graphitization temperature raising rate of 2.5 ° C./min, and then held at 2900 ° C. for 30 minutes to produce a graphite film. The internal volume of the graphitization furnace used here was 1800L.
One obtained 180 mm × 180 mm film was sandwiched between polymer films having a size of 200 mm × 200 mm × thickness of 400 μm, and a back surface pressing step was performed using a compression molding machine. The applied pressure was 10 MPa.
(Example 2)
A graphite film was produced in the same manner as in Example 1 except that the carbonized films were directly laminated with the edges thereof aligned.
(Example 3)
A graphite film was produced in the same manner as in Example 1 except that the carbonized film was directly laminated with 10 edges aligned.
Example 4
A graphite film was produced in the same manner as in Example 1 except that the carbonized film was directly laminated with the edges of 30 sheets aligned.
(Example 5)
A graphite film was produced in the same manner as in Example 1 except that the carbonized film was directly laminated with 100 edges aligned.
(Example 6)
A graphite film was produced in the same manner as in Example 1 except that the carbonized film was directly laminated with the ends of 500 sheets aligned.
(Example 7)
A graphite film was produced in the same manner as in Example 4 except that polyimide film A having a thickness of 45 μm was used as a raw material.
(Example 8)
A graphite film was produced in the same manner as in Example 4 except that a polyimide film A having a thickness of 12.5 μm was used as a raw material.
Example 9
A graphite film was produced in the same manner as in Example 4 except that polyimide film B having a thickness of 25 μm was used as a raw material.
(Example 10)
A graphite film was produced in the same manner as in Example 4 except that polyimide film C having a thickness of 25 μm was used as a raw material.
(Example 11)
Using a graphitization furnace, from room temperature to 1600 ° C or lower, atmospheric pressure- 0.0999 Mpa or lower (actually, with a Pirani vacuum gauge, 100 Pa or lower), a temperature range higher than 1600 ° C is graphite under an argon atmosphere. A graphite film was produced in the same manner as in Example 4 except that the composition was changed.
(Example 12)
A graphite film was produced in the same manner as in Example 4 except that graphitization was performed using a graphitization furnace from room temperature to 2900 ° C. under an argon atmosphere (about atmospheric pressure).
(Example 13)
A graphite film was produced in the same manner as in Example 4 except that 30 sheets of polyimide film A having a thickness of 25 μm were directly laminated and carbonized.
(Example 14)
Preheating (carbonization) was not performed, and the polymer film was processed in a graphitization furnace. Specifically, 30 sheets of polyimide film A having a size of 200 mm × 200 mm and a thickness of 25 μm are directly laminated with the ends aligned, and this laminate is sandwiched between graphite sheets of size 220 mm × 220 mm, and the pressure in the thickness direction is 20 g / cm. as it will be ^2, and placed the size 220 mm × 220 mm, a graphite plate weight 5.12Kg above. Using a graphitization furnace, from room temperature to 2200 ° C. or lower is under a reduced pressure of atmospheric pressure −0.0999 Mpa or lower (actually, with a Pirani vacuum gauge, 100 Pa or lower). The temperature was raised to 2900 ° C. at a graphitization temperature raising rate of 2.5 ° C./min, and then held at 2900 ° C. for 30 minutes to produce a graphite film.

The obtained film was subjected to pressure treatment on the rear surface at a pressure of 10 MPa.
(Example 15)
A graphite film was produced in the same manner as in Example 4 except that the pressure treatment on the rear surface was not performed.
(Example 16)
A graphite film was produced in the same manner as in Example 4 except that the maximum graphitization temperature was 2700 ° C.
(Example 17)
A graphite film was produced in the same manner as in Example 4 except that a graphite plate having a weight of 256 kg was placed on the top so that the pressure in the thickness direction was 1000 g / cm ² .
(Comparative Example 1)
A graphite film was produced in the same manner as in Example 1 except that one carbonized film obtained using the polyimide film A as a raw material was sandwiched between graphite sheets having a size of 220 mm × 220 mm and graphitized.
(Comparative Example 2)
A graphite film was produced in the same manner as in Example 1 except that one carbonized film obtained using the polyimide film B as a raw material was sandwiched between graphite sheets having a size of 220 mm × 220 mm and graphitized.
(Comparative Example 3)
A graphite film was produced in the same manner as in Example 1 except that one carbonized film obtained using polyimide film C as a raw material was sandwiched between graphite sheets having a size of 220 mm × 220 mm and graphitized.
(Comparative Example 4)
A graphite film was produced in the same manner as in Example 4 except that the graphitizing maximum temperature was changed to 2400 ° C.

<Thickness measurement of graphite film>
As a method for measuring the thickness of the graphite film, the obtained graphite film was measured at 10 arbitrary points in a constant temperature room at 25 ° C. using a thickness gauge (Heidenhain Co., Ltd., HEIDENHAIN-CERTO). The average value was taken as the measured value.

<Bend resistance evaluation MIT test of graphite film>
The MIT bending resistance test of the graphite film was performed. A graphite film is cut to 15 × 100 mm, and a test load of 100 gf (0.98 N), a speed of 90 times / min, and a radius of curvature R of a bending clamp using a model D of Toyo Seiki Co., Ltd. Was performed at 2 mm. The bending angle was measured at 90 ° to the left and right.

<Maximum length of graphite film wrinkles>
The maximum wrinkle length of the graphite film generated after graphitization treatment as shown in FIG. 12 was measured. The maximum wrinkle length that can be visually observed is indicated as ◎ for 0 to 5 mm, ○ for 5 to 10 mm, Δ for 10 to 20 mm, and × for 20 mm or more.

<Degree of pressure bonding of graphite film>
The degree of pressure bonding between the graphite films directly laminated and graphitized was measured. The case where it can be peeled without tearing is described as ◎, the one whose peelable maximum length is 0-10 mm can be peeled, the one whose tearable maximum length is 10-20 mm can be peeled, and the one which cannot be peeled is described as x. .

<Measurement of thermal diffusivity in the film surface direction by the optical alternating current method>
The thermal diffusivity of the graphite film was measured by cutting the graphite film into a 4 × 40 mm sample shape using a thermal diffusivity measuring apparatus (“LaserPit” available from ULVAC-RIKO Co., Ltd.) by an optical alternating current method, The measurement was performed at 10 Hz under the atmosphere of The progress of graphitization was determined by measuring the thermal diffusivity in the film surface direction. The higher the thermal diffusivity, the more remarkable the graphitization.

  Tables 2 and 3 summarize the production conditions and various physical properties of the graphite films of Examples and Comparative Examples.

<Film setting method for graphitization process>
When Examples 1-6 and Comparative Example 1 were compared, when the number of laminated layers was 1, a hard graphite film as shown in FIG. 5 was obtained, but by laminating two or more, the structure of FIG. Such a flexible graphite film was obtained. Also in the MIT test, in Comparative Example 1, it was less than 100 times, while in Examples 1 to 6, it was found that the present invention was able to impart flexibility by 1000 times or more. Further, it was found that when the number of laminated layers was increased, the flexibility of the obtained graphite film was increased, and in the lamination of 10 or more, the MIT test was 100,000 times or more and showed very excellent flexibility.

<Thickness of polymer film>
When Examples 4, 7, and 8 are compared with respect to the thickness of the polymer film used as a raw material, the thinner the polymer film, the thinner the graphite film.

<Birefringence>
As for birefringence of the polymer film used as a raw material, when Examples 4, 9, and 10 were compared, a flexible graphite film was obtained when the birefringence was higher. In particular, when polyimide A having a birefringence of 0.14 was used as a raw material, a graphite film having excellent flexibility with an MIT test of 100,000 times or more could be produced. On the other hand, even when the raw material film having a birefringence of 0.10 was graphitized by the same method, the flexibility deteriorated with the MIT test of 500 times or more.

  Further, when Comparative Examples 1 to 3 were compared, even when the number of raw material films to be laminated was one, the higher the birefringence, the better the flexibility of the obtained graphite film.

<Atmosphere of 1000 ° C. or higher and 2400 ° C. or lower>
When Examples 4, 11, and 12 are compared in an atmosphere of not less than 1000 ° C. and not more than 2400 ° C. in the graphitization treatment, a flexible graphite film can be obtained by treating the widest possible temperature range of 1000 to 2400 ° C. under reduced pressure. I understood it.

<Presence / absence of carbonization process and setting method>
Examples 4, 13 and 14 are compared for the presence or absence of the carbonization step and the setting method. When the carbonization step was omitted as in Example 14, wrinkles were generated and the yield was lowered, as well as deterioration in flexibility. Moreover, also when carbonization was implemented by direct lamination | stacking like Example 13, a softness | flexibility deteriorated and a wrinkle generate | occur | produced. From the above, in order to increase flexibility and yield, as in Example 4, after polymerizing the polymer film alternately with the graphite sheet, after obtaining a carbonized film without wrinkles It has been found that it is better to carry out the graphitization again by directly laminating for graphitization.

<Presence / absence of rear surface pressurization process>
When Example 4 and 15 were compared about the presence or absence of a back surface pressurization process, it turned out that the direction which performed the back surface pressurization process shows the outstanding softness | flexibility.

<Maximum graphitization temperature>
When Examples 4, 16 and Comparative Example 4 were compared, it was found that the higher the maximum temperature, the better the flexibility.

<Pressure applied in the thickness direction of the raw film during graphitization>
When Examples 4 and 17 were compared, it was found that if the pressure applied in the thickness direction of the raw material film during graphitization was too high, the films were pressure-bonded and it was difficult to obtain a graphite film. Further, it was found that when the pressure is large, it is difficult to obtain a flexible graphite film which is difficult to foam.

DESCRIPTION OF SYMBOLS 11 Graphite film 21 Graphite layer space 31 Flexible 41 Hardened graphite film 51 Crack 61 Densely packed interlayer 62 Carbonaceous mass 71 developed to inhibit the growth in the surface direction by the action of metal impurities 71 Graphite layer 72 Outgas 73 Small graphite crystallite gap 81 that could not be developed in the plane direction Carbonaceous sheet 82 Raw material film 1 Polyimide film 2 Wedge-shaped sheet 3 Wedge-shaped sheet width 4 Sodium light 5 Interference fringes 121 Wrinkles

Claims (9)

Two or more raw material films made of a polymer film having a thickness of 5 μm to 45 μm or a carbonized polymer film having a thickness of 5 μm to 45 μm are directly laminated and heat-treated at a temperature of 2600 ° C. or more. Including steps,
The said process is performed in the graphitization furnace whose internal volume is 125-17000L, The manufacturing method of the graphite film characterized by the above-mentioned.   2. The method for producing a graphite film according to claim 1, wherein the number of raw material films directly laminated is 2 or more and 100 or less.   3. The method for producing a graphite film according to claim 1, wherein the heat treatment is performed by reducing the pressure to atmospheric pressure−0.08 MPa or less in at least a part of a temperature range of 1000 ° C. or more and 2400 ° C. or less.   The method for producing a graphite film according to claim 1, wherein the polymer film has a birefringence of 0.12 or more.   The method for producing a graphite film according to claim 1, wherein the polymer film is a polyimide film. The graphite film according to any one of claims 1 to 5, wherein heat treatment is performed in a state where a pressure of 1.0 g / cm ² or more and 200 g / cm ² or less is applied in a thickness direction of the directly laminated raw material film. Manufacturing method. The method for producing a graphite film according to claim 1, wherein an area of the raw material film is 100 cm ² or more.   The graphite film according to any one of claims 1 to 7, wherein in the carbonization, the polymer film and the heat conductive sheet that are directly laminated in the range of 2 to 500 are alternately laminated and carbonized. Manufacturing method. A method for producing a graphite film, comprising performing a rear surface pressurizing step of pressurizing the graphite film produced by the production method according to any one of claims 1 to 8 planarly at a pressure of 4 MPa to 20 MPa.