WO2022009972A1 - グラファイトシートの製造方法及びグラファイトシート用のポリイミドフィルム - Google Patents

グラファイトシートの製造方法及びグラファイトシート用のポリイミドフィルム Download PDF

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WO2022009972A1
WO2022009972A1 PCT/JP2021/025896 JP2021025896W WO2022009972A1 WO 2022009972 A1 WO2022009972 A1 WO 2022009972A1 JP 2021025896 W JP2021025896 W JP 2021025896W WO 2022009972 A1 WO2022009972 A1 WO 2022009972A1
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graphite sheet
weight
polyimide film
phosphorus
film
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English (en)
French (fr)
Japanese (ja)
Inventor
幹明 小林
啓介 稲葉
雅司 尾▲崎▼
晃男 松谷
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Kaneka Corp
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Kaneka Corp
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Priority to CN202180047780.3A priority Critical patent/CN115768725B/zh
Priority to JP2022535399A priority patent/JP7367221B2/ja
Publication of WO2022009972A1 publication Critical patent/WO2022009972A1/ja
Priority to US18/069,172 priority patent/US20230128003A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate

Definitions

  • the present invention relates to a method for manufacturing a graphite sheet and a polyimide film for a graphite sheet.
  • the graphite sheet Since the graphite sheet has excellent heat dissipation characteristics, it is used as a heat dissipation component for semiconductor elements and other heat-generating components mounted on various electronic devices such as computers or electrical devices.
  • Such a graphite sheet can be obtained by firing a polyimide film.
  • Patent Document 1 describes a technique for producing a graphite sheet by firing a polyimide film containing inorganic particles.
  • graphite sheets are easily torn from the edges during handling, especially roll-shaped graphite sheets may be used by attaching a slightly adhesive film to one side of the graphite sheet in order to improve its workability.
  • the conventional graphite sheet has a problem in peelability from the fine adhesive film, such as peeling from the layers of graphite when the fine adhesive film is peeled off.
  • One aspect of the present invention is to provide a method for producing a graphite sheet and a polyimide film for the graphite sheet for producing a graphite sheet having good peelability from a slightly adhesive film.
  • the present inventors have obtained a polyimide film containing inorganic particles and a non-metal additive containing phosphorus, and the inorganic particles and the total phosphorus content are within a predetermined range.
  • the present invention has been completed by finding that a graphite sheet having excellent peelability from a slightly adhesive film can be produced by using it as a raw material.
  • the present invention includes the following.
  • a non-metal additive containing inorganic particles and phosphorus the content of the inorganic particles is 0.05% by weight or more and 0.30% by weight or less, and the inorganic particles and the phosphorus are contained.
  • inorganic particles and non-metal additives containing phosphorus The content of the inorganic particles is 0.05% by weight or more and 0.30% by weight or less.
  • a polyimide film for a graphite sheet wherein the total phosphorus content of the inorganic particles and the non-metal additive containing phosphorus is 0.055% by weight or more and 0.097% by weight or less.
  • the present inventors have excellent thermal diffusivity and interlayer strength in the graphite sheet obtained by the above method, and can prevent the fusion of the carbonaceous film in the graphitization step, so that the graphite sheet can be highly productive. I also found for the first time that it can be provided at.
  • a graphite sheet made of a polyimide film containing inorganic particles has an excellent thermal diffusivity, but is significantly inferior in peelability from a slightly adhesive film.
  • the present inventors added "a non-metal additive containing phosphorus", and further, "the total phosphorus content of the inorganic particles and the non-metal additive containing phosphorus” was set within a certain range. By doing so, it has been found that it is possible to provide a method for producing a graphite sheet having excellent peelability from a fine adhesive film while maintaining an excellent heat diffusion rate. Furthermore, it has been found that according to the method for producing a graphite sheet, it is possible to provide a graphite sheet having excellent interlayer strength and to prevent fusing of a film in the production process.
  • the present inventors speculate on the reason why the above-mentioned method for producing a graphite sheet can provide a graphite sheet having excellent peelability from a slightly adhesive film as follows.
  • the phosphorus-containing non-metal additive does not react with carbon (graphite) when sublimated, so it does not easily disturb the orientation of graphite. Therefore, the orientation of graphite in the manufactured graphite sheet is maintained, and delamination of graphite is less likely to occur. That is, it is considered that the peelability of the graphite sheet from the slightly adhesive film is improved.
  • the content of inorganic particles is 0.05% by weight or more and 0.30% by weight or less, and the total phosphorus content is 0.055% by weight or more and 0.097% by weight or less. Anything may include a step of heat-treating the polyimide film to 2400 ° C. or higher.
  • a method for producing a graphite sheet according to an aspect of the present invention may be referred to as "the present production method”.
  • This manufacturing method is a so-called polymer thermal decomposition method in which a polyimide film is heat-treated under an inert gas atmosphere or under reduced pressure. Specifically, a carbonization step of preheating the polyimide film to a temperature of about 1000 ° C. to obtain a carbonized polyimide film and a heat treatment of the carbonized polyimide film produced by the carbonization step to a temperature of 2400 ° C. or higher. A graphite sheet is obtained through a graphitization step of (heating) and graphitization, and optionally a compression step of compressing the graphite.
  • the carbonization step and the graphitization step may be continuously performed, or the carbonization step may be completed and then only the graphitization step may be performed independently.
  • the carbonization step is a step of heat-treating the polyimide film to a temperature of about 1000 ° C. to carbonize (carbonize) the polyimide film.
  • the method for carbonizing the polyimide film in the carbonization step is not particularly limited. For example, in, carbonization may be performed in a state where rectangular polyimide films are laminated, or a roll-shaped polyimide film may be carbonized in a roll-like state. The film may be unwound from the roll-shaped polyimide film and continuously carbonized. Above all, the continuous carbonization method in which the film is unwound from the roll-shaped polyimide film and continuously carbonized is preferable because it is excellent in productivity.
  • the carbonization step is carried out under reduced pressure or in an inert gas, and nitrogen is preferably used as the inert gas.
  • the carbonized polyimide film obtained by the carbonization step may be referred to as a carbonaceous film.
  • the graphitization step is a step of heat-treating the carbonaceous film obtained in the carbonization step to a temperature of 2400 ° C. or higher to graphitize the carbonaceous film. It can be said that the graphitization step is a step of heat-treating a carbonaceous film to obtain a graphite sheet.
  • the temperature (maximum temperature) at which the carbonaceous film obtained in the carbonization step is heat-treated is preferably, for example, 2400 ° C. or higher, 2600 ° C. or higher, 2800 ° C. or higher, 2900 ° C. or higher, or 3000 ° C. or higher. It can be exemplified.
  • the upper limit is not particularly limited, but is preferably 3300 ° C or lower, and more preferably 3200 ° C or lower.
  • the temperature (maximum temperature) at which the carbonic film obtained in the carbonization step is heat-treated is 2400 ° C. or higher, there is an advantage that the heat diffusion rate of the obtained graphite sheet is good, and the temperature is 3300 ° C. If the following, there is an advantage that the sublimation of the graphite member in the graphitization furnace can be suppressed.
  • the graphitization step is carried out under reduced pressure or in an inert gas, and argon or helium is suitable as the inert gas.
  • graphitization may be performed in a state in which rectangular carbonaceous films are laminated, or the roll-shaped carbonaceous film may be graphitized as a roll, and the film is continuously fed out from the roll-shaped carbonaceous film. It may be graphitized. Since a long film can be obtained, a method of graphitizing the roll-shaped film or feeding out the rolled carbonaceous film to continuously graphitize the film is preferable.
  • the foamed graphite sheet after graphitization may be subjected to a compression step. Flexibility can be imparted to the graphite sheet by performing a compression step.
  • a compression step a method of compressing in a planar shape, a method of rolling using a metal roll or the like can be used.
  • the compression step may be carried out at room temperature or during the graphitization step.
  • the compression process can also be said to be a softening process.
  • Graphite sheet > Thermal diffusivity of the graphite sheet obtained by the present production method is preferably 8.0 cm 2 / s or more, more preferably 8.4 cm 2 / s or more, is 8.7cm 2 / s or more Is even more preferable.
  • a graphite sheet having a thermal diffusivity of 8.0 cm 2 / s or more is excellent in heat dissipation, and can be suitably used as a heat dissipation component in a field such as an electronic device where excellent heat dissipation is required.
  • a graphite sheet having a thermal diffusivity of less than 8.0 cm 2 / s does not have sufficient heat dissipation and is not suitable for use as a heat dissipation component. Therefore, it is not regarded as a graphite sheet according to an embodiment of the present invention.
  • the interlayer strength of the graphite sheet according to the embodiment of the present invention is preferably 100 gf / inch or more, more preferably 110 gf / inch or more, and further preferably 120 gf / inch or more.
  • the graphite sheet is excellent in peelability from the slightly adhesive film. That is, when the slightly adhesive film (slightly adhesive process paper) bonded to the graphite sheet is peeled off, delamination, which causes a decrease in the thermal diffusivity of the graphite sheet, does not occur, which is preferable.
  • the thickness of the graphite sheet according to the embodiment of the present invention is preferably 16 to 85 ⁇ m, more preferably 16 ⁇ m to 80 ⁇ m, further preferably 23 ⁇ m to 60 ⁇ m, and even more preferably 30 ⁇ m to 50 ⁇ m. Is even more preferable. If the thickness of the graphite sheet is within the above range, it has an advantage that it exhibits an excellent heat dissipation effect when used in a thin electronic device (for example, a high-performance smartphone or the like).
  • the lower limit of the thickness of the graphite sheet according to the embodiment of the present invention is preferably 16 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 23 ⁇ m or more, still more preferably 30 ⁇ m or more. preferable.
  • the upper limit of the thickness of the graphite sheet is preferably 85 ⁇ m or less, more preferably 80 ⁇ m or less, further preferably 60 ⁇ m or less, still more preferably 50 ⁇ m or less. If the thickness of the graphite sheet is 16 ⁇ m or more, it has a sufficient heat dissipation effect for heat dissipation of electronic devices, and if it is 85 ⁇ m or less, it has an advantage that it can be mounted in a thin electronic device having a small space. ..
  • the density of the graphite sheet according to an embodiment of the present invention is preferably 1.60 g / cm 3 or more, more preferably 1.80 g / cm 3 or more, still be at 1.90 g / cm 3 or more It is preferably 2.00 g / cm 3 or more, and more preferably 2.00 g / cm 3.
  • the upper limit of the density is not particularly determined, but the graphite sheet is usually 2.26 g / cm 3 or less.
  • the density of the graphite sheet is 1.60 g / cm 3 or more, the graphite sheet has an advantage of exhibiting an excellent heat dissipation effect.
  • the polyimide film for a graphite sheet used in this production method is a polyimide film made from an acid dianhydride component and a diamine component as raw materials, and contains a predetermined amount of inorganic particles and phosphorus.
  • the lower limit of the content of the inorganic particles in the polyimide film according to the embodiment of the present invention is preferably 0.05% by weight, more preferably 0.08% by weight, and 0.12% by weight. It is more preferable to have.
  • the upper limit of the content of the inorganic particles is preferably 0.30% by weight, more preferably 0.20% by weight, and even more preferably 0.18% by weight. Within such a range, the physical properties of both the interlayer strength and the thermal diffusivity of the finally obtained graphite sheet are excellent. Further, when the content of the inorganic particles in the polyimide film is 0.05% by weight or more, the polyimide film is excellent in transportability.
  • the manufacturing process for example, carbonization process
  • the yield of the obtained graphite sheet is improved, and the graphite sheet is excellent in productivity.
  • the thermal diffusivity of the finally obtained graphite sheet is excellent.
  • Examples of the inorganic particles that can be used in one embodiment of the present invention include calcium carbonate (CaCO 3 ), silica, calcium hydrogen phosphate (CaHPO 4 ), calcium phosphate (Ca 2 P 2 O 7 ) and the like.
  • calcium hydrogen phosphate containing phosphorus and inorganic particles containing phosphorus such as calcium phosphate can be preferably used because the amount of the non-metal additive containing phosphorus described later can be reduced.
  • the polyimide film according to the embodiment of the present invention preferably contains a non-metal additive containing phosphorus so that the total phosphorus content of the inorganic particles described later and the non-metal additive containing phosphorus is in a preferable range. ..
  • the phosphorus-containing non-metal additive that can be used in one embodiment of the present invention include phosphoric acid esters, phosphin oxides, phosphite esters, phosphins, phosphonic acid esters, phosphinic acid esters, and pyrophosphoric acid. , Metaphosphoric acid, red phosphorus, and the like.
  • organophosphorus compounds such as phosphate esters, phosphin oxides, phosphite esters, phosphins, phosphonic acid esters, and phosphinic acid esters are stable against polyamic acid and polyimide. It can be preferably used. Further, from the viewpoint of stability, it is preferable that the organic phosphorus compound contains pentavalent phosphorus as a main component.
  • the polyimide film according to the embodiment of the present invention contains a non-metal additive containing phosphorus, the polyimide film can provide a graphite sheet having excellent peelability from a slightly adhesive film, and further, heat. Since the diffusivity is excellent and the fusing of the carbonaceous film in the graphitization step can be prevented, the graphite sheet can be provided with high productivity.
  • the temperature at which the weight loss rate of the non-metal additive containing phosphorus is 5% is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and more preferably 300 ° C. The above is more preferable.
  • the temperature at which the weight reduction rate of the non-metal additive containing phosphorus is 5% is 200 ° C. or higher, it is possible to reduce the contamination of the furnace that carbonizes the polyimide film.
  • the non-metal additive containing phosphorus one having excellent compatibility with the polyimide resin is preferably used. With such an additive, it is possible to obtain a graphite sheet that is well dispersed in the polyimide film and has little variation in the degree of in-plane foaming.
  • non-metal additive containing phosphorus a liquid at normal temperature and pressure is preferably used. With such an additive, it is possible to obtain a graphite sheet that does not precipitate in the polyimide film and hardly causes abnormal foaming during graphitization.
  • Total phosphorus content of inorganic particles and non-metal additives containing phosphorus The lower limit of the total phosphorus content of the inorganic particles and the non-metal additive containing phosphorus in the polyimide film according to the embodiment of the present invention is preferably 0.055% by weight, preferably 0.061% by weight. More preferably, it is more preferably 0.068% by weight.
  • the upper limit of the total phosphorus content of the inorganic particles and the non-metal additive containing phosphorus is preferably 0.097% by weight, more preferably 0.091% by weight, and 0.085% by weight. Is even more preferable.
  • the total phosphorus content of the inorganic particles and the non-metal additive containing phosphorus in the polyimide film is 0.055% by weight to 0.097% by weight, it is possible to obtain from the slightly adhesive film of the graphite sheet finally obtained. It has excellent peelability, and also has excellent heat diffusion rate and interlayer strength. Further, in particular, when the total phosphorus content of the inorganic particles and the non-metal additive containing phosphorus in the polyimide film is 0.061% by weight to 0.091% by weight, both the heat diffusion rate and the interlayer strength are both. It has the advantage of having better physical properties.
  • acid dianhydride component (Acid dianhydride component)
  • acid dianhydride component examples include pyromellitic acid dianhydride, 2,3,6,7, -naphthalenetetracarboxylic acid dianhydride, 3,.
  • these acid dianhydrides can be mixed in any proportion.
  • these acid dianhydrides may be used alone, or a plurality of types of these acid dianhydrides may be mixed at an arbitrary ratio.
  • these acid dianhydrides it is preferable to use pyromellitic dianhydride or 3,3', 4,4'-biphenyltetracarboxylic dianhydride.
  • diamine component examples of the diamine component that can be used as a raw material for the polyimide film according to the embodiment of the present invention include 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4,4'-diaminodiphenylmethane, benzidine, and 3,3'-dichloro.
  • Benzidine 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diamino Naphthalene, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenylsilane, 4,4'-diminodiphenylethylphosphine oxide, 4,4'-diaminodiphenylN-methylamine, 4,4'- Examples thereof include diaminodiphenyl N-phenylamine, 1,3-diaminobenzene, 1,2-diaminobenzene and their analogs.
  • the raw material of the polyimide film according to the embodiment of the present invention it is preferable to use pyromellitic acid dianhydride in combination with 4,4'-diaminodiphenyl ether and / or p-phenylenediamine. According to this configuration, there is an advantage that the polyimide film has excellent film-forming properties.
  • the thickness of the polyimide film according to the embodiment of the present invention is preferably 37 ⁇ m to 160 ⁇ m, more preferably 37 ⁇ m to 150 ⁇ m, further preferably 50 ⁇ m to 125 ⁇ m, and 62 ⁇ m to 100 ⁇ m. Even more preferable.
  • a graphite sheet having both thermal diffusivity and interlayer strength can be obtained.
  • the lower limit of the thickness of the polyimide film according to the embodiment of the present invention is preferably 37 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 62 ⁇ m or more.
  • the upper limit of the thickness of the polyimide film is preferably 160 ⁇ m or less, more preferably 150 ⁇ m or less, further preferably 125 ⁇ m or less, still more preferably 100 ⁇ m or less.
  • the thickness of the polyimide film is 37 ⁇ m or more, it has an advantage of excellent interlayer strength, and when it is 160 ⁇ m or less, it has an advantage of excellent thermal diffusivity.
  • the polyimide film according to the embodiment of the present invention can be produced by imidizing (imidoconverting) the polyamic acid as a precursor.
  • a method for imidizing a polyamic acid as a precursor for example, a thermal cure method in which the polyamic acid as a precursor is heated to be imidized, or an acetic anhydride or the like is added to the polyamic acid.
  • an imidization accelerator when the chemical cure method is used, the tertiary amines mentioned above are preferable.
  • the chemical cure method is preferable.
  • the combined use of the dehydrating agent and the imidization accelerator is preferable because the linear expansion coefficient of the obtained film can be smaller, the elastic modulus can be larger, and the birefringence can be larger.
  • the chemical cure method can complete the imidization reaction in a short time in the heat treatment, and is an industrially advantageous method with excellent productivity.
  • the method for producing the polyamic acid is not particularly limited, but for example, aromatic acid dianhydride and diamine are dissolved in an organic solvent in substantially equal molar amounts, and this organic solution is used as an acid dianhydride and diamine.
  • Polyamic acids can be produced by stirring under controlled temperature conditions until the polymerization is complete.
  • the polymerization method is not particularly limited, but for example, any of the following polymerization methods (1)-(5) is preferable.
  • the ratio of the molar amount of two or more kinds of substances different from the substantially equimolar amount is in the range of 100:98 to 100:102.
  • Aromatic tetracarboxylic acid dianhydride is reacted with an aromatic diamine compound in a small molar amount in an organic polar solvent to obtain a prepolyma having an acid anhydride group at both ends. Subsequently, a method of polymerizing an aromatic diamine compound having a substantially equal molar amount with respect to an aromatic tetracarboxylic dianhydride on a prepolyma.
  • a prepolyma having the acid dianhydride at both ends is synthesized using a diamine and an acid dianhydride, and the prepolyma is the same as the diamine used for the synthesis of the prepolyma.
  • examples thereof include a method of synthesizing a polyamic acid by reacting a diamine or a different type of diamine.
  • the aromatic diamine to be reacted with the prepolyma may be the same type of aromatic diamine as the aromatic diamine used for the synthesis of the prepolyma, or may be a different type of aromatic diamine. ..
  • Aromatic tetracarboxylic acid dianhydride is reacted with an excess molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolyma having amino groups at both ends. Subsequently, after the aromatic diamine compound is additionally added to this prepolyma, the prepolyma and the aromatic tetracarboxylic acid dianhydride are so that the aromatic tetracarboxylic acid dianhydride and the aromatic diamine compound have substantially the same molar amount.
  • a method of polymerizing with an object is reacted with an excess molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolyma having amino groups at both ends. Subsequently, after the aromatic diamine compound is additionally added to this prepolyma, the prepolyma and the aromatic tetracarboxylic acid dianhydride are so that the aromatic tetracarboxylic acid dianhydride and the aromatic diamine compound have substantially the
  • an aromatic diamine compound is added so as to have a substantially equal molar amount with respect to the acid dianhydride.
  • One embodiment of the present invention may have the following configuration.
  • It contains inorganic particles and a non-metal additive containing phosphorus, and the content of the inorganic particles is 0.05% by weight or more and 0.30% by weight or less, and the inorganic particles and the non-containing phosphorus are contained.
  • the heat diffusivity is 8.0 cm 2 / s or more, which includes a step of heat-treating a graphite film having a total phosphorus content of 0.055% by weight or more and 0.097% by weight or less to 2400 ° C. or higher.
  • It contains inorganic particles and a non-metal additive containing phosphorus, and the content of the inorganic particles is 0.05% by weight or more and 0.30% by weight or less, and the inorganic particles and the non-containing phosphorus are contained.
  • phosphorus content in polyimide film was determined using a wavelength dispersive fluorescent X-ray analyzer (ZSX PrimusII manufactured by Rigaku Co., Ltd.) in proportion to a polyimide film having a known phosphorus concentration.
  • Transportability of polyimide film was evaluated based on whether or not an abnormality was found in the polyimide film in the continuous carbonization step described in Examples described later.
  • the evaluation criteria for the transportability of the polyimide film were as follows. A: No problem with handling and appearance B: Films stick to each other due to static electricity, but handling is possible without problems with appearance C: Fine scratches and wrinkles are formed during transportation, and the appearance yield decreases ⁇ Continuous Contamination of carbonization furnace> Regarding the contamination of the continuous carbonization furnace, the degree of contamination of the continuous carbonization furnace was evaluated in the continuous carbonization step described in Examples described later.
  • the evaluation criteria for contamination of the continuous carbonization furnace are as follows.
  • the central portion refers to a portion of the obtained graphite sheet that is central in the width direction and also central in the longitudinal direction.
  • the interlayer strength of the graphite sheet was determined as follows. Double-sided tape was attached to both sides of the obtained graphite sheet, and the central portion was punched to a size of 25 mm ⁇ 80 mm to obtain a sample. One side of this sample was fixed to a plate made of SUS, and the double-sided tape on the other side was peeled off so as to maintain an angle of 90 °. At that time, the force when peeling occurred inside the graphite sheet was measured with a digital force gauge (ZTS-5N manufactured by Imada Co., Ltd.) and used as the interlayer strength of the graphite sheet.
  • ZTS-5N manufactured by Imada Co., Ltd.
  • ⁇ Thickness of graphite sheet> In the obtained graphite sheet, the thicknesses at four corners and one center were measured using a micrometer manufactured by Mitutoyo Co., Ltd.
  • the "central one point” indicates the position of the intersection when a diagonal line is drawn from the four measurement points at each corner to the measurement points located diagonally in the obtained graphite sheet. Then, the average value of the measured values of the obtained thickness was taken as the thickness of the graphite sheet.
  • FIG. 1 is a diagram showing immediately after the slightly adhesive film 12 attached to the graphite sheet 11 is peeled off at a tensile speed of 300 mm / min, and the peeled graphite 13 can be observed on the slightly adhesive film 12.
  • the graphite sheet 11 punched into a 25 mm square and the slightly adhesive film 12 (manufactured by Sumiron Co., Ltd., E-203) cut into a 25 mm square were bonded together using a laminator.
  • the evaluation criteria are as follows. A: Even if the graphite is peeled off at a tensile speed of 1000 mm / min, the peeled graphite is not observed. B: Peeled graphite is observed when peeled at a tensile speed of 1000 mm / min, but no peeled graphite is observed even when peeled at 300 mm / min. C: Graphite peeled off is observed even if peeled off at a tensile speed of 300 mm / min.
  • Example 1 ⁇ Method of manufacturing polyimide film>
  • ODA 4,4'-diaminodiphenyl ether
  • PMDA pyromellitic acid dianhydride
  • PDA p-phenylenediamine
  • this mixed solution was applied onto an aluminum foil so as to have a thickness of 62 ⁇ m after drying to obtain a mixed solution layer.
  • the mixed solution layer on the aluminum foil was dried using a hot air oven and a far infrared heater.
  • the specific drying method is as follows. First, the mixed solution layer on the aluminum foil was dried in a hot air oven at 120 ° C. for 200 seconds to obtain a self-supporting gel film. The gel film was peeled off from the aluminum foil and fixed to the frame. Further, the gel film is heated stepwise in a hot air oven at 120 ° C. for 25 seconds, 275 ° C. for 34 seconds, 400 ° C. for 35 seconds, 450 ° C. for 40 seconds, and a far-infrared heater at 460 ° C. for 18 seconds. And dried. A part of resorcinol bis (diphenyl phosphate) volatilized during drying (during film formation).
  • a polyimide film having a calcium hydrogen phosphate content of 0.16% by weight, a resorcinol bis (diphenyl phosphate) content of 0.54% by weight, a total phosphorus content of 0.095% by weight, and a thickness of 62 ⁇ m ( A-1) was produced.
  • a polyimide film (A-1) roll having a thickness of 62 ⁇ m, a width of 250 mm, and a length of 300 m was set on the unwinding side of the device for transporting the film, and a continuous carbonization step was carried out while continuously moving the film to the heat treatment device. ..
  • the continuous carbonization step was performed using a continuous carbonization device as shown in FIG.
  • the continuous carbonization device combines a device 22 for transporting the polyimide film 23, a heat treatment device 21 having an entrance / exit and a heating space, and heat-treats the polyimide film 23 in the heat treatment device 21 (carbonization).
  • Step) is a device that can continuously obtain the carbonized film 24.
  • the heat treatment device 21 has six heating spaces in the MD direction, each heating space has a length of 500 mm in the MD direction and a length of 300 mm in the TD direction, and each heating space is replaced with nitrogen to flow under a nitrogen atmosphere.
  • the temperature was set at (2 L / min), and the set temperatures were adjusted to 600 ° C, 615 ° C, 630 ° C, 645 ° C, 670 ° C, and 720 ° C, respectively.
  • the transport speed of the films (the polyimide film 23 and the carbonaceous film 24) in the continuous carbonization step is adjusted to 1.6 m / min, and the film is transported in the transport direction 25 so that the tension with respect to the film is 10 N. did.
  • the film was sandwiched from above and below by an expanded graphite sheet (thermal conductivity 200 W / m ⁇ K, thickness 400 ⁇ m) which is a material in the furnace, and the film was conveyed.
  • the material in the front furnace is provided so as to be in contact with the film, and in the continuous carbonization step, the film is conveyed so as to slide on the material in the furnace. Further, the material in the furnace was provided so as to cover a wider range than the passing range of the film in the heating space.
  • the carbonaceous film 24 after the continuous carbonization step was cooled to room temperature (23 ° C.) and formed into a roll having an inner diameter of 100 mm to obtain a carbonaceous film roll 31 shown in FIG.
  • the carbonaceous film scroll 31 was set in the hearth 32 so that the width direction of the film was vertical, and the graphitization step was performed at a heating rate of 2 ° C./min up to 2900 ° C.
  • the arrow 33 indicates the direction of gravity.
  • the film after the graphitization step was cooled to room temperature (23 ° C.), and the graphitized film was subjected to a compression step (flexibility step) at room temperature (23 ° C.) at a pressure of 10 MPa to obtain a graphite sheet.
  • the characteristics of the compressed graphite sheet were examined by the above-mentioned test.
  • Examples 2 to 11, Comparative Examples 1 to 5 A polyimide film was prepared in the same manner as in Example 1 except that the amounts of calcium hydrogen phosphate and resorcinol bis (diphenyl phosphate) added were set to the amounts shown in Table 1, and a graphite sheet was prepared using the polyimide film.
  • Example 12 The content of resorcinol bis (diphenyl phosphate) was the same as in Example 1 except that calcium carbonate was used instead of calcium hydrogen phosphate and the amount of resorcinol bis (diphenyl phosphate) added was changed as shown in Table 1.
  • a polyimide film having a total phosphorus content of 0.056% by weight and a thickness of 62 ⁇ m was prepared by 0.53% by weight, and a graphite sheet was prepared using the polyimide film.
  • Example 13 The content of resorcinol bis (diphenyl phosphate) was 0 in the same manner as in Example 1 except that silica was used instead of calcium hydrogen phosphate and the amount of resorcinol bis (diphenyl phosphate) added was changed as shown in Table 1.
  • Example 14 The content of resorcinol bis (diphenyl phosphate) was 0 in the same manner as in Example 1 except that calcium phosphate was used instead of calcium hydrogen phosphate and the amount of resorcinol bis (diphenyl phosphate) added was changed as shown in Table 1.
  • Example 15 Examples except that 1.30% by weight of triphenylphosphate (phosphorus content: 9.5% by weight, 5% weight loss temperature in TG-DTA: 220 ° C.) was added instead of resorcinolbis (diphenylphosphate).
  • a polyimide film having a triphenyl phosphate content of 0.34% by weight, a total phosphorus content of 0.070% by weight, and a thickness of 62 ⁇ m was prepared, and a graphite sheet was prepared using the polyimide film.
  • Example 16 Performed except that 0.80% by weight of triphenylphosphine oxide (phosphorus content: 11.1% by weight, 5% weight loss temperature in TG-DTA: 243 ° C.) was added instead of resorcinolbis (diphenylphosphate).
  • a polyimide film having a triphenylphosphine oxide content of 0.29% by weight, a total phosphorus content of 0.070% by weight, and a thickness of 62 ⁇ m was prepared, and a graphite sheet was prepared using the polyimide film. ..
  • Example 17 Except for the addition of 0.40% by weight of biphenol bis (diphenyl phosphate) (phosphorus content: 9.5% by weight, 5% weight loss temperature in TG-DTA: 395 ° C) instead of resorcinolbis (diphenylphosphate).
  • a polyimide film having a biphenol bis (diphenyl phosphate) content of 0.34% by weight, a total phosphorus content of 0.070% by weight, and a thickness of 62 ⁇ m was prepared, and graphite was used. A sheet was prepared.
  • Example 18 A polyimide film was prepared in the same manner as in Example 4 except that the thickness of the polyimide film was set to the thickness shown in Table 1, and a graphite sheet was prepared using the polyimide film.
  • the firing time was adjusted in proportion to the thickness. For example, in the case of a film having a thickness of 50 ⁇ m, the firing time was set to 1/2 shorter than in the case of a film having a thickness of 100 ⁇ m.
  • Table 1 shows the production conditions and physical properties of the graphite sheets of Examples 1 to 21 and Comparative Examples 1 to 5.
  • the inorganic particles and the non-metal additive containing phosphorus are contained, the content of the inorganic particles is 0.05% by weight or more and 0.30% by weight or less, and the content of phosphorus is 0.055.
  • the graphite sheet obtained from the polyimide film obtained by weight% or more and 0.097% by weight or less is excellent in peelability from the slightly adhesive film and also has excellent physical properties in both interlayer strength and heat diffusion rate.
  • Comparative Examples 1 to 3 it can be seen that the graphite sheet obtained from the polyimide film having a phosphorus content of less than 0.055% by weight is inferior in peelability from the slightly adhesive film.
  • the graphite sheet obtained from the polyimide film having an inorganic particle content of 0.30% by weight or more is inferior in thermal diffusivity.
  • the graphite sheet obtained from the polyimide film having an inorganic particle content of less than 0.05% by weight is inferior in peelability from the slightly adhesive film and inferior in transportability of the polyimide film. It can be seen that the rate decreases and the interlayer strength is inferior.
  • the graphite sheet obtained in the present invention is excellent in peelability from the slightly adhesive film, it can be suitably used as a heat radiating member of an electronic device.

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