WO2020262765A1 - Film de polyimide pour feuille de graphite, et procédé de fabrication associé - Google Patents

Film de polyimide pour feuille de graphite, et procédé de fabrication associé Download PDF

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WO2020262765A1
WO2020262765A1 PCT/KR2019/014620 KR2019014620W WO2020262765A1 WO 2020262765 A1 WO2020262765 A1 WO 2020262765A1 KR 2019014620 W KR2019014620 W KR 2019014620W WO 2020262765 A1 WO2020262765 A1 WO 2020262765A1
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polyimide film
graphite sheet
weight
polyamic acid
parts
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Korean (ko)
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민재호
원동영
최정열
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피아이첨단소재 주식회사
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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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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

Definitions

  • the present invention relates to a polyimide film for a high-thickness graphite sheet and a method of manufacturing the polyimide film for a graphite sheet.
  • Graphite is a material with very excellent thermal conductivity and has been in the spotlight as a means of heat dissipation.
  • the artificial graphite manufactured in the form of a thin sheet has excellent thermal conductivity of about 2 to about 7 times as compared to copper or aluminum, and is therefore preferably used as a heat dissipation means applied to electronic devices.
  • the high-thickness graphite sheet is advantageous in terms of heat capacity compared to a conventional thin graphite sheet, for example, a graphite sheet having a thickness of 30 ⁇ m or less, so that even if the calorific value of an electronic device increases, heat can be efficiently dissipated. There is an advantage.
  • artificial graphite sheets are manufactured by carbonizing and graphitizing a polyimide film as a precursor.
  • a high-thickness polyimide film for example, a polyimide film having a thickness of 100 ⁇ m or more may be used depending on the desired thickness level.
  • One object of the present invention is to provide a polyimide film that has low brittleness when applied to a graphite sheet, has excellent surface quality, and can secure a high thickness at the same time, and a method of manufacturing the same.
  • Another object of the present invention is to provide a method of manufacturing a graphite sheet that has excellent surface quality and thermal conductivity, and is capable of securing a high thickness while having low brittleness.
  • One embodiment of the present invention is polyamic acid; And an imidation catalyst; formed from a composition for forming a polyimide film, having a thickness of about 100 ⁇ m to about 200 ⁇ m, and a first surface damage rate of 0% or about 0.001% to about 0.004 represented by Equation 1 below. %. It relates to a polyimide film for graphite sheets.
  • a 0 is a polyimide film specimen having a size of 200 mm X 25 mm by heat treatment from about 15° C. to about 1200° C. at a heating rate of about 1° C./min to about 5° C./min to carbonize, First graphitized by heat treatment from about 1200°C to about 2200°C at a temperature rising rate of about 1.5°C/min to about 5°C/min, and from about 2200°C at a temperature rising rate of about 0.4°C/min to about 1.3°C/min Secondary graphitization by heat treatment to about 2500°C, and heat treatment from about 2500°C to about 2800°C at a temperature increase rate of about 8.5°C/min to about 20°C/min to obtain a graphite sheet specimen obtained by tertiary graphitization at 10 magnification. It is the area measured by taking a picture (mm 2 ), and A 1 is the area (mm 2 ) of the damaged area measured by taking a picture of the graphite sheet
  • the molar ratio of the amic acid group of the polyamic acid: the imidation catalyst in the composition for forming the polyimide film may be about 1:0.15 to about 1:0.20.
  • the composition for forming a polyimide film is 100 parts by weight of polyamic acid; And about 17 parts by weight to about 36 parts by weight of an imidation catalyst.
  • Another embodiment of the present invention is polyamic acid; And an imidation catalyst; after gelling the composition for forming a polyimide film at about 100° C. to about 200° C., primary imidization at about 200° C. to about 400° C. and secondary at about 300° C. to about 500° C.
  • It is a method for producing a polyimide film for a graphite sheet, comprising imidizing and forming a film to a thickness of about 100 ⁇ m to about 200 ⁇ m, and the polyimide film has a first surface damage rate represented by Equation 1 above. It relates to a method for producing a polyimide film for a graphite sheet having 0% or about 0.001% to about 0.004%.
  • Another embodiment of the present invention is a step of preparing a carbonized sheet by heat-treating the above-described polyimide film from about 15°C to about 1200°C; And graphitizing the carbonized sheet from about 1200° C. to about 2800° C. stepwise while changing the temperature increase rate to produce a graphite sheet having a thickness of about 50 ⁇ m to about 100 ⁇ m.
  • the graphite sheet relates to a method for producing a high-thickness graphite sheet having a second surface damage rate of 0% or about 0.001% to about 0.004% represented by the following Equation 2:
  • Second surface damage rate (%) ⁇ (B 1 / B 0 ) ⁇ 100 ⁇
  • Equation 2 B 0 is the area measured by photographing the graphite sheet specimen at 10 magnification (mm 2 ), and B 1 is the area of the damaged area measured by photographing the graphite sheet specimen at 10 magnification (mm 2 ).
  • the step of preparing the carbonized sheet may include thermally decomposing the polyimide film while heating at a rate of about 1°C/min to about 5°C/min.
  • the carbonized sheet is first graphitized while raising the temperature from about 1200° C. to about 2200° C., followed by secondary graphitization while increasing the temperature from about 2200° C. to about 2500° C., and then from about 2500° C. to about 2800° C. To the tertiary graphitization.
  • the temperature increase rate of the primary graphitization is from about 1.5° C./min to about 5° C./min
  • the temperature increase rate of the secondary graphitization is from about 0.4° C./min to about 1.3° C./min
  • the heating rate may be about 8.5 °C/min to about 20 °C/min.
  • the molar ratio of the amic acid group of the polyamic acid: the imidation catalyst in the composition for forming the polyimide film may be about 1:0.15 to about 1:0.20.
  • the composition for forming a polyimide film is 100 parts by weight of polyamic acid; And about 17 parts by weight to about 36 parts by weight of an imidation catalyst.
  • the composition for forming a polyimide film further comprises an inorganic filler of about 1,500 ppm to about 2,500 ppm based on 100 parts by weight of polyamic acid, and the inorganic filler is calcium carbonate, dicalcium phosphate, phosphoric acid. It may include one or more of calcium hydrogen, barium sulfate, silica, titanium oxide, alumina, silicon nitride, and boron nitride.
  • the present invention is a polyimide film that has low brittleness when applied to a graphite sheet, has excellent surface quality, and can secure a high thickness at the same time, a method for manufacturing the same, and excellent surface quality and thermal conductivity using the same, and low brittleness and high thickness. It provides a graphite sheet manufacturing method that can secure the degree.
  • Example 1 shows the results of evaluating the surface quality of Example 1 of the present invention.
  • FIG 4 is an exemplary illustration of a method of measuring an area when measuring the first surface damage rate of the present invention.
  • the polyimide film for a graphite sheet of the present invention includes polyamic acid; And an imidation catalyst; It is formed from a composition for forming a polyimide film comprising, and is a gelled and imidized product of the composition for forming a polyimide film.
  • the polyimide film for a graphite sheet of the present invention has a thickness of about 100 ⁇ m to about 200 ⁇ m (for example, about 100 ⁇ m, about 110 ⁇ m, about 120 ⁇ m, about 130 ⁇ m, about 140 ⁇ m, about 150 ⁇ m, about 160 ⁇ m ⁇ m, about 170 ⁇ m, about 180 ⁇ m, about 190 ⁇ m, or about 200 ⁇ m) is formed to have a thicker thickness than the conventional one, so that the thickness is about 50 ⁇ m to about 100 ⁇ m (for example, about 50 ⁇ m, after carbonization and graphitization).
  • a graphite sheet having a high thickness of about 60 ⁇ m, about 70 ⁇ m, about 80 ⁇ m, about 90 ⁇ m, or about 100 ⁇ m) is provided.
  • the polyimide film for a graphite sheet of the present invention has a thickness of about 50 ⁇ m to about 100 ⁇ m (e.g., about 50 ⁇ m, about 60 ⁇ m, about 70 ⁇ m, about 80 ⁇ m, about 90 ⁇ m) when applied as a graphite sheet. Or about 100 ⁇ m), and the first surface damage rate represented by the following equation 1 is 0% to about 0.004% (e.g., 0%, about 0.001%, about 0.002%, about 0.003% or about 0.004%, other For example, 0% or about 0.001% to about 0.004%) to achieve excellent surface quality.
  • the first surface damage rate represented by the following equation 1 is 0% to about 0.004% (e.g., 0%, about 0.001%, about 0.002%, about 0.003% or about 0.004%, other For example, 0% or about 0.001% to about 0.004%) to achieve excellent surface quality.
  • a 0 is a polyimide film specimen having a size of 200 mm ⁇ 25 mm from about 1°C/min to about 5°C/min (eg, about 1°C/min, about 2°C/min, about After heat treatment and carbonization from about 15° C. to about 1,200° C.
  • the first surface damage rate is a polyimide film specimen having a size of 200 mm X 25 mm and a thickness of about 100 ⁇ m to about 200 ⁇ m from about 1°C/min to about 5°C/min.
  • heat treatment from about 1,200°C to about 2,200°C at any one of about 1.5°C/min to about 5°C/min
  • secondary graphitization by heat treatment from about 2,200° C. to about 2,500° C. at a temperature rising rate of about 0.4° C./min to about 1.3° C./min, and about 8.5° C./min to about 20° C./min. It may mean the rate of surface damage occurring to the graphite sheet when the graphite sheet specimen is manufactured by third graphitization by heat treatment from about 2,500°C to about 2,800°C at one heating rate.
  • the first surface damage rate is a polyimide film specimen having a size of 200 mm ⁇ 25 mm and a thickness of 125 ⁇ m is carbonized by heat treatment from 15° C. to 1,200° C. at a heating rate of 1° C./min, Heat treatment from 1,200°C to 2,200°C at a rate of 1.5°C/min for primary graphitization, heat treatment at a rate of 0.4°C/min from 2,200°C to 2,500°C for secondary graphitization, and a temperature increase of 8.5°C/min
  • it may mean the rate of surface damage occurring to the graphite sheet.
  • a 0 is the area of the graphite sheet specimen in mm 2 measured after photographing the graphite sheet specimen at 10 magnification using a digital camera
  • a 1 is the graphite sheet specimen using a digital camera. It is the area of the damaged area in mm 2 measured after taking a picture at 10 magnification.
  • each area is measured by applying a filter with a grid drawn at intervals of 1 mm in width and 1 mm in height to a digital image photograph taken at 10 magnification and visually checking the number of squares (mm 2 ) included in the area. It can be done by counting and measuring.
  • FIG. 4 illustrates a method of measuring an area when measuring the first surface damage rate represented by Equation 1.
  • a digital image photograph taken at 10 magnification was prepared for the graphite sheet prepared as in (a), and 1 mm in width and 1 mm in length. Apply a filter with a grid drawn at intervals of. At this time, the area of one space formed by the grid is 1 mm 2 .
  • a 0 is measured by counting the case where the graphite sheet occupies 50% or more of the area of one space formed by the grid as in (b). Since A 0 measured in FIG. 4B is a total of 200, it can be measured as 200 mm 2 .
  • a 1 is measured by counting the cases where the visually visible damage occupies 50% or more of the portion occupied by the graphite sheet in the area of one space formed by the grid as in (c). Since A 1 measured in FIG. 4C is 159 in total, it may be measured as 159 mm 2 . Substituting the A 0 value and A 1 in this example for the surface damage rate of Equation 1, the damage rate in the exemplary 20 mm x 10 mm sized graphite specimen of FIG. 4 is 79.5%.
  • the polyimide film of the present invention is applied to a graphite sheet. It has low brittleness, has excellent surface quality, and can secure a high thickness at the same time.
  • composition for forming a polyimide film includes a polyamic acid and an imidization catalyst as follows.
  • polyamic acid serves as a precursor to be converted to polyimide by an imidization catalyst.
  • the polyamic acid is not particularly limited as long as it is obtained by polymerizing a dianhydride monomer and a diamine monomer.
  • diamines that can be used as a raw material for the polyamic acid are 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 3,3'-dichlorobenzidine, 4 ,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether (4,4'-oxy Cydianiline), 3,3'-diaminodiphenyl ether (3,3'-oxydianiline), 3,4'-diaminodiphenyl ether (3,4'-oxydianiline), 1,5- Diaminonaphthalene, 4,4'-diaminodiphenyl diethyl silane, 4,4'-diaminodiphenyl silane, 4,4'-diamin
  • the dianhydride monomer and diamine monomer that can be used as raw materials for the polyamic acid are about 1:0.9 to about 1:1.1 (e.g., about 1:0.9, about 1:1, or about 1:1.1 ) Can be used in the polymerization of polyamic acid.
  • a polyamic acid having excellent imidization efficiency and improved uniformity.
  • the weight average molecular weight of the polyamic acid is not particularly limited, but about 150,000 g/mole or more to about 1,000,000 g/mole or less (e.g., about 150,000 g/mole, about 200,000 g/mole, about 250,000 g/mole, about 300,000 g/mole, about 350,000 g/mole, about 400,000 g/mole, about 450,000 g/mole, about 500,000 g/mole, about 550,000 g/mole, about 600,000 g/mole, about 650,000 g/mole, about 700,000 g /mole, about 750,000 g/mole, about 800,000 g/mole, about 850,000 g/mole, about 900,000 g/mole, about 950,000 g/mole or about 1,000,000 g/mole), specifically about 170,000 g/mole or more to about It may be 700,000 g/mole or less, more specifically about 190,000 g/mole
  • the viscosity of the polyamic acid is not particularly limited, but about 90,000 cP or more and about 500,000 cP or less (e.g., about 90,000 cP, about 100,000 cP, about 110,000 cP, about 120,000 cP, about 130,000 cP, about 140,000 cP, about 150,000 cP, about 160,000 cP, about 170,000 cP, about 180,000 cP, about 190,000 cP, about 200,000 cP, about 210,000 cP, about 220,000 cP, about 230,000 cP, about 240,000 cP, about 250,000 cP, about 260,000 cP, about 270,000 cP , About 280,000 cP, about 290,000 cP, about 300,000 cP, about 310,000 cP, about 320,000 cP, about 330,000 cP, about 340,000 cP, about 350,000 cP, about 360,000 cP, about 370,000 cP, about 380,000
  • the polyamic acid may be dissolved in an organic solvent and used as a polyamic acid solution.
  • the polyamic acid solution can further improve processability and ease of operation when manufacturing a polyimide film.
  • the organic solvent is not particularly limited as long as it is a solvent in which polyamic acid can be dissolved, but may be specifically an aprotic polar solvent.
  • the aprotic polar solvent is an amide solvent such as N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), p-chlorophenol, o-chlorophenol Phenolic solvents such as N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), and Diglyme.
  • amide solvent such as N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), p-chlorophenol, o-chlorophenol Phenolic solvents such as N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), and Diglyme.
  • the organic solvent may further use an auxiliary solvent as necessary to adjust the solubility of the polyamic acid.
  • the auxiliary solvent may be, for example, toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, water, and the like.
  • the polyamic acid solution contains about 15% by weight to about 20% by weight (e.g., about 15% by weight, about 16% by weight, About 17% by weight, about 18% by weight, about 19% by weight, or about 20% by weight), and about 80% by weight to about 85% by weight of an organic solvent (e.g., about 80% by weight, about 81% by weight) Weight percent, about 82 weight percent, about 83 weight percent, about 84 weight percent, or about 85 weight percent).
  • it is advantageous to control the weight average molecular weight and viscosity of the total polyamic acid solution and may be more advantageous in the film formation process.
  • the imidation catalyst serves to promote the conversion of polyamic acid to polyimide.
  • the imidation catalyst may be an imine-based component such as an aliphatic tertiary amine, an aromatic tertiary amine, and a heterocyclic tertiary amine.
  • a heterocyclic tertiary amine may be preferable from the viewpoint of reactivity as a catalyst.
  • Non-limiting examples of the heterocyclic tertiary amine include quinoline, isoquinoline, ⁇ -picoline (BP), pyridine, and the like, and these may be used alone or in combination of two or more.
  • the content of the imidation catalyst in the precursor composition for a polyimide film is about 0.15 mol to about 0.2 mol, for example about 0.15 mol, about 0.16 mol, based on 1 mol of the amic acid functional group of the polyamic acid. About 0.17 moles, about 0.18 moles, about 0.19 moles, or about 0.20 moles.
  • the imidation catalyst can further improve crystallinity while allowing the matrix structure of the polyimide film of the present invention to be arranged more regularly than before.
  • the content of the imidation catalyst in the precursor composition for the polyimide film is from about 17 parts by weight to about 36 parts by weight based on 100 parts by weight of the amic acid of the polyamic acid (for example, about 17 parts by weight, About 18 parts by weight, about 19 parts by weight, about 20 parts by weight, about 21 parts by weight, about 22 parts by weight, about 23 parts by weight, about 24 parts by weight, about 25 parts by weight, about 26 parts by weight, about 27 parts by weight, About 28 parts by weight, about 29 parts by weight, about 30 parts by weight, about 31 parts by weight, about 32 parts by weight, about 33 parts by weight, about 34 parts by weight, about 35 parts by weight, or about 36 parts by weight).
  • the imidation catalyst can further improve crystallinity while allowing the matrix structure of the polyimide film of the present invention to be arranged more regularly than before.
  • the composition for forming a polyimide film may further include an inorganic filler.
  • the inorganic filler may be present in a dispersed state in a matrix in the polyimide film, and then sublimated during carbonization and/or graphitization to induce a predetermined foaming phenomenon.
  • the polyimide film may form a polyimide spacing with high regularity due to a structure in which inorganic fillers are uniformly dispersed in the polyimide matrix.
  • the predetermined voids formed by such foaming can improve the bending resistance of the graphite sheet, and the inorganic filler is sublimated during carbonization and/or graphitization, and the polyimide is converted into graphite, so that the graphite sheet has excellent regularity and alignment. Can be manufactured.
  • the inorganic filler is sublimated, it can itself serve as a passage for gas discharge, thereby preventing surface defects and damage due to foaming.
  • the inorganic filler is not particularly limited as long as it has sublimability at a temperature of about 1000°C or higher, but specifically, among calcium carbonate, dicalcium phosphate, calcium hydrogen phosphate, barium sulfate, silica, titanium oxide, alumina, silicon nitride, and boron nitride. It may contain one or more.
  • the polyimide film can obtain a graphite sheet having further improved bending resistance and structural uniformity.
  • the inorganic filler of the above example may be used alone or in combination of two or more.
  • the content of the inorganic filler in the precursor composition for a polyimide film is about 1,500 ppm to about 2,500 ppm (e.g., about 1,500 ppm, about 1,600 ppm, about 1,700 ppm, about 1,800 ppm, about 100 parts by weight of polyamic acid). 1,900 ppm, about 2,000 ppm, about 2,100 ppm, about 2,200 ppm, about 2,300 ppm, about 2,400 ppm, or about 2,500 ppm).
  • sublimation gas generated inside the film is smoothly discharged to the outside of the film, further improving the surface quality, and converting the polyimide structure to an artificial graphite structure. It can further improve the efficiency.
  • the average particle diameter of the inorganic filler is not particularly limited, but about 1.5 ⁇ m to about 4.5 ⁇ m (eg, about 1.5 ⁇ m, about 2 ⁇ m, about 2.5 ⁇ m, about 3 ⁇ m, about 3.5 ⁇ m, about 4 ⁇ m, or about 4.5 ⁇ m).
  • the inorganic filler may further reduce the formation of bright spots due to excessive foaming, while preventing the polyimide film surface from being excessively low in roughness, thereby further improving the surface quality.
  • composition for forming a polyimide film may further include additives including a dehydrating agent, in addition to the above-described components.
  • the dehydrating agent promotes a ring closure reaction through a dehydration action on polyamic acid, specifically aliphatic acid anhydride, aromatic acid anhydride, N,N'-dialkylcarbodiimide, halogenated lower aliphatic, halogenated lower fatty acid anhydride, arylphos It may be a fondane dihalide, a thionyl halide, or a mixture of two or more of these.
  • the addition amount of the dehydrating agent in the composition for forming a polyimide film is about 0.5 mol to about 5 mol (e.g., about 0.5 mol, about 1 mol, about 1.5 mol, about 2 mol, about 1 mol of the amic acid group in the polyamic acid). 2.5 moles, about 3 moles, about 3.5 moles, about 4 moles, about 4.5 moles or about 5 moles).
  • the composition for forming a polyimide film may further improve imidization efficiency due to dehydration.
  • a composition for forming a polyimide film comprising a polyimide film of about 100 °C to about 200 °C (for example, about 100 °C, about 110 °C, about 120 °C, about 130 °C, about 140 °C, about 150 °C, about 160 °C, After gelation at about 170°C, about 180°C, about 190°C, or about 200°C), about 200°C to about 400°C (eg, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C , At about 370°C, about 380°C, about 390°C or about 400
  • the polyimide film prepared by the method for producing a polyimide film for a graphite sheet has a surface damage rate of 0% to about 0.004% (e.g., 0%, about 0.001%, about 0.002) represented by the above formula 1 %, about 0.003% or about 0.004%, for example 0% or about 0.001% to about 0.004%).
  • the description of Equation 1 is as described above.
  • composition for forming the polyimide film and the respective components contained therein specific examples, and descriptions of the content are as described above.
  • the molar ratio of the amic acid group of the polyamic acid: the imidization catalyst in the composition for forming the polyimide film is about 1:0.15 to about 1:0.20 (eg, about 1:0.15, about 1:0.16, about 1: 0.17, about 1:0.18, about 1:0.19 or about 1:0.20).
  • the composition for forming a polyimide film is 100 parts by weight of polyamic acid; And about 17 parts by weight to about 36 parts by weight of the imidation catalyst (e.g., about 17 parts by weight, about 18 parts by weight, about 19 parts by weight, about 20 parts by weight, about 21 parts by weight, about 22 parts by weight, about 23 parts by weight) Parts by weight, about 24 parts by weight, about 25 parts by weight, about 26 parts by weight, about 27 parts by weight, about 28 parts by weight, about 29 parts by weight, about 30 parts by weight, about 31 parts by weight, about 32 parts by weight, about 33 Parts by weight, about 34 parts by weight, about 35 parts by weight, or about 36 parts by weight); may be included.
  • the imidation catalyst e.g., about 17 parts by weight, about 18 parts by weight, about 19 parts by weight, about 20 parts by weight, about 21 parts by weight, about 22 parts by weight, about 23 parts by weight
  • Parts by weight e.g., about 24 parts by weight, about 25 parts by weight
  • the composition for forming a polyimide film is about 1,500 ppm to about 2,500 ppm (e.g., about 1,500 ppm, about 1,600 ppm, about 1,700 ppm, about 1,800 ppm, about 1,900 ppm, based on 100 parts by weight of polyamic acid, About 2,000 ppm, about 2,100 ppm, about 2,200 ppm, about 2,300 ppm, about 2,400 ppm or about 2,500 ppm) of an inorganic filler, wherein the inorganic filler is calcium carbonate, dicalcium phosphate, calcium hydrogen phosphate, It may contain at least one of barium sulfate, silica, titanium oxide, alumina, silicon nitride, and boron nitride.
  • inorganic filler is calcium carbonate, dicalcium phosphate, calcium hydrogen phosphate, It may contain at least one of barium sulfate, silica, titanium oxide, alumina, silicon nitrid
  • a step of preparing a polyamic acid may be additionally performed prior to gelling the composition for forming a polyimide film.
  • the step of preparing such a polyamic acid is not particularly limited, and an appropriate method may be employed among methods such as emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization.
  • the composition for forming a polyimide film may be prepared as a solution, applied to a support, and dried to form a sheet-shaped gel.
  • the support may be a glass plate, an aluminum foil, an endless stainless belt, or a stainless drum, but is not limited thereto.
  • the application method is not particularly limited, and may be, for example, a casting method.
  • the sheet-shaped gel may be dried and gelled for about 10 minutes to about 20 minutes in the range of the gelling temperature to be prepared as a sheet-shaped gel having self-support.
  • the sheet-shaped gel prepared in the sheet shape is then peeled off from the support and then from about 200°C to about 400°C (eg, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C , About 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about Primary imidization at 370°C, about 380°C, about 390°C or about 400°C and about 300°C to about 500°C (e.g., about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, about 400°C, about 410°C, about 420°C, about 430°
  • amic acid remaining without reaction may be additionally imidized, and the quality of the polyimide film may be further uniformly improved.
  • the efficiency of converting the polyamic acid to polyimide may be further improved.
  • the polyimide film filmed as described above has a thickness of about 100 ⁇ m to about 200 ⁇ m (for example, about 100 ⁇ m, about 110 ⁇ m, about 120 ⁇ m, about 130 ⁇ m, about 140 ⁇ m, about 150 ⁇ m, about 160 ⁇ m, about 170 ⁇ m, about 180 ⁇ m, about 190 ⁇ m or about 200 ⁇ m).
  • the thickness of the polyimide film is less than about 100 ⁇ m, it is difficult to apply it as a high-thick graphite sheet.
  • the thickness of the polyimide film exceeds about 200 ⁇ m, brittleness is excessively high.
  • Another embodiment of the present invention relates to a method of manufacturing a high-thickness graphite sheet having a second surface damage rate of 0% or about 0.001% to about 0.004% represented by Equation 2 below.
  • the second surface damage rate may be 0%, about 0.001%, about 0.002%, about 0.003%, or about 0.004%.
  • it may be 0% or from about 0.001% to about 0.004%.
  • the high-thickness graphite sheet manufacturing method includes the steps of preparing a carbonized sheet by heat-treating a polyimide film from 15°C to 1200°C; And graphitizing the carbonized sheet from about 1200° C. to about 2800° C. stepwise while changing a temperature increase rate to produce a graphite sheet having a thickness of about 50 ⁇ m to about 100 ⁇ m. Includes.
  • Second surface damage rate (%) ⁇ (B 1 / B 0 ) ⁇ 100 ⁇
  • Equation 2 B 0 is the area measured by photographing the graphite sheet specimen at 10 magnification (mm 2 ), and B 1 is the area of the damaged area measured by photographing the graphite sheet specimen at 10 magnification (mm 2 ).
  • a specific method of measuring the second surface damage rate (%) is the same as the method of measuring the first surface damage rate represented by Equation 1 above.
  • the polyimide film is the polyimide film described above, and includes polyamic acid; And an imidation catalyst; formed from a composition for forming a polyimide film, having a thickness of about 100 ⁇ m to about 200 ⁇ m, and a first surface damage rate represented by Formula 1 described in the description of the polyimide film is 0 % Or from about 0.001% to about 0.004%.
  • the polyimide film in the method for producing a high-thickness graphite sheet of the present invention is the same as the polyimide film of the present invention, and is also manufactured by the polyimide film of the present invention, so a description thereof will be omitted.
  • the step of preparing the carbonized sheet includes the above-described polyimide film of the present invention from about 15°C to about 1200°C, specifically from about 20°C to about 1200°C, more Specifically, it is carbonized by heat treatment at elevated temperature from about 50°C to about 1200°C. Within the above temperature range, the polymer chains of the polyimide film are sufficiently thermally decomposed to produce a carbonized sheet having an amorphous carbon body formed therethrough, and thus can be used for graphitization for the production of a graphite sheet.
  • the carbonization method after putting the polyimide film into a high-temperature furnace facility such as an electric furnace, heating the polyimide film in a nitrogen/argon atmosphere from about 15°C to the maximum temperature of about 1200°C over about 12 hours to about 14 hours. It may be thermally decomposed while converting the polyimide film into a carbonized sheet.
  • a high-temperature furnace facility such as an electric furnace
  • the temperature increase rate during carbonization is about 1°C/min to about 5°C/min (eg, about 1°C/min, about 2°C/min, about 3°C/min, about 4°C/min or about 5°C/min).
  • the polymer chains of the polyimide film are sufficiently thermally decomposed, thereby producing a carbonized sheet in which an amorphous carbon body is formed, and thus can be used for graphitization for producing a graphite sheet.
  • the step of producing a graphite sheet comprises graphitizing the carbonized sheet obtained in the above and the carbonization step in a temperature range of about 1200°C to about 2800°C while changing the temperature increase rate step by step. Is prepared from about 50 ⁇ m to about 100 ⁇ m of graphite sheet. Through such a graphitization process, a graphite sheet formed by rearranging carbon in an amorphous carbon body in a carbonized sheet is prepared.
  • the graphitization method is not particularly limited, but after putting the carbonized sheet into a high-temperature furnace facility such as an electric furnace, in a mixed gas atmosphere containing nitrogen, argon, and a small amount of helium, about 1200° C. to about 2800° C. It can be prepared by raising and maintaining the temperature step by step over 10 hours to about 14 hours.
  • the carbonized sheet is primary graphitized while raising the temperature from about 1200°C to about 2200°C, and then secondary graphitized while raising the temperature from about 2200°C to about 2500°C, Then tertiary graphitization from about 2500° C. to about 2800° C. may be included.
  • the carbon rearrangement efficiency of the amorphous carbon body in the carbonized sheet is further improved, the brittleness is low even in the high thickness range, and the surface quality may be excellent.
  • the heating rate of the primary graphitization is about 1.5°C/min to about 5°C/min (eg, about 1.5°C/min, about 2°C/min, about 2.5°C/min, about 3°C /min, about 3.5°C/min, about 4°C/min, about 4.5°C/min, or about 5°C/min), and the heating rate of the secondary graphitization is about 0.4°C/min to about 1.3°C/min ( For example, about 0.4°C/min, about 0.5°C/min, about 0.6°C/min, about 0.7°C/min, about 0.8°C/min, about 0.9°C/min, about 1°C/min, about 1.1°C/ min, about 1.2°C/min or about 1.3°C/min), and the rate of temperature increase of the tertiary graphitization is about 8.5°C/min to about 20°C/min (eg, about 8.5°C/min, about 9°C /min, about 9.5°C
  • the gas generated during the production of the graphite sheet proceeds stably, further preventing surface damage,
  • the surface damage rates of the above equations 1 and 2 can be further reduced closer to 0%.
  • the high-thickness graphite sheet manufacturing method includes, after performing the step of manufacturing the graphite sheet, the graphitized graphite sheet from about 5°C/min to about 10°C/min (eg, about 5°C/min, about 6°C/min). a cooling step of cooling at a rate of min, about 7°C/min, about 8°C/min, about 9°C/min or about 10°C/min); It may additionally include. In such a case, the brittleness of the graphite sheet is further lowered, and the surface quality may be further improved.
  • Another embodiment of the present invention relates to a high-thickness graphite sheet manufactured by the above-described high-thickness graphite sheet manufacturing method.
  • the thick graphite sheet has a thickness of about 50 ⁇ m to about 100 ⁇ m. In this case, it has excellent heat capacity and is more advantageous for use as a heat dissipation means applied to an electronic device.
  • the high-thickness graphite sheet is formed from a polyimide film having a thickness of about 100 ⁇ m to about 200 ⁇ m.
  • the high-thickness graphite sheet may be a carbonized and graphitized sheet of a polyimide film having a thickness of about 100 ⁇ m to about 200 ⁇ m.
  • the high-thickness graphite sheet has a thickness of about 50 ⁇ m to about 100 ⁇ m, has excellent heat capacity, and is more advantageous for use as a heat dissipation means applied to electronic devices.
  • the high-thickness graphite sheet implements excellent surface quality as the second surface damage rate represented by Equation 2 is 0% or from about 0.001% to about 0.004%. In this case, it has more advantageous properties to be used as a heat dissipation means applied to an electronic device.
  • the high-thickness graphite sheet may have a thermal conductivity of about 800 W/m ⁇ K or more in a planar direction, specifically about 800 W/m ⁇ K to about 1200 W/m ⁇ K. In this case, it has more advantageous properties to be used as a heat dissipation means applied to an electronic device.
  • Oxydianiline ODA, 3,3'-oxydianiline or 4,4'-oxydianiline
  • dianhydride monomer as diamine monomer in dimethylformamide (DMF) as an organic solvent in a nitrogen atmosphere in a 0.5 L reactor
  • PMDA pyromellitic dianhydride
  • beta-picoline as an imidation catalyst was added in an amount of 0.17 molar to 1 mol of amic acid group, and then uniformly mixed and degassed to prepare a composition for forming a polyimide film.
  • composition for forming a polyimide film was cast on a SUS plate (100SA, Sandvik) as a support at 500 ⁇ m using a doctor blade, and dried in a hot air method at a temperature ranging from 100°C to 200°C to prepare a sheet-shaped gel. .
  • the sheet-shaped gel is peeled off the SUS plate, fixed to the pin frame, transferred to a high-temperature tenter, and subjected to primary imidization for 10 minutes at a temperature of 200°C to 400°C in a high-temperature tenter, and then 300°C to 500°C.
  • First imidization was performed for 10 minutes at a temperature of °C.
  • the polyimide films filmed by the primary and secondary imidization were cooled at 25° C. and separated from the pin frame to obtain a polyimide film having a size of 20 cm x 2.5 cm and a thickness of 125 ⁇ m.
  • the polyimide film prepared in Example 1 was subjected to carbonization heat treatment from 50° C. to 1200° C. at a heating rate of 1° C./min to prepare a carbonized sheet.
  • graphitization heat treatment was performed in which the carbonized sheet was calcined while changing the heating rate in steps of 1 to 3 steps in a temperature range of 1200° C. to 2800° C. to prepare a graphite sheet having a final thickness of 50 ⁇ m.
  • the first graphitization was heated from 1200°C to 2200°C at a rate of 1.5°C/min
  • the secondary graphitization was heated from 2200°C to 2500°C at a rate of 0.4°C/min
  • the third graphitization was 2500°C.
  • the temperature was raised from °C to 2800 °C at a rate of 8.5 °C/min.
  • a graphite sheet having a final thickness of 50 ⁇ m was prepared in the same manner as in Example 4, except that the polyimide film was changed to the polyimide film prepared in Example 2.
  • a graphite sheet having a final thickness of 50 ⁇ m was prepared in the same manner as in Example 4, except that the polyimide film was changed to the polyimide film prepared in Example 3.
  • beta-picoline as an imidation catalyst was added in an amount of 0.17 molar to 1 mol of amic acid group, and then uniformly mixed and degassed to prepare a composition for forming a polyimide film.
  • composition for forming a polyimide film was cast on a SUS plate (100SA, Sandvik) as a support at 500 ⁇ m using a doctor blade, and dried in a hot air method at a temperature ranging from 100°C to 200°C to prepare a sheet-shaped gel. .
  • the sheet-shaped gel is peeled off the SUS plate, fixed to the pin frame, transferred to a high-temperature tenter, and subjected to primary imidization for 10 minutes at a temperature of 200°C to 400°C in a high-temperature tenter, and then 300°C to 500°C.
  • First imidization was performed for 10 minutes at a temperature of °C.
  • the polyimide films filmed by the first and second imidizations were cooled at 25° C. and separated from the pin frame to obtain a polyimide film having a size of 20 cm x 25 cm and a thickness of 125 ⁇ m.
  • beta-picoline as an imidation catalyst was added in an amount of 0.17 molar to 1 mol of amic acid group, and then uniformly mixed and degassed to prepare a composition for forming a polyimide film.
  • composition for forming a polyimide film was cast on a SUS plate (100SA, Sandvik) as a support at 500 ⁇ m using a doctor blade, and dried in a hot air method at a temperature ranging from 100°C to 200°C to prepare a sheet-shaped gel. .
  • the sheet-shaped gel is peeled off the SUS plate, fixed to the pin frame, transferred to a high-temperature tenter, and subjected to primary imidization for 10 minutes at a temperature of 200°C to 400°C in a high-temperature tenter, and then 300°C to 500°C.
  • First imidization was performed for 10 minutes at a temperature of °C.
  • the polyimide films filmed by the first and second imidizations were cooled at 25° C. and separated from the pin frame to obtain a polyimide film having a size of 20 cm x 25 cm and a thickness of 125 ⁇ m.
  • the polyimide film prepared in Comparative Example 1 was subjected to carbonization heat treatment from 50° C. to 1200° C. at a heating rate of 1° C./min to prepare a carbonized sheet.
  • graphitization heat treatment was performed in which the carbonized sheet was calcined while changing the heating rate in steps of 1 to 3 steps in a temperature range of 1200° C. to 2800° C. to prepare a graphite sheet having a final thickness of 50 ⁇ m.
  • the first graphitization was heated from 1200°C to 2200°C at a rate of 1.5°C/min
  • the secondary graphitization was heated from 2200°C to 2500°C at a rate of 0.4°C/min
  • the third graphitization was 2500°C.
  • the temperature was raised from °C to 2800 °C at a rate of 8.5 °C/min.
  • a graphite sheet having a final thickness of 50 ⁇ m was prepared in the same manner as in Example 6, except that the polyimide film of Comparative Example 5 was changed to the polyimide film of Comparative Example 2.
  • a graphite sheet having a final thickness of 50 ⁇ m was prepared in the same manner as in Example 6, except that the polyimide film of Comparative Example 5 was changed to the polyimide film of Comparative Example 3.
  • a graphite sheet having a final thickness of 50 ⁇ m was prepared in the same manner as in Example 6, except that the polyimide film of Comparative Example 5 was changed to the polyimide film of Comparative Example 4.
  • the surface quality of the high-thickness graphite sheets prepared in Examples 4 to 6 and Comparative Examples 5 to 8 was evaluated visually. Specifically, in the evaluation of the surface quality, the surface of each high-thickness graphite sheet was observed through the naked eye for cracks or cracks.
  • Second surface damage rate (%) ⁇ (B 1 / B 0 ) ⁇ 100 ⁇
  • Equation 2 B 0 is the area measured by photographing the graphite sheet specimen at 10 magnification (mm 2 ), and B 1 is the area of the damaged area measured by photographing the graphite sheet specimen at 10 magnification (mm 2 ).
  • the thermal diffusivity of the graphite sheet specimens of Examples and Comparative Examples in the plane direction was measured by a laser flash method using a thermal diffusivity measuring equipment (model name LFA 467, Netsch), and the density (weight/volume) in the thermal diffusivity measured value And specific heat (a measure of specific heat using DSC) to calculate thermal conductivity.
  • specific heat a measure of specific heat using DSC
  • the number of bright spots generated is a factor causing surface defects of the graphite sheet, and the number of protrusions having a size of 0.05 mm or more in the 50 mm X 50 mm square of the sheet was measured.
  • the (1) surface quality evaluation cracks or cracks occurred, or a specimen that was not graphitized could not be measured. The results are shown in Table 3 below.

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Abstract

La présente invention concerne un film de polyamide pour une feuille de graphite et un procédé de fabrication associé. Dans un mode de réalisation, le film de polyimide pour une feuille de graphite est formé à partir d'une composition pour former un film de polyimide, la composition comprenant : un acide polyamique ; et un catalyseur d'imidisation, le film de polyimide ayant une épaisseur d'environ 100 µm à environ 200 µm et un premier taux d'endommagement de surface, exprimé par l'équation 1, de 0 % ou d'environ 0,001 % à environ 0,004 %. (L'équation 1 est telle que définie dans la description.)
PCT/KR2019/014620 2019-06-28 2019-10-31 Film de polyimide pour feuille de graphite, et procédé de fabrication associé WO2020262765A1 (fr)

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