TWI747563B - 用於石墨片之聚醯亞胺膜及由此製成之石墨片 - Google Patents

用於石墨片之聚醯亞胺膜及由此製成之石墨片 Download PDF

Info

Publication number
TWI747563B
TWI747563B TW109136247A TW109136247A TWI747563B TW I747563 B TWI747563 B TW I747563B TW 109136247 A TW109136247 A TW 109136247A TW 109136247 A TW109136247 A TW 109136247A TW I747563 B TWI747563 B TW I747563B
Authority
TW
Taiwan
Prior art keywords
polyimide film
graphite sheet
mol
precursor composition
dianhydride
Prior art date
Application number
TW109136247A
Other languages
English (en)
Other versions
TW202122465A (zh
Inventor
孫元鎬
趙亨燮
Original Assignee
南韓商Ｐｉ尖端素材股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南韓商Ｐｉ尖端素材股份有限公司 filed Critical 南韓商Ｐｉ尖端素材股份有限公司
Publication of TW202122465A publication Critical patent/TW202122465A/zh
Application granted granted Critical
Publication of TWI747563B publication Critical patent/TWI747563B/zh

Links

Classifications

    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • 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
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6267—Pyrolysis, carbonisation or auto-combustion reactions
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C04B2235/3212—Calcium phosphates, e.g. hydroxyapatite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/608—Green bodies or pre-forms with well-defined density
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/95—Products characterised by their size, e.g. microceramics
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • 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
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

本文揭露了用於石墨片的聚醯亞胺膜和使用前述聚醯亞胺膜製造的石墨片。聚醯亞胺膜是藉由將前驅組合物醯亞胺化來製備，前述前驅組合物包含：藉由使二酐單體與二胺單體反應來製備的聚醯胺酸；以及有機溶劑，其中基於二胺單體的總莫耳數，二胺單體包含約30 mol%至約70 mol%的4,4’-亞甲基二苯胺和約30 mol%至約70 mol%的4,4’-氧二苯胺，基於二胺單體的總莫耳數，4,4’-亞甲基二苯胺和4,4’-氧二苯胺以約85 mol%或更多的總量存在。

Description

用於石墨片之聚醯亞胺膜及由此製成之石墨片
本申請主張於2019年10月28日在韓國知識產權局提交的韓國專利申請號10-2019-0134830的權益，其全部揭露內容透過引用合併於本文。
本發明係有關於用於石墨片的聚醯亞胺膜及使用其製造的石墨片，且特別有關於具有良好導熱性且可以低成本製造之用於石墨片的聚醯亞胺膜及使用其製造的石墨片。
最近，隨著重量、尺寸和厚度的減少以及積體度(integration degree)的改善，電子裝置受到產熱量增加的困擾。電子裝置中產生的熱量可導致電子裝置失靈、故障和壽命縮短。因此，電子裝置的熱管理正成為重要的議題。
石墨片具有比例如銅或鋁的金屬片更高的導熱率，且作為用於電子裝置的散熱構件而引起關注。可藉由各種方法，例如聚合物膜的碳化和石墨化，來製造這種石墨片。特別是，聚醯亞胺膜由於其良好的機械和熱尺寸穩定性及化學穩定性而被看好作為石墨片的聚合物膜。
已知使用聚醯亞胺膜製造的石墨片的特性取決於聚醯亞胺膜的特性。儘管已開發出各種用於石墨片的聚醯亞胺膜，但仍然需要適合製造導熱率進一步增加的石墨片的聚醯亞胺膜。
本發明的一目的是提供一種具有良好導熱率之用於石墨片的聚醯亞胺膜。
本發明的另一目的是提供一種可以低成本製造之用於石墨片的聚醯亞胺膜。
本發明的又一目的是提供一種使用上述之用於石墨片的聚醯亞胺膜來製造的石墨片。
1.根據本發明的一面向，用於石墨片的聚醯亞胺膜是藉由將前驅組合物醯亞胺化來製備，前述前驅組合物包含：藉由使二酐單體與二胺單體反應來製備的聚醯胺酸；以及有機溶劑，其中基於二胺單體的總莫耳數，二胺單體包含約30mol%至約70mol%的4,4’-亞甲基二苯胺(4,4’-methylenedianiline)和約30mol%至約70mol%的4,4’-氧二苯胺(4,4’-oxydianiline)，基於二胺單體的總莫耳數，4,4’-亞甲基二苯胺和4,4’-氧二苯胺以約85mol%或更多的總量存在。
2.在實施例1中，二酐單體可包含選自均苯四甲酸二酐(pyromellitic dianhydride)、3,3’,4,4’-聯苯四羧酸二酐(3,3’,4,4’-biphenyltetracarboxylic dianhydride)、2,3,3’,4-聯苯四羧酸二酐(2,3,3’,4-biphenyltetracarboxylic dianhydride)、氧雙鄰苯二甲酸酐(oxydiphthalic anhydride)、3,3’,4,4’-二苯基碸四羧酸二酐(3,3’,4,4’-diphenylsulfonetetracarboxylic dianhydride)以及3,3’,4,4’-二苯 甲酮四羧酸二酐(3,3’,4,4’-benzophenonetetracarboxylic dianhydride)的群組中的至少其一。
3.在實施例1或2中，基於前驅組合物的總重量，聚醯胺酸可以約10wt%至約30wt%的量存在。
4.在實施例1至3中之任一者，前驅組合物在23℃的溫度和1sec-1的剪切速率下可具有約100,000cP至約300,000cP的黏度。
5.在實施例1至4中之任一者，前驅組合物可更包含可昇華的(sublimable)無機填料，前述可昇華的無機填料包含選自碳酸鈣(calcium carbonate)和磷酸二鈣(dicalcium phosphate)的群組中的至少其一。
6.在實施例5中，相對於100重量份的聚醯胺酸，可昇華的無機填料可以約0.2重量份至約0.5重量份的量存在。
7.根據本發明的另一面向，使用如實施例1至6中任一者所述之聚醯亞胺膜來製造石墨片。
8.在實施例7中，石墨片可具有約10μm至約250μm的厚度。
9.在實施例7或8中，石墨片可具有約1.8g/cm3至約3.0g/cm3的密度。
10.在實施例7至9的任一者中，石墨片可具有約795mm2/s或更大的熱擴散系數。
本發明提供具有良好導熱率且可以低成本製造之用於石墨片的聚醯亞胺膜，以及使用其來製造的石墨片。
將省略可能會不必要地把本發明的主題模糊之已知功能和構造的描述。
更將理解的是，當在本說明書中使用術語「包括(comprises)」、「包括(comprising)」、「包含(includes)」和/或「包含(including)」時，其是指存在所述特徵、整數、步驟、操作、元件、組件和/或其群組，但不排除存在或增加一或多個其他特徵、整數、步驟、操作、元件、組件和/或其群組。除非上下文另外明確指出，否則如本文所使用地，單數形式的「一」、「一個」和「此」也意圖包含複數形式。
再者，除非另有明確說明，否則與特定組件有關的數值在組件解釋中應視為包含公差範圍。
如本文中用來表示特定數值範圍，「a至b」的表達意味著「
Figure 109136247-A0305-02-0006-2
a且
Figure 109136247-A0305-02-0006-4
b」。
用於石墨片的聚醯亞胺膜
用於石墨片的聚醯亞胺膜可藉由將前驅組合物醯亞胺化來製備，前述前驅組合物包含：藉由使二酐單體與二胺單體反應來製備的聚醯胺酸；以及有機溶劑。常規地，由於其具有例如高反應性、在有機溶劑中的良好溶解性和低價的優點，4,4’-氧二苯胺已作為製造用於石墨片的聚醯亞胺膜的二胺單體。本發明的發明人基於以下確認而開發出了本發明：當使用由二胺單體形成的聚醯亞胺膜來製造石墨片，而前述二胺單體基於二胺單體的總莫耳數包含約 30mol%至約70mol%(例如約30mol%、約35mol%、約40mol%、約45mol%、約50mol%、約55mol%、約60mol%、約65mol%或約70mol%)的4,4’-亞甲基二苯胺、和約30mol%至約70mol%(例如約30mol%、約35mol%、約40mol%、約45mol%、約50mol%、約55mol%、約60mol%、約65mol%、約70mol%)的4,4’-氧二苯胺，其中基於二胺單體的總莫耳數，4,4’-亞甲基二苯胺和4,4’-氧二苯胺以約85mol%更多(例如約85mol%、約90mol%、約95mol%或約100mol%)的總量存在時，石墨片的導熱性進一步增加，而沒有失去4,4’-氧二苯胺所提供的好處。再者，與單獨使用4,4’-氧二苯胺相比，由於4,4’-亞甲基二苯胺可以比4,4’-氧二苯胺更低的價格取得，所以4,4’-亞甲基二苯胺和4,4’-氧二苯胺一起作為二胺單體可減少製造成本。
在一實施例中，基於二胺單體的總莫耳數，二胺單體可包含約50mol%至約70mol%的4,4’-亞甲基二苯胺和約30mol%至約50mol%的4,4’-氧二苯胺。在另一實施例中，基於二胺單體的總莫耳數，二胺單體可包含約60mol%至約70mol%的4,4’-亞甲基二苯胺和約30mol%至約40mol%的4,4’-氧二苯胺。在又一實施例中，基於二胺單體的總莫耳數，二胺單體可包含約65mol%至約70mol%的4,4’-亞甲基二苯胺和約35mol%至約40mol%的4,4’-氧二苯胺。然而，將理解的是，本發明不限於此。
在一實施例中，基於二胺單體的總莫耳數，4,4’-亞甲基二苯胺和4,4’-氧二苯胺可以約90mol%至約100mol%的總量存在。在另一實施例中，基於二胺單體的總莫耳數，4,4’-亞甲基二苯胺和4,4’-氧二苯胺可以約95mol%至約100mol%的總量存在。在又一實施例中，基於二胺單體的總莫耳數，4,4’-亞甲基二 苯胺和4,4’-氧二苯胺可以約100mol%的總量存在。然而，將理解的是，本發明不限於此。
在一實施例中，可進一步將除了4,4’-亞甲基二苯胺和4,4’-氧二苯胺以外的二胺單體用作為二胺單體，而不背離本發明的目的。這種二胺單體的範例可包含對苯二胺(p-phenylenediamine)等，但不限於此。基於二胺單體的總莫耳數，額外二胺單體可以約15mol%或更少(例如約0.1mol%、約1mol%、約2mol%、約3mol%、約4mol%、約5mol%、約6mol%、約7mol%、約8mol%、約9mol%、約10mol%、約11mol%、約12mol%、約13mol%、約14mol%或約15mol%)、例如10mol%或更少、再例如5mol%或更少的量存在。
二酐單體可包含本發明所屬技術領域中常用的任何二酐單體。二酐單體的範例可包含均苯四酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3,3’,4-聯苯四羧酸二酐、氧雙鄰苯二甲酸酐、3,3’,4,4’-二苯基碸四羧酸二酐以及3,3’,4,4’-二苯甲酮四羧酸二酐，但不限於此。在一實施例中，二酐單體可為均苯四酸二酐，其具有例如良好的反應性和低價的優點，但不限於此。
有機溶劑可包含可溶解聚醯胺酸的任何有機溶劑，例如非質子極性有機溶劑。非質子極性有機溶劑的範例可包含醯胺溶劑例如N,N’-二甲基甲醯胺(N,N’-dimethylformamide，DMF)和N,N’-二甲基乙醯胺(N,N’-dimethylacetamide，DMAc)、酚類溶劑例如對氯苯酚(p-chlorophenol)和鄰氯苯酚(o-chlorophenol)、N-甲基-吡咯烷酮(N-methyl-pyrrolidone，NMP)、γ-丁內酯(γ-butyrolactone，GBL)和二乙二醇二甲醚(diglyme)。這些可單獨使用或組合使用。根據需要，可進一步使用輔助溶劑例如甲苯(toluene)、四氫呋喃 (tetrahydrofuran)、丙酮、甲基乙基酮(methyl ethyl ketone)、甲醇、乙醇和水，以調整聚醯胺酸的溶解度。在一實施例中，有機溶劑可為醯胺溶劑，例如N,N’-二甲基甲醯胺或N,N’-二甲基乙醯胺，但不限於此。
在一實施例中，基於前驅組合物的總重量，聚醯胺酸可以約5wt%至約35wt%(例如約5wt%、約10wt%、約15wt%、約20wt%、約25wt%、約30wt%或約35wt%)的量存在。在此範圍內，前驅組合物可具有合適的分子量和溶液黏度以用於形成膜，同時具有良好的儲存穩定性。基於前驅組合物的總重量，聚醯胺酸可以例如約10wt%至約30wt%、再例如約15wt%至20wt%的量存在，但不受限制於此。
在一實施例中，前驅組合物在23℃的溫度和1sec-1的剪切速率下可具有約100,000cP至約300,000cP(例如約100,000cP、約150,000cP、約200,000cP、約250,000cP或約300,000cP)的黏度。在此範圍內，前驅組合物可在聚醯亞胺膜的形成過程中展現出良好的可加工性，同時使聚醯胺酸具有預定的重量平均分子量。在此，可使用HAAKE Mars流變儀(HAAKE Mars rheometer)來測量「黏度」。在23℃的溫度和1sec-1的剪切速率下，前驅組合物可具有例如約150,000cP至約250,000cP、再例如約200,000cP至約250,000cP的黏度，但不限於此。
在一實施例中，聚醯胺酸可具有約100,000g/mol或更多，例如約100,000g/mol至約500,000g/mol的重量平均分子量(Mw)，但不限於此。在此範圍內，使用聚醯亞胺膜製造的石墨片可具有進一步改善的導熱率。在此，可藉由凝膠滲透層析法(gel permeation chromatography，GPC)，來測量「重量平均分子量」。
在一實施例中，前驅組合物可更包含可昇華的無機填料。在此，「可昇華的無機填料」可指在石墨片的製造中的碳化和/或石墨化製程的過程中，可藉由熱來昇華的無機填料。當聚醯亞胺膜包含可昇華的無機填料時，可在製造石墨片的過程中，藉由透過可昇華的無機填料的昇華而產生的氣體，以在石墨片中形成孔洞，從而改善石墨片的柔軟度，因此改善石墨片的可操作性(handleability)和模塑性(moldability)。
在一實施例中，可昇華的無機填料可具有1.5μm至約4.5μm(例如約1.5μm、約2μm、約2.5μm、約3μm、約3.5μm、約4μm或約4.5μm)的平均粒徑(D50)。在此範圍內，可昇華的無機填料可具有良好的分散性，可防止其暴露在聚醯亞胺膜的表面上，從而減少表面缺陷，且可在碳化和/或石墨化製程的過程中引起適當程度的發泡，從而可得到高品質的石墨片。
在一實施例中，相對於100重量份的聚醯胺酸，可昇華的無機填料可以約0.2重量份至約0.5重量份(例如約0.2重量份、約0.3重量份、約0.4重量份或約0.5重量份)的量存在。在此範圍內，可昇華的無機填料可具有良好的分散性，可防止其暴露在聚醯亞胺膜的表面上，從而減少表面缺陷，且可在碳化和/或石墨化製程的過程中引起適當程度的發泡，從而可得到高品質的石墨片。
在一實施例中，可昇華的無機填料可包含選自磷酸二鈣和碳酸鈣的群組中的至少其一，但不限於此。
在一實施例中，用於石墨片的聚醯亞胺膜可具有約20μm至約500μm(例如約20μm、約30μm、約40μm、約50μm、約60μm、約70μm、約80μm、 約90μm、約100μm、約150μm、約200μm或約500μm)的厚度。聚醯亞胺膜可具有例如約32μm至約100μm、再例如約38μm至約62.5μm的厚度，但不限於此。
可藉由本發明所屬技術領域中已知的任何合適方法，來製造上述之用於石墨片的聚醯亞胺膜。
在一實施例中，用於石墨片的聚醯亞胺膜可藉由以下方法製造，方法包含：(a)藉由混合有機溶劑與二胺單體和二酐單體，來製備包含聚醯胺酸的前驅組合物；(b)將前驅組合物醯亞胺化，以形成聚醯亞胺膜。然而，取決於所用的單體的種類和期望的聚醯亞胺膜特性，可在步驟(a)中一次全部地或依序地混合單體。因此，單體之間可能發生部分聚合。視需要而定地，此方法可更包含在步驟(a)之後和步驟(b)之前添加可昇華的無機填料。在此，可藉由本發明所屬技術領域中已知的任何合適方法，來添加可昇華的無機填料。
可藉由例如熱醯亞胺化法、化學醯亞胺化法或組合使用熱醯亞胺化法和化學醯亞胺化法的複合醯亞胺化法，來將用於製造聚醯亞胺膜的前驅組合物醯亞胺化。
熱醯亞胺化法是不使用脫水劑等僅透過加熱，來誘導醯亞胺化的方法，其中在支撐體上將聚醯胺酸形成膜，然後進行約1至8小時的熱處理同時在約40℃至約400℃的溫度範圍內，例如約40℃至約300℃的溫度範圍內，將膜逐漸加熱，從而獲得其中聚醯胺酸被醯亞胺化的聚醯亞胺膜。
化學醯亞胺化法是藉由將脫水劑和/或醯亞胺化劑施加於前驅組合物，來促進醯亞胺化的方法。
複合醯亞胺化法是將脫水劑和/或醯亞胺化劑添加至前驅組合物中，然後將其在支撐體上形成膜，然後將其加熱至約80℃至約200℃，例如約 100℃至約180℃，以活化脫水劑和/或醯亞胺化劑，之後將膜部分硬化並乾燥，然後將膜加熱至約200℃到約400℃約5至400秒，從而獲得聚醯亞胺膜的方法。
在一實施例中，可藉由化學醯亞胺化或複合醯亞胺化法，來將前驅組合物醯亞胺化。因此，根據本發明的方法可包含例如在步驟(a)之後和步驟(b)之前添加脫水劑和/或醯亞胺化劑。
在此，「脫水劑」是指透過脫水促進聚醯胺酸的閉環的物質，且可包含例如脂肪酸酐(aliphatic acid anhydride)、芳香酸酐(aromatic acid anhydride)、N,N’-二烷基碳二亞胺(N,N’-dialkylcarbodiimide)、低級脂肪酸鹵化物(lower aliphatic acid halide)、鹵化之低級脂肪酸酐(halogenated lower fatty acid anhydride)、芳基膦酸二鹵化物(aryl phosphonic dihalide)和亞硫醯鹵化物(thionyl halide)。這些可單獨使用或作為混合物使用。其中，從可得性和成本的觀點，脂肪酸酐例如乙酸酐、丙酸酐和乳酸酐是較佳的。這些可單獨使用或作為混合物使用。
在此，「醯亞胺化劑」是指促進聚醯胺酸的閉環的物質，且可包含例如脂肪族三級胺(aliphatic tertiary amine)、芳香族三級胺(aromatic tertiary amine)和雜環三級胺(heterocyclic tertiary amine)。其中，從催化反應性的觀點，雜環三級胺是較佳的。雜環三級胺的範例可包含喹啉(quinoline)、異喹啉(isoquinoline)、β-甲吡啶(β-picoline)和吡啶(pyridine)。這些可單獨使用或作為混合物使用。
儘管脫水劑和/或醯亞胺化劑的量沒有特別限制，但在聚醯胺酸中，脫水劑可以每莫耳的醯胺酸基團約0.5mol至約5mol，例如約1mol至約4mol的量存在，且在聚醯胺酸中，醯亞胺化劑可以每莫耳的醯胺酸基團約0.05mol至 約3mol，例如約0.2mol至約2mol的量存在。在這些範圍內，可充分實現前驅組合物的醯亞胺化，且可容易地以膜的形式來鑄造(cast)前驅組合物。
在一實施例中，步驟(b)可包含(b-1)藉由將前驅組合物鑄造至支撐體上，然後乾燥來製備凝膠膜；和(b-2)透過凝膠膜的熱處理，來形成聚醯亞胺膜。
在一實施例中，在步驟(b-1)中，可藉由在約40℃至約300℃，例如約80℃至約200℃、再例如約100℃至約180℃的溫度下，將在支撐體(例如玻璃板、鋁箔、環形不銹鋼帶和不銹鋼鼓)上鑄造的前驅組合物乾燥，來獲得凝膠膜。透過乾燥製程，將脫水劑和醯亞胺化劑活化，從而使鑄造的前驅組合物發生部分硬化和乾燥，從而形成凝膠膜。在本文中，「凝膠膜」是指在聚醯胺酸轉化為聚醯亞胺的中間階段中形成的自我支撐膜中間體(self-supported film intermediate)。
根據需要，根據本發明之方法可包含拉伸凝膠膜，以調整最終獲得的聚醯亞胺膜的厚度和尺寸，且改善聚醯亞胺膜的配向(orientation)。在此，可在縱向(machine direction，MD)和橫向(transverse directio，TD)中的至少其一上進行凝膠膜的拉伸。
凝膠膜可具有約5wt%至約500wt%，例如約5wt%至約200wt%、再例如約5wt%至約150wt%的揮發物含量，但不限於此。在此範圍內，有可能避免在隨後用熱處理以獲得聚醯亞胺膜的過程中發生膜破裂、色調不均勻和特性變化等缺陷。在此，可根據等式1來計算凝膠膜的揮發物含量。在等式1中，A表示凝膠膜的初重量，而B表示將凝膠膜加熱至450℃、20分鐘後的凝膠膜的重量。
<等式1> (A-B)×100/B
在一實施例中，在步驟(b-2)中，可在約50℃至約700℃，例如約150℃至約600℃、再例如約200℃至約600℃的可變溫度範圍內，對凝膠膜進行熱處理，以從凝膠膜中除去殘留的溶劑，且將幾乎所有殘留的醯胺酸基團醯亞胺化，從而獲得聚醯亞胺膜。
根據需要，可在約400℃和約650℃的溫度下，將獲得的聚醯亞胺膜進行約5至400秒的熱加工處理(heat-finishing treatment)，以進一步硬化。在此，可在預定的張力下進行熱加工處理，以減輕所獲得的聚醯亞胺膜的任何殘留應力。
石墨片
根據本發明的另一面向，提供了一種使用上述之用於石墨片的聚醯亞胺膜來製造的石墨片。使用聚醯亞胺膜製造的石墨片可具有良好的導熱率。
在一實施例中，石墨片可具有約10μm至約250μm(例如約10μm、約15μm、約20μm、約25μm、約30μm、約35μm、約40μm、約45μm、約50μm、約75μm、約100μm或約250μm)的厚度。石墨片可具有例如約13μm至約75μm、再例如約19μm至約62.5μm的厚度，但不限於此。
在一實施例中，石墨片可具有約1.8g/cm3至約3.0g/cm3(例如約1.8g/cm3、約1.9g/cm3、約2g/cm3、約2.1g/cm3、約2.2g/cm3、約2.3g/cm3、約2.4g/cm3、約2.5g/cm3、約2.6g/cm3、約2.7g/cm3、約2.8g/cm3、約2.9g/cm3或約3g/cm3)的密度。在此範圍內，石墨片可具有增加的熱擴散系數，和因此增加的導熱率。石墨片可具有例如約2.0g/cm3至約2.8g/cm3、再例如約2.2g/cm3至約2.5g/cm3的密度，但不限於此。
在一實施例中，石墨片可具有約795mm2/s或更大(例如約795mm2/s、約800mm2/s、約810mm2/s、約820mm2/s、約830mm2/s、約840mm2/s、約850mm2/s、約860mm2/s、約870mm2/s、約880mm2/s、約890mm2/s或約900mm2/s)的熱擴散系數。石墨片可具有例如約795mm2/s至約900mm2/s、例如約800mm2/s至約850mm2/s的熱擴散系數，但不限於此。
可藉由製造石墨片領域中常用的任何合適方法，來製造石墨片。例如，可藉由聚醯亞胺膜的碳化和石墨化，來製造石墨片。
在此，可在例如約1,000℃至約1,500℃的溫度下執行碳化製程約1至5小時，但不限於此。透過碳化製程，聚醯亞胺膜的聚合物鏈會被熱分解，從而形成包含非晶質(non-crystalline)碳體和/或非晶形(amorphous)碳體的初步石墨片。
在此，可在例如約2,500℃至約3,000℃的溫度下執行石墨化製程約1至10小時，但不限於此。透過石墨化製程，非晶質碳體和/或非晶形碳體的碳原子會被重新排列，從而形成石墨片。
接下來，提及實施例來更詳細地描述本發明。然而，應注意的是，提供這些實施例僅用於舉例說明，且不應以任何方法視為限制本發明。
實施例
實施例1
首先，將作為二酐單體之104.02g的均苯四甲酸二酐、作為二胺單體之47.99g的4,4’-亞甲基二苯胺(MDA)和48.23g的4,4’-氧二苯胺(ODA)及800g的二甲基甲醯胺混合在一起，然後進行聚合，從而製備出最終黏度為244,000cP的聚醯胺酸溶液。
然後，將1,000g之製備的聚醯胺酸溶液與0.5g之作為可昇華的無機填料的磷酸二鈣(平均粒徑(D50)：2.2μm)和在聚醯胺酸中每莫耳的醯胺酸基團的0.5mol之作為醯亞胺化劑的β-甲基吡啶、3mol之作為脫水劑的乙酸酐和2.5mol的二甲基甲醯胺混合，從而製備出前驅組合物。
然後，使用高速旋轉攪拌器，將製備的前驅組合物鑄造至玻璃板上，之後在160℃下乾燥3分鐘，從而製備出凝膠膜。然後，將凝膠膜和玻璃板分開，隨後在280℃下熱處理4分鐘且在420℃下熱處理3分鐘，從而製造出厚度約50μm的聚醯亞胺膜。
使用電爐在氮氣下，以0.8℃/min的加熱速率，將聚醯亞胺膜加熱至1300℃，隨後藉由將溫度維持1小時，使聚醯亞胺膜碳化。然後，在氬氣下以3.5℃/min的加熱速率，將碳化的聚醯亞胺膜加熱至2,800℃，隨後藉由將溫度維持1小時使聚醯亞胺膜石墨化，從而製造出石墨片。
實施例2至8及比較例1和2
除了基於二胺單體的總莫耳數之4,4’-亞甲基二苯胺和4,4’-氧二苯胺的mol%、聚醯胺酸溶液的最終黏度和各石墨片的厚度如表1所示進行更改之外，以與實施例1相同的方法來製造石墨片。
特性評估
(1)黏度(單位：cP)：在23℃的溫度和1sec-1的剪切速率的條件下使用黏度計(HAAKE Mars流變儀，HAAKE Mars)，來測量實施例和比較例中製備的各聚醯胺酸溶液的黏度。
(2)厚度(單位：μm)：使用厚度計(Micrometer,Mitutoyo Co.,Ltd.)，來測量實施例和比較例中製造的各石墨片的厚度。
(3)熱擴散系數(單位：mm2/s)：使用熱擴散系數測量儀(LFA467，NETZSCH Group)，在室溫下於260V電壓和持續時間50ms的條件下，測量實施例和比較例中製造的各石墨片的熱擴散系數。
(4)密度(單位：g/cm3)：使用重量計(GH-252,A&D Company)和厚度計(Micrometer,Mitutoyo Co.,Ltd.)，藉由表觀密度測量法，來測量實施例和比較例中製造的各石墨片的密度。
Figure 109136247-A0305-02-0017-1
從表1中所示的結果可看出，實施例1至8中所有使用4,4’-亞甲基二苯胺和4,4’-氧二苯胺的量在所述範圍內的聚醯亞胺膜來製造的石墨片具有高熱擴散系數，且預期具有高導熱率。
相反地，比較例1之使用不含4,4’-亞甲基二苯胺的聚醯亞胺膜製造的石墨片和比較例2之使用4,4’-亞甲基二苯胺的量少於本文所述範圍且4,4’-氧二苯胺的量超過本文所述範圍的聚醯亞胺膜來製造的石墨片具有比實施例1至8的石墨片還小的熱擴散系數。
此外，4,4’-亞甲基二苯胺的量超過本文所述範圍，且4,4’-氧二苯胺的量小於本文所述範圍的比較例3無法形成聚醯亞胺膜，因此不足以製造石墨片。
應理解的是，本發明所屬技術領域中具有通常知識者可在不脫離本發明的精神和範圍的情況下做出各種修飾、改變、變更和等效實施例。
無。

Claims (10)

  1. 一種用於石墨片的聚醯亞胺膜，該聚醯亞胺膜藉由將一前驅組合物醯亞胺化而製成，該前驅組合物包括：藉由使二酐單體與二胺單體反應來製備的一聚醯胺酸；以及一有機溶劑， 其中基於該二胺單體的總莫耳數，該二胺單體包括30 mol%至70 mol%的4,4’-亞甲基二苯胺和30 mol%至70 mol%的4,4’-氧二苯胺，基於該二胺單體的總莫耳數，4,4’-亞甲基二苯胺和4,4’-氧二苯胺以85 mol%或更多的總量存在。
  2. 如請求項1所述之聚醯亞胺膜，其中該二酐單體包括選自均苯四甲酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3,3’,4-聯苯四羧酸二酐、氧雙鄰苯二甲酸酐、3,3’,4,4’-二苯基碸四羧酸二酐以及3,3’,4,4’-二苯甲酮四羧酸二酐的群組中的至少其一。
  3. 如請求項1所述之聚醯亞胺膜，其中基於該前驅組合物的總重量，該聚醯胺酸以10 wt%至30 wt%的量存在。
  4. 如請求項1所述之聚醯亞胺膜，其中該前驅組合物在23°C的一溫度和1 sec-1 的一剪切速率下具有100,000 cP至300,000 cP的一黏度。
  5. 如請求項1所述之聚醯亞胺膜，其中該前驅組合物更包括複數個可昇華的無機填料，該複數個可昇華的無機填料包括選自碳酸鈣和磷酸二鈣的群組中的至少其一。
  6. 如請求項5所述之聚醯亞胺膜，其中相對於100重量份的該聚醯胺酸，該複數個可昇華的無機填料以0.2重量份至0.5重量份的量存在。
  7. 一種石墨片，其使用如請求項1至6中任一項之聚醯亞胺膜來製造。
  8. 如請求項7所述之石墨片，其中該石墨片具有10 µm至250 µm的一厚度。
  9. 如請求項7所述之石墨片，其中該石墨片具有1.8 g/cm3 至3.0 g/cm3 的一密度。
  10. 如請求項7所述之石墨片，其中該石墨片具有795 mm2 /s或更大的一熱擴散系數。
TW109136247A 2019-10-28 2020-10-20 用於石墨片之聚醯亞胺膜及由此製成之石墨片 TWI747563B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2019-0134830 2019-10-28
KR1020190134830A KR102222571B1 (ko) 2019-10-28 2019-10-28 그라파이트 시트용 폴리이미드 필름 및 이로부터 제조된 그라파이트 시트

Publications (2)

Publication Number Publication Date
TW202122465A TW202122465A (zh) 2021-06-16
TWI747563B true TWI747563B (zh) 2021-11-21

Family

ID=75164144

Family Applications (1)

Application Number Title Priority Date Filing Date
TW109136247A TWI747563B (zh) 2019-10-28 2020-10-20 用於石墨片之聚醯亞胺膜及由此製成之石墨片

Country Status (6)

Country Link
US (1) US20220372224A1 (zh)
JP (1) JP7430787B2 (zh)
KR (1) KR102222571B1 (zh)
CN (1) CN114630856B (zh)
TW (1) TWI747563B (zh)
WO (1) WO2021085851A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102492197B1 (ko) * 2021-03-23 2023-01-27 피아이첨단소재 주식회사 그라파이트 시트용 폴리이미드 필름 및 이로부터 제조된 그라파이트 시트
KR102713071B1 (ko) * 2021-11-16 2024-10-04 피아이첨단소재 주식회사 그라파이트 시트용 폴리이미드 필름 및 이로부터 제조된 그라파이트 시트
CN115974067A (zh) * 2023-01-13 2023-04-18 富优特(山东)新材料科技有限公司 一种吡啶环改性聚酰亚胺的高导热石墨膜及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201524904A (zh) * 2013-11-28 2015-07-01 鐘化股份有限公司 石墨膜之製造方法
WO2019168245A1 (ko) * 2018-02-28 2019-09-06 에스케이씨코오롱피아이 주식회사 그래핀 함유의 구형 pi계 필러를 포함하는 그라파이트 시트용 폴리이미드 필름, 이의 제조방법 및 이를 이용하여 제조되는 그라파이트 시트
CN110272552A (zh) * 2019-06-20 2019-09-24 青岛科思姆新材料有限公司 一种石墨烧结用聚酰亚胺薄膜的制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3824531B2 (ja) 2001-12-27 2006-09-20 三井化学株式会社 ポリイミド、その製造方法、およびそれからなる回路基板
US7745516B2 (en) * 2005-10-12 2010-06-29 E. I. Du Pont De Nemours And Company Composition of polyimide and sterically-hindered hydrophobic epoxy
KR101930282B1 (ko) * 2010-08-25 2018-12-18 가부시키가이샤 가네카 그라파이트 필름 및 그라파이트 필름의 제조 방법
JP6423633B2 (ja) 2014-07-11 2018-11-14 東レ・デュポン株式会社 グラファイトシート用ポリイミドフィルム及びその製造方法
KR101951306B1 (ko) 2017-10-23 2019-02-22 에스케이씨코오롱피아이 주식회사 롤 타입 그라파이트 시트용 폴리이미드 필름
WO2019093821A1 (ko) 2017-11-10 2019-05-16 에스케이씨코오롱피아이 주식회사 도체 피복용 폴리아믹산 조성물
KR101972668B1 (ko) 2017-11-10 2019-04-25 에스케이씨코오롱피아이 주식회사 고성능 그라파이트 시트 및 이의 제조방법
KR102063215B1 (ko) * 2018-02-26 2020-01-07 에스케이씨코오롱피아이 주식회사 향상된 열전도도를 가지는 그라파이트 시트용 폴리이미드 필름, 이의 제조방법 및 이를 이용하여 제조된 그라파이트 시트
JP7012828B2 (ja) 2018-03-29 2022-02-14 株式会社カネカ 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201524904A (zh) * 2013-11-28 2015-07-01 鐘化股份有限公司 石墨膜之製造方法
WO2019168245A1 (ko) * 2018-02-28 2019-09-06 에스케이씨코오롱피아이 주식회사 그래핀 함유의 구형 pi계 필러를 포함하는 그라파이트 시트용 폴리이미드 필름, 이의 제조방법 및 이를 이용하여 제조되는 그라파이트 시트
CN110272552A (zh) * 2019-06-20 2019-09-24 青岛科思姆新材料有限公司 一种石墨烧结用聚酰亚胺薄膜的制备方法

Also Published As

Publication number Publication date
KR102222571B1 (ko) 2021-03-05
CN114630856B (zh) 2023-09-12
JP7430787B2 (ja) 2024-02-13
TW202122465A (zh) 2021-06-16
CN114630856A (zh) 2022-06-14
US20220372224A1 (en) 2022-11-24
JP2023501194A (ja) 2023-01-18
WO2021085851A1 (ko) 2021-05-06

Similar Documents

Publication Publication Date Title
TWI747563B (zh) 用於石墨片之聚醯亞胺膜及由此製成之石墨片
KR20190102561A (ko) 구형의 pi계 필러를 포함하는 그라파이트 시트용 폴리이미드 필름, 이의 제조방법 및 이를 이용하여 제조되는 그라파이트 시트
TWI775102B (zh) 用於石墨片之聚醯亞胺膜及此聚醯亞胺膜之製造方法
JP3729315B2 (ja) ポリイミドフィルムの製造方法及び製造装置
TW201934613A (zh) 具改良儲存穩定性的聚醯胺酸組成物、使用其製備聚醯亞胺膜之方法、以其所製備的聚醯亞胺膜以及電子裝置
TWI790017B (zh) 用於石墨片材之聚醯亞胺膜、其製造方法及由其製造的石墨片材
TWI826744B (zh) 石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片
TWI751776B (zh) 石墨片用之聚醯亞胺膜、其製備方法及由此製得之石墨片
KR20200022902A (ko) 결정성 폴리이미드 수지 및 열전도성 필러를 포함하는 폴리이미드 필름 및 이의 제조방법
TWI762041B (zh) 聚醯亞胺膜及其製造方法
CN113166454B (zh) 具有改善的导热性的聚酰亚胺薄膜及其制备方法
KR102125686B1 (ko) 폴리아믹산 조성물, 및 이의 제조 방법
TW202106620A (zh) 石墨片及包含此的電子裝置
JP7496472B2 (ja) グラファイトシート用ポリイミドフィルム製造方法およびグラファイトシートの製造方法
TWI843190B (zh) 聚醯亞胺膜、其製造方法、包括其的多層膜及電子部件
KR102452445B1 (ko) 그라파이트 시트용 폴리이미드 필름 제조방법 및 그라파이트 시트 제조방법
TWI762040B (zh) 聚醯亞胺膜及其製造方法
TW202225288A (zh) 用於石墨片之聚醯亞胺膜及由其製備的石墨片
TW202323388A (zh) 聚醯亞胺膜、其製備方法及包括其的覆蓋膜
TW202417546A (zh) 聚醯亞胺膜、包括其的可撓性覆金屬箔層壓板及電子部件
TW202126729A (zh) 聚醯亞胺膜的製造方法及由其製造的聚醯亞胺膜