JPH0770335A - Method and apparatus for bonding thermoplastic polyimide - Google Patents

Method and apparatus for bonding thermoplastic polyimide

Info

Publication number
JPH0770335A
JPH0770335A JP5217157A JP21715793A JPH0770335A JP H0770335 A JPH0770335 A JP H0770335A JP 5217157 A JP5217157 A JP 5217157A JP 21715793 A JP21715793 A JP 21715793A JP H0770335 A JPH0770335 A JP H0770335A
Authority
JP
Japan
Prior art keywords
thermoplastic polyimide
treatment
glass transition
bis
transition temperature
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
JP5217157A
Other languages
Japanese (ja)
Other versions
JP3360753B2 (en
Inventor
Shigeki Kijima
重基 木島
Hidesuke Yamanaka
秀介 山中
Nobuyuki Sudo
信行 須藤
Koichi Aizawa
相沢　　浩一
Shigeyuki Shishido
重之 宍戸
Takaaki Tsushima
敬章 津嶋
Kazunori Kojima
一記 小島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Toatsu Chemicals Inc
Original Assignee
Mitsui Toatsu Chemicals Inc
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 Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Priority to JP21715793A priority Critical patent/JP3360753B2/en
Publication of JPH0770335A publication Critical patent/JPH0770335A/en
Application granted granted Critical
Publication of JP3360753B2 publication Critical patent/JP3360753B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1432—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface direct heating of the surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1464—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators
    • B29C65/1467—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators at the same time, i.e. simultaneous welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/024—Thermal pre-treatments
    • B29C66/0242—Heating, or preheating, e.g. drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/028—Non-mechanical surface pre-treatments, i.e. by flame treatment, electric discharge treatment, plasma treatment, wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73117—Tg, i.e. glass transition temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91411—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the parts to be joined, e.g. the joining process taking the temperature of the parts to be joined into account
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91431—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being kept constant over time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9161—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux
    • B29C66/91641—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time
    • B29C66/91643—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-time profile
    • B29C66/91645—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-time profile by steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91941—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined
    • B29C66/91943—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to Tg, i.e. the glass transition temperature, of the material of one of the parts to be joined higher than said glass transition temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
    • B29C65/1412—Infrared [IR] radiation
    • B29C65/1422—Far-infrared radiation [FIR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/95—Measuring or controlling the joining process by measuring or controlling specific variables not covered by groups B29C66/91 - B29C66/94
    • B29C66/959—Measuring or controlling the joining process by measuring or controlling specific variables not covered by groups B29C66/91 - B29C66/94 characterised by specific values or ranges of said specific variables
    • B29C66/9592—Measuring or controlling the joining process by measuring or controlling specific variables not covered by groups B29C66/91 - B29C66/94 characterised by specific values or ranges of said specific variables in explicit relation to another variable, e.g. X-Y diagrams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate

Abstract

PURPOSE:To stably and firmly bond two thermoplastic polyimide substrates to each other by modifying the surfaces of the substrates under electric discharge at the temp. of the surfaces equal to or higher than the glass transition temperature of the polyimide and thermally pressing the substrates to each other at the glass transition temperature or higher. CONSTITUTION:Thermoplastic polyimide substrates 61 and 62 are fed from rolls 51 and 52 and heated with preheaters 15 and 15 and heaters 17 and 17 to raise the surface temp. to the glass transition temperature of the polyimide or higher. Then, the surfaces of the subsrates 61 and 62 are modified by electric discharge, such as corona or plasma treatment, with a rodlike electrode 11. The substrates 61 and 62 are then fed to a heat-press roll 13 while keeping the surfaces at the glass transition temperature or higher, thermally pressed to each other, and wound up with a roll 53. The resulting laminate 63 is uniform in quality, has a high peeling strength, and exhibits no defects such as blisters or separation.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、熱可塑性ポリイミドの
接着性改良方法およびその装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for improving the adhesiveness of thermoplastic polyimide.

【０００２】[0002]

【従来の技術】従来、熱可塑性ポリイミドを接着剤とし
て、積層体、接合材や複合材等を製造するにあたり、接
着強度向上、耐熱性向上、プレス時の温度・圧力・時間
等のプレス条件の容易化または応力緩和処理等の目的の
ために、熱可塑性ポリイミド表面に、コロナ処理、プラ
ズマ処理、スパッタ処理またはイオンプレーティング処
理等の放電による表面改質処理が施されることが多かっ
た。2. Description of the Related Art Conventionally, in manufacturing a laminate, a bonding material, a composite material, etc. using a thermoplastic polyimide as an adhesive, the bonding strength is improved, the heat resistance is improved, and the pressing conditions such as temperature, pressure and time during pressing are used. For the purpose of facilitating or stress relaxation treatment, the surface of thermoplastic polyimide is often subjected to surface modification treatment by electric discharge such as corona treatment, plasma treatment, sputtering treatment or ion plating treatment.

【０００３】しかしながら、このような処理が施されて
いても、熱可塑性ポリイミドの接着性能改善は、充分と
言えず、より困難なプレス条件を必要としていた。さら
に、経時、摩擦、湿度・温度等の環境の影響またはプレ
ス予備加熱時等における表面処理の失活現象による接着
性の不均一は、製品製造上大きな問題となっていた。そ
の上さらに、この失活現象を回避するために過剰な表面
改質処理が行われる傾向にあり、過剰な生産設備を要し
たり、熱可塑性ポリイミドの劣化を伴ったりして必ずし
も有用な方法とは言い難いものであった。However, even if such a treatment is applied, the improvement in the adhesive performance of the thermoplastic polyimide cannot be said to be sufficient, and more difficult pressing conditions are required. Further, the influence of environment such as aging, friction, humidity and temperature, or nonuniform adhesion due to deactivation phenomenon of surface treatment during press preheating has been a serious problem in product manufacturing. Furthermore, there is a tendency that excessive surface modification treatment is carried out in order to avoid this deactivation phenomenon, which requires excessive production equipment, or is accompanied by deterioration of the thermoplastic polyimide, and is not necessarily a useful method. Was hard to say.

【０００４】[0004]

【発明が解決しようとする課題】本発明は、熱可塑性ポ
リイミドの安定したかつ強固な接着性を得ようとするも
のである。DISCLOSURE OF THE INVENTION The present invention is intended to obtain stable and strong adhesion of thermoplastic polyimide.

【０００５】[0005]

【課題を解決するための手段】本発明者らは、ガラス転
移点温度以上に加熱した熱可塑性ポリイミド表面にコロ
ナ処理、プラズマ処理、スパッタ処理またはイオンプレ
ーティング処理等の放電による表面改質処理を施し、熱
可塑性ポリイミドをガラス転移点温度以上に保持した状
態で加熱圧着することにより、安定したかつ強固な接着
性が得られことを発見した。また、できる限り上記の処
理直後に熱圧着することにより、表面改質処理の失活現
象を回避できることも発見した。本発明はかかる知見に
より、なされるに至ったものである。The inventors of the present invention have performed a surface modification treatment by discharge such as corona treatment, plasma treatment, sputtering treatment or ion plating treatment on the surface of a thermoplastic polyimide heated above the glass transition temperature. It was discovered that stable and strong adhesiveness was obtained by thermocompression bonding with the thermoplastic polyimide being kept above the glass transition temperature. It was also discovered that the deactivation phenomenon of the surface modification treatment can be avoided by thermocompression bonding as soon as possible after the above treatment. The present invention has been made based on such knowledge.

【０００６】すなわち、本発明は、ガラス転移点温度以
上に加熱した熱可塑性ポリイミド層表面に、放電による
表面改質処理、好ましくはコロナ処理、プラズマ処理、
スパッタリング処理またはイオンプレーティング処理か
ら選択される放電による表面改質処理を施し、かつ該処
理を施した熱可塑性ポリイミド層表面をガラス転移点温
度以上保持した状態にて加熱圧着することを特徴とする
熱可塑性ポリイミドの接着方法、であり、また好ましく
は、基材搬送用ロールまたは加熱プレスロール上におい
て、熱圧着直前に、熱可塑性ポリイミド層表面を、上記
表面処理を施す熱可塑性ポリイミドの接着方法、であ
り、また、少なくとも、基材搬送用ロールと加熱プレス
ロールとを備える熱可塑性ポリイミド層の接着装置であ
って、該基材搬送用ロールと加熱プレスロール上におい
て、ガラス転移点温度以上に加熱した熱可塑性ポリイミ
ド層表面に、放電による表面改質処理を施す手段、好ま
しくはコロナ処理、プラズマ処理、スパッタリング処理
またはイオンプレーティング処理から選択される放電に
よる表面改質処理を施す手段をさらに備えて、熱圧着直
前に該熱可塑性ポリイミド層表面を表面改質処理し、か
つ該処理を施した熱可塑性ポリイミド層表面をガラス転
移点温度以上保持した状態にて加熱圧着しうるようにし
た熱可塑性ポリイミドの接着装置、である。That is, according to the present invention, a surface modification treatment by discharge, preferably a corona treatment, a plasma treatment, is applied to the surface of a thermoplastic polyimide layer heated to a glass transition temperature or higher.
Characterized by performing surface modification treatment by discharge selected from sputtering treatment or ion plating treatment, and performing thermocompression bonding with the surface of the treated thermoplastic polyimide layer being kept at a glass transition temperature or higher. Adhesion method of the thermoplastic polyimide, and also preferably, on the roll or heating press roll for substrate transfer, immediately before thermocompression bonding, the thermoplastic polyimide layer surface, a method of adhering the thermoplastic polyimide, the surface treatment, Further, at least, a thermoplastic polyimide layer bonding apparatus comprising a substrate conveying roll and a heating press roll, on the substrate conveying roll and the heating press roll, heated to a glass transition temperature or higher. The surface of the thermoplastic polyimide layer, which is subjected to surface modification treatment by electric discharge, preferably corona treatment, A means for performing a surface modification treatment by discharge selected from plasma treatment, sputtering treatment or ion plating treatment is further provided, and the surface modification treatment is performed on the surface of the thermoplastic polyimide layer immediately before thermocompression bonding, and the treatment is performed. The thermoplastic polyimide bonding device is adapted to be thermocompression bonded while the surface of the thermoplastic polyimide layer is maintained at a glass transition temperature or higher.

【０００７】以下、本発明を詳細に説明する。まず、添
付図面について説明するに、図１は、本発明を実施する
ための装置の一例の説明図であり、また、図２は、コロ
ナ処理後加圧圧着までの時間と引き剥し強度の関係の一
例を示すグラフである。図１において、１１はコロナ処
理用棒状電極、１３は加熱プレスロール、１５は基材予
備加熱ヒーター、１７は基材加熱ヒーター、１９は送風
口、２１は排風口、５１は上部繰り出し軸、５２は下部
繰り出し軸、５３は巻取り軸、５５はガイドロール、６
１は上部積層用基材、６２は下部積層用基材、６３は積
層材を示す。本発明に関わる熱可塑性ポリイミドは、ジ
アミン成分とカルボン酸無水物の重縮合よりなる。The present invention will be described in detail below. First, referring to the attached drawings, FIG. 1 is an explanatory view of an example of an apparatus for carrying out the present invention, and FIG. 2 is a relation between a time until corona treatment and pressure bonding and a peeling strength. It is a graph which shows an example. In FIG. 1, 11 is a rod electrode for corona treatment, 13 is a heating press roll, 15 is a base material preheating heater, 17 is a base material heating heater, 19 is a blowing port, 21 is an exhaust port, 51 is an upper feeding shaft, 52 Is a lower feeding shaft, 53 is a winding shaft, 55 is a guide roll, 6
Reference numeral 1 is an upper laminating substrate, 62 is a lower laminating substrate, and 63 is a laminated material. The thermoplastic polyimide relating to the present invention comprises polycondensation of a diamine component and a carboxylic acid anhydride.

【０００８】ジアミン化合物成分としては、例えば、
３，３’−ジアミノジフェニルエーテル、３，３’−ジ
アミノベンゾフェノン、１，３−ビス（３−アミノフェ
ノキシ）ベンゼン、４，４’−ビス（３−アミノフェノ
キシ）ビフェニルからなる群から選ばれるすくなくとも
一つのジアミン化合物からなる。また、ジアミン化合物
の一部代替えすることも可能であり、例えば、ｏ−フェ
ニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニ
レンジアミン、ｍ−アミノベンジルアミン、ｐ−アミノ
ベンジルアミン、２−クロロ−１，２−フェニレンジア
ミン、４−クロロ−１，２−フェニレンジアミン、２，
３−ジアミノトルエン、２，４−ジアミノトルエン、
２，５−ジアミノトルエン、２，６−ジアミノトルエ
ン、３，４−ジアミノトルエン、２−メトキシ−１，４
−フェニレンジアミン、４−メトキシ−１，２−フェニ
レンジアミン、４−メトキシ−１，３−フェニレンジア
ミン、ベンジジン、３，３’−ジクロロベンジジン、
３，３’−ジメチルベンジジン、３，３’−ジメトキシ
ベンジジン、３，３’−ジアミノジフェニルエーテル、
３，４’−ジアミノジフェニルエーテル、４，４’−ジ
アミノジフェニルエーテル、３，３’−ジアミノジフェ
ニルスルフィド、３，４’−ジアミノジフェニルスルフ
ィド、４，４’−ジアミノジフェニルスルフィド、３，
３’−ジアミノジフェニルスルホキシド、３，４’−ジ
アミノジフェニルスルホキシド、４，４’−ジアミノジ
フェニルスルホキシド、３，３’−ジアミノジフェニル
スルホン、３，４’−ジアミノジフェニルスルホン、
４，４’−ジアミノジフェニルスルホン、３，４’−ジ
アミノベンゾフェノン、４，４’−ジアミノベンゾフェ
ノン、３，３’−ジアミノジフェニルメタン、３，４’
−ジアミノジフェニルメタン、４，４’−ジアミノジフ
ェニルメタン、ビス〔４−（３−アミノフェノキシ）フ
ェニル〕メタン、ビス〔４−（４−アミノフェノキシ）
フェニル〕メタン、１，１−ビス〔４−（３−アミノフ
ェノキシ）フェニル〕エタン、１，１−ビス〔４−（４
−アミノフェノキシ）フェニル〕エタン、１，２−ビス
〔４−（３−アミノフェノキシ）フェニル〕エタン、
１，２−ビス〔４−（４−アミノフェノキシ）フェニ
ル〕エタン、２，２−ビス〔４−（３−アミノフェノキ
シ）フェニル〕プロパン、２，２−ビス〔４−（４−ア
ミノフェノキシ）フェニル〕プロパン、２，２−ビス
〔４−（３−アミノフェノキシ）フェニル〕ブタン、
２，２−ビス〔４−（４−アミノフェノキシ）フェニ
ル〕ブタン、２，２−ビス〔４−（３−アミノフェノキ
シ）フェニル〕−１，１，１，３，３，３−ヘキサフル
オロプロパン、２，２−ビス〔４−（４−アミノフェノ
キシ）フェニル〕−１，１，１，３，３，３−ヘキサフ
ルオロプロパン、１，３−ビス（３−アミノフェノキ
シ）ベンゼン、１，４−ビス（３−アミノフェノキシ）
ベンゼン、１，４−ビス（４−アミノフェノキシ）ベン
ゼン、４，４’−ビス（３−アミノフェノキシ）ビフェ
ニル、４，４’−ビス（４−アミノフェノキシ）ビフェ
ニル、ビス〔４−（３−アミノフェノキシ）フェニル〕
ケトン、ビス〔４−（４−アミノフェノキシ）フェニ
ル〕ケトン、ビス〔４−（３−アミノフェノキシ）フェ
ニル〕スルフィド、ビス〔４−（４−アミノフェノキ
シ）フェニル〕スルフィド、ビス〔４−（３−アミノフ
ェノキシ）フェニル〕スルホキシド、ビス〔４−（４−
アミノフェノキシ）フェニル〕スルホキシド、ビス〔４
−（３−アミノフェノキシ）フェニル〕スルホン、ビス
〔４−（４−アミノフェノキシ）フェニル〕スルホン、
ビス〔４−（３−アミノフェノキシ）フェニル〕エーテ
ル、ビス〔４−（４−アミノフェノキシ）フェニル〕エ
ーテル、１，４−ビス〔４−（３−アミノフェノキシ）
ベンゾイル〕ベンゼン、１，３−ビス〔４−（３−アミ
ノフェノキシ）ベンゾイル〕ベンゼン、４，４’−ビス
〔３−（４−アミノフェノキシ）ベンゾイル〕ジフェニ
ルエーテル、４，４’−ビス〔３−（３−アミノフェノ
キシ）ベンゾイル〕ジフェニルエーテル、４，４’−ビ
ス〔４−（４−アミノ−α，α−ジメチルベンジル）フ
ェノキシ〕ベンゾフェノン、４，４’−ビス〔４−（４
−アミノ−α，α−ジメチルベンジル）フェノキシ〕ジ
フェニルスルホン、ビス〔４−｛４−（４−アミノフェ
ノキシ）フェノキシ｝フェニル〕ケトン、ビス〔４−
｛４−（４−アミノフェノキシ）フェノキシ｝フェニ
ル〕スルホン、１，４−ビス〔４−（４−アミノフェノ
キシ）−α，α−ジメチルベンジル〕ベンゼン、１，３
−ビス〔４−（４−アミノフェノキシ）−α，α−ジメ
チルベンジル〕ベンゼン等があげられ、また、これらは
単独あるいは２種以上混合して使用される。As the diamine compound component, for example,
At least one selected from the group consisting of 3,3′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene and 4,4′-bis (3-aminophenoxy) biphenyl. It consists of two diamine compounds. It is also possible to partially substitute the diamine compound, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 2-chloro-1, 2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,
3-diaminotoluene, 2,4-diaminotoluene,
2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2-methoxy-1,4
-Phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,
3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy)
Phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane,
1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane,
2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane , 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4 -Bis (3-aminophenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3- Aminophenoxy) phenyl]
Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfoxide, bis [4- (4-
Aminophenoxy) phenyl] sulfoxide, bis [4
-(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-Aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, bis [4-
{4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3
Examples include -bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like, and these may be used alone or in combination of two or more.

【０００９】一方、テトラカルボン酸無水物成分として
は、ピロメリット酸二無水物、３，３’，４，４’−ビ
フェニルテトラカルボン酸二無水物、３，３’，４，
４’−ジフェニルエーテルテトラカルボン酸二無水物、
３、３’、４、４’−ベンゾフェノンテトラカルボン酸
二無水物からなる群から選ばれるすくなくとも一つのテ
トラカルボン酸無水物からなる。また、テトラカルボン
酸無水物成分の一部代替えすることも可能であり、例え
ば、エチレンテトラカルボン酸二無水物、ブタンテトラ
カルボン酸二無水物等、シクロペンタンテトラカルボン
酸二無水物、シクロヘキサンテトラカルボン酸二無水物
等、１，２，３，４−ベンゼンテトラカルボン酸二無水
物、２，３，６，７−ナフタレンテトラカルボン酸二無
水物、１，４，５，８−ナフタレンテトラカルボン酸二
無水物、１，２，５，６−ナフタレンテトラカルボン酸
二無水物、３，４，９，１０−ペリレンテトラカルボン
酸二無水物、２，３，６，７’−アントラセンテトラカ
ルボン酸二無水物、１，２，７，８−フェナントレンテ
トラカルボン酸二無水物等、２，２’，３，３’−ビフ
ェニルテトラカルボン酸二無水物、２，２’，３，３’
−ベンゾフェノンテトラカルボン酸二無水物、２，２−
ビス（３，４−ジカルボキシフェニル）プロパン二無水
物、２，２−ビス（２，３−ジカルボキシフェニル）プ
ロパン二無水物、ビス（３，４−ジカルボキシフェニ
ル）エーテル二無水物、ビス（２，３−ジカルボキシフ
ェニル）エーテル二無水物、ビス（３，４−ジカルボキ
シフェニル）スルホン二無水物、ビス（２，３−ジカル
ボキシフェニル）スルホン二無水物、１，１−ビス
（２，３−ジカルボキシフェニル）エタン二無水物、ビ
ス（２，３−ジカルボキシフェニル）メタン二無水物、
ビス（３，４−ジカルボキシフェニル）メタン二無水
物、４，４’−（ｐ−フェニレンジオキシ）ジフタル酸
二無水物、４，４’−（ｍ−フェニレンジオキシ）ジフ
タル酸二無水物等が挙げられ、また、これらは単独ある
いは２種類以上混合して用いられる。更に、ポリイミド
樹脂の末端を、ジカルボン酸無水物またはモノアミンで
封止してもよい。On the other hand, as the tetracarboxylic anhydride component, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4.
4'-diphenyl ether tetracarboxylic dianhydride,
It comprises at least one tetracarboxylic acid anhydride selected from the group consisting of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride. It is also possible to partially substitute the tetracarboxylic acid anhydride component, for example, ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, cyclohexane tetracarboxylic acid. 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid, etc. Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7'-anthracenetetracarboxylic dianhydride Anhydrous, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc., 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2', 3,3 '
-Benzophenone tetracarboxylic dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride,
Bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic acid dianhydride, 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride And the like, and these may be used alone or in combination of two or more. Further, the ends of the polyimide resin may be capped with dicarboxylic acid anhydride or monoamine.

【００１０】本発明のポリイミド層のポリマー末端を封
止する目的で使用されるカルボン酸無水物としては、無
水フタル酸、２，３−ベンゾフェノジカルボン酸無水
物、３，４−ベンゾフェノジカルボン酸無水物、２，３
−ジカルボキシルフェニルフェニルエーテル無水物、
２，３−ビフェニルジカルボン酸無水物、３，４−ビフ
ェニルジカルボン酸無水物、２，３−ジカルボキフェニ
ルフェニルスルホン酸無水物、３，４−ジカルボキフェ
ニルフェニルスルホン酸無水物、２，３−ジカルボキシ
ルフェニルフェニルスルフォイド酸無水物、３，４−ジ
カルボキシルフェニルフェニルスルフォイド酸無水物、
１，２−ナフタレンジカルボン酸無水物、２，３−ナフ
タレンジカルボン酸無水物、１，８−ナフタレンジカル
ボン酸無水物、１，２−アントラセンジカルボン酸無水
物、２，３−アントラセンジカルボン酸無水物、１，９
−アントラセンジカルボン酸無水物等が挙げられる。こ
れらのジカルボン酸無水物はアミンまたはジカルボン酸
無水物と反応性を有しない基で置換されても差し支えな
い。The carboxylic acid anhydride used for the purpose of sealing the polymer end of the polyimide layer of the present invention includes phthalic anhydride, 2,3-benzophenodicarboxylic acid anhydride and 3,4-benzophenodicarboxylic acid. Anhydrous, 2,3
-Dicarboxylic phenyl phenyl ether anhydride,
2,3-Biphenyldicarboxylic acid anhydride, 3,4-Biphenyldicarboxylic acid anhydride, 2,3-Dicarboxyphenylphenylsulfonic acid anhydride, 3,4-Dicarboxyphenylphenylsulfonic acid anhydride, 2,3- Dicarboxyl phenyl phenyl sulfonic acid anhydride, 3,4-dicarboxyl phenyl phenyl sulfonic acid anhydride,
1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9
-Anthracene dicarboxylic acid anhydride and the like. These dicarboxylic acid anhydrides may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

【００１１】本発明のポリイミド層のポリマー末端を封
止する目的で使用されるモノアミンとしては、アニリ
ン、ｏ−トルイジン、ｍ−トルイジン、ｐ−トルイジ
ン、２，３−キシリジン、２，４−キシリジン、２，５
−キシリジン、２，６−キシリジン、３，４−キシリジ
ン、３，５−キシリジン、ｏ−クロロアニリン、ｍ−ク
ロロアニリン、ｐ−クロロアニリン、ｏ−ブロモアニリ
ン、ｍ−ブロモアニリン、ｐ−ブロモアニリン、ｏ−ニ
トロアニリン、ｍ−ニトロアニリン、ｐ−ニトロアニリ
ン、ｏ−アミノフェノール、ｍ−アミノフェノール、ｐ
−アミノフェノール、ｏ−アニシジン、ｍ−アニシジ
ン、ｐ−アニシジン、ｏ−フェネチジン、ｍ−フェネチ
ジン、ｐ−フェネチジン、ｏ−アミノベンツアルデヒ
ド、ｍ−アミノベンツアルデヒド、ｐ−アミノベンツア
ルデヒド、ｏ−アミノベンツニトリル、ｍ−アミノベン
ツニトリル、ｐ−アミノベンツニトリル、２−アミノビ
フェニル、３−アミノビフェニル、４−アミノビフェニ
ル、２−アミノフェノールフェノールエーテル、３−ア
ミノフェノールフェノールエーテル、４−アミノフェノ
ールフェノールエーテル、２−アミノベンゾフェノン、
３−アミノベンゾフェノン、３−アミノベンゾフェノ
ン、２−アミノフェノールフェニルスルファイド、３−
アミノフェノールフェニルスルファイド、４−アミノフ
ェノールフェニルスルファイド、２−アミノフェノール
フェニルスルホン、３−アミノフェノールフェニルスル
ホン、４−アミノフェノールフェニルスルホン、α−ナ
フチルアミン、β−ナフチルアミン、１−アミノ−２−
ナフトール、２−アミノ−１−ナフトール、４−アミノ
−１−ナフトール、５−アミノ−１−ナフトール、５−
アミノ−２−ナフトール、７−アミノ−２−ナフトー
ル、８−アミノ−２−ナフトール、１−アミノアントラ
セン、２−アミノアントラセン、９−アミノアントラセ
ン等が挙げられる。The monoamine used for the purpose of sealing the polymer terminal of the polyimide layer of the present invention includes aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, 2,5
-Xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline , O-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p
-Aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenz Nitrile, m-aminobenznitrile, p-aminobenznitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenolphenol ether, 3-aminophenolphenol ether, 4-aminophenolphenol ether, 2-aminobenzophenone,
3-aminobenzophenone, 3-aminobenzophenone, 2-aminophenol phenyl sulfide, 3-
Aminophenol phenyl sulfide, 4-aminophenol phenyl sulfide, 2-aminophenol phenyl sulfone, 3-aminophenol phenyl sulfone, 4-aminophenol phenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-
Naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-
Amino-2-naphthol, 7-amino-2-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned.

【００１２】これら芳香族モノアミンは、単独または２
種類以上混合して用いても問題はない。また前記群のジ
カルボン酸無水物と芳香族モノアミンを併用してもよ
い。熱可塑性ポリイミドの前駆体であるポリアミド酸の
重縮合反応及び熱可塑性ポリイミドの生成反応は、通
常、有機溶媒中で実施する。この反応に用いる溶媒とし
ては、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチル
アセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、１，３
−ジメチル−２−イミダゾリジノン、Ｎ，Ｎ−ジメエル
アセトアミド、Ｎ，Ｎ−ジメエルメトキシアセトアミ
ド、ジメチルスルホキシド、ピリジン、ジメチルスルホ
ン、ヘキサメチルホスホルアミド、テトラメチル尿素、
Ｎ−メチルカプロラクタム、プチロラクタム、テトラヒ
ドロフラン、ｍ−ジオキサン、ｐ−ジオキサン、１，２
−ビス（２−メトキシエトキシ）エタン、ビス２−（２
−メトシエトキシ）エチルエーテル、テトラヒドロフラ
ン、１，４−ジオキサン、ピコリン、ｏ−クレゾール、
ｍ−クレゾール、ｐ−クレゾール、クレゾール酸、ｐ−
クロロフェノール、フェノール、アニソール等挙げられ
る。これらの有機溶媒は、単独もしくは２種類以上混合
して使用される。These aromatic monoamines may be used alone or
There is no problem even if they are used by mixing more than one kind. Further, the dicarboxylic acid anhydride of the above group and the aromatic monoamine may be used in combination. The polycondensation reaction of the polyamic acid which is the precursor of the thermoplastic polyimide and the formation reaction of the thermoplastic polyimide are usually carried out in an organic solvent. As the solvent used in this reaction, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3
-Dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylurea,
N-methylcaprolactam, putilolactam, tetrahydrofuran, m-dioxane, p-dioxane, 1,2
-Bis (2-methoxyethoxy) ethane, bis2- (2
-Methoxyethoxy) ethyl ether, tetrahydrofuran, 1,4-dioxane, picoline, o-cresol,
m-cresol, p-cresol, cresylic acid, p-
Examples include chlorophenol, phenol and anisole. These organic solvents may be used alone or in combination of two or more.

【００１３】本発明に関わるの熱可塑性ポリイミド層を
形成する場合、熱可塑性のポリイミド溶液から所望の熱
可塑性ポリイミド層を得ても、熱可塑性ポリイミドの前
駆体であるポリアミド酸溶液から層形成した後に乾燥・
硬化して所望のポリイミド層を得てもよい。必要なら
ば、前記ポリイミド溶液とポリアミド酸溶液の混合物で
もさしつかえない。熱可塑性ポリイミドの具体的な合成
の一例を示す。例えば、１，３−ビス（アミノフェノキ
シ）ベンゼン２９．２ｇ（０．１モル）とＮ，Ｎ−ジメ
チルアセトアミド２４５．６ｇを、室温窒素雰囲気下で
撹拌・溶解した。これに、３，３’，４，４’−ベンゾ
フェノンテトラカルボン酸３１．８７ｇ（０．０９９モ
ル）を、１０分間隔で４等分割して加え、室温で２４時
間撹拌した。これにより、熱可塑性ポリイミドの前駆体
であるポリアミド酸のＮ，Ｎ−ジメチルアセトアミド溶
液が得られる。When the thermoplastic polyimide layer according to the present invention is formed, even if the desired thermoplastic polyimide layer is obtained from the thermoplastic polyimide solution, after forming the layer from the polyamic acid solution which is the precursor of the thermoplastic polyimide, Dry
It may be cured to obtain the desired polyimide layer. If necessary, a mixture of the polyimide solution and the polyamic acid solution may be used. An example of a specific synthesis of thermoplastic polyimide will be shown. For example, 29.2 g (0.1 mol) of 1,3-bis (aminophenoxy) benzene and 245.6 g of N, N-dimethylacetamide were stirred and dissolved under a nitrogen atmosphere at room temperature. To this, 31.87 g (0.099 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid was added in 4 equal portions at 10 minute intervals, and the mixture was stirred at room temperature for 24 hours. As a result, an N, N-dimethylacetamide solution of polyamic acid, which is a precursor of thermoplastic polyimide, is obtained.

【００１４】さらにその後、このポリアミド酸溶液に、
無水フタル酸１．１８４ｇ（０．００８モル）を加え、
室温で３時間撹拌し、１無水酢酸２０．４ｇ（０．２モ
ル）とトリエチルアミン２０．２ｇを滴下し室温で１０
時間撹拌した。得られた反応混合物を１０００ｇのメタ
ノールに強力な撹拌下に排出し、析出物を濾別分取し
た。得られた粉末状析出物をさらににメタノールで洗浄
後、１８０℃で１２時間乾燥して、熱可塑性ポリイミド
粉５６．９ｇを得る。この得られた熱可塑性ポリイミド
粉のガラス転移点温度は１９２℃（ＤＳＣによる測
定）、対数粘度が０．７６ｄｌ／ｇ（測定はｐ−クロロ
フェノール／フェノール＝９／１重量比の混合溶媒中、
０．５％濃度、３５℃で行った）であった。After that, in this polyamic acid solution,
1.184 g (0.008 mol) of phthalic anhydride was added,
The mixture was stirred at room temperature for 3 hours, 20.4 g (0.2 mol) of acetic anhydride and 20.2 g of triethylamine were added dropwise, and the mixture was stirred at room temperature for 10 hours.
Stir for hours. The obtained reaction mixture was discharged into 1000 g of methanol under strong stirring, and the precipitate was separated by filtration. The obtained powdery precipitate is further washed with methanol and then dried at 180 ° C. for 12 hours to obtain 56.9 g of thermoplastic polyimide powder. The glass transition temperature of the obtained thermoplastic polyimide powder was 192 ° C. (measured by DSC), the logarithmic viscosity was 0.76 dl / g (measured in a mixed solvent of p-chlorophenol / phenol = 9/1 weight ratio,
0.5% concentration, performed at 35 ° C).

【００１５】かくして得られた、熱可塑性ポリイミド粉
を、４０℃のＮ−メチル−２−ピロリドン８０ｇ（濃度
２０％）に溶解させ熱可塑性ポリイミドのＮ−メチル−
２−ピロリドン溶液が得られる。また、熱可塑性ポリイ
ミド溶液を得る場合、溶媒中の熱可塑性ポリイミドの前
駆体であるポリアミド酸を化学的イミド化させても、熱
的にイミド化させてもまたそれらを併用してもよい。さ
らに、特願平０５−１２９０１２に記載されているよう
に、熱可塑性ポリイミド粉の状態を経ずに直接熱可塑性
ポリイミド溶液を得る方法でもよい。前記合成例に示す
ように、本発明の熱可塑性ポリイミドを製造する方法に
は特に限定はなく、従来公知の方法が適用できる。ま
た、複数のアミン化合物および／またはテトラカルボン
酸無水化合物の熱可塑性ポリイミドを製造する場合、共
重合化させても撹拌による混合を用いてもよい。さら
に、実用上の問題の内範囲で、接着性を高めるために各
種カップリング剤を添加したり、表面の平滑性を制御す
るために各種界面活性剤を添加したり、その他熱可塑性
ポリイミドの諸特性を変化させる添加剤やフィラーを添
加してもよい。The thermoplastic polyimide powder thus obtained was dissolved in 80 g (concentration 20%) of N-methyl-2-pyrrolidone at 40 ° C. to obtain N-methyl-
A 2-pyrrolidone solution is obtained. When obtaining a thermoplastic polyimide solution, the polyamic acid which is the precursor of the thermoplastic polyimide in the solvent may be chemically imidized, thermally imidized, or used together. Further, as described in Japanese Patent Application No. 05-129012, a method of directly obtaining a thermoplastic polyimide solution without going through the state of the thermoplastic polyimide powder may be used. As shown in the above synthesis example, the method for producing the thermoplastic polyimide of the present invention is not particularly limited, and a conventionally known method can be applied. Further, in the case of producing a thermoplastic polyimide of a plurality of amine compounds and / or tetracarboxylic anhydride compounds, they may be copolymerized or mixed by stirring. Furthermore, within the range of practical problems, various coupling agents are added to enhance the adhesiveness, various surfactants are added to control the smoothness of the surface, and various other thermoplastic polyimides are added. You may add the additive and filler which change a characteristic.

【００１６】本発明の熱可塑性ポリイミド層は、単一の
層でも、異なるガラス転移点温度を持った多層のポリイ
ミド層から成ってもよい。さらに、表面層が熱可塑性ポ
リイミドであるならば、表層下のポリイミド層に非熱可
塑性のポリイミド層を有していてる複合材料や熱可塑性
ポリイミドと非熱可塑性のポリイミドからなる傾斜材料
でもよい。The thermoplastic polyimide layer of the present invention may be a single layer or a multilayer polyimide layer having different glass transition temperatures. Further, if the surface layer is a thermoplastic polyimide, it may be a composite material having a non-thermoplastic polyimide layer in the polyimide layer below the surface layer or a gradient material composed of a thermoplastic polyimide and a non-thermoplastic polyimide.

【００１７】本発明の熱可塑性ポリイミド層を得るため
に、前記ポリイミド溶液および／または熱可塑性ポリイ
ミドの前駆体であるポリアミド酸溶液を基材上に塗布
し、乾燥・硬化させる。この熱可塑性ポリイミド層を得
る方法に特に限定はなく従来公知のコンマコーター、Ｔ
ダイ、ロールコーター、ナイフコーター、リバースコー
ター等方法を用いればよい。また、熱可塑性ポリイミド
フィルムを得るためには、前記ポリイミド溶液および／
または熱可塑性ポリイミドの前駆体であるポリアミド酸
溶液を、ａ）押出機にてフィルム成形し必要に応じて、
乾燥硬化させる方法。 ｂ）前記の塗布機を用いて離型板／フィルム上に塗布し
た後、剥離・乾燥・硬化させる方法。 ｃ）市販の非熱可塑性ポリイミドフィルムの両面に、前
記塗布機を用いて塗布後、乾燥・硬化させる方法等があ
る。さらに、必要に応じて延伸をしてもよい。In order to obtain the thermoplastic polyimide layer of the present invention, the polyimide solution and / or the polyamic acid solution which is a precursor of the thermoplastic polyimide is applied on a substrate, dried and cured. The method for obtaining this thermoplastic polyimide layer is not particularly limited, and a conventionally known comma coater, T
A die, roll coater, knife coater, reverse coater, or the like may be used. In order to obtain a thermoplastic polyimide film, the polyimide solution and / or
Alternatively, a polyamic acid solution which is a precursor of a thermoplastic polyimide is a) formed into a film by an extruder, and if necessary,
How to dry and cure. b) A method of coating on a release plate / film using the above coating machine, and then peeling, drying and curing. c) There is a method in which both sides of a commercially available non-thermoplastic polyimide film are coated with the coating machine and then dried and cured. Furthermore, you may extend | stretch as needed.

【００１８】また、前記ポリイミド溶液および／または
熱可塑性ポリイミドの前駆体であるポリアミド酸溶液の
乾燥・硬化方法に特に制限はないが、真空乾燥、熱風乾
燥、遠赤外線加熱等による方法またはこれらの方法の併
用が実用的である。また、塗布基材が金属の場合は、基
材の酸化を防止するため窒素等の不活性気体中もしくは
真空中での乾燥が望ましい。The method for drying / curing the polyimide solution and / or the polyamic acid solution which is a precursor of the thermoplastic polyimide is not particularly limited, but a method by vacuum drying, hot air drying, far-infrared heating or the like, or a method thereof is used. The combination of is practical. When the coated substrate is a metal, it is desirable to dry it in an inert gas such as nitrogen or in a vacuum to prevent the substrate from being oxidized.

【００１９】本発明によれば、上記熱可塑性ポリイミド
表面をガラス転移点温度以上に加熱した状態で、放電に
よる改質改質処理、好ましくはコロナ処理、プラズマ処
理、スパッタリング処理またはイオンプレーティング処
理等による表面改質処理（以下、表面改質処理と略す
る）を施した後、この加熱状態を保持したまま、可能な
限り素早く加熱圧着することにより、安定したかつ強固
な接着性が得られる。そのために、基材搬送用ロールま
たは加熱プレスロール上において、熱圧着直前に、熱可
塑性ポリイミド層表面を、表面処理を施し、直後に加熱
圧着することが好ましい。すなわち、基材搬送用ロール
と加熱プレスロール上において、ガラス転移点温度以上
に加熱した熱可塑性ポリイミド層表面に、コロナ処理、
プラズマ処理、スパッタリング処理またはイオンプレー
ティング処理等の放電による表面改質処理を施す手段を
備えることが好ましい。なお、本発明においては、基本
的に熱可塑性ポリイミド表面をガラス転移以上に加熱し
ておくことが前提であり、それでなくては、本発明の効
果を奏することはできないのである。なお、表面改質の
ため樹脂表面をコロナ処理等することは公知であるが、
本発明はガラス転移温度以上に保持した表面をコロナ処
理するものであり、この点、当業者の技術常識とはきわ
めてかけ離れた方法であると云わざるを得ないのであ
る。According to the present invention, in a state where the surface of the thermoplastic polyimide is heated to a glass transition temperature or higher, modification treatment by discharge, preferably corona treatment, plasma treatment, sputtering treatment or ion plating treatment, etc. After performing the surface modification treatment (hereinafter, abbreviated as surface modification treatment) by (1), stable and strong adhesiveness can be obtained by thermocompression bonding as quickly as possible while maintaining this heating state. Therefore, it is preferable that the surface of the thermoplastic polyimide layer is subjected to a surface treatment immediately before thermocompression bonding on the substrate-conveying roll or the heating press roll, and then thermocompression bonding immediately after. That is, on the substrate transfer roll and the heating press roll, on the thermoplastic polyimide layer surface heated to a glass transition temperature or higher, corona treatment,
It is preferable to provide a means for performing surface modification treatment by electric discharge such as plasma treatment, sputtering treatment or ion plating treatment. In addition, in the present invention, it is basically premised that the surface of the thermoplastic polyimide is heated above the glass transition, and otherwise, the effect of the present invention cannot be obtained. Although it is known that the resin surface is subjected to corona treatment for surface modification,
In the present invention, the surface kept at the glass transition temperature or higher is subjected to corona treatment, and in this respect, it must be said that the method is extremely different from the technical common sense of those skilled in the art.

【００２０】また、コロナ処理等で発生することあるオ
ゾンガスは、ガラス転移温度以上に保持されるため、ヒ
ーターの熱で分解され無害化可能となる効果もある。コ
ロナ処理、プラズマ処理、スパッタ処理またはイオンプ
レーティング処理等を得る方式および装置に特に制限は
なく、既知の装置さらには市販の装置を用いて何等問題
はない。放電の形態、電極の形態、直交流、放電圧力ま
たは搬送形態等は、必要に応じて選択すればよい。ま
た、電磁界の印加または帯電防止等の装置を付加するこ
とにより安定した放電処理を得られればさらに好まし
い。Further, since ozone gas which may be generated by corona treatment or the like is maintained above the glass transition temperature, it has an effect that it can be detoxified by being decomposed by the heat of the heater. There is no particular limitation on the method and apparatus for obtaining the corona treatment, plasma treatment, sputtering treatment, ion plating treatment, etc., and there is no problem with using a known apparatus or a commercially available apparatus. The form of discharge, the form of electrodes, the cross flow, the discharge pressure or the form of transport may be selected as necessary. Further, it is more preferable that a stable discharge treatment can be obtained by adding a device for applying an electromagnetic field or preventing charging.

【００２１】放電雰囲気ガスは、空気中でも、窒素中、
酸素中、水素中、二酸化炭素中、アルゴンガス中また
は、これら雰囲気ガスの混合ガスでもよい。しかしなが
ら、安全性と経済性を考慮した場合、開放形のコロナ処
理の場合は、窒素を送風した空気中がより好ましいが、
通常の空気中でも充分な表面処理効果が得られる。ま
た、密閉形減圧下で放電処理を行う場合には、窒素また
は二酸化炭素が、扱いやすく好ましく、放電を安定化さ
せる目的で、アルゴンガスを一部添加することは非常に
効果がある。The discharge atmosphere gas may be air, nitrogen,
It may be oxygen, hydrogen, carbon dioxide, argon gas, or a mixed gas of these atmosphere gases. However, in consideration of safety and economic efficiency, in the case of open corona treatment, it is more preferable to use air blown with nitrogen,
A sufficient surface treatment effect can be obtained even in ordinary air. Further, when the discharge treatment is carried out under a closed type reduced pressure, nitrogen or carbon dioxide is preferable because it is easy to handle, and partial addition of argon gas is very effective for the purpose of stabilizing the discharge.

【００２２】また、前記の表面改質処理後、可能な限り
素早く加熱圧着することにより、表面改質処理の失活現
象を回避できる。さらに、この失活現象が回避できるた
め旧来知られている表面処理強度５分の１から２０００
分の１の処理強度で充分である。さらにまた、過剰な表
面処理による表面劣化も回避できる。例えば、コロナ処
理の場合、通常、例えば、特開平４−３５６５３４によ
れば、ポリイミドフィルム表面処理には、２５００〜８
７０００ｗ・分／ｍ2 のコロナ処理強度が必要と記載さ
れているが、本発明では、５０ｗ・分／ｍ2 〜２０００
ｗ・分／ｍ2 、好ましくは、最大５００ｗ・分／ｍ2 で
充分に効果がある。After the above surface modification treatment, the deactivation phenomenon of the surface modification treatment can be avoided by thermocompression bonding as quickly as possible. Furthermore, since this deactivation phenomenon can be avoided, the surface treatment strength that has been conventionally known is 1/5 to 2000.
A processing strength of one-half is sufficient. Furthermore, surface deterioration due to excessive surface treatment can be avoided. For example, in the case of corona treatment, for example, according to Japanese Patent Laid-Open No. 4-356534, the polyimide film surface treatment is usually performed in a range of 2500-8.
It is described that a corona treatment strength of 7000 w · min / m 2 is required, but in the present invention, 50 w · min / m 2 to 2000.
w · min / m 2 , preferably up to 500 w · min / m 2 is sufficiently effective.

【００２３】本発明の加熱圧着の方法に特に制限はな
い。しかしながら、装置の価格、操作性、簡便性等を考
慮にした場合、熱ロールプレス法、真空プレス法、熱プ
レス法、オートクレブプレス法または寸動プレス法等が
好ましい。さらに、コロナ処理、プラズマ処理、スパッ
タ処理またはイオンプレーティング処理等の表面改質処
理後、可能な限り素早く加熱圧着する方がより好ましい
ため、熱ロールプレス法または寸動プレス法等の連続プ
レス法がより好ましい。The method of thermocompression bonding of the present invention is not particularly limited. However, in consideration of the price, operability, and simplicity of the apparatus, the hot roll pressing method, the vacuum pressing method, the heat pressing method, the autoclave pressing method or the inching press method is preferable. Further, it is more preferable to perform thermocompression bonding as quickly as possible after surface modification treatment such as corona treatment, plasma treatment, sputtering treatment or ion plating treatment. Therefore, continuous press method such as hot roll press method or inching press method. Is more preferable.

【００２４】図２に示したように前記の表面改質処理
後、２分以内、好ましくは１分以内、さらに好ましくは
１０秒以内、さらに可能であれば放電による改質処理と
同時に加熱圧着が可能であれば最も好ましい。実際的
に、真空プレス法、熱プレス法、オートクレーブプレス
法等のバッチ式プレス法の場合、操作性を考慮した場
合、上記処理後、１０秒以内に加熱圧着を開始するの
は、非常に困難である。一方、熱ロールプレス法や寸動
プレス法等の連続プレス法の場合、簡単に前記の表面改
質処理後、１０秒以内の加熱圧着が可能であり好まし
い。特に、熱ロールプレス法の場合は、非常に容易に前
記の表面改質処理と加熱圧着を同時にかつ連続的に行え
るため最も好ましく、前記の表面改質処理後、１秒未満
の加熱圧着が容易に得られる。As shown in FIG. 2, after the above-mentioned surface modification treatment, within 2 minutes, preferably within 1 minute, more preferably within 10 seconds, and if possible, the thermocompression bonding is performed simultaneously with the modification treatment by electric discharge. Most preferred if possible. Practically, in the case of a batch pressing method such as a vacuum pressing method, a heat pressing method and an autoclave pressing method, it is very difficult to start the thermocompression bonding within 10 seconds after the above-mentioned treatment in consideration of operability. Is. On the other hand, in the case of a continuous pressing method such as a hot roll pressing method or an inching pressing method, it is possible to easily carry out thermocompression bonding within 10 seconds after the above surface modification treatment, which is preferable. Particularly, in the case of the hot roll pressing method, it is most preferable because the surface modification treatment and the thermocompression bonding can be performed simultaneously and continuously very easily, and the thermocompression bonding for less than 1 second is easy after the surface modification treatment. Can be obtained.

【００２５】熱可塑性ポリイミドの加熱源は、特に規定
はない。操作性、簡便性さまたは価格等を考慮した場
合、外部ヒーターで直接熱可塑性ポリイミドを加熱する
方法、外部ヒーターにより熱風を発生させ、その熱風に
よって熱可塑性ポリイミドを加熱方法、遠赤外線によっ
て熱可塑性ポリイミドを加熱する方法、熱媒または誘電
加熱等で搬送ロールまたは搬送板を加熱し熱可塑性ポリ
イミドにこれら加熱媒体を直接または間接的に接触させ
ることによって加熱する方法等が好ましい。また、これ
ら複数の方法を併用することで効率的な加熱を行う方法
はさらに好ましい。The heating source of the thermoplastic polyimide is not particularly limited. In consideration of operability, convenience, price, etc., a method of directly heating the thermoplastic polyimide with an external heater, a method of generating hot air with the external heater and heating the thermoplastic polyimide with the hot air, a thermoplastic polyimide with far infrared rays And a method of heating the carrier roll or the carrier plate with a heating medium or dielectric heating to bring the heating medium into direct or indirect contact with the thermoplastic polyimide. Further, a method of performing efficient heating by using these plural methods together is more preferable.

【００２６】本発明に関わる接着形態には、熱可塑性ポ
リイミド同士の接着の他、接着性を持たない非熱可塑性
ポリイミドやテフロン等の耐熱樹脂、金属、ガラス、シ
リコンウエハー等各種半導体用基板、セラミックス等と
熱可塑性ポリイミドとの接着が可能である。以下、実施
例により本発明の実施の態様の一例を説明する。In addition to the adhesion between thermoplastic polyimides, non-thermoplastic polyimides having no adhesiveness, heat resistant resins such as Teflon, metals, glass, various semiconductor substrates such as silicon wafers, and ceramics Etc. and thermoplastic polyimide can be bonded. Hereinafter, an example of an embodiment of the present invention will be described with reference to examples.

【００２７】[0027]

【実施例】【Example】

実施例１ ３−３’−ジアミノベンゾフェノンと３，３’４，４’
−ベンゾフェノンテトラカルボン酸二無水物の重縮合体
と、Ｎ−メチルピロリドン溶媒からなる３０％のポリア
ミド酸溶液（三井東圧化学社製：商品名 ＬＡＲＣ−Ｔ
ＰＩ）を、脱脂処理した厚さ５０μｍのＳＵＳ３０４箔
に塗布し、２６０℃の窒素雰囲気下で２４時間かけて、
乾燥・イミド化させ、熱可塑性ポリイミドの塗工厚さ１
０μｍのＳＵＳ３０４／熱可塑性ポリイミド積層体を得
た。なお、ＬＡＲＣ−ＴＰＩは、ガラス転移点２４５℃
の熱可塑性ポリイミドである。Example 1 3-3′-diaminobenzophenone and 3,3′4,4 ′
A polycondensate of benzophenone tetracarboxylic dianhydride and a 30% polyamic acid solution consisting of an N-methylpyrrolidone solvent (Mitsui Toatsu Chemicals, Inc .: trade name LARC-T
PI) is applied to a degreased SUS304 foil having a thickness of 50 μm, and the coating is performed under a nitrogen atmosphere at 260 ° C. for 24 hours.
Coating thickness of thermoplastic polyimide after drying and imidization 1
A 0 μm SUS304 / thermoplastic polyimide laminate was obtained. LARC-TPI has a glass transition point of 245 ° C.
Is a thermoplastic polyimide.

【００２８】熱媒で加熱した温度２６５℃の真空プレス
板上で、２５０ｗ・分／ｍ2 のコロナ処理を施した約１
５秒後に、厚さ３５μｍの圧延銅箔の処理面と重ね合わ
せ、５℃／分で昇温し、温度２６０℃、圧力８５ｋｇｆ
／ｃｍ2 で１０分間保持し、急冷して、銅／熱可塑性ポ
リイミド／ＳＵＳ３０４積層板を得た。得られた積層板
の引き剥し強度は、１．５ｋｇｆ／ｃｍであり、均一で
膨れ・剥がれ等の欠陥のない積層板が得られた。２６０
℃の半田浴に、１分間浸漬しても、膨れ、剥がれ、変色
等異常はなかった。About 1 after a corona treatment of 250 w · min / m 2 was performed on a vacuum press plate heated at 265 ° C. with a heating medium.
After 5 seconds, the rolled copper foil having a thickness of 35 μm was superposed on the treated surface, and the temperature was raised at 5 ° C./min.
/ Cm 2 and held for 10 minutes and then rapidly cooled to obtain a copper / thermoplastic polyimide / SUS304 laminate. The peel strength of the obtained laminate was 1.5 kgf / cm, and a uniform laminate without defects such as swelling and peeling was obtained. 260
Even when immersed in a solder bath at a temperature of 1 ° C. for 1 minute, there were no abnormalities such as swelling, peeling and discoloration.

【００２９】比較例１ 実施例１と同様の銅／ＳＵＳ３０４積層板を、コロナ処
理をせずに得た。得られた積層板の引き剥し強度は、
０．３〜０．６ｋｇｆ／ｃｍのばらつきがあり、かつ一
部に膨れが観られた。２６０℃の半田浴に、５秒間浸漬
すると激しく膨れを生じた。Comparative Example 1 The same copper / SUS304 laminate as in Example 1 was obtained without corona treatment. The peel strength of the obtained laminate is
There was a variation of 0.3 to 0.6 kgf / cm, and swelling was partially observed. When it was immersed in a solder bath at 260 ° C. for 5 seconds, it swollen violently.

【００３０】実施例２ モル比率で、４：１：５からなる１，３・−ビス（３−
アミノフェノキシ）ベンゼンと４，４’−ビス（３−ア
ミノフェノキシ）ビフェニルと３，３’，４，４’−ベ
ンゾフェノンテトラカルボン酸二無水物の重縮合体の、
Ｎ，Ｎ−ジメチルアセトアミド溶媒からなる２０％のポ
リアミド酸溶液に、モル比率で０．４の無水フタル酸を
加え、１８０℃で４時間加熱し、ポリイミド溶液を得
た。この溶液を、厚さ１８μｍの圧延銅箔の処理面上に
連続的に塗布し、最高温度２６０℃の窒素雰囲気下で２
０分間かけて、連続的に乾燥・イミド化させ、熱可塑性
ポリイミドの塗工厚さ７．５μｍのロール状の銅／熱可
塑性ポリイミド積層体を得た。なお、この熱可塑性ポリ
イミドのガラス転移点温度は、１８９℃であった。以
下、積層方法については、図１を用いて説明する。Example 2 A molar ratio of 1: 3: -bis (3-: 4: 1: 5)
Of a polycondensate of aminophenoxy) benzene, 4,4′-bis (3-aminophenoxy) biphenyl and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride,
To a 20% polyamic acid solution containing N, N-dimethylacetamide solvent, 0.4 molar ratio of phthalic anhydride was added and heated at 180 ° C. for 4 hours to obtain a polyimide solution. This solution was continuously applied onto the treated surface of a rolled copper foil having a thickness of 18 μm, and the solution was applied in a nitrogen atmosphere at a maximum temperature of 260 ° C. for 2 hours.
It was continuously dried and imidized for 0 minute to obtain a roll-shaped copper / thermoplastic polyimide laminate having a thermoplastic polyimide coating thickness of 7.5 μm. The glass transition temperature of this thermoplastic polyimide was 189 ° C. Hereinafter, the stacking method will be described with reference to FIG.

【００３１】熱媒加熱により、温度２２０℃に保持した
上下対称構造の一対の加熱プレスロール１３上にて、基
材予備加熱用ヒーター１５および基材加熱用ヒーター１
７で加熱した、積層基材６１，６２である前記銅／ポリ
イミド積層体の熱可塑性ポリイミド表面に、コロナ処理
用棒状電極１１により、２２５ｗ・分／ｍ2 のコロナ処
理をそれぞれ施した約０．０２５秒後に、２００℃に加
熱した状態で、熱可塑性ポリイミド面同士を重ね合わ
せ、線圧力１７ｋｇｆ／ｃｍ、速度４ｍ／分で連続的
に、加熱圧着して、積層材６３である銅／ポリイミド積
層板を得た。また、送風口１９より２１０℃に加熱した
空気を送風し排風口２１より排出させ、コロナ放電処理
および上下積層用基材６１，６２の温度の安定を促し
た。得られた積層板の引き剥し強度は、２．７ｋｇｆ／
ｃｍであり、均一で膨れ・剥がれ等の欠陥のない積層板
が得られた。２６０℃の半田浴に、１分間浸漬しても、
膨れ、剥がれ、変色等異常は観られなかった。By heating the heating medium, the heater 15 for preheating the base material and the heater 1 for heating the base material 1 are placed on a pair of heating press rolls 13 having a vertically symmetrical structure which is maintained at a temperature of 220 ° C.
The thermoplastic polyimide surface of the copper / polyimide laminate, which is the laminate base materials 61 and 62 heated in Step 7, was subjected to a corona treatment of 225 w · min / m 2 by the corona-treatment rod electrode 11, and the amount was about 0. After 025 seconds, in a state of being heated to 200 ° C., the thermoplastic polyimide surfaces are overlapped with each other, and they are continuously thermocompression bonded at a linear pressure of 17 kgf / cm and a speed of 4 m / min to form a laminated material 63 which is a copper / polyimide laminate. I got a plate. Further, the air heated to 210 ° C. was blown from the blower port 19 and was discharged from the blower port 21 to promote the corona discharge treatment and the stabilization of the temperatures of the upper and lower laminating substrates 61 and 62. The peel strength of the obtained laminated plate is 2.7 kgf /
cm, and a uniform laminate without defects such as swelling and peeling was obtained. Even if immersed in a solder bath at 260 ° C for 1 minute,
No abnormalities such as swelling, peeling and discoloration were observed.

【００３２】比較例２ 実施例２と同様の両面銅張り積層板を、コロナ処理をせ
ずに得た。得られた積層板の引き剥し強度は、０．９ｋ
ｇｆ／ｃｍのばらつきがあり、一部に膨れが観られた。
２６０℃の半田浴に、２秒間浸漬すると一部に膨れを生
じた。Comparative Example 2 A double-sided copper-clad laminate similar to that of Example 2 was obtained without corona treatment. The peel strength of the obtained laminate is 0.9k.
There was variation in gf / cm, and blistering was observed in part.
When immersed in a solder bath at 260 ° C. for 2 seconds, some blisters occurred.

【００３３】実施例３ 実施例２と同様の両面銅張り積層板を、コロナ処理後加
熱圧着するまでの時間を変化させて、引き剥し強度を調
べた。結果を図２に示す。処理後２分を越えて加熱圧着
した場合、引き剥し強度の低下が大きく、２０分を越え
るとほとんど処理が失活することが確認された。Example 3 The same double-sided copper-clad laminate as in Example 2 was tested for peel strength by varying the time period from corona treatment to thermocompression bonding. The results are shown in Figure 2. It was confirmed that the peeling strength was greatly reduced when thermocompression bonding was performed for more than 2 minutes after the treatment, and the treatment was almost deactivated after 20 minutes.

【００３４】実施例４ 真空槽内部を、０．０１Ｐａに排気した後に、窒素を導
入して、１．５Ｐａの雰囲気を得る。この雰囲気中で、
ガラス転移点２４５℃、厚さ１００μｍの熱可塑性ポリ
イミドシート（三井東圧化学社製：商品名 レグルス）
を、遠赤外線ヒーターで両面より加熱し、約２９０℃の
状態で、１００ｋＨｚ、１．５ｋｗの交流放電を印加し
てグロー放電を得て、レグルス両面に２秒間プラズマ処
理を施し約０．０７５秒後に、上下対称構造の一対の２
９０℃に保持した加熱プレスロールに抱かせた、上下各
厚さ１８μｍの電解銅箔の処理面同士を線圧力１５ｋｇ
ｆ／ｃｍ、速度３ｍ／分で連続的に、３層加熱圧着し
て、両面銅張り積層板を得た。得られた積層板の引き剥
し強度は、２．５ｋｇｆ／ｃｍであり、均一で膨れ・剥
がれ等の欠陥のない積層板が得られた。２６０℃の半田
浴に、１分間浸漬しても、膨れ、剥がれ、変色等異常は
観られなかった。Example 4 After evacuating the inside of the vacuum chamber to 0.01 Pa, nitrogen is introduced to obtain an atmosphere of 1.5 Pa. In this atmosphere,
Thermoplastic polyimide sheet with a glass transition point of 245 ° C and a thickness of 100 µm (Mitsui Toatsu Chemical Co., Ltd .: trade name Regulus)
Is heated from both sides with a far-infrared heater, and at about 290 ° C., an AC discharge of 100 kHz and 1.5 kw is applied to obtain glow discharge, and plasma treatment is applied to both sides of the Regulus for about 2 seconds for about 0.075 seconds. Later, a pair of vertically symmetrical 2
A line pressure of 15 kg was applied to the treated surfaces of the electrolytic copper foil having an upper and lower thickness of 18 μm, which were held in a heating press roll held at 90 ° C.
A double-sided copper-clad laminate was obtained by continuously thermocompressing three layers at f / cm and a speed of 3 m / min. The peel strength of the obtained laminate was 2.5 kgf / cm, and a uniform laminate without defects such as swelling and peeling was obtained. Even when immersed in a solder bath at 260 ° C. for 1 minute, no abnormalities such as swelling, peeling and discoloration were observed.

【００３５】比較例３ 実施例４と同様の両面銅張り積層板を、プラズマ処理を
せずに得た。得られた積層板の引き剥し強度は、０．５
〜０．９ｋｇｆ／ｃｍのばらつきがあり、かつ一部に膨
れが観られた。２６０℃の半田浴に、２秒間浸漬すると
一部に膨れを生じた。Comparative Example 3 A double-sided copper-clad laminate similar to that of Example 4 was obtained without plasma treatment. The peel strength of the obtained laminate is 0.5.
There was a variation of up to 0.9 kgf / cm, and swelling was partially observed. When immersed in a solder bath at 260 ° C. for 2 seconds, some blisters occurred.

【００３６】実施例５ 真空槽内部を、０．０１Ｐａに排気した後に、二酸化炭
素を導入して、１．１Ｐａの雰囲気を得る。この雰囲気
中で、厚さ５０μｍのレグルスを、遠赤外線ヒーターで
両面より加熱し、約２９０℃の状態で、１００ｋＨｚ、
１．３ｋｗの交流放電を印加してグロー放電を得て、レ
グルスの両面に２秒間プラズマ処理を施し約０．９５後
に、２８５℃の上部加熱ロールに抱かせた厚さ１８μｍ
の圧延銅箔の処理面と、２８５℃の下部加熱ロールに抱
かせた厚さ５０μｍの非熱可塑性ポリイミドフィルム
（宇部興産社製：商品名 ユーピレクスＳＧＡ）を線圧
力２０ｋｇｆ／ｃｍ、速度２．５ｍ／分で連続的に、加
熱圧着して、銅／ポリイミド積層板を得た。得られた積
層板の引き剥し強度は、２．０ｋｇｆ／ｃｍであり、均
一で膨れ・剥がれ等の欠陥のない積層板が得られた。２
６０℃の半田浴に、１分間浸漬しても、膨れ、剥がれ、
変色等異常は観られなかった。Example 5 After evacuating the inside of the vacuum chamber to 0.01 Pa, carbon dioxide is introduced to obtain an atmosphere of 1.1 Pa. In this atmosphere, Regulus with a thickness of 50 μm is heated from both sides with a far-infrared heater, and at about 290 ° C., 100 kHz,
A glow discharge was obtained by applying an alternating current discharge of 1.3 kw, and plasma processing was performed for 2 seconds on both sides of the Regulus, and after about 0.95, a thickness of 18 μm held in an upper heating roll at 285 ° C.
The treated surface of the rolled copper foil and the non-thermoplastic polyimide film (manufactured by Ube Industries, Ltd .: Upilex SGA) with a thickness of 50 μm held in a lower heating roll at 285 ° C., linear pressure 20 kgf / cm, speed 2.5 m / Min, and continuously thermocompression bonded to obtain a copper / polyimide laminate. The peel strength of the obtained laminate was 2.0 kgf / cm, and a uniform laminate without defects such as swelling and peeling was obtained. Two
Even if immersed in a solder bath at 60 ° C for 1 minute, it swells and peels off,
No abnormalities such as discoloration were observed.

【００３７】比較例４ 実施例５と同様の銅／ポリイミド積層板を、プラズマ処
理をせずに得た。得られた積層板の引き剥し強度は、
０．２〜０．８ｋｇｆ／ｃｍのばらつきがあり、かつ一
部に膨れが観られた。Comparative Example 4 A copper / polyimide laminate similar to that of Example 5 was obtained without plasma treatment. The peel strength of the obtained laminate is
There was a variation of 0.2 to 0.8 kgf / cm, and swelling was partially observed.

【００３８】実施例６ １，３・−ビス（３−アミノフェノキシ）ベンゼンと
３，３’，４，４’−ベンゾフェノンテトラカルボン酸
二無水物の重縮合体の、Ｎ，Ｎ−ジメチルアセトアミド
溶媒からなる３０％のポリアミド酸溶液を、厚さ３５μ
ｍの圧延銅箔上に塗布し、最高温度約２５０℃の窒素雰
囲気中で３０分間かけて乾燥・イミド化させ、熱可塑性
ポリイミドの塗工厚さ６μｍからなる銅／熱可塑性ポリ
イミド積層体を得た。ちなみに、この熱可塑性ポリイミ
ドのガラス転移点温度は、１９２℃であった。Example 6 N, N-dimethylacetamide solvent of polycondensate of 1,3-bis (3-aminophenoxy) benzene and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride A 30% polyamic acid solution consisting of
m on a rolled copper foil, dried and imidized in a nitrogen atmosphere at a maximum temperature of about 250 ° C. for 30 minutes to obtain a copper / thermoplastic polyimide laminate having a thermoplastic polyimide coating thickness of 6 μm. It was Incidentally, the glass transition temperature of this thermoplastic polyimide was 192 ° C.

【００３９】熱媒で加熱した温度２２０℃の加熱ロール
上にて、前記銅／ポリイミド積層体の熱可塑性ポリイミ
ド表面に、２００ｗ・分／ｍ2 のコロナ処理を施し約２
５秒後に、２００℃に加熱した状態で、熱可塑性ポリイ
ミド面同士を重ね合わせ、約２１０℃に保持した状態
で、オートクレーブプレス機に搬入して、２℃／分で昇
温し、２８０℃、１２ｋｇｆ／ｃｍ2 で３時間加熱圧着
し、急冷後、両面銅張り積層板を得た。得られた積層板
の引き剥し強度は、１．７ｋｇｆ／ｃｍであり、均一で
膨れ・剥がれ等の欠陥のない積層板が得られた。２６０
℃の半田浴に、１分間浸漬しても、膨れ、剥がれ、変色
等異常はなかった。The thermoplastic polyimide surface of the copper / polyimide laminate was subjected to a corona treatment of 200 w · min / m 2 on a heating roll heated by a heat medium at a temperature of 220 ° C. to about 2
After 5 seconds, while being heated to 200 ° C., the thermoplastic polyimide surfaces were overlapped with each other, and while being maintained at about 210 ° C., they were loaded into an autoclave press and heated at 2 ° C./min to 280 ° C., After press-bonding with heating at 12 kgf / cm 2 for 3 hours and rapid cooling, a double-sided copper-clad laminate was obtained. The peel strength of the obtained laminate was 1.7 kgf / cm, and a uniform laminate without defects such as swelling and peeling was obtained. 260
Even when immersed in a solder bath at a temperature of 1 ° C. for 1 minute, there were no abnormalities such as swelling, peeling and discoloration.

【００４０】比較例５ 実施例６と同様の両面銅張り積層板を、コロナ処理をせ
ずに得た。得られた積層板の引き剥し強度は、０．８〜
１．２ｋｇｆ／ｃｍのばらつきがあり、かつ一部に膨れ
が観られた。２６０℃の半田浴に、５秒間浸漬すると一
部膨れを生じた。Comparative Example 5 A double-sided copper-clad laminate similar to that of Example 6 was obtained without corona treatment. The peel strength of the obtained laminate is 0.8 to
There was a variation of 1.2 kgf / cm, and swelling was partially observed. When it was immersed in a solder bath at 260 ° C. for 5 seconds, some blistering occurred.

【００４１】実施例７ 実施例２で使用したポリイミド溶液を、厚さ５０μｍの
非熱可塑ポリイミドフィルム（東レ・デュポン社性：商
品名 カプトンＨ）の両面に連続的に塗布し、最高温度
２６０℃の窒素雰囲気下で３０分間かけて、連続的に乾
燥・イミド化させ、熱可塑性ポリイミドの塗工厚さ各１
０μｍのロール状の熱可塑性ポリイミド塗工接着フィル
ムを得た。Example 7 The polyimide solution used in Example 2 was continuously applied to both sides of a non-thermoplastic polyimide film having a thickness of 50 μm (trade name: Kapton H, manufactured by Toray DuPont) and the maximum temperature was 260 ° C. Under a nitrogen atmosphere for 30 minutes to continuously dry and imidize the thermoplastic polyimide to a coating thickness of 1 each
A 0 μm roll-shaped thermoplastic polyimide-coated adhesive film was obtained.

【００４２】基材予備加熱用の遠赤外線ヒーターで約２
３０℃に加熱保持させたの前記熱可塑性ポリイミド塗工
接着フィルムの両表面に、２００ｗ・分／ｍ2 のコロナ
処理をそれぞれ施し約０．０８秒後に、２３０℃に加熱
した状態で、熱媒加熱にて、温度２２５℃に保持した上
下対称構造の一対の加熱プレスロール上に、上部ロール
に厚さ３５μｍの圧延銅箔の処理面を、下部ロールに脱
脂、表面粗化処理した厚さ５０μｍの圧延したアルミニ
ウム箔をそれぞれ処理面が前記の熱可塑性ポリイミド塗
工接着フィルムに接するように抱かせて、線圧力２０ｋ
ｇｆ／ｃｍ、速度２ｍ／分で連続的に、３層加熱圧着し
て、銅／ポリイミド／アルミニウム積層板を得た。得ら
れた積層板は、銅／ポリイミド間の引き剥し強度が１．
８ｋｇｆ／ｃｍ、アルミニウム／ポリイミド間の引き剥
し強度が２．３ｋｇｆ／ｃｍであり、均一で膨れ・剥が
れ等の欠陥のない積層板が得られた。２６０℃の半田浴
に、１０秒間浸漬しても、膨れ、剥がれ、変色等異常は
なかった。Approximately 2 with a far infrared heater for preheating the substrate
Both surfaces of the thermoplastic polyimide-coated adhesive film which had been heated and held at 30 ° C. were subjected to corona treatment of 200 w · min / m 2 respectively, and after about 0.08 seconds, they were heated to 230 ° C. in a heating medium. On a pair of heating press rolls having a vertically symmetrical structure which is maintained at a temperature of 225 ° C. by heating, the upper roll has a treated surface of a rolled copper foil having a thickness of 35 μm, and the lower roll has a degreased surface-roughened thickness of 50 μm. Hold the rolled aluminum foils of the above in such a manner that their treated surfaces are in contact with the above-mentioned thermoplastic polyimide-coated adhesive film, and apply a linear pressure of 20 k.
The copper / polyimide / aluminum laminate was obtained by continuously thermocompressing three layers at gf / cm and a speed of 2 m / min. The resulting laminate had a peel strength between copper / polyimide of 1.
8 kgf / cm, the peel strength between aluminum / polyimide was 2.3 kgf / cm, and a laminate having a uniform and free from defects such as swelling and peeling was obtained. Even when immersed in a solder bath at 260 ° C. for 10 seconds, there were no abnormalities such as swelling, peeling and discoloration.

【００４３】実施例８ 実施例６で使用したポリアミド酸溶液を、スピンコート
にてシリコンウェハー上に塗布し、２５０℃で３０分乾
燥して、厚さ５μｍの熱可塑性ポリイミドの塗布膜を得
た。このシリコンウェハー／熱可塑性ポリイミド塗布膜
積層体を真空槽内部に設置した加熱板上にシリコンウェ
ハーを接触させるように置き、０．０１Ｐａに排気した
後に、水素を導入して、０．８Ｐａの雰囲気を得る。こ
の雰囲気中で、加熱板にてシリコンウェハー／熱可塑性
ポリイミド塗布膜積層体を約２４０℃に保持した状態
で、１００ｋＨｚ、１．０ｋｗの交流放電を印加してグ
ロー放電を得て、２秒間プラズマ処理を施し約９０秒後
に、加熱板にて約２６０℃に予備加熱したサファイアガ
ラスと積層し、熱プレス機にて、２５０℃、１２ｋｇｆ
／ｃｍ2 で１０分間加熱圧着して、積層物を得た。剥離
を試みたが、シリコンウェハーおよびサファイアガラス
が砕けてしまう程強固に接着していた。Example 8 The polyamic acid solution used in Example 6 was applied onto a silicon wafer by spin coating and dried at 250 ° C. for 30 minutes to obtain a thermoplastic polyimide coating film having a thickness of 5 μm. . This silicon wafer / thermoplastic polyimide coating film laminate is placed on a heating plate placed inside a vacuum chamber so that the silicon wafer is in contact with it, and after evacuating to 0.01 Pa, hydrogen is introduced and an atmosphere of 0.8 Pa is set. To get In this atmosphere, while maintaining the silicon wafer / thermoplastic polyimide coating film laminate at about 240 ° C. with a heating plate, an AC discharge of 100 kHz and 1.0 kw was applied to obtain a glow discharge, and a plasma was generated for 2 seconds. About 90 seconds after the treatment, it was laminated with sapphire glass preheated to about 260 ° C with a heating plate, and heated at 250 ° C and 12 kgf with a hot press machine.
The laminate was obtained by thermocompression bonding at 10 cm / cm 2 for 10 minutes. An attempt was made to peel it off, but the silicon wafer and the sapphire glass were bonded so strongly that they were broken.

【００４４】[0044]

【発明の効果】本発明従えば、熱可塑性ポリイミドの強
固で安定した接着が得られ工業的に極めて価値のあるも
のであると云わざるを得ない。Industrial Applicability According to the present invention, it can be said that a strong and stable adhesion of a thermoplastic polyimide is obtained, which is industrially extremely valuable.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明を実施するための装置の一例の説明図。FIG. 1 is an explanatory view of an example of an apparatus for carrying out the present invention.

【図２】コロナ処理後加圧圧着までの時間と引き剥し強
度の関係の一例を示すグラフFIG. 2 is a graph showing an example of the relationship between the time until pressure-bonding after corona treatment and the peel strength.

【符号の説明】[Explanation of symbols]

１１ コロナ処理用棒状電極 １３ 加熱プレスロール １５ 基材予備加熱ヒーター １７ 基材加熱ヒーター １９ 送風口 ２１ 排風口 ５１ 上部繰り出し軸 ５２ 下部繰り出し軸 ５３ 巻取り軸 ５５ ガイドロール ６１ 上部積層用基材 ６２ 下部積層用基材 ６３ 積層材 11 Corona Treatment Rod Electrode 13 Heating Press Roll 15 Preliminary Substrate Heater 17 Substrate Heating Heater 19 Blower 21 Exhaust Vent 51 Upper Feeding Axis 52 Lower Feeding Axis 53 Winding Shaft 55 Guide Roll 61 Upper Laminating Base 62 Lower Laminating material 63 Laminated material

───────────────────────────────────────────────────── フロントページの続き (72)発明者 相沢 浩一 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 宍戸 重之 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 津嶋 敬章 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 小島 一記 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koichi Aizawa, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Shigeyuki Shishido, 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Within the Chemicals Co., Ltd. (72) Inventor Keisho Tsushima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Ikki Kojima 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemicals Within

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 ガラス転移点温度以上に加熱した熱可塑
性ポリイミド層表面に、放電による表面改質処理を施
し、かつ該処理を施した熱可塑性ポリイミド層表面をガ
ラス転移点温度以上保持した状態にて加熱圧着すること
を特徴とする熱可塑性ポリイミドの接着方法。1. A surface modification treatment by electric discharge is applied to a surface of a thermoplastic polyimide layer heated to a glass transition temperature or higher, and the surface of the treated thermoplastic polyimide layer is maintained to a temperature higher than the glass transition temperature. A method for adhering a thermoplastic polyimide, which comprises heat-pressing with heat. 【請求項２】 放電による表面改質処理がコロナ処理、
プラズマ処理、スパッタリング処理またはイオンプレー
ティング処理から選択される請求項１記載の方法。2. The surface modification treatment by electric discharge is corona treatment,
The method according to claim 1, wherein the method is selected from plasma treatment, sputtering treatment, and ion plating treatment. 【請求項３】 基材搬送用ロールまたは加熱プレスロー
ル上において、熱圧着直前に、熱可塑性ポリイミド層表
面を、請求項１または２に記載した表面処理を施す熱可
塑性ポリイミドの接着方法。3. A method for adhering a thermoplastic polyimide, wherein the surface of the thermoplastic polyimide layer is subjected to the surface treatment as set forth in claim 1 or 2 immediately before thermocompression bonding on a base material conveying roll or a hot press roll. 【請求項４】 少なくとも、基材搬送用ロールと加熱プ
レスロールとを備える熱可塑性ポリイミド層の接着装置
であって、該基材搬送用ロールと加熱プレスロール上に
おいて、ガラス転移点温度以上に加熱した熱可塑性ポリ
イミド層表面に、放電による表面改質処理を施す手段を
さらに備えて、熱圧着直前に該熱可塑性ポリイミド層表
面を表面改質処理し、かつ該処理を施した熱可塑性ポリ
イミド層表面をガラス転移点温度以上保持した状態にて
加熱圧着しうるようにした熱可塑性ポリイミドの接着装
置。4. A device for adhering a thermoplastic polyimide layer, which comprises at least a substrate-conveying roll and a heating press roll, wherein the substrate-conveying roll and the heating press roll are heated to a glass transition temperature or higher. The surface of the thermoplastic polyimide layer is further provided with a means for performing a surface modification treatment by electric discharge, the thermoplastic polyimide layer surface is surface-modified immediately before thermocompression bonding, and the thermoplastic polyimide layer surface is subjected to the treatment. A thermoplastic polyimide bonding apparatus capable of being heated and pressure-bonded in a state where the temperature is maintained at a glass transition temperature or higher. 【請求項５】 放電による表面改質処理を施す手段が、
コロナ処理、プラズマ処理、スパッタリング処理または
イオンプレーティング処理から選択される手段である請
求項４記載の装置。5. A means for performing surface modification treatment by electric discharge,
The apparatus according to claim 4, which is a means selected from corona treatment, plasma treatment, sputtering treatment, or ion plating treatment.
JP21715793A 1993-09-01 1993-09-01 Thermoplastic polyimide bonding method and apparatus Expired - Lifetime JP3360753B2 (en)

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WO1999051422A1 (en) * 1998-04-07 1999-10-14 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Adhesive-free polymer component joints for producing closed micro- and nano-channel structures
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