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TWI359076B - Metallic laminate and method of making the same - Google Patents

Metallic laminate and method of making the same Download PDF

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Publication number
TWI359076B
TWI359076B TW094139211A TW94139211A TWI359076B TW I359076 B TWI359076 B TW I359076B TW 094139211 A TW094139211 A TW 094139211A TW 94139211 A TW94139211 A TW 94139211A TW I359076 B TWI359076 B TW I359076B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
polymer film
crystal polymer
film
thermal expansion
Prior art date
Application number
TW094139211A
Other languages
English (en)
Other versions
TW200621480A (en
Inventor
Minoru Onodera
Tadao Yoshikawa
Original Assignee
Kuraray Co
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 Kuraray Co filed Critical Kuraray Co
Publication of TW200621480A publication Critical patent/TW200621480A/zh
Application granted granted Critical
Publication of TWI359076B publication Critical patent/TWI359076B/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • 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
    • 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
    • B29C65/44—Joining a heated non plastics element to a plastics element
    • 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
    • B29C66/40—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
    • 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
    • B29C66/832—Reciprocating joining or pressing tools
    • B29C66/8322—Joining or pressing tools reciprocating along one axis
    • B29C66/83221—Joining or pressing tools reciprocating along one axis cooperating reciprocating tools, each tool reciprocating along one axis
    • 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
    • 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
    • B29C66/91421—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 joining tools
    • 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
    • B29C66/91931—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 the fusion temperature or melting point of the material of one 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
    • B29C66/90—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
    • B29C66/91931—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 the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91933—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 the fusion temperature or melting point of the material of one of the parts to be joined higher than said fusion 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
    • B29C66/90—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
    • B29C66/91931—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 the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91935—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 the fusion temperature or melting point of the material of one of the parts to be joined lower than said fusion temperature
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • 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
    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • 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
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • 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
    • B29C66/03—After-treatments in the joint area
    • B29C66/034—Thermal after-treatments
    • 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
    • B29C66/73111—Thermal expansion coefficient
    • 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
    • B29C66/735—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 extensive physical properties of the parts to be joined
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2305/55—Liquid crystals
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Description

1359076 * > * * 九、發明說明： 【發明所屬之技術領域】 . 本發明係關於一種覆金屬積層板及其製法，其中，該覆 _ 金屬積層板係使用由可形成光學異i向性熔融相之熱可塑 ' 性聚合物（以下，稱此爲熱可塑性液晶聚合物）而成的薄 膜（以下，稱此爲熱可塑性液晶聚合物薄膜）》更詳言之， 根據本發明之覆金屬積層板，不僅具有源自熱可塑性液晶 聚合物薄膜之優異的低吸濕性、耐熱性、耐藥品性與電特 φ 性，也具有優異的尺寸安定性，作爲可撓性配線板或半導 體構裝用電路基板材料等。 【先前技術】 以手機通訊爲主，攜帶用電子儀器之小型化與輕量化之 要求強烈’對於高祖度構裝之期待更趨強烈。因而，朝向 配線板之多層化、配線間距之狹幅化、通孔之微細化、ic 構裝之小型多插針化演進，針對電容器或電阻之被動元 件’也朝向合併小型化與表面構裝化發展。尤其，將此等 Φ 被動元件直接形成於印刷配線板表面或內部的技術，以及 將1C構裝等主動元件直接構裝於印刷配線板表面的技 術’不僅能夠達成高密度構裝，也能夠期待信賴性之提昇。 * 因此，配線板之尺寸安定性，亦即，於導體電路形成前後 . 以及爲了構裝該主動元件或被動元件之加熱製程前後尺寸 變化率的要求水準將變高，再者，消除其異方向性之必要 性也開始提高。 另一方面’具有極佳的低吸濕性、耐熱性'耐藥品性與 電特性之熱可塑性液晶聚合物薄膜係作爲使印刷配線板之 1359076 » . · 信賴性得以提昇的絕緣基板材料，急速朝向其商品化發展。 進行熱可塑性液晶聚合物薄膜與金屬片材之層壓而製 • 造覆金屬積層板，習知使用真空熱壓縮裝置進行。此方法 . 係將熱可塑性液晶聚合物薄膜與金屬片材置於二片熱平盤 之間’於真空狀態下進行加壓黏著的方法（真空熱壓縮積 層法）。爲了利用此方法而得到尺寸安定性良好的覆金屬 積層板，必須使作爲原料使用的熱可塑性液晶聚合物薄膜 之縱橫熱膨脹係數接近金屬片材之熱膨脹係數，藉此，能 φ 夠消除尺寸安定性之異方向性。但是，由於真空熱壓縮積 層法係一種片狀製造方法，其每一片覆金屬積層板耗費材 料設置時間、一次壓縮時間、壓縮後之材料取出時間等之 製造時間，生產速度變慢。若欲加速生產速度而同時能夠 製造數片，設法改善設備的話，因爲設備將大型化而使設 備費變高，導致高成本化。因而，尋求硏發能夠解決此問 題之連續製造方法。 另一方面，爲了充分發揮熱可塑性液晶聚合物薄膜之特 Φ 徵，進一步爲了發揮成本上之優異性，必須連續使其達成 與金屬片材之積層，迄今已於各種領域上進行探討。例如， 習知針對爲了改善與金屬片材接著力之條件或機械強度改 善之技術（例如，專利文獻1 )。再者，習知針對熱可塑 性液晶聚合物薄膜之處理方法，尤其針對熱可塑性液晶聚 合物薄膜的加熱尺寸變化率之技術（例如，專利文獻2)。 專利文獻1 :日本專利特開平5-42603號公報 專利文獻2 :日本專利特開平8-90570號公報 【發明內容】 1359076 發明所欲解決之技術問顆 但是，於專利文獻1中，並未揭示針對熱可塑性液晶聚 • 合物薄膜尺寸安定性之改善，於專利文獻2中，也並未揭 . 示針對覆金屬積層板之特性。而且，根據該文獻技術的話， 難以連續而穩定地得到等方向性與尺寸安定性良好的覆金 屬積層板。亦即，於加熱滾筒間，使熱可塑性液晶聚合物 薄膜與金屬片材予以壓黏之情形，藉由於此等材料之捲出 機與加熱滾筒所形成的運送空間中，至少因本身重量施加 φ 於薄膜長軸方向（拉伸方向）之張力，以及於加熱滾筒間 將推壓施加於薄膜長軸方向，熱可塑性液晶聚合物薄膜分 子便容易於長軸方向上形成定向。其結果，便難以得到等 方向性與尺寸安定性良好的覆金屬積層板》 解決問題之技術手段 本發明之目的在於提供一種覆金屬積層板及其製法，其 係於使用加熱滾筒之連續製造所導致的高生產性之下，等 方向性、外觀上、與金屬片材之接著力以及尺寸安定性均 0 爲優異的。 爲了達成該目的，有關本發明之覆金屬積層板之製法， 其係於熱可塑性液晶聚合物薄膜之至少一側表面製造已接 合金屬片材的方法；該製法包含：第1步驟，於加熱滾筒間， 使熱可塑性液晶聚合物薄膜與該金屬片材予以壓黏，而熱可 塑性液晶聚合物薄膜長軸方向之熱膨脹係數cu( xlO— 6Cm/cm/ °C )係於該薄膜之厚度T ( μΐΏ )、厚度係數yS ( Χΐ/μιη/°(：) 與異方向性係數 7 ( xlO_ 6cm/cm/°C )之關係中，’滿足cu 召丁+ 7之式，同時，厚度係數石於-0.08〜-0.01之範圍 (S) 1359076 內（-0.08各冷S -0.01)，相對於該金屬片材之熱膨 αΜ，異方向性係數 τ 於+6~+l〇(xl〇-6cm/cm/°C) • 內（αΜ + 6各T各αΜ+10) ’並且，相對於該金屬片材之 . 係數αΜ，該薄膜寬度方向之熱膨脹係數ατ於-2〜+ 3 6cm/cm/°C )之範圍內（αΜ-2$ατ$αΜ + 3);及第 2 步驟 可塑性液晶聚合物薄膜熔點以下之加熱處理溫度， 第1步驟所得到的覆金屬積層板之加熱處理。 如上所述，於加熱滾筒間，使連續成型之熱可塑 φ 聚合物薄膜與金屬片材予以壓黏之際’，藉由對此等 加於薄膜長軸方向之張力以及於加熱滾筒間施加於 軸方向之推壓，雖然於熱可塑性液晶聚合物薄膜中 軸方向之熱膨脹特性的異方向性將發生，但是，於 中之第1步驟，此異方向性係藉由使用薄膜長軸（ 向與寬度（橫）方向之熱膨脹係數cu、ατ爲特定範 可塑性液晶聚合物薄膜，使張力連續施加於薄膜長 而於加熱滾筒間予以壓黏之情形，能夠藉由分子方 φ 向於垂直薄膜長軸方向的熱可塑性液晶聚合物薄膜 定向特性而相互抵消，因爲熱可塑性液晶聚合物薄 脹係數之異方向性被消除，可以穩定地得到等方向 異的、外觀上也爲優異的覆金屬積層板。再者，藉 定之溫度條件下，使用此覆金屬積層板而進行加熱 可以得到與金屬片材之接著力爲大的’具有所要求 變化率之尺寸安定性爲優異的覆金屬積層板。進行 式，使用加熱滾筒之連續製造所導致的高生產性之 以得到等方向性、外觀上 '與金屬片材之接著力以 脹係數 之範圍 熱膨脹 (xlO-，於熱 進行於 性液晶 材料施 薄膜長 ，向長 本發明 縱）方 圍之熱 軸方向 向上定 之分子 膜熱膨 性爲優 由於特 處理， 之尺寸 如此方 下，可 及尺寸 1359076 安定性均爲優異的覆金屬積層板。 雖然使用於本發明之熱可塑性液晶聚合物薄膜原料M 無特別之限定’其具體例，可列舉：分類成以下所列舉的 (1 ) ~ ( 4 )之化合物以及其衍生物所衍生的習知向熱性液 晶聚酯與向熱性液晶聚酯醯胺。但是，爲了得到可形成光 學異方向性熔融相之聚合物，當然對於各種原料化合物之 組合具有適當之範圍。 (1 )芳香族或脂肪族二羥基化合物（代表例參照表1 )
〔表1〕
芳香族或脂肪族二羥基化合物代表例的化學構造式 H0-O-0H ( X係氫原子或鹵素原子、低級烷基 苯基等之基） 观 H0
-0H H0"
HO
OH HO.
OH —CH2—、一S—等之 HO (CH2) nOH (n 係 2~i2 之整數） (§) -10- 1359076
(2 )芳香族或脂肪族二羧酸（代表例參照表2) 〔表2〕
(3 )芳香族羥基羧酸（代表例參照表3) 〔表3〕
1359076 (4)芳香族二胺、芳香族羥基胺或芳香族胺基羧酸（代 表例參照表4 ) 〔表4〕 芳香族二胺*芳香族羥基胺或芳香族胺基羧酸代表例的化學構造式 ¥~〇-°H η,ν-Q^coob 從此等原料化合物所得到的熱可塑性液晶聚合物代表 例’可列舉：具有表5所示之構造單位的共聚物（a )〜（e )。
_熱可塑性液晶聚合物代表例 (a) 共聚物
共聚物 "°~0~c〇 _—〇c_〇_co'—^-ΟΌ-0" ^ J L J L J r Τ ~'〇-Ο~γ—C^-0" J 共聚物 (Y係一0—、一Cft—、一s—等之基） 另外’使用於本發明之熱可塑性液晶聚合物的熔點，於 得到薄膜所要求之耐熱性與加工性之目的下，較；t具有Μ 約200~400°C範圍內，尤其於約250〜3 50°C範圍內之培點， 1359076 但是’基於薄膜製造之觀點，較宜具有較低之熔點。因而， 更高之耐熱性或熔點爲必要之情形下，藉由進行暫時所得 • 到的薄膜之加熱處理，能夠提高至所要求之耐熱性或熔 點。若說明一加熱處理條件例的話，即使暫時所得到的薄 膜熔點爲283 °C之情形，於260°C進行5小時加熱的話，熔 點成爲320°C。 使用於本發明之熱可塑性液晶聚合物薄膜可以進行該 熱可塑性液晶聚合物薄膜之擠壓成型而得到。此時，雖然 φ 可以使用任意之擠壓成型法，習知之T模頭製膜拉伸法、 積層板拉伸法、吹塑法等工業上爲有利的》尤其，吹塑法 的話，不僅可以施加應力於薄膜機械軸方向（該薄膜之長 軸方向）（以下，簡稱MD方向），也可以施加應力於與 MD方向成垂直的方向（該薄膜之橫向）（以下，簡稱TD 方向），可得到採取MD方向與TD方向上之機械性質與熱 性質均衡的薄膜》 該熱可塑性液晶聚合物薄膜必須具有：該薄膜長軸方向 φ 之熱膨脹係數〇u ( xl0_ 6cm/cm/°C )係於該薄膜之厚度T (μιη )、厚度係數召（xlMm/°C )與異方向性係數7 (X 10_6cm/cm/°C )之關係中，滿足yST+ r之式，同時， 厚度係數/3於- 0.08〜-0.01之範圍內^(-0.085冷S-0.01)， 相對於該金屬片材之熱膨脹係數αΜ，異方向性係數r於 + 6~+10(xl0_6cm/cm/°C )之範圍內（aM + 6S r $αΜ+1〇)， 並且，相對於該金屬片材之熱膨脹係數αΜ，該薄膜寬度方 向之熱膨脹係數ατ於- 2~ + 3( xlO_6cm/cm/°C )之範圍內（αΜ-2 S ατ S (xm + 3 )。根據該薄膜之適用領域所必需之熱膨脹係
-13- 1359076 數係於該範圍內各不相同。雖然，此範圍之熱可塑性液晶 聚合物薄膜作爲薄膜之該MD方向與TD方向上之機械性質 . 與熱性質爲均衡的，實用上不致於發生問題，如後所述， 具有使作爲覆金屬積層板時之等方向性、外觀上、與金屬 片材之接著力以及尺寸安定性均爲良好的優點。 其中，所謂該薄膜之熱膨脹係數係指從室溫至該薄膜變 形溫度附近，以溫差除以固定升溫速度進行加熱時膨脹率 的係數，如下所示而算出。 φ 首先，使用習知之熱機械分析裝置，將剪切成薄長方形 之薄膜一端予以固定，並將拉伸載重賦與另一端，量測固 定升溫速度下加熱時之膨脹量。例如，若將薄膜拉伸載重 方向之長度設爲L0(mm)、將加熱時薄膜之長度設爲L1 (mm )、將加熱溫度設爲T2 ( °C )、將室溫設爲T1 ( °C ) 的話，熱膨脹係數〇u能夠利用下式而算出。 aL = 〔 ( Ll-LO ) / ( T2-T1 ) 〕/LO ( x 1 0 _ 6cm/cm 厂C ) 於本發明中，採用將L0設爲20mm、將T2設爲150°C、 φ 將T1設爲25°C、將拉伸載重設爲lg。 本發明該薄膜長軸（MD)方向之熱膨脹係數ou( xl(T 6cm/cm/ °C)係於該薄膜之厚度Τ(μιη)、厚度係數冷（χ1/μηι/°(：)與 異方向性係數7 ( X 1 0_ 6cm/cm/°C )之關係中，滿足〇u=)ST + 7式。此式已考量薄膜長軸方向之熱膨賬係數下之薄膜 厚度。 該厚度係數 β 必須於-0.08~-0.01 之範圍內 (-0.08盔0S-0.01)。於厚度係數沒>-0.01或冷<-0.08 之情形下，所得到的覆金屬積層板之尺寸安定性爲不良 ⑧ -14- 1339076 的，MD與TD之異方向性成爲大的。尤其’高尺寸安定性 爲必要的用途領域之情形，厚度係數石較宜爲S /3 S •0.02 ° 相對於金屬片材之熱膨脹係數αΜ ’該異方向性係數r必 須於+6~+10(><10_6£：111/£：111/°(：)之範圍內（“ + 6$7$〇^+10)。 r < αΜ + 6或r > αΜ+10之情形下，所得到的覆金屬積層板之 尺寸安定性爲不良的，MD與TD之異方向性成爲大的。例 如，金屬片材爲銅箔之情形下，因爲銅之熱膨脹係數爲18 (xlO' 6cm/cm/°C )，異方向性係數r爲24 S r彡28 ;鋁箔 之情形下，因爲鋁之熱膨脹係數爲23 ( xl0_ 6cm/chW°C )， 29彡 7 $ 33。 相對於金屬片材之熱膨脹係數αΜ，本發明該薄膜寬度 (TD )方向之熱膨脹係數ατ必須於-2〜+ 3 ( xHT 6cm/cm/°C ) 之範圍內（αΜ-2$ατ$αΜ + 3)。例如，金屬片材爲銅箔之情 形下，16彡ατ$ 21 ;銅箔之情形下，21 S cuS 26。熱膨脹係 數ατ更佳爲（ΧΜ$ατ各ctM + 2。 本發明之熱可塑性液晶聚合物薄膜之厚度T較宜於 10〜250μπι之範圍內（10STS250)。但是，將熱可塑性液 晶聚合物薄膜作爲電絕緣性材料使用之覆金屬積層板，並 作爲可撓性印刷配線板使用之情形下，其薄膜之膜厚更佳 於20~100μιη之範圍內，尤以20~50μιη之範圍內特別理想。 薄膜厚度爲過薄之情形下，由於薄膜之剛性或強度變小， 將電子零件構裝於所得到的印刷配線板之際，因加壓而變 形，配線之位置精確度將惡化而成爲不良之原因。還有， 也可以將潤滑劑、抗氧化劑等之添加劑或塡充劑摻入薄膜 ⑧ -15- 1359076 中ο 【發明之實施態樣】 .· 第2圖係用於有關本發明之覆金屬積層板的熱可塑性液 . 晶聚合物薄膜，顯示製造該薄膜長軸（縱）方向與寬度（橫） 方向之熱膨脹係數cu、（XT爲特定範圍之熱可塑性液晶聚合 物薄膜之一裝置例。此裝置係使從捲出滾筒11捲出的熱可 塑性液晶聚合物薄膜12,與從捲出滾筒13捲出的如鋁箔般 之載體1 4相重疊的狀態下，送入加熱滾筒1 5，經由熱壓黏 φ 使其接合而作成積層板2〇。 此加熱滾筒15係使用一對加熱金屬滾筒或是一對耐熱 橡膠滾筒與加熱金屬滾筒。於第2圖之積層板20之製造 中.，使用一對耐熱橡膠滾筒51與加熱金屬滾筒52,於薄膜 1 2側配置耐熱橡膠滾筒5 1、於載體1 4側配置加熱金屬滾 筒5 2。藉由此裝置，能夠防止薄膜1 2不必要地附著於加熱 金屬滾筒5 2。 之後，將積層板20送入加熱處理裝置16，從較熱可塑 φ 性液晶聚合物薄膜1 2之熔點更低1 〇°C之溫度至較熔點更 高l〇°C之溫度範圍內進行加熱處理。如此方式，藉由從較 熱可塑性液晶聚合物薄膜1 2之熔點更低1 0°C之溫度至較 熔點更高1 0°C之溫度範圍內連續進行熱處理，熱可塑性液 ' 晶聚合物薄膜12之熱膨脹係數將提高，之後，藉由利用上 下二個剝下滾筒1 7、1 7，將積層板20予以剝下，使熱可塑 性液晶聚合物薄膜2與載體1 4得以分離，可以得到已調整 成所要求之熱膨脹係數的熱可塑性液晶聚合物薄膜2。進 行如此方式，可以得到具有該特定範圍之薄膜長軸方向與 ⑧ -16- 1359076 % 寬度方向之熱膨脹係數CU、ατ的熱可塑性液晶聚合物薄膜 2。加熱處理裝置1 6能夠利用例如熱風循環爐、熱滾筒、 . 陶瓷加熱器等之習知裝置。 . 第1圖係顯示實施有關本發明覆金屬積層板連續製造方 法之一裝置例。此裝置係於第1步驟中，使從捲出滾筒1 捲出之具有第2圖所製造的該特定範薄膜長軸方向與寬度 方向之熱膨脹係數cu、ατ的熱可塑性液晶聚合物薄膜2, 與從捲出滾筒3捲出的$卩銅箔般之金屬片材4相重疊的狀 φ 態下’送入加熱滾筒5,經由熱壓黏使其接合而作成單面覆 金屬積層板10。此加熱滾筒5係使用一對加熱金屬滾筒或 是一對耐熱橡膠滾筒與加熱金屬滾筒，於此單面覆金屬積 層板10之製造中，與上述同樣的，使用一對耐熱橡膠滾筒 51與加熱金屬滾筒52。 於第1步驟中，覆金屬積層板10係使熱可塑性液晶聚 合物薄膜2與金屬片材4相重疊的狀態下，藉由將張力施 加於薄膜長軸方向後送入加熱滾筒5，同時，於加熱滾筒 φ 5 1、5 2間將推壓施加於薄膜長軸方向，經由熱壓黏使其接 合後予以層壓。向此時熱可塑性液晶聚合物薄膜2中所發 生的薄膜長軸方向之熱膨脹特性的異方向性係藉由使用具 有該特定範薄膜長軸方向與寬度方向之熱膨賬係數cu、aT 的熱可塑性液晶聚合物薄膜2,使張力連續施加於薄膜長軸 方向而於加熱滾筒51、52間予以壓黏之情形下，藉由分子 方向上定向於垂直於薄膜長軸方向的熱可塑性液晶聚合物 薄膜2之分子定向特性而相互抵消。進行如此方式，因爲 熱可塑性液晶聚合物薄膜2之熱膨脹係數的異方向性被消 -17- 1359076 , * . 除，可以穩定地得到等方向性爲優異的、外觀上也爲優異 的覆金屬積層板10。 .· 此裝置係於第2步驟中，於熱可塑性液晶聚合物薄膜2 . 熔點以下之加熱處理溫度，將第1步驟所得到的覆金屬積 層板10送入加熱處理裝置6後，進行加熱處理。藉此，與 金屬片材4之接著力爲大的，可以得到具有所要求之尺寸 變化率之尺寸安定性優異的覆金屬積層板10。基於更增大 與金屬片材4接著力之目的下，加熱處理溫度較宜較該薄 φ 膜2之熔點更低5~20°C之溫度範圍》加熱處理溫度超過熔 點溫度的情形下，發生發泡現象或明顯之熱膨脹係數變 化’將有無法得到既定品質之情形。加熱處理溫度較熔點 更低20°C以下溫度的情形下，無助於與金屬片材4接著力 的增加，視金屬片材4之種類而定，將有無法滿足所要求 之接著力的情形。與上述同樣地，加熱處理裝置6能夠利 用熱風循環爐、熱滾筒、陶瓷加熱器等。經歷此第2步驟 後，覆金屬積層板10將被捲取滾筒7捲取成滾筒狀。 φ 以下，藉由實施例詳細說明本發明，但是，本發明並不 因此等貫施例而有任何之限制。還有，於下列實施例中， 熱可塑性液晶聚合物薄膜之熔點、積層板之接著強度與尺 ' 寸安定性係利用下列方法進行測定的。 • ( 1 )熔點 熔點係利用微分掃描熱析儀，觀察薄膜之熱行爲後得 到。亦即’以20°C /分鐘之速度進行測試薄膜之升溫，使其 完全熔融之後，以50°C/分鐘之速度，使熔融物急冷至5〇 °C ’再將以20°C /分鐘之速度進行升溫時所出現之吸熱波峰 ⑧ -18- 1359076 的位置作爲薄膜之熔點而加以記錄。 (2 )接著強度 • 從積層板製作1 .5cm寬之剝離測試片，利用雙面黏著膠 . 帶而將其薄膜層固定於平板，遵循JIS C 5016，利用18 0。 法’測定以50mm/分鐘之速度進行金屬箔剝除時的接著強 度（kg/cm)。 (3 )尺寸安定性 尺寸安定性係遵循IPC-TM-6502.2.4進行測定。 • 參考例1 利用；羥基安息香酸與6-羥基-2-苯甲酸之共聚物，一 面進行熔點爲2 8 0 °C之液晶聚合物的熔融擠壓，控制縱與橫 之拉伸比’並一面利用吹塑成型法而得到膜厚爲2 5、5 0、 100與225μπι之薄膜，使已塗布脫模材30μιη厚的鋁箔相重 疊’以20kg/cm2進行260°C加熱金屬滾筒與耐熱橡膠滾筒 間的熱壓黏後，使各膜厚之薄膜MD方向的熱膨脹係數〇u 成爲下述之既定値般之’於已設定溫度之熱處理爐內進行 鲁 30秒鐘熱處理。接著，於氮氣環境中之烘箱內，於260°C 進行6小時熱處理後，剝下鋁箔後得到如下特性之薄膜： 熔點爲305°C，所有膜厚之TD方向的熱膨脹係數αι_均爲 19xl(T 6cm/cm/°C，各別之厚度下’ MD方向的熱膨脹係數cu 分別爲 25.3、24.5、23 與 19.3x10 — 6cm/cm/t：(石=-0 03、 r = 26)。將如此之熱可塑性液晶聚合物薄膜設爲A。
於參考例1中’例如’使熱可塑性液晶聚合物薄膜A與 銅箔（金屬片材）予以相層壓之情形，因爲薄膜之厚度T 爲25、50、100、225μπι’滿足10ST^250;因爲厚度係數 ⑧ -19- 1359076 •» 泠爲-0.03,滿足-0.08 S冷S-0.01;因爲異方向性係數r爲26, 銅箔之熱膨脹係數αΜ爲18xl(T6cm/cm/°C，滿足αΜ + 6各r刍 • αΜ+1〇。因爲所有膜厚之熱膨脹係數ατ均爲I9xl0_ 6cm/cm/°C， . 滿足αΜ-2$ατ彡ctM + 3。於cu= /3T+ 7式中，熱膨脹係數〇u係 與代入各膜厚T、厚度係數/5、異方向性係數r之數値相一 致。亦即，熱可塑性液晶聚合物薄膜A之各値均含於本發明之 範圍內。 參考例2 φ 利用羥基安息香酸與6-羥基-2-苯甲酸之共聚物，一面 進行熔點爲280°C之液晶聚合物的熔融擠壓，控制縱與橫之 拉伸比，並一面利用吹塑成型法而得到膜厚爲25、50、1 00 與225μιη之薄膜，使已塗布脫模材30μπι厚的鋁箔相重疊， 以20kg/cm2進行260°C加熱滾筒與耐熱橡膠滾筒間的熱壓黏 後，使各膜厚之薄膜MD方向的熱膨脹係數αα成爲下述之既 定値般之，於已設定溫度之熱處理爐內進行30秒鐘熱處理。 接著，於氮氣環境中之烘箱內，於2 6 0 °C進行6小時熱處理 φ 後，剝下鋁箔後得到如下特性之薄膜：熔點爲305 °C，所有 膜厚之TD方向的熱膨脹係數ou均爲l9xl(T6cm/cm/°C，各 別之厚度下，MD方向的熱膨脹係數〇u分別爲23.5、23、22 與 19.5xl〇-6cm/cm/°C (冷=-〇_〇2、r = 24)。將如此之熱 可塑性液晶聚合物薄膜設爲B。 於參考例2中，相同於參考例1，使熱可塑性液晶聚合 物薄膜B與銅箔（金屬片材）相層壓之情形，薄膜之厚度 T 同樣滿足；因爲厚度係數 β 爲-0.02，滿足 -0.08S冷$-0.01;因爲異方向性係數r爲24,銅箔之熱膨 ⑧ -20- 1359076 脹係數 αΜ 爲 18xl0_6cm/cm/°C 1 滿足 αΜ + 6$ r $αΜ+10。因 爲所有膜厚之熱膨脹係數ατ均爲i9xlO-6cm/cm/°C，滿足 αΜ-2客ατ$αΜ + 3。同樣地，熱膨脹係數αι_係與將各値代入αι_ =β Τ+ 7 式之數値相一致。亦即，熱可塑性液晶聚合物 薄膜Β之各値均含於本發明之範圍內。 參考例3 利用，羥基安息香酸與6-羥基-2-苯甲酸之共聚物，一 面進行熔點爲2 8 0 °C之液晶聚合物的熔融擠壓，控制縱與橫 φ 之拉伸比，並一面利用吹塑成型法而得到膜厚爲25、50、 100與22 5 μπι之薄膜，使已塗布脫模材30μιη厚的鋁箔相重 疊，以20kg/cm2進行260°C加熱滾筒與耐熱橡膠滾筒間的 熱壓黏後，使各膜厚之薄膜MD方向的熱膨賬係數ou成爲 下述之既定値般之，於已設定溫度之熱處理爐內進行30秒 鐘熱處理。接著，於氮氣環境中之烘箱內，於260°C進行6 小時熱處理後，剝下鋁箔後得到如下特性之薄膜：熔點爲 3 05 t，所有膜厚之TD、MD方向的熱膨脹係數ατ、熱膨脹 • 係數at均爲18xl0_6cm/cm广C (沒=0、r =18)。將如此 之熱可塑性液晶聚合物薄膜設爲C。 於參考例3，相同於參考例1，使熱可塑性液晶聚合物 薄膜C與銅箔（金屬片材）相層壓之情形，薄膜之厚度T 同樣滿足；因爲厚度係數爲〇,不滿足- 0.08‘ySS-0.01; 因爲異方向性係數7爲18，銅箔之熱膨脹係數心爲18x 10_6cm/cm/°C，不滿足aM + 6S r $αΜ+10。因爲所有膜厚之 熱膨脹係數 ατ均爲18xlO—6cm/cm/°C，滿足αΜ-2$ατ5 αΜ + 3。同樣地，熱膨脹係數〇u係與將各値代入〇u=召Τ +
-21 - 1359076 % r式之數値相一致。亦即，熱可塑性液晶聚合物薄膜C之 厚度係數yS與異方向性係數r並不含於本發明之範圍內》 ，· 參考例4 .· 利用P-羥基安息香酸與6-羥基-2-苯甲酸之共聚物，一面 進行熔點爲280 °C之液晶聚合物的熔融擠壓，控制縱與橫之 拉伸比，並一面利用吹塑成型法而得到膜厚爲25、50、1 00 與225 μΐΉ之薄膜，使已塗布脫模材30μΐΏ厚的鋁箔相重疊， 以20kg/cm2進行260°C加熱滾筒與耐熱橡膠滾筒間的熱壓黏 # 後’使各膜厚之薄膜MD方向的熱膨脹係數cu成爲.下述之既 定値般之’於已設定溫度之熱處理爐內進行3 0秒鐘熱處理。 接著，於氮氣環境中之烘箱內，於260°C進行6小時熱處理 後’剝下鋁箔後得到如下特性之薄膜：熔點爲305°C，所有 膜厚之TD方向的熱膨脹係數〇u均爲l9xlO—6cm/cm/°C，各 別之厚度下，MD方向的熱膨脹係數cu分別爲16.5、15、12 與 4.5xl0_6cm/cm/°C (冷= -0.06、r=18)。將如此之熱可 塑性液晶聚合物薄膜設爲D。 φ 於參考例4，相同於參考例1，使熱可塑性液晶聚合物 薄膜D與銅箔（金屬片材）相層壓之情形，薄膜之厚度τ 同樣滿足；因爲厚度係數 β 爲-0.06，滿足 -0.08 彡-0.01;因爲異方向性係數r爲18,銅箔之熱膨 脹係數 cim 爲 lgxl〇_6cm/cm/°C，不滿足 aM + 6S 7 SotM+lO。 因爲所有膜厚之熱膨脹係數ατ均爲19xlO_6cm/cm/°C，滿 足αΜ-2$ατ$αΜ + 3。同樣地，熱膨脹係數〇u係與將各値代 Λ αι= β Ί+ γ式之數値相一致。亦即，熱可塑性液晶聚 合物薄膜D之異方向性係數r並不含於本發明之範圍內。 ⑧ -22- 1359076 實施例1 使用於參考例1所得到的熱可塑性液晶聚合物薄膜A與 厚度18μπι之電解銅箔（熱膨脹係數18xlO_6cm/cm/°C)。 然後，將耐熱橡膠滾筒（硬度90度）與加熱金屬滾筒安裝 於連續熱滾筒壓縮裝置中，已將熱可塑性液晶聚合物薄膜 A與銅箔導入加熱滾筒內之運送空間中，於400mm寬度 .下，使張力成爲2kg，供應至加熱滾筒間，於300 °C加熱狀 態下，以20kg/cm2進行壓黏而製得熱可塑性液晶聚合物薄 φ 膜/電解銅箔構造之積層板。接著，導入270°C氮氣環境中 之烘箱內進行30秒鐘熱處理。將進行針對所得到的積層板 之接著強度與尺寸安定性測試的結果顯示於表6。如表6 所示，可以得到接著強度與尺寸安定性優異的覆金屬積層 板。 實施例2 除了使用於參考例2所得到的熱可塑性液晶聚合物薄膜 B之外，相同於實施例1之方式進行層壓，將進行針對所 φ 得到的覆金屬積層板之接著強度與尺寸安定性測試的結果 顯示於表6。如表6所示，可以得到接著強度與尺寸安定 性優異的覆金屬積層板。 比較例1 除了使用於參考例3所得到的熱可塑性液晶聚合物薄膜 C之外，針對相同於實施例1之方式所得到的覆金屬積層 板之接著強度與尺寸安定性測試的結果顯示於表6。如表6 所示，此覆金屬積層板之MD方向的尺寸安定性爲良好的。 比較例2 ⑧ -23- 1359076 ♦ 除了使用於參考例4所得到的熱可塑性液晶聚合物薄膜 D之外，針對相同於實施例1之方式所得到的覆金屬積層 • 板之接著強度與尺寸安定性測試的結果顯示於表6。如表6 . 所示，此覆金屬積層板之MD方向的尺寸安定性爲良好的。 比較例3 使用於參考例1所得到的熱可塑性液晶聚合物薄膜A與 厚度18μπι之電解銅箔（熱膨脹係數18xl(T 6cm/cm/°C )。 然後，將耐熱橡膠滾筒（硬度90度）與加熱金屬滾筒安裝 φ 於連續熱滾筒壓縮裝置中，已將液晶聚合物薄膜A與銅箔 導入加熱滾筒內之運送空間中，於400mm寬度下，使張力 成爲2 k g，供應至加熱滾筒間，於3 0 0 °C加熱狀態下，以 2 0kg/cm2進行壓黏而製得熱可塑性液晶聚合物薄膜/電解銅 箔構造之積層板。將進行針對所得到的覆金屬積層板之接 著強度與尺寸安定性測試的結果顯示於表6。如表6所示， 由於此覆金屬積層板係利用不含本發明第2步驟之製造方 法所製得的，接著強度爲良好的。 ⑧
-24- 1359076 應 明 說 的 例 施 實 宜 適 列 下 之 面 圖 隨 附 照 明參 說將 單茲 簡明 式發 圖本 示利 圖該 的應 純所 單圍 係範 面之 圖明 與發 例本 施定 實設 ’ 了 而爲 然非 。 並 解’ 理例 地實 瞭之 月 月 爲說 更了 能爲 該與 中 面 圖 發隨 本附 。於。 的。分 用的部 據 根 係 圍 範 之 明 圖 個 數 串 之 定同 設相 所示 圍顯 範係 利號 專編 請件 元 同 目 隨彳 付之 面 厚度係數 異方向性係數 接著強度 尺寸安定性（％) β γ (kg/cm) MD方向 TD方向 實施例1 -0.03 26 1.2 -0.01 +0.01 實施例2 -0.02 24 1.3 +0.01 +0.01 比較例1 0 18 1.0 +0.25 +0.01 比較例2 -0.06 18 1.2 +0.20 +0.01 比較例3 -0.03 26 0.7 -0.01 +0.01 第1圖係顯示實施本發明之一實施態樣的覆金屬積層板 • 連續製造方法之一裝置例的構造圖。 第2圖係顯示製造用於本發明之覆金屬積層板的熱可塑 性液晶聚合物薄膜之一裝置例的構造圖。 【主要元件符號說明】 1〜滾筒 2〜熱可塑性液晶聚合物薄膜 3〜捲出滾筒 4〜金屬片材 5〜加熱滾筒 6〜加熱處理裝置 -25- 1359076 7 ~捲取滾筒 . 10〜覆金屬積層板 1 1 ~捲出滾筒 12 ~熱可塑性液晶聚合物薄膜 13〜捲出滾筒 14〜載體 1 5〜加熱滾筒 1 6〜加熱處理裝置 1 7 ~剝下滾筒 2 0 ~積層.板 51 ~耐熱橡膠滾筒 52〜加熱金屬滾筒
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Claims (1)

  1. 修正本 第094 1 3 921 1號「覆金屬積層板及其製法」專利案 (2011年6月30日修正） 十、申請專利範圍： 1·—種覆金屬積層板之製法，其係於由可形成光學異方向 性熔融相之熱可塑性聚合物而成的薄膜（以下，稱此爲 熱可塑性液晶聚合物薄膜）之至少一側表面接合金屬片 材； 該製法包含： (i)熱膨脹係數調整步驟，藉由將熱可塑性液晶聚合 物薄膜（A)進行熱處理而形成已調整之熱膨脹係數的熱 可塑性液晶聚合物薄膜（B)、 (Π)第1步驟，於加熱滾筒間，使該熱可塑性液晶聚 合物薄膜（B)與該金屬片材予以壓黏、及 (iii)第2步驟，於熱可塑性液晶聚合物薄膜（B)熔點 以下之加熱處理溫度，進行於第1步驟所得到的覆金屬 積層板之加熱處理； 該熱膨脹係數調整步驟係： 將熱可塑性液晶聚合物薄膜（A)與載體相重疊的狀 態下送入加熱滾筒，經由熱壓黏使其接合而做成積層 板，之後，將該積層板從較熱可塑性液晶聚合物薄膜（A) 之熔點更低1 〇°C之溫度至較其熔點更高1 〇°C之溫度範圍 內進行加熱處理後，藉由將積層板予以剝下，調整熱可 塑性液晶聚合物薄膜（A)之熱膨脹係數，而形成已調整之 熱膨脹係數的熱可塑性液晶聚合物薄膜（B)， 1359076 % 修正本 該熱可塑性液晶聚合物薄膜（B)係滿足如下所示的 長軸方向之熱膨脹係數aL及aT ( xlO_6cm/cmrc ): •' 此處，該aL係滿足下式：〇α=|3Τ+γ， ·· 該式中，Τ :該薄膜（Β)之厚度（μπι)， β ··厚度係數（xl/Vm/°C )，及 γ :異方向性係數（xl〇_ 6cm/cm/°C )， 厚度係數β係於-o.omi之範圍內， 相對於該金屬片材之熱膨脹係數αΜ，異方向性係數 </係於+6〜+ 10(\10_6〇〇1/。111/°(3)之範圍內’ 該熱膨脹係數ατ相對於該金屬片材之熱膨脹係數 aw 係於-2 〜+ 3(xl(T6cm/cm/°C)之範圍內； 該第2步驟，係於較熱可塑性液晶聚合物薄膜（B)熔 點更低5〜20 °C之範圍的加熱處理溫度，進行於第1步驟 所得到的覆金屬積層板之加熱處理》 2. 如申請專利範圍第1項之覆金屬積層板之製法1其中熱 φ 可塑性液晶聚合物薄膜之厚度T於10~2 50 μπι之範圍。 3. 如申請專利範圍第1項之覆金屬積層板之製法，其爲一 _ 種於熱可塑性液晶聚合物薄膜兩側表面已接合金屬片材 之雙面覆金屬積層板。 4. —種利用申請專利範圍第1項之製法所製造的覆金屬積 層板。
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