TW202413110A - Elongated layered substrate, elongated sheet roll, and methods of producing the same - Google Patents
Elongated layered substrate, elongated sheet roll, and methods of producing the same Download PDFInfo
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- TW202413110A TW202413110A TW112120274A TW112120274A TW202413110A TW 202413110 A TW202413110 A TW 202413110A TW 112120274 A TW112120274 A TW 112120274A TW 112120274 A TW112120274 A TW 112120274A TW 202413110 A TW202413110 A TW 202413110A
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- substrate
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- thickness
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H75/00—Storing webs, tapes, or filamentary material, e.g. on reels
- B65H75/02—Cores, formers, supports, or holders for coiled, wound, or folded material, e.g. reels, spindles, bobbins, cop tubes, cans, mandrels or chucks
- B65H75/04—Kinds or types
- B65H75/08—Kinds or types of circular or polygonal cross-section
- B65H75/10—Kinds or types of circular or polygonal cross-section without flanges, e.g. cop tubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本發明係關於一種長條積層基材、長條片材捲筒以及該等之製造方法。The present invention relates to a long strip laminate substrate, a long strip sheet roll and a method for manufacturing the same.
四氟乙烯系聚合物之離型性、電絕緣性、撥水撥油性、耐化學品性、耐候性、耐熱性等物性優異。四氟乙烯系聚合物被用於形成浸漬基材、擔載基材、層狀基材等各種成形物。 例如專利文獻1中揭示了一種多層膜，其係於聚醯亞胺基材膜之兩面積層相同厚度之四氟乙烯系聚合物膜而形成。 又，專利文獻2中記載了一種多層膜，其於聚醯亞胺基材膜之兩面具有連續地塗佈四氟乙烯系聚合物而形成之相同厚度之氟樹脂層。 [先前技術文獻] [專利文獻] Tetrafluoroethylene polymers have excellent properties such as release, electrical insulation, water and oil repellency, chemical resistance, weather resistance, and heat resistance. Tetrafluoroethylene polymers are used to form various molded products such as impregnation substrates, support substrates, and layered substrates. For example, Patent Document 1 discloses a multilayer film formed by laminating tetrafluoroethylene polymer films of the same thickness on both sides of a polyimide substrate film. In addition, Patent Document 2 describes a multilayer film having fluororesin layers of the same thickness formed by continuously coating tetrafluoroethylene polymers on both sides of a polyimide substrate film. [Prior Art Document] [Patent Document]
[專利文獻1]國際公開第2010/084867號 [專利文獻2]國際公開第2021/200630號 [Patent Document 1] International Publication No. 2010/084867 [Patent Document 2] International Publication No. 2021/200630
[發明所欲解決之問題][The problem the invention is trying to solve]
將包含四氟乙烯系聚合物之聚合物層分別設置於基材之兩面而成之積層體即長條積層基材，可具備四氟乙烯系聚合物之物性與基材之物性兩者。 但是，當將上述長條積層基材捲繞至捲芯而製成捲筒狀基材後再將長條積層基材捲出時，長條積層基材可能發生起伏。並且，當對發生了起伏之長條積層基材之表面壓接金屬箔而製作覆金屬積層體時，由於長條積層基材之起伏，而有金屬箔容易發生剝離之趨勢。 A laminated body formed by placing polymer layers containing tetrafluoroethylene polymers on both sides of a substrate, i.e., a long-strip laminated substrate, can have both the physical properties of tetrafluoroethylene polymers and the physical properties of the substrate. However, when the long-strip laminated substrate is wound around a winding core to form a roll-shaped substrate and then unrolled, the long-strip laminated substrate may undulate. Furthermore, when a metal foil is pressed onto the surface of the undulating long-strip laminated substrate to produce a metal-clad laminated body, the metal foil tends to be easily peeled off due to the undulation of the long-strip laminated substrate.
又，於基材之兩面積層四氟乙烯系聚合物層而成之積層基材可藉由選擇基材之種類及形狀(厚度等)及四氟乙烯系聚合物之種類及形狀(厚度等)，而任意且容易地控制積層基材整體之物性。因此，上述積層基材可用作印刷配線基板等之材料。 但是，本發明人等得出以下見解：關於將作為長條之上述積層基材之長條積層基材捲取至捲芯而成之長條片材捲筒，於將長條積層基材捲出並製成覆金屬積層體時，金屬箔可能產生皺褶。若金屬箔產生皺褶，則容易引發製造印刷配線基板等時之障礙(良率變差、製品品質之降低等)。 In addition, the laminated substrate formed by laminating tetrafluoroethylene polymer layers on both sides of the substrate can arbitrarily and easily control the overall physical properties of the laminated substrate by selecting the type and shape (thickness, etc.) of the substrate and the type and shape (thickness, etc.) of the tetrafluoroethylene polymer. Therefore, the above-mentioned laminated substrate can be used as a material for printed wiring boards, etc. However, the inventors of the present invention have come to the following conclusion: Regarding the long strip of laminated substrate as a long strip of the above-mentioned laminated substrate wound onto a winding core to form a long sheet roll, when the long strip of laminated substrate is rolled out and made into a metal-clad laminate, wrinkles may occur in the metal foil. If wrinkles occur in the metal foil, it is easy to cause obstacles in the manufacture of printed wiring boards, etc. (yield degradation, reduction in product quality, etc.).
本發明之目的在於提供一種長條積層基材及其製造方法，該長條積層基材即便於捲繞至捲芯而製成捲筒狀基材後再捲出使用並製作覆金屬積層體之情形時，亦抑制由長條積層基材之起伏引起之金屬箔之剝離。The object of the present invention is to provide a long strip laminate substrate and a method for manufacturing the same, wherein even when the long strip laminate substrate is wound around a winding core to form a roll-shaped substrate and then unrolled for use to manufacture a metal-clad laminate, the peeling of the metal foil caused by the undulation of the long strip laminate substrate is suppressed.
又，本發明之目的在於提供一種長條片材捲筒及其製造方法，該長條片材捲筒係將長條積層基材捲出並製成覆金屬積層體時之金屬箔之皺褶之產生得到抑制者。 [解決問題之技術手段] Furthermore, the object of the present invention is to provide a long sheet roll and a method for manufacturing the same, wherein the long sheet roll is used to suppress the generation of wrinkles in the metal foil when the long laminated substrate is rolled out and made into a metal-clad laminate. [Technical means for solving the problem]
本發明包含以下形態。 ＜A1＞一種長條積層基材，其具有：厚度12～50 μm之基材；及2個聚合物層，其等分別設置於上述基材之兩面，包含四氟乙烯系聚合物，各自之厚度為12～40 μm，且基於ISO25178-2：2012對與上述基材相反側之面進行測定而獲得之均方根斜率Sdq之值為5 μm/mm以下。 ＜A2＞如＜A1＞所記載之長條積層基材，其中上述基材包含選自由聚醯亞胺、液晶聚酯、及聚四氟乙烯所組成之群中之至少一種。 ＜A3＞如＜A1＞或＜A2＞所記載之長條積層基材，其中上述2個聚合物層係包含上述四氟乙烯系聚合物粒子之燒結體之層。 ＜A4＞如＜A1＞至＜A3＞中任一項所記載之長條積層基材，上述2個聚合物層之合計厚度為上述基材之厚度之1.8～3.0倍。 ＜A5＞如＜A1＞至＜A4＞中任一項所記載之長條積層基材，其中上述2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍。 ＜A6＞如＜A1＞至＜A5＞中任一項所記載之長條積層基材，其中上述四氟乙烯系聚合物係熔點為260～320℃之四氟乙烯系聚合物。 ＜A7＞如＜A1＞至＜A6＞中任一項所記載之長條積層基材，其中上述四氟乙烯系聚合物具有含氧極性基。 ＜A8＞如＜A1＞至＜A7＞中任一項所記載之長條積層基材，其係捲繞至捲芯之捲筒狀基材。 ＜A9＞一種長條積層基材之製造方法，其包括：於外周面之十點平均粗糙度Rzjis為0.5～10 μm之背輥之外周面，一面以接觸面壓成為100～3000 kPa之方式使厚度12～50 μm之長條基材中之第2面與其接觸一面搬送上述基材，將含有四氟乙烯系聚合物粒子及液狀分散介質之組合物塗佈於上述基材中之第1面並進行熱處理，藉此於上述第1面形成第1層；以及於上述背輥之外周面，一面以接觸面壓成為100～3000 kPa之方式使上述第1層與其接觸一面搬送上述基材，將上述組合物塗佈於上述第2面並進行熱處理，藉此於上述第2面形成第2層；從而獲得包含上述基材、含有上述四氟乙烯系聚合物且厚度為12～40 μm之第1聚合物層、及含有上述四氟乙烯系聚合物且厚度為12～40 μm之第2聚合物層的長條積層基材。 ＜A10＞如＜A9＞所記載之製造方法，其中上述背輥之外周面之十點平均粗糙度Rzjis為0.5～8 μm。 ＜A11＞如＜A9＞或＜A10＞所記載之製造方法，其中上述接觸面壓為250～2000 kPa。 ＜A12＞如＜A9＞至＜A11＞中任一項所記載之製造方法，其中上述液狀分散介質之表面張力為20～30 mN/m。 ＜A13＞如＜A9＞至＜A12＞中任一項所記載之製造方法，其中上述基材包含選自由聚醯亞胺、液晶聚酯、及聚四氟乙烯所組成之群中之至少一種。 ＜A14＞如＜A9＞至＜A13＞中任一項所記載之製造方法，其中上述第1聚合物層及第2聚合物層之合計厚度為上述基材之厚度之1.8～3.0倍。 ＜A15＞如＜A9＞至＜A14＞中任一項所記載之製造方法，其中上述第1聚合物層之厚度為上述第2聚合物層之厚度之0.9～1.1倍。 ＜A16＞如＜A9＞至＜A15＞中任一項所記載之製造方法，其中上述四氟乙烯系聚合物粒子包含熔點為260℃以上之四氟乙烯系聚合物。 ＜A17＞如＜A9＞至＜A16＞中任一項所記載之製造方法，其中上述四氟乙烯系聚合物粒子包含具有含氧極性基之四氟乙烯系聚合物。 ＜A18＞如＜A9＞至＜A17＞中任一項所記載之製造方法，其進而包括將上述長條積層基材捲繞至捲芯而製成捲筒狀基材。 The present invention includes the following forms. ＜A1＞ A long strip laminated substrate, which has: a substrate with a thickness of 12 to 50 μm; and two polymer layers, which are respectively arranged on both sides of the above substrate, and contain tetrafluoroethylene polymers, each of which has a thickness of 12 to 40 μm, and the value of the root mean square slope Sdq obtained by measuring the surface opposite to the above substrate based on ISO25178-2:2012 is 5 μm/mm or less. ＜A2＞ The long strip laminated substrate described in ＜A1＞, wherein the above substrate contains at least one selected from the group consisting of polyimide, liquid crystal polyester, and polytetrafluoroethylene. ＜A3＞ The long strip laminated substrate described in ＜A1＞ or ＜A2＞, wherein the above two polymer layers are layers containing a sintered body of the above tetrafluoroethylene polymer particles. <A4> A long strip laminated substrate as described in any one of <A1> to <A3>, wherein the total thickness of the two polymer layers is 1.8 to 3.0 times the thickness of the substrate. <A5> A long strip laminated substrate as described in any one of <A1> to <A4>, wherein the thickness of one of the two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer. <A6> A long strip laminated substrate as described in any one of <A1> to <A5>, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a melting point of 260 to 320°C. <A7> A long strip laminated substrate as described in any one of <A1> to <A6>, wherein the tetrafluoroethylene polymer has an oxygen-containing polar group. <A8> A long strip laminated substrate as described in any one of <A1> to <A7>, which is a roll-shaped substrate wound on a winding core. <A9> A method for manufacturing a long strip laminated substrate, comprising: conveying the substrate while bringing the second surface of a long strip substrate having a thickness of 12 to 50 μm into contact with the outer peripheral surface of a back roller having a ten-point average roughness Rzjis of 0.5 to 10 μm in a manner such that the contact surface pressure is 100 to 3000 kPa, applying a composition containing tetrafluoroethylene polymer particles and a liquid dispersion medium on the first surface of the substrate and heat-treating the composition to form a first layer on the first surface; and conveying the substrate while bringing the second surface of a long strip substrate having a thickness of 12 to 50 μm into contact with the outer peripheral surface of the back roller having a ten-point average roughness Rzjis of 0.5 to 10 μm in a manner such that the contact surface pressure is 100 to 3000 kPa. kPa, the first layer is conveyed to the contacting side of the substrate, the composition is applied to the second side and heat-treated, thereby forming the second layer on the second side; thereby obtaining a long strip laminated substrate comprising the substrate, the first polymer layer containing the tetrafluoroethylene polymer and having a thickness of 12 to 40 μm, and the second polymer layer containing the tetrafluoroethylene polymer and having a thickness of 12 to 40 μm. ＜A10＞ The manufacturing method described in ＜A9＞, wherein the ten-point average roughness Rzjis of the outer peripheral surface of the back roller is 0.5 to 8 μm. ＜A11＞ The manufacturing method described in ＜A9＞ or ＜A10＞, wherein the contact surface pressure is 250 to 2000 kPa. <A12> The manufacturing method as described in any one of <A9> to <A11>, wherein the surface tension of the liquid dispersion medium is 20 to 30 mN/m. <A13> The manufacturing method as described in any one of <A9> to <A12>, wherein the substrate comprises at least one selected from the group consisting of polyimide, liquid crystal polyester, and polytetrafluoroethylene. <A14> The manufacturing method as described in any one of <A9> to <A13>, wherein the total thickness of the first polymer layer and the second polymer layer is 1.8 to 3.0 times the thickness of the substrate. <A15> The manufacturing method as described in any one of <A9> to <A14>, wherein the thickness of the first polymer layer is 0.9 to 1.1 times the thickness of the second polymer layer. <A16> The manufacturing method as described in any one of <A9> to <A15>, wherein the tetrafluoroethylene polymer particles contain a tetrafluoroethylene polymer having a melting point of 260°C or more. <A17> The manufacturing method as described in any one of <A9> to <A16>, wherein the tetrafluoroethylene polymer particles contain a tetrafluoroethylene polymer having an oxygen-containing polar group. <A18> The manufacturing method as described in any one of <A9> to <A17>, further comprising winding the long strip laminated substrate onto a winding core to form a roll-shaped substrate.
又，本發明亦包含以下形態。 ＜B1＞一種長條片材捲筒，其具有圓筒狀捲芯、及捲繞至上述捲芯之外周面之長條積層基材，上述長條積層基材具有：厚度12～50 μm之基材；及2個聚合物層，其等分別設置於上述基材之兩面，包含四氟乙烯系聚合物，且各自之厚度為12～40 μm；上述2個聚合物層之合計厚度為上述基材之厚度之1.8～3.0倍，上述2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍，上述捲芯之外徑之曲率Cmm -1與上述長條積層基材之合計厚度Tmm之積C×T的值未達0.0015。 ＜B2＞如＜B1＞所記載之長條片材捲筒，其中上述捲芯之外徑之曲率Cmm -1為0.009～0.037 mm -1。 ＜B3＞如＜B1＞或＜B2＞所記載之長條片材捲筒，其中上述長條積層基材之長邊方向之長度為200 m以上。 ＜B4＞如＜B1＞至＜B3＞中任一項所記載之長條片材捲筒，其中上述長條積層基材之短邊方向之寬度為500～1250 mm。 ＜B5＞如＜B1＞至＜B4＞中任一項所記載之長條片材捲筒，其中上述2個聚合物層係包含上述四氟乙烯系聚合物粒子之燒結體之層。 ＜B6＞如＜B1＞至＜B5＞中任一項所記載之長條片材捲筒，其中上述四氟乙烯系聚合物係熔點為260～320℃之四氟乙烯系聚合物。 ＜B7＞如＜B1＞至＜B6＞中任一項所記載之長條片材捲筒，其中將上述長條積層基材捲出500 mm並切下而獲得積層基材片，將該積層基材片靜置於水平面時，上述積層基材片之距離上述水平面之上浮高度為1 cm以下。 ＜B8＞一種長條片材捲筒之製造方法，其包括：準備長條積層基材，該長條積層基材具有厚度12～50 μm之基材、及2個聚合物層，該2個聚合物層分別設置於上述基材之兩面，包含四氟乙烯系聚合物，且各自之厚度為12～40 μm，上述2個聚合物層之合計厚度為上述基材之厚度之1.8～3.0倍，上述2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍；以及將上述長條積層基材捲繞至圓筒狀捲芯之外周面；上述捲芯之外徑之曲率Cmm -1與上述長條積層基材之合計厚度Tmm之積C×T的值未達0.0015。 ＜B9＞如＜B8＞所記載之製造方法，其中將上述長條積層基材捲繞至上述捲芯之外周面時之捲繞應力為1～3 MPa。 ＜B10＞如＜B8＞或＜B9＞所記載之製造方法，其中上述捲芯之外徑之曲率Cmm -1為0.009～0.037 mm -1。 ＜B11＞如＜B8＞至＜B10＞中任一項所記載之製造方法，其中上述長條積層基材之長邊方向之長度為200 m以上。 ＜B12＞如＜B8＞至＜B11＞中任一項所記載之製造方法，其中上述長條積層基材之短邊方向之寬度為500～1250 mm。 ＜B13＞如＜B8＞至＜B12＞中任一項所記載之製造方法，其中上述2個聚合物層係藉由將上述包含四氟乙烯系聚合物粒子及液狀分散介質之組合物塗佈於上述基材之兩面並進行熱處理而獲得。 ＜B14＞如＜B8＞至＜B13＞中任一項所記載之製造方法，其中上述四氟乙烯系聚合物係熔點為260～320℃之四氟乙烯系聚合物。 [發明之效果] In addition, the present invention also includes the following forms. <B1> A long sheet roll, which has a cylindrical winding core and a long laminated substrate wound on the outer peripheral surface of the winding core, the long laminated substrate having: a substrate with a thickness of 12 to 50 μm; and two polymer layers, which are respectively arranged on both sides of the substrate, comprising a tetrafluoroethylene polymer, and each having a thickness of 12 to 40 μm; the total thickness of the two polymer layers is 1.8 to 3.0 times the thickness of the substrate, the thickness of one of the two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer, and the value of the product C×T of the curvature Cmm -1 of the outer diameter of the winding core and the total thickness Tmm of the long laminated substrate is less than 0.0015. <B2> The long sheet roll as described in <B1>, wherein the curvature Cmm -1 of the outer diameter of the above-mentioned winding core is 0.009 to 0.037 mm -1 . <B3> The long sheet roll as described in <B1> or <B2>, wherein the length of the long side direction of the above-mentioned long strip laminated substrate is 200 m or more. <B4> The long sheet roll as described in any one of <B1> to <B3>, wherein the width of the short side direction of the above-mentioned long strip laminated substrate is 500 to 1250 mm. <B5> The long sheet roll as described in any one of <B1> to <B4>, wherein the above-mentioned two polymer layers are layers comprising a sintered body of the above-mentioned tetrafluoroethylene polymer particles. <B6> A long sheet roll as described in any one of <B1> to <B5>, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a melting point of 260 to 320°C. <B7> A long sheet roll as described in any one of <B1> to <B6>, wherein the long laminated substrate is rolled out to 500 mm and cut to obtain a laminated substrate sheet, and when the laminated substrate sheet is placed statically on a horizontal plane, the floating height of the laminated substrate sheet from the horizontal plane is less than 1 cm. ＜B8＞A method for manufacturing a long sheet roll, comprising: preparing a long laminated substrate, the long laminated substrate having a substrate with a thickness of 12 to 50 μm, and two polymer layers, the two polymer layers being respectively arranged on both sides of the above-mentioned substrate, comprising a tetrafluoroethylene polymer, and each having a thickness of 12 to 40 μm, the total thickness of the above-mentioned two polymer layers being 1.8 to 3.0 times the thickness of the above-mentioned substrate, and the thickness of one of the above-mentioned two polymer layers being 0.9 to 1.1 times the thickness of the other polymer layer; and winding the above-mentioned long laminated substrate onto the outer circumferential surface of a cylindrical winding core; the value of the product C×T of the curvature Cmm -1 of the outer diameter of the above-mentioned winding core and the total thickness Tmm of the above-mentioned long laminated substrate does not reach 0.0015. <B9> The manufacturing method as described in <B8>, wherein the winding stress when the long strip laminated substrate is wound around the outer peripheral surface of the winding core is 1 to 3 MPa. <B10> The manufacturing method as described in <B8> or <B9>, wherein the curvature Cmm -1 of the outer diameter of the winding core is 0.009 to 0.037 mm -1 . <B11> The manufacturing method as described in any one of <B8> to <B10>, wherein the length of the long side direction of the long strip laminated substrate is 200 m or more. <B12> The manufacturing method as described in any one of <B8> to <B11>, wherein the width of the short side direction of the long strip laminated substrate is 500 to 1250 mm. <B13> The manufacturing method as described in any one of <B8> to <B12>, wherein the two polymer layers are obtained by applying the composition comprising tetrafluoroethylene polymer particles and a liquid dispersion medium on both sides of the substrate and performing a heat treatment. <B14> The manufacturing method as described in any one of <B8> to <B13>, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a melting point of 260 to 320°C. [Effects of the Invention]
根據本發明，可提供一種長條積層基材及其製造方法，該長條積層基材即便於捲繞至捲芯而製成捲筒狀基材後再捲出使用並製作覆金屬積層體之情形時，亦抑制由長條積層基材之起伏引起之金屬箔之剝離。According to the present invention, a long strip laminate substrate and a method for manufacturing the same can be provided. Even when the long strip laminate substrate is wound around a winding core to form a roll-shaped substrate and then unrolled for use to manufacture a metal-clad laminate, the peeling of the metal foil caused by the undulation of the long strip laminate substrate can be suppressed.
又，根據本發明，可提供一種長條片材捲筒及其製造方法，該長條片材捲筒係將長條積層基材捲出並製成覆金屬積層體時之金屬箔之皺褶之產生得到抑制者。Furthermore, according to the present invention, a long sheet roll and a method for manufacturing the same can be provided, wherein the long sheet roll is used to suppress the generation of wrinkles in the metal foil when a long laminated substrate is rolled out to form a metal-clad laminate.
以下，對用以實施本發明之方式進行詳細說明。但是，本發明並不限於以下實施方式。以下實施方式中，其構成要素(亦包含要素步驟等)除特別明示之情形以外，並非必需。數值及其範圍亦同樣如此，並非限制本發明。 再者，對於實質上具有相同功能之構件，在所有圖式中賦予相同符號，有時省略重複說明。 The following is a detailed description of the method for implementing the present invention. However, the present invention is not limited to the following implementation methods. In the following implementation methods, the constituent elements (including element steps, etc.) are not required unless otherwise specifically stated. The same is true for numerical values and their ranges, and they do not limit the present invention. Furthermore, for components having substantially the same function, the same symbols are given in all drawings, and repeated descriptions are sometimes omitted.
本發明中，「步驟」之用語，除了從其他步驟獨立出之步驟以外，即便於無法與其他步驟明確區分之情形時，只要可達成該步驟之目的，亦包含該步驟。 本發明中，使用「～」所表示之數值範圍中分別包含記載於「～」之前後之數值作為最小值及最大值。 本發明中，各成分亦可包含複數種相當於各成分之物質。於組合物中存在複數種相當於各成分之物質時，各成分之含有率或含量只要無特別記載，便意指組合物中所存在之該複數種物質之合計之含有率或含量。 本發明中，相當於各成分之粒子亦可包含複數種。於組合物中存在複數種相當於各成分之粒子時，各成分之粒徑只要無特別記載，便意指關於組合物中所存在之該複數種粒子之混合物的值。 本發明中，「層」或「膜」之用語，係指於觀察該層或膜所存在之區域時，除了形成於該區域整體之情形以外，亦包含僅形成於該區域之一部分之情形。 本發明中，「積層」之用語表示將層堆積，可為二層以上之層相結合，亦可為二層以上之層處於可固定脫離狀態。 本發明中，於參照圖式來說明實施方式之情形時，該實施方式之構成並不限定於圖式中所示之構成。又，各圖中之構件之大小係概念性者，構件間之大小之相對關係並不限於此。 In the present invention, the term "step" includes steps that are independent of other steps, even if they cannot be clearly distinguished from other steps, as long as the purpose of the step can be achieved. In the present invention, the numerical range represented by "~" includes the numerical values recorded before and after "~" as the minimum and maximum values, respectively. In the present invention, each component may also include a plurality of substances equivalent to each component. When there are a plurality of substances equivalent to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition unless otherwise specified. In the present invention, particles equivalent to each component may also include a plurality of types. When there are multiple particles corresponding to each component in the composition, the particle size of each component, unless otherwise specified, means the value of the mixture of the multiple particles present in the composition. In the present invention, the term "layer" or "film" means that when observing the region where the layer or film exists, in addition to the situation where it is formed in the entire region, it also includes the situation where it is formed only in a part of the region. In the present invention, the term "layer" means stacking layers, which may be two or more layers combined, or two or more layers in a fixed and detachable state. In the present invention, when the embodiment is described with reference to the drawings, the structure of the embodiment is not limited to the structure shown in the drawings. In addition, the sizes of the components in each figure are conceptual, and the relative relationship between the sizes of the components is not limited to this.
本發明中，「聚合物」係單體進行聚合而成之化合物。即，「聚合物」具有複數個基於單體之單元。 本發明中，聚合物中之「單元」意指藉由單體之聚合所形成之基於上述單體之原子團。單元可為藉由聚合反應而直接形成之單元，亦可為藉由對聚合物進行處理而將上述單元之一部分轉換為其他結構所得之單元。以下，亦將基於單體a之單元簡稱為「單體a單元」。 本發明中，「重量平均分子量」係使用凝膠滲透層析法(GPC)，並藉由聚苯乙烯換算而求出。 本發明中，聚合物之「熔點」係與藉由示差掃描熱測定(DSC)法所測得之聚合物之熔解峰之最大值對應之溫度。 本發明中，聚合物之「熔融流動速度」意指JIS K 7210-1：2014(ISO1133-1：2011)所規定之聚合物之熔體質量流率。 本發明中，聚合物之「玻璃轉移點(Tg)」係藉由動態黏彈性測定(DMA)法對聚合物進行分析而測定之值。 In the present invention, "polymer" is a compound formed by polymerization of monomers. That is, "polymer" has a plurality of units based on monomers. In the present invention, "unit" in a polymer means an atomic group based on the above monomer formed by polymerization of the monomer. The unit may be a unit directly formed by polymerization reaction, or a unit obtained by converting a part of the above unit into another structure by treating the polymer. Hereinafter, the unit based on monomer a is also referred to as "monomer a unit". In the present invention, "weight average molecular weight" is obtained by using gel permeation chromatography (GPC) and converted to polystyrene. In the present invention, the "melting point" of a polymer is the temperature corresponding to the maximum value of the melting peak of the polymer measured by differential scanning calorimetry (DSC). In the present invention, the "melt flow rate" of a polymer refers to the melt mass flow rate of a polymer specified in JIS K 7210-1:2014 (ISO1133-1:2011). In the present invention, the "glass transition point (Tg)" of a polymer is a value measured by analyzing the polymer using the dynamic viscoelasticity measurement (DMA) method.
本發明中，聚合物粒子之「體積平均粒徑(D50)」係藉由雷射繞射-散射法而求出之粒子之體積基準累積50%徑。即，係藉由雷射繞射-散射法來測定粒度分佈，並將粒子之集群之總體積設為100%求出累積曲線，該累積曲線上累積體積達到50%之點之粒徑。 聚合物粒子之D50係使粒子分散於水中，藉由使用雷射繞射-散射式之粒度分佈測定裝置(例如堀場製作所公司製造，LA-920測定器)之雷射繞射-散射法進行分析而求出。 本發明中，無機填料之「平均粒徑」採用以掃描式電子顯微鏡(SEM)來觀察粒子時之隨機選擇之100個粒子之圓當量徑之平均值。 本發明中，「比表面積」係藉由氣體吸附(定容法)BET(Brunauer-Emmett-Teller，布厄特)多點法來測定粒子而計算出之值，例如使用NOVA4200e(Quantachrome Instruments公司製造)而求出。 In the present invention, the "volume average particle size (D50)" of polymer particles is the volume standard cumulative 50% diameter of the particles obtained by the laser diffraction-scattering method. That is, the particle size distribution is measured by the laser diffraction-scattering method, and the total volume of the particle cluster is set as 100% to obtain the cumulative curve, and the particle size at the point where the cumulative volume reaches 50% on the cumulative curve. The D50 of polymer particles is obtained by dispersing the particles in water and analyzing them by the laser diffraction-scattering method using a laser diffraction-scattering type particle size distribution measuring device (e.g., LA-920 measuring device manufactured by Horiba, Ltd.). In the present invention, the "average particle size" of the inorganic filler is the average value of the equivalent circular diameters of 100 randomly selected particles when observing the particles with a scanning electron microscope (SEM). In the present invention, the "specific surface area" is a value calculated by measuring the particles using the gas adsorption (constant volume method) BET (Brunauer-Emmett-Teller) multi-point method, for example, using NOVA4200e (manufactured by Quantachrome Instruments).
本發明中，「十點平均粗糙度Rzjis」係JIS B 0601：2013之附件JA所規定之值，係依據JIS B 0601：2013而測定。具體而言，例如可使用高精度形狀測定系統(例如基恩士股份有限公司製造之「KS-1100」，前端頭型號「LT-9510VM」)等進行測定。 本發明中，組合物之「黏度」係使用B型黏度計，於25℃、轉速30 rpm之條件下測定組合物而求出。反覆進行3次測定，採用3次量之測定值之平均值。 In the present invention, "ten-point average roughness Rzjis" is a value specified in Annex JA of JIS B 0601:2013 and is measured in accordance with JIS B 0601:2013. Specifically, it can be measured using a high-precision shape measuring system (such as "KS-1100" manufactured by Keyence Corporation, front end model "LT-9510VM"). In the present invention, the "viscosity" of the composition is obtained by measuring the composition at 25°C and a rotation speed of 30 rpm using a B-type viscometer. The measurement is repeated 3 times, and the average value of the 3 measured values is adopted.
[長條積層基材及其製造方法] 本發明之一實施方式中之長條積層基材具有：厚度12～50 μm之基材；及2個聚合物層，其等分別設置於上述基材之兩面，包含四氟乙烯系聚合物，各自之厚度為12～40 μm，且基於ISO25178-2：2012對與上述基材相反側之面進行測定而獲得之均方根斜率Sdq之值為5 μm/mm以下。以下，亦將四氟乙烯系聚合物稱為「F聚合物」，亦將聚合物層中之與基材相反側之面稱為「露出面」，亦將基於ISO25178-2：2012對測定對象面進行測定而獲得之均方根斜率Sdq之值簡稱為「Sdq」。 [Long-strip laminated substrate and its manufacturing method] The long-strip laminated substrate in one embodiment of the present invention has: a substrate with a thickness of 12 to 50 μm; and two polymer layers, which are respectively arranged on both sides of the above-mentioned substrate, and include tetrafluoroethylene polymers, each with a thickness of 12 to 40 μm, and the value of the root mean square slope Sdq obtained by measuring the surface opposite to the above-mentioned substrate based on ISO25178-2:2012 is 5 μm/mm or less. Hereinafter, the tetrafluoroethylene polymer is also referred to as "F polymer", the surface of the polymer layer opposite to the substrate is also referred to as "exposed surface", and the value of the root mean square slope Sdq obtained by measuring the measured object surface based on ISO25178-2:2012 is also referred to as "Sdq".
本實施方式中，「長條」意指長邊方向之長度為100 m以上。長條積層基材之長邊方向之長度較佳為200 m以上。長邊方向之長度較佳為1000 m以下。 長條積層基材例如被製成捲繞至捲芯而成之捲筒狀基材而保管。以下，亦將長條積層基材被捲繞至捲芯而成之捲筒狀基材稱為「捲筒片材」。並且，自捲筒片材捲出長條積層基材之一部分而獲得之積層基材，例如用於製作覆金屬積層體。具體而言，例如藉由在積層基材之表面壓接金屬箔而獲得覆金屬積層體。 In this embodiment, "strip" means that the length in the long side direction is more than 100 m. The length in the long side direction of the long strip laminated substrate is preferably more than 200 m. The length in the long side direction is preferably less than 1000 m. The long strip laminated substrate is, for example, made into a roll-shaped substrate wound around a winding core and stored. Hereinafter, the roll-shaped substrate in which the long strip laminated substrate is wound around a winding core is also referred to as a "roll sheet". In addition, the laminated substrate obtained by rolling out a part of the long strip laminated substrate from the roll sheet is used, for example, to make a metal-clad laminate. Specifically, for example, a metal-clad laminate is obtained by pressing a metal foil onto the surface of a laminate substrate.
關於將包含F聚合物之聚合物層分別設置於基材之兩面而成之長條積層基材，如上所述，可期待具備F聚合物之物性與基材之物性兩者。例如若使用包含耐熱性樹脂之耐熱性基材作為基材，則可獲得具備耐熱性、尺寸穩定性等物性、與作為F聚合物之物性之低介電常數、低介電損耗因數等電氣物性兩者之長條積層基材。As described above, a long laminated substrate in which polymer layers containing F polymer are disposed on both sides of a substrate can be expected to have both the physical properties of the F polymer and the physical properties of the substrate. For example, if a heat-resistant substrate containing a heat-resistant resin is used as the substrate, a long laminated substrate having both the physical properties such as heat resistance and dimensional stability and the electrical properties such as low dielectric constant and low dielectric dissipation factor, which are the physical properties of the F polymer, can be obtained.
另一方面，當將上述長條積層基材捲繞至捲芯而製成捲筒片材後再將長條積層基材捲出時，長條積層基材可能發生起伏。並且，當對由發生了起伏之長條積層基材獲得之積層基材之表面壓接金屬箔而製作覆金屬積層體時，由於長條積層基材之起伏，使得金屬箔容易發生剝離。尤其當2個聚合物層之厚度之合計較基材之厚度變得相對較厚時，由長條積層基材之起伏引起之金屬箔之剝離變得明顯。On the other hand, when the long strip laminated substrate is wound around a winding core to make a roll sheet and then unrolled, the long strip laminated substrate may undulate. Furthermore, when a metal foil is pressed against the surface of the laminated substrate obtained from the undulating long strip laminated substrate to make a metal-clad laminate, the metal foil is easily peeled off due to the undulation of the long strip laminated substrate. In particular, when the total thickness of the two polymer layers becomes relatively thicker than the thickness of the substrate, the peeling of the metal foil caused by the undulation of the long strip laminated substrate becomes obvious.
相對於此，本實施方式中，2個聚合物層之露出面之Sdq均為5 μm/mm以下。上述Sdq係根據測定對象表面之斜率之均方根而計算出之參數，表示凹凸形狀之局部斜率之平均大小。Sdq越大，則表示表面之起伏越強烈急遽。 本發明人等發現，藉由將Sdq而非露出面之凹凸高度等設為上述範圍，即便於基材之厚度為12～50 μm、聚合物層各自之厚度為12～40 μm，亦可抑制由長條積層基材之起伏引起之金屬箔之剝離。 以下，使用圖式對長條積層基材之一例進行說明，但本發明之長條積層基材並不限於其等。 In contrast, in the present embodiment, the Sdq of the exposed surface of the two polymer layers is less than 5 μm/mm. The above Sdq is a parameter calculated based on the root mean square of the slope of the measured object surface, which indicates the average size of the local slope of the concave-convex shape. The larger the Sdq, the more intense and rapid the surface undulation. The inventors of the present invention have found that by setting Sdq rather than the concave-convex height of the exposed surface to the above range, even when the thickness of the substrate is 12 to 50 μm and the thickness of each polymer layer is 12 to 40 μm, the peeling of the metal foil caused by the undulation of the long strip laminate substrate can be suppressed. Below, an example of a long strip laminate substrate is described using a diagram, but the long strip laminate substrate of the present invention is not limited to it.
圖1係表示一實施方式之長條積層基材之層構成之概略剖視圖。 圖1中所示之長條積層基材10具有基材12、及分別設置於基材12之兩面之聚合物層14及聚合物層16。並且，聚合物層14之露出面14S及聚合物層16之露出面16S之Sdq均為5 μm/mm以下。 以下，對構成長條積層基材之各層進行說明。再者，有時省略符號。 FIG. 1 is a schematic cross-sectional view showing the layer structure of a long-strip laminate substrate of an embodiment. The long-strip laminate substrate 10 shown in FIG. 1 has a substrate 12, and a polymer layer 14 and a polymer layer 16 respectively disposed on both sides of the substrate 12. In addition, the Sdq of the exposed surface 14S of the polymer layer 14 and the exposed surface 16S of the polymer layer 16 are both less than 5 μm/mm. The following describes each layer constituting the long-strip laminate substrate. In addition, symbols are sometimes omitted.
作為基材，可例舉包含樹脂之長條膜等。基材可為單層結構，亦可為多層結構。 基材較佳為耐熱性基材，更佳為包含耐熱性樹脂之膜。 As the substrate, a long film containing resin can be cited as an example. The substrate can be a single-layer structure or a multi-layer structure. The substrate is preferably a heat-resistant substrate, and more preferably a film containing a heat-resistant resin.
基材較佳為包含耐熱性樹脂。作為耐熱性樹脂，可例舉：聚醯亞胺(芳香族聚醯亞胺等)、聚芳酯、聚碸、聚芳碸(聚醚碸等)、芳香族聚醯胺、芳香族聚醚醯胺、聚苯硫醚、聚芳醚酮、聚醯胺醯亞胺、液晶聚酯、液晶聚酯醯胺、聚四氟乙烯等。The substrate preferably comprises a heat-resistant resin. Examples of the heat-resistant resin include polyimide (aromatic polyimide, etc.), polyarylate, polysulfone, polyarylsulfone (polyethersulfone, etc.), aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystal polyester, liquid crystal polyesteramide, polytetrafluoroethylene, etc.
包含耐熱性樹脂之基材可進而包含塑化劑、除耐熱性樹脂以外之樹脂、著色劑、無機填料、各種添加劑等。 作為無機填料，較佳為氮化物填料及無機氧化物填料，更佳為氮化硼填料、氧化鈹填料(鈹之氧化物之填料)、矽酸鹽填料(二氧化矽填料、矽灰石填料、滑石填料)、及金屬氧化物(氧化鈰、氧化鋁、氧化鎂、氧化鋅、氧化鈦等)填料，進而較佳為二氧化矽填料。 作為添加劑，可例舉：抗靜電劑、阻燃劑、熱穩定劑、紫外線吸收劑、潤滑劑、離型劑、結晶成核劑等。 至於包含耐熱性樹脂之基材中之耐熱性樹脂之總含有率，相對於基材整體，較佳為70質量%以上，更佳為80質量%以上，亦可為100質量%。 The substrate containing the heat-resistant resin may further contain a plasticizer, a resin other than the heat-resistant resin, a colorant, an inorganic filler, various additives, etc. As the inorganic filler, nitride fillers and inorganic oxide fillers are preferred, and boron nitride fillers, curium oxide fillers (curium oxide fillers), silicate fillers (silicon dioxide fillers, wollastonite fillers, talc fillers), and metal oxide fillers (zirconia, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) are more preferred, and silicon dioxide fillers are more preferred. As additives, examples include: antistatic agents, flame retardants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, crystallization nucleating agents, etc. As for the total content of the heat-resistant resin in the substrate containing the heat-resistant resin, it is preferably 70% by mass or more, more preferably 80% by mass or more, and may also be 100% by mass relative to the entire substrate.
就耐熱性之觀點而言，上述耐熱性樹脂中，基材較佳為包含選自由聚醯亞胺、液晶聚酯、及聚四氟乙烯所組成之群中之至少一種，更佳為至少包含聚醯亞胺。From the viewpoint of heat resistance, in the above-mentioned heat-resistant resin, the base material preferably includes at least one selected from the group consisting of polyimide, liquid crystal polyester, and polytetrafluoroethylene, and more preferably includes at least polyimide.
作為包含聚醯亞胺之基材中所含之聚醯亞胺，可例舉由使芳香族二胺成分與四羧酸成分聚合而成之聚醯胺酸所獲得之聚醯亞胺。 作為芳香族二胺成分，可例舉：對苯二胺、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、4,4'-雙(胺基苯氧基)聯苯、4,4'-雙(3-胺基苯氧基)聯苯、2,2'-雙(4-胺基苯氧基苯基)丙烷等。芳香族二胺成分可僅使用一種，亦可使用兩種以上。 作為四羧酸成分，可例舉：均苯四甲酸、3,3',4,4'-聯苯四羧酸、二鄰苯二甲酸、2,3',3,4'-聯苯四羧酸、3,3',4,4'-二苯甲酮四羧酸、其等之二酐等。四羧酸成分可僅使用一種，亦可使用兩種以上。 As the polyimide contained in the substrate containing polyimide, there can be exemplified a polyimide obtained by polymerizing an aromatic diamine component and a tetracarboxylic acid component to form a polyamic acid. As the aromatic diamine component, there can be exemplified p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2'-bis(4-aminophenoxyphenyl)propane, etc. The aromatic diamine component may be used alone or in combination of two or more. Examples of the tetracarboxylic acid component include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, diphthalic acid, 2,3',3,4'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, and dianhydrides thereof. Only one tetracarboxylic acid component may be used, or two or more may be used.
作為包含聚醯亞胺之基材中所含之聚醯亞胺之玻璃轉移點，可例舉未達288℃，較佳為未達275℃，更佳為260℃以下。聚醯亞胺之玻璃轉移點較佳為200℃以上。The glass transition point of the polyimide contained in the substrate containing polyimide may be, for example, less than 288° C., preferably less than 275° C., and more preferably less than 260° C. The glass transition point of the polyimide is preferably 200° C. or higher.
作為包含聚醯亞胺之基材之具體例，可例舉：「Kapton 50EN-S」(東麗杜邦股份有限公司製造)、「Kapton 100EN」(東麗杜邦股份有限公司製造)、「Kapton 100H」(東麗杜邦股份有限公司製造)、「Kapton 100KJ」(杜邦公司製造)、「Kapton 100JP」(美國杜邦公司製造)、「Kapton 100LK」(東麗杜邦股份有限公司製造)等。 由起伏引起之金屬箔之剝離變得明顯。 Specific examples of substrates containing polyimide include: "Kapton 50EN-S" (manufactured by DuPont Toray Co., Ltd.), "Kapton 100EN" (manufactured by DuPont Toray Co., Ltd.), "Kapton 100H" (manufactured by DuPont Toray Co., Ltd.), "Kapton 100KJ" (manufactured by DuPont), "Kapton 100JP" (manufactured by DuPont USA), "Kapton 100LK" (manufactured by DuPont Toray Co., Ltd.), etc. The peeling of the metal foil caused by the undulation becomes obvious.
基材在320℃下之拉伸彈性模數較佳為0.2 GPa以上，更佳為0.3 GPa以上。上述拉伸彈性模數較佳為10 GPa以下，更佳為5 GPa以下。藉由使基材在320℃下之拉伸彈性模數處於上述範圍內，而不容易因加熱及冷卻發生變形，處理性優異。具體而言，若基材之上述拉伸彈性模數為上述下限值以上，則於加工時之加熱及冷卻時，聚合物層之變形容易因基材之彈性而得到緩和。又，若基材之拉伸彈性模數為上述上限值以下，則長條積層基材之柔軟性容易變高。The tensile modulus of the substrate at 320°C is preferably 0.2 GPa or more, more preferably 0.3 GPa or more. The above-mentioned tensile modulus is preferably 10 GPa or less, more preferably 5 GPa or less. By making the tensile modulus of the substrate at 320°C within the above-mentioned range, it is not easy to deform due to heating and cooling, and the handleability is excellent. Specifically, if the above-mentioned tensile modulus of the substrate is above the above-mentioned lower limit, the deformation of the polymer layer is easily alleviated by the elasticity of the substrate during heating and cooling during processing. In addition, if the tensile modulus of the substrate is below the above-mentioned upper limit, the flexibility of the long strip laminated substrate is easily increased.
基材之厚度為12～50 μm，就積層基材之尺寸穩定性之觀點而言，較佳為20～44 μm。 關於基材之短邊方向之長度即寬度，就積層基材之尺寸穩定性之觀點而言，較佳為500～1250 mm。 基材之長邊方向之長度較佳為100～1000 m。 基材之長邊方向之長度較佳為基材之寬度之50倍以上，更佳為100倍以上。基材之長邊方向之長度較佳為基材之寬度之1000倍以下。 The thickness of the substrate is 12 to 50 μm, preferably 20 to 44 μm from the perspective of dimensional stability of the laminated substrate. Regarding the length in the short side direction of the substrate, i.e., the width, from the perspective of dimensional stability of the laminated substrate, it is preferably 500 to 1250 mm. The length in the long side direction of the substrate is preferably 100 to 1000 m. The length in the long side direction of the substrate is preferably 50 times or more of the width of the substrate, more preferably 100 times or more. The length in the long side direction of the substrate is preferably 1000 times or less of the width of the substrate.
聚合物層係分別設置於基材之兩面之層。 設置於基材之兩面之2個聚合物層均只要為包含F聚合物，各自之厚度為12～40 μm，且露出面之Sdq為5 μm/mm以下之層，便無特別限定。 2個聚合物層較佳為均與基材直接相接而設置。 2個聚合物層分別可僅包含一種F聚合物，亦可包含兩種以上。2個聚合物層之組成可彼此相通，亦可不同。 The polymer layer is a layer disposed on both sides of the substrate. The two polymer layers disposed on both sides of the substrate are not particularly limited as long as they contain F polymers, each having a thickness of 12 to 40 μm, and an Sdq of the exposed surface of 5 μm/mm or less. The two polymer layers are preferably disposed directly in contact with the substrate. The two polymer layers may each contain only one type of F polymer or may contain two or more types. The compositions of the two polymer layers may be the same or different.
F聚合物係包含基於四氟乙烯(以下，亦記為「TFE」)之單元(以下，亦記為「TFE單元」)之聚合物。F聚合物亦可進而具有基於他其他聚單體之單元。 關於F聚合物中之TFE單元之含有率，就較佳地表現基於TFE單元之特性之觀點而言，相對於F聚合物中之全部單元，較佳為50莫耳%以上，更佳為90莫耳%以上。上述含有率可為99莫耳%以下，亦可為98莫耳%以下。 F polymer is a polymer containing units based on tetrafluoroethylene (hereinafter, also referred to as "TFE") (hereinafter, also referred to as "TFE units"). F polymer may further have units based on other polymonomers. Regarding the content of TFE units in F polymer, from the perspective of better expressing the characteristics based on TFE units, it is preferably 50 mol% or more, and more preferably 90 mol% or more relative to all units in F polymer. The above content may be 99 mol% or less, or 98 mol% or less.
F聚合物可為熱熔性，亦可為非熱熔性。於期待尤其良好地表現導熱性、接著性、加工性等特性之情形時，F聚合物較佳為熱熔性。 熱熔性聚合物意指於負載49 N之條件下存在熔融流動速度成為1～1000 g/10分鐘之溫度之聚合物。非熱熔性聚合物意指於負載49N之條件下不存在熔融流動速度成為1～1000 g/10分鐘之溫度之聚合物。 F polymer can be hot-melt or non-hot-melt. When it is expected that the thermal conductivity, adhesion, processability and other characteristics are particularly good, F polymer is preferably hot-melt. Hot-melt polymer means a polymer having a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49 N. Non-hot-melt polymer means a polymer having no temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49 N.
關於作為熱熔性之F聚合物之熔點，就聚合物層之耐熱性之觀點而言，較佳為200℃以上，更佳為260℃以上。上述F聚合物之熔點就加工容易性之觀點而言，較佳為325℃以下，更佳為320℃以下。 F聚合物較佳為熔點為200～325℃之F聚合物，更佳為熔點為260～320℃之F聚合物。 The melting point of the hot-melt F polymer is preferably 200°C or higher, more preferably 260°C or higher, from the viewpoint of heat resistance of the polymer layer. The melting point of the above F polymer is preferably 325°C or lower, more preferably 320°C or lower, from the viewpoint of ease of processing. The F polymer is preferably an F polymer having a melting point of 200 to 325°C, more preferably an F polymer having a melting point of 260 to 320°C.
關於F聚合物之玻璃轉移點，就耐熱性之觀點而言，較佳為50℃以上，更佳為75℃以上。F聚合物之玻璃轉移點就加工容易性之觀點而言，較佳為150℃以下，更佳為125℃以下。 關於F聚合物之氟含量，就較佳地表現電特性、耐熱性等基於氟原子之特性之觀點而言，較佳為70質量%以上，更佳為72～76質量%。 F聚合物之表面張力較佳為16～26 mN/m。再者，F聚合物之表面張力可於由F聚合物所製作之平板上載置透濕指數試劑(富士膠片和光純藥公司製造)之液滴而測定。 Regarding the glass transition point of the F polymer, from the viewpoint of heat resistance, it is preferably 50°C or more, and more preferably 75°C or more. From the viewpoint of ease of processing, the glass transition point of the F polymer is preferably 150°C or less, and more preferably 125°C or less. Regarding the fluorine content of the F polymer, from the viewpoint of better performance of electrical properties, heat resistance and other properties based on fluorine atoms, it is preferably 70% by mass or more, and more preferably 72-76% by mass. The surface tension of the F polymer is preferably 16-26 mN/m. Furthermore, the surface tension of the F polymer can be measured by placing a drop of a moisture permeability index reagent (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.) on a flat plate made of the F polymer.
F聚合物較佳為聚四氟乙烯(PTFE)、包含TFE單元及基於乙烯之單元之聚合物、包含TFE單元及基於丙烯之單元之聚合物、包含TFE單元及基於全氟(烷基乙烯基醚)(PAVE)之單元(PAVE單元)之聚合物(PFA)、以及包含TFE單元及基於六氟丙烯之單元之聚合物(FEP)，就導熱性、接著性、加工性等特性之觀點而言，更佳為PFA及FEP，進而較佳為PFA。該等聚合物亦可進而包含基於其他共聚單體之單元。 PAVE較佳為CF 2=CFOCF 3、CF 2=CFOCF 2CF 3、及CF 2=CFOCF 2CF 2CF 3(以下，亦記為「PPVE」)，更佳為PPVE。 The F polymer is preferably polytetrafluoroethylene (PTFE), a polymer comprising TFE units and units based on ethylene, a polymer comprising TFE units and units based on propylene, a polymer comprising TFE units and units based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE units) (PFA), and a polymer comprising TFE units and units based on hexafluoropropylene (FEP). From the viewpoint of thermal conductivity, adhesion, processability and other properties, PFA and FEP are more preferred, and PFA is further preferred . These polymers may further comprise units based on other copolymer monomers. PAVE is preferably CF2 = CFOCF3 , CF2 = CFOCF2CF3 , and CF2 = CFOCF2CF2CF3 (hereinafter, also referred to as "PPVE"), and PPVE is further preferred.
F聚合物就與基材之密接性之觀點而言，較佳為具有含氧極性基之F聚合物，更佳為具有含羥基之基或含羰基之基之F聚合物，進而較佳為具有含羰基之基之F聚合物。 含羥基之基較佳為含有醇性羥基之基，更佳為-CF 2CH 2OH及-C(CF 3) 2OH。 含羰基之基係包含羰基(＞C(O))之基。含羰基之基較佳為羧基、烷氧基羰基、醯胺基、異氰酸基、胺基甲酸酯基(-OC(O)NH 2)、酸酐殘基(-C(O)OC(O)-)、醯亞胺殘基(-C(O)NHC(O)-等)、及碳酸酯基(-OC(O)O-)，更佳為酸酐殘基。 由起伏引起之金屬箔之剝離變得明顯。 From the viewpoint of adhesion to the substrate, the F polymer is preferably an F polymer having an oxygen-containing polar group, more preferably an F polymer having a hydroxyl-containing group or a carbonyl-containing group, and further preferably an F polymer having a carbonyl-containing group. The hydroxyl-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF 2 CH 2 OH and -C(CF 3 ) 2 OH. The carbonyl-containing group is a group containing a carbonyl group (>C(O)). The carbonyl-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH 2 ), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.), and a carbonate group (-OC(O)O-), and more preferably an acid anhydride residue. The peeling of the metal foil caused by the undulation becomes noticeable.
於F聚合物具有含氧極性基之情形時，F聚合物中之含氧極性基數係相對於主鏈之碳數每1×10 6個，較佳為100～5000個，更佳為300～3000個，進而較佳為800～1500個。再者，F聚合物中之含氧極性基數可藉由聚合物之組成或國際公開第2020/145133號中所記載之方法進行定量。 When the F polymer has an oxygen-containing polar group, the number of oxygen-containing polar groups in the F polymer is preferably 100 to 5000, more preferably 300 to 3000, and further preferably 800 to 1500 per 1×10 6 carbon number of the main chain. Furthermore, the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or by the method described in International Publication No. 2020/145133.
含氧極性基可包含於F聚合物中之基於單體之單元中，亦可包含於F聚合物之主鏈之末端基中，較佳為前者。作為後者之形態，可例舉：具有含氧極性基作為源自聚合起始劑、鏈轉移劑等之末端基之F聚合物、對F聚合物進行電漿處理或電離輻射處理所獲得之F聚合物等。 關於具有含羰基之基之單體，較佳為伊康酸酐、檸康酸酐、及5-降𦯉烯-2,3-二羧酸酐(以下，以記為「NAH」)，更佳為NAH。 The oxygen-containing polar group may be contained in the monomer-based unit in the F polymer or in the terminal group of the main chain of the F polymer, and the former is preferred. As the latter form, there can be cited: F polymers having oxygen-containing polar groups as terminal groups derived from polymerization initiators, chain transfer agents, etc., F polymers obtained by plasma treatment or ionizing radiation treatment of F polymers, etc. Regarding monomers having a carbonyl-containing group, itaconic anhydride, liconic anhydride, and 5-northene-2,3-dicarboxylic anhydride (hereinafter referred to as "NAH") are preferred, and NAH is more preferred.
F聚合物較佳為包含TFE單元及PAVE單元且具有含氧極性基之F聚合物，更佳為包含TFE單元、PAVE單元、及基於具有含羰基之基之單體之單元的F聚合物(亦記為F聚合物(1))。以下，亦將基於具有含氧極性基之單體之單元稱為「含氧單元」。 F聚合物(1)進而較佳為相對於全部單元，TFE單元、PAVE單元、及含氧單元之含量依序為90～99莫耳%、0.5～9.97莫耳%、0.01～3莫耳%之F聚合物(1)。作為該F聚合物(1)之具體例，可例舉國際公開第2018/016644號中所記載之聚合物。 The F polymer is preferably an F polymer comprising a TFE unit and a PAVE unit and having an oxygen-containing polar group, and more preferably an F polymer comprising a TFE unit, a PAVE unit, and a unit based on a monomer having a carbonyl-containing group (also referred to as F polymer (1)). Hereinafter, the unit based on a monomer having an oxygen-containing polar group is also referred to as an "oxygen-containing unit". F polymer (1) is further preferably an F polymer (1) in which the content of TFE unit, PAVE unit, and oxygen-containing unit is 90-99 mol%, 0.5-9.97 mol%, and 0.01-3 mol%, respectively, relative to all units. As a specific example of the F polymer (1), the polymer described in International Publication No. 2018/016644 can be cited.
F聚合物可為不具有含氧單元之F聚合物(亦記為F聚合物(2))，亦可為不具有含氧極性基之F聚合物。 F聚合物(2)較佳為相對於全部單元含有2.0～5.0莫耳%之PAVE單元且不具有含氧單元之F聚合物(2)。 F聚合物(2)更佳為僅由TFE單元及PAVE單元所構成，且相對於全部單元含有95.0～98.0莫耳%之TFE單元、2.0～5.0莫耳%之PAVE單元之F聚合物(2)。 至於F聚合物(2)中之PAVE單元之含量，相對於全部單元，進而較佳為2.1～5.0莫耳%，尤佳為2.2～5.0莫耳%。 再者，F聚合物(2)不具有含氧極性基意指相對於構成聚合物主鏈之碳原子數每1×10 6個，F聚合物(2)所具有之含氧極性基數未達500個。上述含氧極性基數較佳為100個以下，更佳為未達50個。上述含氧極性基數之下限通常為0個。 The F polymer may be an F polymer without oxygen-containing units (also referred to as F polymer (2)), or an F polymer without oxygen-containing polar groups. The F polymer (2) is preferably an F polymer (2) containing 2.0 to 5.0 mol% of PAVE units relative to all units and having no oxygen-containing units. The F polymer (2) is more preferably an F polymer (2) consisting only of TFE units and PAVE units, and containing 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units relative to all units. As for the content of PAVE units in the F polymer (2), it is further preferably 2.1 to 5.0 mol% relative to all units, and is particularly preferably 2.2 to 5.0 mol%. Furthermore, the fact that the F polymer (2) has no oxygen-containing polar groups means that the number of oxygen-containing polar groups in the F polymer (2) is less than 500 per 1×10 6 carbon atoms constituting the polymer main chain. The number of oxygen-containing polar groups is preferably less than 100, more preferably less than 50. The lower limit of the number of oxygen-containing polar groups is usually 0.
F聚合物(2)可使用不產生含氧極性基作為聚合物鏈之末端基的聚合起始劑或鏈轉移劑等進行製造，亦可對具有含氧極性基之F聚合物(於聚合物之主鏈之末端基具有源自聚合起始劑之含氧極性基之F聚合物等)進行氟化處理而製造。作為氟化處理之方法，可例舉使用氟氣之方法(參照日本專利特開2019-194314號公報等)。The F polymer (2) can be produced by using a polymerization initiator or a chain transfer agent that does not generate an oxygen-containing polar group as the terminal group of the polymer chain, or by fluorinating an F polymer having an oxygen-containing polar group (an F polymer having an oxygen-containing polar group derived from a polymerization initiator at the terminal group of the main chain of the polymer). As a method of fluorination treatment, a method using fluorine gas can be cited (see Japanese Patent Publication No. 2019-194314, etc.).
至於聚合物層中之F聚合物之含有率，較佳為50質量%以上，更佳為60質量%以上。F聚合物之含有率之上限為100質量%。 聚合物層亦可進而包含除F聚合物以外之其他樹脂。其他樹脂可為熱硬化性樹脂，亦可為熱塑性樹脂。 The content of the F polymer in the polymer layer is preferably 50% by mass or more, and more preferably 60% by mass or more. The upper limit of the content of the F polymer is 100% by mass. The polymer layer may further include other resins besides the F polymer. Other resins may be thermosetting resins or thermoplastic resins.
就聚合物層之UV(Ultraviolet，紫外線)吸收性之觀點而言，其他樹脂較佳為芳香族性聚合物。 作為其他樹脂，可例舉：環氧樹脂、馬來醯亞胺樹脂、胺基甲酸酯樹脂、聚醯亞胺、聚醯胺酸、聚醯胺醯亞胺、聚苯醚(polyphenylene ether)、聚氧化伸苯基(polyphenylene oxide)、液晶聚酯、除F聚合物以外之含氟聚合物。就長條積層基材之柔軟性等觀點而言，其他樹脂較佳為馬來醯亞胺樹脂、聚醯亞胺、及聚醯胺酸。作為其他樹脂，更佳為均為芳香族性之馬來醯亞胺樹脂、聚醯亞胺、及聚醯胺酸。聚醯亞胺較佳為熱塑性。 至於聚合物層中之馬來醯亞胺、聚醯亞胺、及聚醯胺酸之合計含量，較佳為0.1～30質量%，更佳為1～10質量%。 馬來醯亞胺、聚醯亞胺、及聚醯胺酸之合計含量相對於F聚合物之含量之比較佳為1.0以下，亦可為0.01～0.5。 From the viewpoint of UV (Ultraviolet) absorption of the polymer layer, other resins are preferably aromatic polymers. As other resins, epoxy resins, maleimide resins, urethane resins, polyimide, polyamide, polyamide imide, polyphenylene ether, polyphenylene oxide, liquid crystal polyester, fluorine-containing polymers other than F polymers can be cited. From the viewpoint of the flexibility of the long strip laminate substrate, other resins are preferably maleimide resins, polyimide, and polyamide. As other resins, maleimide resins, polyimide, and polyamide, which are all aromatic, are more preferably used. Polyimide is preferably thermoplastic. The total content of maleimide, polyimide, and polyamide in the polymer layer is preferably 0.1 to 30% by mass, and more preferably 1 to 10% by mass. The ratio of the total content of maleimide, polyimide, and polyamide to the content of the F polymer is preferably 1.0 or less, and may also be 0.01 to 0.5.
就進一步提高長條積層基材之低線膨脹性及電特性之觀點而言，聚合物層可進而包含無機填料。 作為無機填料，較佳為氮化物填料及無機氧化物填料，更佳為氮化硼填料、氧化鈹填料(鈹之氧化物之填料)、矽酸鹽填料(二氧化矽填料、矽灰石填料、滑石填料)、及金屬氧化物(氧化鈰、氧化鋁、氧化鎂、氧化鋅、氧化鈦等)填料，進而較佳為二氧化矽填料。 無機填料中之二氧化矽之含有率較佳為50質量%以上，更佳為75質量%以上。二氧化矽之含有率之上限為100質量%。 From the viewpoint of further improving the low linear expansion and electrical properties of the long strip laminate substrate, the polymer layer may further include an inorganic filler. As the inorganic filler, nitride fillers and inorganic oxide fillers are preferred, and boron nitride fillers, curium oxide fillers (curium oxide fillers), silicate fillers (silicon dioxide fillers, wollastonite fillers, talc fillers), and metal oxide (zirconia, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) fillers are more preferred, and silicon dioxide fillers are further preferred. The content of silicon dioxide in the inorganic filler is preferably 50% by mass or more, and more preferably 75% by mass or more. The upper limit of the content of silicon dioxide is 100% by mass.
無機填料較佳為其表面之至少一部分經矽烷偶合劑進行了表面處理者。 作為矽烷偶合劑，較佳為3-胺基丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、及3-異氰酸基丙基三乙氧基矽烷。 The inorganic filler is preferably one whose surface is at least partially treated with a silane coupling agent. As the silane coupling agent, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-butyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferred.
作為無機填料之具體例，可例舉：二氧化矽填料(Admatechs公司製造之「Admafine」系列等)、利用二癸酸丙二醇酯等酯進行了表面處理之氧化鋅(堺化學工業股份有限公司製造之「FINEX」系列等)、球狀熔融二氧化矽(DENKA公司製造之「SFP」系列等)、利用多元醇及無機物進行了被覆處理之(石原產業公司製造之「Tipaque」系列等)、利用烷基矽烷進行了表面處理之金紅石型氧化鈦(Tayca公司製造之「JMT」系列等)、中空狀二氧化矽填料(太平洋水泥公司製造之「E-SPHERES」系列、日鐵礦業公司製造之「SiliNax」系列、Emerson & Cuming公司製造之「Ecco sphere」系列等)、滑石填料(NIPPON TALC公司製造之「SG」系列等)、塊滑石填料(NIPPON TALC公司製造之「BST」系列等)、氮化硼填料(昭和電工公司製造之「UHP」系列、DENKA公司製造之「Denka Boron Nitride」系列(「GP」、「HGP」等級)等)。Specific examples of inorganic fillers include silica fillers (such as the "Admafine" series manufactured by Admatechs), zinc oxide surface-treated with esters such as propylene glycol dicaprate (such as the "FINEX" series manufactured by Sakai Chemical Industry Co., Ltd.), spherical fused silica (such as the "SFP" series manufactured by DENKA), coated with polyols and inorganic substances (such as the "Tipaque" series manufactured by Ishihara Sangyo Co., Ltd.), rutile titanium oxide surface-treated with alkyl silane (such as the "JMT" series manufactured by Tayca Co., Ltd.), hollow silica fillers (such as the "E-SPHERES" series manufactured by Pacific Cement Co., Ltd., the "SiliNax" series manufactured by Nippon Steel Mining Co., Ltd., and the "Ecco sphere" series manufactured by Emerson & Cuming Co., Ltd.), talc fillers (such as the "NIPPON TALC's "SG" series, etc.), block talc fillers (NIPPON TALC's "BST" series, etc.), boron nitride fillers (Showa Denko's "UHP" series, DENKA's "Denka Boron Nitride" series ("GP", "HGP" grades), etc.).
聚合物層中之無機填料之含有率較佳為1質量%以上，更佳為3質量%以上。無機填料之含有率較佳為40質量%以下，更佳為30質量%以下，更佳為20質量%以下。 聚合物層中之無機填料之含量相對於F聚合物之含量之比(質量比)較佳為0.01以上，更佳為0.1以上。上述比較佳為1以下，更佳為0.8以下。 聚合物層除上述成分以外，亦可包含矽烷偶合劑、脫水劑、塑化劑、耐候劑、抗氧化劑、熱穩定劑、潤滑劑、抗靜電劑、增白劑、著色劑、導電劑、離型劑、表面處理劑、阻燃劑等添加劑。 The content of inorganic filler in the polymer layer is preferably 1% by mass or more, more preferably 3% by mass or more. The content of inorganic filler is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. The ratio of the content of inorganic filler in the polymer layer to the content of F polymer (mass ratio) is preferably 0.01 or more, more preferably 0.1 or more. The above ratio is preferably 1 or less, more preferably 0.8 or less. In addition to the above ingredients, the polymer layer may also contain additives such as silane coupling agents, dehydrating agents, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, whitening agents, coloring agents, conductive agents, release agents, surface treatment agents, flame retardants, etc.
聚合物層較佳為包含四氟乙烯系聚合物粒子、即包含F聚合物之粒子之燒結體的層。以下，亦將四氟乙烯系聚合物粒子稱為「F粒子」。再者，關於聚合物層是否包含F粒子之燒結體，可藉由以顯微鏡等來觀察聚合物層之剖面而確認。 於聚合物層為包含F粒子之層之情形時，聚合物層亦可包含除F粒子以外之成分。作為除F粒子以外之成分，可例舉上述除F聚合物以外之成分，具體而言，例如可例舉除F聚合物以外之樹脂、無機填料、添加劑等。 The polymer layer is preferably a layer containing tetrafluoroethylene polymer particles, that is, a sintered body of particles containing F polymer. Hereinafter, tetrafluoroethylene polymer particles are also referred to as "F particles". In addition, whether the polymer layer contains a sintered body of F particles can be confirmed by observing the cross section of the polymer layer with a microscope or the like. In the case where the polymer layer is a layer containing F particles, the polymer layer may also contain components other than F particles. As components other than F particles, the above-mentioned components other than F polymers can be cited, and specifically, for example, resins, inorganic fillers, additives, etc. other than F polymers can be cited.
關於F粒子之D50，就在液狀分散介質中之分散穩定性及Sdq之控制容易性之觀點而言，較佳為0.1 μm以上，更佳為超過0.3 μm，進而較佳為1 μm以上。就在液狀分散介質中之分散穩定性及Sdq之控制容易性之觀點而言，F粒子之D50較佳為25 μm以下，更佳為10 μm以下，進而較佳為8 μm以下，尤佳為6 μm以下。 F粒子之比表面積較佳為1～25 m 2/g。 F粒子可單獨使用一種，亦可使用兩種以上。 Regarding the D50 of the F particles, from the viewpoint of dispersion stability in a liquid dispersion medium and ease of control of Sdq, it is preferably 0.1 μm or more, more preferably more than 0.3 μm, and further preferably 1 μm or more. From the viewpoint of dispersion stability in a liquid dispersion medium and ease of control of Sdq, the D50 of the F particles is preferably 25 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 6 μm or less. The specific surface area of the F particles is preferably 1 to 25 m 2 /g. The F particles may be used alone or in combination of two or more.
F粒子中之F聚合物之含量較佳為80質量%以上，更佳為100質量%。即，F粒子較佳為由F聚合物所構成之粒子。 作為F粒子中可包含之除F聚合物以外之成分，可例舉除F聚合物以外之樹脂、無機填料等。 The content of the F polymer in the F particles is preferably 80% by mass or more, and more preferably 100% by mass. That is, the F particles are preferably particles composed of the F polymer. As components other than the F polymer that may be included in the F particles, resins other than the F polymer, inorganic fillers, etc. may be cited.
2個聚合物層各自之厚度為12～40 μm，就積層基材之尺寸穩定性之觀點而言，較佳為16～36 μm，更佳為20～33 μm。 關於2個聚合物層中之一聚合物層之厚度，就抑制長條積層基材發生起伏之觀點而言，較佳為另一聚合物層之厚度之0.9～1.1倍。 關於2個聚合物層之合計厚度，就積層基材之電特性之觀點而言，較佳為基材之厚度之1.8～3.0倍，更佳為1.8～2.4倍。尤佳為2個聚合物層之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍，且2個聚合物層之合計厚度為基材之厚度之1.8～3.0倍。 本實施方式中，聚合物層之露出面之Sdq為5 μm/mm以下，因此即便2個聚合物層之合計厚度為基材之厚度之1.8倍以上，亦抑制長條積層基材發生起伏。 The thickness of each of the two polymer layers is 12 to 40 μm, preferably 16 to 36 μm, and more preferably 20 to 33 μm from the perspective of dimensional stability of the laminated substrate. Regarding the thickness of one of the two polymer layers, from the perspective of suppressing the undulation of the long strip laminated substrate, it is preferably 0.9 to 1.1 times the thickness of the other polymer layer. Regarding the total thickness of the two polymer layers, from the perspective of electrical properties of the laminated substrate, it is preferably 1.8 to 3.0 times the thickness of the substrate, and more preferably 1.8 to 2.4 times. It is particularly preferred that the thickness of one of the two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer, and the total thickness of the two polymer layers is 1.8 to 3.0 times the thickness of the substrate. In this embodiment, the Sdq of the exposed surface of the polymer layer is less than 5 μm/mm, so even if the combined thickness of the two polymer layers is more than 1.8 times the thickness of the substrate, the undulation of the long strip laminate substrate is suppressed.
2個聚合物層均露出面之Sdq為5 μm/mm以下，較佳為4 μm/mm以下，更佳為3 μm/mm以下。Sdq較佳為0 μm/mm以上。The Sdq of the exposed surface of both polymer layers is 5 μm/mm or less, preferably 4 μm/mm or less, and more preferably 3 μm/mm or less. The Sdq is preferably 0 μm/mm or more.
Sdq係依據ISO25178-2：2012對露出面進行測定而獲得。作為測定方式，可例舉：接觸式、白光干涉方式、點自動聚焦式等。 藉由白光干涉方式進行之測定及Sdq之計算例如係使用表面性狀測定機(Zygo公司製造，商品名：Newview7300)，於倍率：1.4×0.5倍、掃描間距：100 μm、解析尺寸：12.621 mm 2、過濾器類型：Spline、過濾器：Low Pass high frequency 1 μm、類型：Gaussian Spline Fixed之條件下進行。 Sdq is obtained by measuring the exposed surface in accordance with ISO25178-2:2012. Examples of measurement methods include contact method, white light interferometry method, and point autofocus method. Measurement by white light interferometry and calculation of Sdq are performed using, for example, a surface property measuring machine (manufactured by Zygo Corporation, trade name: Newview7300) under the conditions of magnification: 1.4×0.5, scanning pitch: 100 μm, resolution size: 12.621 mm 2 , filter type: Spline, filter: Low Pass high frequency 1 μm, type: Gaussian Spline Fixed.
例如於聚合物層為包含F粒子之燒結體之層時，聚合物層之露出面之Sdq可藉由形成聚合物層之方法及形成條件進行控制。具體而言，例如藉由將含有F粒子及液狀分散介質之組合物塗佈於基材之表面並進行熱處理而形成聚合物層，於組合物之塗佈時，將所使用之背輥之外周面之十點平均粗糙度Rzjis及基材相對於背輥之接觸面壓調整為下述範圍。 以下，對聚合物層之露出面之Sdq為5 μm/mm以下之本實施方式之長條積層基材之製造方法之一例進行說明。 For example, when the polymer layer is a layer of a sintered body containing F particles, the Sdq of the exposed surface of the polymer layer can be controlled by the method and formation conditions of the polymer layer. Specifically, for example, the polymer layer is formed by applying a composition containing F particles and a liquid dispersion medium on the surface of a substrate and heat treating it. When applying the composition, the ten-point average roughness Rzjis of the outer peripheral surface of the back roller used and the contact surface pressure of the substrate relative to the back roller are adjusted to the following ranges. Below, an example of a method for manufacturing a long strip laminated substrate of this embodiment in which the Sdq of the exposed surface of the polymer layer is 5 μm/mm or less is described.
＜長條積層基材之製造方法＞ 一實施方式之長條積層基材之製造方法包括：於外周面之十點平均粗糙度Rzjis為0.5～10 μm之背輥之外周面，一面以接觸面壓成為100～3000 kPa之方式使厚度12～50 μm之長條基材中之第2面與其接觸一面搬送上述基材，將含有四氟乙烯系聚合物粒子(即F粒子)及液狀分散介質之組合物塗佈於上述基材中之第1面並進行熱處理，藉此於上述第1面形成第1層；以及於上述背輥之外周面，一面以接觸面壓成為100～3000 kPa之方式使上述第1層與其接觸一面搬送上述基材，將上述組合物塗佈於上述第2面並進行熱處理，藉此於上述第2面形成第2層。 <Method for manufacturing long strip laminated substrate> One embodiment of the method for manufacturing long strip laminated substrate comprises: on the outer peripheral surface of a back roller having a ten-point average roughness Rzjis of 0.5 to 10 μm, while the second surface of a long strip substrate having a thickness of 12 to 50 μm is brought into contact with the outer peripheral surface of the back roller in a manner that the contact surface pressure is 100 to 3000 kPa, and while the above substrate is conveyed, a composition containing tetrafluoroethylene polymer particles (i.e., F particles) and a liquid dispersion medium is applied to the first surface of the above substrate and heat-treated to form a first layer on the above first surface; and on the outer peripheral surface of the back roller, while the contact surface pressure is 100 to 3000 kPa, a composition containing tetrafluoroethylene polymer particles (i.e., F particles) and a liquid dispersion medium is applied to the first surface of the above substrate and heat-treated to form a first layer on the above first surface. kPa, the substrate is transported with the first layer in contact with the first layer, the composition is applied to the second surface and heat-treated, thereby forming the second layer on the second surface.
本實施方式之長條積層基材之製造方法中，藉由經由上述步驟，而獲得包含上述基材、含有F聚合物且厚度為12～40 μm之第1聚合物層、及含有F聚合物且厚度為12～40 μm之第2聚合物層的長條積層基材。 以下，亦將背輥之外周面之十點平均粗糙度Rzjis簡稱為「Rzjis」，亦將基材相對於背輥之外周面之接觸面壓簡稱為「接觸面壓」。 又，亦將第1聚合物層稱為「P-A1層」，將第2聚合物層稱為「P-A2層」。」 In the manufacturing method of the long strip laminated substrate of the present embodiment, by going through the above steps, a long strip laminated substrate including the above substrate, a first polymer layer containing F polymer and having a thickness of 12 to 40 μm, and a second polymer layer containing F polymer and having a thickness of 12 to 40 μm is obtained. Hereinafter, the ten-point average roughness Rzjis of the outer peripheral surface of the back roller is also referred to as "Rzjis", and the contact surface pressure of the substrate relative to the outer peripheral surface of the back roller is also referred to as "contact surface pressure". In addition, the first polymer layer is also referred to as "P-A1 layer", and the second polymer layer is also referred to as "P-A2 layer". ”
藉由以上述製造方法來製造長條積層基材，可獲得2個聚合物層之露出面之Sdq為5 μm/mm以下之長條積層基材。其原因並不明確，但推測其原因在於：藉由將Rzjis及接觸面壓設為上述範圍，可同時抑制隨著基材貼附至背輥而發生之黏滑現象、及抑制背輥外周面之凹凸形狀被轉印至聚合物層之露出面。By manufacturing a long laminated substrate using the above manufacturing method, a long laminated substrate having an Sdq of 5 μm/mm or less on the exposed surface of the two polymer layers can be obtained. The reason is not clear, but it is speculated that the reason is that by setting Rzjis and the contact surface pressure to the above range, the stick-slip phenomenon caused by the substrate being attached to the backing roller and the uneven shape of the outer peripheral surface of the backing roller being transferred to the exposed surface of the polymer layer can be suppressed at the same time.
具體而言，藉由使Rzjis處於上述範圍內，而較小於上述範圍之情形而言基材不易貼附至背輥，可抑制基材相對於背輥之外周面之附著與滑動反覆發生之現象即黏滑現象。因此，推測可抑制所形成之聚合物層之厚度因黏滑現象而週期性地變動，所獲得之聚合物層之露出面之Sdq變小。 又，藉由使Rzjis處於上述範圍內，而較大於上述範圍之情形而言，可抑制基材與背輥之接觸時背輥外周面之凹凸形狀被暫時轉印至聚合物層之露出面。因此，推測可抑制因凹凸形狀之暫時性轉印而導致所塗佈之組合物流動從而產生不均，聚合物層之露出面之Sdq變小。 Specifically, by making Rzjis within the above range, and in the case of being smaller than the above range, the substrate is not easily attached to the back roller, and the phenomenon of repeated adhesion and sliding of the substrate relative to the outer peripheral surface of the back roller, i.e., the stick-slip phenomenon, can be suppressed. Therefore, it is estimated that the thickness of the formed polymer layer can be suppressed from periodically changing due to the stick-slip phenomenon, and the Sdq of the exposed surface of the obtained polymer layer becomes smaller. In addition, by making Rzjis within the above range, and in the case of being larger than the above range, the uneven shape of the outer peripheral surface of the back roller can be suppressed from being temporarily transferred to the exposed surface of the polymer layer when the substrate and the back roller are in contact. Therefore, it is speculated that the uneven flow of the applied composition caused by the temporary transfer of the concave-convex shape can be suppressed, and the Sdq of the exposed surface of the polymer layer becomes smaller.
進而，藉由使接觸面壓處於上述範圍內，而較小於上述範圍之情形而言，可抑制空氣被捲入至基材與背輥外周面之間。此處，若空氣被捲入至基材與背輥外周面之間，則可能於捲入有空氣之部分與未捲入之部分產生組合物之塗佈不均。另一方面，藉由使接觸面壓處於上述範圍內，可抑制上述塗佈不均，結果推測所獲得之聚合物層之露出面之Sdq變小。 又，藉由使接觸面壓處於上述範圍內，而較大於上述範圍之情形而言，基材不易貼附至背輥，從而推測可抑制黏滑現象，所獲得之聚合物層之露出面之Sdq變小。 Furthermore, by making the contact surface pressure within the above range, and in the case where it is smaller than the above range, it is possible to suppress the air from being drawn between the substrate and the outer peripheral surface of the back roller. Here, if the air is drawn between the substrate and the outer peripheral surface of the back roller, uneven coating of the composition may occur between the part where the air is drawn and the part where the air is not drawn. On the other hand, by making the contact surface pressure within the above range, the above uneven coating can be suppressed, and as a result, it is estimated that the Sdq of the exposed surface of the obtained polymer layer becomes smaller. In addition, by making the contact surface pressure within the above range, and in the case where it is larger than the above range, the substrate is not easily attached to the back roller, and it is estimated that the stick-slip phenomenon can be suppressed, and the Sdq of the exposed surface of the obtained polymer layer becomes smaller.
本實施方式之長條積層基材之製造方法可進而包括：將所獲得之長條積層基材捲繞至捲芯而製成捲筒狀基材(即捲筒片材)。藉由經由將所獲得之長條積層基材捲繞至捲芯之步驟，可獲得長條積層基材被捲繞至捲芯而成之捲筒片材。 以下，對本實施方式中之長條積層基材之製造方法之一例進行說明。 再者，關於長條基材、所獲得之長條積層基材中之P-A1層及P-A2層，與上述基材及聚合物層相同，故省略說明。 The manufacturing method of the long-strip laminated substrate of the present embodiment may further include: winding the obtained long-strip laminated substrate onto a winding core to form a roll-shaped substrate (i.e., a roll sheet). By winding the obtained long-strip laminated substrate onto a winding core, a roll sheet formed by winding the long-strip laminated substrate onto a winding core can be obtained. Below, an example of the manufacturing method of the long-strip laminated substrate in the present embodiment is described. Furthermore, the long-strip substrate, the P-A1 layer and the P-A2 layer in the obtained long-strip laminated substrate are the same as the above-mentioned substrate and polymer layer, so the description is omitted.
圖2係模式性地表示本實施方式之長條積層基材之製造方法中所使用之裝置之塗佈部的模式圖。 如圖2所示，本實施方式之長條積層基材之製造方法中所使用之裝置之塗佈部具有：搬送作為塗佈對象之基材12之背輥20、及將塗佈用組合物塗佈於基材12之塗佈面之塗佈構件22。 圖2中所示之塗佈部中，背輥20於基材12之與塗佈面相反側之面被壓接於背輥20之外周面之狀態下進行旋轉，而搬送基材12。另一方面，於基材12之塗佈面側，利用塗佈構件22來塗佈聚合物層形成用組合物，而形成組合物層26。 FIG. 2 is a schematic diagram schematically showing a coating section of the apparatus used in the method for manufacturing a long strip laminated substrate of the present embodiment. As shown in FIG. 2 , the coating section of the apparatus used in the method for manufacturing a long strip laminated substrate of the present embodiment has: a back roller 20 for conveying the substrate 12 to be coated, and a coating member 22 for coating the coating composition on the coating surface of the substrate 12. In the coating section shown in FIG. 2 , the back roller 20 is rotated in a state where the surface of the substrate 12 opposite to the coating surface is pressed against the outer peripheral surface of the back roller 20, thereby conveying the substrate 12. On the other hand, the coating component 22 is used to coat the polymer layer forming composition on the coating surface of the substrate 12 to form a composition layer 26.
背輥20之材質可為金屬、橡膠、及樹脂中之任一種。作為背輥20，例如可例舉於圓筒狀之金屬基材之外周面設置包含選自由橡膠及樹脂所組成之群中之至少一種之彈性層而成之捲筒。再者，作為金屬基材之材質，例如可例舉：鐵、不鏽鋼、鈦、鋁等。 背輥20之外徑並無特別限定，例如可例舉100～500 mm，亦可為150～350 mm。 The material of the back roller 20 can be any one of metal, rubber, and resin. As the back roller 20, for example, a reel including at least one elastic layer selected from the group consisting of rubber and resin is provided on the outer peripheral surface of a cylindrical metal substrate. Furthermore, as the material of the metal substrate, for example, iron, stainless steel, titanium, aluminum, etc. can be cited. The outer diameter of the back roller 20 is not particularly limited, for example, it can be 100 to 500 mm, or 150 to 350 mm.
背輥20之外周面之Rzjis為0.5～10 μm，就形成露出面之Sdq較小之聚合物層之觀點而言，較佳為0.5～8 μm，更佳為1～6 μm。 Rzjis之測定及計算係依據JIS B 0601：2013而進行，例如係使用高精度形狀測定系統(例如基恩士股份有限公司製造之「KS-1100」，前端頭型號「LT-9510VM」)而進行。 Rzjis可藉由對背輥20之外周面進行研磨而調整，亦可藉由在形成背輥20之最外層時所添加之成分(無機填料等)之種類及量進行調整。 The Rzjis of the outer peripheral surface of the back roller 20 is 0.5 to 10 μm, preferably 0.5 to 8 μm, and more preferably 1 to 6 μm from the viewpoint of forming a polymer layer with a smaller Sdq of the exposed surface. The measurement and calculation of Rzjis are performed in accordance with JIS B 0601:2013, for example, using a high-precision shape measurement system (such as "KS-1100" manufactured by Keyence Corporation, front end head model "LT-9510VM"). Rzjis can be adjusted by polishing the outer peripheral surface of the back roller 20, and can also be adjusted by the type and amount of components (inorganic fillers, etc.) added when forming the outermost layer of the back roller 20.
基材12相對於背輥20之外周面之接觸面壓為100～3000 kPa，就形成露出面之Sdq較小之聚合物層之觀點而言，較佳為200～2000 kPa，更佳為250～2000 kPa，進而較佳為250～1000 kPa。 形成第1層時之接觸面壓與形成第2層時之接觸面壓可相同，亦可不同。形成第2層時之接觸面壓較佳為形成第1層時之接觸面壓之0.8～1.2倍，更佳為0.9～1.1倍，進而較佳為實質上相同。 上述接觸面壓例如可利用Nitta公司之表面壓力分佈系統進行測定。 具體而言，例如將表面壓力分佈系統(Nitta股份有限公司製造)之感測器片材夾於背輥20與基材12之間，進行測定，將測定所得之數值作為上述接觸面壓。 上述接觸面壓可藉由基材12之捲出張力進行調整，亦可藉由基材12之捲取張力進行調整。 The contact surface pressure of the substrate 12 relative to the outer peripheral surface of the back roller 20 is 100 to 3000 kPa. From the perspective of forming a polymer layer with a smaller Sdq on the exposed surface, it is preferably 200 to 2000 kPa, more preferably 250 to 2000 kPa, and further preferably 250 to 1000 kPa. The contact surface pressure when forming the first layer and the contact surface pressure when forming the second layer may be the same or different. The contact surface pressure when forming the second layer is preferably 0.8 to 1.2 times the contact surface pressure when forming the first layer, more preferably 0.9 to 1.1 times, and further preferably substantially the same. The contact surface pressure can be measured, for example, using the surface pressure distribution system of Nitta Corporation. Specifically, for example, the sensor sheet of the surface pressure distribution system (manufactured by Nitta Co., Ltd.) is sandwiched between the back roller 20 and the substrate 12 for measurement, and the measured value is used as the contact surface pressure. The contact surface pressure can be adjusted by the unwinding tension of the substrate 12, and can also be adjusted by the winding tension of the substrate 12.
塗佈於基材12之塗佈面之組合物含有F粒子及液狀分散介質。 組合物中之F粒子之含有率較佳為5～60質量%，更佳為25～50質量%。 F粒子之詳情如上所述，故省略說明。 The composition applied to the coating surface of the substrate 12 contains F particles and a liquid dispersion medium. The content of the F particles in the composition is preferably 5 to 60% by mass, and more preferably 25 to 50% by mass. The details of the F particles are as described above, so the description is omitted.
於形成包含除F粒子以外之成分(除F聚合物以外之樹脂、無機填料、添加劑等)之聚合物層之情形時，組合物可包含上述除F粒子以外之成分。 除F聚合物以外之樹脂、及無機填料之詳情亦如上所述，故省略說明。 When a polymer layer containing components other than F particles (resins other than F polymers, inorganic fillers, additives, etc.) is formed, the composition may contain the above-mentioned components other than F particles. The details of the resins other than F polymers and inorganic fillers are also as described above, so the description is omitted.
作為液狀分散介質，係於大氣壓下、25℃下為液體之化合物，較佳為沸點為50～240℃之化合物。液狀分散介質可使用一種，亦可使用兩種以上。於使用兩種液狀分散介質之情形時，兩種液狀分散介質較佳為彼此相容。 液狀分散介質較佳為選自由水、醯胺、酮、及酯所組成之群中之化合物。 作為醯胺，可例舉：N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基丙醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N,N-二乙基甲醯胺、六甲基磷醯三胺、及1,3-二甲基-2-咪唑啶酮。 作為酮，可例舉：丙酮、甲基乙基酮、甲基異丙基酮、甲基異丁基酮、甲基正戊基酮、甲基異戊基酮、2-庚酮、環戊酮、環己酮、及環庚酮。 作為酯，可例舉：乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸甲酯、乳酸乙酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、3-乙氧基丙酸乙酯、γ-丁內酯、及γ-戊內酯。 液狀分散介質就製造中可使用之裝置之通用性之觀點而言，其等中，較佳為包含水之分散介質。 The liquid dispersion medium is a compound that is liquid at 25°C under atmospheric pressure, preferably a compound with a boiling point of 50 to 240°C. One liquid dispersion medium may be used, or two or more liquid dispersion media may be used. When two liquid dispersion media are used, the two liquid dispersion media are preferably compatible with each other. The liquid dispersion medium is preferably a compound selected from the group consisting of water, amide, ketone, and ester. Examples of amides include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-diethylformamide, hexamethylphosphatriamidone, and 1,3-dimethyl-2-imidazolidinone. Examples of ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, γ-butyrolactone, and γ-valerolactone. From the perspective of the versatility of the devices that can be used in the production, the liquid dispersion medium is preferably a dispersion medium containing water.
液狀分散介質就提高F粒子之分散穩定性之觀點而言，較佳為進而包含非離子性界面活性劑。 作為非離子性界面活性劑，可例舉：乙炔系界面活性劑、矽酮系界面活性劑、氟系界面活性劑等。 作為非離子性界面活性劑之具體例，可例舉：「FTERGENT」系列(NEOS公司製造)、「Surflon」(註冊商標)系列(AGC Seimi Chemical公司製造)、「MEGAFAC」(註冊商標)系列(DIC公司製造)、「Unidyne」系列(大金工業公司製造)、「BYK-347」、「BYK-349」、「BYK-378」、「BYK-3450」、「BYK-3451」、「BYK-3455」、「BYK-3456」(BYK-Chemie Japan公司製造)、「KF-6011」、「KF-6043」(信越化學工業公司製造)、及「Tergitol」系列(陶氏化學公司製造，「Tergitol TMN-100X」等)。 於液狀分散介質含有非離子性界面活性劑之情形時，就降低液狀分散介質之表面張力之觀點而言，液狀分散介質中之非離子性界面活性劑之含有率較佳為1～10質量%，更佳為2.5～8質量%，進而較佳為4～6質量%。 From the viewpoint of improving the dispersion stability of the F particles, the liquid dispersion medium preferably further contains a nonionic surfactant. Examples of nonionic surfactants include acetylene-based surfactants, silicone-based surfactants, and fluorine-based surfactants. Specific examples of nonionic surfactants include: "FTERGENT" series (manufactured by NEOS), "Surflon" (registered trademark) series (manufactured by AGC Seimi Chemical Co., Ltd.), "MEGAFAC" (registered trademark) series (manufactured by DIC Corporation), "Unidyne" series (manufactured by Daikin Industries, Ltd.), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by BYK-Chemie Japan Co., Ltd.), "KF-6011", "KF-6043" (manufactured by Shin-Etsu Chemical Co., Ltd.), and "Tergitol" series (manufactured by The Dow Chemical Company, "Tergitol TMN-100X" etc.). When the liquid dispersion medium contains a non-ionic surfactant, from the viewpoint of reducing the surface tension of the liquid dispersion medium, the content of the non-ionic surfactant in the liquid dispersion medium is preferably 1 to 10% by mass, more preferably 2.5 to 8% by mass, and further preferably 4 to 6% by mass.
關於液狀分散介質之表面張力，例如可列舉20～35 mN/m之範圍，較佳為20～30 mN/m。藉由使液狀分散介質之表面張力處於上述範圍內，使得組合物容易親和基材之表面，容易獲得露出面之Sdq較小之聚合物層。 再者，上述液狀分散介質之表面張力係依據JIS K 2241：2007，使用杜諾葉(Du Noüy)表面張力計於25℃下所測定之值。於測定組合物中所含之液狀分散介質之表面張力之情形時，例如自組合物中藉由過濾等去除F粒子等固體成分後再進行測定。 Regarding the surface tension of the liquid dispersion medium, for example, the range is 20 to 35 mN/m, preferably 20 to 30 mN/m. By making the surface tension of the liquid dispersion medium within the above range, the composition is easy to be affinity with the surface of the substrate, and it is easy to obtain a polymer layer with a smaller Sdq on the exposed surface. Furthermore, the surface tension of the above liquid dispersion medium is a value measured at 25°C using a Du Noüy surface tension meter in accordance with JIS K 2241:2007. When measuring the surface tension of the liquid dispersion medium contained in the composition, for example, the solid components such as F particles are removed from the composition by filtering, etc. before measurement.
液狀分散介質之含量相對於組合物之總質量，較佳為30質量%以上，更佳為40質量%以上。液狀分散介質之含量相對於組合物之總質量，較佳為80質量%以下，更佳為60質量%以下。上述液狀分散介質之含量意指自組合物去除固形物成分後之物質之總量。 組合物中之固形物成分濃度相對於組合物之總質量，較佳為20質量%以上，更佳為40質量%以上。固形物成分濃度較佳為70質量%以下，更佳為60質量%以下。再者，固形物成分意指由組合物所形成之成形物中形成固形物成分之物質之總量。具體而言，於F粒子包含於固形物成分中且組合物包含其他樹脂之情形時，其他樹脂亦包含於固形物成分中，於組合物包含無機填料之情形時，無機填料亦包含於固形物成分中。 The content of the liquid dispersion medium relative to the total mass of the composition is preferably 30 mass% or more, and more preferably 40 mass% or more. The content of the liquid dispersion medium relative to the total mass of the composition is preferably 80 mass% or less, and more preferably 60 mass% or less. The above-mentioned content of the liquid dispersion medium means the total amount of the substance after removing the solid components from the composition. The concentration of the solid component in the composition is preferably 20 mass% or more, and more preferably 40 mass% or more relative to the total mass of the composition. The concentration of the solid component is preferably 70 mass% or less, and more preferably 60 mass% or less. Furthermore, the solid component means the total amount of the substance forming the solid component in the molded object formed by the composition. Specifically, when the F particles are contained in the solid component and the composition contains other resins, the other resins are also contained in the solid component, and when the composition contains an inorganic filler, the inorganic filler is also contained in the solid component.
組合物可進而包含觸變性賦予劑、黏度調節劑、消泡劑、脫水劑、塑化劑、耐候劑、抗氧化劑、熱穩定劑、潤滑劑、抗靜電劑、增白劑、著色劑、導電劑、離型劑、表面處理劑、阻燃劑、以導電性填料為代表之各種填料等添加劑。The composition may further include additives such as thixotropic agents, viscosity regulators, defoamers, dehydrating agents, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, release agents, surface treatment agents, flame retardants, and various fillers represented by conductive fillers.
組合物之黏度較佳為10 mPa・s以上，更佳為100 mPa・s以上。組合物之黏度較佳為10000 mPa・s以下，更佳為3000 mPa・s以下。 藉由使組合物之黏度處於上述範圍內，而較低於上述範圍之情形而言，容易於基材之表面保持組合物層，抑制由滴液等引起之組合物層之厚度不均，容易獲得露出面之Sdq較小之聚合物層。又，藉由使組合物之黏度處於上述範圍內，而較高於上述範圍之情形而言，組合物層之厚度容易變得均勻，容易獲得露出面之Sdq較小之聚合物層。 The viscosity of the composition is preferably 10 mPa·s or more, more preferably 100 mPa·s or more. The viscosity of the composition is preferably 10000 mPa·s or less, more preferably 3000 mPa·s or less. By making the viscosity of the composition within the above range, and in the case of being lower than the above range, it is easy to maintain the composition layer on the surface of the substrate, suppress the uneven thickness of the composition layer caused by dripping, etc., and it is easy to obtain a polymer layer with a smaller Sdq on the exposed surface. In addition, by making the viscosity of the composition within the above range, and in the case of being higher than the above range, the thickness of the composition layer is easy to become uniform, and it is easy to obtain a polymer layer with a smaller Sdq on the exposed surface.
可於組合物之液狀分散介質含有增黏劑，以便將組合物之黏度調整至上述範圍。 作為增黏劑，可例舉：胺基甲酸酯系增黏劑、聚丙烯酸系增黏劑、聚醯胺系增黏劑、纖維素系增黏劑、膨潤土等黏土礦物等增黏劑等。 於液狀分散介質包含增黏劑之情形時，作為液狀分散介質中之增黏劑之含有率，可例舉0.1～5質量%之範圍。 The liquid dispersion medium of the composition may contain a thickener so as to adjust the viscosity of the composition to the above range. Examples of the thickener include urethane thickeners, polyacrylic acid thickeners, polyamide thickeners, cellulose thickeners, clay minerals such as bentonite, etc. When the liquid dispersion medium contains a thickener, the content of the thickener in the liquid dispersion medium may be in the range of 0.1 to 5% by mass.
組合物係藉由混合F粒子、以及視需要而定之其他樹脂、無機填料、液狀分散介質、添加劑等而獲得。混合之順序並無特別限制，又，混合之方法亦無特別限制，可一次混合，亦可分為複數次進行混合。 作為用於獲得組合物之混合裝置，可例舉：亨舍爾混合機、加壓捏合機、班布里混合機及行星式混合機等具備葉片之攪拌裝置；球磨機、磨光機、籃式磨機、砂磨機(sand mill)、砂磨機(sand grinder)、DYNO-MILL、Dispermat、SC Mill、釘碎機(spike mill)及攪拌磨機等具備介質之粉碎裝置；以及微噴均質機、Nanomizer、ULTIMAIZER、超音波均質機、溶解器(dissolver)、分散機(disper)、高速葉輪、薄膜迴旋型高速混合機、自轉公轉攪拌機及V型攪拌器等具備其他機構之分散裝置。 The composition is obtained by mixing F particles and other resins, inorganic fillers, liquid dispersion media, additives, etc. as needed. There is no particular restriction on the order of mixing, and there is no particular restriction on the method of mixing. The mixing can be done once or in multiple times. Examples of mixing devices used to obtain the composition include: stirring devices with blades such as Henschel mixers, pressure kneaders, Banbury mixers, and planetary mixers; pulverizing devices with media such as ball mills, polishers, basket mills, sand mills, sand grinders, DYNO-MILLs, Dispermats, SC Mills, spike mills, and agitator mills; and dispersing devices with other mechanisms such as micro-spray homogenizers, Nanomizers, ULTIMAIZERs, ultrasonic homogenizers, dissolvers, dispersers, high-speed impellers, thin-film rotary high-speed mixers, rotational-revolutionary mixers, and V-type mixers.
作為將組合物塗佈於基材12之塗佈面之方法，可例舉：噴霧法、輥式塗佈、旋轉塗佈法、凹版塗佈法、微凹版塗佈法、凹版膠版法、刮塗法、接觸塗佈法、棒式塗佈法、模嘴塗佈法、噴注麥勒棒法、狹縫式模嘴塗佈法、小徑反向凹版法等塗佈法。 將組合物塗佈於基材12之塗佈面時之基材12之搬送速度並無特別限定，例如可例舉2～50 m/分鐘。 Examples of methods for applying the composition to the coating surface of the substrate 12 include spraying, roller coating, rotary coating, gravure coating, micro-gravure coating, gravure stencil coating, doctor blade coating, contact coating, rod coating, die nozzle coating, injection merrer rod coating, slit die nozzle coating, small-diameter reverse gravure coating, etc. The conveying speed of the substrate 12 when applying the composition to the coating surface of the substrate 12 is not particularly limited, and for example, 2 to 50 m/min.
作為對將組合物塗佈於基材12之塗佈面而形成之組合物層26進行熱處理之方法，可例舉：使用烘箱之方法、使用通風乾燥爐之方法、照射紅外線等熱線之方法等。 熱處理時之氛圍可為常壓下、減壓下之任一狀態。又，上述氛圍可為氧化性氣體(氧氣等)氛圍、還原性氣體(氫氣等)氛圍、惰性氣體(稀有氣體、氮氣)氛圍之任一種。 As a method for heat treating the composition layer 26 formed by coating the composition on the coating surface of the substrate 12, there can be cited: a method using an oven, a method using a ventilation drying furnace, a method of irradiating heat rays such as infrared rays, etc. The atmosphere during the heat treatment can be any state of normal pressure or reduced pressure. In addition, the above atmosphere can be any of an oxidizing gas (oxygen, etc.) atmosphere, a reducing gas (hydrogen, etc.) atmosphere, and an inert gas (rare gas, nitrogen) atmosphere.
作為熱處理，可例舉：以去除組合物層26中所含之液狀分散介質之至少一部分之乾燥為目的之熱處理(以下，亦稱為「乾燥處理」)、以焙燒組合物層26中所含之F粒子為目的之熱處理(以下，亦稱為「焙燒處理」)等。 乾燥處理時之加熱溫度較佳為120～200℃。乾燥處理時之加熱溫度之保持時間較佳為0.1～10分鐘。乾燥處理可以1個階段進行，亦可於不同之溫度下以2個階段以上進行。 焙燒處理時之加熱溫度較佳為F聚合物之熔點以上之溫度，具體而言，較佳為280～400℃，更佳為300～380℃。焙燒處理時之加熱溫度之保持時間較佳為0.5～30分鐘。焙燒處理可以1個階段進行，亦可於不同之溫度下以2個階段以上進行。 As heat treatment, there can be cited: heat treatment for the purpose of drying and removing at least a portion of the liquid dispersion medium contained in the composition layer 26 (hereinafter, also referred to as "drying treatment"), heat treatment for the purpose of baking the F particles contained in the composition layer 26 (hereinafter, also referred to as "baking treatment"), etc. The heating temperature during the drying treatment is preferably 120 to 200°C. The holding time of the heating temperature during the drying treatment is preferably 0.1 to 10 minutes. The drying treatment can be carried out in one stage, or in two or more stages at different temperatures. The heating temperature during the baking treatment is preferably a temperature above the melting point of the F polymer, specifically, preferably 280 to 400°C, and more preferably 300 to 380°C. The best time to maintain the heating temperature during the roasting process is 0.5 to 30 minutes. The roasting process can be carried out in one stage or in two or more stages at different temperatures.
對形成於基材12之第1面之組合物層26進行熱處理而形成第1層之步驟中之熱處理，可僅為乾燥處理，亦可僅為焙燒處理，亦可為包括乾燥處理及在乾燥處理後進行之焙燒處理兩者之熱處理。即，第1層可為組合物層26經由乾燥處理而F粒子未經焙燒之狀態之層，亦可為包含F粒子經焙燒而成之燒結體之P-A1層。The heat treatment in the step of forming the first layer by heat-treating the composition layer 26 formed on the first surface of the substrate 12 may be only a drying treatment, only a baking treatment, or a heat treatment including both a drying treatment and a baking treatment performed after the drying treatment. That is, the first layer may be a layer in which the composition layer 26 has been dried but the F particles have not been baked, or may be a P-A1 layer including a sintered body formed by baking the F particles.
於基材12之第1面形成第1層後對形成於基材12之第2面之組合物層26進行熱處理而形成第2層之步驟中之熱處理，可僅為焙燒處理，亦可為包括乾燥處理及在乾燥處理後進行之焙燒處理兩者之熱處理。藉由使形成於基材12之第2面之組合物層26至少經由熱處理，而於基材12之第2面形成作為第2層之第2聚合物層。 於在形成第1層之步驟中未經由焙燒處理之情形時，即第1層之F粒子未經焙燒之情形時，在形成第2層之步驟中之焙燒處理中亦對第1層進行焙燒，而獲得包含F粒子經焙燒而成之燒結體之P-A1層。 The heat treatment in the step of forming the second layer by heat-treating the composition layer 26 formed on the second surface of the substrate 12 after forming the first layer on the first surface of the substrate 12 may be only a baking treatment, or may be a heat treatment including a drying treatment and a baking treatment performed after the drying treatment. By subjecting the composition layer 26 formed on the second surface of the substrate 12 to at least heat treatment, a second polymer layer as the second layer is formed on the second surface of the substrate 12. In the case where the first layer is not subjected to calcination treatment during the step of forming the first layer, that is, the F particles of the first layer are not calcined, the first layer is also calcined during the calcination treatment during the step of forming the second layer, and a P-A1 layer including a sintered body formed by calcining the F particles is obtained.
關於將所獲得之長條積層基材捲繞至捲芯而製成捲筒片材之步驟中所使用之捲芯，並無特別限定，可例舉具有基材12之寬度以上之軸向長度的圓筒狀構件。此處，圓筒狀捲芯可為具有空腔之圓筒狀捲芯，亦可為不具有空腔之圓柱狀捲芯。 捲芯之材質並無特別限定，例如可例舉樹脂、橡膠、金屬、其等之組合等。 於捲芯為圓筒狀之情形時，作為捲芯之外徑，可例舉50～240 mm，作為捲芯之外周面之曲率，可例舉0.009～0.049 mm -1。 於捲芯為具有空腔之圓筒狀捲芯之情形時，捲芯之厚度並無特別限定，就維持捲芯之強度之觀點而言，較佳為5 mm以上。 There is no particular limitation on the core used in the step of winding the obtained long strip laminated substrate onto a core to form a roll sheet, and an example thereof may be a cylindrical member having an axial length greater than the width of the substrate 12. Here, the cylindrical core may be a cylindrical core having a cavity, or a cylindrical core without a cavity. There is no particular limitation on the material of the core, and examples thereof include resin, rubber, metal, and combinations thereof. When the core is cylindrical, the outer diameter of the core may be 50 to 240 mm, and the curvature of the outer circumference of the core may be 0.009 to 0.049 mm -1 . When the winding core is a cylindrical winding core having a cavity, the thickness of the winding core is not particularly limited, but is preferably 5 mm or more from the viewpoint of maintaining the strength of the winding core.
將所獲得之長條積層基材捲繞至捲芯之外周面時對長條積層基材所施加之捲繞應力較佳為1～3 MPa。藉由使捲繞應力處於上述範圍內，而較低於上述範圍之情形而言，可抑制長條積層基材一面向捲芯之軸向偏移一面被捲取之捲繞偏移。又，藉由使捲繞應力處於上述範圍內，而較大於上述範圍之情形而言，可抑制在製成捲筒片材後捲出之長條積層基材之捲曲。The winding stress applied to the obtained long laminated substrate when winding it around the outer peripheral surface of the winding core is preferably 1 to 3 MPa. By making the winding stress within the above range, but lower than the above range, the winding deviation of the long laminated substrate while being wound up while being axially deviated from the winding core can be suppressed. In addition, by making the winding stress within the above range, but greater than the above range, the warping of the long laminated substrate rolled out after the roll sheet is made can be suppressed.
長條積層基材之合計厚度為36 μm以上，就積層基材之尺寸穩定性之觀點而言，較佳為50 μm以上，更佳為75 μm以上。長條積層基材之合計厚度為130 μm以下，就相同觀點而言，較佳為120 μm以下，更佳為100 μm以下。 關於長條積層基材之短邊方向之長度即寬度，就積層基材之尺寸穩定性之觀點而言，較佳為500～1250 mm。 長條積層基材之長邊方向之長度較佳為100～1000 m。 長條積層基材之長邊方向之長度較佳為長條積層基材之寬度之50倍以上，更佳為100倍以上。長條積層基材之長邊方向之長度較佳為長條積層基材之寬度之1000倍以下。 The total thickness of the long strip laminate substrate is 36 μm or more, preferably 50 μm or more, and more preferably 75 μm or more from the perspective of the dimensional stability of the laminate substrate. The total thickness of the long strip laminate substrate is 130 μm or less, preferably 120 μm or less, and more preferably 100 μm or less from the same perspective. Regarding the length of the short side direction of the long strip laminate substrate, i.e. the width, from the perspective of the dimensional stability of the laminate substrate, it is preferably 500 to 1250 mm. The length of the long side direction of the long strip laminate substrate is preferably 100 to 1000 m. The length of the long side of the long strip laminated substrate is preferably more than 50 times the width of the long strip laminated substrate, and more preferably more than 100 times. The length of the long side of the long strip laminated substrate is preferably less than 1000 times the width of the long strip laminated substrate.
本實施方式之長條積層基材例如用於製作印刷配線基板製作用之覆金屬積層體。 覆金屬積層體例如具有切割本實施方式之長條積層基材之一部分而獲得之積層基材、及設置於上述積層基材之一面之金屬箔層。 作為構成金屬箔層之金屬，可例舉：銅、銅合金、不鏽鋼、鎳、鎳合金(亦包含42合金)、鋁、鋁合金、鈦、鈦合金等。 作為用於形成金屬箔層之金屬箔，較佳為銅箔。作為銅箔，可例舉壓延銅箔、電解銅箔、濺鍍銅箔、無電解鍍覆銅箔等。其等中，銅箔更佳為無正反之分之壓延銅箔及有正反之分之電解銅箔，進而較佳為壓延銅箔。壓延銅箔由於表面粗糙度較小，故而即便於將覆金屬積層體加工成印刷配線基板之情形時，亦可降低傳輸損耗。又，壓延銅箔較佳為浸漬於烴系有機溶劑中去除壓延油後使用。 金屬箔層之厚度較佳為未達20 μm，更佳為2～15 μm。 作為覆金屬積層體之製造方法，例如可例舉如下方法：切割本實施方式之長條積層基材之一部分而獲得積層基材後，於上述積層基材中之聚合物層之露出面設置金屬箔層。作為於積層基材設置金屬箔層之方法，可例舉如下方法：將積層基材與金屬箔以金屬箔與積層基材之聚合物層之露出面相接之方式重疊，進行熱壓而使其等貼合之方法；藉由在積層基材之聚合物層之露出面直接進行鍍覆而形成金屬箔層之方法等。覆金屬積層體之製造方法亦可為如下方法：一面將本實施方式之長條積層基材與長條金屬箔同時捲出，一面於長條積層基材之聚合物層之露出面設置金屬箔層，獲得長條覆金屬積層體。 The long strip laminate substrate of the present embodiment is used, for example, for making a metal-clad laminate for use as a printed wiring board. The metal-clad laminate has, for example, a laminate substrate obtained by cutting a portion of the long strip laminate substrate of the present embodiment, and a metal foil layer provided on one surface of the laminate substrate. Examples of metals constituting the metal foil layer include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy, etc. As the metal foil used to form the metal foil layer, copper foil is preferably used. Examples of copper foil include rolled copper foil, electrolytic copper foil, sputter-plated copper foil, and electroless plated copper foil. Among them, rolled copper foil without front and back sides and electrolytic copper foil with front and back sides are preferred, and rolled copper foil is more preferred. Rolled copper foil has a smaller surface roughness, so even when the metal laminate is processed into a printed wiring board, the transmission loss can be reduced. In addition, rolled copper foil is preferably used after being immersed in a hydrocarbon organic solvent to remove the rolling oil. The thickness of the metal foil layer is preferably less than 20 μm, and more preferably 2 to 15 μm. As a method for manufacturing a metal-clad laminate, for example, the following method can be cited: after a portion of the long laminate substrate of the present embodiment is cut to obtain a laminate substrate, a metal foil layer is provided on the exposed surface of the polymer layer in the laminate substrate. As a method for providing a metal foil layer on the laminate substrate, the following method can be cited: a method of laminating the laminate substrate and the metal foil in such a manner that the metal foil and the exposed surface of the polymer layer of the laminate substrate are in contact, and then laminating them by heat pressing; a method of directly plating the exposed surface of the polymer layer of the laminate substrate to form a metal foil layer, etc. The manufacturing method of the metal-clad laminate can also be the following method: on one hand, the long strip laminate substrate and the long strip metal foil of the present embodiment are rolled out simultaneously, and on the other hand, a metal foil layer is provided on the exposed surface of the polymer layer of the long strip laminate substrate to obtain a long strip metal-clad laminate.
上述覆金屬積層體之電特性、耐回流焊性等耐熱性、開孔加工性、耐化學品性、表面平滑性等諸物性優異。因此，上述覆金屬積層體適宜作為印刷配線基板材料，可容易且效率良好地加工成軟性印刷配線基板、剛性印刷配線基板等。 藉由以蝕刻對上述覆金屬積層體之金屬箔層進行加工來形成傳輸電路，可獲得印刷配線基板。即，印刷配線基板之製造方法係以蝕刻對覆金屬積層體之金屬箔進行加工，形成傳輸電路，獲得印刷配線基板之方法。再者，蝕刻時可使用濕式蝕刻法及乾式蝕刻法中之任一種。 於印刷配線基板之製造中，亦可於形成傳輸電路後，在傳輸電路上形成層間絕緣膜，在層間絕緣膜上進而形成導體電路。 The above-mentioned metal-clad laminate has excellent electrical properties, heat resistance such as reflow resistance, hole processing, chemical resistance, surface smoothness and other physical properties. Therefore, the above-mentioned metal-clad laminate is suitable as a printed wiring board material, and can be easily and efficiently processed into a flexible printed wiring board, a rigid printed wiring board, etc. By etching the metal foil layer of the above-mentioned metal-clad laminate to form a transmission circuit, a printed wiring board can be obtained. That is, the manufacturing method of the printed wiring board is a method of processing the metal foil of the metal-clad laminate by etching to form a transmission circuit to obtain a printed wiring board. Furthermore, any one of wet etching and dry etching can be used for etching. In the manufacture of printed wiring boards, after forming a transmission circuit, an interlayer insulating film may be formed on the transmission circuit, and a conductive circuit may be further formed on the interlayer insulating film.
[長條片材捲筒及其製造方法] 本發明之一實施方式中之長條片材捲筒具有圓筒狀捲芯、及捲繞至上述捲芯之外周面之長條積層基材，上述長條積層基材具有厚度12～50 μm之基材、及2個聚合物層，該2個聚合物層分別設置於上述基材之兩面，包含四氟乙烯系聚合物，且各自之厚度為12～40 μm，上述2個聚合物層之合計厚度為上述基材之厚度之1.8～3.0倍，上述2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍，上述捲芯之外徑之曲率Cmm -1與上述長條積層基材之合計厚度Tmm之積C×T的值未達0.0015。 以下，亦將四氟乙烯系聚合物稱為「F聚合物」，亦將捲芯之外徑之曲率稱為「曲率」，亦將長條積層基材之合計厚度稱為「積層厚度」，亦將曲率Cmm -1與積層厚度Tmm之積稱為「積C×T」。 [Long sheet roll and its manufacturing method] The long sheet roll in one embodiment of the present invention has a cylindrical core and a long laminated substrate wound to the outer peripheral surface of the above-mentioned core, the above-mentioned long laminated substrate has a substrate with a thickness of 12 to 50 μm and two polymer layers, the two polymer layers are respectively arranged on both sides of the above-mentioned substrate, and contain tetrafluoroethylene polymers, and each has a thickness of 12 to 40 μm, the total thickness of the above-mentioned two polymer layers is 1.8 to 3.0 times the thickness of the above-mentioned substrate, the thickness of one of the above-mentioned two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer, and the value of the product C×T of the curvature Cmm -1 of the outer diameter of the above-mentioned core and the total thickness Tmm of the above-mentioned long laminated substrate does not reach 0.0015. Hereinafter, the tetrafluoroethylene polymer is referred to as "F polymer", the curvature of the outer diameter of the core is referred to as "curvature", the total thickness of the long strip laminate substrate is referred to as "laminate thickness", and the product of the curvature Cmm -1 and the laminate thickness Tmm is referred to as "product C×T".
本實施方式中，「長條」意指長邊方向之長度為100 m以上。長條積層基材之長邊方向之長度較佳為200 m以上。長邊方向之長度較佳為1000 m以下。 將長條積層基材捲繞至捲芯之外周面所得之長條片材捲筒例如可用於製作覆金屬積層體。具體而言，例如藉由在自長條片材捲筒捲出長條積層基材之一部分而獲得之積層基材之表面壓接金屬箔，而獲得覆金屬積層體。 In this embodiment, "strip" means that the length in the long side direction is 100 m or more. The length in the long side direction of the long strip laminated substrate is preferably 200 m or more. The length in the long side direction is preferably 1000 m or less. The long sheet roll obtained by winding the long strip laminated substrate onto the outer peripheral surface of the winding core can be used, for example, to make a metal-clad laminate. Specifically, for example, a metal-clad laminate is obtained by pressing a metal foil on the surface of a laminated substrate obtained by unrolling a portion of the long strip laminated substrate from a long sheet roll.
對於將包含F聚合物之聚合物層分別設置於基材之兩面而成之長條積層基材，可期待具備F聚合物之物性與基材之物性兩者。例如若使用包含耐熱性樹脂之耐熱性基材作為基材，則可獲得具備耐熱性、尺寸穩定性等物性、與作為F聚合物之物性之低介電常數性、低介電損耗因數性等電氣物性兩者之長條積層基材。A long laminated substrate formed by placing polymer layers containing F polymer on both sides of a substrate can be expected to have both the physical properties of the F polymer and the physical properties of the substrate. For example, if a heat-resistant substrate containing a heat-resistant resin is used as the substrate, a long laminated substrate can be obtained that has both the physical properties such as heat resistance and dimensional stability and the electrical properties such as low dielectric constant and low dielectric dissipation factor that are the physical properties of the F polymer.
另一方面，將上述長條積層基材捲繞至捲芯所得之長條片材捲筒中，於將長條積層基材捲出並製成覆金屬積層體時，金屬箔可能產生皺褶。並且，若金屬箔產生皺褶，則容易引發製造印刷配線基板等時之障礙(良率變差、製品品質之降低等)。關於上述金屬箔產生皺褶之原因，推測由所捲出之長條積層基材中所發生之捲曲所引起。認為尤其使包含F聚合物之聚合物層之合計厚度變得比基材之厚度更厚，使得長條積層基材更容易發生捲曲。On the other hand, when the long strip laminated substrate is wound around a winding core to obtain a long sheet roll, the metal foil may be wrinkled when the long strip laminated substrate is rolled out and made into a metal-clad laminate. In addition, if the metal foil is wrinkled, it is easy to cause troubles in the manufacture of printed wiring boards, etc. (yield degradation, reduced product quality, etc.). The reason for the wrinkles in the metal foil is presumed to be caused by the curling that occurs in the rolled-out long strip laminated substrate. It is believed that the total thickness of the polymer layer containing the F polymer becomes thicker than the thickness of the substrate, making the long strip laminated substrate more prone to curling.
相對於此，本實施方式採用以下構成：2個聚合物層之合計厚度為基材之厚度之1.8～3.0倍，2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍，且將積C×T設為未達0.0015。本發明人等發現，藉由採用上述構成，可抑制長條積層基材發生捲曲，抑制由捲曲引起之金屬箔之皺褶。其原因並不確定，但如下推測。 上述曲率係表示捲芯之外周面之彎曲程度之值，彎曲程度越大則曲率之值越大。例如半徑r之圓周之曲率為1/r。若將長條積層基材捲繞至圓筒狀捲芯，則長條積層基材中之外側之聚合物層與內側之聚合物層中會產生不同之應力。並且，捲芯之曲率越大，則外側之聚合物層中所產生之應力與內側之聚合物層中所產生之應力之差越大，而容易因上述應力之差所引起之應變而發生捲曲。 另一方面，藉由將積C×T設為0.0015而非單單使曲率變小，且將2個聚合物層之合計厚度相對於基材之厚度之比設定得更大即1.8倍以上，使得捲取時之上述應力之差容易被長條積層基材吸收。於是推測在捲出時導致捲曲之聚合物層之應變得到緩和，可抑制捲曲之發生。 以下，使用圖式對本實施方式中之長條片材捲筒之一例進行說明，但本發明之長條片材捲筒並不限於其等。 In contrast, the present embodiment adopts the following structure: the total thickness of the two polymer layers is 1.8 to 3.0 times the thickness of the substrate, the thickness of one of the two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer, and the product C×T is set to less than 0.0015. The inventors of the present invention have found that by adopting the above structure, the curling of the long strip laminated substrate can be suppressed, and the wrinkles of the metal foil caused by the curling can be suppressed. The reason is uncertain, but it is speculated as follows. The above curvature represents the value of the degree of curvature of the outer peripheral surface of the winding core. The greater the degree of curvature, the greater the value of the curvature. For example, the curvature of the circumference of the radius r is 1/r. If a long laminated substrate is wound around a cylindrical core, different stresses will be generated in the outer polymer layer and the inner polymer layer of the long laminated substrate. Moreover, the greater the curvature of the core, the greater the difference between the stress generated in the outer polymer layer and the stress generated in the inner polymer layer, and the curling is more likely to occur due to the strain caused by the above stress difference. On the other hand, by setting the product C×T to 0.0015 instead of simply reducing the curvature, and setting the ratio of the total thickness of the two polymer layers to the thickness of the substrate to be larger, that is, 1.8 times or more, the above stress difference during winding is easily absorbed by the long laminated substrate. Therefore, it is speculated that the strain of the polymer layer that causes curling during unwinding is relieved, which can suppress the occurrence of curling. Below, an example of a long sheet roll in this embodiment is described using a diagram, but the long sheet roll of the present invention is not limited to this example.
圖3係模式性地表示本實施方式之長條片材捲筒之立體圖。圖4係表示圖3中所示之長條片材捲筒中之長條積層基材之層構成的概略剖視圖。 圖3中所示之長條片材捲筒100具有圓筒狀捲芯120、及捲繞至捲芯120之外周面之長條積層基材10。如圖4所示，長條積層基材10具有基材12、及分別設置於基材12之兩面之聚合物層14及聚合物層16。 FIG3 is a perspective view schematically showing a long sheet roll of the present embodiment. FIG4 is a schematic cross-sectional view showing the layer structure of the long laminated substrate in the long sheet roll shown in FIG3. The long sheet roll 100 shown in FIG3 has a cylindrical winding core 120 and a long laminated substrate 10 wound around the outer peripheral surface of the winding core 120. As shown in FIG4, the long laminated substrate 10 has a substrate 12, and a polymer layer 14 and a polymer layer 16 respectively disposed on both sides of the substrate 12.
捲芯只要為圓筒狀捲芯，便無特別限定，可例舉軸向之長度為下述長條積層基材之短邊方向之長度(以下，亦稱為「寬度」)以上的圓筒狀構件。此處，圓筒狀捲芯可為具有空腔之圓筒狀捲芯，亦可為不具有空腔之圓柱狀捲芯。 捲芯之材質並無特別限定，例如可可例舉：樹脂、橡膠、金屬、其等之組成等。就處理性與尺寸穩定性之觀點而言，捲芯之材質較佳為樹脂或橡膠。 The core is not particularly limited as long as it is a cylindrical core, and an example thereof may be a cylindrical member whose axial length is greater than the length of the short side direction of the long strip laminate substrate described below (hereinafter also referred to as "width"). Here, the cylindrical core may be a cylindrical core with a cavity or a cylindrical core without a cavity. The material of the core is not particularly limited, and examples thereof include resin, rubber, metal, and a combination thereof. From the viewpoint of handling and dimensional stability, the core is preferably made of resin or rubber.
作為捲芯之外徑，可例舉50～240 mm，就抑制長條積層基材之捲曲之觀點而言，較佳為80～200 mm，更佳為90～185 mm。 作為曲率，可例舉0.009～0.037 mm -1，就抑制長條積層基材之捲曲之觀點而言，較佳為0.010～0.025 mm -1，更佳為0.011～0.022 mm -1。 捲芯之軸向之長度只要為長條積層基材之短邊方向之長度以上即可，例如可例舉500～1250 mm之範圍。 於捲芯為具有空腔之圓筒狀捲芯之情形時，捲芯之厚度並無特別限定，就維持捲芯之強度之觀點而言，較佳為5 mm以上。 The outer diameter of the winding core may be 50 to 240 mm, preferably 80 to 200 mm, and more preferably 90 to 185 mm from the viewpoint of suppressing the curling of the long strip laminated substrate. The curvature may be 0.009 to 0.037 mm -1 , preferably 0.010 to 0.025 mm -1 , and more preferably 0.011 to 0.022 mm -1 from the viewpoint of suppressing the curling of the long strip laminated substrate. The axial length of the winding core may be greater than the length of the short side of the long strip laminated substrate, and may be, for example, in the range of 500 to 1250 mm. When the winding core is a cylindrical winding core having a cavity, the thickness of the winding core is not particularly limited, but is preferably 5 mm or more from the viewpoint of maintaining the strength of the winding core.
積C×T未達0.0015，就抑制長條積層基材之捲曲之觀點而言，較佳為0.0012以下，更佳為0.00120以下。積C×T之下限值較佳為0.0010以上。The product C×T is less than 0.0015, and is preferably 0.0012 or less, and more preferably 0.00120 or less, from the viewpoint of suppressing the curling of the long-strip laminated substrate. The lower limit of the product C×T is preferably 0.0010 or more.
作為基材，可例舉與上述長條積層基材及其製造方法中之基材相同之基材，較佳之基材形態亦與上述長條積層基材及其製造方法中之基材相同。 又，基材之厚度、及基材之短邊方向之長度即寬度、以及基材之長邊方向之長度亦與上述長條積層基材及其製造方法中之基材之其等相同，較佳之形態亦與上述長條積層基材及其製造方法中之其等相同。 As the substrate, the same substrate as the substrate in the above-mentioned long strip laminated substrate and the manufacturing method thereof can be cited, and the preferred substrate shape is also the same as the substrate in the above-mentioned long strip laminated substrate and the manufacturing method thereof. In addition, the thickness of the substrate, the length of the short side direction of the substrate, that is, the width, and the length of the long side direction of the substrate are also the same as those of the substrate in the above-mentioned long strip laminated substrate and the manufacturing method thereof, and the preferred shape is also the same as those of the above-mentioned long strip laminated substrate and the manufacturing method thereof.
聚合物層係分別設置於基材之兩面之層。 設置於基材之兩面之2個聚合物層只要均為包含F聚合物且各自之厚度為12～40 μm之層，便無特別限定。 2個聚合物層較佳為均與基材直接相接而設置。 2個聚合物層可分別僅包含一種F聚合物，亦可包含兩種以上。2個聚合物層之組成可彼此相通，亦可不同。 The polymer layers are layers disposed on both sides of the substrate. The two polymer layers disposed on both sides of the substrate are not particularly limited as long as they both contain F polymers and each has a thickness of 12 to 40 μm. The two polymer layers are preferably disposed directly in contact with the substrate. The two polymer layers may each contain only one type of F polymer or may contain two or more types. The compositions of the two polymer layers may be the same or different.
關於F聚合物，亦包括其較佳之形態在內，可例舉與上述長條積層基材及其製造方法中之F聚合物相同之F聚合物。The F polymer, including its preferred form, may be the same F polymer as in the above-mentioned long strip laminate substrate and its manufacturing method.
聚合物層中之F聚合物之含有率較佳為50質量%以上，更佳為60質量%以上。F聚合物之含有率之上限為100質量%。 聚合物層可進而包含除F聚合物以外之其他樹脂。其他樹脂可為熱硬化性樹脂，亦可為熱塑性樹脂。 The content of the F polymer in the polymer layer is preferably 50% by mass or more, more preferably 60% by mass or more. The upper limit of the content of the F polymer is 100% by mass. The polymer layer may further contain other resins besides the F polymer. The other resins may be thermosetting resins or thermoplastic resins.
作為其他樹脂，亦包括其較佳之形態在內，可例舉與上述長條積層基材及其製造方法中之其他樹脂相同之其他樹脂。Examples of other resins, including preferred forms thereof, include the same other resins as those in the above-mentioned long strip laminate substrate and method for producing the same.
就進一步提高長條積層基材之低線膨脹性及電特性之觀點而言，聚合物層可進而包含無機填料。 作為無機填料，亦包括其較佳之形態在內，可例舉與上述長條積層基材及其製造方法中之無機填料相同之無機填料。 From the viewpoint of further improving the low linear expansion and electrical properties of the long strip laminated substrate, the polymer layer may further include an inorganic filler. As the inorganic filler, including its preferred form, the same inorganic filler as the inorganic filler in the above-mentioned long strip laminated substrate and its manufacturing method can be cited.
又，關於聚合物層中之無機填料之含有率，亦包括其較佳之範圍在內，可例舉與上述長條積層基材及其製造方法中之無機填料相同之範圍。 聚合物層除上述成分以外，亦可包括矽烷偶合劑、脫水劑、塑化劑、耐候劑、抗氧化劑、熱穩定劑、潤滑劑、抗靜電劑、增白劑、著色劑、導電劑、離型劑、表面處理劑、阻燃劑等添加劑。 In addition, the content of the inorganic filler in the polymer layer also includes its preferred range, which can be exemplified by the same range as the inorganic filler in the above-mentioned long strip laminate substrate and its manufacturing method. In addition to the above-mentioned components, the polymer layer may also include additives such as silane coupling agent, dehydrating agent, plasticizer, weathering agent, antioxidant, thermal stabilizer, lubricant, antistatic agent, whitening agent, coloring agent, conductive agent, release agent, surface treatment agent, flame retardant, etc.
聚合物層較佳為包含四氟乙烯系聚合物粒子、即包含F聚合物之粒子之燒結體的層。以下，亦將四氟乙烯系聚合物粒子稱為「F粒子」。再者，關於聚合物層是否包含F粒子之燒結體，可藉由以顯微鏡等來觀察聚合物層之剖面而確認。 若聚合物層為包含F粒子之燒結體之層，則F粒子間之空隙成為應力緩和層，因此容易抑制長條積層基材發生捲曲。 於聚合物層為包含F粒子之層之情形時，聚合物層亦可包含除F粒子以外之成分。作為除F粒子以外之成分，可例舉上述除F聚合物以外之成分，具體而言，例如可例舉：除F聚合物以外之樹脂、無機填料、添加劑等。 The polymer layer is preferably a layer containing tetrafluoroethylene polymer particles, that is, a sintered body of particles containing F polymer. Hereinafter, tetrafluoroethylene polymer particles are also referred to as "F particles". In addition, whether the polymer layer contains a sintered body of F particles can be confirmed by observing the cross section of the polymer layer with a microscope or the like. If the polymer layer is a layer containing a sintered body of F particles, the gaps between the F particles become a stress relief layer, so it is easy to suppress the curling of the long strip laminate substrate. In the case where the polymer layer is a layer containing F particles, the polymer layer may also contain components other than F particles. As components other than F particles, the above-mentioned components other than F polymers can be cited, and specifically, for example, resins other than F polymers, inorganic fillers, additives, etc. can be cited.
關於F粒子之D50，亦包括其較佳之範圍在內，可例舉與上述長條積層基材及其製造方法中之F粒子之D50相同之範圍。 F粒子之比表面積較佳為1～25 m 2/g。 F粒子可單獨使用一種，亦可使用兩種以上。 The D50 of the F particles, including its preferred range, can be the same as the D50 of the F particles in the above-mentioned long strip laminate substrate and its manufacturing method. The specific surface area of the F particles is preferably 1 to 25 m 2 /g. The F particles can be used alone or in combination of two or more.
關於F粒子中之F聚合物之含量，亦包括其較佳之範圍在內，可例舉與上述長條積層基材及其製造方法中之F粒子中之F聚合物之含量相同之範圍。The content of the F polymer in the F particles, including its preferred range, can be exemplified by the same range as the content of the F polymer in the F particles in the above-mentioned long strip laminated substrate and the method for producing the same.
2個聚合物層各自之厚度為12～40 μm，就積層基材之尺寸穩定性之觀點而言，較佳為16～36 μm，更佳為20～33 μm。 2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍。 2個聚合物層之合計厚度為基材之厚度之1.8～3.0倍，就抑制長條積層基材發生捲曲之觀點而言，更佳為1.8～2.4倍。 The thickness of each of the two polymer layers is 12 to 40 μm, preferably 16 to 36 μm, and more preferably 20 to 33 μm from the perspective of dimensional stability of the laminated substrate. The thickness of one of the two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer. The total thickness of the two polymer layers is 1.8 to 3.0 times the thickness of the substrate, and more preferably 1.8 to 2.4 times from the perspective of suppressing curling of the long strip laminated substrate.
作為長條積層基材之合計厚度之積層厚度為36 μm以上，就積層基材之尺寸穩定性之觀點而言，較佳為50 μm以上，更佳為75 μm以上。長條積層基材之合計厚度為130 μm以下，就相同觀點而言，較佳為120 μm以下，更佳為100 μm以下。 關於長條積層基材之短邊方向之長度即寬度，就積層基材之尺寸穩定性之觀點而言，較佳為500～1250 mm。 長條積層基材之長邊方向之長度較佳為100～1000 m，更佳為200～1000 m。 長條積層基材之長邊方向之長度較佳為長條積層基材之寬度之50倍以上，更佳為100倍以上。長條積層基材之長邊方向之長度較佳為長條積層基材之寬度之1000倍以下。 The total thickness of the long strip laminated substrate is 36 μm or more, preferably 50 μm or more, and more preferably 75 μm or more from the perspective of the dimensional stability of the laminated substrate. The total thickness of the long strip laminated substrate is 130 μm or less, preferably 120 μm or less, and more preferably 100 μm or less from the same perspective. Regarding the length in the short side direction of the long strip laminated substrate, i.e., the width, from the perspective of the dimensional stability of the laminated substrate, it is preferably 500 to 1250 mm. The length in the long side direction of the long strip laminated substrate is preferably 100 to 1000 m, and more preferably 200 to 1000 m. The length of the long side of the long strip laminated substrate is preferably more than 50 times the width of the long strip laminated substrate, and more preferably more than 100 times. The length of the long side of the long strip laminated substrate is preferably less than 1000 times the width of the long strip laminated substrate.
自長條片材捲筒將長條積層基材捲出500 mm並切下而獲得積層基材片，將該積層基材片靜置於水平面時，積層基材片之距離水平面之上浮高度較佳為1 cm以下，更佳為0.5 cm以下。藉由使上浮高度處於上述範圍內，而較高於上述範圍之情形而言，可抑制使用積層基材片來製造覆金屬積層體時金屬箔產生皺褶。 上述上浮高度意指靜置於水平面之積層基材片之隆起中距離水平面最遠之位置處之距離水平面之高度。又，積層基材片之寬度與長條積層基材之寬度相同。 A laminated substrate sheet is obtained by rolling out a long laminated substrate from a long sheet roll for 500 mm and cutting it. When the laminated substrate sheet is placed on a horizontal plane, the floating height of the laminated substrate sheet from the horizontal plane is preferably 1 cm or less, and more preferably 0.5 cm or less. By making the floating height within the above range, and in the case where it is higher than the above range, wrinkles of the metal foil can be suppressed when the laminated substrate sheet is used to manufacture a metal-clad laminate. The above floating height means the height from the horizontal plane at the position farthest from the horizontal plane in the ridge of the laminated substrate sheet placed on a horizontal plane. In addition, the width of the laminated substrate sheet is the same as the width of the long laminated substrate.
＜長條片材捲筒之製造方法＞ 一實施方式之長條片材捲筒之製造方法包括：準備長條積層基材，該長條積層基材具有厚度12～50 μm之基材、及2個聚合物層，該2個聚合物層分別設置於上述基材之兩面，包含F聚合物，且各自之厚度為12～40 μm，上述2個聚合物層之合計厚度為上述基材之厚度之1.8～3.0倍，上述2個聚合物層中之一聚合物層之厚度為另一聚合物層之厚度之0.9～1.1倍；以及將上述長條積層基材捲繞至圓筒狀捲芯之外周面；上述捲芯之外徑之曲率Cmm -1與上述長條積層基材之合計厚度Tmm之積C×T的值未達0.0015。 <Manufacturing method of long sheet roll> One embodiment of the manufacturing method of long sheet roll includes: preparing a long strip laminated substrate, the long strip laminated substrate having a substrate with a thickness of 12 to 50 μm, and two polymer layers, the two polymer layers are respectively arranged on both sides of the above-mentioned substrate, include F polymer, and each has a thickness of 12 to 40 μm, the total thickness of the above-mentioned two polymer layers is 1.8 to 3.0 times the thickness of the above-mentioned substrate, and the thickness of one of the above-mentioned two polymer layers is 0.9 to 1.1 times the thickness of the other polymer layer; and winding the above-mentioned long strip laminated substrate onto the outer circumferential surface of the cylindrical winding core; the value of the product C×T of the curvature Cmm -1 of the outer diameter of the above-mentioned winding core and the total thickness Tmm of the above-mentioned long strip laminated substrate does not reach 0.0015.
關於準備長條積層基材之方法，並無特別限定，可製造長條積層基材，亦可直接使用已完成之長條積層基材。 長條積層基材之製造方法並無特別限定，可為將包含F粒子及液狀分散介質之組合物塗佈於基材之兩面並進行熱處理之方法(以下，亦稱為「方法B1」)，亦可為將包含F聚合物之膜分別貼合於基材之兩面之方法。 長條積層基材較佳為以方法B1進行製造。藉由以方法B1進行製造，使得所形成之2個聚合物層成為包含F粒子之燒結體之層，容易抑制長條積層基材發生捲曲。 以下，對方法B1之一例進行說明。 There is no particular limitation on the method for preparing the long-strip laminated substrate, and the long-strip laminated substrate may be manufactured or the completed long-strip laminated substrate may be used directly. The method for manufacturing the long-strip laminated substrate is not particularly limited, and may be a method of applying a composition containing F particles and a liquid dispersion medium on both sides of the substrate and performing a heat treatment (hereinafter, also referred to as "method B1"), or a method of laminating a film containing an F polymer to both sides of the substrate. The long-strip laminated substrate is preferably manufactured by method B1. By manufacturing by method B1, the two polymer layers formed become layers of a sintered body containing F particles, and it is easy to suppress the long-strip laminated substrate from curling. An example of method B1 is described below.
方法B1中，例如首先一面使基材中之第2面(以下，亦稱為「面B2」)接觸背輥之外周面一面搬送基材，將含有F粒子及液狀分散介質之組合物塗佈於基材中之第1面(以下，亦稱為「面B1」)並進行熱處理，藉此於面B1形成層(以下，亦稱為「層B1」)。繼而，一面使層B1接觸背輥之外周面一面搬送基材，將上述組合物塗佈於面B2並進行熱處理，藉此於面B2形成層(以下，亦稱為「層B2」)。藉此，獲得包含基材、作為層B1經熱處理之層且含有F聚合物之聚合物層、及作為層B2且含有F聚合物之聚合物層的長條積層基材。 以下，亦將層B1經熱處理之聚合物層稱為「P-B1層」，將作為層B2之聚合物層稱為「P-B2層」。 In method B1, for example, first, the second surface of the substrate (hereinafter, also referred to as "surface B2") is brought into contact with the outer peripheral surface of the back roller while the substrate is transported, and a composition containing F particles and a liquid dispersion medium is applied to the first surface of the substrate (hereinafter, also referred to as "surface B1") and heat-treated, thereby forming a layer on surface B1 (hereinafter, also referred to as "layer B1"). Then, the substrate is transported while layer B1 is brought into contact with the outer peripheral surface of the back roller, and the above-mentioned composition is applied to surface B2 and heat-treated, thereby forming a layer on surface B2 (hereinafter, also referred to as "layer B2"). Thus, a long laminated substrate including a substrate, a polymer layer containing F polymer as layer B1 which has been heat-treated, and a polymer layer containing F polymer as layer B2 is obtained. Hereinafter, the polymer layer containing F polymer as layer B1 which has been heat-treated is also referred to as "P-B1 layer", and the polymer layer containing F polymer as layer B2 is also referred to as "P-B2 layer".
塗佈於基材之表面之組合物含有F粒子及液狀分散介質。 關於組合物及組合物中之F粒子各者之詳情，亦包括其較佳之形態在內，與上述長條積層基材及其製造方法中之其等相同。 The composition applied to the surface of the substrate contains F particles and a liquid dispersion medium. The details of the composition and the F particles in the composition, including their preferred morphologies, are the same as those in the above-mentioned long strip laminate substrate and its manufacturing method.
於形成包含除F粒子以外之成分(除F聚合物以外之樹脂、無機填料、添加劑等)之聚合物層之情形時，組合物可包含上述除F粒子以外之成分。 除F聚合物以外之樹脂、及無機填料詳情亦如上所述，故省略說明。 When forming a polymer layer containing components other than F particles (resins other than F polymers, inorganic fillers, additives, etc.), the composition may contain the above-mentioned components other than F particles. The details of the resins other than F polymers and inorganic fillers are also as described above, so the description is omitted.
作為液狀分散介質，亦包括其較佳之形態在內，係與上述長條積層基材及其製造方法中之液狀分散介質相同之形態。The liquid dispersion medium, including its preferred form, has the same form as the liquid dispersion medium in the above-mentioned long strip laminated substrate and its manufacturing method.
就提高F粒子之分散穩定性之觀點而言，液狀分散介質較佳為進而包含非離子性界面活性劑。 作為非離子性界面活性劑，亦包括其較佳之形態在內，係與上述長條積層基材及其製造方法中之非離子性界面活性劑相同之形態。 From the viewpoint of improving the dispersion stability of the F particles, the liquid dispersion medium preferably further contains a non-ionic surfactant. The non-ionic surfactant, including its preferred form, is the same form as the non-ionic surfactant in the above-mentioned long strip laminate substrate and its manufacturing method.
關於液狀分散介質之含量、組合物中之固形物成分濃度、及組合物之黏度之各自之形態，亦包括其較佳之形態在內，係與上述長條積層基材及其製造方法中之其等相同之形態。The respective forms of the content of the liquid dispersion medium, the solid component concentration in the composition, and the viscosity of the composition, including the preferred forms, are the same as those in the above-mentioned long strip laminated substrate and the manufacturing method thereof.
組合物可進而包含觸變性賦予劑、黏度調節劑、消泡劑、脫水劑、塑化劑、耐候劑、抗氧化劑、熱穩定劑、潤滑劑、抗靜電劑、增白劑、著色劑、導電劑、離型劑、表面處理劑、阻燃劑、以導電性填料為代表之各種填料等添加劑。The composition may further include additives such as thixotropic agents, viscosity regulators, defoamers, dehydrating agents, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, release agents, surface treatment agents, flame retardants, and various fillers represented by conductive fillers.
亦可於組合物之液狀分散介質中含有增黏劑，以便將組合物之黏度調整至上述範圍。 作為增黏劑，可例舉：胺基甲酸酯系增黏劑、聚丙烯酸系增黏劑、聚醯胺系增黏劑、纖維素系增黏劑、膨潤土等黏土礦物等增黏劑等。 於液狀分散介質包含增黏劑之情形時，作為液狀分散介質中之增黏劑之含有率，可例舉0.1～5質量%之範圍。 A thickener may also be included in the liquid dispersion medium of the composition to adjust the viscosity of the composition to the above range. Examples of thickeners include urethane thickeners, polyacrylic acid thickeners, polyamide thickeners, cellulose thickeners, clay minerals such as bentonite, etc. When the liquid dispersion medium contains a thickener, the content of the thickener in the liquid dispersion medium may be in the range of 0.1 to 5% by mass.
組合物係藉由混合F粒子、以及視需要而定之其他樹脂、無機填料、液狀分散介質、添加劑等而獲得。混合之順序並無特別限制，又，混合之方法亦無特別限制，可一次混合，亦可分為複數次進行混合。 作為用於獲得組合物之混合裝置，可例舉上述長條積層基材及其製造方法中之裝置。 The composition is obtained by mixing F particles and other resins, inorganic fillers, liquid dispersion media, additives, etc. as required. There is no particular restriction on the order of mixing, and there is no particular restriction on the method of mixing. Mixing can be performed once or in multiple times. As a mixing device for obtaining the composition, the device in the above-mentioned long strip laminate substrate and its manufacturing method can be cited.
作為將組合物塗佈於基材之塗佈面之方法及條件，可例舉上述長條積層基材及其製造方法中之進行塗佈之方法及條件。As the method and conditions for coating the composition on the coating surface of the substrate, the method and conditions for coating in the above-mentioned long strip laminate substrate and the method for producing the same can be cited.
作為對將組合物塗佈於基材之塗佈面而形成之組合物層進行熱處理之方法及條件，可例舉上述長條積層基材及其製造方法中之進行熱處理之方法及條件。As a method and conditions for heat treating the composition layer formed by coating the composition on the coating surface of the substrate, the method and conditions for heat treating in the above-mentioned long strip laminated substrate and the method for producing the same can be cited.
具體而言，對形成於基材之面B1之組合物層進行熱處理而形成層B1之步驟中之熱處理，可僅為乾燥處理，亦可僅為焙燒處理，亦可為包括乾燥處理及在乾燥處理後進行之焙燒處理兩者之熱處理。即，層B1可為組合物層經由乾燥處理而F粒子未經焙燒之狀態之層，亦可為包含F粒子經焙燒而成之燒結體之P-B1層。Specifically, the heat treatment in the step of heat-treating the composition layer formed on the surface B1 of the substrate to form the layer B1 may be only a drying treatment, only a baking treatment, or a heat treatment including both a drying treatment and a baking treatment performed after the drying treatment. That is, the layer B1 may be a layer in which the composition layer has been dried but the F particles have not been baked, or may be a P-B1 layer including a sintered body formed by baking the F particles.
具體而言，於基材之面B1形成層B1後對形成於基材之面B2之組合物層進行熱處理而形成層B2之步驟中之熱處理，可僅為焙燒處理，亦可為包括乾燥處理及在乾燥處理後進行之焙燒處理兩者之熱處理。藉由使形成於基材之面B2之組合物層至少經由熱處理，而於基材之面B2形成作為層B2之P-B2層。 又，於在形成層B1之步驟中未經由焙燒處理之情形時，即層B1之F粒子未經焙燒之情形時，在形成層B2之步驟中之焙燒處理中亦對層B1進行焙燒，而獲得包含F粒子經焙燒而成之燒結體之P-B1層。 Specifically, the heat treatment in the step of forming layer B2 by heat-treating the composition layer formed on surface B2 of the substrate after forming layer B1 on surface B1 of the substrate may be only a baking treatment, or may be a heat treatment including both a drying treatment and a baking treatment performed after the drying treatment. By subjecting the composition layer formed on surface B2 of the substrate to at least heat treatment, a P-B2 layer as layer B2 is formed on surface B2 of the substrate. Furthermore, when the layer B1 is not subjected to calcination treatment in the step of forming the layer B1, that is, when the F particles of the layer B1 are not calcined, the layer B1 is also calcined in the calcination treatment in the step of forming the layer B2, and the P-B1 layer containing the sintered body formed by the calcined F particles is obtained.
將長條積層基材捲繞至捲芯之外周面之方法並無特別限定。 將長條積層基材捲繞至捲芯之外周面時之捲繞張力只要根據長條積層基材之積層厚度進行調整即可，例如可例舉30～200 N，就抑制長條片材捲筒端部之捲繞偏移之觀點而言，較佳為50～200 N。 The method of winding the long laminated substrate onto the outer peripheral surface of the winding core is not particularly limited. The winding tension when winding the long laminated substrate onto the outer peripheral surface of the winding core can be adjusted according to the laminated thickness of the long laminated substrate, for example, 30 to 200 N can be cited. From the perspective of suppressing the winding deviation at the end of the long sheet roll, 50 to 200 N is preferred.
將長條積層基材捲繞至捲芯之外周面時對長條積層基材所施加之捲繞應力較佳為1～3 MPa，更佳為1.5～2.5 MPa，進而較佳為1.7～2.3 MPa。藉由使捲繞應力處於上述範圍內，而較小於上述範圍之情形而言，可抑制長條積層基材一面向捲芯之軸向偏移一面被捲取之捲繞偏移。又，藉由使捲繞應力處於上述範圍內，而較大於上述範圍之情形而言，可抑制自捲筒片材所捲出之長條積層基材之捲曲。 上述捲繞應力係所測得之捲繞張力除以長條積層基材之截面面積所得之值。 The winding stress applied to the long laminated substrate when winding it around the outer peripheral surface of the winding core is preferably 1 to 3 MPa, more preferably 1.5 to 2.5 MPa, and further preferably 1.7 to 2.3 MPa. By making the winding stress within the above range, but less than the above range, the winding deviation of the long laminated substrate while being wound up can be suppressed. In addition, by making the winding stress within the above range, but greater than the above range, the curling of the long laminated substrate rolled out from the roll sheet can be suppressed. The above winding stress is the value obtained by dividing the measured winding tension by the cross-sectional area of the long strip laminate substrate.
本實施方式之長條片材捲筒例如用於製作印刷配線基板製作用之覆金屬積層體。 關於覆金屬積層體之詳情，與上述長條積層基材及其製造方法中之覆金屬積層體相同。 [實施例] The long sheet roll of this embodiment is used, for example, to make a metal-clad laminate for use in manufacturing a printed wiring board. The details of the metal-clad laminate are the same as those of the metal-clad laminate in the above-mentioned long laminate substrate and its manufacturing method. [Example]
以下，利用實施例來詳細地說明本發明之實施方式，但本發明之實施方式並不限於其等。Hereinafter, the implementation of the present invention will be described in detail using examples, but the implementation of the present invention is not limited to the examples.
A1.各成分及各構件之準備(其1) 準備以下之材料及構件 [F聚合物] F聚合物1：TFE單元、NAH單元、及PPVE單元之含量依序為98.0莫耳%、0.1莫耳%、1.9莫耳%之PFA系聚合物(熔點：300℃) F聚合物2：TFE單元及PPVE單元之含量依序為97.5莫耳%、2.5莫耳%之PFA系聚合物(熔點：305℃) 再者，F聚合物1係相對於主鏈碳數每1×10 6個具有1000個含羰基之基，F聚合物2係相對於主鏈碳數每1×10 6個具有40個含羰基之基。 [F粒子] F粒子1：包含F聚合物1且D50為2.1 μm之粒子 F粒子2：包含F聚合物2且D50為1.8 μm之粒子 A1. Preparation of each component and each member (Part 1) Prepare the following materials and members [F polymer] F polymer 1: PFA-based polymer (melting point: 300°C) in which the contents of TFE unit, NAH unit, and PPVE unit are 98.0 mol%, 0.1 mol%, and 1.9 mol%, respectively. F polymer 2: PFA-based polymer (melting point: 305°C) in which the contents of TFE unit and PPVE unit are 97.5 mol% and 2.5 mol%, respectively. Furthermore, F polymer 1 has 1000 carbonyl-containing groups per 1×10 6 carbon atoms in the main chain, and F polymer 2 has 40 carbonyl-containing groups per 1×10 6 carbon atoms in the main chain. [F particles] F particles 1: particles containing F polymer 1 and having a D50 of 2.1 μm. F particles 2: particles containing F polymer 2 and having a D50 of 1.8 μm.
[界面活性劑] 界面活性劑1：非離子性界面活性劑，聚醚改性聚二甲基矽氧烷，商品名：BYK-3450，BYK-Chemie Japan股份有限公司製造 [增黏劑] 增黏劑1：羥甲基纖維素，商品名：HEC-1，住友精化股份有限公司製造 [基材] 聚醯亞胺膜1：厚度為34 μm、寬度為520 mm、長邊方向之長度為500 m、玻璃轉移點為245℃、320℃下之拉伸彈性模數為0.3 GPa之芳香族性聚醯亞胺膜 [Surfactant] Surfactant 1: Non-ionic surfactant, polyether-modified polydimethylsiloxane, trade name: BYK-3450, manufactured by BYK-Chemie Japan Co., Ltd. [Thickener] Thickener 1: Hydroxymethyl cellulose, trade name: HEC-1, manufactured by Sumitomo Seika Co., Ltd. [Substrate] Polyimide film 1: Aromatic polyimide film with a thickness of 34 μm, a width of 520 mm, a length in the long side direction of 500 m, a glass transition point of 245°C, and a tensile modulus of 0.3 GPa at 320°C
A2.組合物之製造(組合物A1～A3) 向坩堝中，以表1中所示之添加量(質量份)投入表1中所示之F粒子、界面活性劑1、增黏劑1及水，投入氧化鋯球。然後，以150 rpm轉動坩堝1小時，製備表1中所示之組合物A1～A3。 對於所獲得之組合物，藉由上述方法來測定組合物之黏度及液狀分散介質之表面張力，將所測定之結果一併示於表1。 A2. Preparation of compositions (compositions A1 to A3) Into a crucible, add the F particles, surfactant 1, thickener 1 and water shown in Table 1 in the amounts (parts by mass) shown in Table 1, and add the zirconia balls. Then, rotate the crucible at 150 rpm for 1 hour to prepare compositions A1 to A3 shown in Table 1. For the obtained compositions, the viscosity of the compositions and the surface tension of the liquid dispersion medium were measured by the above method, and the measured results are shown together in Table 1.
[表1]
A3.長條積層基材之製造及測定(例A1～A7) 使用具有圖2中所示之塗佈部之裝置，使用上述聚醯亞胺膜1作為基材12，於聚醯亞胺膜1之兩面形成聚合物層。 具體而言，首先，於外周面之Rzjis為表2中所示之值之背輥20之外周面，以接觸面壓成為表2中所示之值之方式，使聚醯亞胺膜1之第2面與其接觸。然後，一面搬送聚醯亞胺膜1，一面於聚醯亞胺膜1之第1面藉由狹縫式模嘴塗佈法塗佈表2中所示之組合物，於通風乾燥爐(爐溫150℃)中通過3分鐘，去除水而形成作為乾燥覆膜之第1層。 A3. Production and measurement of long strip laminated substrate (Examples A1 to A7) Using the apparatus having the coating section shown in FIG. 2, the above-mentioned polyimide film 1 is used as the substrate 12, and polymer layers are formed on both sides of the polyimide film 1. Specifically, first, the outer peripheral surface of the back roller 20 whose Rzjis on the outer peripheral surface is the value shown in Table 2 is pressed to the value shown in Table 2, and the second side of the polyimide film 1 is brought into contact with it. Then, while the polyimide film 1 is being transported, the composition shown in Table 2 is applied to the first surface of the polyimide film 1 by a slot die coating method, and the film is passed through a ventilation drying furnace (furnace temperature 150°C) for 3 minutes to remove water and form the first layer as a dry coating.
繼而，一面使第1層與背輥20之外周面接觸一面搬送聚醯亞胺膜1，於聚醯亞胺膜1之第2面塗佈組合物，於通風乾燥爐(爐溫150℃)中通過3分鐘，去除水而形成第2乾燥覆膜。用於形成第2乾燥覆膜之背輥20、接觸面壓、搬送速度、組合物之種類、及組合物之塗佈條件，與用於形成第1層之背輥20、接觸面壓、搬送速度、組合物之種類、及組合物之塗佈條件相同。Next, the polyimide film 1 is conveyed while the first layer is in contact with the outer peripheral surface of the backing roller 20, and the composition is applied to the second surface of the polyimide film 1, and the film is passed through a ventilation drying furnace (furnace temperature 150° C.) for 3 minutes to remove water and form a second dry film. The backing roller 20, contact surface pressure, conveying speed, type of composition, and coating conditions of the composition used to form the second dry film are the same as those used to form the first layer.
繼而，將兩面形成有乾燥覆膜之聚醯亞胺膜1，於遠紅外線爐(爐內入口、出口附近之爐溫度300℃，中心附近之爐溫度340℃)中通過20分鐘，使組合物中所含之F粒子熔融焙燒而形成F粒子之燒結體。 藉此，於聚醯亞胺膜1之兩面形成包含F聚合物之聚合物層，獲得依序直接形成有作為第1層之燒結體之P-A1層(厚度：33 μm)、作為聚醯亞胺膜1之基材(厚度：34 μm)、及作為第2乾燥覆膜之燒結體之P-A2層(厚度：33 μm)，且寬度為520 mm、長邊方向之長度為500 m之長條積層基材。 藉由以上方式，而獲得例A1～A7之長條積層基材。 Next, the polyimide film 1 with dry coating formed on both sides was passed through a far infrared furnace (furnace temperature of 300°C near the inlet and outlet of the furnace, and furnace temperature of 340°C near the center) for 20 minutes to melt and bake the F particles contained in the composition to form a sintered body of the F particles. In this way, polymer layers containing F polymers were formed on both sides of the polyimide film 1, and a long strip laminated substrate with a width of 520 mm and a length of 500 m in the long side direction was obtained, in which the P-A1 layer (thickness: 33 μm) as the first layer of the sintered body, the substrate of the polyimide film 1 (thickness: 34 μm), and the P-A2 layer (thickness: 33 μm) as the second dry coating sintered body were directly formed in sequence. By the above method, the long strip laminate substrates of Examples A1 to A7 are obtained.
對於所獲得之長條積層基材中之2個聚合物層之露出面，分別在各10個部位進行藉由上述白光干涉方式進行之測定及Sdq之計算，並進行平均，藉此求出P-A1層之Sdq及P-A2層之Sdq。將結果示於表2。The above-mentioned white light interferometry method was used to measure and calculate Sdq at 10 locations on the exposed surface of the two polymer layers in the obtained long strip laminate substrate, and the average was taken to obtain the Sdq of the P-A1 layer and the Sdq of the P-A2 layer. The results are shown in Table 2.
將所獲得之長條積層基材捲繞至圓筒狀捲芯(材質：ABS(acrylonitrile-butadiene-styrene，丙烯腈-丁二烯-苯乙烯)樹脂，外徑：152 mm，曲率：0.033 mm -1，軸向長度：520 mm，厚度：8 mm)，製成捲筒片材。 The obtained long strip laminate substrate was wound onto a cylindrical core (material: ABS (acrylonitrile-butadiene-styrene) resin, outer diameter: 152 mm, curvature: 0.033 mm -1 , axial length: 520 mm, thickness: 8 mm) to prepare a roll sheet.
A4.長條積層基材之評價(銅箔剝離評價) 自例A1～A7中之捲筒片材將長條積層基材捲出100 m並切割後，進而將長條積層基材捲出1 m並切割，於所獲得之520 mm×1000 mm之積層基材之兩面之整面，藉由濺鍍使銅附著，藉由硫酸銅鍍覆使各自之銅厚度成為12 μm，獲得覆銅積層體。然後，使切成5 cm見方之覆銅積層體漂浮於260℃之焊料槽之熔融焊料中，10秒後取出並以目視確認外觀，根據下述評價基準進行銅箔隔離評價。將結果示於表2。 ＜評價基準＞ A：未發現銅之隆起及剝離 B：發現微小之銅之隆起 C：發現銅完全剝離之部位。 A4. Evaluation of long strip laminate substrate (copper foil peeling evaluation) After rolling out 100 m of the long strip laminate substrate from the roll sheet in Examples A1 to A7 and cutting it, the long strip laminate substrate is further rolled out 1 m and cut. Copper is attached to the entire surface of both sides of the obtained 520 mm×1000 mm laminate substrate by sputtering, and the copper thickness of each is made 12 μm by copper sulfate plating to obtain a copper-coated laminate. Then, the copper-coated laminate cut into 5 cm squares is floated in the molten solder of a solder tank at 260°C, taken out after 10 seconds and visually confirmed for appearance, and copper foil isolation evaluation is performed according to the following evaluation criteria. The results are shown in Table 2. <Evaluation Criteria> A: No copper bulge or peeling was found B: Minor copper bulge was found C: Parts where copper was completely peeled off were found
[表2]
上述例中，例A1～A3為實施例，例A4～A7為比較例。如表2所示，例A1～A3中，Sdq為5 μm/mm以下，與Sdq超過5 μm/mm之例A4～A7相比，金屬箔之剝離得到抑制。 再者，例A4及例A7中，確認到於組合物之塗佈時發生了黏滑現象。 In the above examples, Examples A1 to A3 are implementation examples, and Examples A4 to A7 are comparative examples. As shown in Table 2, in Examples A1 to A3, Sdq is less than 5 μm/mm, and the peeling of the metal foil is suppressed compared with Examples A4 to A7 where Sdq exceeds 5 μm/mm. Furthermore, in Examples A4 and A7, it was confirmed that the stick-slip phenomenon occurred when the composition was applied.
B1.各成分及各構件之準備(其2) 準備以下之材料及構件。 [F聚合物] F聚合物1：TFE單元、NAH單元、及PPVE單元之含量依序為98.0莫耳%、0.1莫耳%、1.9莫耳%之PFA系聚合物(熔點：300℃) 再者，F聚合物1係相對於主鏈碳數每1×10 6個具有1000個含羰基之基。 [F粒子] F粒子1：包含F聚合物1且D50為2.1 μm之粒子 [界面活性劑] 界面活性劑1：非離子性界面活性劑，聚醚改性聚二甲基矽氧烷，商品名：BYK-3450，BYK-Chemie Japan股份有限公司製造 [增黏劑] 增黏劑1：羥甲基纖維素，商品名：HEC-1，住友精化股份有限公司製造 [基材] 聚醯亞胺膜1：厚度為34 μm、寬度為520 mm、長邊方向之長度為500 m、玻璃轉移點為245℃、320℃下之拉伸彈性模數為0.3 GPa之芳香族性聚醯亞胺膜 聚醯亞胺膜2：厚度為17 μm、寬度為520 mm、長邊方向之長度為500 m、玻璃轉移點為245℃、320℃下之拉伸彈性模數為0.3 GPa之芳香族性聚醯亞胺膜 [捲芯] 捲芯1：材質為ABS樹脂、外徑為168 mm、曲率為0.0119 mm -1、軸向長度為520 mm、厚度為8 mm之圓筒狀捲芯 捲芯2：材質為ABS樹脂、外徑為92 mm、曲率為0.0217 mm -1、軸向長度為520 mm、厚度為8 mm之圓筒狀捲芯 B1. Preparation of each component and each member (Part 2) Prepare the following materials and members. [F polymer] F polymer 1: PFA-based polymer (melting point: 300°C) in which the contents of TFE unit, NAH unit, and PPVE unit are 98.0 mol%, 0.1 mol%, and 1.9 mol%, respectively. Furthermore, F polymer 1 has 1000 carbonyl-containing groups per 1×10 6 carbons in the main chain. [F particles] F particles 1: particles containing F polymer 1 and having a D50 of 2.1 μm [Surfactant] Surfactant 1: non-ionic surfactant, polyether-modified polydimethylsiloxane, trade name: BYK-3450, manufactured by BYK-Chemie Japan Co., Ltd. [Thickener] Thickener 1: Hydroxymethyl cellulose, trade name: HEC-1, manufactured by Sumitomo Seika Co., Ltd. [Substrate] Polyimide film 1: aromatic polyimide film with a thickness of 34 μm, a width of 520 mm, a length in the long direction of 500 m, a glass transition point of 245°C, and a tensile modulus of 0.3 GPa at 320°C Polyimide film 2: a thickness of 17 μm, a width of 520 mm, a length in the long direction of 500 m, glass transition point of 245℃, tensile modulus of 0.3 GPa at 320℃ of aromatic polyimide film [core] Core 1: ABS resin, outer diameter of 168 mm, curvature of 0.0119 mm -1 , axial length of 520 mm, thickness of 8 mm cylindrical core Core 2: ABS resin, outer diameter of 92 mm, curvature of 0.0217 mm -1 , axial length of 520 mm, thickness of 8 mm cylindrical core
B2.組合物之製造 向坩堝中投入F粒子1之50質量份、界面活性劑1之2.5質量份、增黏劑1之0.5質量份、及水之47質量份，投入氧化鋯球。然後，以150 rpm轉動坩堝1小時，製備組合物。 B2. Preparation of the composition 50 parts by mass of F particles 1, 2.5 parts by mass of surfactant 1, 0.5 parts by mass of thickener 1, and 47 parts by mass of water were added to the crucible, and the zirconia ball was added. Then, the crucible was rotated at 150 rpm for 1 hour to prepare the composition.
B3.長條積層基材之製造(長條積層基材1～2) 一面使聚醯亞胺膜1之面B2接觸背輥之外周面並搬送聚醯亞胺膜1，一面於聚醯亞胺膜1之面B1藉由狹縫式模嘴塗佈法塗佈上述組合物，於通風乾燥爐(爐溫150℃)中通過3分鐘，去除水而形成作為乾燥覆膜之層B1。 繼而，一面使層B1接觸背輥之外周面一面搬送聚醯亞胺膜1，於聚醯亞胺膜1之面B2塗佈組合物，於通風乾燥爐(爐溫150℃)中通過3分鐘，去除水而形成乾燥覆膜B2。 繼而，將兩面形成有乾燥覆膜之聚醯亞胺膜1，於遠紅外線爐(爐內入口、出口附近之爐溫度300℃，中心附近之爐溫度340℃)中通過20分鐘，使組合物中所含之F粒子熔融焙燒而形成F粒子之燒結體。 藉此，於聚醯亞胺膜1之兩面形成包含F聚合物之聚合物層，獲得依序直接形成有作為層B1之燒結體之P-B1層(厚度：33 μm)、作為聚醯亞胺膜1之基材(厚度：34 μm)、及作為乾燥覆膜B2之燒結體之P-B2層(厚度：33 μm)，且積層厚度為100 μm之長條積層基材。 藉由以上方式，而獲得長條積層基材1。 B3. Production of long strip laminated substrate (long strip laminated substrate 1-2) The polyimide film 1 is conveyed while the surface B2 of the polyimide film 1 is in contact with the outer peripheral surface of the back roller, and the above composition is applied to the surface B1 of the polyimide film 1 by a narrow slot die coating method, and the film is passed through a ventilation drying furnace (furnace temperature 150°C) for 3 minutes to remove water and form a layer B1 as a dry film. Then, the polyimide film 1 is conveyed while the layer B1 is in contact with the outer peripheral surface of the back roller, and the composition is applied to the surface B2 of the polyimide film 1, and the film is passed through a ventilation drying furnace (furnace temperature 150°C) for 3 minutes to remove water and form a dry film B2. Next, the polyimide film 1 with dry coating formed on both sides was passed through a far infrared furnace (furnace temperature of 300°C near the inlet and outlet of the furnace, and furnace temperature of 340°C near the center) for 20 minutes to melt and bake the F particles contained in the composition to form a sintered body of the F particles. In this way, a polymer layer containing F polymer was formed on both sides of the polyimide film 1, and a P-B1 layer (thickness: 33 μm) as a sintered body of layer B1, a substrate (thickness: 34 μm) as a polyimide film 1, and a P-B2 layer (thickness: 33 μm) as a sintered body of the dry coating B2 were directly formed in sequence, and a long strip laminated substrate with a laminate thickness of 100 μm was obtained. By the above method, a long strip laminate substrate 1 is obtained.
使用聚醯亞胺膜2來代替聚醯亞胺膜1，將P-B1層及P-B2層之厚度分別設為16.5 μm，除此以外，與長條積層基材1同樣地操作而獲得積層厚度為50 μm之長條積層基材2。A long-strip laminated substrate 2 having a laminate thickness of 50 μm was obtained by performing the same operation as the long-strip laminated substrate 1 except that the polyimide film 2 was used instead of the polyimide film 1 and the thickness of the P-B1 layer and the P-B2 layer were set to 16.5 μm respectively.
B4.長條片材捲筒之製造及測定(例B1～B5) 將表3中所示之長條積層基材以表3中所示之捲繞張力捲繞至表3中所示之捲芯，製造長條片材捲筒。將捲繞時對長條積層基材所施加之捲繞應力、及積C×T一併示於表3。 B4. Manufacturing and measurement of long sheet rolls (Examples B1 to B5) The long strip laminated substrate shown in Table 3 is wound around the winding core shown in Table 3 at the winding tension shown in Table 3 to manufacture a long sheet roll. The winding stress applied to the long strip laminated substrate during winding and the product C×T are shown in Table 3.
自例B1～B5中之長條片材捲筒將長條積層基材捲出450 m並切割後，進而將長條積層基材捲出500 mm並切割，將所獲得之520 mm×500 mm之積層基材片靜置於水平面。測定積層基材片之距離水平面之上浮高度，根據下述基準進行捲曲之評價。將結果示於表3。 A：上浮高度為0.5 cm以下 B：上浮高度超過0.5 cm且為1 cm以下 C：上浮高度超過1 cm After rolling out 450 m of the long strip laminated substrate from the long sheet roll in Examples B1 to B5 and cutting it, the long strip laminated substrate was further rolled out 500 mm and cut, and the obtained 520 mm×500 mm laminated substrate sheet was placed statically on a horizontal plane. The floating height of the laminated substrate sheet from the horizontal plane was measured, and the curling was evaluated according to the following criteria. The results are shown in Table 3. A: The floating height is less than 0.5 cm B: The floating height exceeds 0.5 cm and is less than 1 cm C: The floating height exceeds 1 cm
利用鋼尺測定例B1～B5中之長條片材捲筒端部之捲繞偏移。具體而言，將長條積層基材之寬度方向端部中距離捲芯之軸向前端最遠之距離作為「捲繞偏移」，根據下述基準進行捲繞偏移之評價。將結果示於表3。 A：捲繞偏移未達1 cm B：捲繞偏移為1 cm以上且未達2 cm C：捲繞偏移為2 cm以上 The winding offset of the ends of the long sheet rolls in Examples B1 to B5 was measured using a steel ruler. Specifically, the distance from the axial front end of the winding core at the end in the width direction of the long laminate substrate was taken as the "winding offset", and the winding offset was evaluated according to the following criteria. The results are shown in Table 3. A: Winding offset is less than 1 cm B: Winding offset is more than 1 cm and less than 2 cm C: Winding offset is more than 2 cm
B5.長條片材捲筒之評價(銅箔皺褶評價) 在經加熱之2根輥之間，對在自例B1～B5中之長條片材捲筒連續地捲出之同時進行搬送之長條積層基材、與同時自其他捲出部捲出之銅箔，一面施加壓力，一面使其通過而進行積層。直接連續地捲取，製造覆銅積層體之長條體。以目視評價其外觀，根據下述基準進行銅箔皺褶評價。將結果示於表3。 A：於覆銅積層體之長條體之外觀幾乎未發現銅箔之皺褶 B：於覆銅積層體之長條體之寬度方向端部發現銅箔之皺褶 C：於覆銅積層體之寬度方向中央部發現由長條積層基材之捲曲引起之銅箔之彎折皺褶 B5. Evaluation of long sheet rolls (copper foil wrinkle evaluation) The long laminated substrate continuously rolled out from the long sheet rolls in Examples B1 to B5 and the copper foil rolled out from other roll-out sections were laminated while being pressed between two heated rolls. The long strip of copper-coated laminated body was produced by directly rolling it up continuously. The appearance was visually evaluated and the copper foil wrinkle evaluation was performed according to the following criteria. The results are shown in Table 3. A: Almost no wrinkles of copper foil were found on the outside of the copper-clad laminate strip B: Wrinkles of copper foil were found at the ends of the copper-clad laminate strip in the width direction C: Bending and wrinkling of copper foil caused by the curling of the strip laminate substrate were found in the center of the copper-clad laminate strip in the width direction
[表3]
上述例中，例B1～B4為實施例，例B5為比較例。如表3所示，例B1～B4中，與積C×T為0.0015以上之例B5相比，捲曲之發生得到抑制，由捲曲引起之金屬箔之皺褶得到抑制。In the above examples, Examples B1 to B4 are working examples, and Example B5 is a comparative example. As shown in Table 3, in Examples B1 to B4, the occurrence of curling is suppressed, and wrinkles of the metal foil caused by curling are suppressed, compared with Example B5 in which the product C×T is 0.0015 or more.
2022年6月3日提出申請之日本專利申請案第2022-090871號及2022年6月3日提出申請之日本專利申請案第2022-090872號之揭示內容係整體以參照之形式併入本說明書中。又，本說明書中所記載之所有文獻、專利申請案及技術規格以參照之形式併入本說明書中，等同於具體且單獨地記述「各個文獻、專利申請案、及技術規格以參照之形式併入本說明書中」。The disclosures of Japanese Patent Application No. 2022-090871 filed on June 3, 2022 and Japanese Patent Application No. 2022-090872 filed on June 3, 2022 are incorporated herein by reference in their entirety. In addition, all documents, patent applications, and technical specifications described in this specification are incorporated herein by reference, which is equivalent to a specific and individual description of "each document, patent application, and technical specification is incorporated herein by reference."
10:長條積層基材 12:基材 14:聚合物層 14S:露出面 16:聚合物層 16S:露出面 20:背輥 22:塗佈構件 26:組合物層 100:長條片材捲筒 120:捲芯 10: Strip laminate substrate 12: Substrate 14: Polymer layer 14S: Exposed surface 16: Polymer layer 16S: Exposed surface 20: Back roll 22: Coating member 26: Composite layer 100: Strip sheet roll 120: Roll core
圖1係表示一實施方式之長條積層基材之層構成之概略剖視圖。 圖2係模式性地表示一實施方式之長條積層基材之製造方法中所使用之裝置之塗佈部的模式圖。 圖3係模式性地表示一實施方式之長條片材捲筒之立體圖。 圖4係表示圖3中所示之長條片材捲筒中之長條積層基材之層構成的概略剖視圖。 FIG. 1 is a schematic cross-sectional view showing the layer structure of a long laminated substrate in one embodiment. FIG. 2 is a schematic diagram showing a coating section of an apparatus used in a method for manufacturing a long laminated substrate in one embodiment. FIG. 3 is a schematic three-dimensional view showing a long sheet roll in one embodiment. FIG. 4 is a schematic cross-sectional view showing the layer structure of the long laminated substrate in the long sheet roll shown in FIG. 3.
10:長條積層基材 10: Strip laminate substrate
12:基材 12: Base material
14:聚合物層 14: Polymer layer
14S:露出面 14S: Reveal your face
16:聚合物層 16: Polymer layer
16S:露出面 16S: Reveal your face
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