TW202003235A - Method for producing resin-clad metal foil, resin-clad metal foil, laminate, and printed circuit board - Google Patents

Method for producing resin-clad metal foil, resin-clad metal foil, laminate, and printed circuit board Download PDF

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TW202003235A
TW202003235A TW108118229A TW108118229A TW202003235A TW 202003235 A TW202003235 A TW 202003235A TW 108118229 A TW108118229 A TW 108118229A TW 108118229 A TW108118229 A TW 108118229A TW 202003235 A TW202003235 A TW 202003235A
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resin
metal foil
layer
resin layer
polymer
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TWI826452B (en
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山邊敦美
細田朋也
寺田達也
笠井渉
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日商Ａｇｃ股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • B32B2327/18—PTFE, i.e. polytetrafluoroethylene

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided are: a resin-clad metal foil that has excellent electrical characteristics and mechanical strength, that is useful as a printed circuit board material, that comprises a resin layer having excellent adhesiveness, and that is unlikely to warp; a method for producing the resin-clad metal foil; and a printed circuit board. A method for producing a resin-clad metal foil in which a metal foil has a resin layer on the surface thereof, wherein the surface of the metal foil is coated with a powder dispersion liquid containing a tetrafluoroethylene polymer powder, a dispersant having a mass reduction rate of 1 mass%/minute or more in the temperature range of 80-300 DEG C, and a solvent, the metal foil is held at a temperature in the aforementioned temperature range at which the mass reduction rate becomes 1 mass%/minute or more, the tetrafluoroethylene polymer is fired at a temperature exceeding the aforementioned temperature range, and a resin layer containing the tetrafluoroethylene polymer is formed on the surface of the metal foil.

Description

附樹脂之金屬箔之製造方法、附樹脂之金屬箔、積層體及印刷基板Manufacturing method of metal foil with resin, metal foil with resin, laminate and printed circuit board

本發明涉及一種附樹脂之金屬箔之製造方法、附樹脂之金屬箔、積層體及印刷基板。The invention relates to a method for manufacturing resin-attached metal foil, resin-attached metal foil, laminate and printed circuit board.

發明背景 金屬箔表面具有絕緣樹脂層的附樹脂之金屬箔，可藉由蝕刻等將金屬箔加工形成傳輸電路而作為印刷基板使用。 針對用來傳輸高頻訊號的印刷基板，係講求傳輸特性優異。所以為了提高傳輸特性，印刷基板之絕緣樹脂層必須使用相對介電常數及介電正切低的樹脂。相對介電常數及介電正切小的樹脂，已知有聚四氟乙烯(PTFE)等氟聚物。Background of the invention The resin-coated metal foil with an insulating resin layer on the surface of the metal foil can be used as a printed circuit board by processing the metal foil to form a transmission circuit by etching or the like. For printed circuit boards used to transmit high-frequency signals, excellent transmission characteristics are required. Therefore, in order to improve the transmission characteristics, the insulating resin layer of the printed circuit board must use a resin with a low relative dielectric constant and dielectric tangent. Fluoropolymers such as polytetrafluoroethylene (PTFE) are known as resins having a small relative dielectric constant and dielectric tangent.

針對可形成具有包含氟聚物之絕緣樹脂層的附樹脂之金屬箔的材料，有文獻提議一種溶劑中分散有氟聚物粉末的粉末分散液(參照專利文獻1~3)。該粉末分散液摻混其他絕緣樹脂及其清漆時，具有下列優點：可任意調整製得之附樹脂之金屬箔的各項物性的優點，以及僅塗佈乾燥於金屬箔表面即可形成附樹脂之金屬箔的優點。 而且，隨著電子機器之高密度化，已在討論透過預浸體等其他基板使印刷基板彼此接著之印刷基板的多層化。 將從以氟聚物作為絕緣樹脂層的附樹脂之金屬箔所形成的印刷基板進行多層化的討論中，有則文獻是討論於印刷基板之絕緣樹脂層上設置具有矽原子、氮原子或硫原子之矽烷耦合劑的被覆層，並藉由熱壓附使被覆層與以特定氟聚物為主成分之預浸體接著(參考專利文獻4)。Regarding the material that can form a resin-attached metal foil having an insulating resin layer containing a fluoropolymer, there is a literature suggesting a powder dispersion in which a fluoropolymer powder is dispersed in a solvent (refer to Patent Documents 1 to 3). When the powder dispersion is blended with other insulating resins and varnishes, it has the following advantages: it can arbitrarily adjust the physical properties of the prepared metal foil with resin, and can be formed by only coating and drying on the surface of the metal foil The advantages of metal foil. In addition, with the increase in the density of electronic devices, the multilayering of printed substrates in which printed substrates are adhered to each other through prepregs and other substrates has been discussed. In the discussion of multi-layering a printed circuit board formed from a metal foil with a fluoropolymer as the insulating resin layer and a resin, a document discusses the placement of silicon atoms, nitrogen atoms, or sulfur on the insulating resin layer of the printed circuit board The coating layer of the atomic silane coupling agent is adhered to the prepreg containing the specific fluoropolymer as the main component by hot pressing (refer to Patent Document 4).

先前技術文獻 專利文獻 專利文獻1：國際公開第2017/222027號 專利文獻2：國際公開第2016/159102號 專利文獻3：日本專利特開2017-193655號公報 專利文獻4：日本專利特開2018-011033號公報Prior technical literature Patent Literature Patent Literature 1: International Publication No. 2017/222027 Patent Literature 2: International Publication No. 2016/159102 Patent Document 3: Japanese Patent Laid-Open No. 2017-193655 Patent Document 4: Japanese Patent Laid-Open No. 2018-011033

發明概要 發明欲解決之課題 若從所得之印刷基板的電特性及生產性的觀點來看，在於含氟聚物之絕緣樹脂層表面積層其他基板(預浸體等)進行多層化的態樣、或是於前述絕緣樹脂層表面積層其他基板(覆蓋薄膜等)進行封裝的態樣中，前述絕緣樹脂層與其他基板必須牢固積層。 但，氟聚物本質上為疏水性且低黏著性，所以要將前述絕緣樹脂層與其他基板牢固積層並非易事。已知有藉由表面處理(電漿處理、電暈處理、電子射線處理等)將前述樹脂層改質成親水性而賦予接著性的方法。然而，在表面處理中有時會引發歷時性的改質及形狀變化等，從而損傷前述絕緣樹脂層原本的電特性或機械強度。 所以一直在尋求一種方法，用以從包含氟聚物粉末之粉末分散液製造具有包含氟聚物之絕緣樹脂層的附樹脂之金屬箔，並且該絕緣樹脂層具備各種物性且接著性尤佳。Summary of the invention Problems to be solved by invention From the viewpoint of electrical characteristics and productivity of the resulting printed circuit board, the surface layer of the insulating resin layer of the fluoropolymer layered on other substrates (prepregs, etc.), or on the aforementioned insulating resin layer In the case where the surface area layer is encapsulated by another substrate (cover film, etc.), the insulating resin layer and the other substrate must be firmly laminated. However, the fluoropolymer is inherently hydrophobic and has low adhesion, so it is not easy to laminate the aforementioned insulating resin layer and other substrates firmly. There is known a method of imparting adhesiveness by modifying the resin layer to be hydrophilic by surface treatment (plasma treatment, corona treatment, electron beam treatment, etc.). However, the surface treatment may cause diachronic modification, shape change, etc., thereby damaging the original electrical characteristics or mechanical strength of the insulating resin layer. Therefore, a method has been sought for manufacturing a resin-coated metal foil having an insulating resin layer containing a fluoropolymer from a powder dispersion containing a fluoropolymer powder, and the insulating resin layer has various physical properties and has excellent adhesion.

另，氟聚物本質上黏著性低、熱伸縮性亦高，因此要將從附有作為前述絕緣樹脂層之樹脂之金屬箔所形成的印刷基板與預浸體等其他基板牢固接著以進行多層化而無損其尺寸穩定性並非易事。 在專利文獻4之討論中，為了於多層化後保持傳輸特性及機械強度，宜使用高熔點的氟聚物。屆時，在多層化之際必須在高溫下將印刷基板與預浸體熱壓附。所以，有印刷基板之尺寸穩定性因熱壓附時之高溫而降低的課題。在多層化之際，印刷基板之尺寸穩定性若受損，製得之多層印刷基板的翹曲就容易成為問題。 另，若在印刷基板之安裝步驟中採取塗上焊料糊後進行加熱的方式(焊料回焊方式)時，則會因加熱而在前述絕緣樹脂層與預浸體硬化而成之硬化物層之界面產生膨起，因此焊料回焊耐性亦是課題之一。In addition, the fluoropolymer is inherently low in adhesiveness and high in thermal stretchability. Therefore, a printed circuit board formed from a metal foil with a resin as the insulating resin layer described above and other substrates such as a prepreg are firmly adhered to perform multiple layers It is not easy to improve its dimensional stability. In the discussion of Patent Document 4, in order to maintain transmission characteristics and mechanical strength after multilayering, it is preferable to use a fluoropolymer having a high melting point. At that time, at the time of multilayering, the printed substrate and the prepreg must be hot-pressed at high temperature. Therefore, there is a problem that the dimensional stability of the printed circuit board is reduced due to the high temperature at the time of hot pressing. In the case of multi-layering, if the dimensional stability of the printed circuit board is impaired, warpage of the resulting multi-layer printed circuit board may easily become a problem. In addition, if the method of applying a solder paste and then heating (solder reflow method) is used in the mounting process of the printed circuit board, the cured resin layer and the prepreg will be hardened by the heating Bulging occurs at the interface, so solder reflow resistance is also one of the issues.

如此一來，在將以氟聚物作為絕緣樹脂層之印刷基板進行多層化時，需要一種可與預浸體等其他基板低溫接著而無損印刷基板之尺寸穩定性、且在焊料回焊方式等之加熱步驟中不易產生膨起的印刷基板，以及需要一種可形成該印刷基板的附樹脂之金屬箔。 此外，在專利文獻4記載之多層基板中，絕緣樹脂層之電特性容易因設置在含氟聚物之絕緣樹脂層上的矽烷耦合劑之被覆層而降低。而且，在高溫下將前述絕緣樹脂層與預浸體熱壓附時，也很難使用包含耐熱性大致上比氟聚物更低之基質樹脂(不具氟原子之基質樹脂等)的預浸體。 如此一來，就需要一種各層牢固接著而無損形成各層之材料特性、翹曲少之以氟聚物作為絕緣樹脂層且具有金屬箔的積層體。In this way, when multilayering a printed circuit board using a fluoropolymer as an insulating resin layer, a low-temperature bonding with other substrates such as a prepreg is required without deteriorating the dimensional stability of the printed circuit board, and a solder reflow method, etc. In the heating step, the printed substrate is less likely to swell, and a metal foil with resin that can form the printed substrate is required. In addition, in the multilayer substrate described in Patent Document 4, the electrical characteristics of the insulating resin layer are easily degraded by the coating layer of the silane coupling agent provided on the insulating resin layer of the fluoropolymer. Moreover, when the insulating resin layer and the prepreg are thermocompression-bonded at a high temperature, it is also difficult to use a prepreg containing a matrix resin (a matrix resin without a fluorine atom, etc.) that has substantially lower heat resistance than a fluoropolymer. . In this way, there is a need for a layered body in which each layer is firmly adhered without deteriorating the material characteristics of each layer and less warping. The laminated body has a fluoropolymer as an insulating resin layer and a metal foil.

本發明提供一種可有效率地製造電特性及機械強度優異且有用於製造印刷基板的附樹脂之金屬箔之方法，該附樹脂之金屬箔具有包含氟聚物之接著性優異的樹脂層。 本發明提供一種電特性及機械強度優異且有用於製造印刷基板的附樹脂之金屬箔，該附樹脂之金屬箔具有包含氟聚物之接著性優異的樹脂層。 本發明提供一種傳輸特性及機械強度優異、各層牢固接著、翹曲少的積層體及印刷基板。The present invention provides a method for efficiently producing a resin-attached metal foil that is excellent in electrical characteristics and mechanical strength and that is used for manufacturing a printed circuit board. The resin-attached metal foil has a resin layer that includes a fluoropolymer and has excellent adhesion. The present invention provides a metal foil with resin that is excellent in electrical characteristics and mechanical strength and is useful for manufacturing a printed circuit board. The metal foil with resin has a resin layer that includes a fluoropolymer and has excellent adhesion. The present invention provides a laminate and a printed circuit board having excellent transmission characteristics and mechanical strength, strong adhesion of each layer, and low warpage.

用以解決課題之手段 本發明具有下述態樣。 [1]一種附樹脂之金屬箔之製造方法，係金屬箔表面具有樹脂層的附樹脂之金屬箔之製造方法，該製造方法如下： 將粉末分散液塗佈於金屬箔表面，該粉末分散液包含四氟乙烯系聚合物粉末、80~300℃溫度區域內之質量減少率為1質量%/分鐘以上之分散劑、及溶劑， 以前述溫度區域內之質量減少率為1質量%/分鐘以上的溫度來保持金屬箔， 在超過前述溫度區域之溫度下燒成四氟乙烯系聚合物，而於金屬箔表面形成包含四氟乙烯系聚合物之樹脂層。Means to solve the problem The present invention has the following aspects. [1] A method for manufacturing a metal foil with a resin, which is a method for manufacturing a metal foil with a resin layer having a resin layer on the surface of the metal foil. The manufacturing method is as follows: Applying a powder dispersion to the surface of the metal foil, the powder dispersion containing a tetrafluoroethylene polymer powder, a dispersant with a mass reduction rate of 1% by mass/min or more in a temperature range of 80 to 300°C, and a solvent, The metal foil is maintained at a temperature where the mass reduction rate in the aforementioned temperature range is 1% by mass/minute or more, The tetrafluoroethylene-based polymer is fired at a temperature exceeding the aforementioned temperature range, and a resin layer containing the tetrafluoroethylene-based polymer is formed on the surface of the metal foil.

[2]如[1]中記載之製造方法，其中樹脂層之水接觸角為70~100°。 [3]如[1]或[2]中記載之製造方法，其中分散劑係於側鏈具有下述基團之聚合物： 多氟烷基或多氟烯基；及 聚氧伸烷基或醇性羥基。 [4]如[1]~[3]中任一項記載之製造方法，其將金屬箔保持在前述溫度區域時之溫度為100~300℃。 [5]如[1]~[4]中任一項記載之製造方法，其將金屬箔保持在前述溫度區域時之氣體環境為含氧氣之氣體環境。 [6]如[1]~[5]中任一項記載之製造方法，其燒成四氟乙烯系聚合物時之溫度為330~380℃。[2] The production method described in [1], wherein the water contact angle of the resin layer is 70 to 100°. [3] The production method described in [1] or [2], wherein the dispersant is a polymer having the following groups in the side chain: Polyfluoroalkyl or polyfluoroalkenyl; and Polyoxyalkylene or alcoholic hydroxyl. [4] The manufacturing method according to any one of [1] to [3], wherein the temperature when the metal foil is held in the aforementioned temperature range is 100 to 300°C. [5] The manufacturing method according to any one of [1] to [4], wherein the gas environment when the metal foil is held in the aforementioned temperature range is an oxygen-containing gas environment. [6] The production method described in any one of [1] to [5], wherein the temperature at the time of firing the tetrafluoroethylene-based polymer is 330 to 380°C.

[7]一種附樹脂之金屬箔，依序具有金屬箔、包含四氟乙烯系聚合物之樹脂層及包含親水成分之接著部位，前述樹脂層與前述接著部位相接，前述親水成分具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種。 [8]如[7]中記載之附樹脂之金屬箔，其中前述接著部位係以島狀存在。 [9]如[7]或[8]中記載之附樹脂之金屬箔，其中前述親水成分源自聚合物，該聚合物於側鏈具有：多氟烷基或多氟烯基，以及，聚氧伸烷基或醇性羥基。 [10]一種積層體之製造方法，係利用熱壓法使如前述[7]~[9]中任一項記載之附樹脂之金屬箔與其他基板接著而製得積層體。[7] A metal foil with a resin, comprising a metal foil, a resin layer containing a tetrafluoroethylene-based polymer, and a bonding site containing a hydrophilic component in sequence, the resin layer is in contact with the bonding site, and the hydrophilic component has At least one of the group consisting of etheric oxygen atom, hydroxyl group and carboxyl group. [8] The resin-attached metal foil as described in [7], wherein the aforementioned bonding portion exists in an island shape. [9] The metal foil with resin as described in [7] or [8], wherein the aforementioned hydrophilic component is derived from a polymer having a polyfluoroalkyl group or polyfluoroalkenyl group in the side chain, and Oxyalkylene or alcoholic hydroxyl. [10] A method for manufacturing a laminate, wherein a metal foil with resin as described in any one of the aforementioned [7] to [9] is bonded to another substrate by a hot pressing method to obtain a laminate.

[11]一種積層體，依序具有金屬箔、包含四氟乙烯系聚合物之樹脂層及包含基質樹脂之預浸體的硬化物層，且更於前述樹脂層與前述硬化物層之間具有一與前述樹脂層及前述硬化物層相接之相溶層，該相溶層含有具氟原子及氧原子之成分。 [12]如[11]中記載之積層體，其中前述相溶層之厚度為1~500nm。 [13]如[11]或[2]中記載之積層體，其中前述相溶層源自聚合物，該聚合物於側鏈具有：多氟烷基或多氟烯基，以及，聚氧伸烷基或醇性羥基。 [14]如[11]~[13]中任一項記載之積層體，其中前述基質樹脂為不具氟原子的基質樹脂，且選自於由環氧樹脂、聚氧化苯、聚苯醚及聚丁二烯所構成群組中之至少1種。 [15]一種印刷基板，依序具有傳輸電路、包含四氟乙烯系聚合物之樹脂層及包含基質樹脂之預浸體的硬化物層，且更於前述樹脂層與前述硬化物層之間具有一與前述樹脂層及前述硬化物層相接之相溶層，該相溶層含有具氟原子及氧原子之成分。[11] A laminate having a metal foil, a resin layer containing a tetrafluoroethylene-based polymer, and a hardened layer of a prepreg containing a matrix resin in this order, and further between the resin layer and the hardened layer A compatible layer in contact with the resin layer and the hardened material layer, the compatible layer containing a component having fluorine atoms and oxygen atoms. [12] The laminate as described in [11], wherein the thickness of the compatible layer is 1 to 500 nm. [13] The laminate as described in [11] or [2], wherein the aforementioned compatible layer is derived from a polymer having, in the side chain, a polyfluoroalkyl group or a polyfluoroalkenyl group, and Alkyl or alcoholic hydroxyl. [14] The laminate as described in any one of [11] to [13], wherein the matrix resin is a matrix resin having no fluorine atoms, and is selected from the group consisting of epoxy resin, polyoxybenzene, polyphenylene oxide and poly At least one member of the group consisting of butadiene. [15] A printed circuit board having a transmission circuit, a resin layer containing a tetrafluoroethylene-based polymer, and a hardened layer of a prepreg containing a matrix resin in this order, and further provided between the resin layer and the hardened layer A compatible layer in contact with the resin layer and the hardened material layer, the compatible layer containing a component having fluorine atoms and oxygen atoms.

發明效果 根據本發明之製造方法，可有效率地製造一種具備電特性及機械強度且有用於製造印刷基板的附樹脂之金屬箔，該附樹脂之金屬箔具有包含氟聚物之接著性優異的樹脂層。 儘管本發明之附樹脂之金屬箔具有含氟聚物之樹脂層，但不僅可與其他基板進行低溫接著而無損其尺寸穩定性，而且做成印刷基板時，耐熱性優異、不易產生膨起。 本發明之積層體的傳輸特性及機械強度優異、各層牢固接著且翹曲少。 本發明之印刷基板的傳輸特性及機械強度優異、各層牢固接著且翹曲少。根據本發明，可製造一種傳輸特性及機械強度優異、各層牢固接著、翹曲少的印刷基板。Invention effect According to the manufacturing method of the present invention, it is possible to efficiently manufacture a resin-attached metal foil having electrical characteristics and mechanical strength and used for manufacturing a printed circuit board, the resin-attached metal foil having a resin layer including a fluoropolymer and having excellent adhesiveness . Although the resin-attached metal foil of the present invention has a fluoropolymer resin layer, not only can it be adhered to other substrates at low temperature without compromising its dimensional stability, but when it is made into a printed substrate, it has excellent heat resistance and is less likely to swell. The laminate of the present invention is excellent in transmission characteristics and mechanical strength, and each layer is firmly adhered with little warpage. The printed circuit board of the present invention is excellent in transmission characteristics and mechanical strength, and each layer is firmly adhered with little warpage. According to the present invention, it is possible to manufacture a printed circuit board which is excellent in transmission characteristics and mechanical strength, has strong adhesion of each layer, and has little warpage.

用以實施發明之形態 以下用語具有下列意義。 「粉末之D50」係利用雷射繞射散射法求得粉末之體積基準累積50%粒徑。即，利用雷射繞射散射法測定粉末之粒度分布，令粒子群之總體積為100%求出累積曲線後，於該累積曲線上累積體積為50%之點的粒徑。 「粉末之D90」係利用雷射繞射散射法求得粉末之體積基準累積90%粒徑。即，利用雷射繞射散射法測定粉末之粒度分布，令粒子群之總體積為100%求出累積曲線後，於該累積曲線上累積體積為90%之點的粒徑。 「聚合物之熔融黏度」係根據ASTM D 1238，使用流動測試機及2Φ-8L的模具，將已預先在測定溫度下加熱5分鐘後的聚合物試料(2g)，在0.7MPa之荷重下保持於測定溫度下所測得之值。 「聚合物之熔點」係指與示差掃描熱量測定(DSC)法測得之熔解峰之最大值對應的溫度。Forms for carrying out the invention The following terms have the following meanings. "D50 of powder" is the 50% cumulative particle size of powder based on the volume diffraction of laser powder. That is, the particle size distribution of the powder is measured by the laser diffraction scattering method, and the cumulative curve is obtained by setting the total volume of the particle group to 100%, and then the particle size at the point where the cumulative volume is 50% on the cumulative curve. "D90 of powder" is the cumulative 90% particle size of powder based on the volume diffraction of laser powder. That is, the particle size distribution of the powder is measured by the laser diffraction scattering method, the total volume of the particle group is 100%, and after the cumulative curve is obtained, the particle size at the point where the cumulative volume is 90% on the cumulative curve. "The melt viscosity of the polymer" is based on ASTM D 1238, using a flow tester and a 2Φ-8L mold, the polymer sample (2g) that has been pre-heated at the measured temperature for 5 minutes, under a load of 0.7MPa The value measured at the measured temperature. "Polymer melting point" refers to the temperature corresponding to the maximum value of the melting peak measured by differential scanning calorimetry (DSC).

「分散劑之質量減少率」係將分散劑從溫度區域之下限升溫至上限時之分散劑質量減少量除以升溫時間與分散劑之試料量所得的%值。 「翹曲率」係從試樣(附樹脂之金屬箔、積層體等)裁切出180mm四方的四角試驗片，按JIS C 6471：1995(IEC 249-1：1982)中規定之測定方法，針對試驗片所測得之值。 「尺寸變化率」係按下述所求得之值。將試樣(附樹脂之金屬箔、積層體等)裁切出150mm四方，用0.3mm之鑽頭於四隅開孔後，以三維測定器測定孔的位置。以蝕刻去除附樹脂之金屬箔的金屬箔後，在130℃下乾燥30分鐘。以三維測定器測定開在四隅的孔的位置。從蝕刻前後之孔的位置之差算出尺寸變化率。 「算術平均粗度Ra」及「最大高度Rz」係使用Oxford Instruments公司製原子力顯微鏡(AFM)，在下述測定條件下針對試樣(附樹脂之金屬箔、積層體等)之表面(1μm2 範圍)進行測定時之值。 探針：AC160TS-C3(前端R＜7nm、彈簧常數26N/m)、測定模式：AC-Air、掃描速率：1Hz。"The mass reduction rate of the dispersant" is the% value obtained by dividing the amount of decrease in the mass of the dispersant when the temperature of the dispersant is raised from the lower limit to the upper limit of the temperature range divided by the heating time and the sample amount of the dispersant. "Warpage" is a 180mm square test piece cut out from the sample (metal foil with resin, laminate, etc.), according to the measurement method specified in JIS C 6471: 1995 (IEC 249-1: 1982). The value measured by the test piece. The "dimension change rate" is the value obtained as follows. Cut the sample (metal foil with resin, laminate, etc.) into a 150mm square, use a 0.3mm drill to drill holes in the four corners, and measure the position of the hole with a three-dimensional measuring instrument. After removing the metal foil of the metal foil with resin by etching, it was dried at 130°C for 30 minutes. The position of the hole opened in the four corners is measured with a three-dimensional measuring device. The dimensional change rate was calculated from the difference between the positions of the holes before and after etching. "Arithmetic average roughness Ra" and "maximum height Rz" are the surface (1μm 2 range) of the sample (metal foil with resin, laminate, etc.) under the following measurement conditions using an atomic force microscope (AFM) manufactured by Oxford Instruments ) Value at the time of measurement. Probe: AC160TS-C3 (front end R<7nm, spring constant 26N/m), measurement mode: AC-Air, scan rate: 1Hz.

「相對介電常數(20GHz)及介電正切(20GHz)」係利用SPDR(分離後電介質共振器(Split-Post Dielectric Resonator))法，在23℃±2℃、50±5%RH範圍內的環境下以頻率20GHz測得之值。 「耐熱性樹脂」意指熔點為280℃以上之高分子化合物，或是JIS C 4003：2010(IEC 60085：2007)所規定之最高連續使用溫度為121℃以上的高分子化合物。 「(甲基)丙烯酸酯」為丙烯酸酯及甲基丙烯酸酯之總稱。 聚合物之「單元」可為藉由聚合反應從單體直接形成之原子團，亦可為以預定方法處理藉由聚合反應所得之聚合物而使部分結構轉變的原子團。聚合物中所含以單體A為主體之單元亦僅表記為「單元A」。"Relative permittivity (20GHz) and dielectric tangent (20GHz)" are based on SPDR (Split-Post Dielectric Resonator) method at 23℃±2℃, 50±5%RH Measured at a frequency of 20GHz in the environment. "Heat-resistant resin" means a polymer compound having a melting point of 280°C or higher, or a polymer compound having a maximum continuous use temperature of 121°C or higher as specified in JIS C 4003:2010 (IEC 60085:2007). "(Meth)acrylate" is a general term for acrylate and methacrylate. The "unit" of a polymer may be an atomic group formed directly from a monomer by polymerization, or may be an atomic group that partially converts the structure by processing a polymer obtained by polymerization in a predetermined method. The unit containing monomer A as the main component contained in the polymer is also only expressed as "unit A".

本發明之附樹脂之金屬箔之製造方法係將包含特定粉末、特定分散劑及溶劑的粉末分散液塗佈於金屬箔表面，在特定溫度環境下階段性地加熱保持，而於金屬箔表面形成包含四氟乙烯系聚合物(以下亦表記為「TFE系聚合物」)之樹脂層(以下亦表記為「F樹脂層」)的方法。本發明之粉末分散液係TFE系聚合物之粉末分散成粒狀的分散液。The method for manufacturing a resin-attached metal foil of the present invention is to apply a powder dispersion containing a specific powder, a specific dispersant and a solvent to the surface of a metal foil, heat and maintain it stepwise under a specific temperature environment, and form it on the surface of the metal foil A method of including a resin layer (hereinafter also referred to as "F resin layer") of a tetrafluoroethylene-based polymer (hereinafter also referred to as "TFE polymer"). The powder dispersion of the present invention is a dispersion in which TFE-based polymer powder is dispersed into a granular form.

以本發明之製造方法製得的附樹脂之金屬箔之F樹脂層與其他基板之接著性優異的原因尚不明確，惟吾等以為如下。 本發明之粉末分散液包含顯示預定質量減少率(80~300℃溫度區域內之質量減少率為1質量%/分鐘以上)的分散劑，藉由TFE系聚合物之粉末及分散劑的高度相互作用，而有高度的分散穩定性及粉末於塗佈時的充填能力。亦即，若將該粉末分散液塗佈於金屬箔表面並保持在預定溫度(80~300℃溫度區域內之質量減少率為1質量%/分鐘以上的溫度)時，即可在溶劑揮發與分散劑分解進行的同時，形成特定粉末緊密充填之平滑性高的被膜。而且吾等認為，這時分散劑會成親水性而容易被特定粉末排斥，而容易在表面流動。因此，吾等認為也會因該保持而形成親水性成分偏析於表面之狀態。 吾等認為在本發明中係在該狀態下以更高的溫度(超過前述溫度區域之溫度)自前述被膜形成F樹脂層，所以就結果論，前述F樹脂層之表面的親水性及平滑性提高，從而可獲得具有接著性優異之F樹脂層的附樹脂之金屬箔。The reason why the F resin layer of the metal foil with resin produced by the manufacturing method of the present invention is excellent in adhesion with other substrates is not clear, but we think that it is as follows. The powder dispersion of the present invention contains a dispersant that exhibits a predetermined mass reduction rate (the mass reduction rate in the temperature range of 80 to 300°C is 1% by mass/minute or more). The powder of the TFE-based polymer and the dispersant are highly compatible with each other. Function, and has a high degree of dispersion stability and powder filling ability during coating. That is, if the powder dispersion is coated on the surface of the metal foil and maintained at a predetermined temperature (the mass reduction rate in the temperature range of 80 to 300°C is 1% by mass/minute or more), the solvent can be volatilized and At the same time as the dispersant decomposes, it forms a highly smooth coating with the specific powder tightly packed. And we believe that at this time the dispersant will be hydrophilic and easily repelled by the specific powder, and easily flow on the surface. Therefore, we believe that a hydrophilic component segregates on the surface due to this retention. We believe that in the present invention, the F resin layer is formed from the coating at a higher temperature (temperature exceeding the temperature range) in this state, so as a result, the surface of the F resin layer is hydrophilic and smooth By improving, a resin-coated metal foil having an F resin layer with excellent adhesion can be obtained.

本發明之製造方法的附樹脂之金屬箔於金屬箔之至少一表面具有F樹脂層。亦即，附樹脂之金屬箔可僅於金屬箔單面具有F樹脂層，亦可於金屬箔兩面具有F樹脂層。 附樹脂之金屬箔的翹曲率宜為25%以下，7%以下尤佳。翹曲率之下限通常為0%。此時，將附樹脂之金屬箔加工成印刷基板時的處置性及製得之印刷基板的傳輸特性優異。 附樹脂之金屬箔的尺寸變化率宜為±1%以下，±0.2%以下尤佳。此時，容易將從附樹脂之金屬箔製得之印刷基板進行多層化。The resin-attached metal foil of the manufacturing method of the present invention has an F resin layer on at least one surface of the metal foil. That is, the metal foil with resin may have the F resin layer on only one side of the metal foil, or may have the F resin layer on both sides of the metal foil. The warping rate of the metal foil with resin should be 25% or less, especially 7% or less. The lower limit of warpage is usually 0%. At this time, the metal foil with resin is processed into a printed circuit board and the handling properties of the printed circuit board are excellent, and the transmission characteristics of the produced printed circuit board are excellent. The dimensional change rate of the metal foil with resin should be ±1% or less, preferably ±0.2% or less. In this case, the printed circuit board made from the metal foil with resin is easily multilayered.

本發明之金屬箔的材質可舉銅、銅合金、不鏽鋼、鎳、鎳合金(亦含42合金)、鋁、鋁合金、鈦、鈦合金等。 金屬箔可舉軋延銅箔、電解銅箔等。亦可於金屬箔表面形成有防鏽層(鉻酸鹽等之氧化物皮膜等)、耐熱層等。The material of the metal foil of the present invention may include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy and the like. Examples of the metal foil include rolled copper foil and electrolytic copper foil. An anti-rust layer (chromate oxide film, etc.), heat-resistant layer, etc. may also be formed on the surface of the metal foil.

金屬箔表面的十點平均粗度宜為0.2~1.5μm。此時，其與F樹脂層之接著性即良好，容易製得傳輸特性優異的印刷基板。 金屬箔之厚度只要是可在附樹脂之金屬箔用途上發揮功能之厚度即可。金屬箔之厚度宜為2μm以上，3μm以上尤佳。而且金屬箔之厚度宜為40μm以下，20μm以下尤佳。 金屬箔表面可經矽烷耦合劑處理，可以是金屬箔表面整體經矽烷耦合劑處理，亦可為部分金屬箔表面經矽烷耦合劑處理。The ten-point average roughness of the metal foil surface should be 0.2~1.5μm. At this time, the adhesion to the F resin layer is good, and it is easy to produce a printed circuit board having excellent transmission characteristics. The thickness of the metal foil may be as long as it can function in the application of metal foil with resin. The thickness of the metal foil is preferably 2 μm or more, more preferably 3 μm or more. Moreover, the thickness of the metal foil is preferably 40 μm or less, particularly preferably 20 μm or less. The surface of the metal foil can be treated with a silane coupling agent. The entire surface of the metal foil can be treated with a silane coupling agent, or part of the surface of the metal foil can be treated with a silane coupling agent.

本發明之製造方法中的F樹脂層係由粉末分散液形成之層。 如同前述，F樹脂層之表面具有源自分散劑的親水性。F樹脂層表面之水接觸角宜為70~100°，70~90°尤佳。前述範圍只要在上限以下，F樹脂層與其他基材之接著性便更佳。前述範圍只要在下限以上，F樹脂層之電特性(低介電損耗及低介電常數)便更佳。The F resin layer in the production method of the present invention is a layer formed of a powder dispersion. As described above, the surface of the F resin layer has hydrophilicity derived from the dispersant. The water contact angle of the surface of the F resin layer should be preferably 70~100°, preferably 70~90°. As long as the aforementioned range is below the upper limit, the adhesion between the F resin layer and other substrates is better. As long as the aforementioned range is above the lower limit, the electrical characteristics of the F resin layer (low dielectric loss and low dielectric constant) are better.

F樹脂層之厚度宜為1μm以上，2μm以上較佳，5μm以上尤佳。而且F樹脂層之厚度宜為50μm以下，15μm以下較佳，小於10μm尤佳。在該範圍內，可易使印刷基板之傳輸特性及抑制附樹脂之金屬箔翹曲平衡。附樹脂之金屬箔於金屬箔兩面具有F樹脂層時，從可抑制附樹脂之金屬箔翹曲的觀點來看，各F樹脂層之組成及厚度宜分別相同。 F樹脂層之厚度的具體態樣可舉1~50μm，舉例如1~15μm、1μm以上且小於10μm、5~15μm等之態樣。The thickness of the F resin layer is preferably 1 μm or more, preferably 2 μm or more, and more preferably 5 μm or more. Moreover, the thickness of the F resin layer is preferably 50 μm or less, preferably 15 μm or less, and more preferably less than 10 μm. Within this range, it is easy to balance the transmission characteristics of the printed circuit board and suppress the warpage of the metal foil with resin. When the metal foil with resin has F resin layers on both sides of the metal foil, the composition and thickness of each F resin layer should be the same from the viewpoint of suppressing warpage of the metal foil with resin. Specific examples of the thickness of the F resin layer include 1 to 50 μm, for example, 1 to 15 μm, 1 μm or more and less than 10 μm, and 5 to 15 μm.

F樹脂層之相對介電常數宜為2.0~3.5，2.0~3.0較佳。此時，F樹脂層之電特性及接著性兩者皆優異，適合將附樹脂之金屬箔用於要求低介電常數的印刷基板等。 F樹脂層表面之Ra小於F樹脂層之厚度，宜為2.2~8μm。在該範圍內，容易使其與其他基板之接著性與加工性平衡。The relative dielectric constant of the F resin layer is preferably 2.0 to 3.5, preferably 2.0 to 3.0. At this time, the F resin layer is excellent in both electrical characteristics and adhesiveness, and it is suitable for using a metal foil with a resin for a printed circuit board that requires a low dielectric constant. The Ra of the surface of the F resin layer is smaller than the thickness of the F resin layer, preferably 2.2 to 8 μm. Within this range, it is easy to balance the adhesion and workability with other substrates.

本發明之粉末分散液包含：包含TFE系聚合物且體積基準累積50%粒徑為0.05~6.0μm的粉末(以下亦表記為「F粉末」)、80~300℃溫度區域內之質量減少率為1質量%/分鐘以上的分散劑、及溶劑。The powder dispersion of the present invention includes: a powder containing a TFE-based polymer and a cumulative 50% volume basis particle size of 0.05 to 6.0 μm (hereinafter also referred to as “F powder”), and a mass reduction rate in the temperature range of 80 to 300°C It is 1% by mass/minute or more of a dispersant and a solvent.

本發明之製造方法中的TFE系聚合物係包含以四氟乙烯(TFE)為主體之單元(TFE單元)的聚合物。TFE系聚合物可為TFE之均聚物，亦可為TFE及可與TFE共聚之其他單體(以下亦表記為共聚單體)的共聚物。TFE系聚合物宜含有相對於聚合物中所含之總單元為90~100莫耳%之TFE單元。 TFE系聚合物可舉聚四氟乙烯(PTFE)、TFE與乙烯之共聚物(ETFE)、TFE與丙烯之共聚物、TFE與全氟(烷基乙烯基醚)(PAVE)之共聚物(PFA)、TFE與六氟丙烯(HFP)之共聚物(FEP)、TFE與氯三氟乙烯之共聚物。 TFE系聚合物之熔融溫度在380℃下宜為1×102 ~1×106 Pa・s，在340℃下宜為1×102 ~1×106 Pa・s，在300℃下宜為1×102 ~1×106 Pa・s。此時，將粉末分散液塗佈於金屬箔表面並保持在預定溫度(80~300℃溫度區域內之質量減少率為1質量%/分鐘以上的溫度)時，更容易形成粉末緊密充填之平滑性高的被膜。The TFE-based polymer in the production method of the present invention is a polymer containing a unit (TFE unit) mainly composed of tetrafluoroethylene (TFE). The TFE-based polymer may be a homopolymer of TFE, or a copolymer of TFE and other monomers copolymerizable with TFE (hereinafter also referred to as comonomers). The TFE-based polymer preferably contains 90 to 100 mol% of TFE units relative to the total units contained in the polymer. Examples of TFE-based polymers include polytetrafluoroethylene (PTFE), copolymers of TFE and ethylene (ETFE), copolymers of TFE and propylene, and copolymers (PFA) of TFE and perfluoro(alkyl vinyl ether) (PAVE) ), copolymer of TFE and hexafluoropropylene (HFP) (FEP), copolymer of TFE and chlorotrifluoroethylene. The TFE-based polymer melting temperature at 380 deg.] C is suitably 1 × 10 2 ~ 1 × 10 6 Pa · s, at 340 ℃ is suitably 1 × 10 2 ~ 1 × 10 6 Pa · s, at 300 deg.] C should It is 1×10 2 ~1×10 6 Pa·s. At this time, when the powder dispersion is applied to the surface of the metal foil and maintained at a predetermined temperature (the mass reduction rate in the temperature range of 80 to 300°C is 1% by mass/minute or more), it is easier to form a smooth powder tightly packed High-energy coating.

TFE系聚合物的理想態樣可舉低分子量之PTFE。低分子量之PTFE可以是在由內核部分與外殼部分構成之內核-外殼結構中，僅外殼部分滿足上述熔融黏度的PTFE。 低分子量之PTFE可為對高分子量PTFE(熔融黏度為1×109 ~1×1010 Pa・s左右)照射放射線而獲得之PTFE(參考國際公開第2018/026012號、國際公開第2018/026017號等)，亦可為在將TFE聚合來製造PTFE時使用鏈轉移劑減低分子量而獲得之PTFE(參考日本專利特開2009-1745號公報、國際公開第2010/114033號等)。 另，低分子量之PTFE可以是將TFE單獨聚合而製得的聚合物，亦可以是將TFE與共聚單體共聚而製得的共聚物(參照國際公開第2009/20187號等)。相對於聚合物中所含之總單元，TFE單元宜為99.5莫耳%以上，99.8莫耳%以上較佳，99.9莫耳%以上更佳。TFE單元若在前述範圍內，即可維持PTFE物性。共聚單體可舉後述之氟單體，HFP、PAVE或FAE為宜。The ideal form of TFE polymer can be PTFE with low molecular weight. The low-molecular-weight PTFE may be a core-shell structure composed of a core part and a shell part, and only the shell part satisfies the above-mentioned melt viscosity. Low-molecular-weight PTFE may be PTFE obtained by irradiating high-molecular-weight PTFE (melt viscosity of about 1×10 9 to 1×10 10 Pa·s) (refer to International Publication No. 2018/026012 and International Publication No. 2018/026017 No., etc.), or PTFE obtained by reducing the molecular weight using a chain transfer agent when polymerizing TFE to produce PTFE (refer to Japanese Patent Laid-Open No. 2009-1745, International Publication No. 2010/114033, etc.). In addition, the low-molecular-weight PTFE may be a polymer prepared by polymerizing TFE alone, or a copolymer prepared by copolymerizing TFE and a comonomer (refer to International Publication No. 2009/20187, etc.). Relative to the total units contained in the polymer, the TFE unit is preferably 99.5 mol% or more, preferably 99.8 mol% or more, and more preferably 99.9 mol% or more. If the TFE unit is within the aforementioned range, the physical properties of PTFE can be maintained. The comonomer may be a fluorine monomer described later, and HFP, PAVE or FAE is suitable.

具有內核-外殼結構之PTFE可舉如日本特表2005-527652號公報、國際公開第2016/170918號等中記載之PTFE。為了使外殼部分之熔融黏度落在前述範圍內，可舉如使用鏈轉移劑將外殼部分予以低分子量化之方法(參照日本專利特開2015-232082號公報等)，以及在製造外殼部分時將TFE與前述共聚單體共聚之方法(參照日本特開平09-087334號公報)等。 在後者的方法中，共聚單體之使用量宜相對於TFE為0.001~0.05莫耳%左右。又，不僅外殼部分，內核部分亦可藉由共聚製得。在此情況下，亦以共聚單體之使用量相對於TFE為0.001~0.05莫耳%左右為佳。 低分子量PTFE的標準比重宜為2.14~2.22，且2.16~2.20較佳。標準比重可按照ASTM D4895-04測定。Examples of PTFE having a core-shell structure include PTFE described in Japanese Patent Publication No. 2005-527652 and International Publication No. 2016/170918. In order to make the melt viscosity of the shell part fall within the aforementioned range, for example, a method of reducing the molecular weight of the shell part using a chain transfer agent (refer to Japanese Patent Laid-Open No. 2015-232082, etc.), and when manufacturing the shell part The method of copolymerizing TFE with the aforementioned comonomer (refer to Japanese Patent Laid-Open No. 09-087334) and the like. In the latter method, the amount of comonomer used is preferably about 0.001 to 0.05 mole% relative to TFE. Moreover, not only the outer shell part, but also the inner core part can be made by copolymerization. In this case, the amount of comonomer relative to TFE is preferably about 0.001 to 0.05 mole %. The standard specific gravity of low molecular weight PTFE is preferably 2.14 to 2.22, and preferably 2.16 to 2.20. Standard specific gravity can be determined according to ASTM D4895-04.

TFE系聚合物的理想態樣為TFE與共聚單體之共聚物，亦可列舉含有相對於共聚物中所含之總單元超過0.5莫耳%之以共聚單體為主體之單元的氟聚物(以下亦表記為「聚合物F」)。聚合物F之熔點宜為240℃以上且低於330℃，260~320℃較佳，295~310℃尤佳。此時，可使聚合物之耐熱性與熔融成形性平衡。聚合物F可舉ETFE、FEP、PFA等。從電特性(相對介電常數、介電正切)及耐熱性之觀點來看，聚合物F以PFA或FEP較佳，PFA尤佳。The ideal form of the TFE polymer is a copolymer of TFE and a comonomer, and a fluoropolymer containing a unit mainly composed of a comonomer that exceeds 0.5 mole% relative to the total units contained in the copolymer can also be cited. (The following is also expressed as "Polymer F"). The melting point of the polymer F is preferably 240°C or higher and lower than 330°C, preferably 260-320°C, and particularly preferably 295-310°C. At this time, the heat resistance and melt formability of the polymer can be balanced. Examples of the polymer F include ETFE, FEP, and PFA. From the viewpoint of electrical characteristics (relative permittivity, dielectric tangent) and heat resistance, polymer F is preferably PFA or FEP, and PFA is particularly preferable.

從F樹脂層與金屬箔之接著性優異的觀點來看，TFE系聚合物宜為具有選自於由含羰基之基團、羥基、環氧基、醯胺基、胺基及異氰酸酯基所構成群組中之至少1種官能基(以下亦表記為「官能基」)的TFE系聚合物。官能基亦可藉由電漿處理等來賦予。 官能基可含在TFE系聚合物中之單元上，亦可含在聚合物之主鏈的末端基上。後者的聚合物可舉具有官能基作為源自聚合引發劑、鏈轉移劑等之末端基的聚合物。 聚合物F宜為包含具有官能基之單元與TFE單元的聚合物。而且此時的聚合物F更宜包含其他單元(後述之PAVE單元、HFP單元等)。From the viewpoint of excellent adhesion between the F resin layer and the metal foil, the TFE-based polymer is preferably selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, an amide group, an amine group, and an isocyanate group TFE polymer with at least one functional group in the group (hereinafter also referred to as "functional group"). The functional group can also be provided by plasma treatment or the like. The functional group may be contained in the unit in the TFE polymer, or may be contained in the terminal group of the main chain of the polymer. The latter polymer may include a polymer having a functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like. The polymer F is preferably a polymer containing a unit having a functional group and a TFE unit. Furthermore, the polymer F at this time preferably contains other units (PAVE unit, HFP unit, etc. described later).

從F樹脂層與金屬箔之接著性的觀點來看，官能基宜為含羰基之基團。含羰基之基團可舉碳酸酯基、羧基、鹵代甲醯基、烷氧羰基、酸酐殘基(-C(O)O(O)C-)、脂肪酸殘基等，且以羧基及酸酐殘基為宜。 具有官能基之單元宜為以具有官能基之單體為主體的單元，較宜為以具有含羰基之基團之單體為主體的單元、以具有羥基之單體為主體的單元、以具有環氧基之單體為主體的單元及以具有異氰酸酯基之單體為主體的單元，尤宜為以具有含羰基之基團之單體為主體的單元。From the viewpoint of the adhesion between the F resin layer and the metal foil, the functional group is preferably a carbonyl group-containing group. Carbonyl group-containing groups include carbonate groups, carboxyl groups, haloformamide groups, alkoxycarbonyl groups, acid anhydride residues (-C(O)O(O)C-), fatty acid residues, etc., and carboxyl groups and acid anhydrides Residues are appropriate. The unit having a functional group is preferably a unit mainly composed of a monomer having a functional group, preferably a unit mainly composed of a monomer having a group containing a carbonyl group, a unit mainly composed of a monomer having a hydroxyl group, Units mainly composed of monomers having epoxy groups and units mainly composed of monomers having isocyanate groups are particularly preferably units mainly composed of monomers having carbonyl group-containing groups.

具有含羰基之基團之單體宜為：具有酸酐殘基之環狀單體、具有羧基之單體、乙烯基酯及(甲基)丙烯酸酯，且以具有酸酐殘基之環狀單體尤佳。 前述環狀單體宜為：伊康酸酐、檸康酸酐、5-降莰烯-2,3-二羧酸酐(別名：納迪克酸酐，以下亦表記為「NAH」)及馬來酸酐。The monomer having a carbonyl group-containing group is preferably a cyclic monomer having an acid anhydride residue, a monomer having a carboxyl group, a vinyl ester and a (meth)acrylate, and a cyclic monomer having an acid anhydride residue Especially good. The aforementioned cyclic monomers are preferably: itaconic anhydride, citraconic anhydride, 5-norcamene-2,3-dicarboxylic anhydride (alias: Nadic anhydride, hereinafter also referred to as "NAH") and maleic anhydride.

具有官能基之單元及TFE單元以外的其他單元宜為HFP單元、PAVE單元及FAE單元。 PAVE可舉CF2 ＝CFOCF3 、CF2 ＝CFOCF2 CF3 、CF2 ＝CFOCF2 CF2 CF3 (PPVE)、CF2 ＝CFOCF2 CF2 CF2 CF3 、CF2 ＝CFO(CF2 )8 F等，且PPVE為宜。 FAE可舉CH2 ＝CH(CF2 )2 F、CH2 ＝CH(CF2 )3 F、CH2 ＝CH(CF2 )4 F、CH2 ＝CF(CF2 )3 H、CH2 ＝CF(CF2 )4 H等，以CH2 ＝CH(CF2 )4 F、CH2 ＝CH(CF2 )2 F為佳。Units other than functional units and TFE units are preferably HFP units, PAVE units and FAE units. PAVE may be CF 2 =CFOCF 3 , CF 2 =CFOCF 2 CF 3 , CF 2 =CFOCF 2 CF 2 CF 3 (PPVE), CF 2 =CFOCF 2 CF 2 CF 2 CF 3 , CF 2 =CFO(CF 2 ) 8 F, etc., and PPVE is appropriate. FAE can be mentioned CH 2 =CH(CF 2 ) 2 F, CH 2 =CH(CF 2 ) 3 F, CH 2 =CH(CF 2 ) 4 F, CH 2 =CF(CF 2 ) 3 H, CH 2 = CF(CF 2 ) 4 H and the like are preferably CH 2 =CH(CF 2 ) 4 F and CH 2 =CH(CF 2 ) 2 F.

聚合物F宜為包含具有官能基之單元、TFE單元與PAVE單元或HFP單元的聚合物。該聚合物F之具體例可舉國際公開第2018/16644號中記載之聚合體(X)。 聚合物F中之TFE單元的比率宜在構成聚合物F之總單元中為90~99莫耳%。 聚合物F中之PAVE單元或HFP單元的比率宜在構成聚合物F之總單元中為0.5~9.97莫耳%。 聚合物F中之具有官能基之單元的比率宜在構成聚合物F之總單元中為0.01~3莫耳%。The polymer F is preferably a polymer containing a unit having a functional group, a TFE unit, and a PAVE unit or HFP unit. Specific examples of the polymer F include the polymer (X) described in International Publication No. 2018/16644. The ratio of TFE units in polymer F is preferably 90 to 99 mol% in the total units constituting polymer F. The ratio of PAVE units or HFP units in polymer F is preferably 0.5 to 9.97 mole% in the total units constituting polymer F. The ratio of the units having functional groups in the polymer F is preferably 0.01 to 3 mol% in the total units constituting the polymer F.

本發明之製造方法中的粉末(以下亦表記為「F粉末」)係包含TFE系聚合物之粉末。F粉末可在不損及本發明效果之範圍內包含有TFE系聚合物以外的成分，惟宜以TFE系聚合物為主成分。F粉末之TFE系聚合物的含量宜為80質量%以上，且100質量%尤佳。 F粉末之D50宜為0.05~6.0μm，0.1~3.0μm較佳，0.2~3.0μm尤佳。在該範圍內，F粉末之流動性與分散性便良好，而且最容易顯現附樹脂之金屬箔中TFE系聚合物之電特性(低介電常數等)及耐熱性。 F粉末之D90宜為8μm以下，6μm以下較佳，5μm以下尤佳。粉末之D90宜為0.3μm以上，0.8μm以上尤佳。在該範圍內，F粉末之流動性與分散性便良好，而且最容易顯現F樹脂層之電特性(低介電常數等)及耐熱性。 F粉末之鬆裝體密度宜為0.05g/mL以上，0.08~0.5g/mL尤佳。 F粉末之緊密裝填體密度宜為0.05g/mL以上，0.1~0.8g/mL尤佳。 F粉末之製造方法並無特別限定，可採用國際公開第2016/017801號之段落[0065]~[0069]中記載之方法。另，市面上若有符合期望的粉末，F粉末亦可用之。The powder in the production method of the present invention (hereinafter also referred to as "F powder") is a powder containing a TFE-based polymer. The F powder may contain components other than the TFE-based polymer within the range that does not impair the effects of the present invention, but it is preferable to use the TFE-based polymer as the main component. The content of the TFE polymer of the F powder is preferably 80% by mass or more, and 100% by mass is particularly preferable. The D50 of the F powder is preferably 0.05 to 6.0 μm, preferably 0.1 to 3.0 μm, and more preferably 0.2 to 3.0 μm. Within this range, the flowability and dispersibility of the F powder are good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the TFE polymer in the metal foil with resin are most likely to be exhibited. The D90 of the F powder is preferably 8 μm or less, preferably 6 μm or less, and more preferably 5 μm or less. The D90 of the powder is preferably 0.3 μm or more, and more preferably 0.8 μm or more. Within this range, the flowability and dispersibility of the F powder are good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the F resin layer are most likely to be exhibited. The loose body density of F powder should be above 0.05g/mL, especially 0.08~0.5g/mL. The density of the compact packing of F powder should be above 0.05g/mL, preferably 0.1~0.8g/mL. The manufacturing method of the F powder is not particularly limited, and the method described in paragraphs [0065] to [0069] of International Publication No. 2016/017801 can be used. In addition, if powder on the market meets expectations, F powder can also be used.

本發明之製造方法中的分散劑係在80~300℃溫度區域內顯示1質量%/分鐘以上之質量減少率的化合物。分散劑宜為100~200℃溫度區域內之質量減少率為1質量%/分鐘以上的化合物，或是200~300℃溫度區域內之質量減少率為1質量%/分鐘以上的化合物。 分散劑之質量減少率可使用熱重量測定裝置(TG)、熱重量示差熱分析裝置(TG-DTA)，令升溫速度為10℃/分鐘、分散劑之試料量為10mg，在混合氣體(氦90體積%與氧10體積%)環境下進行測定。 譬如，「分散劑之200~300℃溫度區域內的質量減少率」係用熱重量示差熱分析裝置(TG-DTA)，在混合氣體(氦90體積%與氧10體積%)環境下使10mg分散劑在10℃/分鐘之速度下從200℃升溫至300℃，並將其質量減少量除以升溫時間(10分鐘)與分散劑之試料量(10mg)所得之值的百分率值而求得。 質量減少率之上限宜為50質量%/分鐘。 質量減少率宜為2~50質量%/分鐘，4~20質量%/分鐘較佳，6~15質量%/分鐘尤佳。 質量減少率只要為1質量%/分鐘以上，便容易使F樹脂層表面的親水性與平滑性平衡。質量減少率只要在50質量%/分鐘以下，便容易使F樹脂層表面的平滑性及抑制金屬箔因分散劑之分解成分而劣化平衡。The dispersant in the production method of the present invention is a compound that shows a mass reduction rate of 1% by mass/minute or more in the temperature range of 80 to 300°C. The dispersant is preferably a compound having a mass reduction rate of 100% or more in the temperature range of 100 to 200°C, or a compound having a mass reduction rate of 1% or more in the temperature range of 200 to 300°C. For the mass reduction rate of the dispersant, a thermogravimetric measurement device (TG) and a thermogravimetric differential thermal analysis device (TG-DTA) can be used to set the heating rate to 10°C/min, the sample amount of the dispersant to 10 mg, and the mixed gas (helium 90% by volume and 10% by volume of oxygen). For example, "the mass reduction rate of the dispersant in the temperature range of 200 to 300 ℃" is to use a thermogravimetric differential thermal analysis device (TG-DTA) in a mixed gas (helium 90 vol% and oxygen 10 vol%) environment to make 10mg The dispersant is heated from 200°C to 300°C at a rate of 10°C/minute, and the mass reduction is divided by the percentage value of the value obtained by the heating time (10 minutes) and the sample amount of the dispersant (10mg) . The upper limit of the mass reduction rate should be 50 mass%/min. The mass reduction rate is preferably 2-50% by mass/min, 4-20% by mass/min is better, and 6-15% by mass/min is particularly preferable. As long as the mass reduction rate is 1% by mass/minute or more, it is easy to balance the hydrophilicity and smoothness of the surface of the F resin layer. As long as the mass reduction rate is 50% by mass/minute or less, it is easy to balance the smoothness of the surface of the F resin layer and to suppress the deterioration of the metal foil due to the decomposition components of the dispersant.

本發明之製造方法的分散劑宜為具有疏水部位與親水部位之化合物(界面活性劑)，尤宜為具有含氟部位與親水部位之化合物(氟系界面活性劑)。 分散劑宜為多元醇、聚氧伸烷基二醇、聚己內醯胺及聚合物狀多元醇，且聚合物狀多元醇較佳。 聚合物狀多元醇意指具有以具碳-碳不飽和雙鍵之單體為主體的單元與2個以上羥基的聚合物。聚合物狀多元醇尤宜為聚乙烯醇、聚乙烯醇縮丁醛及氟多元醇，氟多元醇最佳。惟，氟多元醇並非F聚合物，而是具有羥基與氟原子之聚合物狀多元醇。又，聚合物狀多元醇亦可部分羥基經化學修飾、改質。 氟多元醇可舉主鏈由源自乙烯性不飽和單體之碳鏈構成、且於側鏈具有含氟烴基與羥基的聚合物狀多元醇。前述含氟烴基宜為具有鍵結有多個(2或3)1價含氟烴基之3級碳原子之基。The dispersant in the production method of the present invention is preferably a compound (surfactant) having a hydrophobic portion and a hydrophilic portion, and particularly preferably a compound (fluorine-based surfactant) having a fluorine-containing portion and a hydrophilic portion. The dispersant is preferably a polyhydric alcohol, polyoxyalkylene glycol, polycaprolactam, and polymer-like polyol, and polymer-like polyol is preferable. The polymer polyol means a polymer having a unit mainly composed of a monomer having a carbon-carbon unsaturated double bond and two or more hydroxyl groups. The polymer-like polyol is particularly preferably polyvinyl alcohol, polyvinyl butyral and fluoropolyol, with fluoropolyol being the best. However, the fluoropolyol is not an F polymer, but a polymer polyol having a hydroxyl group and a fluorine atom. In addition, polymer-like polyols can also be partially chemically modified and modified with hydroxyl groups. Examples of the fluoropolyol include a polymer polyol having a main chain composed of a carbon chain derived from an ethylenically unsaturated monomer, and having a fluorine-containing hydrocarbon group and a hydroxyl group in the side chain. The aforementioned fluorine-containing hydrocarbon group is preferably a group having a third-order carbon atom to which a plurality of (2 or 3) monovalent fluorine-containing hydrocarbon groups are bonded.

分散劑宜為於側鏈具有多氟烷基或多氟烯基、及聚氧伸烷基或醇性羥基之聚合物(以下亦表記為「界面活性劑F」)，且尤宜為具有多氟烷基或多氟烯基之(甲基)丙烯酸酯(以下亦表記為「(甲基)丙烯酸酯F」)與具有聚氧伸烷基單元醇基之(甲基)丙烯酸酯(以下亦表記為「(甲基)丙烯酸酯AO」)的共聚物(以下亦表記為「界面活性劑F1」)。 界面活性劑F之多氟烷基或多氟烯基宜分別為碳數4~12之基。 界面活性劑F可於側鏈具有聚氧伸烷基與醇性羥基兩者，亦可於側鏈僅具有聚氧伸烷基與醇性羥基中之任一基，宜於側鏈至少具有聚氧伸烷基。The dispersant is preferably a polymer having a polyfluoroalkyl group or a polyfluoroalkenyl group on the side chain, and a polyoxyalkylene group or an alcoholic hydroxyl group (hereinafter also referred to as "surfactant F"), and particularly preferably (Meth)acrylate of fluoroalkyl or polyfluoroalkenyl (hereinafter also referred to as "(meth)acrylate F") and (meth)acrylate with polyoxyalkylene unit alcohol group (hereinafter also The copolymer expressed as "(meth)acrylate AO") (hereinafter also expressed as "surfactant F1"). The polyfluoroalkyl group or polyfluoroalkenyl group of the surfactant F is preferably a group having 4 to 12 carbon atoms. Surfactant F may have both polyoxyalkylene groups and alcoholic hydroxyl groups on the side chain, or may have only one of polyoxyalkylene groups and alcoholic hydroxyl groups on the side chain. Oxyalkylene.

本發明人等已知界面活性劑F在前述溫度區域內之質量減少係因多氟烷基或多氟烯基脫離與聚氧伸烷基中之氧伸烷基單元的分解或醇性羥基的存在而進行。此外，吾等亦已知界面活性劑F在前述溫度區域內多氟烷基或多氟烯基會脫離，但聚氧伸烷基很容易停留在氧伸烷基單元的部分分解而形成親水高的成分。該親水成分會有效進行表面偏析，因此吾等認為F樹脂層之表面不僅會變親水性，還會抑制粉末在充填中掉粉，提高F樹脂層之平滑性，故而附樹脂之金屬箔的接著性優異。The inventors have known that the mass reduction of the surfactant F in the aforementioned temperature range is due to the decomposition of the polyfluoroalkyl group or polyfluoroalkenyl group and the decomposition of the oxyalkylene unit in the polyoxyalkylene group or the alcoholic hydroxyl group. Proceed. In addition, we also know that surfactant F will detach polyfluoroalkyl groups or polyfluoroalkenyl groups in the aforementioned temperature range, but polyoxyalkylene groups can easily stay in the oxyalkylene unit and decompose to form a hydrophilic Ingredients. The hydrophilic component will effectively segregate the surface, so we believe that the surface of the F resin layer will not only become hydrophilic, but also suppress the powder from falling off during filling, and improve the smoothness of the F resin layer, so the adhesion of the metal foil with resin Excellent.

(甲基)丙烯酸酯F宜為以式CH2 ＝CR1 C(O)O-X1 -RF 表示之化合物。 R1 表示氫原子或甲基。 X1 表示-(CH2 )2 -、-(CH2 )3 -、-(CH2 )4 -、-(CH2 )2 NHC(O)-、-(CH2 )3 NHC(O)-或-CH2 CH(CH3 )NHC(O)-。 RF 表示-OCF(CF3 )(C(CF(CF3 )2 )(＝C(CF3 )2 )、-OC(CF3 )(＝C(CF(CF3 )2 )(CF(CF3 )2 )、-OCH(CH2 OCH2 CH2 (CF2 )4 F)2 、 -OCH(CH2 OCH2 CH2 (CF2 )6 F)2 、-(CF2 )4 F或-(CF2 )6 F。 (甲基)丙烯酸酯AO宜為以式CH2 ＝CR2 C(O)O-Q2 -OH表示之化合物。 R2 表示氫原子或甲基。 Q2 表示-(CH2 )m (OCH2 CH2 )n -、-(CH2 )m (OCH2 CH(CH3 ))n -或-(CH2 )m (OCH2 CH2 CH2 CH2 )n -(n表示1~4之整數，n表示2~100之整數，n以2~20之整數為宜)。 (甲基)丙烯酸酯F之具體例可舉：CH2 ＝CHCOO(CH2 )4 OCF(CF3 )(C(CF(CF3 )2 )(＝C(CF3 )2 )、CH2 ＝CHCOO(CH2 )4 OC(CF3 )(＝C(CF(CF3 )2 )(CF(CF3 )2 )、CH2 ＝C(CH3 )COO(CH2 )2 NHCOOCH(CH2 OCH2 CH2 (CF2 )6 F)2 、CH2 ＝C(CH3 )COO(CH2 )2 NHCOOCH(CH2 OCH2 CH2 (CF2 )4 F)2 、CH2 ＝C(CH3 )COO(CH2 )2 NHCOOCH(CH2 OCH2 (CF2 )6 F)2 、CH2 ＝C(CH3 )COO(CH2 )2 NHCOOCH(CH2 OCH2 (CF2 )4 F)2 、CH2 ＝C(CH3 )COO(CH2 )3 NHCOOCH(CH2 OCH2 (CF2 )6 F)2 、CH2 ＝C(CH3 )COO(CH2 )3 NHCOOCH(CH2 OCH2 (CF2 )4 F)2 。 (甲基)丙烯酸酯AO之具體例可舉：CH2 ＝CHCOO(CH2 CH2 O)8 OH、CH2 ＝CHCOO(CH2 CH2 O)10 OH、CH2 ＝CHCOO(CH2 CH2 O)12 OH、CH2 ＝C(CH3 )COO(CH2 CH(CH3 )O)8 OH、CH2 ＝C(CH3 )COO(CH2 CH(CH3 )O)12 OH、CH2 ＝C(CH3 )COO(CH2 CH(CH3 )O)16 OH。The (meth)acrylate F is preferably a compound represented by the formula CH 2 =CR 1 C(O)OX 1 -R F. R 1 represents a hydrogen atom or a methyl group. X 1 represents -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 2 NHC(O)-, -(CH 2 ) 3 NHC(O)- Or -CH 2 CH(CH 3 )NHC(O)-. R F represents -OCF(CF 3 )(C(CF(CF 3 ) 2 )(=C(CF 3 ) 2 ), -OC(CF 3 )(=C(CF(CF 3 ) 2 )(CF(CF 3 ) 2 ), -OCH(CH 2 OCH 2 CH 2 (CF 2 ) 4 F) 2 , -OCH(CH 2 OCH 2 CH 2 (CF 2 ) 6 F) 2 , -(CF 2 ) 4 F or- (CF 2 ) 6 F. (Meth)acrylate AO is preferably a compound represented by the formula CH 2 =CR 2 C(O)OQ 2 -OH. R 2 represents a hydrogen atom or a methyl group. Q 2 represents -(CH 2 ) m (OCH 2 CH 2 ) n -, -(CH 2 ) m (OCH 2 CH(CH 3 )) n -or -(CH 2 ) m (OCH 2 CH 2 CH 2 CH 2 ) n -(n Represents an integer from 1 to 4, n represents an integer from 2 to 100, and n is preferably an integer from 2 to 20). Specific examples of (meth)acrylate F include: CH 2 =CHCOO(CH 2 ) 4 OCF( CF 3 )(C(CF(CF 3 ) 2 )(=C(CF 3 ) 2 ), CH 2 =CHCOO(CH 2 ) 4 OC(CF 3 )(=C(CF(CF 3 ) 2 )(CF (CF 3 ) 2 ), CH 2 =C(CH 3 )COO(CH 2 ) 2 NHCOOCH(CH 2 OCH 2 CH 2 (CF 2 ) 6 F) 2 , CH 2 =C(CH 3 )COO(CH 2 ) 2 NHCOOCH(CH 2 OCH 2 CH 2 (CF 2 ) 4 F) 2 , CH 2 =C(CH 3 )COO(CH 2 ) 2 NHCOOCH(CH 2 OCH 2 (CF 2 ) 6 F) 2 , CH 2 =C(CH 3 )COO(CH 2 ) 2 NHCOOCH(CH 2 OCH 2 (CF 2 ) 4 F) 2 , CH 2 =C(CH 3 )COO(CH 2 ) 3 NHCOOCH(CH 2 OCH 2 (CF 2 ) 6 F) 2 , CH 2 =C(CH 3 )COO(CH 2 ) 3 NHCOOCH(CH 2 OCH 2 (CF 2 ) 4 F) 2. Specific examples of (meth)acrylate AO include: CH 2 =CHCOO(CH 2 CH 2 O) 8 OH, CH 2 =CHCOO(CH 2 CH 2 O) 10 OH, CH 2 =CH COO(CH 2 CH 2 O) 12 OH, CH 2 =C(CH 3 )COO(CH 2 CH(CH 3 )O) 8 OH, CH 2 =C(CH 3 )COO(CH 2 CH(CH 3 ) O) 12 OH, CH 2 =C(CH 3 )COO(CH 2 CH(CH 3 )O) 16 OH.

相對於界面活性劑F1中所含之總單元，以(甲基)丙烯酸酯F為主體之單元的比率宜為20~60莫耳%，20~40莫耳%尤佳。 相對於界面活性劑F1中所含之總單元，以(甲基)丙烯酸酯AO為主體之單元的比率宜為40~80莫耳%，60~80莫耳%尤佳。 界面活性劑F1中，以(甲基)丙烯酸酯AO為主體之單元含量相對於以(甲基)丙烯酸酯F為主體之單元含量的比率宜為1~5，1~2尤佳。 界面活性劑F1可僅由以(甲基)丙烯酸酯AO為主體之單元與以(甲基)丙烯酸酯AO為主體之單元構成，並更可進一步包含有其他單元。 界面活性劑F1之氟含量宜為10~45質量%，15~40質量%尤佳。 界面活性劑F1宜為非離子性。 界面活性劑F1之質量平均分子量宜為2000~80000，6000~20000尤佳。Relative to the total units contained in the surfactant F1, the ratio of the unit mainly composed of (meth)acrylate F is preferably 20 to 60 mol%, and 20 to 40 mol% is particularly preferable. Relative to the total units contained in the surfactant F1, the ratio of the unit mainly composed of (meth)acrylate AO is preferably 40 to 80 mol%, preferably 60 to 80 mol%. In the surfactant F1, the ratio of the content of the unit mainly composed of (meth)acrylate AO to the content of the unit mainly composed of (meth)acrylate F is preferably 1 to 5, and 1 to 2 is particularly preferable. The surfactant F1 may be composed of only a unit mainly composed of (meth)acrylate AO and a unit mainly composed of (meth)acrylate AO, and may further include other units. The fluorine content of the surfactant F1 is preferably 10 to 45% by mass, and 15 to 40% by mass is particularly preferable. The surfactant F1 is preferably nonionic. The mass average molecular weight of the surfactant F1 is preferably 2,000 to 80,000, preferably 6,000 to 20,000.

本發明之製造方法中的溶劑為分散媒，在25℃下為液態之非活性且不與F粉末起反應的溶劑(化合物)，宜為沸點比粉末分散液中所含之溶劑以外的成分更低且可藉加熱等揮發去除的溶劑。 將粉末分散液塗佈於金屬箔表面而形成的塗膜中之溶劑在TFE系聚合物之燒成結束以前會被去除。溶劑在前述溫度區域內之質量減少率為1質量%/分鐘以上的溫度下保持金屬箔之前被去除即可，亦可在前述溫度中保持期間被去除，或可在燒成中被去除。溶劑宜至少在前述溫度中保持期間至少被去除一部分。 溶劑可舉：水、醇(甲醇、乙醇、異丙醇等)、含氮化合物(N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等)、含硫化合物(二甲亞碸等)、醚(二乙基醚、二

Figure 108118229-A0304-12-01
烷等)、酯(乳酸乙酯、乙酸乙酯等)、酮(甲基乙基酮、甲基異丙基酮、環戊酮、環己酮等)、甘醇醚(乙二醇單異丙基醚等)、賽璐蘇(甲賽璐蘇、乙賽璐蘇等)等。溶劑化合物可單獨使用1種亦可將2種以上併用。The solvent in the manufacturing method of the present invention is a dispersion medium. The solvent (compound) which is a liquid inactive at 25°C and does not react with the F powder, preferably has a boiling point more than the components other than the solvent contained in the powder dispersion Low solvent that can be removed by heating and other volatile. The solvent in the coating film formed by applying the powder dispersion to the surface of the metal foil is removed before the firing of the TFE-based polymer is completed. The solvent may be removed before holding the metal foil at a temperature with a mass reduction rate of 1% by mass/minute or more in the aforementioned temperature range, or may be removed during the holding at the aforementioned temperature, or may be removed during firing. The solvent is preferably removed at least in part while being maintained at the aforementioned temperature. Examples of solvents include water, alcohols (methanol, ethanol, isopropanol, etc.), nitrogen-containing compounds (N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2 -Pyrrolidone, etc.), sulfur compounds (dimethyl sulfoxide, etc.), ethers (diethyl ether, di
Figure 108118229-A0304-12-01
Alkanes, etc.), esters (ethyl lactate, ethyl acetate, etc.), ketones (methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, etc.), glycol ethers (ethylene glycol monoiso Propyl ether, etc.), celluloid (A cellulose, B cellulose, etc.) and so on. One type of solvent compound may be used alone, or two or more types may be used in combination.

溶劑以不會瞬間揮發而是在保持於前述溫度區域期間揮發的溶劑為佳，且宜為沸點80~275℃之溶劑，沸點125~250℃之溶劑尤佳。在該範圍內，將已塗佈於金屬箔表面上之粉末分散液保持在預定溫度時，就能有效進行溶劑之揮發及分散劑的部分分解及流動，從而分散劑容易表面偏析。 溶劑宜為有機化合物，較宜為環己烷(沸點：81℃)、2-丙醇(沸點：82℃)、1-丙醇(沸點：97℃)、1-丁醇(沸點：117℃)、1-甲氧基-2-丙醇(沸點：119℃)、N-甲基吡咯啶酮(沸點：202℃)、γ-丁內酯(沸點：204℃)、環己酮(沸點：156℃)及環戊酮(沸點：131℃)，尤宜為N-甲基吡咯啶酮、γ-丁內酯、環己酮及環戊酮。The solvent is preferably a solvent that does not evaporate instantaneously but evaporates while being maintained in the aforementioned temperature range, and is preferably a solvent having a boiling point of 80 to 275°C, and a solvent having a boiling point of 125 to 250°C is particularly preferred. Within this range, when the powder dispersion liquid coated on the surface of the metal foil is maintained at a predetermined temperature, the volatilization of the solvent and the partial decomposition and flow of the dispersant can be effectively performed, so that the dispersant is prone to surface segregation. The solvent is preferably an organic compound, preferably cyclohexane (boiling point: 81°C), 2-propanol (boiling point: 82°C), 1-propanol (boiling point: 97°C), 1-butanol (boiling point: 117°C) ), 1-methoxy-2-propanol (boiling point: 119°C), N-methylpyrrolidone (boiling point: 202°C), γ-butyrolactone (boiling point: 204°C), cyclohexanone (boiling point) : 156℃) and cyclopentanone (boiling point: 131℃), especially N-methylpyrrolidone, γ-butyrolactone, cyclohexanone and cyclopentanone.

本發明之製造方法中的粉末分散液可在不損及本發明效果之範圍內含有其他材料。其他材料可溶於粉末分散液，亦可不溶於粉末分散液。 所述其他材料可為非硬化性樹脂，亦可為硬化性樹脂。 非硬化性樹脂可舉熱熔融性樹脂、非熔融性樹脂。熱熔融性樹脂可舉熱塑性聚醯亞胺等。非熔融性樹脂可舉硬化性樹脂之硬化物等。 硬化性樹脂可舉：具有反應性基之聚合物、具有反應性基之寡聚物、低分子化合物、具有反應性基之低分子化合物等。反應性基可舉如含羰基之基團、羥基、胺基、環氧基等。The powder dispersion in the production method of the present invention may contain other materials within a range that does not impair the effects of the present invention. Other materials are soluble in the powder dispersion or insoluble in the powder dispersion. The other material may be non-curable resin or curable resin. Examples of non-curable resins include hot-melt resins and non-melt resins. Examples of the hot-melt resin include thermoplastic polyimide. Examples of the non-melting resin include cured products of curable resin. Examples of the curable resin include polymers having reactive groups, oligomers having reactive groups, low-molecular compounds, and low-molecular compounds having reactive groups. Examples of the reactive group include a carbonyl group-containing group, a hydroxyl group, an amine group, and an epoxy group.

硬化性樹脂可舉：環氧樹脂、熱硬化性聚醯亞胺、聚醯亞胺前驅物之聚醯胺酸、熱硬化性丙烯酸樹脂、苯酚樹脂、熱硬化性聚酯樹脂、熱硬化性聚烯烴樹脂、熱硬化性改質聚苯醚樹脂、多官能氰酸酯樹脂、多官能馬來醯亞胺-氰酸酯樹脂、多官能性馬來醯亞胺樹脂、乙烯基酯樹脂、脲樹脂、酞酸二烯丙酯樹脂、三聚氰胺樹脂、胍胺樹脂、三聚氰胺-脲共縮合樹脂。其中，從有用於印刷基板用途的觀點來看，熱硬化性樹脂以熱硬化性聚醯亞胺、聚醯亞胺前驅物、環氧樹脂、熱硬化性丙烯酸樹脂、雙馬來醯亞胺樹脂及熱硬化性聚苯醚樹脂為佳，環氧樹脂及熱硬化性聚苯醚樹脂尤佳。Examples of the curable resin include epoxy resin, thermosetting polyimide, polyimide of polyimide precursor, thermosetting acrylic resin, phenol resin, thermosetting polyester resin, thermosetting polymer Olefin resin, thermosetting modified polyphenylene ether resin, multifunctional cyanate resin, multifunctional maleimide-cyanate resin, multifunctional maleimide resin, vinyl ester resin, urea resin , Diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea co-condensation resin. Among them, from the viewpoint of use in printed circuit board applications, thermosetting resins include thermosetting polyimide, polyimide precursor, epoxy resin, thermosetting acrylic resin, and bismaleimide resin. And thermosetting polyphenylene ether resin is preferred, epoxy resin and thermosetting polyphenylene ether resin are particularly preferred.

環氧樹脂之具體例可舉：萘型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、甲酚酚醛型環氧樹脂、苯酚酚醛型環氧樹脂、烷基苯酚酚醛型環氧樹脂、芳烷基型環氧樹脂、聯酚型環氧樹脂、二環戊二烯型環氧樹脂、參羥苯基甲烷型環氧化合物、苯酚與具有苯酚性羥基之芳香族醛的縮合物之環氧化物、雙酚之二環氧丙基醚化物、萘二醇之二環氧丙基醚化物、苯酚之環氧丙基醚化物、醇之二環氧丙基醚化物、三聚異氰酸三環氧丙酯等。 雙馬來醯亞胺樹脂可舉日本專利特開平7-70315號公報中所記載之併用雙酚A型氰酸酯樹脂與雙馬來醯亞胺化合物的樹脂組成物(BT樹脂)，或如國際公開第2013/008667號中記載之發明及其發明背景中記載之物。 聚醯胺酸通常具有可與TFE系聚合物之官能基起反應的反應性基。 形成聚醯胺酸之二胺、多元羧酸二酐可舉如：日本專利第5766125號公報之段落[0020]、日本專利第5766125號公報之段落[0019]、日本專利特開2012-145676號公報之段落[0055]、[0057]等中記載之物。其中，又以由4,4’-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷等芳香族二胺與焦蜜石酸二酐、3,3’,4,4’-聯苯四甲酸二酐、3,3’,4,4’-二苯基酮四甲酸二酐等芳香族多元羧酸二酐之組合所構成的聚醯胺酸為佳。Specific examples of epoxy resins include naphthalene epoxy resins, cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and alicyclic epoxy resins. Epoxy resin, aliphatic chain epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, alkylphenol novolac epoxy resin, aralkyl epoxy resin, biphenol epoxy resin 、Dicyclopentadiene epoxy resin, para-hydroxyphenylmethane epoxy compound, epoxy compound of phenol and aromatic aldehyde with phenolic hydroxyl group, diglycidyl ether of bisphenol, Diglycidyl etherate of naphthalene glycol, glycidyl etherate of phenol, diglycidyl etherate of alcohol, triglycidyl isocyanate, etc. The bismaleimide resin may be a resin composition (BT resin) described in Japanese Patent Laid-Open No. 7-70315, which uses a bisphenol A type cyanate resin and a bismaleimide compound together, or as The invention described in International Publication No. 2013/008667 and the thing described in the background of the invention. Polyamic acid usually has a reactive group that can react with the functional group of the TFE-based polymer. Examples of diamines and polycarboxylic acid dianhydrides that form polyamides are: Japanese Patent No. 5766125 paragraph [0020], Japanese Patent No. 5766125 paragraph [0019], Japanese Patent Laid-Open No. 2012-145676 Articles described in paragraphs [0055] and [0057] of the Gazette. Among them, aromatic diamines such as 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and Anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketonetetracarboxylic dianhydride and other aromatic polycarboxylic acid dianhydride Polyamide is preferred.

熱熔融性樹脂可舉熱塑性聚醯亞胺等熱塑性樹脂、硬化性樹脂之熱熔融性硬化物。 熱塑性樹脂可舉：聚酯樹脂、聚烯烴樹脂、苯乙烯樹脂、聚碳酸酯、熱塑性聚醯亞胺、聚芳酯、聚碸、聚芳基碸、芳香族聚醯胺、芳香族聚醚醯胺、聚伸苯硫、聚芳基醚酮、聚醯胺醯亞胺、液晶性聚酯、聚苯醚等，以熱塑性聚醯亞胺、液晶性聚酯及聚苯醚為宜。Examples of the hot-melt resin include thermoplastic resins such as thermoplastic polyimide, and hot-melt cured products of curable resins. Examples of thermoplastic resins include polyester resins, polyolefin resins, styrene resins, polycarbonates, thermoplastic polyimides, polyarylates, polysalts, polyarylsalts, aromatic polyamides, aromatic polyetheramides Amine, polyphenylene sulfide, polyaryl ether ketone, polyamidoamide, liquid crystal polyester, polyphenylene ether, etc., preferably thermoplastic polyimide, liquid crystal polyester and polyphenylene ether.

而且，所述其他材料亦可舉：觸變性賦予劑、消泡劑、無機填料、反應性烷氧矽烷、脫水劑、塑化劑、耐候劑、抗氧化劑、熱穩定劑、滑劑、抗靜電劑、增白劑、著色劑、導電劑、脫模劑、表面處理劑、黏度調節劑、阻燃劑等。Moreover, the other materials may also include: thixotropy-imparting agents, defoamers, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, slip agents, antistatic Agents, brighteners, colorants, conductive agents, release agents, surface treatment agents, viscosity modifiers, flame retardants, etc.

粉末分散液中之F粉末比率宜為5~60質量%，35~45質量%尤佳。在該範圍內，便容易控制壓低F樹脂層之相對介電常數及介電正切。而且粉末分散液的均勻分散性高，F樹脂層之機械強度優異。 粉末分散液中之分散劑的比率宜為0.1~30質量%，5~10質量份尤佳。在該範圍內，便容易使F粉末的均勻分散性與F樹脂層表面之親水性及電特性平衡。 粉末分散液中之溶劑比率宜為15~65質量%，25~50質量份尤佳。在該範圍內，粉末分散液之塗佈性即佳，且不易產生樹脂層的外觀不良。The ratio of F powder in the powder dispersion is preferably 5 to 60% by mass, preferably 35 to 45% by mass. Within this range, it is easy to control the relative dielectric constant and dielectric tangent of the depressed F resin layer. Moreover, the uniformity of the powder dispersion is high, and the F resin layer has excellent mechanical strength. The ratio of the dispersant in the powder dispersion is preferably 0.1 to 30% by mass, particularly preferably 5 to 10 parts by mass. Within this range, it is easy to balance the uniform dispersion of the F powder with the hydrophilicity and electrical characteristics of the surface of the F resin layer. The solvent ratio in the powder dispersion is preferably 15 to 65% by mass, and 25 to 50 parts by mass is particularly preferred. Within this range, the coating properties of the powder dispersion are good, and the appearance of the resin layer is not likely to be poor.

在本發明之製造方法中，係將粉末分散液塗佈於金屬箔表面。 塗佈方法只要是可於塗佈後之金屬箔表面形成由粉末分散液構成且穩定之濕膜的方法即可，可舉：噴塗法、輥塗法、旋塗法、凹版塗佈法、微凹版塗佈法、凹版平板法、刮刀塗佈法、接觸塗佈法、棒塗法、模塗法、噴泉式繞線棒(fountain meyer bar)法、狹縫式模塗法等。 又，將金屬箔供給於80~300℃之溫度區域之前，亦可在低於前述溫度區域之溫度下加熱金屬箔來調整濕膜狀態。該調整是進行成溶劑不完全揮發之程度，通常係進行至使50質量%以下之溶劑揮發的程度。In the production method of the present invention, the powder dispersion is applied to the surface of the metal foil. The coating method may be any method that can form a stable wet film composed of a powder dispersion on the surface of the metal foil after coating, and examples include spray coating, roll coating, spin coating, gravure coating, and micro coating. Gravure coating method, gravure plate method, blade coating method, contact coating method, bar coating method, die coating method, fountain meyer bar method, slot die coating method, etc. In addition, before the metal foil is supplied to the temperature range of 80 to 300° C., the metal foil may be heated at a temperature lower than the temperature range to adjust the wet film state. This adjustment is performed to the extent that the forming solvent is not completely volatilized, and is usually performed to the extent that 50% by mass or less of the solvent is volatilized.

在本發明之製造方法中，係將粉末分散液塗佈於金屬箔表面後，以80~300℃溫度區域內之質量減少率為1質量%/分鐘以上的溫度(以下亦表記為「保持溫度」)來保持金屬箔。保持溫度表示氣體環境之溫度。 保持可以1階段實施，亦可在不同溫度下實施2階段以上。 保持方法可舉：使用烘箱之方法、使用通風乾燥爐之方法、照射紅外線等熱射線之方法等。 保持之氣體環境可為常壓下、減壓下中之任一狀態。又，前述保持之氣體環境可為氧化性氣體(氧氣等)環境、還原性氣體(氫氣等)環境、非活性氣體(氦氣、氖氣、氬氣、氮氣等)環境中之任一者。 從促進分散劑分解、更能提升F樹脂層之接著性的觀點來看，保持氣體環境宜為含氧氣之氣體環境。此時的氧氣濃度(體積基準)宜為1×102 ~3×105 ppm，0.5×103 ~1×104 ppm尤佳。在該範圍中，可易使促進分散劑之分解及抑制金屬箔氧化平衡。In the manufacturing method of the present invention, after the powder dispersion is applied to the surface of the metal foil, the temperature at a mass reduction rate of 80 to 300°C in the temperature range is 1% by mass/minute or more (hereinafter also referred to as "holding temperature"") to keep the metal foil. The holding temperature indicates the temperature of the gas environment. The holding can be carried out in one stage, or more than two stages at different temperatures. The retention method can be exemplified by the method of using an oven, the method of using a vented drying oven, the method of irradiating infrared rays and other heat rays. The gas environment to be maintained can be in either state under normal pressure or under reduced pressure. In addition, the gas environment to be maintained may be any of an oxidizing gas (oxygen, etc.) environment, a reducing gas (hydrogen, etc.) environment, and an inert gas (helium, neon, argon, nitrogen, etc.) environment. From the viewpoint of promoting the decomposition of the dispersant and improving the adhesion of the F resin layer, it is preferable to maintain the gas environment as an oxygen-containing gas environment. The oxygen concentration (volume basis) at this time is preferably from 1×10 2 to 3×10 5 ppm, preferably from 0.5×10 3 to 1×10 4 ppm. Within this range, the decomposition of the dispersant can be promoted easily and the metal foil can be suppressed from oxidizing balance.

保持溫度係80~300℃溫度區域內之質量減少率為1質量%/分鐘以上的溫度，100~300℃較佳。使用100~200℃溫度區域內之質量減少率為1質量%/分鐘以上的分散劑時，保持溫度為100~200℃較佳，160~200℃尤佳。又，使用200~300℃溫度區域內之質量減少率為1質量%/分鐘以上的分散劑時，保持溫度宜為200~300℃，220~260℃尤佳。 在上述溫度範圍中，可有效進行分散劑的部分分解及流動，使分散劑更容易表面偏析。 保持在保持溫度的時間宜為0.1~10分鐘，0.5~5分鐘尤佳。The holding temperature is a temperature at which the mass reduction rate in the temperature range of 80 to 300°C is 1% by mass/minute or more, preferably 100 to 300°C. When using a dispersant with a mass reduction rate of 1% by mass/minute or more in the temperature range of 100 to 200°C, the holding temperature is preferably 100 to 200°C, and 160 to 200°C is particularly preferable. In addition, when using a dispersant with a mass reduction rate of 1% by mass/minute or more in the temperature range of 200 to 300°C, the holding temperature is preferably 200 to 300°C, and 220 to 260°C is particularly preferable. In the above temperature range, the partial decomposition and flow of the dispersant can be effectively carried out, making the dispersant easier to surface segregation. The time for maintaining the temperature should be 0.1~10 minutes, preferably 0.5~5 minutes.

在本發明之製造方法中，係在超過保持溫度之溫度區域(以下亦表記為「燒成溫度」)下燒成TFE系聚合物而於金屬箔表面形成F樹脂層。燒成溫度表示氣體環境之溫度。在本發明之製造方法中，係將F粉末緊密充填、並在源自分散劑之親水成分有效進行了表面偏析之狀態下進行TFE系聚合物之熔接，因此可形成平滑性與親水性優異的F樹脂層。另，粉末分散液只要包含熱熔融性樹脂，便可形成由TFE系聚合物與溶解性樹脂之混合物構成的F樹脂層，粉末分散液只要包含熱硬化性樹脂，即可形成由TFE系聚合物與熱硬化性樹脂之硬化物構成的F樹脂層。 加熱方法可舉：使用烘箱之方法、使用通風乾燥爐之方法、照射紅外線等熱射線之方法等。為了提高F樹脂層表面之平滑性，亦可以加熱板、加熱輥等加壓。從可短時間燒成、遠紅外線爐相較精簡的觀點來看，加熱方法宜為照射遠紅外線之方法。加熱方法亦可組合紅外線加熱與熱風加熱。 從可促進TFE系聚合物均質熔接的觀點來看，遠紅外線之有效波長帶宜為2~20μm，3~7μm較佳。In the manufacturing method of the present invention, the TFE polymer is fired in a temperature range exceeding the holding temperature (hereinafter also referred to as "firing temperature") to form an F resin layer on the surface of the metal foil. The firing temperature indicates the temperature of the gas environment. In the production method of the present invention, the F powder is closely packed, and the TFE-based polymer is welded in a state in which the hydrophilic component derived from the dispersant is effectively segregated on the surface, so that the smoothness and hydrophilicity can be formed. F resin layer. In addition, as long as the powder dispersion contains a hot-melt resin, an F resin layer composed of a mixture of a TFE polymer and a soluble resin can be formed, and as long as the powder dispersion contains a thermosetting resin, a TFE polymer can be formed. F resin layer composed of hardened thermosetting resin. Examples of heating methods include: the method of using an oven, the method of using a ventilated drying furnace, and the method of irradiating infrared rays and other heat rays. In order to improve the smoothness of the surface of the F resin layer, it may be pressed by a heating plate, heating roller, or the like. From the viewpoint that it can be fired in a short time and the far infrared furnace is relatively compact, the heating method is preferably a method of irradiating far infrared rays. The heating method can also combine infrared heating and hot air heating. From the viewpoint of promoting homogeneous fusion of TFE-based polymers, the effective wavelength band of far infrared rays is preferably 2 to 20 μm, preferably 3 to 7 μm.

燒成氣體環境可為常壓下、減壓下中之任一狀態。又，前述燒成之氣體環境可為氧化性氣體(氧氣等)氣體環境、還原性氣體(氫氣等)氣體環境、非活性氣體(氦氣、氖氣、氬氣、氮氣等)氣體環境中之任一者，若從可分別抑制金屬箔、所形成之F樹脂層的氧化劣化之觀點來看，宜為還原性氣體環境或非活性氣體環境。 燒成氣體環境宜為由非活性氣體構成且氧氣濃度低的氣體環境，並以由氮氣構成且氧氣濃度(體積基準)低於500ppm之氣體環境為佳。氧氣濃度(體積基準)在300ppm以下尤佳。又，氧氣濃度(體積基準)通常為1ppm以上。在該範圍內，可抑制分散劑進一步的氧化分解，容易提升F樹脂層之親水性。The firing gas environment can be in either state under normal pressure or under reduced pressure. In addition, the firing gas environment may be an oxidizing gas (oxygen, etc.) gas environment, a reducing gas (hydrogen, etc.) gas environment, or an inert gas (helium, neon, argon, nitrogen, etc.) gas environment. Either one is preferably a reducing gas environment or an inert gas environment from the viewpoint of suppressing the oxidative degradation of the metal foil and the formed F resin layer, respectively. The firing gas environment is preferably a gas environment composed of an inert gas and a low oxygen concentration, and preferably a gas environment composed of nitrogen and having an oxygen concentration (volume basis) of less than 500 ppm. The oxygen concentration (volume basis) is preferably below 300 ppm. In addition, the oxygen concentration (volume basis) is usually 1 ppm or more. Within this range, further oxidative decomposition of the dispersant can be suppressed, and the hydrophilicity of the F resin layer can be easily improved.

燒成溫度超過300℃，宜超過300℃且400℃以下，330~380℃尤佳。在該情況下，TFE系聚合物更容易形成細緻的F樹脂層。 保持在燒成溫度的時間宜為30秒~5分鐘，1~2分鐘尤佳。 附樹脂之金屬箔中之樹脂層為習知之絕緣材料(聚醯亞胺等熱硬化性樹脂之硬化物)時，必須長時間加熱以使熱硬化性樹脂硬化。另一方面，在本發明中，可藉由TFE系聚合物之熔接以短時間之加熱形成樹脂層。另，粉末分散液包含熱硬化性樹脂時，可降低燒成溫度。如此一來，本發明之製造方法係於附樹脂之金屬箔形成樹脂層時對金屬箔之熱負荷小的方法，即對金屬箔破壞小的方法。The firing temperature exceeds 300℃, preferably exceeds 300℃ and below 400℃, 330~380℃ is particularly preferred. In this case, the TFE-based polymer is more likely to form a fine F resin layer. The time for maintaining the firing temperature is preferably 30 seconds to 5 minutes, preferably 1 to 2 minutes. When the resin layer in the metal foil with resin is a conventional insulating material (hardened material of thermosetting resin such as polyimide), it must be heated for a long time to harden the thermosetting resin. On the other hand, in the present invention, the resin layer can be formed by short-time heating by welding of TFE-based polymer. In addition, when the powder dispersion contains a thermosetting resin, the firing temperature can be lowered. In this way, the manufacturing method of the present invention is a method in which the thermal load on the metal foil is small when the resin layer is formed with the metal foil, that is, the metal foil is less damaged.

對以本發明之製造方法製得之附樹脂之金屬箔，為了控制F樹脂層之線膨脹係數、或進一步改善F樹脂層之接著性，亦可對F樹脂層之表面進行表面處理。表面處理之方法可舉：退火處理、電暈放電處理、大氣壓電漿處理、真空電漿處理、UV臭氧處理、準分子處理、化學蝕刻、矽烷耦合處理、微粗面化處理等。 在退火處理中，宜分別為：溫度為120~180℃、壓力為0.005~0.015MPa、時間為30~120分鐘。 電漿處理之電漿照射裝置可舉：高頻感應方式、電容耦合型電極方式、電暈放電電極-電漿噴射方式、平行板型、遠程電漿型、大氣壓電漿型、ICP型高密度電漿型等。 電漿處理使用之氣體可舉氧氣、氮氣、稀有氣體(氬等)、氫氣、氨氣等，且宜為稀有氣體或氮氣。電漿處理使用之氣體的具體例可舉氬氣；氫氣與氮氣之混合氣體；氫氣、氮氣與氬氣之混合氣體。 電漿處理之氣體環境宜為稀有氣體或氮氣之體積分率為70體積%以上的氣體環境，100體積%之氣體環境尤佳。在該範圍內，將F樹脂層之表面之Ra調整至2.0μm以下，容易於F樹脂層表面形成微細凹凸。For the metal foil with resin produced by the manufacturing method of the present invention, in order to control the linear expansion coefficient of the F resin layer or to further improve the adhesion of the F resin layer, the surface of the F resin layer may also be surface-treated. The surface treatment methods include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, micro-roughening treatment, etc. In the annealing process, the temperature should be 120~180℃, the pressure should be 0.005~0.015MPa, and the time should be 30~120 minutes. Plasma irradiation devices for plasma treatment include: high-frequency induction method, capacitive coupling electrode method, corona discharge electrode-plasma spray method, parallel plate type, remote plasma type, atmospheric piezoelectric plasma type, ICP type high density Plasma type, etc. The gas used for plasma treatment may include oxygen, nitrogen, rare gas (argon, etc.), hydrogen, ammonia, etc., and is preferably a rare gas or nitrogen. Specific examples of the gas used in plasma treatment include argon; mixed gas of hydrogen and nitrogen; mixed gas of hydrogen, nitrogen, and argon. The gas environment for plasma treatment should be a gas environment with a rare gas or nitrogen volume fraction of 70% by volume or more, and a gas environment with 100% by volume is particularly preferred. Within this range, by adjusting the Ra of the surface of the F resin layer to 2.0 μm or less, it is easy to form fine irregularities on the surface of the F resin layer.

以本發明之製造方法製得的附樹脂之金屬箔之F樹脂層表面的親水性高、接著性優異，因此可輕易地與其他基板牢固積層。 其他基板可舉耐熱性樹脂薄膜、屬纖維強化樹脂板之前驅物的預浸體、具有耐熱性樹脂薄膜層之積層體、具有預浸體層之積層體等。 預浸體係使強化纖維(玻璃纖維、碳纖維等)之基材(纖維束、織布等)浸潤熱硬化性樹脂或熱塑性樹脂後的片狀基板。 耐熱性樹脂薄膜係包含1種以上耐熱性樹脂之薄膜，可為單層薄膜亦可為多層薄膜。 耐熱性樹脂可舉聚醯亞胺、聚芳酯、聚碸、聚芳基碸、芳香族聚醯胺、芳香族聚醚醯胺、聚伸苯硫、聚芳基醚酮、聚醯胺醯亞胺、液晶性聚酯等。The surface of the F resin layer of the metal foil with resin produced by the manufacturing method of the present invention has high hydrophilicity and excellent adhesiveness, so it can be easily laminated firmly with other substrates. Other substrates include heat-resistant resin films, prepregs that are precursors to fiber-reinforced resin plates, laminates with heat-resistant resin film layers, and laminates with prepreg layers. The prepreg system impregnates the substrate (fiber bundle, woven fabric, etc.) of the reinforcing fibers (glass fibers, carbon fibers, etc.) with a thermosetting resin or a thermoplastic resin sheet substrate. The heat-resistant resin film is a film containing more than one type of heat-resistant resin, and may be a single-layer film or a multilayer film. Examples of heat-resistant resins include polyimide, polyarylate, polybenzyl, polyarylate, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, and polyamidoamide Imine, liquid crystal polyester, etc.

於附樹脂之金屬箔之F樹脂層表面積層其他基材的方法，可舉將附樹脂之金屬箔與其他基板熱壓之方法。 其他基板為預浸體時的加壓溫度宜為TFE系聚合物之熔點以下，120~300℃較佳，160~220℃尤佳。在該範圍內，可抑制預浸體之熱劣化，同時可將F樹脂層與預浸體牢固接著。 基板為耐熱性樹脂薄膜時的加壓溫度宜為310~400℃。在該範圍內，可抑制耐熱性樹脂薄膜之熱劣化，同時可將F樹脂層與耐熱性樹脂薄膜牢固接著。 熱壓宜在減壓環境下進行，且在20kPa以下之真空度下進行尤佳。在該範圍內，可抑制氣泡混入積層體之F樹脂層、基板、金屬箔之各個界面，從而可抑制因氧化而劣化。 而且，熱壓時宜在到達前述真空度後進行升溫。若在到達前述真空度之前升溫，F樹脂層就會在已軟化之狀態、亦即在具有一定程度流動性、密著性之狀態下被壓接，而形成氣泡。 熱壓之壓力宜為0.2MPa以上。而壓力之上限宜為10MPa以下。在該範圍內，可抑制基板破損，同時可使F樹脂層與基板牢固密著。The method of layering other substrates on the surface area of the F resin layer of the metal foil with resin can be a method of hot pressing the metal foil with resin and other substrates. When the other substrate is a prepreg, the pressing temperature is preferably below the melting point of the TFE polymer, preferably 120 to 300°C, and more preferably 160 to 220°C. Within this range, the thermal deterioration of the prepreg can be suppressed, and at the same time, the F resin layer and the prepreg can be firmly adhered. When the substrate is a heat-resistant resin film, the pressing temperature is preferably 310 to 400°C. Within this range, the thermal degradation of the heat-resistant resin film can be suppressed, and at the same time, the F resin layer and the heat-resistant resin film can be firmly bonded. Hot pressing should be carried out under a reduced pressure environment, and it is particularly preferable to perform under a vacuum of 20 kPa. Within this range, air bubbles can be prevented from being mixed into each interface of the F resin layer of the laminate, the substrate, and the metal foil, and deterioration due to oxidation can be suppressed. Moreover, it is preferable to increase the temperature after reaching the aforementioned vacuum degree during hot pressing. If the temperature is increased before reaching the aforementioned vacuum degree, the F resin layer will be pressure-bonded in a softened state, that is, in a state with a certain degree of fluidity and adhesion, and bubbles will form. The pressure of hot pressing should be more than 0.2MPa. The upper limit of the pressure should be 10 MPa or less. Within this range, the breakage of the substrate can be suppressed, and the F resin layer can be firmly adhered to the substrate.

以本發明之製造方法製得之附樹脂之金屬箔及其積層體，可作為撓性覆銅積層板或剛性覆銅積層板用於製造印刷基板。 譬如，使用下列方法即可從本發明之附樹脂之金屬箔製造印刷基板：利用蝕刻等將本發明之附樹脂之金屬箔的金屬箔加工成預定圖案之導體電路(圖案電路)的方法，或是用電鍍法(半加成法(SAP法)、改良半加成法(MSAP法)等)將本發明之附樹脂之金屬箔加工成圖案電路的方法。 在製造印刷基板時，亦可於形成圖案電路後，於圖案電路上形成層間絕緣膜，並於層間絕緣膜上進一步形成圖案電路。層間絕緣膜譬如亦可藉由本發明之粉末分散液形成。 製造印刷基板時亦可於圖案電路上積層防焊層。防焊層可藉由本發明之粉末分散液形成。 在製造印刷基板時，亦可於圖案電路上積層覆蓋薄膜。覆蓋薄膜亦可藉由本發明之粉末分散液形成。The resin-attached metal foil and its laminate obtained by the manufacturing method of the present invention can be used as a flexible copper-clad laminate or a rigid copper-clad laminate for the production of printed boards. For example, a printed circuit board can be manufactured from the metal foil with resin of the present invention using the following method: a method of processing the metal foil of the metal foil with resin of the present invention into a conductor circuit (pattern circuit) of a predetermined pattern by etching, or It is a method of processing the metal foil with resin of the present invention into a patterned circuit by an electroplating method (semi-additive method (SAP method), modified semi-additive method (MSAP method), etc.). When manufacturing a printed circuit board, after forming a pattern circuit, an interlayer insulating film may be formed on the pattern circuit, and a pattern circuit may be further formed on the interlayer insulating film. The interlayer insulating film can also be formed by the powder dispersion of the present invention, for example. When manufacturing a printed circuit board, a solder resist layer can also be deposited on the pattern circuit. The solder mask layer can be formed by the powder dispersion of the present invention. When manufacturing a printed circuit board, a cover film may be laminated on the pattern circuit. The cover film can also be formed by the powder dispersion of the present invention.

本發明之附樹脂之銅箔係具有金屬箔、包含TFE系聚合物之樹脂層(以下亦表記為「F1樹脂層」)、及與F1樹脂層相接之特定接著部位的附樹脂之金屬箔。本發明之附樹脂之金屬箔(亦包含由本發明之附樹脂之銅箔製得之積層體或印刷基板，以下皆同)可與其他基板低溫接著而無損其尺寸穩定性的原因尚不明確，惟吾等以為如下。 特定接著部位包含親水成分，該親水成分具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種，吾等認為接著性係藉由該親水成分之特性(極性、反應性等)而顯現。接著部位係形成為與F1樹脂層相接，所以吾等亦認為在本發明之附樹脂之金屬箔與其他基材之接著積層物的F1樹脂層與其他基材之邊界，親水成分分別高度相溶而形成有接著層。亦即，吾等認為本發明之附樹脂之金屬箔的接著性主要來自接著部位，具體上來說未必是來自對TFE系聚合物高溫加熱所致的熔接接著。所以，本發明之附樹脂之金屬箔即使以非黏著性且熱伸縮性之TFE系聚合物作為F1樹脂層，就算在較為低溫下依舊可與其他基板接著而無損其尺寸穩定性，而可加工成翹曲少的多層基板(多層印刷基板等)。The resin-coated copper foil of the present invention is a resin-coated metal foil having a metal foil, a resin layer containing a TFE-based polymer (hereinafter also referred to as "F1 resin layer"), and a specific bonding portion in contact with the F1 resin layer . The reason why the metal foil with resin of the present invention (including the laminate or printed circuit board made of the copper foil with resin of the present invention, the same below) can be adhered to other substrates at low temperature without compromising the dimensional stability is not clear. But we thought it was as follows. The specific adhesion site includes a hydrophilic component having at least one selected from the group consisting of etheric oxygen atoms, hydroxyl groups, and carboxyl groups. We believe that adhesion depends on the characteristics of the hydrophilic component (polarity, reaction Sex, etc.). The next part is formed to be in contact with the F1 resin layer, so we also believe that at the boundary between the F1 resin layer of the metal foil with resin of the present invention and the subsequent laminate of the other substrate and the other substrate, the hydrophilic components are highly Dissolve to form an adhesive layer. That is, we believe that the adhesion of the resin-attached metal foil of the present invention mainly comes from the bonding site, and specifically does not necessarily come from the fusion bonding caused by high-temperature heating of the TFE-based polymer. Therefore, even if the metal foil with resin of the present invention uses a non-adhesive and thermally stretchable TFE polymer as the F1 resin layer, even at a relatively low temperature, it can still be bonded to other substrates without compromising its dimensional stability and can be processed It becomes a multilayer substrate (multilayer printed substrate, etc.) with less warpage.

本發明之附樹脂之銅箔依序具有金屬箔、F1樹脂層、與F1樹脂層相接之接著部位。本發明之附樹脂之銅箔的層構成可舉如：金屬箔/F1樹脂層/接著部位、F1樹脂層/金屬箔/F1樹脂層/接著部位、接著部位/F1樹脂層/金屬箔/F1樹脂層/接著部位、金屬箔/F1樹脂層/金屬箔/F1樹脂層/接著部位。「金屬箔/F1樹脂層/接著部位」意指依序積層有金屬箔、F1樹脂層、接著部位，其他之層構成亦同。 本發明之附樹脂之金屬箔的翹曲率宜為25%以下，7%以下尤佳。此時，將附樹脂之金屬箔加工至印刷基板時的處置性及製得之印刷基板的傳輸特性優異。 本發明之附樹脂之金屬箔的尺寸變化率宜為±1%以下，±0.2%以下尤佳。此時，容易將附樹脂之金屬箔加工至印刷基板並進一步使其多層化。The resin-coated copper foil of the present invention has a metal foil, an F1 resin layer, and a bonding part in contact with the F1 resin layer in this order. The layer structure of the resin-coated copper foil of the present invention may include: metal foil/F1 resin layer/adhesion site, F1 resin layer/metal foil/F1 resin layer/adhesion site, adhesive site/F1 resin layer/metal foil/F1 Resin layer/adhesion part, metal foil/F1 resin layer/metal foil/F1 resin layer/adhesion part. "Metal foil/F1 resin layer/adhesion part" means that a metal foil, an F1 resin layer, and an adhesion part are sequentially stacked, and the other layer configurations are also the same. The metal foil with resin of the present invention preferably has a warpage rate of 25% or less, particularly preferably 7% or less. In this case, the metal foil with resin is processed into a printed circuit board and the handling property of the printed circuit board is excellent, and the transmission characteristics of the printed circuit board are excellent. The rate of dimensional change of the metal foil with resin of the present invention is preferably ±1% or less, more preferably ±0.2% or less. In this case, it is easy to process the metal foil with resin onto the printed circuit board and further multilayer it.

本發明之附樹脂之金屬箔的樹脂部分(F1樹脂層及接著部位)之相對介電常數(20MHz)宜為2.0~3.5，2.0~3.0尤佳。在該範圍內，F1樹脂層之電特性(低相對介電常數等)及接著性兩者皆優異，適合將附樹脂之金屬箔用在要求優異傳輸特性的印刷基板等。 本發明之附樹脂之金屬箔的樹脂部分(F1樹脂層及接著部位)之表面Ra宜為2nm~3μm，3nm~1μm較佳，4nm~500nm更佳，5nm~300nm尤佳。在該範圍內，容易使與其他基板之接著性及樹脂部分之表面加工易性平衡。 本發明之附樹脂之金屬箔的金屬箔態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的金屬箔態樣相同。The relative dielectric constant (20 MHz) of the resin part (F1 resin layer and the adhering part) of the metal foil with resin of the present invention is preferably 2.0 to 3.5, preferably 2.0 to 3.0. Within this range, the F1 resin layer is excellent in both electrical characteristics (low relative dielectric constant, etc.) and adhesion, and is suitable for the use of resin-attached metal foils on printed circuit boards that require excellent transmission characteristics. The surface Ra of the resin portion (F1 resin layer and adhesive part) of the metal foil with resin of the present invention is preferably 2 nm to 3 μm, preferably 3 nm to 1 μm, more preferably 4 nm to 500 nm, and particularly preferably 5 nm to 300 nm. Within this range, it is easy to balance the adhesion with other substrates and the ease of surface processing of the resin portion. The metal foil aspect of the resin-attached metal foil of the present invention includes appropriate aspects and is the same as the metal foil aspect in the method of manufacturing the resin-attached metal foil of the present invention.

本發明之F1樹脂層包含TFE系聚合物。 F1樹脂層亦可在無損本發明效果之範圍內視需求包含無機填料、TFE系聚合物以外之樹脂、添加劑等。 F1樹脂層之厚度宜為1~100μm，3~75μm較佳，5~50μm尤佳。F1樹脂層之厚度只要在前述下限值以上，作為印刷基板之傳輸特性便更為優異。F1樹脂層之厚度只要在前述上限值以下，附樹脂之金屬箔便不易翹曲。 在本發明之附樹脂之金屬箔中，F1樹脂層厚度相對於金屬箔厚度之比宜為0.1~5.0，0.2~2.5尤佳。F1樹脂層厚度相對於金屬箔厚度之比只要在前述下限值以上，作為印刷基板之傳輸特性便更為優異。本發明之附樹脂之金屬箔具有接著部位，因此即使當前述比大時(譬如F1樹脂層厚的情況)，依舊可與其他基板低溫接著而無損本發明之附樹脂之金屬箔的尺寸穩定性，抑制多層化後之翹曲。 本發明之附樹脂之金屬箔的TFE系聚合物態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的TFE系聚合物態樣相同。The F1 resin layer of the present invention contains a TFE-based polymer. The F1 resin layer may also include inorganic fillers, resins other than TFE-based polymers, additives, etc., as needed, without impairing the effects of the present invention. The thickness of the F1 resin layer is preferably from 1 to 100 μm, preferably from 3 to 75 μm, particularly preferably from 5 to 50 μm. As long as the thickness of the F1 resin layer is at least the aforementioned lower limit, the transmission characteristics as a printed circuit board are more excellent. As long as the thickness of the F1 resin layer is below the aforementioned upper limit, the metal foil with resin is less likely to warp. In the resin-attached metal foil of the present invention, the ratio of the thickness of the F1 resin layer relative to the thickness of the metal foil is preferably 0.1 to 5.0, and more preferably 0.2 to 2.5. As long as the ratio of the thickness of the F1 resin layer to the thickness of the metal foil is at least the aforementioned lower limit, the transmission characteristics as a printed circuit board are more excellent. The metal foil with resin of the present invention has a bonding portion, so even when the aforementioned ratio is large (such as the case where the F1 resin layer is thick), it can still be bonded to other substrates at low temperature without compromising the dimensional stability of the metal foil with resin of the present invention To suppress warpage after multilayering. The TFE-based polymer aspect of the resin-attached metal foil of the present invention includes appropriate aspects and is the same as the TFE-based polymer aspect in the method of manufacturing the resin-attached metal foil of the present invention.

本發明之附樹脂之金屬箔的接著部位包含親水成分，該親水成分具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種。 接著部位可僅由親水成分構成，亦可由親水成分與親水成分以外之成分(TFE系聚合物等)構成。The adhesion part of the resin-attached metal foil of the present invention contains a hydrophilic component having at least one selected from the group consisting of etheric oxygen atoms, hydroxyl groups, and carboxyl groups. The next site may be composed of only the hydrophilic component, or may be composed of the hydrophilic component and components other than the hydrophilic component (TFE-based polymer, etc.).

親水成分宜為具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種的有機化合物(惟，TFE系聚合物除外，以下皆同)，並且具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種且水接觸角為30°~90°的有機化合物尤佳。另，前述有機化合物宜不具矽原子。 有機化合物宜為具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種的聚合物，以具有醚性氧原子與羥基或羧基之聚合物較佳，具有醚性氧原子與羥基或羧基之氟聚物尤佳。此時，如同前述，在F1樹脂層與接著部位之邊界的TFE系聚合物與親水成分之相溶性會提升，而更容易提升F1樹脂層與接著部位之接著強度。 親水成分宜為源自本發明之附樹脂之金屬箔之製造方法中之分散劑的親水成分。前述親水成分宜為本發明之附樹脂之金屬箔之製造方法中的界面活性劑F，本發明之附樹脂之金屬箔之製造方法中的界面活性劑F1尤佳。The hydrophilic component is preferably an organic compound having at least one kind selected from the group consisting of an etheric oxygen atom, a hydroxyl group, and a carboxyl group (except for TFE-based polymers, which are the same below), and having an organic compound selected from the group consisting of ether Organic compounds having at least one kind of group consisting of a sex oxygen atom, a hydroxyl group and a carboxyl group and having a water contact angle of 30° to 90° are particularly preferred. In addition, the aforementioned organic compound preferably does not have silicon atoms. The organic compound is preferably a polymer having at least one kind selected from the group consisting of an etheric oxygen atom, a hydroxyl group, and a carboxyl group, and a polymer having an etheric oxygen atom and a hydroxyl group or a carboxyl group is preferable, and has an etheric oxygen Fluoropolymers with atoms and hydroxyl or carboxyl groups are particularly preferred. At this time, as described above, the compatibility between the TFE polymer and the hydrophilic component at the boundary between the F1 resin layer and the bonding part is improved, and it is easier to increase the bonding strength between the F1 resin layer and the bonding part. The hydrophilic component is preferably a hydrophilic component derived from a dispersant in the method of manufacturing a resin-attached metal foil of the present invention. The aforementioned hydrophilic component is preferably the surfactant F in the method of manufacturing the resin-attached metal foil of the present invention, and the surfactant F1 in the method of manufacturing the resin-attached metal foil of the present invention is particularly preferred.

本發明之附樹脂之金屬箔的接著部位可以層狀存在，亦可以島狀存在，且以島狀存在為佳。此時，便容易使附樹脂之金屬箔之F1樹脂層的電特性(低相對介電常數、低介電正切等)與來自形成接著部位之親水成分的接著性平衡。亦即，可抑制親水成分存在所得的電特性之降低，而容易顯現接著性。 以層狀存在之接著部位的厚度及以島狀存在之接著部位的高度宜為1~1000nm，5~500nm較佳，5~300nm更佳，5~200nm尤佳。此時，便容易使附樹脂之金屬箔之F1樹脂層的電特性與接著部位之接著性平衡。The bonding part of the resin-attached metal foil of the present invention may exist in a layer shape or an island shape, and the island shape is preferable. At this time, it is easy to balance the electrical characteristics (low relative dielectric constant, low dielectric tangent, etc.) of the F1 resin layer of the metal foil with resin and the adhesion of the hydrophilic component from the formation of the adhesion site. That is, it is possible to suppress the decrease in electrical characteristics due to the presence of the hydrophilic component, and it is easy to develop adhesion. The thickness of the bonding part in the form of a layer and the height of the bonding part in the form of an island are preferably 1 to 1000 nm, preferably 5 to 500 nm, more preferably 5 to 300 nm, and particularly preferably 5 to 200 nm. At this time, it is easy to balance the electrical characteristics of the F1 resin layer of the metal foil with resin and the adhesion of the bonding portion.

本發明之附樹脂之金屬箔之製造方法可舉下述方法：(i)於具有金屬箔及F1樹脂層的附樹脂之金屬箔之F1樹脂層表面塗佈包含親水成分之塗敷液的方法；(ii)於金屬箔表面塗佈包含TFE系聚合物及親水成分之塗敷液的方法。若從F1樹脂層與接著部位之邊界的TFE系聚合物與親水成分相溶而容易提升附樹脂之金屬箔之F1樹脂層與接著部位之接著性的觀點來看，以方法(ii)為佳。 方法(ii)之具體例可舉以下方法：將粉末分散液塗佈於金屬箔表面且該粉末分散液包含含TFE系聚合物之粉末、親水成分與液態介質，以100~300℃溫度區域內之溫度來保持金屬箔，並在超過前述溫度區域之溫度區域下燒成TFE系聚合物，藉此於金屬箔表面形成包含TFE系聚合物之F1樹脂層的同時，於F1樹脂層表面形成包含親水成分之接著部位的方法。 具體而言，本發明之附樹脂之金屬箔宜藉由本發明之附樹脂之金屬箔之製造方法來製造。此時的製造態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法的態樣相同。The manufacturing method of the resin-attached metal foil of the present invention may include the following methods: (i) A method of applying a coating liquid containing a hydrophilic component on the surface of the F1 resin layer of the resin-attached metal foil having a metal foil and an F1 resin layer (Ii) A method of applying a coating solution containing a TFE-based polymer and a hydrophilic component on the surface of a metal foil. From the viewpoint that the TFE-based polymer at the boundary between the F1 resin layer and the bonding part is compatible with the hydrophilic component and easily improves the adhesion between the F1 resin layer of the metal foil with resin and the bonding part, method (ii) is preferred . Specific examples of method (ii) include the following method: applying a powder dispersion to the surface of a metal foil and the powder dispersion contains a powder containing a TFE polymer, a hydrophilic component, and a liquid medium, within a temperature range of 100 to 300°C The temperature of the metal foil is maintained, and the TFE-based polymer is fired in a temperature region exceeding the aforementioned temperature region, thereby forming the F1 resin layer containing the TFE-based polymer on the surface of the metal foil, and forming the inclusion on the surface of the F1 resin layer. The method of attaching the hydrophilic component. Specifically, the metal foil with resin of the present invention is preferably manufactured by the method of manufacturing a metal foil with resin of the present invention. The manufacturing aspect at this time including the appropriate aspect is the same as the aspect of the manufacturing method of the resin-attached metal foil of the present invention.

在本發明之附樹脂之金屬箔中，接著部位以層狀存在時，為了進一步改善接著部位之接著性，亦可將接著部位之表面進行表面處理。接著部位以島狀存在時，為了控制F1樹脂層之線膨脹係數、或進一步改善F1樹脂層或接著部位之接著性，亦可將F1樹脂層及接著部位之表面進行表面處理。 表面處理可舉：退火處理、電暈放電處理、大氣壓電漿處理、真空電漿處理、UV臭氧處理、準分子處理、化學蝕刻、矽烷耦合處理、微粗面化處理等。退火處理及電漿處理各自的態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的態樣相同。In the resin-attached metal foil of the present invention, when the adhesion part exists in a layer, in order to further improve the adhesion of the adhesion part, the surface of the adhesion part may be surface-treated. When the next part exists in an island shape, in order to control the linear expansion coefficient of the F1 resin layer, or to further improve the adhesion of the F1 resin layer or the next part, the surface of the F1 resin layer and the next part may be surface-treated. The surface treatment may include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, micro-roughening treatment, etc. The respective aspects of the annealing treatment and the plasma treatment including appropriate aspects are the same as those in the method of manufacturing a resin-attached metal foil of the present invention.

本發明之附樹脂之金屬箔於F1樹脂層表面存在接著部位且接著性優異，因此可與其他基板牢固地進行低溫接著。亦即，本發明之附樹脂之金屬箔可將本質上為熱伸縮性之TFE系聚合物做成樹脂層，同時可在不受樹脂層厚度與金屬箔之種類或厚度影響的情況下與其他基板低溫接著而無損尺寸穩定性。 宜利用熱壓法使本發明之附樹脂之金屬箔與其他基板接著來製造積層體。 其他基材之態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的態樣相同。 而且熱壓法之態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的態樣相同。The resin-attached metal foil of the present invention has bonding sites on the surface of the F1 resin layer and is excellent in adhesion, so it can be firmly bonded to other substrates at a low temperature. That is, the resin-attached metal foil of the present invention can be made of a TFE polymer that is thermally stretchable in nature as a resin layer, and at the same time, it can be used with other resins without being affected by the thickness of the resin layer and the type or thickness of the metal foil The low temperature of the substrate is followed without compromising dimensional stability. Preferably, the metal foil with resin of the present invention is bonded to other substrates by a hot pressing method to produce a laminate. The aspects of other substrates including the appropriate aspects are the same as those in the method of manufacturing a resin-attached metal foil of the present invention. In addition, the aspects of the hot pressing method including the appropriate aspects are the same as those in the method for manufacturing a resin-attached metal foil of the present invention.

本發明之附樹脂之金屬箔係將電特性、耐藥性(蝕刻耐性)等物性優異之TFE系聚合物作為樹脂層，所以本發明之附樹脂之金屬箔及其積層體可作為撓性覆銅積層板或剛性覆銅積層板用於製造印刷基板。 將本發明之附樹脂之金屬箔用於製造印刷基板時的態樣包含適當態樣皆與將以本發明之製造方法製得之附樹脂之金屬箔用於製造印刷基板時的態樣相同。The resin-attached metal foil of the present invention uses a TFE-based polymer excellent in electrical properties, chemical resistance (etch resistance) and other physical properties as a resin layer, so the resin-attached metal foil and its laminate of the present invention can be used as a flexible coating Copper laminates or rigid copper-clad laminates are used to manufacture printed circuit boards. When the metal foil with resin of the present invention is used for manufacturing a printed circuit board, the appropriate state is the same as the state when the metal foil with resin produced by the manufacturing method of the present invention is used for manufacturing a printed circuit board.

本發明之積層體係將附樹脂之金屬箔與特定預浸體熱壓而成的積層體，該附樹脂之金屬箔具有金屬箔、包含TFE系聚合物之樹脂層(以下亦表記為「F2樹脂層」)、及與F2樹脂層相接之特定相溶層。本發明之積層體(亦包含由本發明之積層體製得之印刷基板，以下皆同)的傳輸特性及機械強度優異、各層牢固接著且翹曲少的原因尚不明確，惟吾等以為如下。 特定相溶層含有具氟原子及氧原子之成分，吾等認為其係藉由具有氟原子之部位的特性(相溶性等)顯現其與F2樹脂層之接著性，並藉由具有氧原子之部位的特性(極性、反應性等)顯現其與預浸體之硬化物層的接著性。而且，相較於F2樹脂層中所含TFE系聚合物顯現熱熔接性的溫度，源自相溶層之接著性可在較低溫度下顯現。所以，即使TFE系聚合物之熔點高，依舊可在較低溫度下將預浸體牢固地接著於附樹脂之金屬箔的樹脂側。 由於可在較低溫度下接著附樹脂之金屬箔與預浸體，因此預浸體之硬化物層的特性(電特性及機械強度)不易降低。而且，預浸體可採用包含耐熱性大致上比TFE系聚合物更低且電特性、機械強度等優異之基質樹脂(不具氟原子之基質樹脂等)的預浸體。又，F2樹脂層包含TFE系聚合物，所以電氣特性佳。又，相溶層就像矽烷耦合劑之被覆層，不易使F2樹脂層之電特性降低。如此一來，由於硬化物層的電特性及機械強度優異、F2樹脂層的電特性優異、且其等之特性不易因熱或相溶層而降低，故以積層體整體來說傳輸特性及機械強度優異。 而且，藉由將非黏著性且熱伸縮性之TFE系聚合物做成F2樹脂層，並在較低溫度下使附樹脂之金屬箔與預浸體接著而無損附樹脂之金屬箔的尺寸穩定性，可製得翹曲少的積層體。The laminate system of the present invention is a laminate obtained by hot-pressing a metal foil with a resin and a specific prepreg. The metal foil with a resin has a metal foil and a resin layer containing a TFE polymer (hereinafter also referred to as "F2 resin" Layer"), and a specific compatible layer in contact with the F2 resin layer. The laminated body of the present invention (including the printed circuit board obtained by the laminated system of the present invention, which is the same hereinafter) is excellent in transmission characteristics and mechanical strength, and the reason why each layer is firmly adhered and less warpage is not clear, but we think it is as follows. The specific compatible layer contains components with fluorine atoms and oxygen atoms, and we believe that it shows its adhesion to the F2 resin layer by the characteristics of the sites with fluorine atoms (compatibility, etc.), and by the The characteristics of the part (polarity, reactivity, etc.) show its adhesion to the hardened layer of the prepreg. Furthermore, the adhesiveness derived from the compatible layer can be expressed at a lower temperature than the temperature at which the TFE-based polymer contained in the F2 resin layer exhibits thermal fusion bonding. Therefore, even if the melting point of the TFE polymer is high, the prepreg can still be firmly attached to the resin side of the metal foil with resin at a relatively low temperature. Since the metal foil and prepreg with resin can be attached at a relatively low temperature, the characteristics (electrical characteristics and mechanical strength) of the hardened layer of the prepreg are not likely to decrease. Moreover, a prepreg containing a matrix resin (matrix resin without fluorine atoms, etc.) having substantially lower heat resistance than a TFE-based polymer and excellent electrical characteristics, mechanical strength, and the like can be used. In addition, since the F2 resin layer contains a TFE-based polymer, it has excellent electrical characteristics. Moreover, the compatible layer is like a coating layer of the silane coupling agent, and it is not easy to reduce the electrical characteristics of the F2 resin layer. In this way, since the electrical characteristics and mechanical strength of the hardened layer are excellent, the electrical characteristics of the F2 resin layer are excellent, and their characteristics are not likely to be reduced by heat or a compatible layer, the transmission characteristics and mechanical properties of the laminate as a whole Excellent strength. Moreover, by making the non-adhesive and heat-stretchable TFE polymer into the F2 resin layer, and at a relatively low temperature, the metal foil with resin and the prepreg are adhered without damaging the size of the metal foil with resin It can produce a laminate with less warpage.

本發明之積層體依序具有金屬箔、F2樹脂層、與F2樹脂層相接之相溶層、及與相溶層相接之硬化物層。本發明之積層體的層構成可舉如：金屬箔/F2樹脂層/相溶層/硬化物層、金屬箔/F2樹脂層/相溶層/硬化物層/相溶層/F2樹脂層/金屬箔。「金屬箔/F2樹脂層/相溶層/硬化物層」係表示依序積層有金屬箔、F2樹脂層、相溶層、硬化物層，其他之層構成亦同。 本發明之積層體的翹曲率宜為5%以下，1%以下尤佳。此時，將積層體加工至印刷基板時的處置性及製得之印刷基板的傳輸特性優異。 本發明之積層體的基板部分(F2樹脂層、相溶層及硬化物層)之相對介電常數(20GHz)宜為5.5以下，4.7以下較佳，4.0以下更佳，3.6以下尤佳。基板部分之介電正切(20GHz)宜為0.02以下，0.009以下較佳，0.005以下更佳，0.003以下尤佳。在該範圍內，基板部分之電特性(低相對介電常數、低介電正切等)及接著性兩者皆優異，適合將積層體用在要求優異傳輸特性的印刷基板等。 本發明之積層體的金屬箔態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的金屬箔態樣相同。The laminate of the present invention has a metal foil, an F2 resin layer, a compatible layer in contact with the F2 resin layer, and a hardened layer in contact with the compatible layer in this order. The layer structure of the laminate of the present invention includes, for example, metal foil/F2 resin layer/compatible layer/hardened layer, metal foil/F2 resin layer/compatible layer/hardened layer/compatible layer/F2 resin layer/ Metal foil. "Metal foil/F2 resin layer/miscible layer/hardened material layer" means that the metal foil, F2 resin layer, compatible layer, and hardened material layer are sequentially stacked, and the other layer structures are also the same. The warpage rate of the laminate of the present invention is preferably 5% or less, particularly preferably 1% or less. In this case, the handleability when processing the laminate to the printed circuit board and the transmission characteristics of the produced printed circuit board are excellent. The relative dielectric constant (20 GHz) of the substrate portion (F2 resin layer, compatible layer and hardened material layer) of the laminate of the present invention is preferably 5.5 or less, preferably 4.7 or less, more preferably 4.0 or less, and particularly preferably 3.6 or less. The dielectric tangent (20 GHz) of the substrate portion is preferably 0.02 or less, preferably 0.009 or less, more preferably 0.005 or less, and particularly preferably 0.003 or less. Within this range, both the electrical characteristics (low relative dielectric constant, low dielectric tangent, etc.) and adhesiveness of the substrate portion are excellent, and the laminate is suitable for a printed circuit board or the like that requires excellent transmission characteristics. The aspect of the metal foil of the laminate of the present invention including the appropriate aspect is the same as the aspect of the metal foil in the method of manufacturing the resin-attached metal foil of the present invention.

本發明之積層體的F2樹脂層包含TFE系聚合物。 F2樹脂層亦可在無損本發明效果之範圍內視需求包含無機填料、TFE系聚合物以外之樹脂、添加劑等。 F2樹脂層之厚度宜為1~100μm，3~75μm較佳，5~50μm尤佳。F2樹脂層之厚度只要在前述下限值以上，作為印刷基板之傳輸特性便更為優異。F2樹脂層之厚度只要在前述上限值以下，積層體便不易翹曲。 在本發明之積層體中，F2樹脂層厚度相對於金屬箔厚度之比宜為0.1~5.0，0.2~2.5尤佳。F2樹脂層厚度相對於金屬箔厚度之比只要在前述下限值以上，作為印刷基板之傳輸特性便更為優異。本發明之積層體具有相溶層，因此即使當前述比大時(譬如F2樹脂層厚的情況)，製造積層體時依舊可將附樹脂之金屬箔與預浸體低溫接著而無損附樹脂之金屬箔的尺寸穩定性，抑制積層體翹曲。 本發明之積層體的TFE系聚合物態樣包含適當態樣皆與本發明之附樹脂之金屬箔之製造方法中的TFE系聚合物態樣相同。The F2 resin layer of the laminate of the present invention contains a TFE-based polymer. The F2 resin layer may also include inorganic fillers, resins other than TFE-based polymers, additives, etc. as needed within the range that does not impair the effects of the present invention. The thickness of the F2 resin layer is preferably 1-100 μm, preferably 3-75 μm, and more preferably 5-50 μm. As long as the thickness of the F2 resin layer is at least the aforementioned lower limit, the transmission characteristics as a printed circuit board are more excellent. As long as the thickness of the F2 resin layer is below the above upper limit, the laminate is less likely to warp. In the laminate of the present invention, the ratio of the thickness of the F2 resin layer to the thickness of the metal foil is preferably 0.1 to 5.0, and more preferably 0.2 to 2.5. As long as the ratio of the thickness of the F2 resin layer to the thickness of the metal foil is at least the aforementioned lower limit, the transmission characteristics as a printed circuit board are more excellent. The laminated body of the present invention has a compatible layer, so even when the aforementioned ratio is large (such as the case where the F2 resin layer is thick), the metal foil with resin and the prepreg can be bonded at a low temperature without damaging the resin. The dimensional stability of the metal foil suppresses the warpage of the laminate. The aspect of the TFE-based polymer of the laminate of the present invention including the appropriate aspect is the same as the aspect of the TFE-based polymer in the method of manufacturing the resin-attached metal foil of the present invention.

本發明之積層體的相溶層含有具氟原子及氧原子之成分。 相溶層可僅由前述成分構成，亦可由前述成分與前述成分以外之成分(TFE系聚合物等)構成。 前述成分之態樣包含適當態樣皆與本發明之附樹脂之金屬箔中的親水成分之態樣相同。尤其在適當態樣中，在F2樹脂層與相溶層之邊界的TFE系聚合物與前述成分之相溶性會提升，而更容易提升F2樹脂層與相溶層之接著強度。而且，在相溶層與預浸體之硬化物層之邊界的前述成分與預浸體之基質樹脂的相溶性或反應性會提升，而更容易提升相溶層與預浸體之硬化物層的接著強度。 相溶層之厚度宜為1~500nm，5~100nm尤佳。此時，便容易使附樹脂之金屬箔之F2樹脂層的電特性與相溶層之接著性平衡。The compatible layer of the laminate of the present invention contains a component having fluorine atoms and oxygen atoms. The compatible layer may be composed only of the aforementioned components, or may be composed of the aforementioned components and components other than the aforementioned components (TFE-based polymer, etc.). The aspect of the foregoing components including the appropriate aspect is the same as the aspect of the hydrophilic component in the metal foil with resin of the present invention. Especially in an appropriate aspect, the compatibility between the TFE polymer and the aforementioned components at the boundary between the F2 resin layer and the compatible layer is improved, and it is easier to increase the adhesive strength between the F2 resin layer and the compatible layer. Moreover, the compatibility or reactivity of the aforementioned components at the boundary between the compatible layer and the hardened layer of the prepreg and the matrix resin of the prepreg is improved, and it is easier to enhance the hardened layer of the compatible layer and the prepreg The strength of the following. The thickness of the compatible layer is preferably 1 to 500 nm, preferably 5 to 100 nm. At this time, it is easy to balance the electrical characteristics of the F2 resin layer of the metal foil with resin and the adhesion of the compatible layer.

本發明之積層體的硬化物層係包含基質樹脂之預浸體的硬化物。基質樹脂宜為不具氟原子之基質樹脂。 預浸體可舉使強化纖維片材中浸潤有基質樹脂的預浸體。 強化纖維片可列舉：多條強化纖維所構成之強化纖維束、將該強化纖維束編織而成之布帛、多條強化纖維已朝一方向併線之單方向性強化纖維束、由該單方向性強化纖維束所構成之單方向性布帛、將該等予以組合而成之片材及將多條強化纖維束堆疊而成之片材等。 強化纖維以長度為10mm以上之連續性長纖維為宜。強化纖維無須在強化纖維片之長度方向整個長度上或寬度方向整個寬度上呈現連續狀態，可在中途截斷。 強化纖維可列舉無機纖維、金屬纖維、有機纖維等。 無機纖維可列舉碳纖維、石墨纖維、玻璃纖維、碳化矽纖維、氮化矽纖維、氧化鋁纖維、碳化矽纖維、硼纖維等。 金屬纖維可列舉鋁纖維、黃銅纖維、不鏽鋼纖維等。 有機纖維可列舉芳香族聚醯胺纖維、聚芳醯胺纖維、聚對伸苯基苯并

Figure 108118229-A0304-12-01
唑(PBO)纖維、聚伸苯硫纖維、聚酯纖維、丙烯酸纖維、尼龍纖維、聚乙烯纖維等。 強化纖維可施有表面處理。 強化纖維可單獨使用1種亦可將2種以上併用。 在印刷基板用途上，強化纖維宜為玻璃纖維。The cured product layer of the laminate of the present invention is a cured product of a prepreg containing a matrix resin. The matrix resin is preferably a matrix resin having no fluorine atoms. The prepreg includes a prepreg in which the matrix resin is impregnated in the reinforcing fiber sheet. Examples of the reinforcing fiber sheet include: a reinforcing fiber bundle composed of a plurality of reinforcing fibers, a fabric woven from the reinforcing fiber bundle, a unidirectional reinforcing fiber bundle in which a plurality of reinforcing fibers are aligned in one direction, and the unidirectional Unidirectional fabric composed of reinforced fiber bundles, a sheet composed of a combination of these, and a sheet formed by stacking a plurality of reinforced fiber bundles, etc. Reinforcing fibers are preferably continuous long fibers with a length of 10 mm or more. Reinforced fibers need not be in a continuous state over the entire length of the reinforced fiber sheet in the length direction or the entire width in the width direction, and can be cut off halfway. Examples of the reinforcing fibers include inorganic fibers, metal fibers, and organic fibers. Examples of the inorganic fiber include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, and boron fiber. Examples of metal fibers include aluminum fibers, brass fibers, and stainless steel fibers. Examples of organic fibers include aromatic polyamide fibers, polyarylamide fibers, and poly-p-phenylenebenzo
Figure 108118229-A0304-12-01
Pazole fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, polyethylene fiber, etc. Reinforcing fibers can be surface treated. One type of reinforcing fiber may be used alone, or two or more types may be used in combination. For printed circuit board applications, the reinforcing fiber is preferably glass fiber.

基質樹脂可為熱塑性樹脂，亦可為熱硬化性樹脂，而宜為熱硬化性樹脂。 熱硬化性樹脂可舉與在本發明之附樹脂之金屬箔之製造方法之說明中所列舉之熱硬化性樹脂相同的樹脂。 熱塑性樹脂可舉與在本發明之附樹脂之金屬箔之製造方法之說明中所列舉之熱塑性樹脂相同的樹脂。 基質樹脂可單獨使用1種亦可將2種以上併用。 從加工性的觀點來看，預浸體之基質樹脂宜為選自於由環氧樹脂、聚氧化苯、聚苯醚及聚丁二烯所構成群組中之至少1種基質樹脂。 預浸體之厚度宜為10μm以上且5mm，30μm以上且3mm以下較佳，80μm以上且1mm以下尤佳。惟，預浸體之厚度可依照印刷基板之用途適宜設定。The matrix resin may be a thermoplastic resin or a thermosetting resin, and is preferably a thermosetting resin. The thermosetting resin may be the same as the thermosetting resin listed in the description of the method for manufacturing a resin-attached metal foil of the present invention. The thermoplastic resin may be the same as the thermoplastic resin listed in the description of the method for producing a resin-attached metal foil of the present invention. The matrix resin may be used alone or in combination of two or more. From the viewpoint of processability, the matrix resin of the prepreg is preferably at least one matrix resin selected from the group consisting of epoxy resin, polyoxybenzene, polyphenylene oxide, and polybutadiene. The thickness of the prepreg is preferably 10 μm or more and 5 mm, preferably 30 μm or more and 3 mm or less, and more preferably 80 μm or more and 1 mm or less. However, the thickness of the prepreg can be appropriately set according to the purpose of the printed substrate.

預浸體可舉以下商品名之預浸體。 Panasonic公司製MEGTRON GX系列R-G520、R-1410W、R-1410A、R-1410E；MEGTRON系列R-1410W、R-1410A、R-1410E；MEGTRON系列R-5680、R-5680(J)、R-5680(NJ)、R-5670、R-5670(N)、R-5620S、R-5620、R-5630、R-1570；HIPER系列R-1650V、R-1650D、R-1650M、R-1650E、R-5610、CR-5680、CR-5680(N)、CR-5680(J)。 日立化成工業公司製GEA-770G、GEA-705G、GEA-700G、GEA-679FG、GEA-679F(R)、GEA-78G、TD-002、GEA-75G、GEA-67、GEA-67G。 Sumitomo Bakelite Co., Ltd.製EI-6765、panasonic公司製R-5785。 MITSUBISHI GAS CHEMICAL公司製GEPL-190T、GEPL-230T、GHPL-830X TypeA、GHPL-830NS、GHPL-830NSR、GHPL-830NSF。 DOOSAN CORPORATION公司製GEPL-190T、GEPL-230T、GHPL-830X TypeA、GHPL-830NS、GHPL-830NSR、GHPL-830NSF。The prepreg can be exemplified by the following trade names. MEGTRON GX series R-G520, R-1410W, R-1410A, R-1410E made by Panasonic; MEGTRON series R-1410W, R-1410A, R-1410E; MEGTRON series R-5680, R-5680(J), R -5680(NJ), R-5670, R-5670(N), R-5620S, R-5620, R-5630, R-1570; HIPER series R-1650V, R-1650D, R-1650M, R-1650E , R-5610, CR-5680, CR-5680(N), CR-5680(J). Hitachi Chemical Co., Ltd. makes GEA-770G, GEA-705G, GEA-700G, GEA-679FG, GEA-679F(R), GEA-78G, TD-002, GEA-75G, GEA-67, GEA-67G. Sumitomo Bakelite Co., Ltd. makes EI-6765, and Panasonic makes R-5785. GEPL-190T, GEPL-230T, GHPL-830X TypeA, GHPL-830NS, GHPL-830NSR, GHPL-830NSF manufactured by MITSUBISHI GAS CHEMICAL. GEPL-190T, GEPL-230T, GHPL-830X TypeA, GHPL-830NS, GHPL-830NSR, GHPL-830NSF manufactured by DOOSAN CORPORATION.

廣東生益科技股份有限公司製SP120N、S1151G、S1151GB、S1170G、S1170GB、S1150G、S1150GB、S1140F、S1140FB、S7045G、SP175M、S1190、S1190B、S1170、S0701、S1141KF、S0401KF、S1000-2M、S1000-2MB、S1000-2、S1000-2B、S1000、S1000B、S1000H、S1000HB、S7136H、S7439、S7439B。 SHANGHAI NANYA公司製NY1135、NY1140、NY1150、NY1170、NY2150、NY2170、NY9135、NY9140、NY9600、NY9250、NY9140HF、NY6200、NY6150、NY3170LK、NY6300、NY3170M、NY6200、NY3150HF CTI600、NY3170HF、NY3150D、NY3150HF、NY2170H、NY2170、NY2150、NY2140、NY1600、NY1140、NY9815HF、NY9810HF、NY9815、NY9810。 聯茂電子股份有限公司製IT-180GN、IT-180I、IT-180A、IT-189、IT-180、IT-258GA3、IT-158、IT-150GN、IT-140、IT-150GS、IT-150G、IT-168G1、IT-168G2、IT-170G、IT-170GRA1、IT-958G、IT-200LK、IT-200D、IT-150DA、IT-170GLE、IT-968G、IT-968G SE、IT-968、IT-968 SE。SP120N, S1151G, S1151GB, S1170G, S1170GB, S1150G, S1150GB, S1140F, S1140FB, S7045G, SP175M, S1190, S1190B, S1170, S0701, S1141KF, S0401KF, S1000-2M, S1000-2MB S1000-2, S1000-2B, S1000, S1000B, S1000H, S1000HB, S7136H, S7439, S7439B. SHANGHAI NANYA company made NY1135, NY1140, NY1150, NY1170, NY2150, NY2170, NY9135, NY9140, NY9600, NY9250, NY9140HF, NY6200, NY6150, NY3170LK, NY6300, NY3170M, NY6200, NY3150HF CTI600, NY3170HF, NY3170D, NY3170D , NY2150, NY2140, NY1600, NY1140, NY9815HF, NY9810HF, NY9815, NY9810. IT-180GN, IT-180I, IT-180A, IT-189, IT-180, IT-258GA3, IT-158, IT-150GN, IT-140, IT-150GS, IT-150G , IT-168G1, IT-168G2, IT-170G, IT-170GRA1, IT-958G, IT-200LK, IT-200D, IT-150DA, IT-170GLE, IT-968G, IT-968G SE, IT-968, IT-968 SE.

南亞塑膠工業股份有限公司製UV BLOCK FR-4-86、NP-140 TL/B、NP-140M TL/B、NP-150 R/TL/B、NP-170 R/TL/B、NP-180 R/TL/B、NPG R/TL/B、NPG-151、NPG-150N、NPG-150LKHD、NPG-170N、NPG-170 R/TL/B、NPG-171、NPG-170D R/TL/B、NPG-180ID/B、NPG-180IF/B、NPG-180IN/B、NPG-180INBK/B(BP)、NPG-186、NPG-200R/TL、NPG-200WT、FR-4-86 PY、FR-140TL PY、NPG-PY R/TL、CEM-3-92、CEM-3-92PY、CEM-3-98、CEM-3-01PY、CEM-3-01HC、CEM-3-09、CEM-3-09HT、CEM-3-10、NP-LDII、NP-LDIII、NP-175R/TL/B、NP-155F R/TL/B、NP-175F R/TL/B、NP-175F BH、NP-175FM BH。 台燿科技股份有限公司製ULVP系列、LDP系列。 ISOLA GROUP公司製A11、R406N、P25N、TerraGreen、I-Tera MT40、IS680 AG、IS680、Astra MT77、G200、DE104、FR408、ED130UV、FR406、IS410、FR402、FR406N、IS420、IS620i、370TURBO、254、I-Speed、FR-408HR、IS415、370HR。UV BLOCK FR-4-86, NP-140 TL/B, NP-140M TL/B, NP-150 R/TL/B, NP-170 manufactured by Nanya Plastic Industry Co., Ltd. R/TL/B, NP-180 R/TL/B, NPG R/TL/B, NPG-151, NPG-150N, NPG-150LKHD, NPG-170N, NPG-170 R/TL/B, NPG-171 , NPG-170D R/TL/B, NPG-180ID/B, NPG-180IF/B, NPG-180IN/B, NPG-180INBK/B (BP), NPG-186, NPG-200R/TL, NPG-200WT , FR-4-86 PY, FR-140TL PY, NPG-PY R/TL, CEM-3-92, CEM-3-92PY, CEM-3-98, CEM-3-01PY, CEM-3-01HC, CEM-3-09, CEM-3-09HT, CEM-3-10, NP-LDII, NP-LDIII, NP-175R/TL/B, NP-155F R/TL/B, NP-175F R/TL/ B, NP-175F BH, NP-175FM BH. ULVP series and LDP series manufactured by Taiyao Technology Co., Ltd. A11, R406N, P25N, TerraGreen, I-Tera MT40, IS680 AG, IS680, Astra MT77, G200, DE104, FR408, ED130UV, FR406, IS410, FR402, FR406N, IS420, IS620i, 370TURBO, 254, I -Speed, FR-408HR, IS415, 370HR.

PARK ELECTROCHEMICAL公司製NY9000、NX9000、NL9000、NH9000、N9000-13 RF、N8000Q、N8000、N7000-1、N7000-2 HT Slash-3、N7000-3、N5000、N5000-30、N-5000-32、N4000-12、N4000-12SI、N4000-13、N4000-13SI、N4000-13SI、N4000-13EP、N4000-13EP SI、N4350-13RF、N4380-13RF、N4800-20、N4800-20SI、Meteorwave1000、Meteorwave2000、Meteorwave3000、Meteorwave4000、Mercurywave9350、N4000-6、N4000-6FC、N4000-7、N4000-7SI、N4000-11、N4000-29。NY9000, NX9000, NL9000, NH9000, N9000-13 RF, N8000Q, N8000, N7000-1, N7000-2 HT Slash-3, N7000-3, N5000, N5000-30, N-5000-32, N4000 manufactured by PARK ELECTROCHEMICAL -12, N4000-12SI, N4000-13, N4000-13SI, N4000-13SI, N4000-13EP, N4000-13EP SI, N4350-13RF, N4380-13RF, N4800-20, N4800-20SI, Meteorwave1000, Meteorwave2000, Meteorwave3000, Meteorwave4000, Mercurywave9350, N4000-6, N4000-6FC, N4000-7, N4000-7SI, N4000-11, N4000-29.

ROGERS CORPORATION公司製RO4450B、RO4450F、CLTE-P、3001 Bonding Film、2929 Bondply、CuClad 6700 Bonding Film、ULTRALAM 3908 Bondply、CuClad 6250 Bonding Film。 利昌工業公司製ES-3329、ES-3317B、ES-3346、ES-3308S、ES-3310A、ES-3306S、ES-3350、ES-3352、ES-3660、ES-3351S、ES-3551S、ES-3382S、ES-3940、ES-3960V、ES-3960C、ES-3753、ES-3305、ES-3615、ES-3306S、ES-3506S、ES-3308S、ES-3317B、ES-3615。RO4450B, RO4450F, CLTE-P, 3001 Bonding Film, 2929 Bondply, CuClad 6700 Bonding Film, ULTRALAM 3908 Bondply, CuClad 6250 Bonding Film manufactured by ROGERS CORPORATION. ES-3329, ES-3317B, ES-3346, ES-3308S, ES-3310A, ES-3306S, ES-3350, ES-3352, ES-3660, ES-3351S, ES-3551S, ES- 3382S, ES-3940, ES-3960V, ES-3960C, ES-3753, ES-3305, ES-3615, ES-3306S, ES-3506S, ES-3308S, ES-3317B, ES-3615.

本發明之積層體可藉由熱壓法使具有金屬箔、F2樹脂層及相溶層的附樹脂之金屬箔與預浸體接著來製造。具體上，本發明之附樹脂之金屬箔宜藉由熱壓法使本發明之附樹脂之金屬箔與預浸體接著來製造。 本發明之積層體中的附樹脂之銅箔之相溶層可以層狀存在，亦可以島狀存在。附樹脂之金屬箔中，相溶層以層狀存在時，因相溶層之表面接著性佳，故可與預浸體牢固地低溫接著。而附樹脂之金屬箔中，相溶層以島狀存在時，因F2樹脂層及相溶層之表面接著性佳，故可與預浸體牢固地低溫接著。亦即，本發明之附樹脂之金屬箔可將本質上為熱伸縮性之TFE系聚合物做成樹脂層，同時可在不受樹脂層厚度與金屬箔之種類或厚度影響的情況下與預浸體低溫接著而無損尺寸穩定性。 製造該附樹脂之金屬箔的方法可舉：(i)於具有金屬箔及F2樹脂層之附樹脂之金屬箔的F2樹脂層表面塗佈包含形成相溶層之成分(如前述，80~300℃內之重量減少率為1質量%/分鐘以上的分散劑等)的塗敷液之方法；(ii)於金屬箔表面塗佈包含TFE系聚合物及前述成分之塗敷液的方法。若從F2樹脂層與相溶層之邊界的TFE系聚合物與前述成分相溶而容易提升附樹脂之金屬箔之F2樹脂層與相溶層之接著性的觀點來看，以方法(ii)為佳。 方法(ii)之具體例可舉以下方法：將粉末分散液塗佈於金屬箔表面且該粉末分散液包含TFE系聚合物之粉末、前述分散劑(前述之於側鏈具有多氟烷基或多氟烯基及聚氧伸烷基或醇性羥基的聚合物等)及液態介質，以80~300℃溫度區域來保持金屬箔，並在超過前述溫度區域之溫度區域下燒成TFE系聚合物，藉此於金屬箔表面形成包含TFE系聚合物之F2樹脂層的同時，於F2樹脂層表面形成相溶層的方法。The laminate of the present invention can be manufactured by hot pressing a metal foil with a metal foil, an F2 resin layer, and a compatible layer and a prepreg. Specifically, the metal foil with resin of the present invention is preferably produced by bonding the metal foil with resin of the present invention and a prepreg by a hot pressing method. The compatible layer of the resin-coated copper foil in the laminate of the present invention may exist in layers or islands. In the metal foil with resin, when the compatible layer exists in the form of a layer, the surface compatibility of the compatible layer is good, so it can be firmly adhered to the prepreg at a low temperature. On the other hand, in the metal foil with resin, when the compatible layer exists in an island shape, the F2 resin layer and the compatible layer have good surface adhesion, so they can be firmly adhered to the prepreg at a low temperature. That is, the metal foil with resin of the present invention can be made into a resin layer by a TFE-based polymer that is essentially thermally stretchable, and at the same time, it can be used without being affected by the thickness of the resin layer and the type or thickness of the metal foil. The low temperature of the immersion body is followed without compromising dimensional stability. The method of manufacturing the resin-attached metal foil may include: (i) coating the surface of the F2 resin layer with the metal foil and the resin-attached metal foil of the F2 resin layer, including a component forming a compatible layer (as described above, 80 to 300) A method of applying a coating solution containing a dispersant such as a dispersant having a weight reduction rate of 1% by mass/minute or more at ℃; (ii) A method of applying a coating solution containing a TFE-based polymer and the aforementioned components on the surface of a metal foil. From the viewpoint that the TFE polymer at the boundary between the F2 resin layer and the compatible layer is compatible with the aforementioned components to easily improve the adhesion between the F2 resin layer and the compatible layer of the metal foil with resin, method (ii) Better. Specific examples of the method (ii) include the following method: applying a powder dispersion to the surface of a metal foil and the powder dispersion contains a powder of a TFE-based polymer, and the aforementioned dispersant (the aforementioned has a polyfluoroalkyl group on the side chain or Polyfluoroalkenyl and polyoxyalkylene or alcoholic hydroxyl polymer, etc.) and liquid medium, the metal foil is held at a temperature range of 80 to 300 ℃, and the TFE-based polymerization is fired in a temperature range exceeding the aforementioned temperature range This is a method of forming a compatible layer on the surface of the F2 resin layer while forming an F2 resin layer containing a TFE-based polymer on the surface of the metal foil.

製造本發明之積層體時，於附樹脂之金屬箔的相溶層表面或F2樹脂層及相溶層的表面積層預浸體的方法，可舉將附樹脂之金屬箔與預浸體熱壓之方法。 加壓溫度宜為TFE系聚合物之熔點以下，120~300℃較佳，160~220℃尤佳。在該範圍內，可抑制預浸體之熱劣化，同時可將相溶層與預浸體牢固接著。 熱壓宜在減壓環境下進行，且在20kPa以下之真空度下進行尤佳。在該範圍內，可抑制氣泡混入積層體中金屬箔、F2樹脂層、相溶層、硬化物層的各個界面，從而可抑制因氧化而劣化。 而且，熱壓時宜在到達前述真空度後進行升溫。若在到達前述真空度之前升溫，F2樹脂層就會在已軟化之狀態、亦即在具有一定程度流動性、密著性之狀態下被壓接，而形成氣泡。 熱壓之壓力宜為0.2~10MPa。在該範圍內，可抑制預浸體破損，同時可將相溶層與預浸體牢固接著。When manufacturing the laminate of the present invention, the method of layering a prepreg on the surface of the compatible layer of the resin-attached metal foil or the surface area of the F2 resin layer and the compatible layer includes hot pressing of the resin-attached metal foil and the prepreg Method. The pressing temperature is preferably below the melting point of the TFE-based polymer, preferably 120-300°C, especially 160-220°C. Within this range, the thermal degradation of the prepreg can be suppressed, and at the same time, the compatible layer and the prepreg can be firmly adhered. Hot pressing should be carried out under a reduced pressure environment, and it is particularly preferable to perform under a vacuum of 20 kPa. Within this range, bubbles can be prevented from being mixed into each interface of the metal foil, the F2 resin layer, the compatible layer, and the hardened material layer in the laminate, thereby suppressing deterioration due to oxidation. Moreover, it is preferable to increase the temperature after reaching the aforementioned vacuum degree during hot pressing. If the temperature is increased before reaching the aforementioned vacuum degree, the F2 resin layer will be pressure-bonded in a softened state, that is, in a state with a certain degree of fluidity and adhesion, and bubbles will form. The pressure of hot pressing should be 0.2~10MPa. Within this range, damage to the prepreg can be suppressed, and at the same time, the compatible layer and the prepreg can be firmly adhered.

本發明之積層體係將電特性、耐藥性(蝕刻耐性)等物性優異之TFE系聚合物作為樹脂層，所以本發明之積層體可作為撓性覆銅積層板或剛性覆銅積層板用於製造印刷基板。 譬如，藉由下列方法即可從本發明之積層體製造印刷基板：將本發明之積層體的金屬箔進行蝕刻處理而加工成預定圖案之導體電路(傳輸電路)的方法，或是用電鍍法(半加成法(SAP法)、改良半加成法(MSAP法)等)將本發明之積層體的金屬箔加工成傳輸電路的方法。 從本發明之積層體製得的印刷基板依序具有傳輸電路、F2樹脂層、硬化物層，且在F2樹脂層與硬化物層之間更具有與F2樹脂層及硬化物層相接之相溶層。本發明之印刷基板的層構成可舉如：傳輸電路/F2樹脂層/相溶層/硬化物層、傳輸電路/F2樹脂層/相溶層/硬化物層/相溶層/F2樹脂層/傳輸電路。 在製造印刷基板時，亦可於形成傳輸電路後，於傳輸電路上形成層間絕緣膜，並於層間絕緣膜上進一步形成傳輸電路。層間絕緣膜譬如亦可藉由本發明之粉末分散液形成。 製造印刷基板時，亦可於傳輸電路上積層防焊層。防焊層可藉由本發明之粉末分散液形成。 製造印刷基板時，亦可於傳輸電路上積層覆蓋薄膜。覆蓋薄膜亦可藉由本發明之粉末分散液形成。 實施例The laminate system of the present invention uses a TFE-based polymer excellent in electrical properties, chemical resistance (etching resistance) and other physical properties as a resin layer, so the laminate of the present invention can be used as a flexible copper-clad laminate or a rigid copper-clad laminate Manufacturing printed circuit boards. For example, the printed circuit board can be manufactured from the layered body of the present invention by the following method: a method of etching the metal foil of the layered body of the present invention into a conductor circuit (transmission circuit) of a predetermined pattern, or using a plating method (Semi-additive method (SAP method), modified semi-additive method (MSAP method), etc.) A method of processing the metal foil of the laminate of the present invention into a transmission circuit. The printed circuit board obtained from the laminated system of the present invention has a transmission circuit, an F2 resin layer, and a cured product layer in this order, and further has a compatibility with the F2 resin layer and the cured product layer between the F2 resin layer and the cured product layer Floor. The layer structure of the printed circuit board of the present invention includes, for example, a transmission circuit/F2 resin layer/compatible layer/hardened layer, a transmission circuit/F2 resin layer/compatible layer/hardened layer/compatible layer/F2 resin layer/ Transmission circuit. When manufacturing a printed circuit board, after the transmission circuit is formed, an interlayer insulating film may be formed on the transmission circuit, and a transmission circuit may be further formed on the interlayer insulating film. The interlayer insulating film can also be formed by the powder dispersion of the present invention, for example. When manufacturing a printed circuit board, a solder resist layer can also be deposited on the transmission circuit. The solder mask layer can be formed by the powder dispersion of the present invention. When manufacturing a printed circuit board, a cover film can also be laminated on the transmission circuit. The cover film can also be formed by the powder dispersion of the present invention. Examples

以下，以實施例詳細說明本發明，惟本發明不受該等限定。 各種測定方法顯示如下。 ＜聚合物之熔融黏度＞ 根據ASTM D 1238，使用流動測試機及2Φ-8L的模具，將已預先在測定溫度下加熱5分鐘後的聚合物試料(2g)，在0.7MPa之荷重下保持於測定溫度下進行測定。 ＜聚合物之熔點＞ 使用示差掃描熱量計(Seiko Instruments Inc.製，DSC-7020)，在10℃/分鐘之速度下使TFE系聚合物升溫並進行測定。 ＜粉末之D50及D90＞ 使用雷射繞射・散射式粒度分布測定裝置(堀場製作所公司製，LA-920測定器)，使粉末分散於水中後進行測定。Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these. Various measurement methods are shown below. <The melt viscosity of the polymer> According to ASTM D 1238, using a flow tester and a 2Φ-8L mold, the polymer sample (2 g) that had been previously heated at the measurement temperature for 5 minutes was held at the measurement temperature under a load of 0.7 MPa for measurement. <Melting point of polymer> Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC-7020), the temperature of the TFE-based polymer was increased at a rate of 10° C./min to measure. <D50 and D90 of powder> A laser diffraction/scattering particle size distribution measuring device (Horiba Manufacturing Co., Ltd., LA-920 measuring instrument) was used to disperse the powder in water and then measure.

＜樹脂層之平滑性＞ 從斜上方目測經光照射後之樹脂層，並按下述基準做評估。 A：未確認到圖樣。 B：未確認到條紋圖樣，但確認到橘皮圖樣。 C：確認到條紋圖樣。 ＜樹脂層之水接觸角＞ 在25℃下使用接觸角計(協和界面科學公司製CA-X型號)測定於附樹脂之金屬箔的樹脂層表面上放置純水(約2μL)時，水滴與樹脂層表面所夾角度，並按下述基準做評估。 A：水接觸角為70°以上且90°以下。 B：水接觸角超過90°且在100°以下。 C：水接觸角超過100°。 ＜樹脂層之翹曲率＞ 從積層體裁切出180mm四方的四角試驗片。針對該試驗片，依照JIS C 6471：1995中規定之測定方法測定翹曲率。<Smoothness of resin layer> The resin layer after light irradiation was visually observed from diagonally above and evaluated according to the following criteria. A: The pattern is not confirmed. B: Stripe pattern was not confirmed, but orange peel pattern was confirmed. C: A striped pattern was confirmed. <Water contact angle of resin layer> The angle between the water droplets and the surface of the resin layer was measured using a contact angle meter (CA-X model manufactured by Kyowa Interface Science Co., Ltd.) at 25°C when pure water (about 2 μL) was placed on the surface of the resin layer of the metal foil with resin. The evaluation is based on the following criteria. A: The water contact angle is 70° or more and 90° or less. B: The water contact angle exceeds 90° and is below 100°. C: The water contact angle exceeds 100°. <Warpage of resin layer> Triangular test pieces of 180 mm square are cut out from the laminate. For this test piece, the warpage rate was measured in accordance with the measurement method specified in JIS C 6471:1995.

＜樹脂層表面之Ra及Rz＞ 使用Oxford Instruments公司製AFM，在下述測定條件下測定樹脂層表面1μm2 範圍的Ra及Rz。 探針：AC160TS-C3(前端R＜7nm、彈簧常數26N/m)、測定模式：AC-Air、掃描速率：1Hz。 ＜積層體之剝離強度＞ 從積層體裁切出長度100mm、寬度10mm的矩形試驗片。將附樹脂之銅箔與預浸體之硬化物剝離至距離試驗片之長度方向一端50mm之位置為止。接著，以與試驗片之長度方向之一端距離50mm的位置為中央，使用拉伸試驗機(Orientec Co.,LTD製)，在拉伸速度50mm/分鐘下進行90度剝離並以最大負載作為剝離強度(N/cm)。 ＜相對介電常數及介電正切＞ 針對印刷基板之基板部分(樹脂層、相溶層及硬化物層)，利用SPDR(分離後電介質共振器)法在23℃±2℃、50±5%RH範圍內的環境下，以頻率20GHz測定相對介電常數(20GHz)及介電正切(20GHz)。<Ra and Rz on the surface of the resin layer> Using AFM manufactured by Oxford Instruments, Ra and Rz in the range of 1 μm 2 on the surface of the resin layer were measured under the following measurement conditions. Probe: AC160TS-C3 (front end R<7nm, spring constant 26N/m), measurement mode: AC-Air, scan rate: 1Hz. <Peel strength of laminate> A rectangular test piece having a length of 100 mm and a width of 10 mm was cut from the laminate. The copper foil with resin and the cured product of the prepreg were peeled to a position 50 mm away from the longitudinal end of the test piece. Next, using a tensile tester (manufactured by Orientec Co., Ltd.) at a position at a distance of 50 mm from one end in the longitudinal direction of the test piece as the center, 90-degree peeling was performed at a tensile speed of 50 mm/min and the maximum load was used as peeling Strength (N/cm). <Relative permittivity and dielectric tangent> For the substrate part (resin layer, compatible layer and hardened layer) of the printed circuit board, the SPDR (dielectric resonator after separation) method is used at 23°C±2°C and 50±5% In an environment within the RH range, the relative dielectric constant (20 GHz) and dielectric tangent (20 GHz) were measured at a frequency of 20 GHz.

使用材料顯示於下。 [粉末] 粉末1：由包含依序為97.9莫耳%、0.1莫耳%、2.0莫耳%之TFE單元、NAH單元及PPVE單元且具有酸酐基的共聚物(熔點：300℃)所構成之粉末(D50：1.7μm，D90：3.8μm)。 聚合物2：由包含99.5莫耳%以上TFE單元而實質上為TFE之均聚物(380℃下之熔融黏度：1.4×104 )所構成的粉末(D50：0.3μm，D90：0.6μm)。 [分散劑] 分散劑1：具有全氟烯基之(甲基)丙烯酸酯與具有聚氧伸乙基之(甲基)丙烯酸酯的共聚物(非離子性界面活性劑，100~200℃內之質量減少率低於1質量%/分鐘，200~300℃內之質量減少率為6質量%/分鐘)。 分散劑2：具有全氟烷基之甲基丙烯酸酯與甲基丙烯酸羥丁酯的共聚物(非離子性界面活性劑，100~200℃及200~300℃內之質量減少率分別低於1質量%/分鐘)。 分散劑3：CH2 ＝CHC(O)O(CH2 )4 OCF(CF3 )C(CF(CF3 )2 )(＝C(CF3 )2 )與CH2 ＝CHC(O)O(CH2 CH2 O)10 H之共聚物(100~200℃內之質量減少率為低於1質量%/分鐘，200~300℃內之質量減少率為6質量%/分鐘)。 [金屬箔] 銅箔1：超低粗度電解銅箔(福田金屬箔粉工業公司製，CF-T4X-SV，厚度：18μm)。 [預浸體] 預浸體1：FR-4(日立化成公司製，GEA-67N 0.2t(HAN)，強化纖維：玻璃纖維，基質樹脂：環氧樹脂，厚度：0.2mm)。The materials used are shown below. [Powder] Powder 1: It is composed of a copolymer (melting point: 300° C.) containing TFE units, NAH units, and PPVE units of 97.9 mol%, 0.1 mol%, and 2.0 mol% in this order. Powder (D50: 1.7 μm, D90: 3.8 μm). Polymer 2: A powder composed of a homopolymer containing 99.5 mol% or more of TFE units and substantially TFE (melt viscosity at 380°C: 1.4×10 4 ) (D50: 0.3 μm, D90: 0.6 μm) . [Dispersant] Dispersant 1: Copolymer of (meth)acrylate having a perfluoroalkenyl group and (meth)acrylate having a polyoxyethylene group (nonionic surfactant, within 100~200℃ The mass reduction rate is less than 1 mass%/min, and the mass reduction rate within 200~300℃ is 6 mass%/min). Dispersant 2: Copolymer of methacrylate with perfluoroalkyl and hydroxybutyl methacrylate (non-ionic surfactant, the mass reduction rate within 100~200℃ and 200~300℃ is less than 1 respectively Mass %/min). Dispersant 3: CH 2 =CHC(O)O(CH 2 ) 4 OCF(CF 3 )C(CF(CF 3 ) 2 )(=C(CF 3 ) 2 ) and CH 2 =CHC(O)O( CH 2 CH 2 O) 10 H copolymer (the mass reduction rate at 100~200℃ is less than 1 mass%/min, the mass reduction rate at 200~300℃ is 6 mass%/min). [Metal foil] Copper foil 1: Ultra-low-thickness electrolytic copper foil (made by Futian Metal Foil Industry Co., Ltd., CF-T4X-SV, thickness: 18 μm). [Prepreg] Prepreg 1: FR-4 (manufactured by Hitachi Chemical Co., Ltd., GEA-67N 0.2t (HAN), reinforced fiber: glass fiber, matrix resin: epoxy resin, thickness: 0.2 mm).

(例1)附樹脂之銅箔之製造例 (例1-1)附樹脂之銅箔1之製造例 混合50質量份之粉末1、5質量份之分散劑1、45質量份之N-甲基吡咯啶酮而調製出粉末分散液。 使用模塗機將粉末分散液塗佈於銅箔1之表面後，使銅箔1通過通風乾燥爐(氣體環境溫度：230℃，環境氣體：氧氣濃度8000ppm之氮氣)並保持1分鐘後，再通過遠紅外線爐(溫度：340℃，氣體：氧氣濃度低於100ppm之氮氣)並保持1分鐘，而製得於銅箔1之表面具有聚合物1之樹脂層(厚度5μm)的附樹脂之銅箔1。(Example 1) Manufacturing example of copper foil with resin (Example 1-1) Production example of copper foil with resin 1 50 parts by mass of powder 1, 5 parts by mass of dispersant 1, and 45 parts by mass of N-methylpyrrolidone were mixed to prepare a powder dispersion. After applying the powder dispersion to the surface of the copper foil 1 using a die coater, the copper foil 1 was passed through a ventilated drying furnace (gas ambient temperature: 230°C, ambient gas: nitrogen with an oxygen concentration of 8000 ppm) and held for 1 minute, then A resin-coated copper with a resin layer (thickness 5 μm) of the polymer 1 on the surface of the copper foil 1 was passed through a far-infrared furnace (temperature: 340° C., gas: nitrogen with an oxygen concentration of less than 100 ppm) and held for 1 minute. Foil 1.

(例1-2)~(例1-6)附樹脂之銅箔2~6之製造例 除了變更粉末及分散劑之種類，以及通風乾燥爐之氣體環境溫度及通風乾燥爐之環境氣體的氧氣濃度以外，以與例1同樣方式製得附樹脂之銅箔2~6。 評估各附樹脂之銅箔之樹脂層的物性(水接觸角與平滑性)。將結果統整顯示於下表1。 [表1]

Figure 02_image001
(Example 1-2) ~ (Example 1-6) The manufacturing examples of resin-coated copper foil 2~6 except changing the type of powder and dispersant, and the gas ambient temperature of the ventilation drying furnace and the oxygen of the ambient gas of the ventilation drying furnace Other than the concentration, copper foils 2 to 6 with resin were prepared in the same manner as in Example 1. Evaluate the physical properties (water contact angle and smoothness) of the resin layer of each copper foil with resin. The results are shown in Table 1 below. [Table 1]
Figure 02_image001

(例2)積層體之製造例 (例2-1)積層體1之製造例 將附樹脂之銅箔1之樹脂層表面進行真空電漿處理。處理條件係設為：輸出：4.5kW、導入氣體：氬氣、導入氣體流量：50cm3 /分鐘、壓力：50mTorr(6.7Pa)、處理時間：2分鐘。 於處理後之附樹脂之銅箔1的樹脂層表面重疊預浸體1，並在185℃、3.0MPa之加壓條件下真空熱壓60分鐘而獲得積層體1。(Example 2) Manufacturing example of laminate (Example 2-1) Manufacturing example of laminate 1 The surface of the resin layer of the copper foil with resin 1 was subjected to vacuum plasma treatment. The processing conditions were set to: output: 4.5 kW, introduction gas: argon, introduction gas flow rate: 50 cm 3 /min, pressure: 50 mTorr (6.7 Pa), treatment time: 2 minutes. The prepreg 1 was overlaid on the surface of the resin layer of the resin-coated copper foil 1 after the treatment, and was vacuum hot-pressed for 60 minutes under a pressure condition of 185°C and 3.0 MPa to obtain a laminate 1.

(例2-2)~(例2-4)積層體2~4之製造例 除了變更附樹脂之銅箔以外，以與例2-1同樣方式製造積層體2~4。 測定各積層體之剝離強度。將結果統整顯示於下表2。 [表2]

Figure 02_image003
(Example 2-2) to (Example 2-4) Production examples of laminates 2 to 4 The laminates 2 to 4 were produced in the same manner as in Example 2-1, except that the copper foil with resin was changed. The peel strength of each laminate was measured. The results are shown in Table 2 below. [Table 2]
Figure 02_image003

(例3)積層體A之製造例 使用模塗機將包含50質量份之粉末1、5質量份之分散劑3及45質量份之N-甲基吡咯啶酮的粉末分散液塗佈於銅箔1之表面。使已塗佈粉末分散液之銅箔1通過通風乾燥爐(氣體環境溫度：230℃，環境氣體：氧氣濃度8000ppm之氮氣)並保持1分鐘後，再通過遠紅外線爐(溫度：340℃，氣體：氧氣濃度低於100ppm之氮氣)進行燒成1分鐘。製得於銅箔1之表面具有聚合物1之F樹脂層(厚度5μm)的附樹脂之銅箔A。 將附樹脂之銅箔A之F樹脂層及接著部位的表面進行真空電漿處理。處理條件係設為：輸出：4.5kW、導入氣體：氬氣、導入氣體流量：50cm3 /分鐘、壓力：50mTorr(6.7Pa)、處理時間：2分鐘。(Example 3) Production example of laminate A A powder coating liquid containing 50 parts by mass of powder 1, 5 parts by mass of dispersant 3, and 45 parts by mass of N-methylpyrrolidone was applied to copper using a die coater The surface of the foil 1. The copper foil 1 coated with the powder dispersion liquid was passed through a ventilation drying furnace (gas ambient temperature: 230°C, ambient gas: nitrogen with an oxygen concentration of 8000 ppm) and kept for 1 minute, and then passed through a far infrared furnace (temperature: 340°C, gas : Nitrogen with an oxygen concentration below 100 ppm) is fired for 1 minute. The copper foil A with resin having the F resin layer (thickness 5 μm) of the polymer 1 on the surface of the copper foil 1 was prepared. The surface of the F resin layer of the copper foil A with resin and the surface of the adhering part are vacuum plasma treated. The processing conditions were set to: output: 4.5 kW, introduction gas: argon, introduction gas flow rate: 50 cm 3 /min, pressure: 50 mTorr (6.7 Pa), treatment time: 2 minutes.

利用全反射-紅外線吸收光譜法(ATR-IR分析法)分析附樹脂之銅箔A的F樹脂層表面的結果，確認了羧基之吸收峰。並以AFM-IR法分析附樹脂之銅箔A的F樹脂層表面。將以AFM-IR法分析附樹脂之銅箔A之表面所得的影像顯示於圖1。圖1中之白點部12係與F樹脂層10相接之島狀凸部，可從凸部檢測出源自醚性氧原子、羧基與-CF-結構的紅外線吸收光譜。即，圖1中之白點部12係散佈在F樹脂層10之表面的島狀接著部位，接著部位包含源自分散劑3之具有醚性氧原子及羧基的親水成分。 於真空電漿處理後之附樹脂之銅箔A的F樹脂層及接著部位的表面重疊預浸體1，並在185℃、3.0MPa之加壓條件下真空熱壓60分鐘而獲得積層體A。積層體A之翹曲率為0.3%，剝離強度為12N/cm。 又，將積層體A供於漂浮在焊料浴之焊料耐熱性試驗的結果，以積層體A來說即使在288℃之焊料中於5秒中漂浮5次，依舊未發生膨起。另一方面，不具島狀凸部的積層體在288℃之焊料中於5秒中漂浮2次的階段下便已發生膨起。The surface of the F resin layer of the copper foil A with resin was analyzed by total reflection-infrared absorption spectroscopy (ATR-IR analysis method), and the absorption peak of the carboxyl group was confirmed. The surface of F resin layer of copper foil A with resin was analyzed by AFM-IR method. The image obtained by analyzing the surface of the copper foil A with resin by the AFM-IR method is shown in FIG. 1. The white dot portion 12 in FIG. 1 is an island-shaped convex portion that is in contact with the F resin layer 10, and an infrared absorption spectrum derived from an etheric oxygen atom, a carboxyl group, and a -CF- structure can be detected from the convex portion. That is, the white dot portion 12 in FIG. 1 is an island-shaped adhesion portion scattered on the surface of the F resin layer 10, and the adhesion portion includes a hydrophilic component having an etheric oxygen atom and a carboxyl group derived from the dispersant 3. The prepreg 1 was superimposed on the surface of the F resin layer of the copper foil with resin A after vacuum plasma treatment and the surface of the adhesive part, and was vacuum-heated under vacuum at 185°C and 3.0 MPa for 60 minutes to obtain a laminate A . The warpage rate of the laminate A was 0.3%, and the peel strength was 12 N/cm. In addition, as a result of the solder heat resistance test of the laminate A floating in the solder bath, the laminate A did not swell even if it floated 5 times in 5 seconds in solder at 288°C. On the other hand, the laminate without the island-shaped convex portions swelled at a stage where it floated twice in 5 seconds in solder at 288°C.

(例4)積層體B之製造例 使用模塗機將包含50質量份之粉末1、5質量份之分散劑3及45質量份之N-甲基吡咯啶酮的粉末分散液塗佈於銅箔1之表面。使已塗佈粉末分散液之銅箔1通過通風乾燥爐(氣體環境溫度：230℃，環境氣體：氧氣濃度8000ppm之氮氣)並保持1分鐘後，再通過遠紅外線爐(溫度：340℃，氣體：氧氣濃度低於100ppm之氮氣)進行燒成1分鐘。製得於銅箔1之表面具有樹脂部分(厚度5μm)的附樹脂之銅箔B。 將附樹脂之銅箔B的樹脂部分表面進行電漿處理。電漿處理裝置係使用NORDSON MARCH公司之AP-1000。電漿處理條件係設為：RF輸出：300W、電極間間隔：2英吋、導入氣體：氬氣、導入氣體流量：50cm3 /分鐘、壓力：13Pa、處理時間：1分鐘。電漿處理後之樹脂部分表面的Ra為14.5nm，Rz為195nm。 於電漿處理後之附樹脂之銅箔B的樹脂部分表面重疊預浸體1，在加壓溫度：185℃、加壓壓力：3.0MPa、加壓時間：60分鐘之條件下進行真空熱壓，而製得依序具有銅箔1、樹脂部分、預浸體之硬化物層的積層體B。 用掃描型穿透電子顯微鏡觀察積層體B之截面的結果，如圖2所示在F樹脂層10’與硬化物層14’之間形成有厚度60nm之相溶層12’。利用能量分散型X射線分析進行分析的結果，確認相溶層12’有包含氧原子與氟原子。積層體B之翹曲率為0.3%，剝離強度為12N/cm。 於積層體B形成傳輸電路而製得之印刷基板的相對介電常數(20GHz)為4.32，介電正切(20GHz)為0.01568。(Example 4) Production example of laminate B A powder coating liquid containing 50 parts by mass of powder 1, 5 parts by mass of dispersant 3, and 45 parts by mass of N-methylpyrrolidone was applied to copper using a die coater The surface of the foil 1. The copper foil 1 coated with the powder dispersion liquid was passed through a ventilation drying furnace (gas ambient temperature: 230°C, ambient gas: nitrogen with an oxygen concentration of 8000 ppm) and kept for 1 minute, and then passed through a far infrared furnace (temperature: 340°C, gas : Nitrogen with an oxygen concentration below 100 ppm) is fired for 1 minute. A copper foil B with resin having a resin portion (thickness 5 μm) on the surface of the copper foil 1 was prepared. The surface of the resin portion of the copper foil B with resin is plasma treated. The plasma processing device is the AP-1000 from NORDSON MARCH. The plasma processing conditions were set as follows: RF output: 300 W, inter-electrode interval: 2 inches, introduced gas: argon, introduced gas flow rate: 50 cm 3 /min, pressure: 13 Pa, and processing time: 1 minute. After the plasma treatment, Ra on the surface of the resin portion was 14.5 nm, and Rz was 195 nm. The prepreg 1 was superimposed on the surface of the resin portion of the copper foil B with resin after plasma treatment, and vacuum hot pressing was performed under the conditions of pressure temperature: 185°C, pressure pressure: 3.0 MPa, pressure time: 60 minutes , And a laminate B having a copper foil 1, a resin portion, and a hardened layer of prepreg in this order was prepared. As a result of observing the cross-section of the laminate B with a scanning transmission electron microscope, as shown in FIG. 2, a compatible layer 12 ′ having a thickness of 60 nm was formed between the F resin layer 10 ′ and the cured product layer 14 ′. As a result of analysis by energy dispersive X-ray analysis, it was confirmed that the compatible layer 12' contains oxygen atoms and fluorine atoms. The warpage rate of the laminate B was 0.3%, and the peel strength was 12 N/cm. The relative dielectric constant (20 GHz) of the printed circuit board formed by forming the transmission circuit on the laminate B is 4.32, and the dielectric tangent (20 GHz) is 0.01568.

(例5)積層體B’之製造例 除了粉末分散液不含分散劑3以外，以與例4同樣方式製得積層體B’。積層體B’不具相溶層，F樹脂層與硬化物層直接相接，且其剝離強度為6N/cm。(Example 5) Production example of laminate B' A laminate B'was prepared in the same manner as in Example 4 except that the powder dispersion did not contain the dispersant 3. The laminate B'does not have a compatible layer, and the F resin layer is directly in contact with the hardened layer, and its peel strength is 6 N/cm.

產業上之可利用性 本發明之附樹脂之金屬箔之製造方法係適合製造具有包含氟聚物且接著性優異之樹脂層的附樹脂之金屬箔的方法，且有用於印刷基板等之製造。 本發明之附樹脂之金屬箔及積層體可有用作為印刷基板之材料。 至於，在此係援引已於2018年05月30日提申之日本專利申請案2018-104011號、已於2018年07月18日提申之日本專利申請案2018-134926號及已於2018年07月18日提申之日本專利申請案2018-134927號之說明書、申請專利範圍、摘要及圖式之全部內容，並納入作為本發明說明書之揭示。Industrial availability The manufacturing method of the resin-attached metal foil of the present invention is a method suitable for manufacturing a resin-attached metal foil having a resin layer containing a fluoropolymer and having excellent adhesiveness, and is useful for the manufacture of printed boards and the like. The resin-attached metal foil and laminate of the present invention can be useful as materials for printed boards. As for, here are cited Japanese Patent Application No. 2018-104011 filed on May 30, 2018, Japanese Patent Application No. 2018-134926 filed on July 18, 2018 and filed in 2018 The entire contents of the specification, patent application scope, abstract and drawings of Japanese Patent Application No. 2018-134927 filed on July 18 are incorporated as disclosure of the specification of the present invention.

10‧‧‧F樹脂層 12‧‧‧白點部 10’‧‧‧F樹脂層 12’‧‧‧相溶層 14’‧‧‧硬化物層10‧‧‧F resin layer 12‧‧‧White dot 10’‧‧‧F resin layer 12’‧‧‧Compatible layer 14’‧‧‧ Hardened layer

圖1係用AFM-IR法分析實施例之例3-1中附樹脂之銅箔A之樹脂層表面所得的影像。 圖2係實施例之例4-1中積層體B之截面的掃描型電子顯微鏡照片。FIG. 1 is an image obtained by analyzing the surface of the resin layer of the copper foil A with resin in Example 3-1 of the Example by the AFM-IR method. 2 is a scanning electron microscope photograph of the cross section of the laminate B in Example 4-1 of the embodiment.

Claims (15)

一種附樹脂之金屬箔之製造方法，係金屬箔表面具有樹脂層的附樹脂之金屬箔之製造方法，該製造方法如下： 將粉末分散液塗佈於金屬箔表面，該粉末分散液包含四氟乙烯系聚合物粉末、80~300℃溫度區域內之質量減少率為1質量%/分鐘以上之分散劑、及溶劑， 以前述溫度區域內之質量減少率為1質量%/分鐘以上的溫度來保持金屬箔， 在超過前述溫度區域之溫度下燒成四氟乙烯系聚合物，而於金屬箔表面形成包含四氟乙烯系聚合物之樹脂層。A manufacturing method of resin-attached metal foil is a manufacturing method of resin-attached metal foil with a resin layer on the surface of the metal foil. The manufacturing method is as follows: Applying a powder dispersion to the surface of the metal foil, the powder dispersion containing a tetrafluoroethylene polymer powder, a dispersant with a mass reduction rate of 1% by mass/min or more in a temperature range of 80 to 300°C, and a solvent, The metal foil is maintained at a temperature where the mass reduction rate in the aforementioned temperature range is 1% by mass/minute or more, The tetrafluoroethylene-based polymer is fired at a temperature exceeding the aforementioned temperature range, and a resin layer containing the tetrafluoroethylene-based polymer is formed on the surface of the metal foil. 如請求項1之製造方法，其中樹脂層之水接觸角為70~100°。The manufacturing method according to claim 1, wherein the water contact angle of the resin layer is 70 to 100°. 如請求項1或2之製造方法，其中分散劑係於側鏈具有下述基團之聚合物： 多氟烷基或多氟烯基；及 聚氧伸烷基或醇性羥基。The manufacturing method according to claim 1 or 2, wherein the dispersant is a polymer having the following groups in the side chain: Polyfluoroalkyl or polyfluoroalkenyl; and Polyoxyalkylene or alcoholic hydroxyl. 如請求項1至3中任一項之製造方法，其將金屬箔保持在前述溫度區域時之溫度為100~300℃。The manufacturing method according to any one of claims 1 to 3, wherein the temperature when the metal foil is held in the aforementioned temperature range is 100 to 300°C. 如請求項1至4中任一項之製造方法，其將金屬箔保持在前述溫度區域時之氣體環境為含氧氣之氣體環境。The manufacturing method according to any one of claims 1 to 4, wherein the gas environment when the metal foil is maintained in the aforementioned temperature region is an oxygen-containing gas environment. 如請求項1至5中任一項之製造方法，其燒成四氟乙烯系聚合物時之溫度為330~380℃。According to the manufacturing method of any one of claims 1 to 5, the temperature at the time of firing the tetrafluoroethylene-based polymer is 330 to 380°C. 一種附樹脂之金屬箔，依序具有金屬箔、包含四氟乙烯系聚合物之樹脂層及包含親水成分之接著部位，前述樹脂層與前述接著部位相接，前述親水成分具有選自於由醚性氧原子、羥基及羧基所構成群組中之至少1種。A metal foil with a resin, which has a metal foil, a resin layer containing a tetrafluoroethylene-based polymer, and a bonding part containing a hydrophilic component in sequence, the resin layer is in contact with the bonding part, and the hydrophilic component has a material selected from the group consisting of ether At least one of the group consisting of sex oxygen atom, hydroxyl group and carboxyl group. 如請求項7之附樹脂之金屬箔，其中前述接著部位係以島狀存在。The metal foil with resin according to claim 7, wherein the aforementioned bonding part exists in an island shape. 如請求項7或8之附樹脂之金屬箔，其中前述親水成分源自聚合物，該聚合物於側鏈具有：多氟烷基或多氟烯基，以及，聚氧伸烷基或醇性羥基。A metal foil with a resin as claimed in claim 7 or 8, wherein the aforementioned hydrophilic component is derived from a polymer, the polymer having in the side chain: polyfluoroalkyl or polyfluoroalkenyl, and, polyoxyalkylene or alcoholic Hydroxyl. 一種積層體之製造方法，係利用熱壓法使如請求項7至9中任一項之附樹脂之金屬箔與其他基板接著而製得積層體。A method for manufacturing a laminate, which uses a hot pressing method to bond the metal foil with resin as described in any one of claims 7 to 9 to another substrate to obtain a laminate. 一種積層體，依序具有金屬箔、包含四氟乙烯系聚合物之樹脂層及包含基質樹脂之預浸體的硬化物層，且更於前述樹脂層與前述硬化物層之間具有一與前述樹脂層及前述硬化物層相接之相溶層，該相溶層含有具氟原子及氧原子之成分。A laminate having a metal foil, a resin layer containing a tetrafluoroethylene-based polymer, and a hardened layer of a prepreg containing a matrix resin in sequence, and further comprising one and the above between the resin layer and the hardened layer A compatible layer in which the resin layer and the hardened material layer are in contact with each other. The compatible layer contains a component having fluorine atoms and oxygen atoms. 如請求項11之積層體，其中前述相溶層之厚度為1~500nm。The laminated body according to claim 11, wherein the thickness of the aforementioned compatible layer is 1 to 500 nm. 如請求項11或12之積層體，其中前述相溶層源自聚合物，該聚合物於側鏈具有：多氟烷基或多氟烯基，以及，聚氧伸烷基或醇性羥基。The laminate according to claim 11 or 12, wherein the aforementioned compatible layer is derived from a polymer having, in the side chain, a polyfluoroalkyl group or a polyfluoroalkenyl group, and a polyoxyalkylene group or an alcoholic hydroxyl group. 如請求項11至13中任一項之積層體，其中前述基質樹脂為不具氟原子的基質樹脂，且選自於由環氧樹脂、聚氧化苯、聚苯醚及聚丁二烯所構成群組中之至少1種。The laminate according to any one of claims 11 to 13, wherein the aforementioned matrix resin is a matrix resin having no fluorine atoms, and is selected from the group consisting of epoxy resin, polyoxybenzene, polyphenylene oxide, and polybutadiene At least 1 species in the group. 一種印刷基板，依序具有傳輸電路、包含四氟乙烯系聚合物之樹脂層及包含基質樹脂之預浸體的硬化物層，且更於前述樹脂層與前述硬化物層之間具有一與前述樹脂層及前述硬化物層相接之相溶層，該相溶層含有具氟原子及氧原子之成分。A printed circuit board having a transmission circuit, a resin layer containing a tetrafluoroethylene-based polymer, and a hardened layer of a prepreg containing a matrix resin in sequence, and further comprising one and the above between the resin layer and the hardened layer A compatible layer in which the resin layer and the hardened material layer are in contact with each other. The compatible layer contains a component having fluorine atoms and oxygen atoms.
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