1296272 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種改質含氟基材的方法，特別是關於一 種藉由電漿/臭氧處理改質含氟基材的方法，及其在氟系金屬 積層板製程的應用。 【先前技術】 聚四氟乙烯（polytetrafluoroethylene; PTFE)具有各式優 良的性質，例如：熱穩定性、優異的化學惰性、低界電常數、 低吸水性、低摩擦阻抗性與絲面能，因此，其應用十分廣泛， 刷電路版、多層電子封裝、低縣魏細、保護油 ϋίί材ϋ然而’由於聚四氟乙烯的疏水性太強與接 I曰墓入二用上的麵關。改質聚四氟乙烯的方法主 能ί至聚四氟乙烯的表面以增強其接著性 其傳級f方法包含化學侧法、紫外 nJifieal〇 祕衫錢理與魏改肢（Pl_ :電 電漿聚合反應 inducedgramngpo, Ji2^ (P^ma 多研究者競相投入，然而，;磁率之優點吸引了眾 此難以於工業製程中施行。^一3使用*空系統，因 導接枝聚合反應無她齡子匕，’電^合反應與電襞誘 化。有鑑於此，仍有必要發展新^含ϋ子結構建築 合產業上的需求。 的改貝3鼠材料的方法，以符 【發明内容】 1296272 鑒於上述之發明背景中，為了克服 點，本發明提供一種新的改質含氟基材的生貝技術的缺 /¾'及其應用。 本發明之-目的在於藉由臭氧處理 Ϊ=為C-F鍵結太強’臭氧處理技術“ ίΐΐΐ 化物團基，藉歧f錢紐之表面。較鍵為過虱 率較低，以減少含氟基材表面過度1296272 IX. Description of the Invention: [Technical Field] The present invention relates to a method for modifying a fluorine-containing substrate, and more particularly to a method for modifying a fluorine-containing substrate by plasma/ozone treatment, and Application of fluorine metal laminated board process. [Prior Art] Polytetrafluoroethylene (PTFE) has various excellent properties such as thermal stability, excellent chemical inertness, low dielectric constant, low water absorption, low friction resistance and silk surface energy. Its application is very extensive, brush circuit board, multi-layer electronic package, low county Wei fine, protective oil ϋ ί ϋ ϋ ' ' 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于The method of modifying polytetrafluoroethylene can be used to enhance the adhesion of the surface of the PTFE to the passivation. The method includes the chemical side method, the ultraviolet nJifieal, and the Wei modified limb (Pl_: electro-plasma polymerization). The reaction inducedgramngpo, Ji2^ (P^ma multi-researcher competing for input, however; the advantage of magnetic rate has attracted many people to do it in industrial processes. ^3 using *empty system, because the graft polymerization is not her age匕, 'Electrical reaction and electric enthalpy. In view of this, it is still necessary to develop new ϋ 结构 结构 结构 结构 结构 。 。 。 。 。 。 。 。 。 。 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 In view of the above-mentioned background of the invention, in order to overcome the point, the present invention provides a novel modified fluorinated substrate which lacks the technology of raw scallops and its application. The present invention - the object is to treat Ϊ = CF bond by ozone The knot is too strong 'ozone treatment technology' ί ΐΐΐ 团 , 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借 借
本發明之另—目的在於提供低溫氟系金屬積 在大氣壓力下進行且不需使用額外的接i劑。ϊϊ 金=層板的製造方㈣i經由賴/臭氧處理改質含 ίίΐϊί氧化侧基’紐藉由過氧化物起始，'於 于接枝聚合反應’其係與一積層程序同時進行 改=氣ΐ;之間的重疊介面進 合反應係在一包含至少一功能性單體之化學組成下進行。上 之接枝聚合反應/懸鱗之溫度低縣氣紐找點或其^ 結溫度（smteringtemperature)。據此，本發明能符合經濟工二 效益與產業上的利用性。 、、4上的 根據以上所述之目的，本發明揭示了一種改質含氟基 的方法，首先提供-含氟基材，對含氟基材進行—氫氣電J 理以導入C-H團基於含氟基材表面上，藉此形成一中間物。 然後，對第一中間物進行一臭氧處理，其中，第一中間物表面 之C-H團基係作為臭氧反應活性點，並與臭氧反應形成過氧 化物團基以形成一第一改質含氟基材。最後，對第一改質含氟 基材進行一接枝聚合反應，接枝聚合反應係藉由第二中間物的 過氧化物團基起始，且接枝聚合反應係在一包含至少一功能性 1296272 ^之組成下進行，藉此形成一第二改質含氟A枯另 方面，本發明亦揭示氟系金屬積層板的製造氣基材。另一 【實施方式】 其應用錢絲的方法及 食J碰為了徹底地瞭解本發明，將在下列的插述中描屮謀 。顯然地’本發明的施行並未限定於Ϊ以 之技藝者所熟習的特殊細節。另 Ζ ，Another object of the present invention is to provide a low temperature fluorine-based metal product which is carried out under atmospheric pressure without the use of an additional agent. Ϊϊ Gold = the manufacturer of the laminate (4) i modified by Lai / ozone treatment containing ίίίί oxidized side group 'news by peroxide starting, 'in the graft polymerization reaction' is linked with a layering procedure The overlap interface between the reactions is carried out in a chemical composition comprising at least one functional monomer. The graft polymerization reaction/suspension scale temperature is low and the gas temperature is found or its temperature is smtering temperature. Accordingly, the present invention can meet the economic and industrial benefits and industrial utilization. According to the above purposes, the present invention discloses a method for modifying a fluorine-containing group, firstly providing a fluorine-containing substrate, and performing hydrogen-hydrogenation on the fluorine-containing substrate to introduce a CH group based on On the surface of the fluorine substrate, an intermediate is thereby formed. Then, the first intermediate is subjected to an ozone treatment, wherein the CH group of the surface of the first intermediate acts as an ozone reactive site, and reacts with ozone to form a peroxide group to form a first modified fluorine-containing group. material. Finally, a graft polymerization reaction is carried out on the first modified fluorine-containing substrate, the graft polymerization is initiated by a peroxide group of the second intermediate, and the graft polymerization reaction comprises at least one function. The composition is carried out under the composition of 1296272, thereby forming a second modified fluorine-containing A. In addition, the present invention also discloses a gas substrate for producing a fluorine-based metal laminate. [Embodiment] The method of applying the money and the food J in order to thoroughly understand the present invention will be described in the following description. It is apparent that the practice of the present invention is not limited to the specific details familiar to those skilled in the art. Another Ζ,
中，以避免造成本發明;必i二二S ^ 會詳細描述如下，然崎了這些詳細描述之 ^圍可，泛地施行在其他的實施例中1本發明的 靶圍不文限疋，其以之後的專利範圍為準。 本發明之第一實施例揭露一種改質含氟基材的方法，首 先共一含氟基材，對含氟基材進行一氫氣電漿處理以導入 C-H團基於含氟基材表面上，藉此形成一中間物。然後，對第 一中間物進行一臭氧處理，其中，第一中間物表面之團 基係作為臭氧反應活性點，並與臭氧反應形成過氧化物團基 (peroxide)以形成一第一改質含氟基材，其中，上述之過氧 化物團基包含alkyl-peroxide與hydroxyl-peroxide。此外，上述 之含氟基材包含下列族群中之任一者或其任意組合： poly(tetrafluoroethylene)(PTFE)， copolymers of tetrafluoroethylene and hexafluoropropylene，copolymers of tetrafluoroethylene and perfluoro(propyl vinyl ether), copolymers of tetrafluoroethylene and perfluoro-2,3-dimethyl-1，3-dioxole， copolymers of tetrafluoroethylene and vinyl fluoride, poly(vinyl fluoride), poly(vinylidene fluoride), polychlorotrifluorethylene, vinyl fluoride/vinylidene fluoride copolymers, and vinylidene fluoride/hexafluoroethylene copolymers 〇 上述之含氟基材的型態 1296272 : 列族群中之-者：薄膜（film)、馳（_)、厚板 =b)、纖維（flber)、棒狀（r〇d)、粉末（p〇wder)、複合 膜（compositemembrane)或多孔膜（p〇r〇usmembrane)。 於本實施例中，上述之氫氣電漿處理之功率範圍約 low至70W，處理時間範圍約為5秒至300秒，電漿頻率範 圍約為5 kHz至50 kHz。本發明所選用之氫氣電漿功率較低， 1 以減少含氟基材表面過度氧化與過度姓刻等情形發生。此外， 亡述之臭氧處理係使用臭氧/氧氣混合流體，其中，臭氧濃度 ‘範圍約為5 g/m3至50 g/m3，處理時間範圍約為5分鐘'至3〇 $ _ 鐘。 於本實施例中，上述之改質含氟基材的方法更包含對第 一改質含氟基材進行一接枝聚合反應[例如：活性自由基聚合 反應（controlled/living free radical polymerization)]，其係在 一包含至少一功能性單體之化學組成中與一大氣壓力下進 行，藉此形成一第二改質含氟基材，其可應用於金屬積層板 (metal_clad laminate)的製造。上述之接枝聚合反應係藉由第 一改質含氟基材的過氧化物團基（peroxide)起始，不需另外 添加起始劑。其溫度低於含氟基材之熔點或其燒結溫度 瞻 （sintering temperature)，但高於過氧化物團基（per〇xide)的 裂解溫度（約70°C)。 於本實施例中之一較佳範例中，上述之功能性單體包含 ‘ 具有至少一個乙烯基（vinyl group)之單體或具有至少一個丙 烯基（allyl group )之單體，例如：hydroxy methacrylate，amine methacrylate, hydroxylethyl acrylate, N-hydroxylmethylmethacrylamide? acrylamide (AAm)，acrylic acid (AAc)， glycidyl methacrylate (GMA)， 2-(2-bromoisobutyryloxy) ethyl acrylate (BIEA)， sodium 4_styrenesulfonate(NaSS)及其衍生物。當功能性單體為s〇dium 1296272 間物。織，料二巾嶋進行—接枝聚合反 f 反應係藉由第二中間物的過氧化物團基 聚合反觸與—積層程序同時 i 第間物，接枝聚合反應係於金屬層與 弟-中間物之間的重豐介面進行，且紐 至少-功雛單體之化學組成下進行。在匕3 人-ίί述ί發明之實關+，本發簡由錄處理以改質 ii面。原本因為c錢結太強，臭氧處理技術上的 直^質含氟基材，但本發喃由預先以氫氣電聚處 乙烯表面以產生碳氫鍵’接著再藉由臭氧處理以轉換 石厌風鍵為過氧化侧基’ #此改質含氟基材之表面。較佳者， ，發明所之氫氣電漿神較低，以減少含氟基材表面過度 ίϊίΐ度侧等情職生n面，本發供低溫氟系 板的製造方法，其可在域壓力下進行且不需使用額 外^接者劑。上述之㈣金屬㈣板的製造方法首紐由電裝 /臭氧處理改質含氟基材喊生過氧化物團基，然後藉由過氧 化物團基起始，於改質基材表面進行接枝聚合反應，其係與一 積層程序同時進行以積層一金屬層與改質後之含氟基材。上述 之接枝系合反應係於金屬層與改質後之含氟基材之間的重疊 介面進行，且接枝聚合反應係在一包含至少一功能性單體之化 ，組成下進行。上述之接枝聚合反應/積層程序之溫度低於含 氟基材之炼點或其燒結溫度（sintering。據此，本 發明能符合經濟上的效益與產業上的利用性。 、、综合以上所述，本發明揭示了一種改質含氟基材的方 法，首先提供一含氟基材，對含氟基材進行一氫氣電漿處理以 導入C-H團基於含氟基材表面上，藉此形成一中間物。然後， 對第了中間物進行一臭氧處理，其中，第一中間物表面之c_H 團基係作為臭氧反應活性點，並與臭氧反應形成過氧化物團基 以形成一第一改質含氟基材。最後，對第一改質含氟基材進$ 1296272 一接枝聚合反應，接枝聚合反應係藉由第二中間物的過氧化物 團基起始，且接枝聚合反應係在一包含至少一功能性單體之化 學組成下進行，藉此形成一第二改質含氟基材。另一方面，本 發明亦揭示氟系金屬積層板的製造方法。 顯然地，依照上面實施例中的描述，本發明可能有許多 =正iif。因此需要在其附加_利要求項之細内加以 實施例月本發明還可以廣泛地在其他的 限定本發狀憎佳細箱已，並非用以 神下所完朗等魏變離b未麟本發贿揭示之精 内。 > 飾’均應包含在下述申請專利範圍In order to avoid causing the present invention; it will be described in detail below, and the detailed description of these details can be applied in other embodiments. It is subject to the scope of the patents that follow. A first embodiment of the present invention discloses a method for modifying a fluorine-containing substrate. First, a fluorine-containing substrate is mixed, and a fluorine-containing substrate is subjected to a hydrogen plasma treatment to introduce a CH group based on the surface of the fluorine-containing substrate. This forms an intermediate. Then, the first intermediate is subjected to an ozone treatment, wherein the group of the first intermediate surface acts as an ozone reactive site, and reacts with ozone to form a peroxide group to form a first modified content. A fluorine substrate, wherein the above-mentioned peroxide group comprises an alkyl-peroxide and a hydroxyl-peroxide. Further, the above fluorine-containing substrate comprises any one of the following groups or any combination thereof: poly(tetrafluoroethylene) (PTFE), copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoro (propyl vinyl ether), copolymers of tetrafluoroethylene and Perfluoro-2,3-dimethyl-1,3-dioxole, copolymers of tetrafluoroethylene and vinyl fluoride, poly(vinyl fluoride), poly(vinylidene fluoride), polychlorotrifluorethylene, vinyl fluoride/vinylidene fluoride copolymers, and vinylidene fluoride/hexafluoroethylene copolymers The type of fluorine-containing substrate 1926272: in the group of people: film, chi (_), thick plate = b), fiber (flber), rod (r〇d), powder (p〇 Wder), composite membrane or porous membrane (p〇r〇usmembrane). In the present embodiment, the hydrogen plasma treatment described above has a power range of about low to 70 W, a processing time range of about 5 seconds to 300 seconds, and a plasma frequency range of about 5 kHz to 50 kHz. The hydrogen plasma selected for use in the present invention has a low power, 1 to reduce the excessive oxidation of the surface of the fluorine-containing substrate and excessive surnames. In addition, the ozone treatment used in the ozone/oxygen mixed fluid, wherein the ozone concentration is in the range of about 5 g/m3 to 50 g/m3, and the treatment time ranges from about 5 minutes to 3 〇 $ _ clock. In the present embodiment, the method for modifying the fluorine-containing substrate further comprises performing a graft polymerization reaction on the first modified fluorine-containing substrate (for example, controlled/living free radical polymerization). It is carried out in a chemical composition comprising at least one functional monomer and at atmospheric pressure, thereby forming a second modified fluorine-containing substrate which is applicable to the manufacture of metal_clad laminates. The above graft polymerization is initiated by the peroxide of the first modified fluorine-containing substrate, without the need for additional initiator. The temperature is lower than the melting point of the fluorine-containing substrate or its sintering temperature, but higher than the per-xide cracking temperature (about 70 ° C). In a preferred embodiment of the present embodiment, the functional monomer comprises 'a monomer having at least one vinyl group or a monomer having at least one allyl group, for example: hydroxy methacrylate , amine methacrylate, hydroxylethyl acrylate, N-hydroxylmethylmethacrylamide? acrylamide (AAm), acrylic acid (AAc), glycidyl methacrylate (GMA), 2-(2-bromoisobutyryloxy) ethyl acrylate (BIEA), sodium 4_styrenesulfonate (NaSS) and its derivatives . When the functional monomer is s〇dium 1296272. The weaving, the material is carried out, and the grafting polymerization is carried out by the peroxide-based polymerization of the second intermediate, and the layering process is simultaneous with the first layer, and the graft polymerization is carried out in the metal layer. - The heavy interface between the intermediates is carried out, and the nucleus is carried out at least under the chemical composition of the monomer. In the case of 匕 3 people - ί 述 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明Originally, because the c-money knot is too strong, the ozone treatment technology is a straight-line fluorine-containing substrate, but the hair is pre-hydrogenated by hydrogen to the surface of the ethylene to generate a carbon-hydrogen bond, and then treated by ozone to convert the stone. The wind key is a peroxide side group '# This is the surface of the modified fluorine-containing substrate. Preferably, the hydrogen plasma of the invention is lower in order to reduce the surface of the fluorine-containing substrate, and the surface of the fluorine-based substrate is manufactured by a method for manufacturing a low-temperature fluorine-based plate. It is carried out without the use of an additional agent. The above-mentioned (4) metal (four) plate manufacturing method first from the electrification / ozone treatment modified fluorine-containing substrate shouting peroxide group, and then starting from the surface of the modified substrate by the peroxide group The branch polymerization is carried out simultaneously with a lamination procedure to laminate a metal layer with the modified fluorine-containing substrate. The above grafting reaction is carried out on the overlapping interface between the metal layer and the modified fluorine-containing substrate, and the graft polymerization is carried out in a composition containing at least one functional monomer. The temperature of the graft polymerization/layering procedure described above is lower than the melting point of the fluorine-containing substrate or the sintering temperature thereof. Accordingly, the present invention can meet economic benefits and industrial applicability. The invention discloses a method for modifying a fluorine-containing substrate, firstly providing a fluorine-containing substrate, and performing a hydrogen plasma treatment on the fluorine-containing substrate to introduce a CH group on the surface of the fluorine-containing substrate, thereby forming An intermediate is then subjected to an ozone treatment, wherein the c_H group on the surface of the first intermediate acts as an ozone reactive site and reacts with ozone to form a peroxide group to form a first modification. Fluorine-containing substrate. Finally, a graft polymerization of the first modified fluorine-containing substrate is carried out by grafting polymerization, and the graft polymerization is initiated by a peroxide group of the second intermediate, and graft polymerization is carried out. The reaction is carried out under a chemical composition comprising at least one functional monomer to form a second modified fluorine-containing substrate. In another aspect, the present invention also discloses a method for producing a fluorine-based metal laminate. According to the above In the description of the example, the present invention may have many = positive iif. Therefore, it is necessary to carry out the embodiment within the scope of its additional requirements. The present invention can also be broadly defined in other limited embodiments. It is used in the fines of the sacred sects of the sacred sects of the sacred sects.