TW202311422A

TW202311422A - Sheet

Info

Publication number: TW202311422A
Application number: TW111120850A
Authority: TW
Inventors: 笠井涉; 佐藤崇; 藤岡藏
Original assignee: 日商Ａｇｃ股份有限公司
Priority date: 2021-06-09
Filing date: 2022-06-06
Publication date: 2023-03-16
Also published as: CN117425694A; JPWO2022259992A1; WO2022259992A1; KR20240020269A

Abstract

To provide a sheet that contains unsintered polytetrafluoroethylene and inorganic particles, in which the inorganic particles are unlikely to peel off, and that has excellent electrical properties, low linear expansion properties, physical strength, and adhesion to other materials. This sheet contains: unsintered polytetrafluoroethylene; inorganic particles; and a resin having at least one type of functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group-containing group, an epoxy group, and an amino group. The total content of the polytetrafluoroethylene, the inorganic particles, and the resin is at least 90 mass%.

Description

片材Sheet

本發明涉及一種包含未燒成之聚四氟乙烯之預定之片材、該片材之製造方法及包含該片材之積層體之製造方法。The present invention relates to a predetermined sheet comprising unfired polytetrafluoroethylene, a method for producing the sheet, and a method for producing a laminate comprising the sheet.

聚四氟乙烯因具有優異之低介電常數或低介電正切等電特性，故作為印刷基板之介電質層之材料而備受矚目。專利文獻1中記載了從由聚四氟乙烯與無機粒子構成之片材來形成介電質層。專利文獻2中記載了一種經強化織布補強之介電質層，且該介電質層包含聚四氟乙烯、無機粒子及強化織布。先前技術文獻專利文獻 Due to its excellent electrical properties such as low dielectric constant or low dielectric tangent, polytetrafluoroethylene has attracted much attention as a material for the dielectric layer of printed substrates. Patent Document 1 describes that a dielectric layer is formed from a sheet made of polytetrafluoroethylene and inorganic particles. Patent Document 2 describes a dielectric layer reinforced with reinforced woven fabric, and the dielectric layer includes polytetrafluoroethylene, inorganic particles and reinforced woven fabric. prior art literature patent documents

專利文獻1：日本專利特開2021-061406號公報專利文獻2：日本專利特表2020-507888號公報 Patent Document 1: Japanese Patent Laid-Open No. 2021-061406 Patent Document 2: Japanese Patent Application Publication No. 2020-507888

發明欲解決之課題由包含未燒成之聚四氟乙烯與無機粒子的片材來形成具有包含聚四氟乙烯與無機粒子之層的層狀成形物時，前述片材有無機粒子容易凝集而難以充分展現其物性之課題。又，在加工前述片材時，有無機粒子容易剝落之課題及韌性等之物理性強度不足而容易斷裂之課題。並且，該片材還被要求與金屬箔等之其他基材層的接著性，但其接著性卻尚不充分。本發明人等發現以預定比率包含未燒成之聚四氟乙烯、無機粒子及具有預定官能基之樹脂的片材，其無機粒子不易剝落，且具有優異之電特性、低線膨脹性、物理性強度及與其他材料之接著性，而達成本發明。 The problem to be solved by the invention When a layered molded article having a layer containing polytetrafluoroethylene and inorganic particles is formed from a sheet containing unfired polytetrafluoroethylene and inorganic particles, the inorganic particles in the sheet are likely to agglomerate and it is difficult to fully exhibit its physical properties. of the topic. In addition, when the aforementioned sheet is processed, there is a problem that the inorganic particles are easily peeled off, and physical strength such as toughness is insufficient and the problem is easy to break. In addition, the sheet is required to have adhesiveness to other substrate layers such as metal foil, but the adhesiveness is not sufficient. The inventors of the present invention have found that a sheet comprising unfired polytetrafluoroethylene, inorganic particles and a resin having a predetermined functional group in a predetermined ratio has an inorganic particle that is not easy to peel off, and has excellent electrical properties, low linear expansion, and physical properties. The strength and adhesion with other materials achieve the present invention.

用以解決課題之手段本發明具有下述態樣。 [1]一種片材，包含：未燒成之聚四氟乙烯、無機粒子及樹脂，且該樹脂具有選自於由含羰基之基團、含羥基之基團、環氧基及胺基所構成群組中之至少1種官能基；並且，前述聚四氟乙烯、前述無機粒子及前述樹脂之總含量為90質量%以上。 [2]如前述[1]之片材，其中前述無機粒子係包含選自於由二氧化矽、氮化硼及二氧化鈦所構成群組中之至少1種無機物的粒子。 [3]如前述[1]或[2]之片材，其中前述樹脂包含下述中之至少任一者：熱熔融性四氟乙烯系聚合物；以及，芳香族聚合物或其前驅物。 [4]如前述[1]至[3]中任一項之片材，其中前述樹脂包含：熱熔融性四氟乙烯系聚合物；以及，芳香族聚合物或其前驅物。 [5]如前述[3]或[4]之片材，其中前述熱熔融性四氟乙烯系聚合物之熔融溫度為260至320℃。 [6]如前述[3]或[4]之片材，其中前述芳香族聚合物或其前驅物為聚醯亞胺、聚醯胺醯亞胺、聚醯亞胺前驅物或聚醯胺醯亞胺前驅物。 [7]如前述[1]至[6]中任一項之片材，其中前述聚四氟乙烯之含量為10質量%以上。 [8]如前述[1]至[7]中任一項之片材，其中前述樹脂之含量為5質量%以上。 [9]如前述[1]至[8]中任一項之片材，其中相對於前述聚四氟乙烯之含量與前述樹脂之含量之合計，前述無機粒子之含量之比為0.1以上。 [10]如前述[1]至[9]中任一項之片材，其厚度為50µm以上。 [11]一種片材之製造方法，係將包含前述聚四氟乙烯之粒子、前述無機粒子及前述樹脂之液態組成物進行流延，而獲得如前述[1]至[10]中任一項之片材。 [12]如前述[11]之製造方法，其中前述聚四氟乙烯之粒子之平均粒徑為0.1至10µm。 [13]如前述[11]或[12]之製造方法，其係將前述液態組成物進行流延而得之流延物互相積層並貼合。 [14]一種燒成片之製造方法，係加熱如前述[1]至[10]中任一項之片材來燒成前述聚四氟乙烯。 [15]一種積層體之製造方法，係將如前述[1]至[10]中任一項之片材與基材予以熱壓附，而獲得具有基材層與聚合物層之積層體。 means to solve problems The present invention has the following aspects. [1] A sheet comprising: unfired polytetrafluoroethylene, inorganic particles and a resin, and the resin has a compound selected from the group consisting of carbonyl-containing groups, hydroxyl-containing groups, epoxy groups, and amine groups. At least one functional group constituting the group; and the total content of the polytetrafluoroethylene, the inorganic particles, and the resin is 90% by mass or more. [2] The sheet according to the aforementioned [1], wherein the inorganic particles include particles of at least one inorganic substance selected from the group consisting of silicon dioxide, boron nitride, and titanium dioxide. [3] The sheet according to the aforementioned [1] or [2], wherein the aforementioned resin contains at least any one of the following: a hot-melt tetrafluoroethylene polymer; and an aromatic polymer or a precursor thereof. [4] The sheet according to any one of the aforementioned [1] to [3], wherein the aforementioned resin contains: a hot-melt tetrafluoroethylene polymer; and an aromatic polymer or a precursor thereof. [5] The sheet according to the aforementioned [3] or [4], wherein the melting temperature of the aforementioned hot-melt tetrafluoroethylene polymer is 260 to 320°C. [6] The sheet according to the aforementioned [3] or [4], wherein the aforementioned aromatic polymer or its precursor is polyimide, polyimide imide, polyimide precursor, or polyimide Imine precursors. [7] The sheet according to any one of the aforementioned [1] to [6], wherein the content of the aforementioned polytetrafluoroethylene is 10% by mass or more. [8] The sheet according to any one of the aforementioned [1] to [7], wherein the content of the aforementioned resin is 5% by mass or more. [9] The sheet according to any one of [1] to [8] above, wherein the ratio of the content of the inorganic particles to the sum of the content of the polytetrafluoroethylene and the content of the resin is 0.1 or more. [10] The sheet according to any one of the aforementioned [1] to [9], which has a thickness of 50 µm or more. [11] A method for producing a sheet, comprising casting a liquid composition comprising the aforementioned polytetrafluoroethylene particles, the aforementioned inorganic particles, and the aforementioned resin, to obtain any one of the aforementioned [1] to [10] The sheet. [12] The production method according to [11] above, wherein the polytetrafluoroethylene particles have an average particle diameter of 0.1 to 10 µm. [13] The production method according to the aforementioned [11] or [12], wherein the castings obtained by casting the aforementioned liquid composition are laminated and bonded together. [14] A method for producing a fired sheet, comprising heating the sheet according to any one of the aforementioned [1] to [10] and firing the aforementioned polytetrafluoroethylene. [15] A method for producing a laminate, comprising hot-pressing the sheet according to any one of [1] to [10] above and a substrate to obtain a laminate having a substrate layer and a polymer layer.

發明效果根據本發明，可獲得一種片材，其包含未燒成之聚四氟乙烯、無機粒子及具有預定官能基之樹脂，該片材之無機粒子不易剝落，且具有優異之電特性、低線膨脹性、物理性強度及與其他材料之接著性。 Invention effect According to the present invention, a sheet can be obtained, which includes unfired polytetrafluoroethylene, inorganic particles, and a resin with predetermined functional groups. The inorganic particles of the sheet are not easy to peel off, and have excellent electrical properties and low linear expansion. properties, physical strength and adhesion to other materials.

以下用語具有以下意義。所謂「四氟乙烯系聚合物」係含有以四氟乙烯(以下亦表記為「TFE」)為主體之單元的聚合物。所謂「熱熔融性四氟乙烯系聚合物」，意指在荷重49N之條件下，存在有熔融流速成為1至1000g/10分鐘之溫度的四氟乙烯系聚合物。「聚合物之熔融溫度(熔點)」係指對應於以示差掃描熱量測定(DSC)法測定聚合物之熔解峰之最大值的溫度。「聚合物之玻璃轉移點(Tg)」係指以動態黏彈性測定(DMA)法分析聚合物所測定之值。「粒子之D50」係粒子的平均粒徑，其係藉由雷射繞射散射法求得之粒子的體積基準累積50%粒徑。即，藉由雷射繞射散射法測定粒子的粒度分布，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成為50%之點的粒徑。「粒子之D90」係粒子的累積體積粒徑，其係依與「D50」相同方式求得之粒子的體積基準累積90%粒徑。「液態組成物之黏度」係使用B型黏度計，在室溫下(25℃)且旋轉數為30rpm之條件下對液態組成物測定之值。重複測定3次後，取3次測定值之平均值。所謂「以單體為主體之單元」，意指藉由單體聚合而形成之以前述單體為主體之原子團。單元可為藉由聚合反應直接形成之單元，亦可為藉由對聚合物進行處理使前述單元之一部分轉換成另一結構之單元。以下，以單體a為主體之單元亦僅表記為「單體a單元」。 The following terms have the following meanings. The term "tetrafluoroethylene-based polymer" is a polymer containing units mainly composed of tetrafluoroethylene (hereinafter also referred to as "TFE"). The term "hot-melt tetrafluoroethylene-based polymer" means a tetrafluoroethylene-based polymer having a melt flow rate of 1 to 1000 g/10 minutes under a load of 49 N. The "melting temperature (melting point) of a polymer" refers to the temperature corresponding to the maximum value of the melting peak of a polymer measured by differential scanning calorimetry (DSC). "Glass transition point (Tg) of a polymer" refers to the value measured by analyzing a polymer with a dynamic viscoelasticity measurement (DMA) method. "D50 of particles" is the average particle diameter of the particles, which is the volume-based cumulative 50% particle diameter of the particles obtained by the laser diffraction scattering method. That is, the particle size distribution of the particles is measured by the laser diffraction scattering method, and the cumulative curve is calculated with the total volume of the particle group as 100%, and the particle diameter at the point where the cumulative volume becomes 50% on the cumulative curve. "D90 of particles" refers to the cumulative volume particle diameter of particles, which refers to the cumulative 90% particle diameter based on the volume of particles obtained in the same way as "D50". The "viscosity of the liquid composition" is a value measured on the liquid composition at room temperature (25° C.) and at a rotation speed of 30 rpm using a B-type viscometer. After the measurement was repeated 3 times, the average value of the 3 measurements was taken. The "unit mainly composed of a monomer" means an atomic group mainly composed of the aforementioned monomer formed by polymerization of a monomer. The unit may be a unit formed directly by a polymerization reaction, or may be a unit in which a part of the aforementioned unit is converted into another structure by treating the polymer. Hereinafter, the unit mainly composed of the monomer a is also simply referred to as "the monomer a unit".

本發明片材(以下亦表記為「本片材」)包含：未燒成之聚四氟乙烯(以下亦將聚四氟乙烯表記為「PTFE」，且將未燒成之聚四氟乙烯表記為「未燒成PTFE」)、無機粒子及樹脂(以下亦表記為「本樹脂」)，且該樹脂具有選自於由含羰基之基團、含羥基之基團、環氧基及胺基所構成群組中之至少1種官能基；並且，未燒成PTFE、無機粒子及本樹脂之總含量為90質量%以上。換言之，本片材係一將未燒成PTFE、無機粒子及本樹脂作為主成分的自支撐膜狀片材。The sheet of the present invention (hereinafter also referred to as "this sheet") includes: unfired polytetrafluoroethylene (hereinafter also referred to as "PTFE" for polytetrafluoroethylene, and the expression of unfired polytetrafluoroethylene is "unfired PTFE"), inorganic particles and resin (hereinafter also referred to as "this resin"), and the resin has a group selected from carbonyl-containing groups, hydroxyl-containing groups, epoxy groups and amino groups At least one functional group in the formed group; and, the total content of unfired PTFE, inorganic particles, and this resin is 90% by mass or more. In other words, this sheet is a self-supporting film-like sheet mainly composed of unfired PTFE, inorganic particles and this resin.

吾等認為，本片材中，具有前述官能基之本樹脂會與無機粒子相互作用，藉此，不僅可抑制無機粒子的凝集、促進無機粒子在片材中均一分散，還能作為黏結劑成分強固載持未燒成PTFE與無機粒子。換言之，本片材係以本樹脂為基質，且具有本樹脂中強固保持有未燒成PTFE與無機粒子並且該等均一分散於其中之結構。結果，本片材能抑制無機粒子之剝落，高度展現PTFE與無機粒子兩者之物性，從而提升物理性強度。且，藉由含有具有本官能基之本樹脂，本片材還具有優異之與金屬箔等其他基材的親和性，從而提升其接著性。We believe that in this sheet, the resin with the aforementioned functional groups will interact with the inorganic particles, thereby not only inhibiting the aggregation of the inorganic particles, promoting the uniform dispersion of the inorganic particles in the sheet, but also serving as a binder component Strongly support unfired PTFE and inorganic particles. In other words, this sheet is based on this resin, and has a structure in which unfired PTFE and inorganic particles are firmly held in this resin and dispersed uniformly therein. As a result, this sheet can suppress the peeling of inorganic particles, and highly exhibit the physical properties of both PTFE and inorganic particles, thereby improving physical strength. Moreover, by containing the resin with this functional group, this sheet also has excellent affinity with other substrates such as metal foil, thereby improving its adhesiveness.

本發明中之PTFE可為TFE之均聚物，亦可為極微量之全氟(烷基乙烯基醚)(以下亦表記為「PAVE」)、六氟丙烯(以下亦表記為「HFP」)、氟烷基乙烯等共聚單體與TFE的共聚物，即所謂的改質PTFE。PTFE中之TFE單元的比率宜在全部單元中為99.5莫耳%以上，較宜為99.9莫耳%以上。The PTFE in the present invention can be a homopolymer of TFE, or a very small amount of perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE"), hexafluoropropylene (hereinafter also referred to as "HFP") , fluoroalkylethylene and other comonomers and copolymers of TFE, the so-called modified PTFE. The ratio of TFE units in PTFE is preferably at least 99.5 mole %, more preferably at least 99.9 mole %, in all units.

PTFE宜為根據下式(1)算出之數量平均分子量Mn為20萬以上之PTFE。 Mn=2.1×10 ¹⁰×ΔHc ^-5 ^. ¹⁶・・・ (1) 式(1)中，Mn表示PTFE之數量平均分子量，ΔHc表示PTFE藉由示差掃描熱量分析法測定之結晶化熱量(cal/g)。 PTFE is preferably PTFE having a number average molecular weight Mn calculated from the following formula (1) of 200,000 or more. Mn=2.1×10 ¹⁰ ×ΔHc ^-5 ^. ¹⁶・・・ (1) In formula (1), Mn represents the number average molecular weight of PTFE, and ΔHc represents the heat of crystallization of PTFE measured by differential scanning calorimetry (cal/ g).

本發明中之未燒成PTFE意指在藉由聚合製造後未暴露於PTFE之熔融溫度以上之溫度下的PTFE。又，燒成PTFE意指在藉由聚合製造後有暴露於PTFE之熔融溫度以上之溫度下的PTFE。此外，在本說明書中，PTFE之熔融溫度設為327℃。Unfired PTFE in the present invention means PTFE that has not been exposed to a temperature above the melting temperature of PTFE after being produced by polymerization. Also, fired PTFE means PTFE exposed to a temperature higher than the melting temperature of PTFE after being produced by polymerization. In addition, in this specification, the melting temperature of PTFE is set to 327 degreeC.

未燒成PTFE可為原纖維狀，亦可為非原纖維狀，宜為原纖維狀。未燒成PTFE若為原纖維狀，在本片材中未燒成PTFE便容易載持無機粒子，使無機粒子不易從本片材剝落。且，未燒成PTFE變得容易與無機粒子或本樹脂纏繞，而容易提升本片材之韌性。換言之，原纖維狀之未燒成PTFE亦可看作容易與無機粒子或本樹脂聚結。The unfired PTFE may be fibrillated or non-fibrillated, and fibrillated is preferable. If the unfired PTFE is in the form of fibrils, the unfired PTFE will easily support the inorganic particles in the sheet, and the inorganic particles will not be easily peeled off from the sheet. In addition, unfired PTFE becomes easy to be entangled with inorganic particles or this resin, and it is easy to improve the toughness of this sheet. In other words, unfired PTFE in the form of fibrils can be easily aggregated with inorganic particles or the present resin.

本片材中之未燒成PTFE宜以粒狀存在。此時，未燒成PTFE之粒子宜為與後述液態組成物中所含之未燒成PTFE之粒子相同的粒子。未燒成PTFE可為藉由乳化聚合法所得之PTFE，亦可為藉由懸濁聚合法所得之PTFE。由結晶度小、容易提高片材之韌性的觀點來看，宜為藉由乳化聚合法所得之PTFE。 The unfired PTFE in this sheet is preferably present in granular form. In this case, the particles of unfired PTFE are preferably the same particles as the particles of unfired PTFE contained in the liquid composition described later. Unfired PTFE may be PTFE obtained by emulsion polymerization or PTFE obtained by suspension polymerization. From the viewpoint of low crystallinity and easy improvement of the toughness of the sheet, PTFE obtained by emulsion polymerization is preferable.

本發明中之無機粒子之形狀宜為球狀、針狀或板狀，較宜為球狀、鱗片狀或層狀，更宜為球狀或鱗片狀。球狀無機粒子宜為大致真球狀。所謂大致真球狀，意指在藉由掃描型電子顯微鏡(SEM)觀察無機粒子時，短徑相對於長徑的比為0.7以上。大致真球狀無機粒子所佔之比率宜為95%以上。非球狀無機粒子之高寬比宜為2以上，且宜為5以上。高寬比宜為10000以下。 The shape of the inorganic particles in the present invention is preferably spherical, needle-like or plate-like, more preferably spherical, scaly or layered, more preferably spherical or scaly. The spherical inorganic particles are preferably substantially spherical. The term "substantially spherical" means that when the inorganic particles are observed with a scanning electron microscope (SEM), the ratio of the short axis to the long axis is 0.7 or more. The proportion of roughly true spherical inorganic particles is preferably 95% or more. The aspect ratio of the non-spherical inorganic particles is preferably 2 or more, and preferably 5 or more. The aspect ratio should be less than 10000.

無機粒子亦可為中空狀。此時，本片材容易具有優異之電特性。無機粒子為包含至少1種無機物的粒子，宜為包含碳、無機氮化物或無機氧化物的粒子。無機物之具體例可列舉：碳、氮化硼、氮化鋁、氧化鈹、二氧化矽、矽灰石、滑石、氧化鈰、氧化鋁、氧化鎂、氧化鋅及二氧化鈦。由提升本片材之電特性與低線膨脹性的觀點來看，無機粒子宜為包含選自於由二氧化矽、氮化硼及二氧化鈦所構成群組中之至少1種無機物的粒子。二氧化矽宜為非晶質二氧化矽。氮化硼宜為六方晶氮化硼。二氧化鈦宜為金紅石二氧化鈦。 Inorganic particles may also be hollow. In this case, the present sheet tends to have excellent electrical characteristics. The inorganic particles are particles containing at least one type of inorganic substance, and are preferably particles containing carbon, inorganic nitrides, or inorganic oxides. Specific examples of inorganic substances include carbon, boron nitride, aluminum nitride, beryllium oxide, silicon dioxide, wollastonite, talc, cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, and titanium dioxide. From the viewpoint of improving the electrical characteristics and low linear expansion of the present sheet, the inorganic particles are preferably particles containing at least one inorganic substance selected from the group consisting of silicon dioxide, boron nitride, and titanium dioxide. Silica is preferably amorphous silica. Boron nitride is preferably hexagonal boron nitride. The titanium dioxide is preferably rutile titanium dioxide.

無機粒子之D50宜為20µm以下，較宜為10µm以下。D50宜為0.01µm以上，較宜為0.1µm以上。無機粒子之比表面積宜為1至20m ²/g。 The D50 of inorganic particles is preferably less than 20 µm, more preferably less than 10 µm. D50 is preferably not less than 0.01 µm, more preferably not less than 0.1 µm. The specific surface area of the inorganic particles is preferably 1 to 20 m ² /g.

無機粒子之表面亦可經以矽烷耦合劑進行表面處理。此時，無機粒子、未燒成PTFE及本樹脂之親和性會提升，從而無機粒子不易從本片材剝落。且，本片材容易具有優異之電特性與低線膨脹性。矽烷耦合劑宜為：3-胺丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷等具有官能基之矽烷耦合劑。 The surface of the inorganic particles can also be treated with a silane coupling agent. At this time, the affinity between the inorganic particles, the unfired PTFE, and the present resin increases, so that the inorganic particles are less likely to peel off from the present sheet. Moreover, the present sheet is easy to have excellent electrical characteristics and low linear expansion. The silane coupling agent is preferably: 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane and other silane coupling agents with functional groups.

包含二氧化矽之粒子的具體例可舉「Admafine」系列(Admatechs公司製)、「SFP」系列(Denka公司製)、「E-SPHERES」系列(太平洋水泥公司製)。包含氧化鈦之粒子的具體例可舉「TIPAQUE」系列(石原產業公司製)、「JMT」系列(Tayca公司製)。包含氮化硼之粒子的具體例可舉「UHP」系列(昭和電工公司製)、「Denka Boron Nitride」系列之「GP」、「HGP」等級(Denka公司製)。 Specific examples of particles containing silica include "Admafine" series (manufactured by Admatechs), "SFP" series (manufactured by Denka), and "E-SPHERES" series (manufactured by Pacific Cement). Specific examples of particles containing titanium oxide include "TIPAQUE" series (manufactured by Ishihara Sangyo Co., Ltd.) and "JMT" series (manufactured by Tayca Corporation). Specific examples of particles containing boron nitride include "UHP" series (manufactured by Showa Denko), "GP" and "HGP" grades of "Denka Boron Nitride" series (manufactured by Denka).

無機粒子可使用1種，亦可使用2種以上。例如，亦可併用二氧化矽粒子、氮化硼粒子及二氧化鈦粒子作為無機粒子。此時，無機粒子之總量中二氧化矽粒子、氮化硼粒子及二氧化鈦粒子各自所佔之含量，按順序宜為10至60質量%、10至60質量%、5至40質量%。One type of inorganic particles may be used, or two or more types may be used. For example, silica particles, boron nitride particles, and titanium dioxide particles may be used together as inorganic particles. In this case, the respective contents of silicon dioxide particles, boron nitride particles and titanium dioxide particles in the total amount of inorganic particles are preferably 10 to 60% by mass, 10 to 60% by mass, and 5 to 40% by mass in that order.

本樹脂為具有選自於由含羰基之基團、含羥基之基團、環氧基及胺基所構成群組中之至少1種官能基(以下亦表記為「本官能基」)的樹脂，宜為選自於由下述樹脂所構成群組中之至少1種之具有本官能基的樹脂：氟樹脂、液晶性芳香族聚酯等之聚酯樹脂、醯亞胺樹脂、環氧樹脂、馬來醯亞胺樹脂、胺甲酸乙酯樹脂、聚苯醚樹脂、聚氧化苯樹脂及聚伸苯硫醚樹脂。This resin is a resin having at least one functional group selected from the group consisting of carbonyl-containing groups, hydroxyl-containing groups, epoxy groups, and amine groups (hereinafter also referred to as "this functional group") , preferably at least one resin having this functional group selected from the group consisting of the following resins: fluororesins, polyester resins such as liquid crystalline aromatic polyesters, imide resins, epoxy resins , Maleimide resin, urethane resin, polyphenylene ether resin, polyphenylene oxide resin and polyphenylene sulfide resin.

含羥基之基團係含有羥基之基，宜為含有醇性羥基之基。含羰基之基團係含有羰基之基，可列舉：羧基、烷氧羰基、醯胺基、異氰酸酯基、胺甲酸酯基(-OC(O)NH ₂)、酸酐殘基(-C(O)OC(O)-)、醯亞胺殘基(-C(O)NHC(O)-等)及碳酸酯基(-OC(O)O-)，宜為羧基、醯胺基、醯亞胺殘基或酸酐殘基。 The hydroxyl-containing group is a group containing a hydroxyl group, preferably a group containing an alcoholic hydroxyl group. The carbonyl-containing group is a group containing a carbonyl group, such as: carboxyl group, alkoxycarbonyl group, amide group, isocyanate group, carbamate group (-OC(O)NH ₂ ), acid anhydride residue (-C(O) )OC(O)-), imide residues (-C(O)NHC(O)-, etc.) and carbonate groups (-OC(O)O-), preferably carboxyl, amido, amido Amine residues or anhydride residues.

本樹脂宜包含下述中之至少任一者：具有本官能基之熱熔融性四氟乙烯系聚合物(以下亦表記為「F聚合物」)；或者，具有前述本官能基之芳香族聚合物或前述芳香族聚合物之前驅物(以下亦將前述芳香族聚合物或前述前驅物表記為「AR聚合物」)，較宜包含F聚合物與AR聚合物。This resin preferably contains at least one of the following: hot-melt tetrafluoroethylene polymers with this functional group (hereinafter also referred to as "F polymers"); or, aromatic polymers with the aforementioned functional groups or the precursor of the aforementioned aromatic polymer (the aforementioned aromatic polymer or the aforementioned precursor is also referred to as "AR polymer" hereinafter), preferably including F polymer and AR polymer.

F聚合物之熔融溫度宜為200℃以上，更宜為260℃以上。F聚合物之熔融溫度宜為325℃以下，較宜為320℃以下。此時，本片材容易具有優異之耐熱性與低線膨脹性、加工性。 F聚合物之玻璃轉移點宜為50℃以上，較宜為75℃以上。F聚合物之玻璃轉移點宜為150℃以下，較宜為125℃以下。 F聚合物之氟含量宜為70質量%以上，較宜為72至76質量%。此時，F聚合物與未燒成PTFE更容易相互作用。 F聚合物之表面張力宜為16至26mN/m。此外，F聚合物之表面張力可將濕潤指數試藥(和光純藥公司製)之液滴載置於以F聚合物製作之平板上來測定。 The melting temperature of the F polymer is preferably above 200°C, more preferably above 260°C. The melting temperature of F polymer is preferably below 325°C, more preferably below 320°C. In this case, the present sheet is likely to have excellent heat resistance, low linear expansion, and processability. The glass transition point of the F polymer is preferably above 50°C, more preferably above 75°C. The glass transition point of the polymer F is preferably below 150°C, more preferably below 125°C. The fluorine content of the F polymer is preferably at least 70% by mass, more preferably 72 to 76% by mass. At this time, the F polymer interacts more easily with the unfired PTFE. The surface tension of the F polymer is preferably 16 to 26 mN/m. In addition, the surface tension of the F polymer can be measured by placing a droplet of a wettability index reagent (manufactured by Wako Pure Chemical Industries, Ltd.) on a flat plate made of the F polymer.

F聚合物宜為：包含TFE單元與以乙烯為主體之單元的聚合物、包含TFE單元與以丙烯為主體之單元的聚合物、包含TFE單元與以PAVE為主體之單元(PAVE單元)的聚合物(PFA)、包含TFE單元與以HFP為主體之單元的聚合物(FEP)，較宜為PFA及FEP，更宜為PFA。該等聚合物亦可更包含以其他共聚單體為主體之單元。The F polymer is preferably: a polymer comprising TFE units and ethylene-based units, a polymer comprising TFE units and propylene-based units, a polymer comprising TFE units and PAVE-based units (PAVE units) (PFA), a polymer (FEP) comprising TFE units and HFP-based units, preferably PFA and FEP, more preferably PFA. These polymers may further comprise units based on other comonomers.

PAVE宜為CF ₂=CFOCF ₃、CF ₂=CFOCF ₂CF ₃及CF ₂=CFOCF ₂CF ₂CF ₃(以下亦表記為「PPVE」)，較宜為PPVE。作為F聚合物具有之官能基，宜為含羥基之基團或含羰基之基團，更宜為含羰基之基團。此時，F聚合物與未燒成PTFE或無機粒子之相互作用不僅會更提高，還容易提升本片材之接著性。 PAVE is preferably CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ and CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter also denoted as "PPVE"), more preferably PPVE. The functional group contained in the F polymer is preferably a hydroxyl-containing group or a carbonyl-containing group, more preferably a carbonyl-containing group. At this time, the interaction between F polymer and unfired PTFE or inorganic particles will not only be improved, but also the adhesiveness of the sheet will be easily improved.

F聚合物具有之含羥基之基團宜為-CF ₂CH ₂OH及C(CF ₃) ₂OH。 F聚合物具有之含羰基之基團宜為：羧基、烷氧羰基、醯胺基、異氰酸酯基、胺甲酸酯基、酸酐殘基、醯亞胺殘基或碳酸酯基，較宜為酸酐殘基。 The hydroxyl-containing groups of the polymer F are preferably -CF ₂ CH ₂ OH and C(CF ₃ ) ₂ OH. The carbonyl-containing group of F polymer is preferably: carboxyl group, alkoxycarbonyl group, amido group, isocyanate group, urethane group, acid anhydride residue, imide residue or carbonate group, preferably acid anhydride Residues.

F聚合物具有含羥基之基團或含羰基之基團時，F聚合物中含羥基之基團或含羰基之基團之數量以主鏈碳數計，每1×10 ⁶個主鏈碳數宜為10至5000個，較宜為100至3000個。此外，F聚合物中含羥基之基團或含羰基之基團之數量可藉由聚合物之組成或國際公開第2020/145133號中記載之方法來定量。 When the F polymer has a hydroxyl-containing group or a carbonyl-containing group, the number of the hydroxyl-containing group or carbonyl-containing group in the F polymer is calculated by the carbon number of the main chain, per 1×10 ⁶ main chain carbons The number is preferably 10 to 5000, more preferably 100 to 3000. In addition, the number of hydroxyl-containing groups or carbonyl-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.

F聚合物具有之本官能基可包含於F聚合物中以單體為主體之單元中，亦可包含於F聚合物之主鏈的末端基中，宜為前者。後者之態樣可舉：具有含氧極性基作為源自聚合引發劑、鏈轉移劑等之末端基的F聚合物、對F聚合物進行電漿處理或游離射線處理而得之F聚合物。具有含羰基之基團的單體宜為伊康酸酐、檸康酸酐及5-降𦯉烯-2,3-二羧酸酐(以下亦表記為「NAH」)，較宜為NAH。 The functional group possessed by the F polymer may be contained in the monomer-based unit of the F polymer, or may be contained in the terminal group of the main chain of the F polymer, and the former is preferable. Examples of the latter include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, and the like, and an F polymer obtained by subjecting the F polymer to plasma treatment or ion ray treatment. The monomer having a carbonyl-containing group is preferably itaconic anhydride, citraconic anhydride, and 5-northene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), more preferably NAH.

F聚合物宜為包含TFE單元及PAVE單元之具有含羰基之基團的聚合物，更宜為下述聚合物：包含TFE單元、PAVE單元及以具有含羰基之基團的單體為主體之單元，且相對於全部單元，按順序以90至99莫耳%、0.99至9.97莫耳%、0.01至3莫耳%包含該等單元。該F聚合物之具體例可舉國際公開第2018/16644號中記載之聚合物。The F polymer is preferably a polymer with a carbonyl-containing group comprising a TFE unit and a PAVE unit, more preferably the following polymer: a monomer comprising a TFE unit, a PAVE unit, and a monomer with a carbonyl-containing group units, and contain these units at 90 to 99 mol%, 0.99 to 9.97 mol%, 0.01 to 3 mol%, in order, relative to the total units. Specific examples of the F polymer include polymers described in International Publication No. 2018/16644.

本片材中之F聚合物之形狀可為粒狀，亦可為非粒狀。F聚合物亦可與未燒成PTFE或無機粒子聚結。F聚合物為粒狀時，作為F聚合物之粒子宜為與後述之亦可包含於液態組成物中之F聚合物之粒子相同的粒子。The shape of the F polymer in this sheet can be granular or non-granular. F polymers can also be coalesced with unfired PTFE or inorganic particles. When the F polymer is in the form of particles, the particles of the F polymer are preferably the same as the particles of the F polymer that may be contained in the liquid composition described later.

AR聚合物可為熱硬化性，亦可為熱塑性。作為AR聚合物具有之官能基，宜為胺基或含羰基之基團，較宜為選自於由胺基、醯胺基、羧基及醯亞胺殘基所構成群組中之至少1種。此時，AR聚合物與未燒成PTFE或無機粒子之相互作用不僅更提高，還容易提升本片材之接著性。 AR聚合物可列舉：芳香族聚醯亞胺、聚醯胺酸或屬其鹽的芳香族聚醯亞胺前驅物、芳香族聚醯胺醯亞胺、芳香族聚醯胺醯亞胺前驅物、芳香族聚醚醯亞胺、芳香族聚醚醯亞胺前驅物，較宜為芳香族聚醯亞胺、聚醯胺酸或屬其鹽的芳香族聚醯亞胺前驅物、芳香族聚醯胺醯亞胺或芳香族聚醯胺醯亞胺前驅物。 AR polymers can be thermosetting or thermoplastic. The functional group of the AR polymer is preferably an amine group or a carbonyl-containing group, preferably at least one selected from the group consisting of an amine group, an amido group, a carboxyl group, and an imide residue. . At this time, the interaction between AR polymer and unfired PTFE or inorganic particles is not only improved, but also the adhesiveness of the sheet is easily improved. Examples of AR polymers include aromatic polyimides, polyamide acids or their salts, aromatic polyamide imide precursors, aromatic polyamide imides, and aromatic polyamide imide precursors. , aromatic polyetherimide, aromatic polyetherimide precursor, preferably aromatic polyimide, polyamic acid or its salt aromatic polyimide precursor, aromatic polyimide Amidoimide or aromatic polyamidoimide precursor.

AR聚合物亦可為水溶性。水溶性AR聚合物可舉水溶性芳香族聚醯亞胺前驅物、水溶性聚醯胺醯亞胺、其前驅物。水溶性芳香族聚醯亞胺前驅物可舉使二胺與四甲酸二酐聚合而成之聚醯胺酸及其鹽。水溶性芳香族聚醯胺醯亞胺或其前驅物可舉使二異氰酸酯或二胺之至少一者與三元酸酐反應所得之聚醯胺醯亞胺或其前驅物。 AR polymers can also be water soluble. Examples of the water-soluble AR polymer include water-soluble aromatic polyimide precursors, water-soluble polyamideimides, and precursors thereof. Examples of the water-soluble aromatic polyimide precursor include polyamic acid and its salts obtained by polymerizing diamine and tetracarboxylic dianhydride. Examples of the water-soluble aromatic polyamide-imide or its precursor include polyamide-imide or its precursor obtained by reacting at least one of diisocyanate or diamine with a tribasic acid anhydride.

四甲酸二酐可舉焦蜜石酸酐、聯苯四甲酸酐。二胺可舉苯二胺、3,3'-二甲基聯苯-4,4'-二胺、4,4'-二胺二苯甲烷、4,4'-二胺二苯基醚。二異氰酸酯可舉4,4'-二苯甲烷二異氰酸酯、伸茬基二異氰酸酯、3,3'-二甲基聯苯-4,4'-二異氰酸酯、3,3'-二苯甲烷二異氰酸酯。 Tetraformic dianhydride includes pyromellitic anhydride and biphenyltetracarboxylic anhydride. Examples of diamine include phenylenediamine, 3,3'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminediphenylmethane, and 4,4'-diaminediphenylether. Diisocyanates include 4,4'-diphenylmethane diisocyanate, stubble diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-diphenylmethane diisocyanate .

AR聚合物之數量平均分子量(Mn)宜為5000至50000。 AR聚合物之酸價宜為20至100mg/KOH。此外，AR聚合物之酸價係藉由使用0.05莫耳/L的乙醇性氫氧化鉀溶液的電位差滴定裝置，對AR聚合物0.5g、1,4-二氮雜雙環[2.2.2]辛烷0.15g、N-甲基-2-吡咯啶酮60g及離子交換水1mL之混合溶液進行滴定來求得。此外，AR聚合物具有酸酐基時，係將已使酸酐基開環後之酸價作為AR聚合物的酸價。 The AR polymer preferably has a number average molecular weight (Mn) of 5,000 to 50,000. The acid value of the AR polymer is preferably 20 to 100 mg/KOH. In addition, the acid value of the AR polymer was determined by using a potentiometric titration device using a 0.05 mol/L ethanolic potassium hydroxide solution for 0.5 g of the AR polymer, 1,4-diazabicyclo[2.2.2]octane It can be obtained by titrating a mixed solution of 0.15 g of alkanes, 60 g of N-methyl-2-pyrrolidone, and 1 mL of ion-exchanged water. In addition, when the AR polymer has an acid anhydride group, the acid value after ring-opening the acid anhydride group is used as the acid value of the AR polymer.

AR聚合物之具體例可列舉：「UPIA-AT」系列(宇部興產公司製)、「Neopulim(註冊商標)」系列(MITSUBISHI GAS CHEMICAL公司製)、「SPIXAREA(註冊商標)」系列(SOMAR公司製)、「Q-PILON(註冊商標)」系列(PI技術研究所製)、「WINGO」系列(Wingo Technology公司製)、「Tohmide(註冊商標)」系列(T&K TOKA公司製)、「KPI-MX」系列(河村產業公司製)、「HPC-1000」、「HPC-2100D」(皆為SHOWA DENKO MATERIALS公司製)。在本片材中，AR聚合物可為粒狀，亦可為非粒狀，宜為非粒狀。AR聚合物亦可與未燒成PTFE及無機粒子聚結。 Specific examples of AR polymers include: "UPIA-AT" series (manufactured by Ube Industries, Ltd.), "Neopulim (registered trademark)" series (manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.), "SPIXAREA (registered trademark)" series (manufactured by SOMAR Co., Ltd. ), "Q-PILON (registered trademark)" series (manufactured by PI Technology Research Institute), "WINGO" series (manufactured by Wingo Technology), "Tohmide (registered trademark)" series (manufactured by T&K TOKA), "KPI- MX" series (produced by Kawamura Sangyo Co., Ltd.), "HPC-1000", "HPC-2100D" (both produced by SHOWA DENKO MATERIALS Co., Ltd.). In this sheet, the AR polymer may be granular or non-granular, preferably non-granular. AR polymers can also be coalesced with unfired PTFE and inorganic particles.

本片材中之本樹脂宜包含下述中之任一者：F聚合物與具有本官能基之芳香族聚合物；F聚合物與具有本官能基之芳香族聚合物的前驅物；或F聚合物、具有本官能基之芳香族聚合物及具有本官能基之芳香族聚合物的前驅物。此時，來自本樹脂之強固的基質會形成於本片材中，而容易於其中強固且均一地載持未燒成PTFE與無機粒子，從而更容易提升本片材之物性與接著性。尤其若本樹脂包含F聚合物與AR聚合物兩者時，由於與PTFE親和性高之F聚合物高度地載持未燒成PTFE，且同時AR聚合物能提高成分間的黏結效果，因此該傾向容易變明顯。且，本樹脂包含F聚合物與AR聚合物兩者時，於本片材中F聚合物與AR聚合物亦可形成交聯物。The resin in this sheet preferably includes any one of the following: F polymer and aromatic polymer with this functional group; F polymer and the precursor of aromatic polymer with this functional group; or F The polymer, the aromatic polymer with the functional group and the precursor of the aromatic polymer with the functional group. At this time, a strong matrix from the resin will be formed in the sheet, and unfired PTFE and inorganic particles can be supported therein strongly and uniformly, so that the physical properties and adhesiveness of the sheet can be improved more easily. Especially if this resin contains both F polymer and AR polymer, because the F polymer with high affinity to PTFE can highly support unfired PTFE, and at the same time, the AR polymer can improve the bonding effect between the components, so the Tendencies are easy to become apparent. Moreover, when the present resin contains both the F polymer and the AR polymer, the F polymer and the AR polymer may also form a cross-linked product in the present sheet.

本片材中之未燒成PTFE、無機粒子及本樹脂的總含量為90質量%以上，宜為95質量%以上。總含量的上限為100質量%。換言之，在本片材中，與未燒成PTFE、無機粒子及本樹脂不同之成分的含量小於10質量%，宜為5質量%以下。所謂不同成分可舉例如強化纖維等。前述不同成分之含量的下限為0質量%。藉由上述作用機構，即使在所述成分含有比率下，本片材亦具有優異之柔軟性、韌性等之物性，且可以高度平衡展現PTFE及無機粒子各自的物性。The total content of unfired PTFE, inorganic particles, and the present resin in the sheet is at least 90% by mass, preferably at least 95% by mass. The upper limit of the total content is 100% by mass. In other words, in this sheet, the content of components other than unfired PTFE, inorganic particles, and this resin is less than 10% by mass, preferably 5% by mass or less. The different components include, for example, reinforcing fibers and the like. The lower limit of the content of the aforementioned different components is 0% by mass. Through the above mechanism, the sheet has excellent physical properties such as flexibility and toughness even at the content ratio of the above-mentioned components, and can exhibit the respective physical properties of PTFE and inorganic particles in a high degree of balance.

本片材中未燒成PTFE之含量宜為10質量%以上，較宜為15質量%以上。未燒成PTFE之含量宜為60質量%以下，較宜為40質量%以下。本片材中無機粒子之含量宜為20質量%以上，較宜為40質量%以上。無機粒子之含量宜為80質量%以下，較宜為70質量%以下。 The content of the unfired PTFE in the sheet is preferably at least 10% by mass, more preferably at least 15% by mass. The content of unfired PTFE is preferably not more than 60% by mass, more preferably not more than 40% by mass. The content of the inorganic particles in the sheet is preferably at least 20% by mass, more preferably at least 40% by mass. The content of the inorganic particles is preferably not more than 80% by mass, more preferably not more than 70% by mass.

本片材中，相對於未燒成PTFE之含量與無機粒子之含量之合計，無機粒子之含量之比宜為0.1以上，較宜為0.2以上，更宜為0.3以上。該比宜小於1，較宜為0.8以下，更宜為0.6以下。藉由上述作用機構，前述比即使為所述較高之值，仍容易高度展現片材中之無機粒子之物性。In this sheet, the ratio of the content of the inorganic particles to the sum of the content of the unfired PTFE and the content of the inorganic particles is preferably at least 0.1, more preferably at least 0.2, and more preferably at least 0.3. The ratio is preferably less than 1, more preferably 0.8 or less, more preferably 0.6 or less. With the above-mentioned mechanism, even if the above-mentioned ratio is the above-mentioned high value, it is easy to highly express the physical properties of the inorganic particles in the sheet.

本片材中本樹脂之含量宜為0.1質量%以上，較宜為5質量%以上。本樹脂之含量宜為60質量%以下，較宜為30質量%以下。本片材中，相對於未燒成PTFE之含量與本樹脂之含量之合計，本樹脂之含量之比宜為0.05以上，較宜為0.2以上，更宜為0.5以上。該比宜小於1，較宜為0.5以下。 The content of this resin in the sheet is preferably at least 0.1% by mass, more preferably at least 5% by mass. The content of this resin is preferably not more than 60% by mass, more preferably not more than 30% by mass. In this sheet, the ratio of the content of this resin to the sum of the content of unfired PTFE and the content of this resin is preferably at least 0.05, more preferably at least 0.2, and more preferably at least 0.5. The ratio is preferably less than 1, more preferably 0.5 or less.

本樹脂為F聚合物時，本片材中F聚合物之含量宜為10質量%以上，較宜為15質量%以上。F聚合物之含量宜為60質量%以下，較宜為30質量%以下。本片材中AR聚合物之含量宜為0.1質量%以上，較宜為1質量%以上。AR聚合物之含量宜為10質量%以下，較宜為5質量%以下。本樹脂包含F聚合物與AR聚合物兩者時，本樹脂中，相對於F聚合物之含量與AR聚合物之含量之合計，F聚合物之含量之比宜為0.6以上，較宜為0.9以上。該比宜小於1，較宜為0.99以下。 When the resin is an F polymer, the content of the F polymer in the sheet is preferably at least 10% by mass, more preferably at least 15% by mass. The content of the F polymer is preferably not more than 60% by mass, more preferably not more than 30% by mass. The content of the AR polymer in the sheet is preferably at least 0.1% by mass, more preferably at least 1% by mass. The content of the AR polymer is preferably not more than 10% by mass, more preferably not more than 5% by mass. When the resin contains both the F polymer and the AR polymer, the ratio of the F polymer content to the sum of the F polymer content and the AR polymer content in the resin is preferably 0.6 or more, more preferably 0.9 above. The ratio is preferably less than 1, more preferably 0.99 or less.

本片材中未燒成PTFE、無機粒子及本樹脂之含量為所述範圍時，更容易展現上述作用機構。本片材亦可在小於10質量%的範圍內進一步包含後述之其他成分：液態潤滑劑、液態分散介質、凝集劑、非離子性界面活性劑、pH調整劑及pH緩衝劑、或有機粒子、有機顏料、金屬皂、潤滑劑、有機單體、聚合度50以下之有機寡聚物等之有機物、觸變性賦予劑、黏度調節劑、消泡劑、矽烷耦合劑、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、阻燃劑等。 When the contents of the unfired PTFE, inorganic particles, and the resin in this sheet are in the above-mentioned ranges, it is easier to exhibit the above-mentioned mechanism of action. This sheet can also further include other components described below within a range of less than 10% by mass: liquid lubricant, liquid dispersion medium, coagulant, nonionic surfactant, pH regulator and pH buffer, or organic particles, Organic pigments, metal soaps, lubricants, organic monomers, organic oligomers with a polymerization degree of 50 or less, thixotropy imparting agents, viscosity regulators, defoamers, silane coupling agents, dehydrating agents, plasticizers, Weather resistance agent, antioxidant, heat stabilizer, slip agent, antistatic agent, whitening agent, colorant, conductive agent, release agent, surface treatment agent, flame retardant, etc.

本片材之厚度宜為50µm以上，較宜為100µm以上。本片材之厚度宜為1000µm以下，較宜為500µm以下。藉由上述作用機構，即使在所述厚度下，本片材仍具有優異之韌性等物理性強度。本片材之拉伸強度宜為200MPa以上，較宜為300MPa以上。本片材之拉伸強度宜為800MPa以下。此外，拉伸強度可使用TENSILON(TOYO BALDWIN CO., LTD.製，型號：UTM-5T)，在荷重元額定稱量為5000kg、夾頭間距離為110mm、速度為10mm/分鐘之條件下進行測定。 The thickness of the sheet is preferably at least 50 µm, more preferably at least 100 µm. The thickness of the sheet is preferably not more than 1000 µm, more preferably not more than 500 µm. With the above mechanism, the sheet still has excellent physical strength such as toughness even at the above-mentioned thickness. The tensile strength of the sheet is preferably above 200MPa, more preferably above 300MPa. The tensile strength of this sheet is preferably below 800MPa. In addition, the tensile strength can be measured using TENSILON (manufactured by TOYO BALDWIN CO., LTD., model: UTM-5T) under the conditions of a load cell with a rated weighing capacity of 5000kg, a distance between chucks of 110mm, and a speed of 10mm/min. Determination.

本片材宜為將包含未燒成PTFE之粒子、無機粒子及本樹脂之液態組成物(以下亦表記為「本組成物」)進行流延而得者。此外，所謂流延意指將有流動性之組成物攤開，流延可藉由如後述之方法進行。本組成物中之未燒成PTFE之粒子之D50宜為10µm以下，較宜為1µm以下。未燒成PTFE之粒子之D50宜為0.1µm以上。又，未燒成PTFE之粒子之D90宜為20µm以下。此時，未燒成PTFE、無機粒子及本樹脂容易相互作用，而容易獲得成分分布之均一性優異的本片材。本組成物中之無機粒子宜為與上述本片材中所含之無機粒子相同的無機粒子。 This sheet is preferably obtained by casting a liquid composition (hereinafter also referred to as "this composition") containing unfired PTFE particles, inorganic particles, and this resin. In addition, the so-called casting means spreading a fluid composition, and casting can be performed by a method as described later. The D50 of the unfired PTFE particles in this composition is preferably less than 10 µm, more preferably less than 1 µm. The D50 of unfired PTFE particles should be above 0.1µm. Also, the D90 of unfired PTFE particles is preferably 20 µm or less. In this case, the unfired PTFE, the inorganic particles, and the present resin are likely to interact with each other, and the present sheet having excellent component distribution uniformity is easily obtained. The inorganic particles in this composition are preferably the same as the inorganic particles contained in the above-mentioned sheet.

本組成物中之本樹脂可為粒狀，可為非粒狀，亦可溶解於本組成物中。本樹脂包含F聚合物時，在本組成物中F聚合物宜為粒狀。本組成物中F聚合物之粒子(以下亦表記為「F粒子」)之D50宜為0.1µm以上，較宜為1µm以上。F粒子之D50宜為8µm以下。 F粒子之比表面積宜為1至25m ²/g。此時，F聚合物、未燒成PTFE及無機粒子容易相互作用，而容易獲得成分分布之均一性優異的本片材。 The resin in this composition can be granular or non-granular, and can also be dissolved in this composition. When the present resin contains the F polymer, the F polymer in the present composition is preferably granular. The D50 of the F polymer particles (hereinafter also referred to as "F particles") in this composition is preferably 0.1 µm or more, more preferably 1 µm or more. The D50 of F particles should be below 8µm. The specific surface area of the F particles is preferably 1 to 25 m ² /g. In this case, the F polymer, the unfired PTFE, and the inorganic particles are likely to interact with each other, and the present sheet having excellent component distribution uniformity is easily obtained.

本樹脂包含AR聚合物時，在本組成物中AR聚合物宜為液態、或宜溶解於後述液態分散介質中。此時，AR聚合物容易作為未燒成PTFE及無機粒子的黏結劑發揮功用，從而容易於本片材中強固地載持未燒成PTFE與無機粒子。未燒成PTFE、無機粒子及本樹脂亦可以互相聚結而成之複合粒子之形態包含於本組成物中。複合粒子亦可形成下述內核-外殼結構：以未燒成PTFE、無機粒子及本樹脂中之任一者為內核，且以未燒成PTFE、無機粒子及本樹脂中之任一者中未包含於內核之成分為外殼。 When the present resin contains an AR polymer, the AR polymer in the present composition is preferably in a liquid state, or is preferably dissolved in a liquid dispersion medium described later. In this case, the AR polymer is likely to function as a binder for the unfired PTFE and the inorganic particles, and it is easy to support the unfired PTFE and the inorganic particles in this sheet strongly. Unfired PTFE, inorganic particles, and the resin can also be included in the composition in the form of composite particles formed by mutual aggregation. Composite particles can also form the following core-shell structure: any one of unfired PTFE, inorganic particles, and this resin is used as the core, and any one of unfired PTFE, inorganic particles, and this resin is used as the core. The components contained in the inner core are called the outer shell.

本組成物宜將未燒成PTFE之粒子、無機粒子、本樹脂及液態潤滑劑混合而得，較宜將未燒成PTFE之粒子、無機粒子及本樹脂之凝集體與液態潤滑劑混合而得。此時，在本片材中各成分容易均一地分散。本組成物可藉由從包含有未燒成PTFE之粒子、無機粒子及本樹脂、與液態分散介質或液態潤滑劑的狀態餾去液態分散介質而得，亦可藉由於包含未燒成PTFE之粒子、無機粒子及本樹脂且不包含液態分散介質或液態潤滑劑等之液態成分的混合粉體中加入微量的前述液態成分而得。 This composition is preferably obtained by mixing unfired PTFE particles, inorganic particles, this resin and a liquid lubricant, preferably by mixing unfired PTFE particles, inorganic particles, and aggregates of this resin with a liquid lubricant . In this case, it is easy to uniformly disperse each component in this sheet. This composition can be obtained by distilling off the liquid dispersion medium from the state containing unfired PTFE particles, inorganic particles and this resin, and the liquid dispersion medium or liquid lubricant, or by It is obtained by adding a small amount of the above-mentioned liquid components to the mixed powder of particles, inorganic particles and this resin, which does not contain liquid components such as liquid dispersion medium or liquid lubricant.

液態潤滑劑宜為可藉由加熱、餾去、萃取等手段去除之液態化合物，較宜為可藉由加熱去除且沸點為300℃以下之液態化合物。液態潤滑劑可舉石油腦、白油、液態石蠟、甲苯、二甲苯、己烷、正癸烷、十四烷、十二烷、聚乙二醇，宜為十四烷或十二烷。液態潤滑劑可使用1種，亦可使用2種以上。本組成物中液態潤滑劑之含量宜為10至60質量%，較宜為20至40質量%。 The liquid lubricant is preferably a liquid compound that can be removed by heating, distillation, extraction, etc., more preferably a liquid compound that can be removed by heating and has a boiling point below 300°C. Liquid lubricants can include petroleum naphtha, white oil, liquid paraffin, toluene, xylene, hexane, n-decane, tetradecane, dodecane, polyethylene glycol, preferably tetradecane or dodecane. One type of liquid lubricant may be used, or two or more types may be used. The content of the liquid lubricant in the composition is preferably 10 to 60% by mass, more preferably 20 to 40% by mass.

用以獲得本組成物之混合裝置可列舉：亨氏混合機、加壓捏合機、班布瑞密閉式混合機及行星式混合機等具備槳葉之攪拌裝置；球磨機、磨碎機、籃式磨機、混砂機、砂磨機、Dyno-Mill、DISPERMAT、SC-MILL、釘磨機及攪拌磨機等具備介質之粉碎裝置；微細流體均質機、Nanomizer、Ultimizer、超音波均質機、溶解器、分散機、高速葉輸分散機、薄膜旋轉型高速混合機、自轉公轉攪拌機及V型混合機等具備有其他機構之分散裝置，宜為V型混合機。The mixing device used to obtain this composition can be listed: Heinz mixer, pressurized kneader, Banbury closed mixer and planetary mixer and other mixing devices with paddles; ball mill, attritor, basket mill Mill, sand mixer, sand mill, Dyno-Mill, DISPERMAT, SC-MILL, nail mill and stirring mill and other crushing devices with media; fine fluid homogenizer, Nanomizer, Ultimizer, ultrasonic homogenizer, dissolver , disperser, high-speed impeller disperser, thin film rotary high-speed mixer, self-rotating and revolving mixer, V-type mixer and other dispersing devices with other mechanisms, preferably V-type mixer.

未燒成PTFE之粒子、無機粒子及本樹脂之凝集體可藉由例如從包含未燒成PTFE之粒子、無機粒子、本樹脂及液態分散介質之分散液中去除液態分散介質而得。液態分散介質係在大氣壓下、在25℃下為液體之化合物。液態分散介質可使用1種，亦可使用2種以上。使用2種液態分散介質時，2種液態分散介質宜相互相溶。 Agglomerates of unfired PTFE particles, inorganic particles, and the present resin can be obtained, for example, by removing the liquid dispersion medium from a dispersion containing the unfired PTFE particles, the inorganic particles, the present resin, and the liquid dispersion medium. The liquid dispersion medium is a compound that is liquid at 25°C under atmospheric pressure. One type of liquid dispersion medium may be used, or two or more types may be used. When two liquid dispersion media are used, the two liquid dispersion media should be compatible with each other.

液態分散介質宜為選自於由水、醯胺、酮、酯及乙二醇所構成群組中之化合物。具體上可列舉水、N-甲基-2-吡咯啶酮、γ-丁內酯、甲基乙基酮、環己酮、環戊酮、乙二醇、丙二醇，較宜為水。此時，容易獲得均一分散有未燒成PTFE之粒子、無機粒子及本樹脂之本片材。分散液中液態分散介質之含量宜為40質量%以上，較宜為60質量%以上。液態分散介質之含量宜為90質量%以下，較宜為80質量%以下。 The liquid dispersion medium is preferably a compound selected from the group consisting of water, amide, ketone, ester and glycol. Specifically, water, N-methyl-2-pyrrolidone, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, cyclopentanone, ethylene glycol, and propylene glycol are mentioned, and water is preferable. In this case, it is easy to obtain the present sheet in which unfired PTFE particles, inorganic particles, and the present resin are uniformly dispersed. The content of the liquid dispersion medium in the dispersion is preferably at least 40% by mass, more preferably at least 60% by mass. The content of the liquid dispersion medium is preferably not more than 90% by mass, more preferably not more than 80% by mass.

分散液為了提升分散穩定性，亦可進一步包含非離子性界面活性劑。非離子性界面活性劑宜為乙二醇系界面活性劑、乙炔系界面活性劑、聚矽氧系界面活性劑或氟系界面活性劑，較宜為聚矽氧系界面活性劑。非離子性界面活性劑可使用1種，亦可使用2種以上。使用2種非離子性界面活性劑時，非離子性界面活性劑宜為聚矽氧系界面活性劑與乙二醇系界面活性劑。 The dispersion liquid may further contain a nonionic surfactant in order to improve dispersion stability. The nonionic surfactant is preferably ethylene glycol-based surfactant, acetylene-based surfactant, polysiloxane-based surfactant or fluorine-based surfactant, more preferably polysiloxane-based surfactant. One type of nonionic surfactant may be used, and two or more types may be used. When two types of nonionic surfactants are used, the nonionic surfactants are preferably polysiloxane-based surfactants and glycol-based surfactants.

非離子性界面活性劑之具體例可列舉：「Ftergent」系列(NEOS公司製)、「Surflon」系列(AGC SEIMI CHEMICAL公司製)、「MEGAFACE」系列(DIC公司製)、「UNIDYNE」系列(大金工業公司製)、「BYK-347」、「BYK-349」、「BYK-378」、「BYK-3450」、「BYK-3451」、「BYK-3455」、「BYK-3456」(BYK Japan公司製)、「KF-6011」、「KF-6043」(信越化學工業公司製)、「Tergitol」系列(陶氏化學公司製，「Tergitol TMN-100X」等)。分散液含有非離子性界面活性劑時，分散液中之非離子性界面活性劑之含量宜為1至15質量%。 Specific examples of nonionic surfactants include: "Ftergent" series (manufactured by NEOS), "Surflon" series (manufactured by AGC SEIMI CHEMICAL), "MEGAFACE" series (manufactured by DIC), "UNIDYNE" series (manufactured by Large Gold Industry Co., Ltd.), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (BYK Japan company), "KF-6011", "KF-6043" (Shin-Etsu Chemical Co., Ltd.), "Tergitol" series (Dow Chemical Company, "Tergitol TMN-100X", etc.). When the dispersion contains a nonionic surfactant, the content of the nonionic surfactant in the dispersion is preferably 1 to 15% by mass.

液態分散介質為水時，分散液亦可包含pH調整劑或pH緩衝劑。此時，容易提升分散液之穩定性。pH調整劑可舉胺、氨、檸檬酸。pH緩衝劑可舉參(羥甲基)胺基甲烷、乙二胺四乙酸、碳酸氫銨、碳酸銨、醋酸銨。分散液亦可進一步包含上述之亦可包含於本片材中之其他成分。 When the liquid dispersion medium is water, the dispersion may also contain a pH adjuster or a pH buffer. In this case, it is easy to improve the stability of the dispersion. Examples of pH adjusters include amines, ammonia, and citric acid. Examples of pH buffering agents include (hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium bicarbonate, ammonium carbonate, and ammonium acetate. The dispersion liquid may further contain the above-mentioned other components that may also be contained in the present sheet.

分散液藉由混合未燒成PTFE、無機粒子、本樹脂及液態分散介質來獲得即可。本樹脂包含F聚合物時，分散液宜將包含未燒成PTFE及液態分散介質的混合物與包含無機粒子、F聚合物之粒子及液態分散介質的混合物混合而得。本樹脂包含AR聚合物時，分散液宜將包含未燒成PTFE、AR聚合物及液態分散介質的混合物與無機粒子混合而得。用以獲得分散液之混合裝置可舉與上述之為了獲得本組成物而可使用之混合裝置相同者，宜為行星式混合機。 The dispersion can be obtained by mixing unfired PTFE, inorganic particles, this resin and a liquid dispersion medium. When the resin contains F polymer, the dispersion is preferably obtained by mixing a mixture containing unfired PTFE and a liquid dispersion medium with a mixture containing inorganic particles, F polymer particles, and a liquid dispersion medium. When the resin contains AR polymer, the dispersion is preferably obtained by mixing a mixture containing unfired PTFE, AR polymer and liquid dispersion medium with inorganic particles. The mixing device used to obtain the dispersion can be the same as the above-mentioned mixing device that can be used to obtain the present composition, and is preferably a planetary mixer.

從包含未燒成PTFE、無機粒子、本樹脂及液態分散介質之分散液中去除液態分散介質，可藉由過濾、加熱、餾去等來進行，宜藉由加熱來進行。去除液態分散介質宜藉由下述方式來進行：添加凝集劑至分散液之後，去除液態分散介質並視需要去除凝集劑。藉由加熱進行去除時，加熱溫度宜為液態分散介質與凝集劑之沸點以上。凝集劑宜為一級醇，較宜為甲醇、乙醇、異丙醇及丁醇。相對於分散液中之液態分散介質之含量，一級醇宜添加使質量比成為0.2至1之量。 Removal of the liquid dispersion medium from the dispersion containing unfired PTFE, inorganic particles, the present resin, and the liquid dispersion medium can be carried out by filtration, heating, distillation, etc., preferably by heating. The removal of the liquid dispersion medium is preferably performed by removing the liquid dispersion medium and optionally the coagulant after adding the coagulant to the dispersion. When removing by heating, the heating temperature is preferably above the boiling point of the liquid dispersion medium and the coagulant. The coagulant is preferably primary alcohol, more preferably methanol, ethanol, isopropanol and butanol. The primary alcohol is preferably added in such an amount that the mass ratio becomes 0.2 to 1 relative to the content of the liquid dispersion medium in the dispersion.

本片材宜為將本組成物進行流延而得者。此時，未燒成PTFE容易原纖維化，而容易獲得無機粒子不易剝落之本片材。且，容易獲得具有優異之電特性與韌性的本片材。本組成物之流延宜藉由壓製成形、擠製成形或砑光成形來進行，較宜藉由砑光成形來進行。此外，所謂砑光成形意指使組成物通過複數支輥件間進行軋延之方法。 This sheet is preferably obtained by casting this composition. In this case, the unfired PTFE tends to be fibrillated, and the present sheet in which the inorganic particles do not easily peel off can be easily obtained. Moreover, it is easy to obtain the present sheet having excellent electrical characteristics and toughness. Casting of the present composition is preferably performed by press molding, extrusion molding or calender forming, more preferably by calender forming. In addition, the so-called calendering means a method of rolling a composition through a plurality of rollers.

本組成物之流延可使用1種成形法來進行，亦可組合2種以上成形法來進行。又，流延亦可反覆進行複數次1種成形法。例如，可將本組成物進行擠製成形而得之母片材進一步進行砑光成形來流延，亦可將本組成物進行砑光成形而得之母片材進一步進行砑光成形來流延。此時，容易獲得韌性與均一性優異之任意厚度之本片材。砑光成形之輥件使用複數支即可，宜組合4支來使用。4支輥件的配列方式可舉I型、S型、倒L型、Z型、斜Z型。本組成物之流延可在低於未燒成PTFE之熔融溫度的溫度下邊加熱邊進行，亦可不加熱便進行。 Casting of the present composition may be performed using one molding method, or may be performed in combination of two or more molding methods. In addition, casting can also be performed by repeating one molding method a plurality of times. For example, the master sheet obtained by extruding the composition can be further calendered for casting, and the master sheet obtained by calendering the composition can be further calendered for casting. . In this case, it is easy to obtain the present sheet having an arbitrary thickness excellent in toughness and uniformity. Rolls for calender forming can be used in multiples, and it is advisable to use 4 rolls in combination. The arrangements of the four rollers can be I-shaped, S-shaped, inverted L-shaped, Z-shaped, or inclined Z-shaped. Casting of this composition may be performed at a temperature lower than the melting temperature of unfired PTFE while heating, or may be performed without heating.

本片材亦可將本組成物進行流延而得之流延物互相積層並貼合來獲得。此時，容易提升本片材之韌性。該方法可舉將複數個片狀本組成物之流延物進行積層並軋延之方法。亦可反覆該積層與軋延來調整所得之本片材的厚度或物性。在反覆積層與軋延時，宜變更流延物之流延方向。具體上可舉下述方法：於1片流延物的表面以使其流延方向互相垂直相交之方式疊合，將本組成物進行流延。 This sheet can also be obtained by laminating and laminating casts obtained by casting this composition. In this case, it is easy to improve the toughness of the sheet. As such a method, there may be mentioned a method of laminating and rolling a plurality of casts of the present composition in the form of sheets. It is also possible to adjust the thickness and physical properties of the resulting sheet by repeating the lamination and rolling. During repeated lamination and rolling, it is advisable to change the casting direction of the casting. Specifically, the following method can be mentioned: the surface of one cast product is laminated so that the casting directions are perpendicular to each other, and the present composition is cast.

流延物之積層數宜為10至1000。流延物之流延倍率宜為100至20000倍。此時之流延亦可藉由與將本組成物進行流延之成形法相同之方法來進行，宜藉由砑光成形來進行。 The number of laminated layers of the casting is preferably 10 to 1000. The casting ratio of the cast material is preferably 100 to 20000 times. Casting at this time can also be performed by the same method as the molding method of casting this composition, and it is preferably performed by calender molding.

本組成物包含液態潤滑劑時，本片材宜將本組成物進行流延並去除液態潤滑劑而得。去除液態潤滑劑之方法可舉加熱、餾去及萃取，宜為加熱。液態潤滑劑亦可不完全去除，去除至本片材中之未燒成PTFE、無機粒子及本樹脂之總含量成為90質量%以上、且本片材可以自支撐膜之形態形成片材的程度即可。加熱溫度宜為100至200℃。加熱裝置可舉烘箱、通風乾燥爐。裝置中之熱源可為熱風、加熱板等接觸式熱源，亦可為紅外線等非接觸式熱源。又，各加熱可在常壓下進行，亦可在減壓下進行。又，各加熱中之氣體環境亦可為空氣環境、氦氣、氖氣、氬氣或氮氣等非活性氣體環境中之任一者。 When the composition contains a liquid lubricant, the sheet is preferably obtained by casting the composition and removing the liquid lubricant. Methods for removing liquid lubricants include heating, distillation and extraction, preferably heating. The liquid lubricant may not be completely removed, but it is removed to the extent that the total content of unfired PTFE, inorganic particles, and this resin in this sheet becomes 90% by mass or more, and this sheet can be formed into a sheet in the form of a self-supporting film. Can. The heating temperature is preferably 100 to 200°C. The heating device can be an oven, a ventilated drying furnace. The heat source in the device can be a contact heat source such as hot air, a heating plate, or a non-contact heat source such as infrared rays. In addition, each heating may be performed under normal pressure or under reduced pressure. In addition, the gas environment in each heating may be any one of an air environment, an inert gas environment such as helium, neon, argon, or nitrogen.

若將本片材在PTFE之熔融溫度以上來進行加熱，便可獲得包含經燒成之PTFE的片材(以下亦表記為「燒成片」)。燒成片係與本片材同樣地，其無機粒子不易剝落，且具有優異之電特性、低線膨脹性、物理性強度及與其他材料之接著性。加熱溫度為PTFE之熔融溫度以上，宜為360至400℃。加熱時間宜為0.1至30分鐘。加熱之方法及條件可舉與上述用以去除液態潤滑劑之加熱相同的方法及條件。 If this sheet is heated above the melting temperature of PTFE, a sheet containing fired PTFE (hereinafter also referred to as "fired sheet") can be obtained. The fired sheet is the same as this sheet, its inorganic particles are not easy to peel off, and it has excellent electrical properties, low linear expansion, physical strength and adhesion with other materials. The heating temperature is above the melting temperature of PTFE, preferably 360 to 400°C. The heating time is preferably 0.1 to 30 minutes. The heating method and conditions may be the same as the above-mentioned heating method and conditions for removing the liquid lubricant.

燒成片之厚度宜為50µm以上，較宜為100µm以上。燒成片之厚度宜為500µm以下，較宜為300µm以下。此時，容易使燒成片之機械強度與低線膨脹性、電特性等之物理物性平衡。若將本片材與基材予以熱壓附，便可獲得具有基材層與包含PTFE及無機粒子之聚合物層的積層體。 The thickness of the fired sheet is preferably at least 50 µm, more preferably at least 100 µm. The thickness of the fired sheet is preferably not more than 500µm, more preferably not more than 300µm. In this case, it is easy to balance the mechanical strength of the fired sheet with physical properties such as low linear expansion and electrical properties. If the sheet is bonded to the substrate by heat and pressure, a laminate having a substrate layer and a polymer layer containing PTFE and inorganic particles can be obtained.

基材可列舉：銅、鎳、鋁、鈦、其等合金等之金屬箔等的金屬基板、聚醯亞胺、聚醯胺、聚醚醯胺、聚伸苯硫醚、聚芳基醚酮、聚醯胺醯亞胺、液晶性聚酯及四氟乙烯系聚合物等之耐熱性樹脂膜的耐熱性樹脂膜、屬纖維強化樹脂基板之前驅物的預浸體基板、碳化矽、氮化鋁或氮化矽等的陶瓷基板、玻璃基板。基材之形狀可舉平面狀、曲面狀、凹凸狀。又，基材之形狀亦可為箔狀、板狀、膜狀、纖維狀中之任一者。基材之表面的十點平均粗度宜為0.01至0.05µm。 Substrates include metal substrates such as metal foils of copper, nickel, aluminum, titanium, and alloys thereof, polyimide, polyamide, polyetheramide, polyphenylene sulfide, and polyaryl ether ketone , polyamideimide, liquid crystalline polyester, and heat-resistant resin films of tetrafluoroethylene polymers, etc., prepreg substrates that are precursors of fiber-reinforced resin substrates, silicon carbide, nitride Ceramic substrates such as aluminum or silicon nitride, and glass substrates. The shape of the substrate can be flat, curved, or concave-convex. In addition, the shape of the base material may be any of foil shape, plate shape, film shape, and fiber shape. The ten-point average roughness of the surface of the substrate is preferably 0.01 to 0.05 µm.

基材之表面可業經矽烷耦合劑進行表面處理，亦可業經電漿處理。矽烷耦合劑宜為：3-胺丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷等具有官能基之矽烷耦合劑。 The surface of the substrate can be treated with silane coupling agent or plasma. The silane coupling agent is preferably: 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane and other silane coupling agents with functional groups.

熱壓附之方法可舉：以一對相對向之加熱板對基材與本片材施加夾持壓力之方法；使基材與本片材通過一對相對向之輥件間之方法；在加熱板上以輥件對基材與本片材施加壓力之方法。熱壓附之溫度宜為200℃以上，較宜為PTFE之熔融溫度以上，更宜為350℃以上。熱壓附之溫度宜為400℃以下。宜藉由熱壓附時之加熱來燒成PTFE。 The method of hot pressing can be mentioned: the method of applying clamping pressure to the substrate and the sheet with a pair of opposing heating plates; the method of passing the substrate and the sheet through a pair of opposing rollers; The method of applying pressure to the substrate and the sheet with rollers on the heating plate. The temperature of hot pressing is preferably above 200°C, more preferably above the melting temperature of PTFE, more preferably above 350°C. The temperature of hot pressing should be below 400°C. It is suitable to burn PTFE by heating while hot pressing.

熱壓附亦可在減壓下進行。此時，由抑制基材與本片材之氧化造成之劣化的觀點來看，宜在20kPa以下之真空度下進行。熱壓附宜藉由真空壓製來進行。在熱壓附時，由抑制本片材附著於加熱板或輥件的觀點來看，宜於本片材之表面與加熱板或輥件之間配置脫模膜，或宜藉由脫模劑將加熱板或輥件之表面進行表面處理。 Hot pressing can also be carried out under reduced pressure. At this time, from the viewpoint of suppressing deterioration due to oxidation of the base material and the present sheet, it is preferable to carry out under a vacuum degree of 20 kPa or less. Hot pressing is preferably performed by vacuum pressing. From the point of view of preventing the sheet from adhering to the heating plate or roller during hot pressing, it is preferable to arrange a release film between the surface of the sheet and the heating plate or roller, or to use a release agent Surface treatment of heating plate or roller.

脫模膜之厚度宜為50至150µm。脫模膜可舉聚醯亞胺膜，具體例可舉「APICAL NPI」(Kaneka公司製)、「Kapton EN」(DU PONT-TORAY公司)、「UPILEX S」(宇部興產公司)。 The thickness of the release film is preferably 50 to 150 µm. Examples of the release film include polyimide films, and specific examples thereof include "APICAL NPI" (manufactured by Kaneka), "Kapton EN" (DU PONT-TORAY), and "UPILEX S" (Ube Industries, Ltd.).

本片材可僅熱壓附至基材一表面，亦可熱壓附至基材之兩面。為前者之情形時，可獲得具有基材層與位於該基材層一表面之聚合物層的積層體；為後者之情形時，可獲得具有基材層與位於該基材層兩表面之聚合物層的積層體。積層體之適宜具體例可舉：具有金屬箔與位於其金屬箔之至少一表面之聚合物層的覆金屬積層體、具有聚醯亞胺膜與位於其聚醯亞胺膜兩表面之聚合物層的多層膜。聚合物層與基材層之剝離強度宜為10至100N/cm。亦可進一步從積層體去除基材層，而獲得包含PTFE、無機粒子及本樹脂之片材。 The sheet can be attached to only one surface of the base material by hot pressing, or it can be attached to both sides of the base material by hot pressing. In the case of the former, a laminate having a substrate layer and a polymer layer positioned on one surface of the substrate layer can be obtained; A laminate of layers. Suitable specific examples of the laminate include: a metal-clad laminate having a metal foil and a polymer layer located on at least one surface of the metal foil, a polyimide film and a polymer layer located on both surfaces of the polyimide film. layers of multilayer films. The peel strength between the polymer layer and the substrate layer is preferably 10 to 100 N/cm. It is also possible to further remove the substrate layer from the laminate to obtain a sheet containing PTFE, inorganic particles, and the present resin.

本片材、燒成片及具有基材層與聚合物層之積層體可有效作為天線零件、印刷基板、航空機用零件、汽車零件、運動用具、食品工業用品、散熱零件、塗料、化妝品等。具體上可有效作為：航空機用電線等之電線被覆材、使用於電動汽車等之馬達等的漆包線被覆材、電氣絕緣膠帶、石油鑽探用絕緣膠帶、石油輸送軟管、氫氣槽、印刷基板用材料、微孔濾膜、超濾膜、逆滲透膜、離子交換膜、透析膜及氣體分離膜等的分離膜、鋰蓄電池用及燃料電池用等的電極及電解質黏結劑、複製輥、傢俱、汽車儀錶板、家電製品等之外殼、滑動構件、張力索、耐磨墊、耐磨條、燈管、測試插座、晶圓導向器、離心泵之磨耗零件、供藥泵及供水泵、鏟、銼、錐及鋸等之工具、鍋爐、料斗、管子、烘箱、烤模、滑槽、球拍線、模具、馬桶、容器被覆材、功率器件、電晶體、閘流體、整流器、變壓器、功率MOSFET、CPU、散熱片、金屬散熱板、風車或風力發電設備或航空機等之槳葉、電腦或顯示器之殼體、電子器件材料、汽車之內外裝、在低氧下進行加熱處理之加工機或真空烘箱、電漿處理裝置等之密封材、濺鍍或各種乾式蝕刻裝置等之處理單元內之散熱零件、電磁波屏蔽件。滑動構件可列舉：荷重軸承、偏航軸承、滑動軸、閥、軸承、軸襯、密封件、止推墊圈、耐磨環、活塞、滑動開關、齒輪、凸輪、輸送帶及食品輸送用帶。 The sheet, fired sheet, and laminate having a substrate layer and a polymer layer can be effectively used as antenna parts, printed substrates, aircraft parts, auto parts, sports equipment, food industry supplies, heat dissipation parts, paints, cosmetics, etc. Specifically, it can be effectively used as wire coating materials for aircraft wires, enameled wire coating materials for motors such as electric vehicles, electrical insulating tapes, insulating tapes for oil drilling, oil transportation hoses, hydrogen tanks, materials for printed circuit boards , Separation membranes such as microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, and gas separation membranes, electrodes and electrolyte binders for lithium batteries and fuel cells, replica rolls, furniture, automobiles Instrument panels, shells of home appliances, sliding components, tension cables, wear-resistant pads, wear-resistant strips, lamp tubes, test sockets, wafer guides, wear parts of centrifugal pumps, drug supply pumps and water supply pumps, shovels, files , tools such as cones and saws, boilers, hoppers, pipes, ovens, baking molds, chutes, racket strings, molds, toilets, container covering materials, power devices, transistors, thyristors, rectifiers, transformers, power MOSFETs, CPUs , heat sinks, metal heat sinks, blades of windmills or wind power generation equipment or aircraft, casings of computers or displays, electronic device materials, interior and exterior decoration of automobiles, processing machines or vacuum ovens for heat treatment under low oxygen, Sealing materials for plasma processing devices, heat dissipation parts and electromagnetic wave shielding parts in processing units for sputtering or various dry etching devices. Sliding members include load bearings, yaw bearings, sliding shafts, valves, bearings, bushings, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, conveyor belts, and food conveyor belts.

以上，針對本片材、本片材之製造方法及包含本片材之積層體之製造方法進行了說明，惟本發明不受上述實施形態之構成所限。例如，本片材可在上述實施形態之構成中追加其他任意之構成，亦可置換成發揮相同功能之任意構成。又，本片材之製造方法及包含本片材之積層體之製造方法可在上述實施形態之構成中藉由追加而具有其他任意步驟，亦可置換成能產生相同作用之任意步驟。 The sheet, the manufacturing method of the sheet, and the method of manufacturing a laminate including the sheet have been described above, but the present invention is not limited to the configurations of the above embodiments. For example, in this sheet, other arbitrary structures may be added to the structures of the above-mentioned embodiments, or may be replaced with arbitrary structures that perform the same functions. In addition, the manufacturing method of this sheet and the manufacturing method of the laminated body containing this sheet may add other arbitrary steps to the structure of the said embodiment, and may replace with arbitrary steps which can produce the same effect.

實施例以下藉由實施例來詳細說明本發明，惟本發明不受該等所限。 1.各成分及各構件之準備 [分散液] 分散液1：包含60質量%之由未燒成之PTFE(PTFE1；熔融溫度：327℃)構成之粒子(D50：0.3µm)的水分散液(AGC公司製「AD-911E」) [無機粒子] 無機粒子1：球狀二氧化矽(D50：1µm) [樹脂粒子] 樹脂粒子1：為由四氟乙烯系聚合物(F樹脂1；熔融溫度：300℃)構成之粒子(D50：2.1µm)，其按順序以97.9莫耳%、0.1莫耳%、2.0莫耳%包含TFE單元、NAH單元及PPVE單元，且每1×10 ⁶個主鏈碳數具有1000個含羰基之基團樹脂粒子2：為由四氟乙烯系聚合物(F樹脂2；熔融溫度：305℃)構成之粒子(D50：1.8µm)，其按順序以98.7莫耳%、1.3莫耳%包含TFE單元及PPVE單元，且不具有含羰基之基團、羥基、環氧基及胺基樹脂粒子3：由去除分散液1之水而得之粉末狀未燒成PTFE構成的粒子 [樹脂清漆] 清漆1：包含芳香族聚醯胺醯亞胺之前驅物(PAI1；具有羧基及醯胺基；酸價：50mgKOH/g)的水清漆 [界面活性劑] 界面活性劑1：於主鏈具有二甲基矽氧烷單元且於側鏈具有氧伸乙基之聚氧伸乙基改質聚二甲基矽氧烷 [玻璃布] 玻璃布1：玻璃布(Arisawa Fiber Glass公司製「1078」) EXAMPLES The present invention will be described in detail below by means of examples, but the present invention is not limited thereto. 1. Preparation of each component and each member [Dispersion] Dispersion 1: Aqueous dispersion containing 60% by mass of particles (D50: 0.3µm) composed of unfired PTFE (PTFE1; melting temperature: 327°C) ("AD-911E" manufactured by AGC Corporation) [Inorganic Particles] Inorganic Particles 1: Spherical silica (D50: 1 µm) [Resin Particles] Resin Particles 1: made of tetrafluoroethylene polymer (F resin 1; Particles (D50: 2.1µm) composed of temperature: 300°C, which contain TFE units, NAH units and PPVE units in order of 97.9 mol%, 0.1 mol%, and 2.0 mol%, and each 1×10 ⁶ The carbon number of the main chain has 1000 carbonyl-containing group resin particle 2: It is a particle (D50: 1.8µm) composed of a tetrafluoroethylene polymer (F resin 2; melting temperature: 305°C), and its order is 98.7 Mole %, 1.3 mole % contains TFE unit and PPVE unit, and does not have groups containing carbonyl groups, hydroxyl groups, epoxy groups, and amine-based resin particles 3: unburned powder obtained by removing water from dispersion liquid 1 Particles made of PTFE [resin varnish] Varnish 1: Aqueous varnish [surfactant] interface containing aromatic polyamide imide precursor (PAI1; having carboxyl group and amide group; acid value: 50mgKOH/g) Active agent 1: polyoxyethylene modified polydimethylsiloxane [glass cloth] having a dimethylsiloxane unit in the main chain and an oxyethylene group in the side chain Glass cloth 1: glass cloth ( "1078" made by Arisawa Fiber Glass Co., Ltd.)

2.片材之製造例 (例1) 將無機粒子1、樹脂粒子1之乾摻物、水及界面活性劑1投入行星式混合機中捏合。接著，將分散液1及清漆1之混合物與水分複數次添加並攪拌，而獲得混合物1。邊攪拌混合物1邊添加甲醇，並回收包含PTFE粒子1、無機粒子1、樹脂粒子1及PAI1之凝集物1，該凝集物1係由20質量份之PTFE1、60質量份之無機粒子1、18.5質量份之樹脂粒子1、1.5質量份之PAI1、1質量份之界面活性劑1、100質量份之水及70質量份之甲醇的組成物1所形成者。將在真空下且在60℃下加熱24小時後之凝集物1與十二烷投入V型混合機中，在24℃下且旋轉數為10rpm之條件下混合5分鐘，而獲得糊狀液態組成物1。 2. Manufacturing example of sheet (example 1) Put the dry mixture of inorganic particles 1, resin particles 1, water and surfactant 1 into a planetary mixer and knead. Next, the mixture of the dispersion liquid 1 and the varnish 1 and water were added and stirred several times to obtain a mixture 1 . Add methanol while stirring the mixture 1, and recover aggregate 1 comprising PTFE particles 1, inorganic particles 1, resin particles 1 and PAI1, the aggregate 1 is composed of 20 parts by mass of PTFE1, 60 parts by mass of inorganic particles 1, 18.5 Composition 1 formed of 1 part by mass of resin particle, 1.5 parts by mass of PAI1, 1 part by mass of surfactant 1, 100 parts by mass of water and 70 parts by mass of methanol. Put the condensate 1 and dodecane heated at 60°C under vacuum for 24 hours into a V-type mixer, and mix for 5 minutes at 24°C at a rotation speed of 10 rpm to obtain a paste-like liquid composition Object 1.

使液態組成物1通過1對軋延輥間進行流延，而獲得厚度3mm的母片材1。藉由倒L字型砑光機將母片材1進行流延，進一步在150℃下加熱30分鐘去除十二烷，而獲得厚度200µm的片材1。在片材1中，PTFE1、無機粒子1、F樹脂1及屬PAI1或PAI1之反應物的聚醯胺醯亞胺之總含量為98質量%以上，PTFE1之含量為15質量%以上，F樹脂1與屬PAI1或PAI1之反應物的聚醯胺醯亞胺之總含量為15質量%以上，無機粒子之含量為50質量%以上。The liquid composition 1 was cast through a pair of calender rolls to obtain a mother sheet 1 with a thickness of 3 mm. The master sheet 1 was cast by an inverted L-shaped calender, and further heated at 150° C. for 30 minutes to remove dodecane to obtain a sheet 1 with a thickness of 200 μm. In sheet 1, the total content of PTFE1, inorganic particles 1, F resin 1, and polyamideimide that is PAI1 or a reactant of PAI1 is 98% by mass or more, the content of PTFE1 is 15% by mass or more, and F resin 1. The total content of polyamideimide which is PAI1 or the reactant of PAI1 is 15% by mass or more, and the content of inorganic particles is 50% by mass or more.

(例2) 除了將樹脂粒子1變更成樹脂粒子2外，依與例1相同方式而獲得混合物2。使用混合物2取代混合物1，並依與例1相同方式而獲得片材2。 (例3) 除了將樹脂粒子1變更成樹脂粒子2、且不使用清漆1外，依與例1相同方式而獲得片材3。 (例4) 將玻璃布1浸漬混合物2後，在100℃下加熱使其乾燥，而獲得玻璃布1中浸滲有PTFE粒子1的母片材。藉由倒L字型砑光機將前述母片材進行流延，而獲得厚度200µm且片材中之玻璃布1之含量大於10質量的片材4。 (例5) 將15質量份之樹脂粒子3、13質量份之樹脂粒子1、60質量份之無機粒子1、2質量份之PAI1及10質量份之十四烷加至亨氏混合機中，在1000rpm下攪拌2分鐘，而獲得凝集物5。除了將凝集物5變更成凝集物1外，依與例1相同方式而獲得片材5。 (Example 2) Mixture 2 was obtained in the same manner as in Example 1 except that resin particle 1 was changed to resin particle 2 . Mixture 2 was used instead of Mixture 1, and Sheet 2 was obtained in the same manner as in Example 1. (Example 3) Sheet 3 was obtained in the same manner as in Example 1 except that resin particle 1 was changed to resin particle 2 and varnish 1 was not used. (Example 4) After impregnating the glass cloth 1 with the mixture 2, it heated and dried at 100 degreeC, and obtained the mother sheet which impregnated the glass cloth 1 with the PTFE particle 1. The above-mentioned master sheet was cast by an inverted L-shaped calender to obtain a sheet 4 with a thickness of 200 μm and a glass cloth 1 content greater than 10 mass in the sheet. (Example 5) Add 15 parts by mass of resin particles 3, 13 parts by mass of resin particles 1, 60 parts by mass of inorganic particles 1, 2 parts by mass of PAI1 and 10 parts by mass of tetradecane into the Heinz mixer, and stir at 1000rpm for 2 Minutes to obtain agglutinate 5. A sheet 5 was obtained in the same manner as in Example 1 except that the aggregate 5 was changed to the aggregate 1 .

3.片材之評估例 3-1.耐撓曲性之評估從片材1至5分別裁切出50mm×100mm之四角形試驗片。針對試驗片，依循JIS K 5600-5-1中規定之方法，沿著2mm之心軸以180°的角度彎折。以肉眼確認彎折後之試驗片，依以下基準評估耐撓曲性。 [評估基準] 〇：未於試驗片確認到龜裂。 ×：有於試驗片確認到龜裂。 3. Evaluation example of sheet 3-1. Evaluation of flex resistance Cut out 50mm×100mm quadrangular test pieces from sheets 1 to 5, respectively. For the test piece, follow the method specified in JIS K 5600-5-1, and bend at an angle of 180° along a 2mm mandrel. Check the bent test piece with the naked eye, and evaluate the flex resistance according to the following criteria. [Evaluation benchmark] ○: Cracks were not confirmed on the test piece. ×: Cracks were observed in the test piece.

3-2.掉粉之評估於進行3-1之評估後，從心軸移除各片材。以肉眼確認粉末對心軸之附著，依以下基準評估掉粉之容易度。[評估基準] 〇：未確認有粉末附著於心軸。 ×：確認有粉末附著於心軸。 3-2. Evaluation of Losing Followers After performing the evaluation of 3-1, each sheet was removed from the mandrel. Confirm the adhesion of the powder to the mandrel with the naked eye, and evaluate the ease of powder falling according to the following criteria. [Evaluation benchmark] 〇: Adhesion of powder to the mandrel was not confirmed. ×: Adhesion of powder to the mandrel was confirmed.

3-3.接著性之評估將片材1至5各自與長條銅箔(厚度：18µm，表面之十點平均粗度：0.8µm)疊合，在380℃下進行真空壓製予以熱壓附，而獲得具有銅箔與其表面包含PTFE粒子1之燒成物之聚合物層的積層體1至5。從積層體1至5分別裁切出長100mm、寬10mm之矩形試驗片。將距離試驗片之長度方向一端50mm之位置固定後，以拉伸速度50mm/分鐘，從長度方向之一端以相對於試驗片呈90°使銅箔與聚合物層剝離。將使其剝離時之最大荷重作為剝離強度(N/cm)，依以下基準評估片材之接著性。 [評估基準] 〇：剝離強度為12N/cm以上。 △：剝離強度為10N/cm以上且小於12N/cm。 ×：剝離強度小於10N/cm。 3-3. Adherence evaluation Sheets 1 to 5 are laminated with strip copper foil (thickness: 18µm, ten-point average roughness of the surface: 0.8µm), vacuum pressing at 380°C and hot-pressed to obtain copper foil and its surface Laminates 1 to 5 including a polymer layer of a fired product of PTFE particles 1 . Rectangular test pieces with a length of 100 mm and a width of 10 mm were cut out from laminates 1 to 5. After fixing the position 50 mm away from one end of the test piece in the longitudinal direction, the copper foil and the polymer layer were peeled off from one end in the longitudinal direction at 90° relative to the test piece at a tensile speed of 50 mm/min. The maximum load at the time of peeling was taken as the peel strength (N/cm), and the adhesiveness of the sheet was evaluated according to the following criteria. [Evaluation benchmark] ○: The peel strength is 12 N/cm or more. Δ: The peel strength is 10 N/cm or more and less than 12 N/cm. ×: Peel strength is less than 10 N/cm.

3-4.電特性之評估針對積層體1至4，分別使用氯化鐵水溶液進行蝕刻去除銅箔，而獲得由單獨的聚合物層構成之燒成片1至4。以SPDR(分離後介電質共振器)法測定燒成片之介電常數與介電正切(測定頻率：10GHz)。將各自之評估結果統整顯示於下表1。 3-4. Evaluation of electrical characteristics For the laminates 1 to 4, the copper foils were removed by etching using an aqueous solution of ferric chloride to obtain fired sheets 1 to 4 composed of individual polymer layers. The dielectric constant and dielectric tangent of the fired sheet were measured by SPDR (Separated Dielectric Resonator) method (measurement frequency: 10GHz). The respective evaluation results are shown in Table 1 below.

[表1]

[Table 1]

產業上之可利用性由上述結果明顯可知，本發明片材具有優異之耐撓曲性、接著性，且不易掉粉。又，從本發明片材獲得之燒成片具有優異之低介電常數與低介電正切。因此，可認為本發明片材具有優異之成分分布之均一性，且高度展現未燒成PTFE、無機粒子及本樹脂之性質。本發明片材、或從本發明片材所得之燒成片及積層體，其無機粒子不易剝落，且具有優異之電特性、低線膨脹性、物理性強度及與其他材料之接著性，可有效作為印刷基板材料。 Industrial availability From the above results, it is obvious that the sheet of the present invention has excellent flex resistance, adhesiveness, and is not easy to drop powder. Also, the fired sheet obtained from the sheet of the present invention has excellent low dielectric constant and low dielectric tangent. Therefore, it can be considered that the sheet of the present invention has excellent uniformity of component distribution, and highly exhibits the properties of unfired PTFE, inorganic particles and the resin. The sheet of the present invention, or the fired sheet and laminate obtained from the sheet of the present invention, its inorganic particles are not easy to peel off, and has excellent electrical properties, low linear expansion, physical strength and adhesion with other materials, and can be Effective as a printed substrate material.

(無)(none)

Claims

一種片材，包含：未燒成之聚四氟乙烯、無機粒子及樹脂，且該樹脂具有選自於由含羰基之基團、含羥基之基團、環氧基及胺基所構成群組中之至少1種官能基；並且，前述聚四氟乙烯、前述無機粒子及前述樹脂之總含量為90質量%以上。A sheet, comprising: unfired polytetrafluoroethylene, inorganic particles and resin, and the resin has a group selected from the group consisting of carbonyl-containing groups, hydroxyl-containing groups, epoxy groups and amine groups at least one functional group; and the total content of the polytetrafluoroethylene, the inorganic particles and the resin is 90% by mass or more.

如請求項1之片材，其中前述無機粒子係包含選自於由二氧化矽、氮化硼及二氧化鈦所構成群組中之至少1種無機物的粒子。The sheet according to claim 1, wherein the inorganic particles include particles of at least one inorganic substance selected from the group consisting of silicon dioxide, boron nitride, and titanium dioxide.

如請求項1之片材，其中前述樹脂包含下述中之至少任一者：熱熔融性四氟乙烯系聚合物；以及，芳香族聚合物或其前驅物。The sheet according to claim 1, wherein the aforementioned resin contains at least any one of the following: hot-melt tetrafluoroethylene polymer; and aromatic polymer or its precursor.

如請求項1之片材，其中前述樹脂包含：熱熔融性四氟乙烯系聚合物；以及，芳香族聚合物或其前驅物。The sheet according to claim 1, wherein the aforementioned resin comprises: a hot-melt tetrafluoroethylene polymer; and an aromatic polymer or its precursor.

如請求項3之片材，其中前述熱熔融性四氟乙烯系聚合物之熔融溫度為260至320℃。The sheet according to claim 3, wherein the melting temperature of the aforementioned hot-melt tetrafluoroethylene polymer is 260 to 320°C.

如請求項3之片材，其中前述芳香族聚合物或其前驅物為聚醯亞胺、聚醯胺醯亞胺、聚醯亞胺前驅物或聚醯胺醯亞胺前驅物。The sheet according to claim 3, wherein the aforementioned aromatic polymer or its precursor is polyimide, polyamideimide, polyamideimide precursor or polyamideimide precursor.

如請求項1之片材，其中前述聚四氟乙烯之含量為10質量%以上。The sheet according to claim 1, wherein the content of the aforementioned polytetrafluoroethylene is 10% by mass or more.

如請求項1之片材，其中前述樹脂之含量為5質量%以上。The sheet according to claim 1, wherein the content of the aforementioned resin is 5% by mass or more.

如請求項1之片材，其中相對於前述聚四氟乙烯之含量與前述樹脂之含量之合計，前述無機粒子之含量之比為0.1以上。The sheet according to claim 1, wherein the ratio of the content of the inorganic particles to the sum of the content of the polytetrafluoroethylene and the content of the resin is 0.1 or more.

如請求項1之片材，其厚度為50µm以上。As in the sheet of claim 1, its thickness is more than 50 µm.

一種片材之製造方法，係將包含前述聚四氟乙烯之粒子、前述無機粒子及前述樹脂之液態組成物進行流延，而獲得如請求項1之片材。A method for manufacturing a sheet, which is to cast a liquid composition comprising the aforementioned polytetrafluoroethylene particles, the aforementioned inorganic particles, and the aforementioned resin to obtain the sheet according to Claim 1.

如請求項11之製造方法，其中前述聚四氟乙烯之粒子之平均粒徑為0.1至10µm。The manufacturing method according to claim 11, wherein the average particle size of the polytetrafluoroethylene particles is 0.1 to 10 µm.

如請求項11或12之製造方法，其係將前述液態組成物進行流延而得之流延物互相積層並貼合。According to the manufacturing method of claim 11 or 12, the castings obtained by casting the aforementioned liquid composition are laminated and pasted together.

一種燒成片之製造方法，係加熱如請求項1至10中任一項之片材來燒成前述聚四氟乙烯。A method for producing a fired sheet is to heat the sheet according to any one of Claims 1 to 10 to burn the aforementioned polytetrafluoroethylene.

一種積層體之製造方法，係將如請求項1至10中任一項之片材與基材予以熱壓附，而獲得具有基材層與聚合物層之積層體。A method for manufacturing a laminate, comprising hot-pressing the sheet according to any one of Claims 1 to 10 and a substrate to obtain a laminate having a substrate layer and a polymer layer.