TWI784041B - Polymer film, film laminate, and method for producing polymer film - Google Patents

Abstract

(前述通式(1)中，X¹ 及X² 為相同或不同，分別表示氫原子、鹵原子、經取代或無取代之烷基、經取代或無取代之烷氧基、經取代或無取代之烯基、羥基或羧基，X¹ 及X² 亦可互相結合形成環)。The polymer film of the present invention is characterized in that it contains a norbornene-based polymer (A) containing 10 mol% or more of a constituent unit represented by the following general formula (1), has a thickness of 10 nm to 1000 nm, and has self-supporting properties.

(In the aforementioned general formula (1), X ¹ and X ² are the same or different, respectively representing a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Substituted alkenyl, hydroxyl or carboxyl, X1 and X2 can also combine with each other to form ^a ring ⁾ .

Description

Polymer film, film laminate, and method for producing polymer film

The present invention relates to a polymer film, a film laminate, and a method for producing the polymer film.

Films made of cyclic olefin-based resins have been used, for example, as dielectric films for film condensers. For example, in Document 1 (Japanese Patent Laid-Open No. 2015-183181), a high-insulation film mainly composed of resin is described. In this highly insulating film, the aforementioned resin is an amorphous resin. In addition, assuming that the minimum value of the refractive index in the plane direction of the above-mentioned high-insulation film is Ny, and the refractive index in the direction perpendicular to the above-mentioned Ny in the plane direction of the above-mentioned high-insulation film is Nx, the above-mentioned high-insulation film When the thickness is d, the retardation (R) represented by the following formula 1 is 10 nm or less. R=(Nx-Ny)・d (Equation 1) Regarding the literature resin film, if the thickness is in the range of tens to hundreds of nm, there is electrostatic force and wettability, even without using adhesives, etc. For the case where the adhered object is tightly adhered. However, the highly insulating film described in Document 1 cannot be adhered to the adherend. Furthermore, Document 1 describes that the average thickness is preferably from 0.5 μm to 7.0 μm, but the method for producing a high insulating film described in Document 1 cannot achieve a film thickness of the nanometer order. Furthermore, in Document 1, for example, stretching treatment is performed on a film produced by a solution casting method, but this method also cannot make the film thickness into the nanometer order.

前述本發明之一態樣中，較好前述降冰片烯系聚合物(A)係降冰片烯系共聚物。 　　前述本發明之一態樣中，較好前述高分子薄膜含有50質量%以上之前述降冰片烯系聚合物(A)。 　　前述本發明之一態樣中，較好前述降冰片烯系聚合物(A)之玻璃轉移點為140℃以下。 　　前述本發明之一態樣中，較好前述降冰片烯系聚合物(A)於溫度260℃、荷重2.16kgf下之熔融流動速率為20g/10min以上。 　　前述本發明之一態樣中，較好前述高分子薄膜之表面碳濃度為90原子%以上。 　　依據本發明之一態樣，提供一種膜狀層合體，其特徵係具備工程膜與形成於前述工程膜上之前述本發明一態樣之高分子薄膜。 　　前述本發明之一態樣中，較好前述工程膜之表面自由能為40mJ/m² 以下。 　　前述本發明之一態樣中，較好前述工程膜之表面算術平均粗糙度為40nm以下。 　　依據本發明之一態樣，提供一種高分子薄膜之製造方法，其係製造前述本發明一態樣之高分子薄膜者，其特徵為具備下述步驟：於工程膜上塗佈包含前述降冰片烯系聚合物(A)之高分子薄膜形成用溶液，並乾燥，形成前述高分子薄膜之步驟，及自前述工程膜剝離前述高分子薄膜之步驟。 　　前述本發明之一態樣中，較好前述工程膜之表面自由能為40mJ/m² 以下。 　　前述本發明之一態樣中，較好前述工程膜之表面算術平均粗糙度為40nm以下。 　　依據本發明，可提供不使用接著劑等，亦可對被接著物密著，且具有高撥水性之高分子薄膜、膜狀層合體及高分子薄膜的製造方法。The object of the present invention is to provide a polymer film, a film-like laminate, and a method for producing a polymer film that can be adhered to an adherend without using an adhesive or the like and has high water repellency. According to one aspect of the present invention, there is provided a polymer film characterized by comprising a norbornene-based polymer (A) containing 10 mol% or more of a constituent unit represented by the following general formula (1), and having a thickness of 10 nm to 1000 nm. below, and is self-supporting. Also, in the following general formula (1), X ¹ and X ² are the same or different, respectively representing a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted Or unsubstituted alkenyl, hydroxyl or carboxyl, X ¹ and X ² can also combine with each other to form a ring.

In the aforementioned aspect of the present invention, it is preferable that the aforementioned norbornene-based polymer (A) is a norbornene-based copolymer. In one aspect of the present invention, it is preferable that the polymer film contains 50% by mass or more of the norbornene-based polymer (A). In the aforementioned aspect of the present invention, it is preferable that the glass transition point of the aforementioned norbornene-based polymer (A) is 140° C. or lower. In one aspect of the present invention, the norbornene-based polymer (A) preferably has a melt flow rate of 20 g/10 min or more at a temperature of 260° C. and a load of 2.16 kgf. In the aforementioned aspect of the present invention, it is preferable that the surface carbon concentration of the aforementioned polymer film is 90 atomic % or more. According to one aspect of the present invention, there is provided a film-like laminate characterized by comprising an engineering film and the polymer film of the aforementioned aspect of the present invention formed on the aforementioned engineering film. In the aforementioned aspect of the present invention, preferably, the surface free energy of the aforementioned engineering film is 40 mJ/m ² or less. In the aforementioned aspect of the present invention, it is preferable that the surface arithmetic average roughness of the aforementioned engineering film is 40 nm or less. According to one aspect of the present invention, there is provided a method for manufacturing a polymer film, which is to manufacture the above-mentioned polymer film according to one aspect of the present invention, and is characterized in that it has the following steps: coating the engineering film comprising the aforementioned norbornene A step of forming the polymer film-forming solution of the ethylenic polymer (A) and drying it to form the polymer film, and a step of peeling the polymer film from the process film. In the aforementioned aspect of the present invention, preferably, the surface free energy of the aforementioned engineering film is 40 mJ/m ² or less. In the aforementioned aspect of the present invention, it is preferable that the surface arithmetic average roughness of the aforementioned engineering film is 40 nm or less. According to the present invention, it is possible to provide a polymer film, a film-like laminate, and a method for producing a polymer film that can be adhered to an adherend without using an adhesive or the like and has high water repellency.

前述通式(1)中，X¹ 及X² 為相同或不同，分別表示氫原子、鹵原子、經取代或無取代之烷基、經取代或無取代之烷氧基、經取代或無取代之烯基、羥基或羧基，X¹ 及X² 亦可互相結合形成環。 　　作為烷基、烷氧基及烯基之取代基，舉例為鹵原子、羥基、羧基、丙烯醯基、甲基丙烯醯基及環氧基等。 　　烷基之碳數較好為1至5，更好為1至3。烷氧基之碳數較好為1至5，更好為1至3。烯基之碳數較好為2至5，更好為2至3。 (降冰片烯系聚合物(A)) 　　降冰片烯系聚合物(A)只要含有10mol%之上述通式(1)表示之構成單位即可，可為降冰片烯系均聚物，亦可為降冰片烯系共聚物。 　　該降冰片烯系聚合物(A)係以降冰片烯系化合物為單體之至少一種的聚合物。 　　作為降冰片烯系化合物舉例為降冰片烯(雙環[2.2.1]庚-2-烯)、具有包含降冰片烯相關之雙環的環狀構造之化合物(例如二環戊二烯)及該等之衍生物。該等可單獨使用1種，亦可混合2種以上使用。 　　作為降冰片烯系化合物以外之單體，舉例為環戊二烯及四環十二碳烯等。該等可單獨使用1種，亦可混合2種以上使用。 　　藉由將降冰片烯系化合物設為單體之至少一種，使單體聚合所得之聚合物(均聚物或共聚物)具有前述通式(1)表示之構成單位。 　　作為降冰片烯系聚合物(A)舉例有降冰片烯系單體之開環複分解聚合物氫化聚合物(具體為以日本ZEON股份有限公司製ZEONEX(註冊商標)系列取得)、降冰片烯與乙烯之共聚物(具體為以POLYPLASTIC股份有限公司製TOPAS(註冊商標)系列取得)、基於二環戊二烯與四環戊十二碳烯之開環聚合的共聚物(具體為以日本ZEON股份有限公司製ZEONOR(註冊商標)系列取得)、乙烯與四環十二碳烯之共聚物(具體為以三井化學股份有限公司製APEL(註冊商標)系列取得)、以及以二環戊二烯及甲基丙烯酸酯為原料之含有極性基之環狀烯烴樹脂(具體為以JSR股份有限公司製ARTON(註冊商標)系列取得)等。該等可單獨使用1種，亦可混合2種以上使用。 　　降冰片烯系聚合物(A)可具有交聯構造。此處，造成交聯構造之交聯劑種類為任意。作為該交聯劑，舉例為有機過氧化物(例如二異丙苯基過氧化物等)及具有環氧基之化合物等。該等可單獨使用1種，亦可混合2種以上使用。 　　交聯劑可於構成降冰片烯系聚合物(A)之高分子之一種類彼此間交聯，亦可於不同種類高分子間交聯。交聯劑之結合部位亦為任意。亦可與構成降冰片烯系聚合物(A)之高分子中之構成主鏈之原子交聯，亦可與側鏈或官能基等之構成主鏈以外之原子交聯。交聯程度亦為任意，但交聯程度過度進行時，由於有包含降冰片烯系聚合物(A)之高分子薄膜1之加工性(尤其成形性)過度降低，高分子薄膜1之表面性狀過度劣化，高分子薄膜1之耐脆性降低之顧慮，故應侷限在不發生此等問題之範圍。 　　降冰片烯系聚合物(A)具備熱塑性。該熱塑性程度可以表示熔融時之黏度的熔融流動速率(MFR)表示。 　　降冰片烯系聚合物(A)於溫度260℃、荷重2.16kgf下之熔融流動速率(MFR)較好為20g/10min以上，更好為20g/10min以上，150g/10min以下，特佳為25g/10min以上，50g/10min以下。MFR若為前述範圍內，則熱塑性可充分提高，可提高成形等之加工性。MFR可依據ASTM D1238之記載測定。 　　降冰片烯系聚合物(A)之玻璃轉移點，基於高分子薄膜形成用溶液之塗佈性之觀點，較好為140℃以下，更好為30℃以上120℃以下。玻璃轉移點若為140℃以下，則更提高溶劑可溶性，另一方面，玻璃轉移點若為30℃以上，則即使於室溫亦具有自力膜形成能力。玻璃轉移點可使用示差掃描熱量計測定。例如使用示差掃描熱量計(TA Instruments公司製之「DSC(Q2000)」)，以升溫速度10℃/min，自-40℃至200℃之溫度範圍實施測定，作成圖表，自該圖表確認拐點，可求出玻璃轉移點。 (降冰片烯系聚合物(A)以外之烯烴系聚合物(B)) 　　高分子薄膜1亦可包含降冰片烯系聚合物(A)以外之烯烴系聚合物(B)(以下依情況稱為「非NB烯烴系聚合物(B)」)。 　　使用非NB烯烴系聚合物(B)時，基於自我支撐性及撥水性之觀點，降冰片烯系聚合物(A)含量，以聚合物總量基準，較好為50質量%以上，更好為70質量%以上，特佳為90質量%以上。 　　非NB烯烴系聚合物(B)可為直鏈狀，亦可具有側鏈。且，非NB烯烴系聚合物(B)只要不包含降冰片烯環亦可具有任何官能基，其種類及取代密度為任意。可為如烷基之反應性低的官能基，亦可為如羧酸基之反應性高的官能基。 　　非NB烯烴系聚合物(B)為將烯烴設為單體之至少一種的烯烴系聚合物，係不具有降冰片烯系化合物作為單體之烯烴系聚合物。因此，非NB烯烴系聚合物(B)只要於高分子中不含有降冰片烯環，則未特別限制，可為芳香族環式聚烯烴，亦可為非環式聚烯烴。作為芳香族環式聚烯烴，舉例為以具有芳香族環之環狀構造的烯烴作為單體之至少一種的聚烯烴。非NB烯烴系聚合物(B)可為均聚物，亦可為共聚物。 (被接著物) 　　高分子薄膜1即使不使用接著劑等，亦可對於被接著物密著。此處，作為被接著物，並未特別限定，但可舉例不鏽鋼、聚乙烯、聚丙烯、聚碳酸酯、玻璃、PTFE(聚四氟乙烯)、PVDF(聚偏氟化乙烯)及半導體電路基板等。藉由將該等作為被接著物，可簡便地對任意被接著物賦予撥水性。且，作為上述以外之被接著物，舉例為人、動物、衣類、帽子、鞋子及裝飾品等。以該等作為被接著物時，高分子薄膜1由於非常薄，故貼附部位不顯眼，且為輕量故而較佳。 　　又，高分子薄膜1由於具有高的撥水性，故對汗或雨等具有耐性。因此，高分子薄膜1可特別較好地使用於作為將穿戴終端等密著於皮膚等之膜。 [高分子薄膜之製造方法] 　　本實施形態之高分子薄膜之製造方法係製造高分子薄膜1之高分子薄膜的製造方法。因此，本實施形態之高分子薄膜之製造方法係具備下述步驟之方法：於工程膜上塗佈包含前述降冰片烯系聚合物(A)之高分子薄膜形成用溶液，並乾燥，形成前述高分子薄膜之步驟(高分子薄膜形成步驟)，及自前述工程膜剝離前述高分子薄膜之步驟(剝離步驟)。 (高分子薄膜形成步驟) 　　圖2係顯示本實施形態之高分子薄膜之製造方法所用之工程膜2的剖面概略圖。工程膜2具有第一面2A及第二面2B。 　　高分子薄膜形成步驟中，如圖2所示之工程膜的第一面2A及第二面2B中，於第一面2A上，塗佈包含前述降冰片烯系聚合物(A)之高分子薄膜形成用溶液，並乾燥，形成高分子薄膜1，獲得如圖3所示之膜狀層合體100。 　　此處，針對高分子薄膜形成步驟所用之工程膜及高分子薄膜形成用溶液加以說明。 (工程膜) 　　作為工程膜2並未特別限制。例如基於處理容易之觀點，工程膜2較好具備剝離基材21及形成於剝離基材21之至少一面上之剝離劑層22。本實施形態中，剝離劑層22之表面相當於第一面2A，與剝離基材21之形成有剝離劑層22之面相反側之面相當於第二面2B。 　　作為剝離基材21，舉例為例如紙基材、於該紙基材上層合聚乙烯等之熱塑性樹脂而成之層合紙、以及塑膠膜等。 　　作為紙基材舉例為玻璃紙、上等紙、銅版紙及塗料紙等。作為塑膠膜舉例為例如聚酯膜(例如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯及聚萘二甲酸乙二酯等)，以及聚烯烴膜等(例如聚丙烯及聚乙烯等)。該等可單獨使用1種，亦可組合2種以上使用。 　　剝離劑層22亦可塗佈剝離劑而形成。作為剝離劑舉例為例如烯烴系樹脂、橡膠系彈性體(例如丁二烯系樹脂、異戊二烯系樹脂等)、長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂及聚矽氧系樹脂。該等中，作為剝離劑較好為選自烯烴系樹脂、橡膠系彈性體(例如丁二烯系樹脂、異戊二烯系樹脂等)、長鏈烷基系樹脂、醇酸系樹脂及氟系樹脂所成之群中選擇之任一種剝離劑。該等可單獨使用1種，亦可組合2種以上使用。剝離劑層亦可進而含有抗靜電劑，亦可未含有抗靜電劑。 　　工程膜2較好藉由剝離劑層22，調整第一面2A之表面自由能及算術平均粗糙度。 　　工程膜2之第一面2A之表面自由能較好為40mJ/m² 以下，更好為20mJ/m² 以上40mJ/m² 以下。表面自由能若為20mJ/m² 以上，則於工程膜2上可良好地塗佈高分子薄膜形成用溶液，且表面自由能若為40mJ/m² 以下，則容易自工程膜2剝離高分子薄膜1，可提高生產性。表面自由能可測定各種液滴之接觸角(測定溫度：25℃)，以其值為基礎藉由北崎・畑理論求得。 　　工程膜2之第一面2A的表面算術平均粗糙度(Ra)較好為40nm以下，更好為0.1nm以上30nm以下，特佳為0.5nm以上25nm以下。表面算術平均粗糙度若為前述範圍內，則可充分抑制形成於高分子薄膜1之凹凸，可提高高分子薄膜1之膜強度。算術平均粗糙度例如可使用Veeco Instruments公司製之光干涉顯微鏡NT1100測定。 　　工程膜2之厚度並未特別限定。工程膜2之厚度通常為20μm以上200μm以下，較好為25μm以上150μm以下。 　　剝離劑層22之厚度並未特別限定。於剝離基材上塗佈包含剝離劑之溶液形成剝離劑層22時，剝離劑層22之厚度較好為0.01μm以上2.0μm以下，更好為0.03μm以上1.0μm以下。 　　使用塑膠膜作為剝離基材21時，該塑膠膜之厚度較好為3μm以上50μm以下，更好為5μm以上90μm以下，特佳為10μm以上40μm以下。 (高分子薄膜形成用溶液) 　　高分子薄膜形成用溶液中作為溶質之高分子薄膜形成用的材料物質為降冰片烯系聚合物(A)。又，作為該材料物質亦可進而使用非NB烯烴系聚合物(B)。降冰片烯系聚合物(A)及非NB烯烴系聚合物(B)由於已予說明，故省略。 　　作為高分子薄膜形成用溶液之溶劑種類，若為可使高分子薄膜形成用的材料物質溶解或均一分散，且可藉由加熱蒸發之溶劑，則未特別限定。例如作為溶劑較好使用乙醇、丙醇、異丙醇、丙酮、甲苯、環己酮、乙酸乙酯、乙酸丁酯、四氫呋喃、甲基乙基酮、二氯甲烷及氯仿等。該等可單獨使用1種，亦可組合2種以上使用。 　　又，作為溶劑之沸點，較好設為30℃以上160℃以下之範圍內之值，更好為35℃以上120℃以下之範圍內之值。 　　又，高分子薄膜形成用溶液中的材料物質濃度較好設為0.1質量%以上20質量%以下之範圍內之值。 　　高分子薄膜形成用溶液中的材料物質濃度若為0.1質量%以上，則可抑制有無法獲得必要厚度之情況的缺點及無法使溶液黏度成最適之缺點。另一方面，高分子薄膜形成用溶液中的材料物質之濃度若為20質量%以下，則可抑制無法獲得均一塗膜之情況的缺點。 　　又，由上述觀點，高分子薄膜形成用溶液中的材料物質濃度更好設為0.3質量%以上15質量%以下之範圍內之值，又更好設為0.5質量%以上10質量%以下之範圍內之值。 　　且，高分子薄膜形成用溶液之黏度(測定溫度：25℃)較好設為1mPa・s以上500mPa・s以下之範圍內之值。 　　高分子薄膜形成用溶液之黏度若為1mPa・s以上，則可抑制塗膜發生不均之缺點。另一方面，高分子薄膜形成用溶液之黏度若為500mPa・s以下，則可抑制無法獲得均一塗膜之缺點。 　　且，基於上述觀點，高分子薄膜形成用溶液之黏度(測定溫度：25℃)更好設為1.5mPa・s以上400mPa・s以下之範圍內之值，又更好設為2mPa・s以上300mPa・s以下之範圍內之值。 　　又，高分子薄膜形成用溶液之黏度係依據JIS K7117-1之4.1(布魯克菲爾德型旋轉黏度計)測定者。 　　又，對形成於工程膜2上之高分子薄膜形成用溶液的塗佈層，用以成為高分子薄膜1之乾燥條件並未特別限定。塗佈層之乾燥較好以40℃以上120℃以下之溫度條件且6秒以上300秒以下之乾燥時間進行。 　　乾燥溫度若為40℃以上，則可抑制乾燥過於耗費時間或乾燥不足之缺點。另一方面，乾燥溫度若為120℃以下，則可抑制產生起皺或捲曲之缺點。 　　又，乾燥時間若為6秒以上，則可防止乾燥不足之缺點。另一方面，乾燥時間若為300秒以下，則可抑制產生起皺或捲曲之缺點。 　　又，基於上述觀點，對高分子薄膜形成用溶液的塗佈層用以成為高分子薄膜1之乾燥條件，更好設為50℃以上110℃以下之溫度條件且12秒以上180秒以下之乾燥時間，又更好設為60℃以上100℃以下之溫度條件且18秒以上120秒以下之乾燥時間。 　　又，高分子薄膜形成用溶液的塗佈較好藉由輥對輥(Roll to Roll)法進行。 　　其理由係若為輥對輥法，則可更有效率地形成具有特定厚度之高分子薄膜1，故而可更有效率地大量生產膜狀層合體100之故。 　　又，實施輥對輥法時，作為塗佈裝置，較好為棒塗佈器、凹版塗佈器或模嘴塗佈器，更好為逆凹版塗佈器或狹縫模嘴塗佈器。 　　其理由係若為該等塗佈裝置，則可更有效率地形成具有特定厚度之高分子薄膜1之故。 　　亦即，若為棒塗佈器、逆凹版塗佈器及狹縫模嘴塗佈器，則可不於表面產生皺紋且以均一厚度形成奈米等級厚之高分子薄膜1。而且，棒塗佈器、逆凹版塗佈器及狹縫模嘴塗佈器除了其構造簡單以外，經濟性亦優異。 (剝離步驟) 　　剝離步驟中，自工程膜2剝離圖3所示之膜狀層合體100之高分子薄膜1，獲得具有自我支撐性之高分子薄膜1。 　　剝離步驟中工程膜2之自高分子薄膜1之剝離力較好為5mN/20mm以上、100mN/20mm以下，更好為10mN/20mm以上、50mN/20mm以下，特佳為15mN/20mm以上、30mN/20mm以下。 　　上述剝離力若為5mN/20mm以上，則高分子薄膜形成步驟中，可抑制工程膜與高分子薄膜容易剝落之缺點。又，上述剝離力若為100mN/20mm以下，則剝離步驟中，可抑制工程膜不易自高分子薄膜剝離或高分子薄膜破裂之缺點。 　　上述剝離力例如可藉由變更工程膜2所用之剝離劑種類而調整。 [膜狀層合體] 　　本實施形態之膜狀層合體100係如圖3所示，具備高分子薄膜1與工程膜2。該膜狀層合體100係藉由於工程膜2上塗佈前述高分子薄膜形成用溶液，使塗佈層乾燥，形成高分子薄膜1而獲得。亦即，該膜狀層合體100可藉由前述本實施形態之高分子薄膜之製造方法中之高分子薄膜形成步驟而獲得。 (本實施形態之作用效果) 　　依據本實施形態，可發揮如下作用效果。 　　(1)可效率良好地製造包含含有10mol%以上之前述通式(1)表示之構成單位的降冰片烯系聚合物(A)，厚度為10nm以上1000nm以下，且具有自我支撐性之高分子薄膜1。 　　(2)可提供即使不使用接著劑等，亦可對於被接著物密著，且具有高撥水性之高分子薄膜1。 [實施形態之變化] 　　本實施形態不限定於前述實施形態，在可達成本實施形態目的之範圍內的變化、改良等包含於本實施形態。 　　例如，前述實施形態中，雖使用具備剝離基材21及剝離劑層22之工程膜2，但不限定於此。例如於剝離基材21之表面自由能及表面算術平均粗糙度在適當範圍內時，亦可使用由剝離基材21所成之單層膜作為工程膜2。 實施例 　　以下列舉實施例進一步詳細說明本發明，但本發明絕非限定於該等實施例。 [試驗例1] 1.工程膜之選定 (1)工程膜之製造 　　試驗例1之工程膜具有剝離基材與設於剝離基材上之剝離劑層。 　　將聚矽氧改性醇酸樹脂與胺基樹脂之混合物(信越化學工業股份有限公司製：商品名「KS-882」) 100重量份與對-甲苯磺酸(硬化劑) 1重量份以甲苯稀釋，調製固形分濃度2質量%之塗佈液。 　　其次，於厚38μm之聚對苯二甲酸乙二酯(PET)膜(三菱化學股份有限公司製之「DIAFOIL T100」)上以馬亞棒塗佈所得塗佈液，於140℃、60秒加熱並乾燥，獲得形成有平均厚0.1μm之剝離劑層的工程膜。接著，所得工程膜之剝離劑層表面之表面自由能及算術平均粗糙度示於表1。 (2)高分子薄膜形成用溶液之調製 　　將環狀烯烴共聚物(三井化學股份有限公司製之「APEL6011T」、玻璃轉移點105℃、MFR 26g/10min)之溶液(固形分10質量%)以甲苯溶解，稀釋至固形分3質量%，製作高分子薄膜形成用溶液。 (3)膜狀層合體之形成 　　其次，使用逆凹版塗佈器，於準備好的工程膜上以使乾燥後之高分子薄膜厚度成為800nm之方式塗佈高分子薄膜形成用溶液後，於100℃乾燥60秒，獲得膜狀層合體。 2.測定・評價 (1)工程膜之表面自由能之測定 　　工程膜中之塗佈高分子薄膜形成用溶液之面(與高分子薄膜之接觸面)之表面自由能(mJ/m² )係測定各種液滴之接觸角(測定溫度：25℃)，以該值為基礎藉由北崎・畑理論求得。 　　亦即，將使用作為「分散成分」之二碘甲烷，作為「偶極成分」之1-溴萘，作為「氫鍵結成分」之蒸餾水作為液滴，使用協和界面科學(股)製之DM-70，藉由靜滴法，依據JIS R3257測定接觸角(測定溫度：25℃)，以該值為基礎藉由北崎・畑理論求得表面自由能(mJ/m² )。 (2)工程膜之算術平均粗糙度Ra之測定 　　剝離薄片中之塗佈高分子薄膜形成用溶液之面(與高分子薄膜之接觸面)之算術平均粗糙度Ra(nm)係使用Veeco Instruments公司製之光干涉顯微鏡NT1100，針對250,000μm² (500μm×500μm)之區域進行觀察，求出算術平均粗糙度(Ra)。 (3)高分子薄膜形成用溶液對工程膜之塗佈性 　　評價形成膜狀層合體時之塗佈性。高分子薄膜形成用溶液可對於工程膜均一塗佈時判定為「A」，於工程膜發生不均等而無法均一塗佈時判定為「B」。所得結果示於表1。 (4)高分子薄膜之剝離性 　　評價膜狀層合體中自工程膜剝離高分子薄膜時之剝離性。容易自工程膜剝離高分子薄膜時判定為「A」，高分子薄膜破裂無法剝離時判定為「B」。所得結果示於表1。 [試驗例2] 　　試驗例2中，除了作為工程膜使用聚對苯二甲酸乙二酯膜(三菱化學股份有限公司製之「DIAFOIL T100」，厚38μm)以外，藉與試驗例1同樣方法，製造膜狀層合體及高分子薄膜，並評價。所得結果示於表1。且，試驗例2所用之工程膜表面的表面自由能及算術平均粗糙度示於表1。 [試驗例3] 　　試驗例3中，除了作為工程膜使用LINTEC股份有限公司製之「SP-PET381031」)以外，藉與試驗例1同樣方法，製造膜狀層合體及高分子薄膜，並評價。所得結果示於表1。且，試驗例3所用之工程膜之剝離劑層表面的表面自由能及算術平均粗糙度示於表1。 [試驗例4] 　　試驗例4中，除了作為工程膜使用LINTEC股份有限公司製之「SP-PET38T100X」)以外，藉與試驗例1同樣方法，製造膜狀層合體及高分子薄膜，並評價。所得結果示於表1。且，試驗例4所用之工程膜之剝離劑層表面的表面自由能及算術平均粗糙度示於表1。

如由表1所示之結果所了解，可知使用含有環狀烯烴共聚物之高分子薄膜形成用溶液時，較好使用試驗例1所用之工程膜。因此，以下實施例及比較例中，使用試驗例1所用之工程膜。 [實施例1] 1.高分子薄膜之製造 (1)工程膜之製造 　　實施例1之工程膜具有基材及設於基材上之剝離劑層。 　　將聚矽氧改性醇酸樹脂與胺基樹脂之混合物(信越化學工業股份有限公司製：商品名「KS-882」) 100重量份與對-甲苯磺酸(硬化劑) 1重量份以甲苯稀釋，調製固形分濃度2質量%之塗佈液。 　　其次，於厚38μm之聚對苯二甲酸乙二酯(PET)膜(三菱化學股份有限公司製之「DIAFOIL T100」)上以馬亞棒塗佈所得塗佈液，於140℃、60秒加熱並乾燥，獲得形成有平均厚0.1μm之剝離劑層的工程膜。 (2)高分子薄膜形成用溶液之調製 　　將環狀烯烴共聚物(三井化學股份有限公司製之「APEL6011T」、玻璃轉移點105℃、MFR 26g/10min)之溶液(固形分10質量%)以甲苯溶解，稀釋至固形分3質量%，製作高分子薄膜形成用溶液(黏度2.4mPa・s)。而且，實施例1所用之環狀烯烴共聚物之玻璃轉移點(T_g )及MFR示於表2。 (3)膜狀層合體之形成 　　其次，使用逆凹版塗佈器，於準備好的工程膜上以使乾燥後之高分子薄膜厚度成為800nm之方式塗佈高分子薄膜形成用溶液後，於100℃乾燥60秒，獲得膜狀層合體。 (4)高分子薄膜之製造 　　其次，藉由剝離膜狀層合體之工程膜，獲得高分子薄膜。 2.測定・評價 (1)高分子薄膜之表面碳濃度 　　為了求出高分子薄膜之表面碳濃度，進行高分子薄膜之表面XPS測定。測定係使用PHI Quantera SXM(ULVAC-PHI股份有限公司製)。X射線源係使用單色化Al・Kα以光電子取出角度45°進行測定，算出表面存在之碳元素濃度(單位：原子%)。所得結果示於表2。 (2)高分子薄膜之剝離力 　　測定所得膜狀層合體之自工程膜剝離高分子薄膜時之剝離力。 　　亦即，對膜狀層合體之高分子薄膜貼合黏著膠帶(日東電工股份有限公司製，No.31B)後，測定貼合黏著膠帶之狀態的高分子薄膜自工程膜180°剝離時之剝離力(mN/20mm)。所得結果示於表2。 (3)高分子薄膜之貼附性 　　首先，於支撐基材(東洋紡股份有限公司製之「CRISPR 75K2323」)之四方端部貼附雙面膠帶，製作具有雙面膠帶貼附部之支撐體。其次，將該支撐體之雙面膠帶貼附部貼附於膜狀層合體之高分子薄膜上。接著，自工程膜剝離支撐體及高分子薄膜，高分子薄膜轉移至支撐體表面。其次，自經轉移高分子薄膜之支撐體切掉雙面膠帶貼附部，製作高分子薄膜與支撐基材之層合體。該層合體以使高分子薄膜側與下述被接著物接觸之方式配置於被接著物上，自支撐基材上往返2次2kg滾輪，壓著高分子薄膜與被接著物。評價此時之貼附性。壓著後，以高分子薄膜全面貼附於被接著物而未剝離時判定為「A」，壓著後，高分子薄膜未貼附於被接著物，而有浮起或剝落時判定為「B」。所得結果示於表2。 　　PP：聚丙烯板(日立化成股份有限公司製之「PP-N-BN」，大小2mm×70mm×150mm) 　　玻璃：浮法板玻璃(旭玻璃股份有限公司製之「浮法板玻璃R3202 絲面加工」，大小2mm×70mm×150mm) (4)高分子薄膜上之水接觸角 　　為了評價高分子薄膜之對水的濡濕性，進行高分子薄膜上之水接觸角之測定。測定係使用接觸角計(協和界面科學股份有限公司製，DM-701)。測定對水之接觸角(23℃，50%RH)。所得結果示於表2。 (5)高分子薄膜上之水滑落角 　　為了評估高分子薄膜對水之撥水性，進行高分子薄膜上之水滑落角測定。於水平設置之高分子薄膜上放置水滴，測定將高分子薄膜緩緩傾斜時水滴開始流動之高分子薄膜的角度作為滑落角。所得結果示於表2。 (6)膜強度 　　膜強度係以蠕變計(山電股份有限公司製之商品名「Creep Meter RE2-3305CYAMADEN」)測定。具體而言，於溫度23℃、濕度50%RH之環境下靜置24小時後之膜狀層合體之高分子薄膜面貼附於開孔直徑1cm的孔之治具，剝離工程膜。將直徑1mmφ之圓柱型柱塞進入高分子薄膜之與治具孔中心部對應之部位。又，柱塞之進入速度設為0.5mm/秒。測定柱塞於孔深度方向進入至深度5mm時之最大應力(單位：mN/1mmφ)。又，測定進行10次，將平均值設為高分子薄膜之膜強度。所得結果示於表2。 [實施例2～4] 　　除了如表2所示變更環狀烯烴共聚物種類及高分子薄膜厚度以外，以與實施例1同樣方法，製造膜狀層合體及高分子薄膜並評價。所得結果示於表2。又，實施例2～4所用之環狀烯烴共聚物之玻璃轉移點(T_g )、MFR及高分子薄膜形成用溶液之黏度示於表2。 [比較例1及2] 　　除了如表2所示變更環狀烯烴共聚物種類及高分子薄膜厚度以外，以與實施例1同樣方法，製造膜狀層合體及高分子薄膜並評價。所得結果示於表2。又，比較例1及2所用之環狀烯烴共聚物之玻璃轉移點(T_g )、MFR及高分子薄膜形成用溶液之黏度示於表2。又，比較例1中，無法將聚合物溶解至期望濃度，無法以與實施例1同樣方法製造膜狀層合體及高分子薄膜。

如表2所示之結果，確認包含降冰片烯系聚合物(A)且厚度為10nm以上1000nm以下之高分子薄膜(實施例1～4)貼附性良好，水的接觸角大，水的滑落角小。由此確認實施例1～4所得之高分子薄膜即使不使用接著劑等，亦可對於被接著物密著，具有高的撥水性。且，實施例1～4所得之高分子薄膜確認膜強度高，且具有自我支撐性。Hereinafter, embodiments of the present invention will be taken as examples and described based on the drawings. The present invention is not limited to the contents of the embodiments. In addition, in the drawings, for ease of explanation, some parts are shown enlarged or reduced. [Polymer Film] The polymer film 1 of this embodiment is a self-supporting film as shown in FIG. 1 . Also, the so-called "self-supporting property" in this specification refers to the property that the polymer film 1 can form a film alone when the polymer film 1 is not laminated on other supports. More specifically, it can be said that the film strength is 5mN/ 1mmφ or more. Yes, for a "self-supporting" membrane, the membrane strength is preferably at least 10mN/1mmφ, more preferably at least 20mN/1mmφ. The film strength can be measured with a creep meter (for example, "Creepmeter RE2-3305CYAMADEN" manufactured by Shandian Co., Ltd.). Specifically, it can be measured by the method described in the Examples described later. The thickness of the polymer thin film 1 must be not less than 10 nm and not more than 1000 nm. When the thickness of the polymer film 1 is not less than 10 nm and not more than 1000 nm, it can be attached to a desired adherend such as skin without using an adhesive or the like. The thickness of the polymer film 1 can be measured by a spectroscopic ellipsometer (product name "M-2000") manufactured by JA Woollam. The thickness of the polymer thin film 1 is preferably at least 30 nm, more preferably at least 50 nm, more preferably at least 100 nm, particularly preferably at least 150 nm. Furthermore, the thickness of the polymer thin film 1 is preferably at most 900 nm, more preferably at most 700 nm, still more preferably at most 550 nm, particularly preferably at most 400 nm. From the viewpoint of water repellency, the surface carbon concentration of the polymer film 1 is preferably at least 90 atomic %, more preferably at least 95 atomic %, most preferably at least 99 atomic %. The surface carbon concentration can be measured by X-ray photoelectron spectroscopy (XPS). The polymer film 1 must contain a norbornene-based polymer (A) containing 10 mol% or more of a constituent unit represented by the following general formula (1). When the norbornene-based polymer (A) does not contain 10 mol% or more of the constituent unit represented by the following general formula (1), a polymer film having self-supporting properties at a desired thickness and high water repellency cannot be obtained. The content of the constituent unit represented by the following general formula (1) in the polymer film 1 is preferably at least 20 mol%, more preferably at least 50 mol%.

In the aforementioned general formula (1), X ¹ and X ² are the same or different, respectively representing a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted The alkenyl, hydroxyl or carboxyl, X ¹ and X ² can also combine with each other to form a ring. Examples of the substituents of the alkyl group, alkoxy group and alkenyl group include a halogen atom, a hydroxyl group, a carboxyl group, an acryl group, a methacryl group, an epoxy group and the like. The carbon number of the alkyl group is preferably from 1 to 5, more preferably from 1 to 3. The number of carbon atoms in the alkoxy group is preferably from 1 to 5, more preferably from 1 to 3. The carbon number of the alkenyl group is preferably from 2 to 5, more preferably from 2 to 3. (Norbornene-Based Polymer (A)) The norbornene-based polymer (A) only needs to contain 10 mol% of the constituent unit represented by the above general formula (1), and may be a norbornene-based homopolymer or It is a norbornene-based copolymer. The norbornene-based polymer (A) is a polymer comprising at least one norbornene-based compound as a monomer. Examples of norbornene-based compounds include norbornene (bicyclo[2.2.1]hept-2-ene), compounds having a ring structure containing a bicyclic ring related to norbornene (such as dicyclopentadiene), and the like Derivatives of These may be used individually by 1 type, and may mix and use 2 or more types. Examples of monomers other than norbornene-based compounds include cyclopentadiene, tetracyclododecene, and the like. These may be used individually by 1 type, and may mix and use 2 or more types. By using a norbornene-based compound as at least one type of monomer, the polymer (homopolymer or copolymer) obtained by polymerizing the monomer has a constituent unit represented by the aforementioned general formula (1). Examples of norbornene-based polymers (A) include ring-opening metathesis polymer hydrogenated polymers of norbornene-based monomers (specifically, ZEONEX (registered trademark) series manufactured by Japan ZEON Co., Ltd.), norbornene and Copolymers of ethylene (specifically obtained as TOPAS (registered trademark) series manufactured by POLYPLASTIC Co., Ltd.), copolymers based on ring-opening polymerization of dicyclopentadiene and tetracyclopentadodecene (specifically obtained from Japan ZEON Co., Ltd. Co., Ltd. ZEONOR (registered trademark) series), copolymers of ethylene and tetracyclododecene (specifically obtained from Mitsui Chemicals Co., Ltd. APEL (registered trademark) series), and dicyclopentadiene and Polar group-containing cyclic olefin resins (specifically, available as ARTON (registered trademark) series manufactured by JSR Co., Ltd.) and the like made of methacrylate as a raw material. These may be used individually by 1 type, and may mix and use 2 or more types. The norbornene-based polymer (A) may have a crosslinked structure. Here, the type of the crosslinking agent that causes the crosslinked structure is arbitrary. Examples of the crosslinking agent include organic peroxides (for example, dicumyl peroxide, etc.), compounds having epoxy groups, and the like. These may be used individually by 1 type, and may mix and use 2 or more types. The crosslinking agent can crosslink between one kind of polymers constituting the norbornene-based polymer (A), or crosslink between different kinds of polymers. The bonding site of the crosslinking agent is also optional. It may also be cross-linked with atoms constituting the main chain in the polymer constituting the norbornene-based polymer (A), or may be cross-linked with atoms other than the main chain constituting side chains or functional groups. The degree of crosslinking is also optional, but when the degree of crosslinking is excessively advanced, the processability (especially formability) of the polymer film 1 containing the norbornene-based polymer (A) is excessively reduced, and the surface properties of the polymer film 1 Excessive deterioration may reduce the brittleness of the polymer film 1, so it should be limited to the range where these problems do not occur. The norbornene-based polymer (A) has thermoplasticity. The degree of thermoplasticity can be expressed by the melt flow rate (MFR) which represents the viscosity at the time of melting. The melt flow rate (MFR) of the norbornene-based polymer (A) at a temperature of 260°C and a load of 2.16kgf is preferably at least 20g/10min, more preferably at least 20g/10min, and at most 150g/10min, most preferably 25g More than /10min, less than 50g/10min. When MFR is within the above-mentioned range, thermoplasticity can be sufficiently improved, and processability such as molding can be improved. MFR can be measured according to the description of ASTM D1238. The glass transition point of the norbornene-based polymer (A) is preferably at most 140°C, more preferably at least 30°C and at most 120°C, from the viewpoint of coatability of the polymer film-forming solution. If the glass transition point is 140° C. or lower, the solvent solubility will be further improved. On the other hand, if the glass transition point is 30° C. or higher, it will have a self-supporting film-forming ability even at room temperature. The glass transition point can be determined using a differential scanning calorimeter. For example, using a differential scanning calorimeter ("DSC(Q2000)" manufactured by TA Instruments Co., Ltd.), the temperature rise rate is 10°C/min, and the temperature range is measured from -40°C to 200°C, and a graph is made, and the inflection point is confirmed from the graph. The glass transition point can be found. (Olefin-based polymers (B) other than norbornene-based polymers (A)) The polymer film 1 may also contain olefin-based polymers (B) other than norbornene-based polymers (A) (hereinafter referred to as is "non-NB olefin-based polymer (B)"). When using a non-NB olefin-based polymer (B), the content of the norbornene-based polymer (A) is preferably at least 50% by mass based on the total amount of the polymer, more preferably from the standpoint of self-supporting and water-repellent properties 70% by mass or more, and preferably 90% by mass or more. The non-NB olefin-based polymer (B) may be linear or may have a side chain. In addition, the non-NB olefin-based polymer (B) may have any functional group as long as it does not contain a norbornene ring, and its type and substitution density are arbitrary. It may be a low-reactivity functional group such as an alkyl group, or may be a high-reactivity functional group such as a carboxylic acid group. The non-NB olefin-based polymer (B) is an olefin-based polymer comprising at least one type of olefin as a monomer, and is an olefin-based polymer that does not contain a norbornene-based compound as a monomer. Therefore, the non-NB olefin-based polymer (B) is not particularly limited as long as it does not contain a norbornene ring in the polymer, and may be an aromatic ring polyolefin or an acyclic polyolefin. Examples of the aromatic ring polyolefin include at least one polyolefin comprising an olefin having an aromatic ring ring structure as at least one monomer. The non-NB olefin-based polymer (B) may be a homopolymer or a copolymer. (Adhesive) The polymer film 1 can adhere to an adhered object without using an adhesive or the like. Here, the substrate is not particularly limited, but examples include stainless steel, polyethylene, polypropylene, polycarbonate, glass, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), and semiconductor circuit boards Wait. By using these as adherends, water repellency can be easily imparted to arbitrary adherends. In addition, examples of adhered objects other than those described above include human beings, animals, clothing, hats, shoes, accessories, and the like. When these are used as an adherend, since the polymer film 1 is very thin, the sticking part is not conspicuous, and it is preferable because it is lightweight. In addition, since the polymer film 1 has high water repellency, it is resistant to sweat, rain, and the like. Therefore, the polymer film 1 can be used particularly preferably as a film for adhering a wearable terminal or the like to the skin or the like. [Method for Producing Polymer Film] The method for producing a polymer film in this embodiment is a method for producing a polymer film 1 . Therefore, the production method of the polymer film of the present embodiment is a method comprising the steps of: coating a solution for forming a polymer film containing the aforementioned norbornene-based polymer (A) on a process film, and drying it to form the aforementioned A step of polymer thin film (polymer thin film forming step), and a step of peeling said polymer thin film from said process film (stripping step). (Polymer Thin Film Formation Step) FIG. 2 is a schematic cross-sectional view showing the process film 2 used in the method of manufacturing the polymer thin film of the present embodiment. The engineering film 2 has a first surface 2A and a second surface 2B. In the step of forming the polymer film, in the first surface 2A and the second surface 2B of the engineering film shown in FIG. The film-forming solution was dried to form a polymer film 1 to obtain a film-like laminate 100 as shown in FIG. 3 . Here, the process film used in the polymer thin film forming step and the polymer thin film forming solution will be described. (Engineering Film) The engineering film 2 is not particularly limited. For example, from the viewpoint of ease of handling, the process film 2 preferably includes a release base material 21 and a release agent layer 22 formed on at least one surface of the release base material 21 . In this embodiment, the surface of the release agent layer 22 corresponds to the first surface 2A, and the surface opposite to the surface on which the release agent layer 22 of the release base material 21 is formed corresponds to the second surface 2B. As the peeling base material 21, for example, a paper base material, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper base material, a plastic film, and the like are exemplified. Examples of paper substrates include cellophane, fine paper, coated paper, coated paper, and the like. Examples of plastic films include polyester films (such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, etc.), and polyolefin films (such as polypropylene and polyethylene vinyl, etc.). These may be used alone or in combination of two or more. The release agent layer 22 may also be formed by applying a release agent. Examples of release agents include olefin-based resins, rubber-based elastomers (such as butadiene-based resins, isoprene-based resins, etc.), long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and silicones. Department of resin. Among these, the release agent is preferably selected from olefin-based resins, rubber-based elastomers (such as butadiene-based resins, isoprene-based resins, etc.), long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins. Any release agent selected from the group consisting of resins. These may be used alone or in combination of two or more. The release agent layer may further contain an antistatic agent, or may not contain an antistatic agent. The engineering film 2 preferably uses the release agent layer 22 to adjust the surface free energy and arithmetic average roughness of the first surface 2A. The surface free energy of the first surface 2A of the engineering film 2 is preferably not more than 40 mJ/m ² , more preferably not less than 20 mJ/m ² and not more than 40 mJ/m ² . If the surface free energy is 20 mJ/m ² or more, the solution for forming a polymer thin film can be well coated on the engineering membrane 2, and if the surface free energy is 40 mJ/m ² or less, the polymer can be easily peeled off from the engineering membrane 2. Film 1, can improve productivity. The surface free energy can be used to measure the contact angle of various droplets (measurement temperature: 25°C), and based on the value, it can be obtained by Kitazaki・Hata's theory. The surface arithmetic mean roughness (Ra) of the first surface 2A of the engineering film 2 is preferably not less than 40 nm, more preferably not less than 0.1 nm and not more than 30 nm, most preferably not less than 0.5 nm and not more than 25 nm. If the surface arithmetic mean roughness is within the aforementioned range, the unevenness formed on the polymer thin film 1 can be sufficiently suppressed, and the film strength of the polymer thin film 1 can be improved. The arithmetic mean roughness can be measured using the optical interference microscope NT1100 by Veeco Instruments, for example. The thickness of the engineering film 2 is not particularly limited. The thickness of the engineering film 2 is usually not less than 20 μm and not more than 200 μm, preferably not less than 25 μm and not more than 150 μm. The thickness of the release agent layer 22 is not particularly limited. When coating a solution containing a release agent on a release substrate to form the release agent layer 22, the thickness of the release agent layer 22 is preferably from 0.01 μm to 2.0 μm, more preferably from 0.03 μm to 1.0 μm. When a plastic film is used as the release substrate 21, the thickness of the plastic film is preferably from 3 μm to 50 μm, more preferably from 5 μm to 90 μm, particularly preferably from 10 μm to 40 μm. (Solution for forming a polymer film) The material substance for forming a polymer film as a solute in the solution for forming a polymer film is a norbornene-based polymer (A). Moreover, you may further use a non-NB olefin type polymer (B) as this material substance. The norbornene-based polymer (A) and the non-NB olefin-based polymer (B) are omitted since they have already been described. The type of solvent for the solution for forming the polymer film is not particularly limited as long as it can dissolve or uniformly disperse the material substance for forming the polymer film and can be evaporated by heating. For example, ethanol, propanol, isopropanol, acetone, toluene, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, methylene chloride, and chloroform are preferably used as solvents. These may be used alone or in combination of two or more. Moreover, as a boiling point of a solvent, it is preferable to set it as the value in the range of 30 to 160 degreeC, More preferably, it is the value in the range of 35 to 120 degreeC. Also, the concentration of the material substance in the solution for forming a polymer thin film is preferably set to a value within the range of 0.1% by mass or more and 20% by mass or less. If the concentration of the material substance in the solution for forming the polymer film is 0.1% by mass or more, the disadvantages that the required thickness cannot be obtained and the disadvantage that the solution viscosity cannot be optimized can be suppressed. On the other hand, if the concentration of the material substance in the solution for forming a polymer thin film is 20% by mass or less, the disadvantage that a uniform coating film cannot be obtained can be suppressed. Also, from the above viewpoint, the concentration of the material substance in the solution for forming the polymer thin film is more preferably set to a value in the range of 0.3% by mass to 15% by mass, and more preferably set to a range of 0.5% by mass to 10% by mass value within. Furthermore, the viscosity (measurement temperature: 25° C.) of the solution for forming a polymer thin film is preferably set to a value within a range of not less than 1 mPa·s and not more than 500 mPa·s. If the viscosity of the solution for forming a polymer film is 1 mPa·s or more, the defect of unevenness of the coating film can be suppressed. On the other hand, if the viscosity of the solution for forming a polymer film is 500 mPa·s or less, the disadvantage that a uniform coating film cannot be obtained can be suppressed. In addition, from the above point of view, the viscosity of the polymer thin film forming solution (measurement temperature: 25°C) is more preferably set to a value in the range of 1.5 mPa·s to 400 mPa·s, more preferably 2 mPa·s to 300 mPa・The value within the range below s. In addition, the viscosity of the solution for forming a polymer film was measured in accordance with 4.1 of JIS K7117-1 (Brookfield type rotational viscometer). In addition, drying conditions for forming the polymer thin film 1 for the coating layer of the polymer thin film forming solution formed on the process film 2 are not particularly limited. Drying of the coating layer is preferably carried out at a temperature of 40° C. to 120° C. and a drying time of 6 seconds to 300 seconds. If the drying temperature is 40° C. or higher, it is possible to suppress the disadvantages of excessively time-consuming drying or insufficient drying. On the other hand, when the drying temperature is 120° C. or lower, it is possible to suppress generation of wrinkles and curls. In addition, when the drying time is 6 seconds or more, it is possible to prevent insufficient drying. On the other hand, when the drying time is 300 seconds or less, it is possible to suppress generation of wrinkles and curls. Also, based on the above point of view, the drying conditions for the coating layer of the polymer film forming solution to become the polymer film 1 are more preferably set at a temperature of 50° C. to 110° C. and drying for 12 seconds to 180 seconds. The time is more preferably set at a temperature of 60° C. to 100° C. and a drying time of 18 seconds to 120 seconds. Moreover, it is preferable to apply|coat the solution for polymer film formation by the roll-to-roll (Roll to Roll) method. The reason is that if the roll-to-roll method is used, the polymer film 1 having a specific thickness can be formed more efficiently, so that the film-like laminate 100 can be mass-produced more efficiently. Also, when the roll-to-roll method is carried out, the coating device is preferably a bar coater, a gravure coater, or a die coater, more preferably a reverse gravure coater or a slot die coater. The reason for this is that the polymer thin film 1 having a specific thickness can be formed more efficiently with such a coating device. That is, if it is a bar coater, a reverse gravure coater, or a slot die coater, it is possible to form a nanometer-order thick polymer film 1 with a uniform thickness without causing wrinkles on the surface. Furthermore, bar coaters, reverse gravure coaters, and slot die coaters are excellent in economical efficiency in addition to their simple structures. (Peeling Step) In the peeling step, the polymer film 1 of the film laminate 100 shown in FIG. 3 is peeled from the process film 2 to obtain a self-supporting polymer film 1 . In the peeling step, the peeling force of the engineering film 2 from the polymer film 1 is preferably more than 5mN/20mm and less than 100mN/20mm, more preferably more than 10mN/20mm and less than 50mN/20mm, most preferably more than 15mN/20mm and less than 30mN /20mm or less. If the above-mentioned peeling force is 5 mN/20mm or more, the disadvantage of easy peeling of the engineering film and the polymer film can be suppressed in the step of forming the polymer film. In addition, if the above-mentioned peeling force is 100 mN/20 mm or less, in the peeling step, the disadvantages that the process film is not easily peeled from the polymer film or the polymer film is broken can be suppressed. The aforementioned peeling force can be adjusted by changing the type of peeling agent used for the engineering film 2, for example. [Film-like laminate] The film-like laminate 100 of this embodiment includes a polymer film 1 and a process film 2 as shown in FIG. 3 . This film-like laminate 100 is obtained by coating the aforementioned solution for forming a polymer thin film on a process film 2 and drying the coating layer to form a polymer thin film 1 . That is, the film-like laminate 100 can be obtained by the polymer film forming step in the above-mentioned polymer film production method of this embodiment. (Advantages and Effects of the Present Embodiment) According to the present embodiment, the following functions and effects can be exhibited. (1) It is possible to efficiently produce a self-supporting polymer having a thickness of 10 nm to 1000 nm, comprising a norbornene-based polymer (A) containing 10 mol% or more of the constituent unit represented by the aforementioned general formula (1) Film 1. (2) It is possible to provide a polymer film 1 that can adhere to an adherend without using an adhesive or the like and has high water repellency. [Variations of Embodiment] This embodiment is not limited to the aforementioned embodiment, and changes, improvements, etc. within the scope of achieving the purpose of this embodiment are included in this embodiment. For example, in the above-mentioned embodiment, although the process film 2 provided with the release base material 21 and the release agent layer 22 was used, it is not limited to this. For example, when the surface free energy and surface arithmetic average roughness of the peeling substrate 21 are within an appropriate range, a single-layer film formed from the peeling substrate 21 can also be used as the engineering film 2 . EXAMPLES The following examples are given to further describe the present invention in detail, but the present invention is by no means limited to these examples. [Test Example 1] 1. Selection of Engineering Film (1) Manufacturing of Engineering Film The engineering film of Experimental Example 1 has a release base material and a release agent layer provided on the release base material. Mix 100 parts by weight of a mixture of silicone-modified alkyd resin and amino resin (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardener) with toluene Dilute and prepare a coating solution with a solid content concentration of 2% by mass. Next, apply the obtained coating liquid on a polyethylene terephthalate (PET) film ("DIAFOIL T100" manufactured by Mitsubishi Chemical Co., Ltd.) with a thickness of 38 μm with a Mayer bar, and heat at 140°C for 60 seconds and dried to obtain a process film having a release agent layer having an average thickness of 0.1 μm. Next, the surface free energy and arithmetic average roughness of the release agent layer surface of the obtained engineering film are shown in Table 1. (2) Preparation of a solution for forming a polymer film A solution (solid content 10% by mass) of a cyclic olefin copolymer ("APEL6011T" manufactured by Mitsui Chemicals Co., Ltd., glass transition point 105°C, MFR 26g/10min) was mixed with Toluene was dissolved and diluted to a solid content of 3% by mass to prepare a solution for forming a polymer thin film. (3) Formation of a film-like laminate Next, use a reverse gravure coater to coat the solution for forming a polymer film on the prepared engineering film so that the thickness of the polymer film after drying becomes 800 nm, and then apply the solution at 100 It dried at 60°C for 60 seconds to obtain a film-like laminate. 2. Measurement and evaluation ( ¹ ) Measurement of surface free energy of engineering film Measure the contact angle of various droplets (measurement temperature: 25°C), and obtain it based on the value based on the theory of Kitazaki and Hata. That is, diiodomethane as the "dispersion component", 1-bromonaphthalene as the "dipole component", and distilled water as the "hydrogen bonding component" were used as droplets, and DM produced by Kyowa Interface Science Co., Ltd. was used. -70, the contact angle was measured according to JIS R3257 by the static drop method (measurement temperature: 25°C), based on this value, the surface free energy (mJ/m ² ) was obtained by the Kitazaki Hata theory. (2) Determination of the arithmetic average roughness Ra of the engineering film The arithmetic average roughness Ra (nm) of the surface (the contact surface with the polymer film) coated with the solution for forming the polymer film in the peeling sheet is used by Veeco Instruments The optical interference microscope NT1100 manufactured by the company observes a region of 250,000 μm ² (500 μm×500 μm), and calculates the arithmetic mean roughness (Ra). (3) Coatability of the solution for forming a polymer thin film to a process film The coating property when forming a film-like laminate was evaluated. The solution for forming a polymer thin film can be judged as "A" when the process film is applied uniformly, and it can be judged as "B" when the process film is not uniformly coated due to unevenness. The obtained results are shown in Table 1. (4) Peelability of Polymer Film The peelability when the polymer film was peeled from the process film in the film-like laminate was evaluated. When the polymer film is easily peeled from the process film, it is judged as "A", and when the polymer film is broken and cannot be peeled, it is judged as "B". The obtained results are shown in Table 1. [Test Example 2] In Test Example 2, except that a polyethylene terephthalate film ("DIAFOIL T100" manufactured by Mitsubishi Chemical Corporation, thickness 38 μm) was used as the engineering film, by the same method as in Test Example 1, Film-like laminates and polymer films were produced and evaluated. The obtained results are shown in Table 1. In addition, the surface free energy and arithmetic mean roughness of the surface of the engineering film used in Test Example 2 are shown in Table 1. [Test Example 3] In Test Example 3, except that "SP-PET381031" manufactured by Lintec Co., Ltd. was used as the engineering film, a film-like laminate and a polymer film were produced and evaluated in the same manner as in Test Example 1. The obtained results are shown in Table 1. In addition, the surface free energy and arithmetic mean roughness of the release agent layer surface of the process film used in Test Example 3 are shown in Table 1. [Test Example 4] In Test Example 4, except that "SP-PET38T100X" manufactured by Lintec Co., Ltd. was used as the engineering film, a film-like laminate and a polymer film were produced and evaluated in the same manner as in Test Example 1. The obtained results are shown in Table 1. In addition, the surface free energy and arithmetic mean roughness of the surface of the release agent layer of the process film used in Test Example 4 are shown in Table 1.

As understood from the results shown in Table 1, it can be seen that when using a solution for forming a polymer film containing a cyclic olefin copolymer, it is preferable to use the process film used in Test Example 1. Therefore, in the following examples and comparative examples, the engineering film used in Test Example 1 was used. [Example 1] 1. Manufacture of polymer film (1) Manufacture of engineering film The engineering film of Example 1 has a base material and a release agent layer provided on the base material. Mix 100 parts by weight of a mixture of silicone-modified alkyd resin and amino resin (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardener) with toluene Dilute and prepare a coating solution with a solid content concentration of 2% by mass. Next, apply the obtained coating liquid on a polyethylene terephthalate (PET) film ("DIAFOIL T100" manufactured by Mitsubishi Chemical Co., Ltd.) with a thickness of 38 μm with a Mayer bar, and heat at 140°C for 60 seconds and dried to obtain a process film having a release agent layer having an average thickness of 0.1 μm. (2) Preparation of a solution for forming a polymer film A solution (solid content 10% by mass) of a cyclic olefin copolymer ("APEL6011T" manufactured by Mitsui Chemicals Co., Ltd., glass transition point 105°C, MFR 26g/10min) was mixed with Toluene was dissolved and diluted to a solid content of 3% by mass to prepare a solution for forming a polymer film (viscosity: 2.4mPa·s). Furthermore, the glass transition point (T _g ) and MFR of the cyclic olefin copolymer used in Example 1 are shown in Table 2. (3) Formation of a film-like laminate Next, use a reverse gravure coater to coat the solution for forming a polymer film on the prepared engineering film so that the thickness of the polymer film after drying becomes 800 nm, and then apply the solution at 100 It dried at 60°C for 60 seconds to obtain a film-like laminate. (4) Manufacture of polymer thin film Next, the polymer thin film was obtained by peeling off the engineering film of the film-like laminate. 2. Measurement and evaluation (1) Surface carbon concentration of the polymer film In order to obtain the surface carbon concentration of the polymer film, the surface XPS measurement of the polymer film was performed. As the measurement system, PHI Quantera SXM (manufactured by ULVAC-PHI Co., Ltd.) was used. The X-ray source is measured by monochromatic Al・Kα at a photoelectron extraction angle of 45°, and the concentration of carbon element present on the surface (unit: atomic %) is calculated. The obtained results are shown in Table 2. (2) Peeling Force of Polymer Film The peeling force of the obtained film laminate was measured when the polymer film was peeled off from the engineering film. That is, after sticking an adhesive tape (manufactured by Nitto Denko Co., Ltd., No. 31B) to the polymer film of the film-like laminate, the peeling of the polymer film with the adhesive tape attached at 180° from the process film was measured. Force (mN/20mm). The obtained results are shown in Table 2. (3) Adherence of polymer film First, a double-sided tape was attached to the square ends of the support substrate ("CRISPR 75K2323" manufactured by Toyobo Co., Ltd.) to produce a support with a double-sided tape attached portion. Next, the double-sided tape attachment part of the support is attached to the polymer film of the film-like laminate. Next, the support body and the polymer film are peeled off from the engineering membrane, and the polymer film is transferred to the surface of the support body. Next, the attached part of the double-sided tape is cut off from the support of the transferred polymer film to make a laminate of the polymer film and the support substrate. The laminate was placed on the adherend so that the polymer film side was in contact with the adherend described below, and a 2 kg roller reciprocated twice from the supporting substrate to press the polymer film and the adherend. The adhesiveness at this time was evaluated. After pressing, when the polymer film is fully attached to the adhered object without peeling off, it is judged as "A". After pressing, when the polymer film is not attached to the adhered object, it is judged as "A". B". The obtained results are shown in Table 2. PP: Polypropylene sheet ("PP-N-BN" manufactured by Hitachi Chemical Co., Ltd., size 2mm×70mm×150mm) Glass: Float glass ("Float glass R3202 silk surface" manufactured by Asahi Glass Co., Ltd. Processing", size 2mm×70mm×150mm) (4) Water contact angle on the polymer film In order to evaluate the wettability of the polymer film to water, the water contact angle on the polymer film was measured. For the measurement, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM-701) was used. Measure the contact angle to water (23°C, 50%RH). The obtained results are shown in Table 2. (5) Water sliding angle on the polymer film In order to evaluate the water repellency of the polymer film to water, the water sliding angle on the polymer film was measured. Water droplets are placed on a horizontal polymer film, and the angle of the polymer film at which water droplets start to flow when the polymer film is gently tilted is measured as the slip angle. The obtained results are shown in Table 2. (6) Film strength The film strength was measured with a creep meter (trade name "Creep Meter RE2-3305CYAMADEN" manufactured by Shandian Co., Ltd.). Specifically, after standing for 24 hours in an environment with a temperature of 23°C and a humidity of 50%RH, the polymer film surface of the film-like laminate was attached to a jig with a hole diameter of 1 cm, and the engineering film was peeled off. Insert a cylindrical plunger with a diameter of 1mmφ into the part of the polymer film corresponding to the center of the jig hole. Also, the entry speed of the plunger was set at 0.5 mm/sec. Measure the maximum stress (unit: mN/1mmφ) when the plunger enters the depth of the hole to a depth of 5mm. In addition, the measurement was performed 10 times, and the average value was used as the film strength of the polymer thin film. The obtained results are shown in Table 2. EXAMPLES 2-4 Except having changed the kind of cyclic olefin copolymer and polymer film thickness as shown in Table 2, it carried out similarly to Example 1, and produced and evaluated the film-like laminated body and polymer film. The obtained results are shown in Table 2. Also, Table 2 shows the glass transition point (T _g ) and MFR of the cyclic olefin copolymers used in Examples 2 to 4, and the viscosity of the solution for forming a polymer film. [Comparative Examples 1 and 2] A film-like laminate and a polymer film were produced and evaluated in the same manner as in Example 1, except that the type of cyclic olefin copolymer and the thickness of the polymer film were changed as shown in Table 2. The obtained results are shown in Table 2. Also, Table 2 shows the glass transition point (T _g ), MFR, and viscosity of the polymer film-forming solution of the cyclic olefin copolymers used in Comparative Examples 1 and 2. Also, in Comparative Example 1, the polymer could not be dissolved to a desired concentration, and a film-like laminate and a polymer film could not be produced by the same method as in Example 1.

As shown in the results in Table 2, it was confirmed that the polymer films (Examples 1-4) containing the norbornene-based polymer (A) and having a thickness of 10 nm to 1000 nm (Examples 1 to 4) had good adhesion, a large contact angle of water, and a large water contact angle. The slip angle is small. From this, it was confirmed that the polymer films obtained in Examples 1 to 4 can be adhered to the adherend even without using an adhesive or the like, and have high water repellency. Furthermore, it was confirmed that the polymer thin films obtained in Examples 1 to 4 had high film strength and self-supporting properties.

1‧‧‧polymer film 2‧‧‧engineering film 2A‧‧‧first surface 2B‧‧‧second surface 21‧‧‧peeling substrate 22‧‧‧release agent layer 100‧‧‧film laminate

Fig. 1 is a schematic view showing a polymer film according to an embodiment of the present invention. Fig. 2 is a schematic diagram showing the engineering film used in the manufacturing method of the polymer thin film according to the embodiment of the present invention. Fig. 3 is a schematic view showing the state in which a polymer film is formed on a process film and a film-like laminate is produced in the method for producing a polymer film according to an embodiment of the present invention.

1‧‧‧polymer film

2‧‧‧Engineering film

2A‧‧‧first side

2B‧‧‧Second side

21‧‧‧Peel off substrate

22‧‧‧Release agent layer

100‧‧‧film laminate

Claims (12)

A polymer film characterized by comprising a norbornene-based polymer (A) containing 10 mol% or more of a constituent unit represented by the following general formula (1), having a thickness of 10 nm to 1000 nm, and having self-supporting properties, and It can still adhere to the adhered object without using adhesive;

In the aforementioned general formula (1), X ¹ and X ² are the same or different, respectively representing a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted The alkenyl, hydroxyl or carboxyl, X ¹ and X ² can also combine with each other to form a ring. The polymer film according to claim 1, wherein the norbornene-based polymer (A) is a norbornene-based copolymer. The polymer film according to claim 1, wherein the polymer film contains 50% by mass or more of the norbornene-based polymer (A). Such as the polymer film of claim 1, wherein the aforementioned norbornene is polymerized The glass transition point of the substance (A) is 140°C or lower. The polymer film according to claim 1, wherein the melt flow rate of the norbornene-based polymer (A) at a temperature of 260° C. and a load of 2.16 kgf is 20 g/10 min or more. The polymer thin film according to any one of claims 1 to 5, wherein the surface carbon concentration of the aforementioned polymer thin film is 90 atomic % or more. A film-like laminate characterized by comprising an engineering film and the polymer film according to any one of Claims 1 to 6 formed on the aforementioned engineering film. The film-like laminate according to claim 7, wherein the surface free energy of the aforementioned engineering film is 40 mJ/m ² or less. The film-like laminate according to claim 7 or 8, wherein the surface arithmetic average roughness of the aforementioned engineering film is 40 nm or less. A method for producing a polymer film, which is to manufacture the polymer film according to any one of claims 1 to 6, characterized in that it has the following steps: coating the engineering film comprising the aforementioned norbornene-based polymer ( A) The solution for forming a polymer thin film, and drying, forming the step of the aforementioned polymer thin film, and the step of peeling the aforementioned polymer thin film from the aforementioned engineering film. The method for producing a polymer thin film according to claim 10, wherein the surface free energy of the engineering film is 40 mJ/m ² or less. The method for manufacturing a polymer thin film according to claim 10 or 11, wherein the arithmetic average roughness of the surface of the engineering film is 40 nm or less.

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