TW201920390A - Polymer thin film, film-form laminate, and method for producing polymer thin film - Google Patents

Abstract

This polymer thin film is characterized by containing a norbornene polymer (A) containing at least 10 mol% of a constituent unit represented by general formula (1), having a thickness of 10 nm to 1000 nm, and having self-supporting properties. (In general formula (1), X1 and X2 may be the same or different, and may respectively represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, a hydroxyl group, or a carboxyl group, and X1 and X2 may be bonded to one another to form a ring).

Description

Polymer film, film-like laminate, and method for manufacturing polymer film

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

A film made of a cyclic olefin-based resin has been used as, for example, a dielectric film for a film condenser. For example, Document 1 (Japanese Patent Application Laid-Open No. 2015-183181) document describes a highly insulating film mainly composed of a resin. In this highly insulating film, the resin-based amorphous resin is used. Further, the minimum refractive index in the plane direction of the highly insulating film is set to Ny, the refractive index in a direction orthogonal to the Ny in the plane direction of the highly insulating film is set to Nx, and the highly insulating film is 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) About the literature, if the thickness of the resin film is in the range of several tens to several hundreds of nm, there are electrostatic forces and wettability, even without using an adhesive, etc. In the case of adherence to the adherend. However, the highly insulating film described in Document 1 cannot adhere to the adherend. In addition, although Document 1 states that the average thickness is preferably 0.5 μm or more and 7.0 μm or less, according to the method for manufacturing a highly insulating film described in Document 1, the film thickness cannot be made into a nanometer grade. Further, in Document 1, for example, although a film produced by a solution casting method is subjected to an extension treatment, by this method, the film thickness cannot be made into a nanometer grade.

An object of the present invention is to provide a polymer film, a film-like laminate, and a polymer film having high water repellency, which can be adhered to an adherend without using an adhesive or the like. According to one aspect of the present invention, there is provided a polymer film characterized by comprising a norbornene polymer (A) containing a constituent unit represented by the following general formula (1) in an amount of 10 mol% or more, and having a thickness of 10 nm or more and 1000 nm or less. Below, and self-supporting. In the following general formula (1), X ¹ and X ² are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted Or unsubstituted alkenyl, hydroxyl or carboxyl group, X ¹ and X ² may be combined with each other to form a ring. In one aspect of the present invention, the norbornene-based polymer (A) -based norbornene-based copolymer is preferable. In one aspect of the present invention, the polymer film preferably contains the norbornene-based polymer (A) in an amount of 50% by mass or more. In one aspect of the present invention, the glass transition point of the norbornene-based polymer (A) is preferably 140 ° C or lower. In one aspect of the present invention described above, the melt flow rate of the norbornene-based polymer (A) at a temperature of 260 ° C and a load of 2.16 kgf is preferably 20 g / 10 min or more. In one aspect of the present invention, the surface carbon concentration of the polymer film is preferably 90 atomic% or more. According to an aspect of the present invention, there is provided a film-like laminate, which is 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 one aspect of the present invention, the surface free energy of the engineered film is preferably 40 mJ / m ² or less. In one aspect of the present invention, it is preferred that the arithmetic mean roughness of the surface of the engineering film is 40 nm or less. According to one aspect of the present invention, a method for manufacturing a polymer film is provided. The method for manufacturing the polymer film according to one aspect of the present invention is characterized by having the following steps: coating the engineering film with the aforementioned norborneol A solution for forming a polymer film of the olefin polymer (A), and drying to form the polymer film; and a step of peeling the polymer film from the engineering film. In one aspect of the present invention, the surface free energy of the engineered film is preferably 40 mJ / m ² or less. In one aspect of the present invention, it is preferred that the arithmetic mean roughness of the surface of the 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 polymer film having high water repellency without using an adhesive or the like, and which can be adhered to an adherend.

The embodiment of the present invention will be described below as an example 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, there are portions shown enlarged or reduced. [Polymer film] As shown in FIG. 1, the polymer film 1 of this embodiment is a film having self-supporting properties. The “self-supporting property” in this specification refers to the property that the polymer thin film 1 alone can form a film when the polymer thin film 1 is not laminated on another support, and more specifically, the film strength is 5 mN / 1mmφ or more. Yes, for a "self-supporting" film, the film strength is preferably 10 mN / 1 mmφ or more, and more preferably 20 mN / 1 mmφ or more. The film strength can be measured with a creep meter (for example, a trade name "Creepmeter RE2-3305CYAMADEN" manufactured by Yamaden Corporation). Specifically, it can measure by the method described in the Example mentioned later. The thickness of the polymer film 1 must be 10 nm to 1000 nm. When the thickness of the polymer film 1 is 10 nm or more and 1000 nm or less, a desired adherend such as skin can be adhered 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 film 1 is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and particularly preferably 150 nm or more. The thickness of the polymer film 1 is preferably 900 nm or less, more preferably 700 nm or less, still more preferably 550 nm or less, and particularly preferably 400 nm or less. From the viewpoint of water repellency, the surface carbon concentration of the polymer film 1 is preferably 90 atomic% or more, more preferably 95 atomic% or more, and particularly preferably 99 atomic% or more. 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 a constituent unit represented by the following general formula (1) in an amount of 10 mol% or more, a polymer film having self-supporting properties and high water repellency at a desired thickness cannot be obtained. The content of the constituent units represented by the following general formula (1) occupied in the polymer film 1 is preferably 20 mol% or more, and more preferably 50 mol% or more. In the aforementioned general formula (1), X ¹ and X ² are the same or different, and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group, respectively. X ¹ and X ² may be bonded to each other to form a ring. Examples of the substituents of the alkyl group, the alkoxy group, and the alkenyl group include a halogen atom, a hydroxyl group, a carboxyl group, an allyl group, a methacryl group, and an epoxy group. The carbon number of the alkyl group is preferably from 1 to 5, more preferably from 1 to 3. The carbon number of the alkoxy group is preferably from 1 to 5, more preferably from 1 to 3. The carbon number of the alkenyl group is preferably 2 to 5, more preferably 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 general formula (1), and may be a norbornene-based homopolymer or may be It is a norbornene-based copolymer. The norbornene-based polymer (A) is a polymer containing at least one kind of a norbornene-based compound as a monomer. Examples of norbornene-based compounds include norbornene (bicyclo [2.2.1] hept-2-ene), compounds having a cyclic structure containing a norbornene-related bicyclic ring (such as dicyclopentadiene), and the like Of its derivatives. These can be used alone or in combination of two or more. Examples of the monomer other than the norbornene-based compound include cyclopentadiene and tetracyclododecene. These can be used alone or in combination of two or more. A polymer (homopolymer or copolymer) obtained by polymerizing a monomer by using a norbornene-based compound as at least one monomer has a constituent unit represented by the aforementioned general formula (1). Examples of the norbornene-based polymer (A) include a ring-opening metathesis polymer hydrogenated polymer of a norbornene-based monomer (specifically obtained from the ZEONEX (registered trademark) series made by Japan Zeon Corporation), norbornene and Copolymers of ethylene (specifically obtained from TOPAS (registered trademark) series manufactured by POLYPLASTIC Co., Ltd.), copolymers based on ring-opening polymerization of dicyclopentadiene and tetracyclododecadiene (specifically, Japan Zeon shares 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 Cyclic olefin resin containing a polar group as a raw material of methacrylate (specifically, it is obtained from ARTON (registered trademark) series manufactured by JSR Corporation) and the like. These can be used alone or in combination of two or more. The norbornene-based polymer (A) may have a crosslinked structure. Here, the kind of crosslinking agent which causes a crosslinking structure is arbitrary. Examples of the cross-linking agent include organic peroxides (for example, dicumyl peroxide, etc.) and compounds having an epoxy group. These can be used alone or in combination of two or more. The cross-linking agent may be cross-linked between one kind of polymers constituting the norbornene-based polymer (A), or may be cross-linked between different kinds of polymers. The binding site of the crosslinking agent is also arbitrary. It may be crosslinked with atoms constituting the main chain in the polymer constituting the norbornene-based polymer (A), and may be crosslinked with atoms other than the main chain constituting the side chain or the functional group. The degree of cross-linking is also arbitrary, but when the degree of cross-linking is excessive, the processability (especially moldability) of the polymer film 1 containing the norbornene-based polymer (A) is excessively reduced, and the surface properties of the polymer film 1 There is a concern that the degradation of the polymer film 1 due to excessive degradation will reduce the brittleness, so it should be limited to a range where such problems do not occur. The norbornene-based polymer (A) has thermoplasticity. This degree of thermoplasticity can be expressed by a melt flow rate (MFR), which indicates a viscosity at the time of melting. The melt flow rate (MFR) of the norbornene polymer (A) at a temperature of 260 ° C and a load of 2.16 kgf is preferably 20 g / 10 min or more, more preferably 20 g / 10 min or more, 150 g / 10 min or less, and particularly preferably 25 g Above / 10min, below 50g / 10min. When the MFR is within the above range, the 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 140 ° C. or lower, more preferably 30 ° C. or higher and 120 ° C. or lower, from the viewpoint of the applicability of the solution for forming a polymer film. When the glass transition point is 140 ° C or lower, the solvent solubility is further improved. On the other hand, when the glass transition point is 30 ° C or higher, the film has the ability to form a self-supporting film even at room temperature. The glass transition point can be measured using a differential scanning calorimeter. For example, a differential scanning calorimeter ("DSC (Q2000)" manufactured by TA Instruments) is used to perform a measurement at a temperature rise rate of 10 ° C / min and a temperature range from -40 ° C to 200 ° C, and a graph is formed. The inflection point is confirmed from the graph. The glass transition point can be determined. (Olefin polymer (B) other than norbornene polymer (A)) The polymer film 1 may contain an olefin polymer (B) other than norbornene polymer (A) (hereinafter referred to as the case may be "Non-NB olefin polymer (B)"). When a non-NB olefin-based polymer (B) is used, the content of the norbornene-based polymer (A) is preferably 50% by mass or more based on the total amount of the polymer from the viewpoint of self-supporting property and water repellency. It is 70% by mass or more, and particularly preferably 90% by mass or more. The non-NB olefin polymer (B) may be linear or may have a side chain. In addition, the non-NB olefin polymer (B) may have any functional group as long as it does not contain a norbornene ring, and its kind and substitution density are arbitrary. It may be a functional group having a low reactivity such as an alkyl group, or a functional group having a high reactivity such as a carboxylic acid group. The non-NB olefin-based polymer (B) is an olefin-based polymer having at least one olefin as a monomer, and is an olefin-based polymer that does not have a norbornene-based compound as a monomer. Therefore, the non-NB olefin polymer (B) is not particularly limited as long as it does not contain a norbornene ring in the polymer, and may be an aromatic cyclic polyolefin or an acyclic polyolefin. Examples of the aromatic cyclic polyolefin include polyolefins having at least one kind of olefin having an cyclic structure of an aromatic ring as a monomer. The non-NB olefin-based polymer (B) may be a homopolymer or a copolymer. (Subject) The polymer film 1 can be adhered to the adherend without using an adhesive or the like. Here, the adherend is not particularly limited, but examples thereof include stainless steel, polyethylene, polypropylene, polycarbonate, glass, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), and a semiconductor circuit board. Wait. By using these as adherends, water repellency can be easily provided to any adherend. Examples of the adherend other than the above include humans, animals, clothing, hats, shoes, and accessories. When these are used as adherends, since the polymer film 1 is very thin, the attachment portion is not conspicuous, and it is preferable to be lightweight. Moreover, 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 suitably as a film which adheres a wearable terminal etc. to the skin etc. [Manufacturing method of polymer film] The manufacturing method of polymer film of this embodiment is a manufacturing method of polymer film for manufacturing polymer film 1. Therefore, the method for manufacturing a polymer film according to this embodiment is a method including the steps of applying a polymer film-forming solution containing the aforementioned norbornene-based polymer (A) to an engineering film, and drying the solution to form the foregoing. A step of polymer film (polymer film forming step), and a step of peeling the polymer film from the engineering film (peeling step). (Polymer film forming step) FIG. 2 is a schematic cross-sectional view showing an engineering film 2 used in the method for manufacturing a polymer film according to the present embodiment. The engineering film 2 has a first surface 2A and a second surface 2B. In the polymer film formation step, the first surface 2A and the second surface 2B of the engineering film shown in FIG. 2 are coated on the first surface 2A with a polymer containing the aforementioned norbornene-based polymer (A). The film-forming solution is dried and formed into a polymer film 1 to obtain a film-like laminate 100 as shown in FIG. 3. Here, the engineering film used in the polymer film formation step and the polymer film formation solution will be described. (Engineered Film) The engineering film 2 is not particularly limited. For example, from the viewpoint of easy handling, the engineering film 2 preferably includes a release substrate 21 and a release agent layer 22 formed on at least one surface of the release substrate 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 of the release substrate 21 on which the release agent layer 22 is formed corresponds to the second surface 2B. Examples of the release substrate 21 include a paper substrate, a laminated paper in which a thermoplastic resin such as polyethylene is laminated on the paper substrate, and a plastic film. Examples of the paper substrate include cellophane, fine paper, coated paper and coated paper. Examples of plastic films include, for example, polyester films (such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), and polyolefin films (such as polypropylene and polyethylene). Ethylene, etc.). These may be used individually by 1 type, and may be used in combination of 2 or more type. The release agent layer 22 may be formed by applying a release agent. Examples of the release agent include olefin-based resins, rubber-based elastomers (e.g., 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 (for example, butadiene-based resins, isoprene-based resins, etc.), long-chain alkyl-based resins, alkyd-based resins, and fluorine. Any release agent selected from the group of resins. These may be used individually by 1 type, and may be used in combination of 2 or more type. The release agent layer may further contain an antistatic agent, or may not contain an antistatic agent. The engineered film 2 preferably adjusts the surface free energy and the arithmetic average roughness of the first surface 2A by the release agent layer 22. The surface free energy of the first surface 2A of the engineering film 2 is preferably 40 mJ / m ² or less, more preferably 20 mJ / m ² or more and 40 mJ / m ² or less. If the surface free energy is 20 mJ / m ² or more, the polymer film-forming solution can be well coated on the engineering film 2, and if the surface free energy is 40 mJ / m ² or less, the polymer can be easily peeled from the engineering film 2 Film 1 can improve productivity. The surface free energy can be used to measure the contact angle (measurement temperature: 25 ° C) of various droplets, and the value can be obtained by the Kitazaki- 畑 theory based on the value. The surface arithmetic average roughness (Ra) of the first surface 2A of the engineering film 2 is preferably 40 nm or less, more preferably 0.1 nm or more and 30 nm or less, and particularly preferably 0.5 nm or more and 25 nm or less. If the surface arithmetic average roughness is within the aforementioned range, the unevenness formed on the polymer film 1 can be sufficiently suppressed, and the film strength of the polymer film 1 can be improved. The arithmetic average roughness can be measured using, for example, a light interference microscope NT1100 manufactured by Veeco Instruments. The thickness of the engineering film 2 is not particularly limited. The thickness of the engineering film 2 is usually 20 μm or more and 200 μm or less, and preferably 25 μm or more and 150 μm or less. The thickness of the release agent layer 22 is not particularly limited. When the release agent layer 22 is formed by applying a solution containing a release agent on a release substrate, the thickness of the release agent layer 22 is preferably 0.01 μm or more and 2.0 μm or less, and more preferably 0.03 μm or more and 1.0 μm or less. When a plastic film is used as the release substrate 21, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 90 μm or less, and particularly preferably 10 μm or more and 40 μm or less. (Solution for Polymer Thin Film Formation) The material for polymer thin film formation as a solute in the polymer thin film formation solution is a norbornene-based polymer (A). Further, as the material substance, a non-NB olefin polymer (B) may be further used. Since the norbornene-based polymer (A) and the non-NB olefin-based polymer (B) have been described, they are omitted. The type of the solvent for the polymer film-forming solution is not particularly limited as long as it is a solvent that can dissolve or uniformly disperse the material material for polymer film formation and can be evaporated by heating. For example, as the solvent, ethanol, propanol, isopropanol, acetone, toluene, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, dichloromethane, chloroform, and the like are preferably used. These may be used individually by 1 type, and may be used in combination of 2 or more type. The boiling point of the solvent is preferably a value in a range of 30 ° C to 160 ° C, and more preferably a value in a range of 35 ° C to 120 ° C. The concentration of the material substance in the polymer film-forming solution is preferably set to a value in the range of 0.1% by mass to 20% by mass. If the concentration of the material substance in the solution for forming a polymer film is 0.1% by mass or more, the disadvantages that the necessary 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. From the above viewpoint, the concentration of the material substance in the solution for forming a polymer film is more preferably set to a value in a 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. Within the value. In addition, the viscosity (measurement temperature: 25 ° C) of the solution for forming a polymer film is preferably set to a value within a range of 1 mPa · s to 500 mPa · s. If the viscosity of the polymer film-forming solution is 1 mPa · s or more, the disadvantage of unevenness in the coating film can be suppressed. On the other hand, if the viscosity of the polymer thin film forming solution is 500 mPa · s or less, the disadvantage that a uniform coating film cannot be obtained can be suppressed. From the above viewpoint, the viscosity (measurement temperature: 25 ° C) of the solution for forming a polymer film is more preferably set to a value within a range of 1.5 mPa · s or more and 400 mPa · s or less, and more preferably 2 mPa · s or more and 300 mPa.・ Values in the range below s. The viscosity of the polymer film-forming solution was measured in accordance with JIS K7117-1, 4.1 (Brookfield Rotary Viscometer). In addition, the drying conditions for the coating layer of the polymer film-forming solution formed on the engineering film 2 for forming the polymer film 1 are not particularly limited. The drying of the coating layer is preferably performed under a temperature condition 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, the disadvantages of excessive drying or insufficient drying can be suppressed. On the other hand, if the drying temperature is 120 ° C or lower, the disadvantage of wrinkles or curling can be suppressed. If the drying time is 6 seconds or more, the disadvantage of insufficient drying can be prevented. On the other hand, if the drying time is 300 seconds or less, the occurrence of wrinkles and curls can be suppressed. Based on the above viewpoint, the coating layer of the solution for forming a polymer film is used as a drying condition for the polymer film 1, and is more preferably set to a temperature condition of 50 ° C or higher and 110 ° C or lower and a drying time of 12 seconds to 180 seconds. The time is more preferably set to a temperature condition of 60 ° C. to 100 ° C. and a drying time of 18 seconds to 120 seconds. The application of the polymer film-forming solution is preferably performed by a roll-to-roll method. The reason for this is that if the roll-to-roll method is used, the polymer film 1 having a specific thickness can be formed more efficiently, and thus the film-like laminate 100 can be produced more efficiently in large quantities. When the roll-to-roll method is performed, the coating device is preferably a bar coater, a gravure coater, or a die coater, and more preferably a reverse gravure coater or a slit die coater. The reason is that if such a coating device is used, the polymer film 1 having a specific thickness can be formed more efficiently. That is, if it is a bar coater, a reverse gravure coater, or a slit die coater, a nano-thick polymer film 1 can be formed with a uniform thickness without generating wrinkles on the surface. In addition, the bar coater, reverse gravure coater, and slot die coater are excellent in economy in addition to the simple structure. (Peeling step) In the peeling step, the polymer film 1 of the film-like laminate 100 shown in FIG. 3 is peeled from the engineering film 2 to obtain a polymer film 1 having a self-supporting property. In the peeling step, the peeling force of the engineering film 2 from the polymer film 1 is preferably 5 mN / 20 mm or more and 100 mN / 20 mm or less, more preferably 10 mN / 20 mm or more, 50 mN / 20 mm or less, and particularly preferably 15 mN / 20 mm or more and 30 mN. / 20mm or less. If the above-mentioned peeling force is 5 mN / 20 mm or more, in the step of forming the polymer film, the disadvantage that the engineering film and the polymer film are easily peeled off can be suppressed. In addition, if the peeling force is 100 mN / 20 mm or less, in the peeling step, it is possible to suppress the disadvantage that the engineered film is not easily peeled from the polymer film or the polymer film is cracked. The peeling force can be adjusted, for example, by changing the type of the release agent used in the engineering film 2. [Membrane-Laminated Body] As shown in FIG. 3, the film-laminar body 100 of this embodiment includes a polymer film 1 and an engineering film 2. The film-like laminate 100 is obtained by coating the engineering film 2 with the aforementioned polymer film-forming solution, drying the coating layer, and forming the polymer film 1. That is, the film-like laminate 100 can be obtained by the polymer thin film forming step in the method for manufacturing a polymer thin film according to the embodiment. (Effects of this embodiment) According to this embodiment, the following effects can be exhibited. (1) It is possible to efficiently produce a self-supporting polymer containing a norbornene-based polymer (A) containing a structural unit represented by the aforementioned general formula (1) in an amount of 10 mol% or more, having a thickness of 10 nm or more and 1000 nm or less. Film 1. (2) A polymer film 1 having a high water repellency and capable of being adhered to an adherend without using an adhesive or the like can be provided. [Changes of Embodiment] This embodiment is not limited to the foregoing embodiment, and changes, improvements, and the like within a range that can achieve the purpose of the embodiment are included in this embodiment. For example, although the engineering film 2 provided with the release base material 21 and the release agent layer 22 was used in the said embodiment, it is not limited to this. For example, when the surface free energy and the surface arithmetic average roughness of the peeling substrate 21 are within appropriate ranges, a single-layer film made of the peeling substrate 21 may be used as the engineering film 2. EXAMPLES The present invention will be described in more detail with reference to the following examples, 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 Test Example 1 has a release substrate and a release agent layer provided on the release substrate. 100 parts by weight of a mixture of a polysiloxane modified alkyd resin and an amine-based resin (made by Shin-Etsu Chemical Industry Co., Ltd .: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardener) was toluene. Dilute to prepare a coating solution with a solid content concentration of 2% by mass. Next, the obtained coating solution was coated on a 38 μm thick polyethylene terephthalate (PET) film ("DIAFOIL T100" manufactured by Mitsubishi Chemical Corporation) with a Maya rod, and heated at 140 ° C for 60 seconds. Then, it was dried to obtain an engineered 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 surface of the release agent layer of the obtained engineering film are shown in Table 1. (2) Preparation of polymer thin film forming solution A solution (solid content: 10% by mass) of a cyclic olefin copolymer ("APEL6011T" manufactured by Mitsui Chemicals Co., Ltd., a glass transition point of 105 ° C, and an MFR of 26g / 10min) The toluene was dissolved and diluted to a solid content of 3% by mass to prepare a solution for forming a polymer film. (3) Formation of a film-like laminate. Next, use a reverse gravure coater to apply a polymer film-forming solution on the prepared engineering film so that the thickness of the polymer film after drying becomes 800 nm. It dried at 60 degreeC for 60 second, and obtained the film-like laminated body. 2. Measurement and evaluation (1) Measurement of surface free energy of engineering film The surface free energy (mJ / m ² ) of the surface (contact surface with polymer film) on which the solution for forming a polymer film is applied in the engineering film is measured The contact angles (measurement temperature: 25 ° C) of various droplets were measured, and based on this value, they were obtained by the Kitazaki- 畑 theory. That is, diiodomethane as a "dispersing component", 1-bromonaphthalene as a "dipolar component", and distilled water as a "hydrogen bonding component" are used as droplets, and DM manufactured by Kyowa Interface Science Co., Ltd. is used. -70. The contact angle (measurement temperature: 25 ° C) was measured by the static drop method in accordance with JIS R3257, and based on this value, the surface free energy (mJ / m ² ) was calculated based on the Kitasaki- 畑 theory. (2) Measurement of the arithmetic mean roughness Ra of the engineering film The arithmetic mean roughness Ra (nm) of the surface (contact surface with the polymer film) coated with the solution for forming a polymer film in the release sheet is from Veeco Instruments The manufactured optical interference microscope NT1100 was observed on an area of 250,000 μm ² (500 μm × 500 μm), and the arithmetic average roughness (Ra) was determined. (3) Evaluation of the applicability of the polymer film-forming solution to the engineered film The applicability when forming a film-like laminate. The solution for forming a polymer film can be judged as "A" when the engineering film is uniformly applied, and can be judged as "B" when the engineering film is not uniformly applied. The results obtained are shown in Table 1. (4) Evaluation of peelability of polymer film When the polymer film is peeled from the engineering film in the film-like laminate, the peelability is evaluated. When the polymer film is easily peeled from the engineering film, it is judged as "A", and when the polymer film is broken, it is judged as "B". The results obtained 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, 38 µm thick) was used as an engineering film, the same method as in Test Example 1 was used. A film-like laminate and a polymer film were produced and evaluated. The results obtained are shown in Table 1. In addition, Table 1 shows the surface free energy and the arithmetic average roughness of the surface of the engineered film used in Test Example 2. [Test Example 3] In Test Example 3, except that "SP-PET381031" (manufactured by LINTEC Corporation) was used as an engineering film, a film-like laminate and a polymer film were produced and evaluated in the same manner as in Test Example 1. The results obtained are shown in Table 1. The surface free energy and arithmetic average roughness of the surface of the release agent layer of the engineering 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 Corporation) was used as an engineering film, a film-like laminate and a polymer film were produced and evaluated in the same manner as in Test Example 1. The results obtained are shown in Table 1. The surface free energy and arithmetic average roughness of the surface of the release agent layer of the engineering film used in Test Example 4 are shown in Table 1. As can be understood from the results shown in Table 1, when using a solution for forming a polymer film containing a cyclic olefin copolymer, it is understood that the engineered film used in Test Example 1 is preferably used. Therefore, in the following Examples and Comparative Examples, the engineered film used in Test Example 1 was used. [Example 1] 1. Manufacturing of polymer film (1) Manufacturing of engineering film The engineering film of Example 1 has a substrate and a release agent layer provided on the substrate. 100 parts by weight of a mixture of a polysiloxane modified alkyd resin and an amine-based resin (made by Shin-Etsu Chemical Industry Co., Ltd .: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardener) was toluene. Dilute to prepare a coating solution with a solid content concentration of 2% by mass. Next, the obtained coating solution was coated on a 38 μm thick polyethylene terephthalate (PET) film ("DIAFOIL T100" manufactured by Mitsubishi Chemical Corporation) with a Maya rod, and heated at 140 ° C for 60 seconds. Then, it was dried to obtain an engineered film having a release agent layer having an average thickness of 0.1 μm. (2) Preparation of polymer thin film forming solution A solution (solid content: 10% by mass) of a cyclic olefin copolymer ("APEL6011T" manufactured by Mitsui Chemicals Co., Ltd., a glass transition point of 105 ° C, and an MFR of 26g / 10min) The toluene was dissolved and diluted to a solid content of 3% by mass to prepare a solution for forming a polymer film (viscosity 2.4 mPa · s). 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 apply a polymer film-forming solution on the prepared engineering film so that the thickness of the polymer film after drying becomes 800 nm. It dried at 60 degreeC for 60 second, and obtained the film-like laminated body. (4) Production of polymer film Next, the polymer film is obtained by peeling the engineering film of the film-like laminate. 2. Measurement and Evaluation (1) Surface carbon concentration of 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 was measured using a monochromatic Al · Kα at a photoelectron extraction angle of 45 ° to calculate the concentration of carbon elements (unit: atomic%) present on the surface. The results obtained are shown in Table 2. (2) Peeling force of polymer film The peeling force when the polymer film was peeled from the engineering film of the obtained film-like laminate was measured. That is, after the adhesive tape (the Nitto Denko Corporation, No. 31B) was adhered to the polymer film of the film-like laminate, the polymer film in the state where the adhesive tape was attached was measured for peeling at 180 ° from the engineering film. Force (mN / 20mm). The results obtained are shown in Table 2. (3) Adhesiveness of polymer film First, a double-sided tape is attached to a square end of a supporting substrate ("CRISPR 75K2323" manufactured by Toyobo Co., Ltd.) to produce a support having a double-sided tape attachment portion. Next, the double-sided tape attachment portion of the support is attached to the polymer film of the film-like laminate. Next, the support and the polymer film are peeled from the engineering film, and the polymer film is transferred to the surface of the support. Secondly, the support body of the polymer film is cut away from the double-sided adhesive tape attachment portion to produce a laminate of the polymer film and the support substrate. This 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 was reciprocated twice from the self-supporting base material, and the polymer film and the adherend were pressed. The adhesion at this time was evaluated. After pressing, the polymer film was completely attached to the adherend without peeling, and it was judged as "A". After pressing, the polymer film was not attached to the adherend, and it was judged as "if it floated or peeled." B ". The results obtained are shown in Table 2. PP: Polypropylene sheet ("PP-N-BN" manufactured by Hitachi Chemical Co., Ltd., size 2mm × 70mm × 150mm) Glass: Float sheet glass ("Float sheet glass R3202 silk surface made 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. The measurement system used a contact angle meter (produced by Kyowa Interface Science Co., Ltd., DM-701). The contact angle to water (23 ° C, 50% RH) was measured. The results obtained are shown in Table 2. (5) Water slip angle on the polymer film In order to evaluate the water repellency of the polymer film to water, the water slip angle on the polymer film was measured. Water droplets were placed on the horizontally-positioned polymer film, and the angle of the polymer film where the water droplets started to flow when the polymer film was slowly tilted was measured as the slip angle. The results obtained are shown in Table 2. (6) Film strength The film strength is measured with a creep meter (trade name "Creep Meter RE2-3305CYAMADEN" manufactured by Yamaden Corporation). Specifically, the polymer film surface of the film-like laminate after standing for 24 hours in an environment with a temperature of 23 ° C. and a humidity of 50% RH is attached to a jig with a hole having a diameter of 1 cm, and the engineering film is peeled off. A cylindrical plunger with a diameter of 1 mmφ is inserted into a portion of the polymer film corresponding to the center portion of the fixture hole. The plunger entering speed was set to 0.5 mm / sec. Measure the maximum stress (unit: mN / 1mmφ) when the plunger enters the hole depth direction to a depth of 5mm. The measurement was performed 10 times, and the average value was defined as the film strength of the polymer film. The results obtained are shown in Table 2. [Examples 2 to 4] 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 the cyclic olefin copolymer and the thickness of the polymer film were changed as shown in Table 2. The results obtained are shown in Table 2. 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 Examples 2 to 4. [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 the cyclic olefin copolymer and the thickness of the polymer film were changed as shown in Table 2. The results obtained are shown in Table 2. 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. 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 in the same manner as in Example 1. As shown in the results in Table 2, it was confirmed that the polymer film (Examples 1 to 4) containing norbornene polymer (A) and having a thickness of 10 nm to 1000 nm has good adhesion, a large contact angle with water, Small slip angle. From this, it was confirmed that the polymer films obtained in Examples 1 to 4 can be adhered to an adherend without using an adhesive or the like, and have high water repellency. In addition, the polymer films obtained in Examples 1 to 4 were confirmed to have high film strength and self-supporting properties.

1‧‧‧ polymer film

2‧‧‧Engineering film

2A‧‧‧First side

2B‧‧‧Second Side

21‧‧‧ peeling substrate

22‧‧‧Releasing 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 view showing an engineering film used in a method for manufacturing a polymer film according to an embodiment of the present invention. FIG. 3 is a schematic view showing a state in which a polymer thin film is formed on an engineering film to produce a film-like laminate in a method for manufacturing a polymer thin film according to an embodiment of the present invention.

Claims (12)

A polymer film characterized by comprising a norbornene polymer (A) containing 10 mol% or more of a constituent unit represented by the following general formula (1), having a thickness of 10 nm or more and 1000 nm or less, and having self-supporting properties, (In the aforementioned general formula (1), X ¹ and X ² are the same or different and each represents 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 groups, X ¹ and X ² may also be combined 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). For example, the polymer film of claim 1, wherein the glass transition point of the norbornene-based polymer (A) is 140 ° C or lower. For example, the polymer film of claim 1, wherein the melt flow rate of the norbornene polymer (A) at a temperature of 260 ° C and a load of 2.16 kgf is 20 g / 10 min or more. The polymer film according to any one of claims 1 to 5, wherein the surface carbon concentration of the polymer film is 90 atomic% or more. A film-like laminate, which is characterized by comprising an engineering film and a polymer film according to any one of claims 1 to 6 formed on the aforementioned engineering film. For example, the film-like laminate of claim 7, wherein the surface free energy of the aforementioned engineering film is 40 mJ / m ² or less. For example, the film-like laminate of claim 7 or 8, wherein the arithmetic average roughness of the surface of the aforementioned engineering film is 40 nm or less. A method for manufacturing a polymer film, which is a polymer film manufacturer according to any one of claims 1 to 6, and is characterized by having the following steps: (1) coating an engineering film containing the aforementioned norbornene-based polymer ( A) A solution for forming a polymer film and drying to form the polymer film, and a step of peeling the polymer film from the engineering film. The method for manufacturing a polymer film according to claim 10, wherein the surface free energy of the aforementioned engineering film is 40 mJ / m ² or less. The method for manufacturing a polymer film according to claim 10 or 11, wherein the arithmetic average roughness of the surface of the aforementioned engineering film is 40 nm or less.