WO2019039392A1

WO2019039392A1 - Polymer thin film, film-form laminate, and method for producing polymer thin film

Info

Publication number: WO2019039392A1
Application number: PCT/JP2018/030476
Authority: WO
Inventors: 千春平野; 宮田　壮
Original assignee: リンテック株式会社
Priority date: 2017-08-23
Filing date: 2018-08-17
Publication date: 2019-02-28
Also published as: JP6586545B2; TWI784041B; JPWO2019039392A1; CN111032752A; TW201920390A; KR102548028B1; KR20200043973A

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 thin film, film-like laminate, and method for producing polymer thin film

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

Films made of cyclic olefin resins are used, for example, as dielectric films for film capacitors.
For example, Patent Document 1 describes a highly insulating film containing a resin as a main component. In this highly insulating film, the resin is an amorphous resin. Further, the minimum value of the refractive index in the surface direction of the high insulating film is Ny, the refractive index in the direction orthogonal to the Ny in the surface direction of the high insulating film is Nx, and the thickness of the high insulating film When d is d, the retardation (R) represented by the following formula 1 is 10 nm or less.
R = (Nx-Ny) · d (Equation 1)

JP, 2015-183181, A

When the thickness of the resin film is in the range of several tens to several hundreds of nm, due to electrostatic force and wettability, the resin film may be in close contact with the adherend without using an adhesive or the like.
However, the highly insulating film described in Patent Document 1 could not be adhered to an adherend. Further, Patent Document 1 describes that the average thickness is preferably 0.5 μm or more and 7.0 μm or less, but in the method for producing a high insulation film described in Patent Document 1, the thickness of the film is reduced to It was not possible to place an order. Moreover, although the extending | stretching process is performed to the film produced by the solution casting method, for example in patent document 1, the thickness of a film was not able to be made into nano order also by this method.

An object of the present invention is to provide a polymer thin film having high water repellency, a film-like laminate, and a method for producing a polymer thin film, which can be adhered to an adherend without using an adhesive or the like. It is.

According to one aspect of the present invention, the self-supporting polymer is a self-supporting polymer comprising a norbornene-based polymer (A) containing 10 mol% or more of a constitutional unit represented by the following general formula (1) and having a thickness of 10 nm to 1000 nm. A polymer thin film characterized by having a property is provided.
In the following general formula (1), X ¹ and X ² are the same or different, and respectively a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted group Or X represents an unsubstituted alkenyl group, a hydroxy group or a carboxy group, and X ¹ and X ² may combine with each other to form a ring.

In the above-mentioned one aspect of the present invention, the norbornene-based polymer (A) is preferably a norbornene-based copolymer.
In one aspect of the present invention described above, the polymer thin film preferably contains 50% by mass or more of the norbornene-based polymer (A).
In the above-mentioned one aspect of the present invention, the glass transition point of the norbornene-based polymer (A) is preferably 140 ° C. or less.
In the above-mentioned one aspect of the present invention, the melt flow rate at a temperature of 260 ° C. and a load of 2.16 kgf of the norbornene-based polymer (A) is preferably 20 g / 10 min or more.
In the above-mentioned one aspect of the present invention, the surface carbon concentration of the polymer thin film is preferably 90 atomic% or more.

According to one aspect of the present invention, there is provided a film-like laminate comprising a process film and the polymer thin film according to the above-mentioned one aspect of the invention formed on the process film. .
In the above-mentioned one aspect of the present invention, the surface free energy of the process film is preferably 40 mJ / m ² or less.
In the above-mentioned one aspect of the present invention, the arithmetic mean roughness of the surface of the step film is preferably 40 nm or less.

According to one aspect of the present invention, there is provided a method of producing a polymer thin film for producing a polymer thin film according to one aspect of the present invention described above, wherein the polymer comprising the norbornene-based polymer (A) on a process film A method for producing a polymer thin film, comprising the steps of applying a solution for forming a thin film and drying to form the polymer thin film, and peeling the polymer thin film from the step film. Is provided.
In the above-mentioned one aspect of the present invention, the surface free energy of the process film is preferably 40 mJ / m ² or less.
In the above-mentioned one aspect of the present invention, the arithmetic mean roughness of the surface of the step film is preferably 40 nm or less.

According to the present invention, a polymer thin film, a film-like laminate, and a method for producing a polymer thin film having high water repellency can be provided, which can be adhered to an adherend without using an adhesive or the like. .

It is the schematic which shows the polymer thin film which concerns on embodiment of this invention. It is the schematic which shows the process film used by the manufacturing method of the polymer thin film which concerns on embodiment of this invention. In the manufacturing method of the polymer thin film which concerns on embodiment of this invention, a polymer thin film is formed on a process film, and it is the schematic which shows the state which produced the film-like laminated body.

Hereinafter, embodiments of the present invention will be described by way of example with reference to the drawings. The present invention is not limited to the contents of the embodiments. Note that, in the drawings, there are portions illustrated in an enlarged or reduced scale to facilitate the description.

[Polymer thin film]
The polymer thin film 1 according to the present embodiment is a thin film having a self-supporting property, as shown in FIG. In the present specification, "self-supporting property" refers to the property that the polymer thin film 1 can form a film alone when the polymer thin film 1 is not laminated on another support, and more specifically In fact, it means that the film strength is 5 mN / 1 mmφ or more. In the film having “self-supporting property”, the film strength is preferably 10 mN / 1 mmφ or more, more preferably 20 mN / 1 mmφ or more. The film strength can be measured with a creep meter (for example, trade name “cree meter RE2-3305 CYAMADEN” manufactured by Yamaden Co., Ltd.). Specifically, it can be measured by the method described in the examples described later.

The thickness of the polymer thin film 1 needs to be 10 nm or more and 1000 nm or less. When the thickness of the polymer thin film 1 is 10 nm or more and 1000 nm or less, it is possible to bond to a desired adherend such as skin without using an adhesive or the like. The thickness of the polymer thin film 1 is described in J.I. A. It can be measured by a spectral ellipsometer (product name "M-2000") manufactured by Woollam.
The thickness of the polymer thin 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 thin 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.

The surface carbon concentration of the polymer thin film 1 is preferably 90 atomic% or more, more preferably 95 atomic% or more, and particularly preferably 99 atomic% or more from the viewpoint of water repellency. The surface carbon concentration can be measured by X-ray photoelectron spectroscopy (XPS).

The polymer thin film 1 needs to contain a norbornene-based polymer (A) containing 10 mol% or more of a structural unit represented by the following general formula (1). When the norbornene-based polymer (A) does not contain 10 mol% or more of a constitutional unit represented by the following general formula (1), a polymer thin film having a desired thickness and having a self-supporting property and high water repellency Can not be obtained. The content of the constituent unit represented by the following general formula (1) in the polymer thin film 1 is preferably 20 mol% or more, and more preferably 50 mol% or more.

In the general formula (1), X ¹ and X ² are the same or different, and each is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group X ¹ represents a substituted alkenyl group, a hydroxy group or a carboxy group, and X ¹ and X ² may combine with each other to form a ring.
Examples of the substituent of the alkyl group, the alkoxy group and the alkenyl group include a halogen atom, a hydroxy group, a carboxy group, an acryloyl group, a methacryloyl group and an epoxy group.
The carbon number of the alkyl group is preferably 1 to 5, and more preferably 1 to 3. The carbon number of the alkoxy group is preferably 1 to 5, and more preferably 1 to 3. The carbon number of the alkenyl group is preferably 2 to 5, and more preferably 2 to 3.

(Norbornene-based polymer (A))
The norbornene polymer (A) may contain 10 mol% of the constituent unit represented by the general formula (1), and may be a norbornene homopolymer or a norbornene copolymer.
The norbornene-based polymer (A) is a polymer having a norbornene-based compound as at least one monomer.

Examples of norbornene compounds include norbornene (bicyclo [2.2.1] hept-2-ene), compounds having a cyclic structure containing a bicyclo ring related to norbornene (for example, dicyclopentadiene), and derivatives thereof. One of these may be used alone, or two or more may be mixed and used.
Examples of monomers other than norbornene compounds include cyclopentadiene and tetracyclododecene. One of these may be used alone, or two or more may be mixed and used.

A polymer (homopolymer or copolymer) obtained by polymerizing a monomer by using a norbornene-based compound as at least one of the monomers has a structural unit represented by the general formula (1).

As the norbornene-based polymer (A), a ring-opening metathesis polymer hydrogenated polymer of a norbornene-based monomer (specifically, available as Nippon Zeon Co., Ltd. as ZEONEX (registered trademark) series), norbornene and ethylene Copolymer (specifically, available as Polyplastics Co., Ltd. TOPAS (registered trademark) series), copolymer based on ring-opening polymerization of dicyclopentadiene and tetracyclopentadodecene (specifically, Nippon Zeon Available as ZEONOR (registered trademark) series manufactured by ltd.), Copolymer of ethylene and tetracyclododecene (specifically, available as Mitsui (registered trademark) APEL (registered trademark) series), And dicyclopentadiene and methacrylic acid esters The cyclic olefin resin containing a polar group as a raw material (specifically available as JSR Corporation ARTON (registered trademark) series.), And the like. One of these may be used alone, or two or more may be mixed and used.

The norbornene-based polymer (A) may have a crosslinked structure. Here, the kind of crosslinking agent which brings about a crosslinked structure is arbitrary. Examples of the crosslinking agent include organic peroxides (eg, dicumyl peroxide etc.), compounds having an epoxy group, and the like. One of these may be used alone, or two or more may be mixed and used.
The crosslinking agent may crosslink between one kind of polymers constituting the norbornene-based polymer (A), or may crosslink between different kinds of polymers. The binding site of the crosslinker is also optional. The polymer may be crosslinked with an atom constituting the main chain of the polymer constituting the norbornene-based polymer (A), or may be crosslinked with an atom constituting other than the main chain such as a side chain or a functional group. The degree of crosslinking is also optional, but if the degree of crosslinking progresses excessively, the processability (particularly the formability) of the polymer thin film 1 containing the norbornene-based polymer (A) may be excessively reduced. There is a concern that the surface properties may be excessively deteriorated or the brittleness of the polymer thin film 1 may be reduced, and therefore, such problems should not occur.

The norbornene-based polymer (A) has thermoplasticity. The degree of thermoplasticity can be expressed as a melt flow rate (MFR) indicating the viscosity upon melting.
The melt flow rate (MFR) at a temperature of 260 ° C. and a load of 2.16 kgf of the norbornene polymer (A) is preferably 20 g / 10 min or more, more preferably 20 g / 10 min or more and 150 g / 10 min or less It is particularly preferable to be 25 g / 10 min or more and 50 g / 10 min or less. If MFR is in the said range, thermoplasticity can be made high enough and processability, such as shaping | 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 less, more preferably 30 ° C. or more and 120 ° C. or less, from the viewpoint of the coatability of the solution for forming a polymer thin film. If the glass transition point is 140 ° C. or less, the solvent solubility can be further improved, and on the other hand, if the glass transition point is 30 ° C. or more, it has a self-supporting film forming ability even at room temperature. The glass transition temperature can be measured using a differential scanning calorimeter. For example, using a differential scanning calorimeter (“DSC (Q2000)” manufactured by TA Instruments), measurement is performed in a temperature range of −40 ° C. to 200 ° C. at a heating rate of 10 ° C./min to create a graph The inflection point can be confirmed from the graph to determine the glass transition point.

(Olefin-based polymer (B) other than norbornene-based polymer (A))
The polymer thin film 1 may contain an olefin-based polymer (B) other than the norbornene-based polymer (A) (hereinafter, sometimes referred to as “non-NB olefin-based polymer (B)”).
When the non-NB olefin polymer (B) is used, the content of the norbornene polymer (A) is preferably 50% by mass or more on the basis of the total amount of polymers, from the viewpoint of self-supporting property and water repellency. It is more preferable that it is mass% or more, and it is especially preferable that it is 90 mass% or more.

The non-NB olefin polymer (B) may be linear or have a side chain. Also, the non-NB olefin polymer (B) may have any functional group as long as it does not contain a norbornene ring, and the type and substitution density are arbitrary. It may be a less reactive functional group such as an alkyl group, or may be a highly reactive functional group such as a carboxylic acid group.
The non-NB olefin-based polymer (B) is an olefin-based polymer having an olefin as at least one monomer, and is an olefin-based polymer having no 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 either an aromatic cyclic polyolefin or an acyclic polyolefin. The aromatic cyclic polyolefin includes polyolefins having an olefin having a cyclic structure of an aromatic ring as at least one of monomers. The non-NB olefin polymer (B) may be a homopolymer or a copolymer.

(Attachment)
The polymer thin film 1 can be adhered to an adherend without using an adhesive or the like. Here, examples of the adherend include, but are not limited to, stainless steel, polyethylene, polypropylene, polycarbonate, glass, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), and a semiconductor circuit board. By making these into adherends, water repellency can be easily given to arbitrary adherends. In addition, examples of the adherend other than the above include humans, animals, clothes, hats, shoes, and decorations. When these are used as the adherend, the polymer thin film 1 is preferable because it is very thin, so the site of application is inconspicuous and lightweight.
In addition, since the polymer thin film 1 has high water repellency, it is also resistant to sweat or rain. Therefore, the polymer thin film 1 can be particularly suitably used as a film for bringing a wearable terminal or the like into close contact with the skin.

[Method for producing polymer thin film]
The method for producing a polymer thin film according to the present embodiment is a method for producing a polymer thin film for producing the polymer thin film 1. And the manufacturing method of the polymer thin film which concerns on this embodiment apply | coats the solution for polymer thin film formation containing the said norbornene-type polymer (A) on a process film, it dries, and forms the said polymer thin film. It is a method comprising: a step (polymer thin film forming step); and a step of peeling the polymer thin film from the step film (peeling step).

(Polymer thin film formation process)
FIG. 2 is a schematic cross-sectional view showing a step film 2 used in the method for producing a polymer thin film according to the present embodiment. The process film 2 has a first surface 2A and a second surface 2B.
In the polymer thin film forming step, a polymer containing the norbornene-based polymer (A) on the first surface 2A of the first surface 2A and the second surface 2B of the process film as shown in FIG. 2 The solution for forming a thin film is applied and dried to form a polymer thin film 1 to obtain a film-like laminate 100 as shown in FIG.
Here, the process film and the solution for forming a polymer thin film used in the polymer thin film forming process will be described.

(Process film)
The process film 2 is not particularly limited. For example, from the viewpoint of easy handling, the process film 2 preferably includes the release substrate 21 and the release agent layer 22 formed on at least one surface of the release substrate 21. In the present embodiment, the surface of the release agent layer 22 corresponds to the first surface 2A, and the surface of the release substrate 21 opposite to the surface 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 obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
Paper substrates include glassine paper, wood free paper, coated paper, and cast coated paper. Plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. These may be used singly or in combination of two or more.
The release agent layer 22 may be formed by applying a release agent. Examples of the release agent include olefin resins, rubber elastomers (for example, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins. Among these, as the release agent, any one selected from the group consisting of an olefin resin, a rubber elastomer (for example, a butadiene resin, an isoprene resin, etc.), a long chain alkyl resin, an alkyd resin, and a fluorine resin It is preferable that it is a release agent. These may be used singly or in combination of two or more. The release agent layer may further contain an antistatic agent or may not contain an antistatic agent.

In the process film 2, it is preferable that the surface free energy and the arithmetic mean roughness of the first surface 2A be adjusted by the release agent layer 22.
The first surface free energy of the surface 2A of the casting film 2 is preferably 40 mJ / ^{m 2} or less, more preferably 20 mJ / ^{m 2} or more 40 mJ / ^{m 2} or less. If the surface free energy is 20 mJ / m ² or more, the solution for forming a polymer thin film can be favorably coated on the process film 2, and if the surface free energy is 40 mJ / m ² or less, the process film 2 is high. The molecular thin film 1 can be easily peeled off, and the productivity can be improved. The surface free energy can be determined by Kitazaki-Hata theory based on the measured contact angles (measurement temperature: 25 ° C.) of various droplets.
The arithmetic mean roughness (Ra) of the surface of the first surface 2A of the process film 2 is preferably 40 nm or less, more preferably 0.1 nm to 30 nm, and still more preferably 0.5 nm to 25 nm Is particularly preferred. If the arithmetic mean roughness of the surface is within the above 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. Arithmetic mean roughness can be measured using, for example, an optical interference microscope NT1100 manufactured by Veeco Instruments.

The thickness of the process film 2 is not particularly limited. The thickness of the process 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 the release substrate, the thickness of the release agent layer 22 is preferably 0.01 μm to 2.0 μm, and 0.03 μm. It is more preferable that the thickness is not less than 1.0 μm.
When a plastic film is used as the peeling 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 forming polymer thin film)
A material for forming a polymer thin film as a solute in a solution for forming a polymer thin film is a norbornene-based polymer (A). A non-NB olefin polymer (B) may be further used as this material. The norbornene-based polymer (A) and the non-NB olefin-based polymer (B) are omitted because they have already been described.

The type of the solvent in the solution for forming a polymer thin film is not particularly limited as long as it can dissolve or uniformly disperse the material for forming a polymer thin film, and evaporates by heating. For example, as the solvent, ethanol, propanol, isopropyl alcohol, acetone, toluene, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, dichloromethane, chloroform and the like are preferable. These may be used singly or in combination of two or more.
The boiling point of the solvent is preferably in the range of 30 ° C. to 160 ° C., and more preferably in the range of 35 ° C. to 120 ° C.

Moreover, it is preferable to make the density | concentration of the material substance in the solution for polymer thin film formation into the value within the range of 0.1 mass% or more and 20 mass% or less.
If the concentration of the material in the solution for forming a polymer thin film is 0.1% by mass or more, the problem that the required thickness may not be obtained and the problem that the viscosity of the solution is not optimum are suppressed it can. On the other hand, when the concentration of the material in the solution for forming a polymer thin film is 20% by mass or less, it is possible to suppress a problem that a uniform coating film may not be obtained.
Further, from the above viewpoint, it is more preferable to set the concentration of the material in the solution for forming a polymer thin film to a value within the range of 0.3% by mass to 15% by mass, and 0.5% by mass to 10% by mass It is further preferable to set the value within the following range.

Moreover, it is preferable to make the viscosity (measurement temperature: 25 degreeC) of the solution for polymer thin film formation into the value within the range of 1 mPa * s or more and 500 mPa * s or less.
If the viscosity of the solution for forming a polymer thin film is 1 mPa · s or more, it is possible to suppress the problem that repelling of the coating film occurs. On the other hand, when the viscosity of the solution for forming a polymer thin film is 500 mPa · s or less, it is possible to suppress the problem that a uniform coating film can not be obtained.
Further, from the above viewpoint, it is more preferable to set the viscosity (measurement temperature: 25 ° C.) of the solution for forming a polymer thin film to a value within the range of 1.5 mPa · s to 400 mPa · s, and 2 mPa · s to 300 mPa · s. More preferably, the value is in the range of s or less.
The viscosity of the solution for forming a polymer thin film is measured in accordance with JIS K 7117-1 4.1 (Brookfield type rotational viscometer).

The drying conditions for forming the polymer thin film 1 on the coated layer of the solution for forming a polymer thin film formed on the step film 2 are not particularly limited. The drying of the coating layer is preferably performed 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 more, it is possible to suppress the problem that the drying takes time or the drying becomes insufficient. On the other hand, if the drying temperature is 120 ° C. or less, it is possible to suppress a defect that wrinkles or curls occur.
In addition, if the drying time is 6 seconds or more, it is possible to prevent the problem of insufficient drying. On the other hand, if the drying time is 300 seconds or less, problems such as wrinkles or curling can be suppressed.
Further, from the above viewpoint, the drying conditions for forming the coating layer of the polymer thin film forming solution as the polymer thin film 1 are the temperature conditions of 50 ° C. or more and 110 ° C. or less, and the drying time of 12 seconds or more and 180 seconds or less. It is more preferable that the temperature condition be 60 ° C. or more and 100 ° C. or less and the drying time be 18 seconds or more and 120 seconds or less.

Moreover, it is preferable to perform application | coating of the solution for polymer thin film formation by the roll-to-roll (Roll to Roll) method.
The reason is that the roll-to-roll method can form the polymer thin film 1 having a predetermined thickness more efficiently, so that the film-like laminate 100 can be mass-produced more efficiently. It is for.
Moreover, when implementing a roll-to-roll method, as a coating apparatus, a bar coater, a gravure coater, or a die coater is preferable, and a reverse gravure coater or a slot die coater is more preferable.
The reason is that, with these coating devices, the polymer thin film 1 having a predetermined thickness can be formed more efficiently.
That is, if it is a bar coater, a reverse gravure coater, and a slot die coater, the polymer thin film 1 of nanometer order thickness can be formed with uniform thickness without generating wrinkles on the surface. Moreover, the bar coater, the reverse gravure coater and the slot die coater are simple in their structure and excellent in economics.

(Peeling process)
In the peeling step, the polymer thin film 1 in the film-like laminate 100 as shown in FIG. 3 is peeled from the process film 2 to obtain the polymer thin film 1 having a self-supporting property.
The peeling force of the step film 2 from the polymer thin film 1 in the peeling step is preferably 5 mN / 20 mm or more and 100 mN / 20 mm or less, more preferably 10 mN / 20 mm or more and 50 mN / 20 mm or less, 15 mN / It is particularly preferable that the diameter is 20 mm or more and 30 mN / 20 mm or less.
If the peeling force is 5 mN / 20 mm or more, it is possible to suppress the problem that the process film and the polymer thin film are easily peeled off in the polymer thin film forming step. In addition, when the above peeling force is 100 mN / 20 mm or less, in the peeling step, it becomes difficult to peel the step film from the polymer thin film, and it is possible to suppress the problem that the polymer thin film is broken.
The above peeling force can be adjusted, for example, by changing the type of the release agent used for the process film 2.

[Film-like laminate]
The film-like laminate 100 according to the present embodiment includes a polymer thin film 1 and a process film 2 as shown in FIG. The film-like laminate 100 is obtained by applying the solution for forming a polymer thin film on a process film 2 and drying the applied layer to form a polymer thin film 1. That is, the film-like laminate 100 is obtained by the polymer thin film forming step in the method of manufacturing a polymer thin film according to the above-described embodiment.

(Operation and effect of the present embodiment)
According to the present embodiment, the following effects can be achieved.
(1) A polymer thin film containing a norbornene-based polymer (A) containing 10 mol% or more of the constitutional unit represented by the general formula (1), having a thickness of 10 nm to 1000 nm, and having self-supporting properties 1 can be manufactured efficiently.
(2) It can be adhered to an adherend without using an adhesive or the like, and a polymer thin film 1 having high water repellency can be provided.

[Modification of the embodiment]
The present embodiment is not limited to the above-described embodiment, but includes modifications, improvements, and the like as long as the object of the present embodiment can be achieved.
For example, in above-mentioned embodiment, although the process film 2 provided with the peeling base material 21 and the release agent layer 22 was used, it is not limited to this. For example, when the surface free energy of the release substrate 21 and the arithmetic mean roughness of the surface are within appropriate ranges, a single layer film composed of the release substrate 21 may be used as the process film 2.

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Test Example 1]
1. Selection of Process Film (1) Production of Process Film The process film of Test Example 1 has a release substrate and a release agent layer provided on the release substrate.
Dilute 100 parts by weight of a mixture of silicone-modified alkyd resin and amino resin (Shin-Etsu Chemical Co., Ltd .: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardening agent) with toluene, and solidify it. A coating solution having a concentration of 2% by mass was prepared.
Next, the obtained coating solution is coated on a 38 μm thick polyethylene terephthalate (PET) film ("Diafoil T100" manufactured by Mitsubishi Chemical Corporation) using a Meyer bar, and heated at 140 ° C for 60 seconds. It dried and the process film which formed the release agent layer of average thickness 0.1 micrometer was obtained. Then, the surface free energy on the surface of the release agent layer of the obtained process film and the arithmetic mean roughness are shown in Table 1.

(2) Preparation of a solution for forming a polymer thin film A solution (solid content: 10% by mass) of a cyclic olefin copolymer (“APEL6011T” manufactured by Mitsui Chemicals, Inc., glass transition point 105 ° C., MFR 26 g / 10 min) is dissolved in toluene, It diluted to 3 mass% of solid content, and the solution for polymer thin film formation was produced.

(3) Formation of film-like laminate Then, using a reverse gravure coater, after applying a solution for forming a polymer thin film on the prepared step film so that the thickness of the dried polymer thin film is 800 nm. And dried at 100 ° C. for 60 seconds to obtain a film-like laminate.

2. Measurement / Evaluation (1) Measurement of Surface Free Energy of Process Film The surface free energy (mJ / m ² ) on the surface (contact surface with the polymer thin film) to which the solution for forming a polymer thin film in the process film is applied is various liquids. The contact angle of the drop (measurement temperature: 25 ° C.) was measured, and based on that value, it was determined by Kitazaki-Hata theory.
That is, using diiodomethane as “dispersion component”, 1-bromonaphthalene as “dipolar component”, and distilled water as “hydrogen bond component” as droplets, DM-70 manufactured by Kyowa Interface Science Co., Ltd. is used. Using the static drop method, measure the contact angle (measurement temperature: 25 ° C) according to JIS R3257, and based on the value, determine the surface free energy (mJ / m ² ) by Kitazaki-Hata theory. The
(2) Measurement of Arithmetic Average Roughness Ra of Process Film Arithmetic average roughness Ra (nm) of the surface on which the solution for forming a polymer thin film is applied (contact surface with the polymer film) in the release sheet is Veeco Instruments Inc. A region of 250,000 μm ² (500 μm × 500 μm) was observed using a light interference microscope NT1100 manufactured by Shin-Etsu Chemical Co., Ltd., and the arithmetic mean roughness (Ra) was determined.
(3) Coatability of Solution for Forming Polymer Thin Film to Processed Film The coatability when forming a film-like laminate was evaluated. The case where the solution for polymer thin film formation could be uniformly applied to the process film was judged as "A", and the case where repelling etc. occurred on the process film and could not be uniformly applied was judged as "B". The obtained results are shown in Table 1.
(4) Peelability of Polymer Thin Film The peelability at the time of peeling the polymer thin film from the process film in the film-like laminate was evaluated. The case where the polymer thin film could be easily peeled from the process film was judged as "A", and the case where the polymer thin film was broken or could not be peeled was judged as "B". The obtained results are shown in Table 1.

[Test Example 2]
In Test Example 2, a film-like laminate and a polymer are prepared in the same manner as in Test Example 1 except that a polyethylene terephthalate film ("Diafoil T100" manufactured by Mitsubishi Chemical Corporation, 38 μm thick) is used as the process film. Thin films were produced and evaluated. The obtained results are shown in Table 1. The surface free energy and the arithmetic mean roughness on the surface of the process film used in Test Example 2 are shown in Table 1.

[Test Example 3]
In Test Example 3, a film-like laminate and a polymer thin film were produced and evaluated in the same manner as in Test Example 1 except that “SP-PET 381031” manufactured by Lintec Corporation was used as the process film. The obtained results are shown in Table 1. Further, the surface free energy on the surface of the release agent layer of the step film used in Test Example 3 and the arithmetic mean roughness are shown in Table 1.

[Test Example 4]
In Test Example 4, a film-like laminate and a polymer thin film were produced and evaluated in the same manner as in Test Example 1 except that “SP-PET38T100X” manufactured by Lintec Corporation was used as the process film. The obtained results are shown in Table 1. Further, the surface free energy on the surface of the release agent layer of the step film used in Test Example 4 and the arithmetic mean roughness are shown in Table 1.

As apparent from the results shown in Table 1, it was found that when using a solution for forming a polymer thin 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 process film used in Test Example 1 was used.

Example 1
1. Production of Polymer Thin Film (1) Production of Process Film The process film of Example 1 has a substrate and a release agent layer provided on the substrate.
Dilute 100 parts by weight of a mixture of silicone-modified alkyd resin and amino resin (Shin-Etsu Chemical Co., Ltd .: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardening agent) with toluene, and solidify it. A coating solution having a concentration of 2% by mass was prepared.
Next, the obtained coating solution is coated on a 38 μm thick polyethylene terephthalate (PET) film ("Diafoil T100" manufactured by Mitsubishi Chemical Corporation) using a Meyer bar, and heated at 140 ° C for 60 seconds. It dried and the process film which formed the release agent layer of average thickness 0.1 micrometer was obtained.

(2) Preparation of a solution for forming a polymer thin film A solution (solid content: 10% by mass) of a cyclic olefin copolymer (“APEL6011T” manufactured by Mitsui Chemicals, Inc., glass transition point 105 ° C., MFR 26 g / 10 min) is dissolved in toluene, The solid content was diluted to 3% by mass to prepare a solution for forming a polymer thin film (viscosity: 2.4 mPa · s). And, the glass transition point (T _g ) and MFR of the cyclic olefin copolymer used in Example 1 are shown in Table 2.

(4) Production of Polymer Thin Film Subsequently, the step film of the film-like laminate was peeled off to obtain a polymer thin film.

2. Measurement / Evaluation (1) Surface Carbon Concentration of Polymer Thin Film In order to obtain the surface carbon concentration of the polymer thin film, XPS measurement of the surface of the polymer thin film was performed. For the measurement, PHI Quantera SXM (manufactured by ULVAC-PHI, Inc.) was used. The measurement was carried out at a photoelectron extraction angle of 45 ° using monochromatized Al · Kα as the X-ray source, and the elemental concentration (unit: atomic%) of carbon present on the surface was calculated. The obtained results are shown in Table 2.
(2) Peeling force of polymer thin film The peeling force at the time of peeling a polymer thin film from the process film in the obtained film-like laminate was measured.
That is, after bonding an adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) to a polymer thin film in a film-like laminate, the polymer thin film in a state where the adhesive tape is bonded is 180 ° from the process film The peeling force (mN / 20 mm) at the time of peeling was measured. The obtained results are shown in Table 2.
(3) Sticking Property of Polymer Thin Film First, a double-sided tape was stuck to the square end of a support base (“Crisper 75K2323” manufactured by Toyobo Co., Ltd.) to prepare a support having a double-sided tape-sticked part. Next, the double-sided tape sticking part of this support was stuck on the polymer thin film of the film-like laminate. Then, the support and the polymer thin film were peeled off from the process film to transfer the polymer thin film to the surface of the support. Subsequently, the double-sided tape sticking part was cut off from the support body to which the polymer thin film transferred, and the laminated body of a polymer thin film and a support base material was produced. This laminate was placed on the adherend so that the polymer thin film side was in contact with the following adherend, and the polymer thin film and the adherend were pressed together by moving the 2 kg roller twice from the support base . The stickability at that time was evaluated. If the polymer thin film is not peeled off with the entire surface of the polymer thin film stuck to the adherend after pressure bonding, it is judged as “A”, and if the polymer thin film does not stick to the adherend after pressure bonding, the case where there is floating or peeling It was determined that "B". The obtained results are shown in Table 2.
PP: Polypropylene board ("PP-N-BN" manufactured by Hitachi Chemical Co., Ltd., size 2 mm x 70 mm x 150 mm)
Glass: float plate glass ("float plate glass R3202 thread surface processing" manufactured by Asahi Glass Co., Ltd., size 2 mm x 70 mm x 150 mm)

(4) Contact Angle of Water on Polymer Thin Film In order to evaluate the wettability of the polymer thin film to water, the contact angle of water on the polymer thin film was measured. For the measurement, a contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.) was used. The contact angle to water was measured (23 ° C., 50% RH). The obtained results are shown in Table 2.
(5) Sliding Angle of Water on Polymer Film In order to evaluate the water repellency of the polymer film to water, the sliding angle of water on the polymer film was measured. A drop of water was placed on a polymer thin film placed horizontally, and when the polymer thin film was gradually inclined, the angle of the polymer thin film from which the drop of water began to flow was measured as the sliding angle. The obtained results are shown in Table 2.
(6) Film Strength The film strength was measured with a creep meter (trade name “cree meter RE2-3305 CYAMADEN” manufactured by Yamaden Co., Ltd.). Specifically, the polymer thin film surface of the film-like laminate, which was allowed to stand for 24 hours in an environment of temperature 23 ° C. and humidity 50% RH, was attached to a jig with a hole of 1 cm in diameter, and the process film was peeled off . A cylindrical plunger with a diameter of 1 mmφ was advanced to a location corresponding to the center of the hole of the polymer thin film jig. The penetration speed of the plunger was 0.5 mm / sec. The maximum stress (unit: mN / 1 mmφ) was measured when the plunger was advanced to a depth of 5 mm in the depth direction of the hole. The measurement was performed 10 times, and the average value was taken as the film strength of the polymer thin film. The obtained results are shown in Table 2.

[Examples 2 to 4]
Film-like laminates and polymer thin films 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 thin film were changed as shown in Table 2. The obtained results are shown in Table 2. Further, the glass transition point (T _g ), MFR and viscosity of the solution for forming a polymer thin film of the cyclic olefin copolymer used in Examples 2 to 4 are shown in Table 2.

[Comparative Examples 1 and 2]
Film-like laminates and polymer thin films 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 thin film were changed as shown in Table 2. The obtained results are shown in Table 2. Further, the glass transition point (T _g ), the MFR and the viscosity of the solution for forming a polymer thin film of the cyclic olefin copolymer used in Comparative Examples 1 and 2 are shown in Table 2. In Comparative Example 1, the polymer could not be dissolved to a desired concentration, and it was not possible to produce a film-like laminate and a polymer thin film in the same manner as in Example 1.

As shown in Table 2, the polymer thin film (Examples 1 to 4) containing a norbornene-based polymer (A) and having a thickness of 10 nm or more and 1000 nm or less has good adhesion and a contact angle of water is It was confirmed that the sliding angle of water was small. From this, it was confirmed that the polymer thin 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. Also, it was confirmed that the polymer thin films obtained in Examples 1 to 4 have high film strength and have self-supporting properties.

DESCRIPTION OF SYMBOLS 1 ... Polymer thin film, 2 ... Process film, 2A ... 1st surface, 2B ... 2nd surface, 100 ... film-like laminated body.

Claims

A polymer comprising a norbornene-based polymer (A) containing 10 mol% or more of a constitutional 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. Molecular thin film.

(In the above general formula (1), X 1 and X 2 are the same or different and each is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group X represents an unsubstituted alkenyl group, a hydroxy group or a carboxy group, and X 1 and X 2 may be combined with each other to form a ring)
In the polymer thin film according to claim 1,
The polymer thin film characterized in that the norbornene-based polymer (A) is a norbornene-based copolymer.
In the polymer thin film according to claim 1 or 2,
The polymer thin film, wherein the polymer thin film contains 50% by mass or more of the norbornene-based polymer (A).
The polymer thin film according to any one of claims 1 to 3
The glass transition point of the norbornene-based polymer (A) is 140 ° C. or less.
The polymer thin film according to any one of claims 1 to 4
The polymer thin film characterized in that the melt flow rate at a temperature of 260 ° C. and a load of 2.16 kgf of the norbornene-based polymer (A) is 20 g / 10 min or more.
In the polymer thin film according to any one of claims 1 to 5,
The surface carbon concentration of the said polymer thin film is 90 atomic% or more. The polymer thin film characterized by the above-mentioned.
A film-like laminate comprising a process film and the polymer thin film according to any one of claims 1 to 6 formed on the process film.
In the film-like laminate according to claim 7,
The film-like laminate, wherein the surface free energy of the process film is 40 mJ / m 2 or less.
In the film-like laminate according to claim 7 or 8,
The film-like laminate, wherein the arithmetic mean roughness of the surface of the process film is 40 nm or less.
A method of producing a polymer thin film for producing the polymer thin film according to any one of claims 1 to 6,
Coating a solution for forming a polymer thin film containing the norbornene-based polymer (A) on a process film, and drying the solution to form the polymer thin film;
And exfoliating the polymer thin film from the step film.
In the method of producing a polymer thin film according to claim 10,
The surface free energy of the process film is 40 mJ / m 2 or less.
In the method for producing a polymer thin film according to claim 10 or 11,
The method for producing a polymer thin film, wherein the arithmetic mean roughness of the surface of the step film is 40 nm or less.