CN111032752A - Polymer film, film-like laminate, and method for producing polymer film - Google Patents
Polymer film, film-like laminate, and method for producing polymer film Download PDFInfo
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- CN111032752A CN111032752A CN201880052493.XA CN201880052493A CN111032752A CN 111032752 A CN111032752 A CN 111032752A CN 201880052493 A CN201880052493 A CN 201880052493A CN 111032752 A CN111032752 A CN 111032752A
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- Prior art keywords
- film
- polymer
- polymer film
- norbornene
- laminate
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- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 110
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 50
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 112
- 238000000034 method Methods 0.000 claims description 83
- 230000008569 process Effects 0.000 claims description 77
- 239000010409 thin film Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
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- 238000005096 rolling process Methods 0.000 description 3
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 239000005060 rubber Substances 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
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- 239000002033 PVDF binder Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 150000001451 organic peroxides Chemical class 0.000 description 1
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The present invention relates to a polymer film which comprises a norbornene-based polymer (A) containing 10 mol% or more of a structural unit represented by the following general formula (1), and has a thickness of 10nm or more and 1000nm or less and has self-supporting properties. (in the general formula (1), X1And X2The same or differentEach represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a hydroxyl group, or a carboxyl group, X1And X2Optionally bonded to each other to form a ring. )
Description
Technical Field
The present invention relates to a polymer film, a film-like laminate, and a method for producing a polymer film.
Background
Films formed from cycloolefin resins have been used as dielectric films for thin film capacitors, for example.
For example, patent document 1 describes a high-insulating film containing a resin as a main component. In the high insulating film, the resin is an amorphous resin. When the minimum value of the refractive index in the surface direction of the high-insulation film is Ny, the refractive index in the direction perpendicular to Ny in the surface direction of the high-insulation film is Nx, and the thickness of the high-insulation film is d, the retardation (R) represented by the following formula 1 is 10nm or less.
R ═ n (Nx-Ny) · d (formula 1)
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-183181
Disclosure of Invention
Problems to be solved by the invention
When the thickness of the resin film is in the range of several tens to several hundreds nm, adhesion to an adherend may be achieved without using an adhesive or the like due to the action of electrostatic force and wettability.
However, the high-insulating film described in patent document 1 cannot adhere to an adherend. Further, although patent document 1 discloses that the average thickness is preferably 0.5 μm or more and 7.0 μm or less, the method for producing a high-insulating film disclosed in patent document 1 cannot make the thickness of the film nano-scale. In patent document 1, for example, a film produced by a solution casting method is subjected to stretching treatment, but the thickness of the film cannot be brought to the order of nanometers by this method.
The invention aims to provide a polymer film, a film-shaped laminate and a method for producing the polymer film, wherein the polymer film can realize adhesion to an adhered object without using an adhesive or the like and has high water repellency.
Means for solving the problems
According to one embodiment of the present invention, there is provided a polymer film comprising a norbornene-based polymer (A) containing 10 mol% or more of a structural unit represented by the following general formula (1), the norbornene-based polymer (A) having a thickness of 10nm or more and 1000nm or less and having a self-supporting property.
In the following general formula (1), X1And X2The same or different, each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a hydroxyl group, or a carboxyl group, X1And X2Optionally bonded to each other to form a ring.
[ chemical formula 1]
In one embodiment of the present invention, the norbornene-based polymer (a) is preferably a norbornene-based copolymer.
In one embodiment of the present invention, the polymer film preferably contains 50% by mass or more of the norbornene-based polymer (a).
In one embodiment of the present invention, the glass transition temperature of the norbornene-based polymer (A) is preferably 140 ℃ or lower.
In one embodiment of the present invention, the norbornene-based polymer (A) preferably has a melt flow rate of 20g/10min or more at a temperature of 260 ℃ and a load of 2.16 kgf.
In one embodiment of the present invention, the surface carbon concentration of the polymer thin film is preferably 90 atomic% or more.
According to one embodiment of the present invention, there is provided a film-like laminate including a process film and the polymer thin film according to one embodiment of the present invention formed on the process film.
In one embodiment of the present invention, the process film preferably has a surface free energy of 40mJ/m2The following.
In one embodiment of the present invention, the arithmetic average roughness of the surface of the process film is preferably 40nm or less.
According to one embodiment of the present invention, there is provided a method for producing a polymer film according to one embodiment of the present invention, the method including: a step of forming the polymer film by applying a solution for forming a polymer film containing the norbornene polymer (A) on a process film and drying the solution, and a step of peeling the polymer film from the process film.
In one embodiment of the present invention, the process film preferably has a surface free energy of 40mJ/m2The following.
In one embodiment of the present invention, the arithmetic average roughness of the surface of the process film is preferably 40nm or less.
The present invention can provide a polymer film, a film-like laminate, and a method for producing a polymer film, which can achieve adhesion to an adherend without using an adhesive or the like and have high water repellency.
Drawings
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 a process film used in the method for producing a polymer thin film according to the embodiment of the present invention.
Fig. 3 is a schematic view showing a state in which a polymer thin film is formed on a process film to produce a film-like laminate in the method for producing a polymer thin film according to the embodiment of the present invention.
Description of the symbols
1 … Polymer film
2 … Process film
2A … first side
2B … second side
100 … film laminate
Detailed Description
The present invention will be described below with reference to the accompanying drawings by way of examples of embodiments. The present invention is not limited to the embodiments. In the drawings, portions shown enlarged or reduced for convenience of description are included.
[ Polymer film ]
The polymer film 1 according to the present embodiment is a film having self-supporting properties, as shown in fig. 1. In the present specification, "self-supporting" refers to a property of being able to form a film from the polymer film 1 alone without laminating the polymer film 1 on another support, and more specifically, refers to a film strength of 5mN/1mm Φ or more. In addition, in the film having "self-supporting properties", the film strength is preferably 10mN/1 mm. phi. or more, and more preferably 20mN/1 mm. phi. or more. The film strength can be measured by a Creep tester (for example, trade name "Creep Meter RE2-3305 CYAMADEN" manufactured by seiko corporation). Specifically, the measurement can be carried out by the method described in the examples below.
The thickness of the polymer thin film 1 must be 10nm to 1000 nm. When the thickness of the polymer film 1 is 10nm or more and 1000nm or less, it can be adhered to a desired adherend such as skin without using an adhesive or the like. The thickness of the polymer film 1 can be measured by an spectroscopic ellipsometer (product name "M-2000") manufactured by j.a. woollam.
The thickness of the polymer thin film 1 is preferably 30nm or more, more preferably 50nm or more, still more preferably 100nm or more, and particularly preferably 150nm or more. The thickness of the polymer thin film 1 is preferably 900nm or less, more preferably 700nm or less, still more preferably 550nm or less, and particularly preferably 400nm 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 is required to contain a norbornene polymer (A) containing 10 mol% or more of a structural unit represented by the following general formula (1). When the norbornene polymer (a) does not have 10 mol% or more of the structural unit represented by the following general formula (1), a polymer film having a self-supporting property with a desired thickness and having high water repellency cannot be obtained. The content of the structural unit represented by the following general formula (1) in the polymer film 1 is preferably 20 mol%, and more preferably 50 mol% or more.
[ chemical formula 2]
In the above general formula (1), X1And X2The same or different, each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a hydroxyl group, or a carboxyl group, X1And X2The ring may be bonded to each other to form a ring.
Examples of the substituent for the alkyl group, the alkoxy group, and the alkenyl group include: halogen atom, hydroxyl group, carboxyl group, acryloyl group, methacryloyl group, epoxy group and the like.
The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms of the alkoxy group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms of the alkenyl group is preferably 2 to 5, more preferably 2 to 3.
(norbornene Polymer (A))
The norbornene-based polymer (A) may be a norbornene-based homopolymer or a norbornene-based copolymer as long as it contains 10 mol% of the structural unit represented by the above general formula (1).
The norbornene polymer (A) is a polymer comprising at least one norbornene compound as a monomer.
Examples of the norbornene-based compound include: norbornene (bicyclo [2.2.1] hept-2-ene), a compound having a cyclic structure including a bicyclo ring of norbornene (e.g., dicyclopentadiene), and derivatives thereof. These norbornene-based compounds may be used alone or in combination of two or more.
Examples of the monomer other than the norbornene-based compound include: cyclopentadiene, tetracyclododecene, and the like. These monomers may be used alone or in combination of two or more.
A polymer (homopolymer or copolymer) obtained by polymerizing monomers using a norbornene-based compound as at least one of the monomers may have a structural unit represented by the above general formula (1).
Examples of the norbornene-based polymer (a) include: a hydrogenated polymer of a ring-opening metathesis polymer of a norbornene-based monomer (specifically, available as ZEONEX (registered trademark) series manufactured by kushoku corporation), a copolymer of norbornene and ethylene (specifically, available as TOPAS (registered trademark) series manufactured by polyplasics corporation), a copolymer obtained by ring-opening polymerization of dicyclopentadiene and tetracyclododecene (specifically, available as ZEONOR (registered trademark) series manufactured by kushoku corporation), a copolymer of ethylene and tetracyclododecene (specifically, available as an APEL (registered trademark) series manufactured by mitsui chemical co., ltd.), a cyclic olefin resin containing a polar group using dicyclopentadiene and a methacrylate as raw materials (specifically, available as an ARTON (registered trademark) series manufactured by JSR corporation), and the like. These polymers may be used alone or in combination of two or more.
The norbornene-based polymer (A) may have a crosslinked structure. Here, the kind of the crosslinking agent which brings about the crosslinked structure is arbitrary. Examples of the crosslinking agent include: organic peroxides (e.g., dicumyl peroxide), and compounds having epoxy groups. These polymers may be used alone or in combination of two or more.
The crosslinking agent may crosslink between one kind of polymers constituting the norbornene polymer (A) or between different kinds of polymers. The binding site of the crosslinking agent is also arbitrary. The norbornene polymer (A) may be crosslinked with an atom constituting the main chain of the polymer, or may be crosslinked with an atom other than the main chain, such as a side chain or a functional group. The degree of crosslinking is also arbitrary, but if the degree of crosslinking is excessively advanced, there is a possibility that the processability (particularly, moldability) of the polymer film 1 containing the norbornene-based polymer (a) is excessively lowered, the surface properties of the polymer film 1 are excessively deteriorated, or the brittleness resistance of the polymer film 1 is deteriorated, and therefore, the degree should be controlled within a range in which such a problem does not occur.
The norbornene polymer (A) has thermoplasticity. The degree of thermoplasticity can be expressed in terms of Melt Flow Rate (MFR) which characterizes the viscosity at melting.
The norbornene-based polymer (A) has a Melt Flow Rate (MFR) of preferably 20g/10min, more preferably 20g/10min to 150g/10min, particularly preferably 25g/10min to 50g/10min at a temperature of 260 ℃ under a load of 2.16 kgf. When the MFR is within the above range, the thermoplasticity can be sufficiently improved, and the processability such as molding can be improved. MFR can be determined based on the description of ASTM D1238.
The glass transition temperature of the norbornene-based polymer (A) is preferably 140 ℃ or lower, more preferably 30 ℃ to 120 ℃ from the viewpoint of coatability of the polymer film-forming solution. When the glass transition temperature is 140 ℃ or lower, the solvent solubility can be further improved, while when the glass transition temperature is 30 ℃ or higher, the self-standing film-forming ability is exhibited at room temperature. The glass transition temperature can be measured using a differential scanning calorimeter. For example, the glass transition temperature can be determined by measuring the temperature in the range of-40 ℃ to 200 ℃ at a temperature rise rate of 10 ℃/min using a differential scanning calorimeter ("DSC (Q2000)" manufactured by TAInstructions Co., Ltd.), making a graph, and confirming the inflection point from the graph.
(olefin-based Polymer (B) other than norbornene-based Polymer (A))
The polymer film 1 may contain an olefin polymer (B) other than the norbornene polymer (a) (hereinafter, referred to as "non-NB olefin polymer (B)" as the case may be).
When the non-NB olefin-based polymer (B) is used, the content of the norbornene-based polymer (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more based on the total amount of the polymer, from the viewpoint of self-supporting property and water repellency.
The non-NB olefin-based polymer (B) may be linear or have a side chain. The non-NB olefin-based polymer (B) may have any functional group as long as it does not contain a norbornene ring, and the type and substitution density thereof are arbitrary. The functional group may be a functional group having low reactivity such as an alkyl group or a functional group having high reactivity such as a carboxylic acid group.
The non-NB olefin polymer (B) is an olefin polymer which is at least one kind of olefin as a monomer and does not contain a norbornene compound as a monomer. Therefore, the non-NB olefin-based polymer (B) is not particularly limited as long as it does not contain a norbornene ring in the polymer, and may be an aromatic ring-type polyolefin or a non-cyclic polyolefin. The aromatic cyclic polyolefin includes at least one kind of polyolefin in which an olefin having a cyclic structure of an aromatic ring is used as a monomer. The non-NB olefin-based polymer (B) may be a homopolymer or a copolymer.
(adherend)
The polymer film 1 can achieve adhesion to an adherend without using an adhesive or the like. Here, the adherend is not particularly limited, and examples thereof include: stainless steel, polyethylene, polypropylene, polycarbonate, glass, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), and a semiconductor circuit board. By using these materials as an adherend, water repellency can be easily imparted to any adherend. Examples of the adherend other than the above include: people, animals, clothes, hats, shoes, ornaments, and the like. By using these materials as the adherend, the polymer film 1 is very thin, so that the adhered portion is inconspicuous and is lightweight, which is preferable.
The polymer film 1 has high water repellency, and therefore has resistance to sweat, rain, and the like. Therefore, the polymer film 1 can be suitably used as a film that adheres to the skin, particularly for use in wearable terminals and the like.
[ method for producing Polymer film ]
The method for producing a polymer film according to the present embodiment is a method for producing a polymer film for producing the polymer film 1. The method for producing a polymer film according to the present embodiment includes the steps of: a step (polymer film forming step) of applying a polymer film forming solution containing the norbornene polymer (A) on a process film and drying the solution to form the polymer film; and a step (peeling step) of peeling the polymer film from the process film.
(Polymer film Forming step)
Fig. 2 is a schematic cross-sectional view showing a process 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 thin film forming solution containing the norbornene-based polymer (a) is applied to the first surface 2A of the first surface 2A and the second surface 2B of the step film as shown in fig. 2, and dried to form a polymer thin film 1, thereby obtaining a film-like laminate 100 shown in fig. 3.
Here, a process film and a polymer thin film forming solution used in the polymer thin film forming process will be described.
(Process film)
The process film 2 is not particularly limited. For example, the process film 2 preferably has a release substrate 21 and a release agent layer 22 formed on at least one surface of the release substrate 21 from the viewpoint of ease of handling. 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 in which a thermoplastic resin such as polyethylene is laminated on the paper substrate, a plastic film, and the like.
As the paper base material, there can be mentioned: cellophane, fine paper, coated paper, cast paper, and the like. As the plastic film, there may be mentioned: polyester films (e.g., polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), and polyolefin films (e.g., polypropylene and polyethylene). These paper substrates may be used alone in 1 kind, or two or more kinds may be used in combination.
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 silicone-based resins. Among these, as the release agent, any release agent selected from olefin resins, rubber elastomers (e.g., butadiene resins, isoprene resins, etc.), long-chain alkyl resins, alkyd resins, and fluorine resins is preferable. These release agents may be used alone in 1 kind, or two or more kinds may be used in combination. The release agent layer may further contain an antistatic agent or may not contain an antistatic agent.
The process film 2 is preferably adjusted in surface free energy and arithmetic mean roughness of the first surface 2A by the release agent layer 22.
The surface free energy of the first surface 2A of the process film 2 is preferably 40mJ/m2Below, more preferably 20mJ/m2Above and 40mJ/m2The following. The surface free energy is 20mJ/m2In the above case, the solution for forming a polymer thin film can be favorably applied to the process film 2, and the surface free energy is 40mJ/m2In the following case, the polymer film 1 can be easily peeled from the process film 2, and productivity can be improved. The surface free energy can be determined by measuring the contact angle of each liquid droplet (measurement temperature: 25 ℃ C.), and based on the value, by the theory of northern Kazaki-Chazu.
The arithmetic average roughness (Ra) of the surface of the first surface 2A of the process film 2 is preferably 40nm or less, more preferably 0.1nm or more and 30nm or less, and particularly preferably 0.5nm or more and 25nm or less. When 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. The arithmetic mean roughness can be measured using, for example, a light 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, preferably 25 μm or more and 150 μm or less.
The thickness of the release agent layer 22 is not particularly limited. In the case where the release agent layer 22 is formed by applying a solution containing a release agent onto 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.
(Polymer film-forming solution)
The material for forming a polymer thin film as a solute in the solution for forming a polymer thin film is a norbornene polymer (A). As the material substance, the non-NB olefin-based polymer (B) may be further used. The norbornene-based polymer (A) and the non-NB olefin-based polymer (B) are not described above.
The solvent in the polymer film-forming solution is not particularly limited as long as it can dissolve or uniformly disperse the polymer film-forming material substance and can be evaporated by heating. For example, as the solvent, preferred are: ethanol, propanol, isopropanol, acetone, toluene, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, dichloromethane, chloroform, and the like. These solvents may be used alone in 1 kind, or two or more kinds may be used in combination.
The boiling point of the solvent is preferably a value in the range of 30 ℃ to 160 ℃, and more preferably a value in the range of 35 ℃ to 120 ℃.
The concentration of the material substance in the polymer thin film forming solution is preferably set to a value in the range of 0.1 mass% to 20 mass%.
When the concentration of the material substance in the polymer thin film-forming solution is 0.1 mass% or more, the problem that a necessary thickness may not be obtained and the problem that the solution may not have an optimal viscosity can be suppressed. On the other hand, when the concentration of the material substance in the polymer thin film forming solution is 20% by mass or less, the problem that a uniform coating film may not be obtained can be suppressed.
From the above viewpoint, the concentration of the material substance in the polymer thin film forming solution is more preferably set to a value within a range of 0.3 mass% or more and 15 mass% or less, and still more preferably 0.5 mass% or more and 10 mass% or less.
The viscosity (measurement temperature: 25 ℃) of the polymer film-forming solution is preferably set to a value in the range of 1 mPas to 500 mPas.
When the viscosity of the polymer film-forming solution is 1 mPas or more, the occurrence of a problem such as a coating film sagging can be suppressed. On the other hand, when the viscosity of the polymer film-forming solution is 500 mPas or less, the problem that a uniform coating film cannot be obtained can be suppressed.
From the above-mentioned viewpoint, the viscosity (measurement temperature: 25 ℃) of the polymer film-forming solution is more preferably set to a value within a range of 1.5 mPas to 400 mPas, and still more preferably within a range of 2 mPas to 300 mPas.
The viscosity of the polymer film-forming solution was measured with a Brookfield rotational viscometer (4.1) according to JIS K7117-1.
The drying conditions for forming the coating layer of the polymer film forming solution formed on the process film 2 into the polymer film 1 are not particularly limited. The coating layer is preferably dried at a temperature of 40 to 120 ℃ for a drying time of 6 to 300 seconds.
When the drying temperature is 40 ℃ or higher, the inconvenience of requiring an excessive time for drying or insufficient drying can be suppressed. On the other hand, when the drying temperature is 120 ℃ or lower, the occurrence of wrinkles or curling can be suppressed.
Further, when the drying time is 6 seconds or more, such a disadvantage that the drying is insufficient can be prevented. On the other hand, when the drying time is 300 seconds or less, the occurrence of wrinkles or curling can be suppressed.
From the above-described viewpoint, the drying conditions for forming the coating layer of the solution for forming a polymer film into the polymer film 1 are more preferably 50 ℃ to 110 ℃ inclusive and the drying time is 12 seconds to 180 seconds inclusive, and still more preferably 60 ℃ to 100 ℃ inclusive and the drying time is 18 seconds to 120 seconds inclusive.
Further, it is preferable to apply the solution for forming a polymer thin film by a Roll-to-Roll method.
The reason for this is that, when the roll-to-roll method is used, the polymer film 1 having a predetermined thickness can be formed more efficiently, and therefore, the film-shaped laminate 100 can be mass-produced more efficiently.
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 for this is that when these coating apparatuses are used, the polymer film 1 having a predetermined thickness can be more efficiently formed.
That is, when a bar coater, a reverse gravure coater, or a slit die coater is used, the polymer thin film 1 having a thickness of nanometer order can be formed with a uniform thickness without generating wrinkles on the surface. Further, the bar coater, the reverse gravure coater, and the slit die coater are simple in structure and excellent in economical efficiency.
(peeling step)
In the peeling step, the polymer film 1 in the film-like laminate 100 as shown in fig. 3 is peeled from the process film 2 to obtain the polymer film 1 having self-supporting properties.
The peeling force of the process film 2 relative to the polymer film 1 in the peeling process is preferably 5mN/20mm or more and 100mN/20mm or less, more preferably 10mN/20mm or more and 50mN/20mm or less, and particularly preferably 15mN/20mm or more and 30mN/20mm or less.
When the peeling force is 5mN/20mm or more, the problem that the process film and the polymer film are easily peeled off in the polymer film forming process can be suppressed. Further, when the peeling force is 100mN/20mm or less, it is possible to suppress a problem that the polymer film is not easily peeled from the polymer film in the peeling step and the polymer film is broken.
The peeling force can be adjusted by changing the type of the peeling agent used for the process film 2, for example.
[ film-shaped laminate ]
As shown in fig. 3, the film-shaped laminate 100 according to the present embodiment includes a polymer film 1 and a process film 2. The film laminate 100 can be obtained by applying the polymer film forming solution to the process film 2 and drying the applied layer to form the polymer film 1. That is, the film-shaped laminate 100 can be obtained by the polymer thin film forming step in the polymer thin film manufacturing method according to the present embodiment.
(Effect of the present embodiment)
According to the present embodiment, the following operational effects can be obtained.
(1) The norbornene polymer (A) containing 10 mol% or more of the structural unit represented by the general formula (1) and the polymer film 1 having a thickness of 10nm or more and 1000nm or less and having a self-supporting property can be efficiently produced.
(2) A polymer film (1) which can be adhered to an object without using an adhesive or the like and has high water repellency can be provided.
[ variation of embodiment ]
The present embodiment is not limited to the above-described embodiments, and modifications, improvements, and the like that are made within a range that can achieve the object of the present embodiment are included in the present embodiment.
For example, in the above-described embodiment, the process film 2 including the release substrate 21 and the release agent layer 22 is used, but the present invention is not limited thereto. For example, when the surface free energy and the arithmetic mean roughness of the surface of the release substrate 21 are in appropriate ranges, a single-layer film including the release substrate 21 may be used as the process film 2.
Examples
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples at all.
[ test example 1]
1. Selection of Process films
(1) Process film production
The process film of test example 1 includes a release substrate and a release agent layer provided on the release substrate.
100 parts by weight of a mixture of a silicone-modified alkyd resin and an amino resin (product name "KS-882" from shin-Etsu chemical Co., Ltd.) and 1 part by weight of p-toluenesulfonic acid (curing agent) were diluted with toluene to prepare a coating solution having a solid content of 2% by mass.
Subsequently, the obtained coating liquid was applied to a polyethylene terephthalate (PET) film ("DIAFOILT 100" manufactured by Mitsubishi chemical corporation) having a thickness of 38 μm using a Meyer bar coater, and dried by heating at 140 ℃ for 60 seconds to obtain a process film in which a release agent layer having an average thickness of 0.1 μm was formed. The surface free energy and arithmetic mean roughness of the release agent layer surface of the obtained process film are shown in table 1.
(2) Preparation of solution for forming polymer film
A solution (solid content 10% by mass) of a cyclic olefin copolymer ("APEL 6011T", manufactured by Mitsui chemical Co., Ltd., "glass transition temperature 105 ℃ C., MFR 26g/10min) was dissolved in toluene and diluted to a solid content of 3% by mass to prepare a solution for forming a polymer film.
(3) Formation of film-like laminate
Next, the polymer film-forming solution was applied using a reverse gravure coater, the thickness of the polymer film dried on the prepared process film was set to 800nm, and then the polymer film was dried at 100 ℃ for 60 seconds to obtain a film-like laminate.
2. Measurement and evaluation
(1) Measurement of surface free energy of Process film
Surface free energy (mJ/m) of one surface (surface in contact with polymer thin film) of the process film coated with the polymer thin film forming solution2) The following is obtained: the contact angles of the respective droplets were measured (measurement temperature: 25 ℃ C.), and the contact angles were determined by northern Kazaki-Usche-zucchini theory based on the values.
That is, using diiodomethane as a "dispersion component", 1-bromonaphthalene as a "dipole component", and distilled water as a "hydrogen bond component" as droplets, a contact angle (measurement temperature: 25 ℃) was measured by a static drop method based on JIS R3257 using DM-70 manufactured by Kyowa interface science, Ltd., and a surface free energy (mJ/m) was determined based on the value by the northern Kazaki-Hazu theory2)。
(2) Measurement of arithmetic average roughness Ra of Process film
The arithmetic average roughness ra (nm) of the surface of the release sheet coated with the polymer film forming solution (surface in contact with the polymer film) was determined as follows: the optical interference microscope NT1100 manufactured by Veeco Instruments was used for a sample of 250,000. mu.m2The region (500. mu. m.times.500. mu.m) was observed to determine the arithmetic average roughness (Ra).
(3) Coatability of solution for forming polymer thin film to process film
The coatability when forming a film-like laminate was evaluated. The case where the polymer thin film forming solution can be uniformly applied to the process film is determined as "a", and the case where the process film is not uniformly applied due to occurrence of a dent or the like is determined as "B". The results obtained are shown in table 1.
(4) Peelability of polymer film
The peelability of the polymer film in the film-like laminate when peeled from the process film was evaluated. The case where the polymer film could be easily peeled off from the process film was judged as "a", and the case where the polymer film was damaged and could not be peeled off was judged as "B". The results obtained are shown in table 1.
[ test example 2]
A film-like laminate and a polymer film were produced and evaluated in the same manner as in test example 1, except that a polyethylene terephthalate film ("DIAFOILT 100" manufactured by mitsubishi chemical corporation, 38 μm in thickness) was used as the process film in test example 2. The results obtained are shown in table 1. The surface free energy and arithmetic mean roughness of the process film surface used in test example 2 are shown in table 1.
[ test example 3]
A film-shaped 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 lyideko corporation was used as the process film in test example 3. The results obtained are shown in table 1. The surface free energy and arithmetic mean roughness of the release agent layer surface of the process film used in test example 3 are shown in table 1.
[ test example 4]
In test example 4, a film-shaped laminate and a polymer film were produced and evaluated in the same manner as in test example 1, except that "SP-PET 38T 100X" manufactured by lyrec corporation was used as the process film. The results obtained are shown in table 1. The surface free energy and arithmetic mean roughness of the release agent layer surface of the process film used in test example 4 are shown in table 1.
[ Table 1]
From the results shown in table 1, it is understood that when a solution for forming a polymer thin film containing a cyclic olefin copolymer is used, the process film used in test example 1 is preferably used. Thus, in the following examples and comparative examples, the process film used in test example 1 was used.
[ example 1]
1. Production of polymer film
(1) Process film production
The process film of example 1 had a substrate and a release agent layer provided on the substrate.
100 parts by weight of a mixture of a silicone-modified alkyd resin and an amino resin (product name "KS-882" from shin-Etsu chemical Co., Ltd.) and 1 part by weight of p-toluenesulfonic acid (curing agent) were diluted with toluene to prepare a coating solution having a solid content of 2% by mass.
Subsequently, the obtained coating liquid was applied to a polyethylene terephthalate (PET) film ("DIAFOILT 100" manufactured by Mitsubishi chemical corporation) having a thickness of 38 μm using a Meyer bar coater, and dried by heating at 140 ℃ for 60 seconds to obtain a process film in which a release agent layer having an average thickness of 0.1 μm was formed.
(2) Preparation of solution for forming polymer film
A solution (solid content 10% by mass) of a cyclic olefin copolymer ("APEL 6011T", manufactured by Mitsui chemical Co., Ltd., "glass transition temperature 105 ℃ C., MFR 26g/10min) was dissolved in toluene, and the solution was diluted to a solid content of 3% by mass to prepare a solution (viscosity 2.4 mPas) for forming a polymer film. Among them, the glass transition temperature (T) of the cyclic olefin copolymer used in example 1g) And MFR are shown in Table 2.
(3) Formation of film-like laminate
Next, the polymer film-forming solution was applied using a reverse gravure coater, the thickness of the polymer film dried on the prepared process film was set to 800nm, and then the polymer film was dried at 100 ℃ for 60 seconds to obtain a film-like laminate.
(4) Production of polymer film
Next, the process film of the film-like laminate was peeled off, thereby obtaining a polymer thin film.
2. Measurement and evaluation
(1) Surface carbon concentration of polymer film
The results of XPS measurement of the surface of the polymer film were obtained by using PHI Quantera SXM (manufactured by Ulvac-PHI), measuring the surface carbon concentration of the polymer film at a photoelectron extraction angle of 45 ° using a monochromated Al K α as an X-ray source, and calculating the element concentration (unit: atomic%) of carbon present on the surface, as shown in table 2.
(2) Peeling force of polymer film
The peeling force when the polymer thin film in the obtained film-shaped laminate was peeled from the process film was measured.
That is, after an adhesive tape (No. 31B, manufactured by hitong electric corporation) was bonded to the polymer film in the film laminate, the polymer film in a state where the adhesive tape was bonded was peeled from the process film at 180 °, and the peel force (mN/20mm) at this time was measured. The results obtained are shown in Table 2.
(3) Adhesiveness of Polymer film
First, a double-sided tape was attached to the peripheral end of a support base material ("crisp 75K 2323" manufactured by toyoyo textile corporation) to prepare a support having a double-sided tape attachment portion. Next, the double-sided tape attaching portion of the support is attached to the polymer film of the film-like laminate. Then, the support and the polymer film are peeled off from the process film, and the polymer film is transferred to the surface of the support. Next, the double-sided tape-attached portion was cut out from the support to which the polymer film was transferred, and a laminate of the polymer film and the support base material was produced. The laminate was placed on an adherend so that the polymer film side of the laminate was in contact with the adherend described below, and a 2kg roller was reciprocated 2 times from above the support base to press the polymer film against the adherend. The adhesiveness at this time was evaluated. The case where the entire surface of the polymer film after the press-bonding was adhered to the adherend without peeling was judged as "a", and the case where the polymer film after the press-bonding was not adhered to the adherend and lifted up or peeled off was judged as "B". The results obtained are shown in Table 2.
PP: polypropylene plate (PP-N-BN, 2mm X70 mm X150 mm in size, manufactured by Hitachi chemical Co., Ltd.)
Glass: float plate glass (manufactured by Asahi glass Co., Ltd. "float plate glass R3202 wire chamfer processing", size 2 mm. times.70 mm. times.150 mm)
(4) Contact angle of water on polymer film
In order to evaluate the wettability of the polymer film with respect to water, the contact angle of water on the polymer film was measured. A contact angle meter (DM-701, manufactured by Kyowa Kagaku K.K.) was used for the measurement. The contact angle with water (23 ℃ C., 50% RH) was measured. The results obtained are shown in Table 2.
(5) Angle of water slip on polymer film
In order to evaluate the water repellency of the polymer film with respect to water, the slip angle of water on the polymer film was measured. The water drop was placed on a polymer film horizontally placed, and the angle of the polymer film at which the water drop started to flow when the polymer film was gently inclined was measured as the falling angle. The results obtained are shown in Table 2.
(6) Film strength
The film strength was measured by a Creep tester (trade name "Creep Meter RE2-3305 CYAMADEN", manufactured by yamamoto corporation). Specifically, the polymer film surface of the film laminate after standing still for 24 hours in an atmosphere at a temperature of 23 ℃ and a humidity of 50% RH was attached to a jig having a hole with a diameter of 1cm, and the process film was peeled off. And a cylindrical plunger with the diameter of 1mm phi enters the part of the polymer film corresponding to the central part of the hole of the clamp. Wherein the entry speed of the plunger was set to 0.5 mm/sec. The maximum stress (unit: mN/1 mm. phi.) until the plunger was advanced to a depth of 5mm in the depth direction of the hole was measured. 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. Further, the glass transition temperature (T) of the cyclic olefin copolymer used in examples 2 to 4g) The MFR and the viscosity of the polymer film-forming solution are shown in Table 2。
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. In addition, the glass transition temperature (T) of the cyclic olefin copolymer used in comparative examples 1 and 2g) The MFR and the viscosity of the polymer film-forming solution are shown in Table 2. In comparative example 1, the polymer could not be dissolved to a desired concentration, and a film-like laminate and a polymer thin film could not be produced by the same method as in example 1.
As shown in Table 2, it was confirmed that the polymer thin films (examples 1 to 4) comprising the norbornene polymer (A) and having a thickness of 10nm or more and 1000nm or less had good adhesion, a large contact angle with water, and a small water slip angle. From this, it was confirmed that the polymer films obtained in examples 1 to 4 can achieve adhesion to an adherend without using an adhesive or the like, and have high water repellency. In addition, the polymer thin films obtained in examples 1 to 4 were confirmed to have high film strength and self-supporting properties.
Claims (12)
1. A polymer film comprising a norbornene-based polymer (A) having a thickness of 10nm to 1000nm and having a self-supporting property, wherein the norbornene-based polymer (A) contains 10 mol% or more of a structural unit represented by the following general formula (1),
in the general formula (1), X1And X2The same or different, each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group,Hydroxy, or carboxy, X1And X2Optionally bonded to each other to form a ring.
2. The polymer film according to claim 1, wherein,
the norbornene-based polymer (A) is a norbornene-based copolymer.
3. The polymer film according to claim 1 or 2,
the polymer film contains 50 mass% or more of the norbornene-based polymer (A).
4. The polymer film according to any one of claims 1 to 3,
the norbornene polymer (A) has a glass transition temperature of 140 ℃ or lower.
5. The polymer film according to any one of claims 1 to 4,
the norbornene polymer (A) has a melt flow rate of 20g/10min or more at a temperature of 260 ℃ and a load of 2.16 kgf.
6. The polymer film according to any one of claims 1 to 5,
the surface carbon concentration of the polymer film is more than 90 atom%.
7. A film-like laminate comprising:
process film, and
a polymer thin film according to any one of claims 1 to 6 formed on the process film.
8. The membrane stack of claim 7,
the surface free energy of the process film is 40mJ/m2The following.
9. The membrane-like laminate according to claim 7 or 8,
the arithmetic average roughness of the surface of the process film is 40nm or less.
10. A method for producing a polymer film according to any one of claims 1 to 6, comprising:
a step of forming a polymer film by applying a polymer film-forming solution containing the norbornene polymer (A) on a process film and drying the solution; and
and a step of peeling the polymer film from the process film.
11. The method for producing a polymer film according to claim 10,
the surface free energy of the process film is 40mJ/m2The following.
12. The method for producing a polymer film according to claim 10 or 11, wherein,
the arithmetic average roughness of the surface of the process film is 40nm or less.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-160644 | 2017-08-23 | ||
| JP2017160644 | 2017-08-23 | ||
| PCT/JP2018/030476 WO2019039392A1 (en) | 2017-08-23 | 2018-08-17 | Polymer thin film, film-form laminate, and method for producing polymer thin film |
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| Publication Number | Publication Date |
|---|---|
| CN111032752A true CN111032752A (en) | 2020-04-17 |
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| CN201880052493.XA Pending CN111032752A (en) | 2017-08-23 | 2018-08-17 | Polymer film, film-like laminate, and method for producing polymer film |
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| Country | Link |
|---|---|
| JP (1) | JP6586545B2 (en) |
| KR (1) | KR102548028B1 (en) |
| CN (1) | CN111032752A (en) |
| TW (1) | TWI784041B (en) |
| WO (1) | WO2019039392A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113059730A (en) * | 2021-03-29 | 2021-07-02 | 中金液压胶管股份有限公司 | Multilayer vulcanization support for hydraulic rubber tube production |
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| JPH10130402A (en) * | 1996-10-29 | 1998-05-19 | Nippon Zeon Co Ltd | Polymer film and preparation thereof |
| JP2008031319A (en) * | 2006-07-28 | 2008-02-14 | Fujifilm Corp | Norbornene polymer, film, polarizing plate and liquid crystal display |
| WO2015045414A1 (en) * | 2013-09-30 | 2015-04-02 | 三井化学株式会社 | Pellicle film, pellicle using same, exposure original plate and exposure device, and method for manufacturing semiconductor device |
| JP2016169349A (en) * | 2015-03-16 | 2016-09-23 | 昭和電工株式会社 | Method fo producing cast film of addition polymer of norbornene compound |
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| EP1548063A4 (en) * | 2002-10-03 | 2008-10-08 | Sekisui Chemical Co Ltd | Thermoplastic saturated norbornene based resin film, ans method for producing thermoplastic saturated norbornene based resin film |
| EP2372433B1 (en) * | 2009-02-03 | 2018-04-11 | LG Chem, Ltd. | Method for manufacturing an optical filter for a stereoscopic image display device |
| JP5566040B2 (en) * | 2009-03-30 | 2014-08-06 | 日本ゴア株式会社 | Laminated body and method for producing the same |
| JP6085185B2 (en) * | 2013-02-06 | 2017-02-22 | 株式会社ダイセル | Release film and laminate for manufacturing fuel cell, and method for manufacturing fuel cell |
| JP2015183181A (en) | 2014-03-26 | 2015-10-22 | 京セラ株式会社 | High insulation film and film capacitor using the same |
| JP6424033B2 (en) * | 2014-07-15 | 2018-11-14 | デクセリアルズ株式会社 | Cyclic olefin resin composition film |
| JP6539431B2 (en) * | 2014-07-17 | 2019-07-03 | リンテック株式会社 | Sheet-like laminate and method of manufacturing sheet-like laminate |
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2018
- 2018-08-17 JP JP2019529655A patent/JP6586545B2/en active Active
- 2018-08-17 WO PCT/JP2018/030476 patent/WO2019039392A1/en active Application Filing
- 2018-08-17 CN CN201880052493.XA patent/CN111032752A/en active Pending
- 2018-08-17 KR KR1020207000857A patent/KR102548028B1/en active IP Right Grant
- 2018-08-21 TW TW107129075A patent/TWI784041B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10130402A (en) * | 1996-10-29 | 1998-05-19 | Nippon Zeon Co Ltd | Polymer film and preparation thereof |
| JP2008031319A (en) * | 2006-07-28 | 2008-02-14 | Fujifilm Corp | Norbornene polymer, film, polarizing plate and liquid crystal display |
| WO2015045414A1 (en) * | 2013-09-30 | 2015-04-02 | 三井化学株式会社 | Pellicle film, pellicle using same, exposure original plate and exposure device, and method for manufacturing semiconductor device |
| JP2016169349A (en) * | 2015-03-16 | 2016-09-23 | 昭和電工株式会社 | Method fo producing cast film of addition polymer of norbornene compound |
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| CN113059730A (en) * | 2021-03-29 | 2021-07-02 | 中金液压胶管股份有限公司 | Multilayer vulcanization support for hydraulic rubber tube production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6586545B2 (en) | 2019-10-02 |
| KR102548028B1 (en) | 2023-06-26 |
| WO2019039392A1 (en) | 2019-02-28 |
| TW201920390A (en) | 2019-06-01 |
| KR20200043973A (en) | 2020-04-28 |
| JPWO2019039392A1 (en) | 2019-11-07 |
| TWI784041B (en) | 2022-11-21 |
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