WO2018181191A1 - 機能性フィルム及びデバイス - Google Patents
機能性フィルム及びデバイス Download PDFInfo
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- WO2018181191A1 WO2018181191A1 PCT/JP2018/012163 JP2018012163W WO2018181191A1 WO 2018181191 A1 WO2018181191 A1 WO 2018181191A1 JP 2018012163 W JP2018012163 W JP 2018012163W WO 2018181191 A1 WO2018181191 A1 WO 2018181191A1
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- 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
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- 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to a functional film excellent in optical isotropy, bending resistance, and workability in use, and a device obtained using the functional film.
- a transparent plastic film has been used instead of a glass plate as a substrate having electrodes in order to realize a reduction in thickness and weight. It was.
- a transparent plastic film is required to have excellent optical isotropy and gas barrier properties.
- flexible displays have been developed, and the plastic film used at this time is required to have excellent bending resistance.
- Patent Document 1 as a film having excellent optical isotropy and gas barrier properties, a ceramic layer (A layer) formed from polysilazane and a specific cured resin layer (B layer) on at least one surface of a transparent polymer film. And a transparent gas barrier laminate film characterized in that it has a layer formed in contact with each other.
- Patent Document 1 describes that a transparent gas barrier laminate film having excellent optical isotropy can be obtained by using a polycarbonate film or a polyarylate film as a transparent polymer film.
- a film having more excellent optical isotropy and bending resistance has been a demand for a film having more excellent optical isotropy and bending resistance.
- the present inventor has intensively studied a functional film excellent in optical isotropy, flex resistance, and gas barrier properties.
- a functional film excellent in optical isotropy and bending resistance can be obtained, and a function not having a base material layer
- the handling film is difficult to handle at the time of manufacture and transportation, but until it is used, the handling film is improved by providing a process film that can function as a support as at least one outer layer. I understood.
- the present inventor has formed a resin coat layer using a specific curable composition on the process film, thereby providing a functional film excellent in workability at the time of use. As a result, the present invention was completed.
- the following functional films [1] to [13] and a device [14] are provided.
- the organic compound used for modifying the surface of the inorganic filler includes a group containing a reactive unsaturated bond.
- a composite compound in which the gas barrier layer contains silicon oxide, silicon nitride, silicon fluoride, silicon carbide, metal oxide, metal nitride, metal fluoride, metal carbide, and elements constituting these compounds The functional film according to any one of [1] to [7], which contains at least one selected from the group consisting of: [9] Any one of [1] to [8], wherein the gas barrier layer is obtained by modifying a surface of a layer that can be changed to a layer containing an inorganic compound by undergoing a modification treatment. Functional film described in 2. [10] The functional film according to any one of [1] to [9], wherein the thickness of the gas barrier layer is 20 to 3000 nm.
- the functional film in any one of.
- [12] After performing a mandrel bending test at a diameter of 6 mm in accordance with JIS K5600-5, the water vapor transmission rate at a temperature of 40 ° C. and a relative humidity of 90% is 0.2 g ⁇ m ⁇ 2 ⁇ day.
- a functional film excellent in optical isotropy, flex resistance, and workability when used, and a device obtained using the functional film are provided.
- the functional film of the present invention includes a process film, a resin coat layer directly provided on the process film, and a gas barrier layer provided directly or via another layer on the resin coat layer. It is a curable film,
- the said resin coat layer consists of hardened
- the process film constituting the functional film of the present invention functions as a support during the production or use of the functional film, and improves the handleability in these operations.
- this process film plays a role as a protective layer when the functional film is stored or transported, and protects the resin coat layer and the bus barrier layer. As will be described later, usually, the process film is finally peeled off.
- a resin film is preferable.
- the resin film preferably has no easy-adhesion layer or release layer on the surface.
- components contained in these layers contaminate the resin coat layer, destroy the resin coat layer when removing the process film, There is a risk of making the film winding work difficult.
- the resin component of the resin film includes polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester resin, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, and cycloolefin. Based polymers, aromatic polymers, and the like.
- a polyester resin a polycarbonate, a cycloolefin polymer, or an aromatic polymer is preferable, and a polyester resin is more preferable because it is more excellent in transparency and versatile.
- polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate and the like, and polyethylene terephthalate is preferable.
- Polycarbonates include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1, Examples thereof include polymers obtained by reacting bisphenols such as 1-bis (4-hydroxyphenyl) isobutane and 1,1-bis (4-hydroxyphenyl) ethane with phosgene and diphenyl carbonate.
- cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Specific examples thereof include Apel (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), Arton (a norbornene polymer manufactured by JSR), Zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like. .
- Apel an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals
- Arton a norbornene polymer manufactured by JSR
- Zeonoa a norbornene polymer manufactured by Nippon Zeon
- aromatic polymer examples include polystyrene.
- the resin film may contain various additives as long as the effects of the present invention are not hindered.
- the additive include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. What is necessary is just to determine suitably content of these additives according to the objective.
- the resin film can be obtained by preparing a resin composition containing a resin component and optionally various additives, and molding the resin composition into a film.
- the molding method is not particularly limited, and a known method such as a casting method or a melt extrusion method can be used.
- the thickness of the process film is preferably 10 to 300 ⁇ m, more preferably 20 to 125 ⁇ m from the viewpoint of handling properties.
- the resin coat layer constituting the functional film of the present invention is a layer directly provided on the process film, and is composed of a cured product of a curable composition containing an energy curable resin and an inorganic filler. .
- the process film can be efficiently peeled and removed without damaging the gas barrier layer or the like.
- the energy curable resin refers to a resin that is turned into a cured product when a curing reaction is started by irradiation with an energy beam such as an electron beam or ultraviolet ray, or by heating.
- the energy curable resin is usually a mixture containing a polymerizable compound as a main component.
- the polymerizable compound is a compound having an energy polymerizable functional group.
- the energy polymerizable functional group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyl group, an allyl group, and a styryl group.
- the energy polymerizable functional group is preferably a (meth) acryloyl group because of its high reactivity.
- the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
- Examples of the polymerizable compound having a (meth) acryloyl group include polyfunctional acrylate compounds.
- a polyfunctional acrylate compound refers to an acrylic ester compound or a methacrylic ester compound having two or more unsaturated bonds involved in the polymerization reaction.
- polyfunctional acrylate compounds include tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth).
- the energy curable resin may contain an oligomer.
- oligomers include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyol acrylate oligomers, and the like.
- the energy curable resin may contain a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator.
- photopolymerization initiator examples include ketone photopolymerization initiators such as 2,2-dimethoxy-1,2-diphenylethane-1-one and 1-hydroxy-cyclohexyl-phenylketone; 2,4,6-trimethylbenzoyl- Diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) -phenylphosphinate, bis (2,6-dimethoxybenzoyl) -2,4 Phosphorus photopolymerization initiators such as 4-trimethyl-pentylphosphine oxide; bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) ) -Phenyl] titanium and other titanocene photopolymerization initiators; oxime ester photopolymerization initiators;
- thermal polymerization initiator examples include hydrogen peroxide; peroxodisulfates such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4 Azo compounds such as' -azobis (4-cyanovaleric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide Organic peroxides such as lauroyl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like. These can be used individually by 1 type or in combination of 2 or more types.
- the content is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- the energy curable resin may contain a polyisocyanate-based crosslinking agent.
- the polyisocyanate crosslinking agent is not particularly limited, and a compound having two or more isocyanate groups in the molecule is used.
- Examples of such polyisocyanate-based crosslinking agents include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate.
- Alicyclic polyisocyanates such as narate and hydrogenated diphenylmethane diisocyanate; biurets and isocyanurates of these compounds, and further these compounds and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, And adduct bodies which are a reaction product with a low molecular active hydrogen-containing compound such as castor oil.
- These can be used individually by 1 type or in combination of 2 or more types.
- the energy curable resin contains a polyisocyanate-based crosslinking agent
- the content thereof is usually 1 to 10 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- the energy curable resin is preferably a resin that is cured by ultraviolet (UV) irradiation (ultraviolet curable resin).
- UV ultraviolet
- a layer made of a cured product of an energy curable resin can be efficiently formed.
- the inorganic filler contained in the curable composition is used for enhancing the peelability of the process film in the functional film.
- inorganic substances constituting the inorganic filler include metal oxides such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide; And metal fluorides such as magnesium fluoride and sodium fluoride.
- metal oxides such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide
- metal fluorides such as magnesium fluoride and sodium fluoride.
- the shape of the inorganic filler may be spherical or non-spherical. When it is non-spherical, it may be indefinite, or may have a shape with a high aspect ratio such as a needle shape or a scale shape. Since a functional film with more excellent optical isotropy can be easily obtained, those having a low aspect ratio are preferred, and those having a spherical shape are more preferred.
- the average particle size of the inorganic filler is not particularly limited, but is usually 5 to 100 nm. If the average particle size of the inorganic filler is too small, it may be difficult to sufficiently improve the peelability of the process film. On the other hand, if the average particle size of the inorganic filler is too large, the gas barrier properties of the gas barrier layer formed on the resin coat layer may be reduced.
- the average particle size of the inorganic filler can be measured by a dynamic light scattering method using a particle size distribution measuring device.
- the surface of the inorganic filler may be modified with an organic compound.
- organic compounds containing a group containing a reactive unsaturated bond examples include organic compounds containing a group containing a reactive unsaturated bond.
- the inorganic filler modified with an organic compound containing a group containing a reactive unsaturated bond has a group containing a reactive unsaturated bond on the surface.
- the group containing a reactive unsaturated bond examples include a vinyl group, an allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a glycidyl group.
- a silane coupling agent As the organic compound containing a group containing a reactive unsaturated bond, a silane coupling agent can be used.
- silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- Examples thereof include glycidyloxypropyltrimethoxysilane.
- the inorganic filler having a group containing a reactive unsaturated bond on the surface can be obtained by surface treatment of the inorganic filler by a known method using a silane coupling agent.
- the curable composition may contain a solvent.
- Solvents include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, mono Halogenated hydrocarbon solvents such as chlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; ethyl acetate, butyl acetate Ester solvent such as ethyl cellosolve; ether solvent such as 1,3-dioxolane; and the like.
- the resin coat layer constituting the functional film of the present invention is obtained by applying the curable composition onto the process film by a known application method, and drying the obtained coating film as necessary. It can be formed by curing the film.
- a normal wet coating method can be used as a method for applying the curable composition. Examples include dipping method, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing method, spray coating, gravure offset method and the like.
- Examples of the method for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
- the method for curing the coating film is not particularly limited, and a known method can be appropriately selected according to the characteristics of the energy curable resin.
- the coating film is irradiated by irradiating the active energy rays to the coating film using a high pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like. It can be cured.
- the wavelength of the active energy ray is preferably 200 to 400 nm, and more preferably 350 to 400 nm.
- Irradiation dose is usually illuminance 50 ⁇ 1000mW / cm 2, light amount 50 ⁇ 5000mJ / cm 2, preferably in the range of 1000 ⁇ 5000mJ / cm 2.
- the irradiation time is usually 0.1 to 1000 seconds, preferably 1 to 500 seconds, more preferably 10 to 100 seconds. In order to satisfy the above-mentioned light quantity in consideration of the heat load of the light irradiation process, irradiation may be performed a plurality of times.
- the coating film can be cured by heating the coating film to a temperature at which the curing reaction proceeds.
- the content of the resin component (component derived from the energy curable resin) contained in the resin coat layer is not particularly limited, but is usually 30 to 90% by mass and 50 to 70% by mass based on the entire resin coat layer. preferable.
- the content of the inorganic filler contained in the resin coat layer is not particularly limited, but is usually 10 to 70% by mass, preferably 50 to 70% by mass, based on the entire resin coat layer.
- the thickness of the resin coat layer is not particularly limited, but is usually 0.1 to 10 ⁇ m, preferably 0.5 to 5 ⁇ m. If the resin coat layer is too thin, the gas barrier layer or the like may be destroyed when the process film is peeled and removed. On the other hand, if the resin coat layer is too thick, the bending resistance may decrease.
- the maximum cross-sectional height (Rt) of the roughness curve of the surface of the resin coat layer opposite to the side in contact with the process film is not particularly limited, but is usually 1 to 200 nm, and preferably 2 to 150 nm.
- the surface of the resin coat layer opposite to the side in contact with the process film is an exposed surface when the resin coat layer is formed on the process film. As will be described later, a gas barrier layer is formed on this surface directly or via another layer.
- the maximum cross-sectional height (Rt) of the roughness curve can be measured by observing the exposed surface of the resin coating layer with an optical interference microscope, as long as the functional film is in the process of being produced.
- the maximum cross-sectional height (Rt) of the roughness curve is too small, it may be difficult to sufficiently improve the peelability of the process film. On the other hand, if the cross-section maximum height (Rt) of the roughness curve is too large, the gas barrier property of the gas barrier layer formed on the resin coat layer may be reduced.
- the maximum cross-sectional height (Rt) of the roughness curve can be optimized by adjusting the average particle size and amount of the inorganic filler used.
- the gas barrier layer constituting the functional film of the present invention is a layer having a characteristic (gas barrier property) for suppressing permeation of gases such as oxygen and water vapor.
- This gas barrier layer is laminated on the resin coat layer directly or via another layer such as a primer layer.
- the gas barrier layer contains silicon oxide, silicon nitride, silicon fluoride, silicon carbide, metal oxide, metal nitride, metal fluoride, metal carbide, and a composite compound containing elements constituting these compounds. Those are preferred.
- a gas barrier layer for example, an inorganic vapor-deposited film or a layer obtained by modifying the surface of a layer that can be changed to a layer containing an inorganic compound by undergoing a modification treatment [in this case, a gas barrier layer]
- the term “means a layer including a modified region”, not only a modified region. ] Etc. are mentioned.
- the inorganic vapor deposition film examples include vapor deposition films of inorganic compounds and metals.
- inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide and tin oxide
- inorganic nitrides such as silicon nitride, aluminum nitride and titanium nitride
- inorganic carbides Inorganic sulfides
- inorganic oxynitrides such as silicon oxynitride
- Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin. These can be used singly or in combination of two or more. Among these, an inorganic vapor-deposited film using an inorganic oxide, inorganic nitride or metal as a raw material is preferable from the viewpoint of gas barrier properties, and further, an inorganic material using an inorganic oxide or inorganic nitride as a raw material from the viewpoint of transparency. A vapor deposition film is preferred.
- a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a thermal CVD (chemical vapor deposition) method, a plasma CVD method, a photo CVD method, etc.
- the CVD method is mentioned.
- the thickness of the inorganic vapor-deposited film varies depending on the inorganic compound and metal used, but is preferably in the range of 20 to 3000 nm, more preferably 20 to 1000 nm, and more preferably 20 to 500 nm from the viewpoint of gas barrier properties and handling properties. .
- Examples of the layer that can be changed to a layer containing an inorganic compound by undergoing a modification treatment include a layer containing a silicon-containing polymer compound (hereinafter sometimes referred to as “polymer layer”).
- a layer that can be changed to a layer containing an inorganic compound by undergoing a modification treatment includes a layer containing an inorganic polymer compound such as inorganic polysilazane described later. In this case, by undergoing the modification treatment, at least a part of the layer containing the inorganic polymer compound is changed to a layer containing an inorganic compound having a different composition.
- the polymer layer may contain other components as long as the object of the present invention is not impaired.
- other components include a curing agent, an anti-aging agent, a light stabilizer, and a flame retardant.
- the content of the silicon-containing polymer compound in the polymer layer is preferably 50% by mass or more, and more preferably 70% by mass or more because a gas barrier layer having better gas barrier properties can be formed.
- the thickness of the polymer layer is not particularly limited, but is usually in the range of 20 to 3000 nm, more preferably 20 to 1000 nm, and more preferably 20 to 500 nm.
- the polymer layer is, for example, a coating film obtained by applying a solution obtained by dissolving or dispersing a silicon-containing polymer compound in an organic solvent directly or via another layer by a known coating method. Can be formed by drying.
- organic solvent examples include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane, n-hexane, n -An aliphatic hydrocarbon solvent such as heptane; an alicyclic hydrocarbon solvent such as cyclopentane or cyclohexane; These solvents can be used alone or in combination of two or more.
- aromatic hydrocarbon solvents such as benzene and toluene
- ester solvents such as ethyl acetate and butyl acetate
- ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
- n-pentane n-hexane
- Coating methods include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, and gravure offset. Law.
- Examples of the method for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
- the heating temperature is usually 80 to 150 ° C.
- the heating time is usually several tens of seconds to several tens of minutes.
- Examples of the method for modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.
- the ion implantation treatment is a method of injecting accelerated ions into the polymer layer to modify the polymer layer.
- the plasma treatment is a method for modifying the polymer layer by exposing the polymer layer to plasma.
- plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
- the ultraviolet irradiation treatment is a method for modifying the polymer layer by irradiating the polymer layer with ultraviolet rays.
- the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
- silicon-containing polymer compounds examples include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylene phenylene) compounds, and poly (disilanylene ethynylene) compounds. And polysilazane compounds are more preferred.
- the polysilazane compound is a compound having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule. Specifically, the formula (1)
- the compound which has a repeating unit represented by these is preferable.
- the number average molecular weight of the polysilazane compound to be used is not particularly limited, but is preferably 100 to 50,000.
- n represents an arbitrary natural number.
- Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group;
- alkyl group of the unsubstituted or substituted alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
- Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- alkenyl group of an unsubstituted or substituted alkenyl group examples include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like having 2 to 2 carbon atoms. 10 alkenyl groups are mentioned.
- substituents for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
- halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
- hydroxyl group such as hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
- An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
- aryl group of the unsubstituted or substituted aryl group examples include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- substituent of the aryl group examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon numbers such as methoxy group and ethoxy group 1-6 alkoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth) acryloyloxy groups; unsubstituted phenyl groups, 4-methylphenyl groups, 4-chlorophenyl groups, etc.
- alkylsilyl group examples include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.
- Rx, Ry, and Rz a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.
- Examples of the polysilazane compound having a repeating unit represented by the formula (1) include inorganic polysilazanes in which Rx, Ry, and Rz are all hydrogen atoms, and organic polysilazanes in which at least one of Rx, Ry, and Rz is not a hydrogen atom. It may be.
- a modified polysilazane compound can also be used as the polysilazane compound.
- the modified polysilazane include, for example, JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, and JP-A-2-175726.
- JP-A-5-238827, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-31333 Examples thereof include those described in Kaihei 5-345826 and JP-A-4-63833.
- the polysilazane compound perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferable from the viewpoint of easy availability and the ability to form an ion-implanted layer having excellent gas barrier properties.
- a polysilazane compound a commercially available product as a glass coating material or the like can be used as it is.
- the polysilazane compounds can be used alone or in combination of two or more.
- ions implanted into the polymer layer ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc .; methane, ethane, etc.
- rare gases such as argon, helium, neon, krypton, and xenon
- fluorocarbon hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc .
- Ion of alkane gases such as ethylene and propylene
- Ions of alkadiene gases such as pentadiene and butadiene
- Ions of alkyne gases such as acetylene
- Aromatic carbonization such as benzene and toluene
- Examples include ions of hydrogen-based gases; ions of cycloalkane-based gases such as cyclopropane; ions of cycloalkene-based gases such as cyclopentene; ions of metals; ions of organosilicon compounds. These ions can be used alone or in combination of two or more.
- ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be more easily implanted and a gas barrier layer having better gas barrier properties can be formed.
- the ion implantation amount can be appropriately determined in accordance with the purpose of use of the functional film (necessary gas barrier properties, transparency, etc.).
- Examples of the method of implanting ions include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma, and the like. Of these, the latter method of injecting ions in plasma (plasma ion implantation method) is preferable because the target gas barrier layer can be easily formed.
- plasma is generated in an atmosphere containing a plasma generation gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer to thereby remove ions (positive ions) in the plasma. It can be performed by injecting into the surface portion of the polymer layer. More specifically, the plasma ion implantation method can be carried out by a method described in WO2010 / 107018 pamphlet or the like.
- the thickness of the region into which ions are implanted can be controlled by implantation conditions such as ion type, applied voltage, and processing time, depending on the thickness of the polymer layer and the purpose of use of the functional film. Although it may be determined, it is usually 10 to 400 nm.
- the ion implantation can be confirmed by performing an elemental analysis measurement in the vicinity of 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the thickness of the gas barrier layer is not particularly limited, but is usually 20 to 3000 nm, preferably 20 to 1000 nm, more preferably 20 to 500 nm.
- the functional film of the present invention is a layer other than the process film, the resin coat layer, and the gas barrier layer [hereinafter referred to as “other layer (I)”.
- the other layer (I) may include an adhesive layer.
- the adhesive layer is usually directly or other layer [hereinafter referred to as “other layer (II)” on the gas barrier layer. ] Are stacked. Examples of the other layer (II) include a primer layer.
- the adhesive layer is a layer used when the functional film of the present invention is adhered to an adherend.
- the adhesive layer can be formed, for example, by applying an adhesive on the gas barrier layer directly or through another layer and drying the obtained coating film.
- adhesive is used in a broad sense including “pressure-sensitive adhesive (pressure-sensitive adhesive)”.
- the adhesive resin contained in the adhesive include a rubber adhesive resin, a polyolefin adhesive resin, an epoxy adhesive resin, and an acrylic adhesive resin.
- rubber-based adhesive resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene, and (meth) acrylonitrile on natural rubber.
- an adhesive resin mainly composed of a polyisobutylene resin is preferable.
- the “main component” refers to a component occupying 50% by mass or more in the solid content.
- polyolefin-based adhesive resin examples include an adhesive resin mainly composed of a modified polyolefin resin.
- the modified polyolefin resin is a polyolefin resin having a functional group introduced, obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier.
- polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), and ethylene-propylene.
- VLDPE very low density polyethylene
- LDPE low density polyethylene
- MDPE medium density polyethylene
- HDPE high density polyethylene
- PP polypropylene
- ethylene-propylene examples include a polymer, an olefin elastomer (TPO), an ethylene-vinyl acetate copolymer (EVA), an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid ester copolymer.
- the modifier used for the modification treatment of the polyolefin resin is a compound having a functional group in the molecule, that is, a group that can contribute to a crosslinking reaction described later.
- Functional groups include carboxyl groups, carboxylic anhydride groups, carboxylic ester groups, hydroxyl groups, epoxy groups, amide groups, ammonium groups, nitrile groups, amino groups, imide groups, isocyanate groups, acetyl groups, thiol groups, ether groups. Thioether group, sulfone group, phosphone group, nitro group, urethane group, halogen atom and the like.
- a carboxyl group, a carboxylic anhydride group, a carboxylic ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, and an isocyanate group are preferable, a carboxylic anhydride group and an alkoxysilyl group are more preferable, and a carboxylic anhydride Physical groups are particularly preferred.
- epoxy adhesive resins include aliphatic chain-modified epoxy resins, cyclopentadiene-modified epoxy resins and hydrocarbon-modified epoxy resins such as naphthalene-modified epoxy resins, elastomer-modified epoxy resins, and adhesive resins mainly composed of silicone-modified epoxy resins. Can be mentioned.
- the acrylic adhesive resin mainly comprises an acrylic copolymer having a repeating unit derived from a (meth) acrylic acid ester having a hydrocarbon group having 1 to 20 carbon atoms and a repeating unit derived from a functional group-containing monomer. Adhesive resin to be used.
- Examples of the (meth) acrylic acid ester having a hydrocarbon group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl ( Examples include meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.
- Examples of the functional group-containing monomer include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer.
- a hydroxy group-containing monomer and a carboxy group-containing monomer are preferable.
- Hydroxy group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) An acrylate etc. are mentioned.
- Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid.
- adhesive resins can be hardeners, crosslinkers, polymerization initiators, light stabilizers, antioxidants, tackifiers, plasticizers, UV absorbers, colorants, resin stabilizers, fillers as necessary. , Pigments, extenders, antistatic agents, and the like. These components can be appropriately selected and used according to each adhesive resin.
- the thickness of the adhesive layer can be appropriately selected in consideration of the purpose of use of the functional film.
- the thickness is not particularly limited, but is usually 0.1 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m, more preferably 1 to 100 ⁇ m.
- the functional film of the present invention When the functional film of the present invention has an adhesive layer, the functional film preferably has a release film next to the adhesive layer in a state before use (for example, during storage and transport).
- the release film protects the adhesive layer until the functional film of the present invention is used, and is peeled and removed before use, thereby exposing the adhesive layer.
- the release film examples include those in which a release agent is applied to a release substrate such as paper or a plastic film and a release agent layer is provided.
- a release substrate paper substrates such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene on these paper substrates; cellulose, starch, polyvinyl Paper base materials subjected to sealing treatment with alcohol, acrylic-styrene resin, etc .; or plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyolefin films such as polyethylene and polypropylene; .
- release agents include olefin resins such as polyethylene and polypropylene; rubber elastomers such as isoprene resins and butadiene resins; long chain alkyl resins; alkyd resins; fluorine resins; silicone resins; Can be mentioned.
- olefin resins such as polyethylene and polypropylene
- rubber elastomers such as isoprene resins and butadiene resins
- long chain alkyl resins alkyd resins
- fluorine resins silicone resins
- the thickness of the release agent layer is not particularly limited, but is preferably 0.02 to 2.0 ⁇ m, more preferably 0.05 to 1.5 ⁇ m when the release agent is applied in a solution state.
- Examples of the layer configuration of the functional film of the present invention include, but are not limited to, the following.
- the thickness of the functional film of the present invention is not particularly limited, but is preferably 1 to 1000 ⁇ m, more preferably 2 to 200 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
- the functional film of the present invention is excellent in optical isotropy.
- the in-plane retardation Re (550) is measured by the method described in the examples, the value is preferably less than 10 nm.
- the functional film of the present invention is excellent in gas barrier properties.
- the water vapor permeability of the functional film of the present invention is preferably less than 0.2 g ⁇ m ⁇ 2 ⁇ day ⁇ 1 in an atmosphere of 40 ° C. and a relative humidity of 90%.
- the functional film of the present invention is excellent in bending resistance.
- the functional film of the present invention has a water vapor transmission rate of 0.2 g ⁇ under a temperature of 40 ° C. and a relative humidity of 90% after performing a mandrel bending test at a diameter of 6 mm. It is preferably less than m ⁇ 2 ⁇ day ⁇ 1 .
- the water vapor transmission rate can be measured by the method described in the examples.
- the functional film of the present invention is suitably used as a film for optical devices.
- the device of the present invention is formed by peeling and removing the process film after the functional film of the present invention is attached to an object.
- Examples of the device of the present invention include a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, and a solar battery. Since the device of the present invention includes the laminate derived from the functional film of the present invention, failure due to intrusion of water vapor or the like hardly occurs, and the flex resistance is excellent.
- UV curable hexafunctional acrylate resin manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH
- acrylic group-modified silica nanofiller manufactured by Nissan Chemical Co., Ltd., trade name: MIBK-2140Z
- BASF trade name: Irgacure 184
- a functional film (1a) having a layer structure of process film / resin coat layer / gas barrier layer was obtained by performing plasma ion implantation at and forming a gas barrier layer.
- Plasma generation gas Ar Gas flow rate: 100sccm Duty ratio: 0.5% Applied voltage: -6kV RF power supply: frequency 13.56 MHz, applied power 1000 W Chamber internal pressure: 0.2 Pa Pulse width: 5 ⁇ sec Processing time (ion implantation time): 200 seconds
- an acrylate-based pressure-sensitive adhesive manufactured by Seiden Chemical Co., Ltd., trade name: Cybinol LT-55
- Cybinol LT-55 acrylate-based pressure-sensitive adhesive
- Example 2 In Example 1, in place of the acrylic group-modified silica nanofiller, an alumina filler (manufactured by BYK, trade name: NANOBYK-3610) was used in the same manner as in Example 1, except that the process film / resin coat layer / A functional film (2a) having a layer structure of a gas barrier layer and a functional film (2b) having a layer structure of process film / resin coat layer / gas barrier layer / adhesive layer / release film were obtained.
- an alumina filler manufactured by BYK, trade name: NANOBYK-3610
- Example 3 In Example 1, in place of the acrylic group-modified silica nanofiller, a process film / resin coat layer was obtained in the same manner as in Example 1 except that a zirconia filler (manufactured by Nissan Chemical Co., Ltd., trade name: ZR-20AS) was used.
- the functional film (3a) having a layer structure of / gas barrier layer and the functional film (3b) having a layer structure of process film / resin coat layer / gas barrier layer / adhesive layer / release film were obtained.
- Example 4 In Example 1, a functional film having a layer structure of process film / resin coat layer / gas barrier layer is formed in the same manner as in Example 1 except that a gas barrier layer is formed on the resin coat layer by the following method. A functional film (4b) having a layer structure of (4a) and process film / resin coat layer / gas barrier layer / adhesive layer / release film was obtained.
- a silicon oxide material (SiO2 manufactured by Canon Optron) is evaporated by electron beam heating, and a SiOx film having a cured film thickness of 50 nm under a pressure of 0.015 Pa during film formation.
- the deposition conditions are an acceleration voltage of 40 kV and an emission current of 0.2 A.
- Example 1 a functional film having a layer structure of a process film / gas barrier layer was formed in the same manner as in Example 1 except that the resin barrier layer was not formed and the gas barrier layer was formed directly on the process film.
- a functional film (5b) having a layer structure of 5a) and process film / gas barrier layer / adhesive layer / release film was obtained.
- the functional films of Examples 1 to 4 are excellent in optical isotropy and bending resistance. Further, the process film can be peeled and removed without adversely affecting the remaining laminate. On the other hand, the functional film of Comparative Example 1 could not remove the process film cleanly, and could not perform optical isotropy evaluation and flex resistance evaluation. Moreover, the functional film of Comparative Example 2 is inferior in bending resistance.
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Abstract
Description
また、近年、フレキシブルディスプレイの開発も進められており、このときに用いられるプラスチックフィルムは耐屈曲性に優れることが求められる。
しかしながら、近年、さらに優れた光学等方性や耐屈曲性を有するフィルムが要望されていた。
その結果、基材層を使用しないことで(いわゆる、ノンキャリアフィルムとすることで)、光学等方性や耐屈曲性に優れる機能性フィルムが得られること、及び、基材層を有しない機能性フィルムは、その製造時や運搬時の取扱いが困難であるが、使用するまでの間は、支持体として機能し得る工程フィルムを少なくとも一方の最外層として設けることで、取扱い性が向上することが分かった。
このように、工程フィルムを有する機能性フィルムは、使用する際の作業性に劣るという問題があった。
〔1〕工程フィルムと、前記工程フィルム上に直接設けられた樹脂コート層と、前記樹脂コート層上に、直接又はその他の層を介して設けられたガスバリア層とを有する機能性フィルムであって、前記樹脂コート層が、エネルギー硬化性樹脂と無機フィラーとを含有する硬化性組成物の硬化物からなるものである機能性フィルム。
〔2〕前記無機フィラーが、その表面が有機化合物で修飾されたものである、〔1〕に記載の機能性フィルム。
〔3〕前記無機フィラーの表面の修飾に用いられた有機化合物が反応性不飽和結合を含有する基を含むものである、〔2〕に記載の機能性フィルム。
〔4〕前記工程フィルムの樹脂成分が、ポリエステル系樹脂である、〔1〕~〔3〕のいずれかに記載の機能性フィルム。
〔5〕前記工程フィルムの厚みが10~300μmである、〔1〕~〔4〕のいずれかに記載の機能性フィルム。
〔6〕前記樹脂コート層の厚みが0.1~10μmである、〔1〕~〔5〕のいずれかに記載の機能性フィルム。
〔7〕前記樹脂コート層の、工程フィルムと接する側とは反対側の面の粗さ曲線の断面最大高さ(Rt)が1~200nmである、〔1〕~〔6〕のいずれかに記載の機能性フィルム。
〔8〕前記ガスバリア層が、ケイ素酸化物、ケイ素窒化物、ケイ素フッ化物、ケイ素炭化物、金属酸化物、金属窒化物、金属フッ化物、金属炭化物、及びこれらの化合物を構成する元素を含む複合化合物からなる群から選択される少なくとも一種を含有するものである、〔1〕~〔7〕のいずれかに記載の機能性フィルム。
〔9〕前記ガスバリア層が、改質処理を受けることで無機化合物を含有する層に変化し得る層の表面を改質して得られたものである、〔1〕~〔8〕のいずれかに記載の機能性フィルム。
〔10〕前記ガスバリア層の厚みが20~3000nmである、〔1〕~〔9〕のいずれかに記載の機能性フィルム。
〔11〕さらに、接着剤層を有する機能性フィルムであって、前記接着剤層が、前記ガスバリア層上に、直接又はその他の層を介して設けられたものである、〔1〕~〔10〕のいずれかに記載の機能性フィルム。
〔12〕JIS K5600-5に準拠して、マンドレル屈曲試験を直径6mmで行った後において、温度40℃、相対湿度90%条件下での水蒸気透過率が、0.2g・m-2・day-1未満である、〔1〕~〔11〕のいずれかに記載の機能性フィルム。
〔13〕光学デバイスに用いる、〔1〕~〔12〕のいずれかに記載の機能性フィルム。
〔14〕前記〔1〕~〔13〕のいずれかに記載の機能性フィルムを対象物に貼付した後、工程フィルムを剥離除去してなるデバイス。
本発明の機能性フィルムを構成する工程フィルムは、機能性フィルムの製造時や使用時においては支持体として機能し、これらの作業における取り扱い性を向上させるものである。また、この工程フィルムは、機能性フィルムの保管時や運搬時においては保護層としての役割を担い、樹脂コート層やバスバリア層を保護する。後述するように、通常は、工程フィルムは最終的に剥離除去される。
本発明の機能性フィルムを構成する樹脂コート層は、前記工程フィルム上に直接設けられる層であり、それはエネルギー硬化性樹脂と無機フィラーとを含有する硬化性組成物の硬化物からなるものである。
樹脂コート層を設けることで、ガスバリア層等を傷つけることなく、工程フィルムを効率よく剥離除去することができる。
トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、プロピオン酸変性ジペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、プロピレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、トリス(2-アクリロイロキシエチル)イソシアヌレート等の3官能アクリレート系化合物;
ジグリセリンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート等の4官能アクリレート系化合物;
プロピオン酸変性ジペンタエリスリトールペンタ(メタ)アクリレート等の5官能アクリレート系化合物;
ジペンタエリスリトールヘキサ(メタ)アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレート等の6官能アクリレート系化合物;等が挙げられる。
これらの多官能アクリレート系化合物は一種単独で、あるいは二種以上を組み合わせて用いることができる。
より光学等方性に優れる機能性フィルムが得られ易いことから、アスペクト比が低いものが好ましく、球状であるものがより好ましい。
無機フィラーの平均粒径は、粒度分布測定装置を使用して、動的光散乱法により測定することができる。
反応性不飽和結合を含有する基としては、ビニル基、アリル基、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、グリシジル基等が挙げられる。
表面に反応性不飽和結合を含有する基を有する無機フィラーは、シランカップリング剤を用いて、公知の方法により無機フィラーの表面処理をすることで得ることができる。
溶剤としては、n-ヘキサン、n-ヘプタン等の脂肪族炭化水素系溶媒;トルエン、キシレン等の芳香族炭化水素系溶媒;ジクロロメタン、塩化エチレン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、モノクロロベンゼン等のハロゲン化炭化水素系溶媒;メタノール、エタノール、プロパノール、ブタノール、プロピレングリコールモノメチルエーテル等のアルコール系溶媒;アセトン、メチルエチルケトン、2-ペンタノン、イソホロン、シクロヘキサノン等のケトン系溶媒;酢酸エチル、酢酸ブチル等のエステル系溶媒;エチルセロソルブ等のセロソルブ系溶剤;1,3-ジオキソラン等のエーテル系溶媒;等が挙げられる。
例えば、エネルギー硬化性樹脂が活性エネルギー線を受けて硬化するものである場合、高圧水銀ランプ、無電極ランプ、キセノンランプ等を用いて、活性エネルギー線を塗膜に照射することにより、塗膜を硬化させることができる。
樹脂コート層に含まれる無機フィラーの含有量は特に限定されないが、樹脂コート層全体を基準として、通常、10~70質量%であり、50~70質量%が好ましい。
樹脂コート層に含まれる無機フィラーの含有量が少な過ぎると、工程フィルムを効率よく剥離除去するのが困難になるおそれがある。一方、樹脂コート層に含まれる無機フィラーの含有量が多過ぎると、機能性フィルムの透明性、耐屈曲性が低下するおそれがある。
樹脂コート層が薄すぎると、工程フィルムを剥離除去する際に、ガスバリア層等が破壊されるおそれがある。一方、樹脂コート層が厚すぎると、耐屈曲性が低下するおそれがある。
樹脂コート層の、工程フィルムと接する側とは反対側の面とは、工程フィルム上に樹脂コート層を形成したときに、露出している面である。後述するように、この面上に、直接又はその他の層を介してガスバリア層が形成される。
この粗さ曲線の断面最大高さ(Rt)は、機能性フィルムの製造途中の状態であれば、露出している樹脂コート層の表面を光干渉顕微鏡により観察することにより測定することができる。
粗さ曲線の断面最大高さ(Rt)が小さ過ぎると、工程フィルムの剥離性を十分に高めることが困難になるおそれがある。一方、粗さ曲線の断面最大高さ(Rt)が大き過ぎると、樹脂コート層上に形成するガスバリア層のガスバリア性を低下させるおそれがある。
粗さ曲線の断面最大高さ(Rt)は、用いる無機フィラーの平均粒径や量を調節することにより最適化することができる。
本発明の機能性フィルムを構成するガスバリア層は、酸素や水蒸気等のガスの透過を抑制する特性(ガスバリア性)を有する層である。このガスバリア層は、前記樹脂コート層上に、直接又はプライマー層等のその他の層を介して積層されてなるものである。
このようなガスバリア層としては、例えば、無機蒸着膜や、改質処理を受けることで無機化合物を含有する層に変化し得る層の表面を改質して得られたもの〔この場合、ガスバリア層とは、改質された領域のみを意味するのではなく、「改質された領域を含む層」を意味する。〕等が挙げられる。
無機化合物の蒸着膜の原料としては、酸化珪素、酸化アルミニウム、酸化マグネシウム、酸化亜鉛、酸化インジウム、酸化スズ等の無機酸化物;窒化ケイ素、窒化アルミニウム、窒化チタン等の無機窒化物;無機炭化物;無機硫化物;酸化窒化ケイ素等の無機酸化窒化物;無機酸化炭化物;無機窒化炭化物;無機酸化窒化炭化物等が挙げられる。
金属の蒸着膜の原料としては、アルミニウム、マグネシウム、亜鉛、及びスズ等が挙げられる。
これらは、1種単独で、あるいは2種以上を組み合わせて用いることができる。
これらの中では、ガスバリア性の観点から、無機酸化物、無機窒化物又は金属を原料とする無機蒸着膜が好ましく、さらに、透明性の観点から、無機酸化物又は無機窒化物を原料とする無機蒸着膜が好ましい。
高分子層中のケイ素含有高分子化合物の含有量は、よりガスバリア性に優れるガスバリア層を形成し得ることから、50質量%以上が好ましく、70質量%以上がより好ましい。
これらの溶媒は、1種単独で、あるいは2種以上を組み合わせて用いることができる。
イオン注入処理は、後述するように、加速させたイオンを高分子層に注入して、高分子層を改質する方法である。
プラズマ処理は、高分子層をプラズマ中に晒して、高分子層を改質する方法である。例えば、特開2012-106421号公報に記載の方法に従って、プラズマ処理を行うことができる。
紫外線照射処理は、高分子層に紫外線を照射して高分子層を改質する方法である。例えば、特開2013-226757号公報に記載の方法に従って、紫外線改質処理を行うことができる。
これらの中でも、ポリシラザン系化合物としては、入手容易性、及び優れたガスバリア性を有するイオン注入層を形成できる観点から、Rx、Ry、Rzが全て水素原子であるペルヒドロポリシラザンが好ましい。
また、ポリシラザン系化合物としては、ガラスコーティング材等として市販されている市販品をそのまま使用することもできる。
ポリシラザン系化合物は、1種単独で、あるいは2種以上を組み合わせて用いることができる。
これらのイオンは1種単独で、あるいは2種以上を組み合わせて用いることができる。
これらの中でも、より簡便にイオンを注入することができ、より優れたガスバリア性を有するガスバリア層を形成し得ることから、アルゴン、ヘリウム、ネオン、クリプトン、キセノン等の希ガスのイオンが好ましい。
本発明の機能性フィルムは、工程フィルム、樹脂コート層、及びガスバリア層以外にその他の層〔以下、「その他の層(I)」という。〕を有していてもよい
その他の層(I)としては、接着剤層が挙げられる。接着剤層は、通常、前記ガスバリア層上に、直接又はその他の層〔以下、「その他の層(II)」という。〕を介して積層される。その他の層(II)としては、プライマー層等が挙げられる。
接着剤に含まれる接着性樹脂としては、ゴム系接着性樹脂、ポリオレフィン系接着性樹脂、エポキシ系接着性樹脂、アクリル系接着性樹脂等が挙げられる。
これらの中でもポリイソブチレン系樹脂を主成分とする接着性樹脂が好ましい。
本明細書において、「主成分」とは、固形分中、50質量%以上を占める成分をいう。
変性ポリオレフィン系樹脂は、前駆体としてのポリオレフィン樹脂に、変性剤を用いて変性処理を施して得られる、官能基が導入されたポリオレフィン樹脂である。
官能基としては、カルボキシル基、カルボン酸無水物基、カルボン酸エステル基、水酸基、エポキシ基、アミド基、アンモニウム基、ニトリル基、アミノ基、イミド基、イソシアネート基、アセチル基、チオール基、エーテル基、チオエーテル基、スルホン基、ホスホン基、ニトロ基、ウレタン基、ハロゲン原子等が挙げられる。これらの中でも、カルボキシル基、カルボン酸無水物基、カルボン酸エステル基、水酸基、アンモニウム基、アミノ基、イミド基、イソシアネート基が好ましく、カルボン酸無水物基、アルコキシシリル基がより好ましく、カルボン酸無水物基が特に好ましい。
ヒドロキシ基含有モノマーとしては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等が挙げられる。
カルボキシ基含有モノマーとしては、(メタ)アクリル酸、マレイン酸、フマル酸、イタコン酸等が挙げられる。
これらの成分は、各接着性樹脂に応じて適宜選択して用いることができる。
剥離基材としては、グラシン紙、コート紙、上質紙等の紙基材;これらの紙基材にポリエチレンやポリプロピレン等の熱可塑性樹脂をラミネートしたラミネート紙;上記基材に、セルロース、デンプン、ポリビニルアルコール、アクリル-スチレン樹脂等で目止め処理を行った紙基材;あるいはポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルムやポリエチレンやポリプロピレン等のポリオレフィンフィルム等のプラスチックフィルム;等が挙げられる。
(i)工程フィルム/樹脂コート層/ガスバリア層
(ii)工程フィルム/樹脂コート層/ガスバリア層/接着剤層
(iii)工程フィルム/樹脂コート層/ガスバリア層/接着剤層/剥離フィルム
(iv)工程フィルム/樹脂コート層/ガスバリア層/プライマー層/接着剤層/剥離フィルム
水蒸気透過率は、実施例に記載の方法により測定することができる。
本発明のデバイスは、本発明の機能性フィルムを対象物に貼付した後、工程フィルムを剥離除去してなるものである。
本発明のデバイスとしては、液晶ディスプレイ、有機ELディスプレイ、無機ELディスプレイ、電子ペーパー、太陽電池等が挙げられる。
本発明のデバイスは、本発明の機能性フィルム由来の積層体を備えているので、水蒸気等の浸入による故障が発生し難く、また、耐屈曲性に優れる。
各例中の部及び%は、特に断りのない限り、質量基準である。
UV硬化性6官能アクリレート樹脂(新中村化学工業社製、商品名:A-DPH)とアクリル基修飾シリカナノフィラー(日産化学社製、商品名:MIBK-2140Z)とを体積比で45:55となるように混合し、これにヒドロキシケトン系光重合開始剤(BASF社製、商品名:イルガキュア184)を1%加えて、硬化性組成物を調製した。
工程フィルムとしてのポリエチレンテレフタレートフィルム(東洋紡株式会社製、PET50A4100)のプレーン面上に、上記の硬化性組成物を塗布し、得られた塗膜にUV照射することによりこれを硬化させ、厚み3μmの樹脂コート層を形成した。
この樹脂コート層上に、ペルヒドロポリシラザン含有液(メルクパフォーマンスマテリアルズ社製、AZ NL110A-20、溶媒:キシレン、濃度:20%)を塗布し、120℃で2分間乾燥することで、厚みが200nmのペルヒドロポリシラザン層を形成した。
次いで、プラズマイオン注入装置(RF電源:日本電子株式会社製、RF56000、高電圧パルス電源:株式会社栗田製作所製、PV-3-HSHV-0835)を用いて、ペルヒドロポリシラザン層に対し、下記条件にてプラズマイオン注入を行い、ガスバリア層を形成することで、工程フィルム/樹脂コート層/ガスバリア層、の層構造を有する機能性フィルム(1a)を得た。
ガス流量:100sccm
Duty比:0.5%
印加電圧:-6kV
RF電源:周波数 13.56MHz、印加電力 1000W
チャンバー内圧:0.2Pa
パルス幅:5μsec
処理時間(イオン注入時間):200秒
実施例1において、アクリル基修飾シリカナノフィラーに代えて、アルミナフィラー(BYK社製、商品名:NANOBYK-3610)を使用したこと以外は、実施例1と同様にして、工程フィルム/樹脂コート層/ガスバリア層、の層構造を有する機能性フィルム(2a)、及び、工程フィルム/樹脂コート層/ガスバリア層/接着剤層/剥離フィルム、の層構造を有する機能性フィルム(2b)を得た。
実施例1において、アクリル基修飾シリカナノフィラーに代えて、ジルコニアフィラー(日産化学社製、商品名:ZR-20AS)を使用したこと以外は、実施例1と同様にして、工程フィルム/樹脂コート層/ガスバリア層、の層構造を有する機能性フィルム(3a)、及び、工程フィルム/樹脂コート層/ガスバリア層/接着剤層/剥離フィルム、の層構造を有する機能性フィルム(3b)を得た。
実施例1において、樹脂コート層上に、以下の方法によりガスバリア層を形成したことを除き、実施例1と同様にして、工程フィルム/樹脂コート層/ガスバリア層、の層構造を有する機能性フィルム(4a)、及び、工程フィルム/樹脂コート層/ガスバリア層/接着剤層/剥離フィルム、の層構造を有する機能性フィルム(4b)を得た。
電子ビーム加熱方式の真空蒸着装置を用いて、酸化ケイ素化材料(キヤノンオプトロン社製SiO)を電子ビーム加熱により蒸発させ、製膜中の圧力が0.015Paの条件で硬化膜厚50nmのSiOx膜を製膜した。蒸着条件は加速電圧40kV、エミッション電流0.2Aである。
実施例1において、樹脂コート層を形成せず、工程フィルム上に直接ガスバリア層を形成したこと以外は、実施例1と同様にして、工程フィルム/ガスバリア層、の層構造を有する機能性フィルム(5a)、及び、工程フィルム/ガスバリア層/接着剤層/剥離フィルム、の層構造を有する機能性フィルム(5b)を得た。
UV硬化性6官能アクリレート樹脂(新中村化学工業社製、商品名:A-DPH)に、ヒドロキシケトン系光重合開始剤(BASF社製、商品名:イルガキュア184)を1%加えて、硬化性組成物を調製した。
この硬化性組成物を使用して樹脂コート層を形成したこと以外は、実施例1と同様にして、工程フィルム/樹脂コート層/ガスバリア層、の層構造を有する機能性フィルム(6a)、及び、工程フィルム/樹脂コート層/ガスバリア層/接着剤層/剥離フィルム、の層構造を有する機能性フィルム(6b)を得た。
機能性フィルム(1b)~(6b)の剥離フィルムを剥離除去して接着剤層を露出させ、無アルカリガラス(イーグルXG)に貼り合わせた後、工程フィルムを剥離除去した。これを測定試料として、王子測定機器社製KOBRA-WRを用いて、面内位相差Re(550)を測定した。
機能性フィルム(1b)~(6b)の工程フィルムを剥離除去した後、残りの積層体を目視で観察し、以下の基準で評価した。
○:露出面に、破壊やクラックの発生がない。
×:露出面に、破壊又はクラックが発生した。
機能性フィルム(1b)~(6b)の剥離フィルムを剥離除去して接着剤層を露出させ、ポリエチレンテレフタレートフィルム(東洋紡株式会社製、商品名:PET100A4300、厚さ:100μm)にハンドラミネータを用いて貼り合せた後、工程フィルムを剥離除去した。これを測定試料として用いて、JIS K5600-5-1:1999に準拠して、樹脂コート面が外側になるように、マンドレル屈曲試験を直径6mmで行った。次いで、MOCON製AQUATRANを用いて、その水蒸気透過率を、温度40℃、相対湿度90%条件下で測定した。
実施例1~4の機能性フィルムは、光学等方性及び耐屈曲性に優れる。また、工程フィルムを、残りの積層体に悪影響を与えることなく剥離除去することができる。
一方、比較例1の機能性フィルムは、工程フィルムをきれいに剥がすことができず、光学等方性評価と耐屈曲性評価を行うことができなかった。
また、比較例2の機能性フィルムは、耐屈曲性に劣っている。
Claims (14)
- 工程フィルムと、前記工程フィルム上に直接設けられた樹脂コート層と、前記樹脂コート層上に、直接又はその他の層を介して設けられたガスバリア層とを有する機能性フィルムであって、
前記樹脂コート層が、エネルギー硬化性樹脂と無機フィラーとを含有する硬化性組成物の硬化物からなるものである機能性フィルム。 - 前記無機フィラーが、その表面が有機化合物で修飾されたものである、請求項1に記載の機能性フィルム。
- 前記無機フィラーの表面の修飾に用いられた有機化合物が反応性不飽和結合を含有する基を含むものである、請求項2に記載の機能性フィルム。
- 前記工程フィルムの樹脂成分が、ポリエステル系樹脂である、請求項1~3のいずれかに記載の機能性フィルム。
- 前記工程フィルムの厚みが10~300μmである、請求項1~4のいずれかに記載の機能性フィルム。
- 前記樹脂コート層の厚みが0.1~10μmである、請求項1~5のいずれかに記載の機能性フィルム。
- 前記樹脂コート層の、工程フィルムと接する側とは反対側の面の粗さ曲線の断面最大高さ(Rt)が1~200nmである、請求項1~6のいずれかに記載の機能性フィルム。
- 前記ガスバリア層が、ケイ素酸化物、ケイ素窒化物、ケイ素フッ化物、ケイ素炭化物、金属酸化物、金属窒化物、金属フッ化物、金属炭化物、及びこれらの化合物を構成する元素を含む複合化合物からなる群から選択される少なくとも一種を含有するものである、請求項1~7のいずれかに記載の機能性フィルム。
- 前記ガスバリア層が、改質処理を受けることで無機化合物を含有する層に変化し得る層の表面を改質して得られたものである、請求項1~8のいずれかに記載の機能性フィルム。
- 前記ガスバリア層の厚みが20~3000nmである、請求項1~9のいずれかに記載の機能性フィルム。
- さらに、接着剤層を有する機能性フィルムであって、前記接着剤層が、前記ガスバリア層上に、直接又はその他の層を介して設けられたものである、請求項1~10のいずれかに記載の機能性フィルム。
- JIS K5600-5に準拠して、マンドレル屈曲試験を直径6mmで行った後において、温度40℃、相対湿度90%条件下での水蒸気透過率が、0.2g・m-2・day-1未満である、請求項1~11のいずれかに記載の機能性フィルム。
- 光学デバイスに用いる、請求項1~12のいずれかに記載の機能性フィルム。
- 請求項1~13のいずれかに記載の機能性フィルムを対象物に貼付した後、工程フィルムを剥離除去してなるデバイス。
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TW201841773A (zh) | 2018-12-01 |
TWI791502B (zh) | 2023-02-11 |
CN110431012B (zh) | 2022-05-03 |
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JP7227124B2 (ja) | 2023-02-21 |
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