WO2017038141A1 - ガスバリアフィルム、ガスバリアフィルムの転写方法、波長変換フィルム、ガスバリア層付位相差フィルム、および有機ｅｌ積層体 - Google Patents

ガスバリアフィルム、ガスバリアフィルムの転写方法、波長変換フィルム、ガスバリア層付位相差フィルム、および有機ｅｌ積層体 Download PDF

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WO2017038141A1
WO2017038141A1 PCT/JP2016/060617 JP2016060617W WO2017038141A1 WO 2017038141 A1 WO2017038141 A1 WO 2017038141A1 JP 2016060617 W JP2016060617 W JP 2016060617W WO 2017038141 A1 WO2017038141 A1 WO 2017038141A1
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Prior art keywords
layer
gas barrier
film
organic
substrate
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PCT/JP2016/060617
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English (en)
French (fr)
Japanese (ja)
Inventor
英二郎 岩瀬
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富士フイルム株式会社
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Priority to CN201680043656.9A priority Critical patent/CN107848254B/zh
Priority to KR1020187004262A priority patent/KR102103091B1/ko
Publication of WO2017038141A1 publication Critical patent/WO2017038141A1/ja

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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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED

Definitions

  • the present invention relates to a gas barrier film, a gas barrier film transfer method, a wavelength conversion film using the gas barrier film, a retardation film with a gas barrier layer, and an organic EL laminate.
  • Patent Document 1 discloses, as a method for improving gas barrier properties, a configuration using an inorganic layer as a gas barrier layer, a configuration in which gas barrier layers are multilayered, and a glass transition temperature. It describes that a gas barrier layer is formed on a resin film having a high Tg.
  • a gas barrier film having a high gas barrier property As described above, by using a gas barrier film having a high gas barrier property, various electronic devices such as a display can be made thinner, lighter and more flexible. Therefore, if the gas barrier film can be made thinner, the electronic device can be made thinner and lighter.
  • a gas barrier film As described in Patent Document 1 and the like, such a gas barrier film has a configuration in which a gas barrier layer is formed on a resin film as a substrate. Therefore, in order to make the gas barrier film thinner, it is conceivable to make the substrate thinner.
  • the gas barrier layer having a high gas barrier property is a thin inorganic layer. For this reason, the gas barrier layer is easily cracked even by minute buckling or contact, and the performance deteriorates when cracked. Therefore, when laminating the gas barrier layer on a thin substrate, it is necessary to stabilize the conveyance so that the substrate can be prevented from buckling.
  • Patent Document 4 by attaching a protective material to the back side of the substrate, self-supporting property of the substrate can be ensured, and even when a thin substrate is used, the substrate does not buckle properly. It is described that a gas barrier layer can be formed. If such a method is used, a gas barrier layer can be formed even on a thin substrate of about a few tens of micrometers. However, if the thickness is smaller than this, it becomes difficult to attach a reinforcing protective material to the substrate while transporting the thin substrate.
  • Patent Document 5 describes that a release layer is formed between a substrate and a gas barrier layer, and the gas barrier layer is peeled off from the substrate and transferred to a transfer target.
  • An object of the present invention is to provide a gas barrier film and a gas barrier film transfer method that are thin, transferable, and have high gas barrier properties even after transfer, and to solve such problems of the prior art.
  • Another object of the present invention is to provide a wavelength conversion film, a retardation film with a gas barrier layer, and an organic EL laminate using the gas barrier film.
  • the present inventor has provided a gas barrier having one or more combinations of a substrate and an organic layer which is provided on one surface side of the substrate and which is the surface on which the inorganic layer is formed.
  • a layer, and a release resin layer provided between the substrate and the gas barrier layer, in close contact with the organic layer, and for peeling the substrate and the gas barrier layer finds that the above problem can be solved.
  • the present invention has been completed. That is, this invention provides the gas barrier film of the following structures, the manufacturing method of a gas barrier film, the wavelength conversion film using this gas barrier film, the phase difference film with a gas barrier layer, and an organic electroluminescent laminated body.
  • a substrate (1) a substrate; A gas barrier layer that is provided on one surface side of the substrate and has one or more combinations of an inorganic layer and an organic layer that is a formation surface of the inorganic layer; A gas barrier film provided between a substrate and a gas barrier layer, having a release resin layer in close contact with an organic layer and for peeling the substrate and the gas barrier layer.
  • the material for forming the release resin layer is a cyclic olefin resin having a glass transition temperature Tg of 100 ° C. or higher.
  • the substrate is a polyethylene terephthalate film provided with a release layer.
  • the water vapor transmission rate of the structure excluding the substrate is less than 0.01 g / (m 2 ⁇ day).
  • An element substrate that supports the organic EL element is further included, and the element substrate includes a gas barrier layer and a release resin layer obtained by removing the substrate from the gas barrier film according to any one of (1) to (17).
  • a gas barrier film that is thin, transferable, and has a high gas barrier property after transfer, a method for producing the gas barrier film, a wavelength conversion film using the gas barrier film, and a gas barrier layer positioning A phase difference film and an organic EL laminate can be provided.
  • FIG. 1A is a diagram conceptually showing an example of the gas barrier film of the present invention
  • FIG. 1B is a diagram conceptually showing a state in which the substrate is peeled from the gas barrier film of FIG. It is.
  • FIG. 2 (A) and FIG. 2 (B) are diagrams conceptually showing another example of the gas barrier film of the present invention. It is a figure which shows notionally another example of the gas barrier film of this invention.
  • 4 (A) to 4 (C) are conceptual diagrams for explaining the gas barrier film transfer method of the present invention. It is a figure which shows notionally an example of the phase difference film with a gas barrier layer of this invention. It is a figure which shows notionally an example of the wavelength conversion film of this invention.
  • FIG. 7A to FIG. 7C are diagrams conceptually showing an example of the organic EL laminate of the present invention.
  • FIG. 8A and FIG. 8B are diagrams conceptually showing an example of a film forming apparatus for producing the gas barrier film of the present invention.
  • the gas barrier film of the present invention includes a substrate, a gas barrier layer that is provided on one surface of the substrate, and includes one or more combinations of an inorganic layer and an organic layer on which the inorganic layer is formed, a substrate, and a gas barrier layer. It is a gas barrier film which is provided between and has a release resin layer for adhering to the organic layer and for releasing from the substrate. This gas barrier film is used by peeling only a substrate and transferring a transfer layer including a gas barrier layer and a release resin layer to a transfer target.
  • FIG. 1A conceptually shows an example of the gas barrier film of the present invention.
  • a gas barrier film 10a shown in FIG. 1A basically includes a substrate 12, a gas barrier layer 18 having an organic layer 14 and an inorganic layer 16 laminated on one surface of the substrate 12, and the substrate 12 and the gas barrier layer. And a release resin layer 20 laminated between the two.
  • the gas barrier layer 18 is laminated with the organic layer 14 facing the release resin layer 20, and the inorganic layer 16 is laminated on the organic layer 14. That is, the release resin layer 20 is laminated between the substrate 12 and the organic layer 14.
  • the release resin layer 20 is in close contact with the organic layer 14 and is configured to be peelable from the substrate 12 at the interface with the substrate 12. That is, the peel force (adhesion force) between the organic layer 14 and the release resin layer 20 is greater than the peel force between the substrate 12 and the release resin layer 20.
  • the gas barrier film 10a can peel only the board
  • the transfer of the transfer layer 30 to the transfer target is basically performed by attaching the gas barrier layer 18 side of the gas barrier film 10a to the transfer target, and then peeling the substrate 12 from the gas barrier film 10a.
  • the substrate 12 is peeled off from the gas barrier film 10a and the transfer layer 30 is taken out, and then the transfer layer 30 may be bonded to the transfer body.
  • a transfer type gas barrier film is proposed in which a release layer is formed between the substrate and the gas barrier layer, and the gas barrier layer is peeled off from the substrate and transferred to the transfer target.
  • a shearing force is applied to the gas barrier layer, so that the inorganic layer is broken by the shearing force. Therefore, it was found that the gas barrier layer after transfer may not exhibit a sufficient gas barrier property.
  • this invention has the organic layer 14 as a foundation
  • the release resin layer 20 is configured to be in close contact with the organic layer 14 and to be peelable from the substrate 12 at the interface with the substrate 12.
  • the peeling resin layer 20 existing between the inorganic layer 16 and the peeling surface becomes a stress relaxation layer by peeling at the interface between the peeling resin layer 20 and the substrate 12, and when peeling the substrate 12.
  • Such an shearing force can prevent the inorganic layer 16 from being broken.
  • the release resin layer 20 needs to adjust the peeling force so as to peel off at the interface with the substrate 12, and also needs to have a function as a stress relaxation layer. Therefore, it is difficult to make it suitable as a base layer for the inorganic layer 16.
  • the layer serving as the base of the inorganic layer 16 needs to have an appropriate hardness and higher heat resistance. Therefore, in the case where the organic layer 14 is not provided between the release resin layer 20 and the inorganic layer 16, that is, when the inorganic layer 16 is formed directly on the release resin layer 20, the inorganic layer 16 is appropriate. Cannot be formed, and high gas barrier properties cannot be obtained.
  • the gas barrier film of the present invention since the gas barrier film of the present invention has the organic layer 14 on the release resin layer 20 as the surface on which the inorganic layer 16 is formed, it is provided with a suitable underlayer. Therefore, the inorganic layer 16 can be formed appropriately and high gas barrier properties can be obtained.
  • the gas barrier film of the present invention preferably further has a protective film on the gas barrier layer 18 for protecting the gas barrier layer 18 (more specifically, the inorganic layer 16).
  • the protective film By having the protective film, the inorganic layer 16 can be prevented from cracking when the gas barrier film is transported or wound.
  • the protective film may be peeled to expose the gas barrier layer 18 and then transferred to the transfer target.
  • the organic protective layer 24 may be an adhesive layer having adhesiveness. Since the organic protective layer 24 has adhesiveness, when the transfer layer 30 is transferred to the transfer target, transfer can be easily performed without applying an adhesive or the like.
  • the organic protective layer 24 may be provided on the gas barrier layer 18, and the protective film 26 may be further provided on the organic protective layer 24.
  • the organic protective layer 24 and the protective film 26 it is possible to prevent the inorganic layer 16 from being broken when the gas barrier film is transported or wound.
  • the organic protective layer 24 is an adhesive layer, by having the protective film 26, the transport and winding of the gas barrier film can be facilitated, and dust or the like adheres to the adhesive layer, It can prevent that adhesiveness falls.
  • the gas barrier layer 18 includes one organic layer 14 and one inorganic layer 16.
  • the present invention is not limited to this, and the organic layer and the inorganic layer are not limited thereto.
  • Each of which may have one or more layers, and may have two or more combinations of the inorganic layer 16 and the organic layer 14 serving as a base layer of the inorganic layer 16.
  • the gas barrier film 10d shown in FIG. 3 has the gas barrier layer 18 in which the organic layer 14, the inorganic layer 16, the organic layer 14, and the inorganic layer 16 are formed in this order on the release resin layer 20. That is, the gas barrier layer 18 of the gas barrier film 10 d has a configuration having two combinations of the organic layer 14 and the inorganic layer 16.
  • the gas barrier property can be further improved.
  • the water vapor transmission rate of the structure obtained by removing the substrate 12 from the gas barrier film is preferably less than 0.01 [g / (m 2 ⁇ day)], and 0.005 [ g / (m 2 ⁇ day)] or less is more preferable, and 0.001 [g / (m 2 ⁇ day)] or less is particularly preferable.
  • the configuration in which the substrate 12 is removed from the gas barrier film includes the transfer layer 30 composed of the gas barrier layer 18 and the release resin layer 20. means.
  • the configuration in which the substrate 12 is removed from the gas barrier film includes the gas barrier layer 18 and the release resin layer 20.
  • the gas barrier film of the present invention preferably has a low water vapor transmission rate. Even if the gas barrier film of the present invention is the transfer layer 30 having a high gas barrier property, the inorganic layer 16 can be prevented from cracking and transferred appropriately while maintaining the high gas barrier property.
  • the visible light transmittance of the structure obtained by removing the substrate 12 from the gas barrier film is 85% or more.
  • the retardation value of the transfer layer 30 is preferably 30 nm or less.
  • gas barrier film 10 the gas barrier films 10a to 10d may be collectively referred to as “gas barrier film 10”.
  • low density polyethylene LDPE
  • high density polyethylene HDPE
  • polyethylene naphthalate PEN
  • polyamide PA
  • polyethylene terephthalate PET
  • polyvinyl chloride PVC
  • polyvinyl Alcohol PVA
  • polyacrylonitrile PAN
  • polyimide PI
  • PC polycarbonate
  • PP polypropylene
  • PS polystyrene
  • Films (resin films) made of various resin materials such as ABS, cycloolefin copolymer (COC), cycloolefin polymer (COP), and triacetyl cellulose (TAC) are preferably exemplified.
  • a protective layer on the surface of such a film, necessary functions such as a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, a stress relaxation layer, a release layer
  • a substrate in which a layer (film) that expresses a film is formed may be used as the substrate 12.
  • the elongation at break is high and difficult to break at the time of transportation, it can be made thinner, the melting point is high and heat resistance, it can be easily peeled at the interface with the release resin layer 20, and it is inexpensive.
  • a PET film on which a release layer is formed is preferable. More specifically, a PET film having a release layer formed on the surface on which the release resin layer 20 is formed is preferable.
  • the thickness of the substrate 12 is preferably 5 to 125 ⁇ m, more preferably 5 to 100 ⁇ m, and particularly preferably 10 to 50 ⁇ m.
  • the mechanical strength of the gas barrier film 10 is sufficiently ensured and peeling can be easily performed at the time of transfer.
  • the organic layer 14 is a layer made of an organic compound, and is basically obtained by polymerizing (crosslinking) a monomer, an oligomer, or the like that becomes the organic layer 14.
  • the organic layer 14 is a surface on which the inorganic layer 16 is formed. Specifically, the organic layer 14 mainly functions as a base layer for properly forming the inorganic layer 16 that exhibits gas barrier properties in the gas barrier film 10. By having such an organic layer 14, irregularities on the surface of the release resin layer 20 (or the lower inorganic layer 16), foreign matters attached to the surface of the release resin layer 20 (or the lower inorganic layer 16), and the like The surface on which the inorganic layer 16 is formed can be made into a state suitable for the formation of the inorganic layer 16.
  • An appropriate inorganic layer 16 can be formed on the entire surface of 20 (or the lower inorganic layer 16) without any gap, and the inorganic layer 16 having high gas barrier properties can be formed.
  • the glass transition temperature Tg of the organic layer 14 is higher than the glass transition temperature Tg of the peeling resin layer 20, and it is preferable that it is 200 degreeC or more.
  • the inorganic layer 16 can be appropriately formed.
  • the organic layer 14 preferably has appropriate flexibility in order to prevent the inorganic layer 16 from cracking.
  • the glass transition temperature Tg may be measured according to JIS K7121.
  • the material for forming the organic layer 14 is not limited, and various known organic compounds can be used. Specifically, polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Thermoplastic resins such as ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acrylic compounds; polysiloxane and other An organosilicon compound film is preferably exemplified. A plurality of these may be used in combination.
  • the organic layer 14 composed of a polymer of a radical curable compound and / or a cationic curable compound having an ether group as a functional group is preferable in terms of excellent glass transition temperature and strength.
  • acrylic resins and methacrylic resins mainly composed of acrylate and / or methacrylate monomers and oligomer polymers are used in the organic layer 14 in terms of low refractive index, high transparency and excellent optical properties. As a preferred example.
  • DPGDA dipropylene glycol di (meth) acrylate
  • TMPTA trimethylolpropane tri (meth) acrylate
  • DPHA dipentaerythritol hexa (meth) acrylate
  • Acrylic resins and methacrylic resins mainly composed of polymers such as acrylate and / or methacrylate monomers and oligomers are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.
  • the material for forming the organic layer 14 is preferably an ultraviolet curable resin or an electron beam curable resin.
  • an ultraviolet curable resin or an electron beam curable resin as a material for forming the organic layer 14, the peeling force with the release resin layer 20 can be easily adjusted by the irradiation amount of the ultraviolet ray or the electron beam. Can be realized. Therefore, the gas barrier film 10 can be configured to peel at the interface between the release resin layer 20 and the substrate 12.
  • the material for forming the organic layer 14 is a resin material containing 5% or more and less than 50% monofunctional or higher acrylate having an adamantane skeleton, or 5% or more and less than 50% bifunctional or higher acrylate having a fluorene skeleton.
  • the resin material is preferably included.
  • Such an organic layer 14 may be formed (film formation) by a known method for forming a layer made of an organic compound in accordance with the organic layer 14 to be formed. As an example, a coating method is illustrated.
  • the organic layer 14 is prepared by, for example, preparing a coating composition containing an organic solvent, an organic compound (monomers, dimers, trimers, oligomers, polymers, etc.) to be the organic layer 14, and a crosslinking agent. It can be applied on 20 to form a coating film, and the coating film can be formed by drying and curing. By forming by a coating method, a thin organic layer 14 is obtained.
  • metal oxides and nitrides specifically, silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, and mixtures of two or more thereof are highly transparent and can exhibit excellent gas barrier properties. In this respect, it is preferably used.
  • silicon nitride, silicon oxide, and a mixture thereof are more preferably used because they have high gas barrier properties, high transparency, and high flexibility.
  • Such an inorganic layer 16 is formed by CCP-CVD (capacitive coupling type plasma chemical vapor deposition) or ICP-CVD (inductively coupled plasma chemical vapor deposition) depending on the material of the inorganic layer 16 and the like.
  • CCP-CVD capactive coupling type plasma chemical vapor deposition
  • ICP-CVD inductively coupled plasma chemical vapor deposition
  • Sputtering, vacuum deposition or the like may be performed by a known vapor deposition method.
  • the thickness of the inorganic layer 16 may be determined as appropriate according to the forming material so that the target gas barrier property can be exhibited. According to the study by the present inventors, the thickness of the inorganic layer 16 is preferably 10 to 200 nm, more preferably 15 to 100 nm, and particularly preferably 20 to 75 nm. By setting the thickness of the inorganic layer 16 to 10 nm or more, sufficient gas barrier performance is stably exhibited. In addition, the inorganic layer 16 is generally brittle, and if it is too thick, there is a possibility of causing cracks, cracks, peeling, etc. However, if the thickness of the inorganic layer 16 is 200 nm or less, cracks will occur. Can be prevented.
  • each inorganic layer 16 may be the same or different.
  • the forming material of each inorganic layer 16 may be the same or different.
  • a release resin layer 20 is provided between the substrate 12 and the organic layer 14.
  • the release resin layer 20 is a resin layer that is in close contact with the organic layer 14 and can be peeled off from the substrate 12 at the interface with the substrate 12.
  • the release resin layer 20 peels the substrate 12 and the gas barrier layer 18 from each other.
  • the release resin layer 20 is a layer that also functions as a stress relaxation layer that suppresses the application of shear force to the inorganic layer 16 when the substrate 12 is peeled off. Further, after the substrate 12 is peeled, the release resin layer 20 also functions as a support.
  • the release resin layer 20 preferably has low water content and high heat resistance.
  • the inorganic layer 16 exhibiting high gas barrier properties is formed by vacuum film formation such as plasma CVD.
  • the moisture content of the release resin layer 20 is high, moisture is released even if evacuation is performed, so that the degree of vacuum cannot be increased and the inorganic layer 16 may not be formed.
  • the release resin layer 20 expands and contracts due to absorption and release of moisture, the inorganic layer 16 may be broken and high gas barrier properties may not be obtained. Therefore, it is preferable that the release resin layer 20 has a low water content.
  • the inorganic layer 16 is formed by plasma CVD etc., it is preferable that heat resistance is high.
  • the organic layer 14 is formed on the release resin layer 20 by, for example, coating. Therefore, cycloolefin copolymer (COC) is used as a material for forming the release resin layer 20 from the viewpoint of the coating property of the coating composition to be the organic layer 14, solvent resistance, and optical properties such as retardation. preferable.
  • COC cycloolefin copolymer
  • Such a release resin layer 20 can be formed by, for example, the same coating method as that for the organic layer 14. By forming by a coating method, a thin release resin layer 20 is obtained.
  • the thickness of the release resin layer 20 is set to 25 ⁇ m or less, it is preferable to cause problems such as cracks in the release resin layer 20 and curling of the gas barrier film 10 due to the release resin layer 20 being too thick.
  • the gas barrier film 10 can be easily wound into a roll shape.
  • the hardness of the release resin layer 20 is preferably lower than the hardness of the organic layer 14, and the Young's modulus of the release resin layer 20 is the organic layer 14.
  • the Young's modulus is preferably lower. That is, the release resin layer 20 is preferably softer than the organic layer 14.
  • the release resin layer 20 is preferably thicker than the organic layer 14.
  • the organic layer 14 serving as the base layer of the inorganic layer 16 has higher heat resistance. Therefore, it is preferable to use a material having a higher glass transition temperature Tg as a material for forming the organic layer 14.
  • a material having a high glass transition temperature Tg is hard and difficult to stretch. Therefore, by reducing the thickness of the hard organic layer 14 and increasing the thickness of the soft release resin layer 20, the release resin is obtained.
  • the layer 20 can function properly as a stress relaxation layer, and cracking of the inorganic layer 16 when the substrate 12 is peeled can be prevented to obtain high gas barrier properties.
  • the peeling force between the release resin layer 20 and the substrate 12 and the peeling force between the release resin layer 20 and the organic layer 14 are the same as the peeling force between the release resin layer 20 and the organic layer 14. If it is higher than the peeling force with 12, there is no limitation. Further, the peeling force between the release resin layer 20 and the substrate 12 is preferably 0.04 N / 25 mm to 1 N / 25 mm. By setting the peeling force between the release resin layer 20 and the substrate 12 in the above range, it is possible to prevent the peeling force from being weakened during transportation due to the peeling force being too weak, and the peeling force is too strong. It is possible to suppress inconveniences such as damage to the inorganic layer 16 and peeling of the gas barrier film 10 during peeling. In addition, what is necessary is just to measure peeling force (adhesion force) according to the 180 degree peeling test method of JISZ0237.
  • the material for forming the organic protective layer 24 is not particularly limited, and various known organic compounds similar to the organic layer 14 can be used.
  • the organic protective layer 24 is an adhesive layer
  • various known adhesive materials can be used. From the viewpoint of optical properties, particularly retardation and haze, it is preferable to use an acrylic pressure-sensitive adhesive as the pressure-sensitive adhesive material.
  • the acrylic pressure-sensitive adhesive include SK Dyne series (manufactured by Soken Chemical Co., Ltd.).
  • the thickness of the organic protective layer 24 may be appropriately set according to the material for forming the organic protective layer 24 and the characteristics of the inorganic layer 16. According to the study by the present inventors, the thickness of the organic protective layer 24 is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 25 ⁇ m, and particularly preferably 1 to 10 ⁇ m. preferable. By setting the thickness of the organic protective layer 24 to 0.1 ⁇ m or more, the inorganic layer 16 can be appropriately protected. Moreover, the workability
  • the protective film 26 various known sheet-like materials that are used as known protective films can be used.
  • the film (resin film) which consists of various resin materials illustrated with the above-mentioned board
  • the material for forming the protective film 26 has a Young's modulus of 6 GPa or less.
  • the protective film 26 is stuck on the inorganic layer 16 that is the uppermost layer of the gas barrier layer 18 of the gas barrier film 10, and is used by being peeled off from the inorganic layer 16 when transferring the gas barrier film 10. .
  • the Young's modulus of the forming material of the protective film 26 is set to 6 GPa or less, damage to the inorganic layer 16 when the protective film 26 is peeled can be more suitably prevented, and high gas barrier properties can be obtained.
  • LDPE, HDPE, PP, PET, PEN, PVC, PI, and the like are preferably exemplified as the material for forming the protective film 26.
  • an adhesive layer may be formed on the surface of the inorganic layer 16 side.
  • the gas barrier film transfer method of the present invention is a method of attaching a transfer layer comprising a gas barrier layer and a release resin layer by attaching the surface of the gas barrier film opposite to the substrate to the transfer target and peeling the substrate. Transfer to the transfer body.
  • the transfer method of the present invention will be described below with reference to FIGS. 4 (A) to 4 (C) and FIG.
  • the surface of the gas barrier film 10b opposite to the substrate 12, that is, the organic protective layer 24 side is pasted toward the retardation film 112 side.
  • Match There is no limitation in the method of bonding, and various methods for bonding known film-like materials can be used. Such bonding may be performed in a sheet form, or by roll-to-roll (hereinafter also referred to as RtoR) using the long gas barrier film 10b and the retardation film 112. May be.
  • the gas barrier film 10b has an adhesive layer.
  • an adhesive is applied to an object to be transferred before bonding to the gas barrier film 10b. Bonding with the film 10b may be performed.
  • the protective film 26 is provided on the organic protective layer 24 (or the inorganic layer 16)
  • the protective film 26 is peeled off and bonded to the transferred body before the gas barrier film is bonded to the transferred body. Just do it.
  • the substrate 12 is peeled from the gas barrier film 10 b bonded to the retardation film 112.
  • substrate 12 there is no limitation also on the peeling method of the board
  • the transfer layer 30 of the gas barrier film 10b is transferred to the phase difference film 112 which is a transfer target, and a phase difference film 110 with a gas barrier layer as shown in FIG. 5 can be obtained.
  • the inorganic layer 16 can be prevented from cracking when the substrate 12 is peeled off, so that the transfer layer 30 can be transferred to the transfer object while maintaining high gas barrier properties.
  • the thickness of the transfer layer 30 can be made very thin, the influence on the optical properties such as transparency and retardation value can be reduced.
  • the transfer target to which the gas barrier film is transferred there is no limitation on the transfer target to which the gas barrier film is transferred.
  • High gas barrier properties are required, and it is suitable for sealing optical members such as organic EL elements and wavelength conversion materials. .
  • the transfer layer 30 having the resin layer 20 has a configuration laminated on the retardation film 112.
  • the retardation film 110 with a gas barrier layer is a film having a high gas barrier property in addition to the optical characteristics of the retardation film itself while suppressing an increase in thickness because the thickness of the transfer layer 30 is very thin. be able to.
  • FIG. 6 is an example of a wavelength conversion film in which the gas barrier film of the present invention is transferred to seal the wavelength conversion layer.
  • the wavelength conversion film 100 shown in FIG. 6 includes a wavelength conversion layer 102, a gas barrier film 104 laminated on one surface of the wavelength conversion layer 102, and a transfer layer 30 laminated on the other surface of the wavelength conversion layer 102. Have.
  • the gas barrier film 104 is for sealing the wavelength conversion layer 102, and is not particularly limited as long as it has gas barrier properties required for sealing the wavelength conversion layer 102, and a known gas barrier film can be used as appropriate. It is.
  • one surface of the wavelength conversion layer 102 is sealed with a conventional gas barrier film 104, and the other surface is transferred from the gas barrier film 10 of the present invention. It is sealed using Thus, the thickness of the whole wavelength conversion film can be made thin by sealing at least one surface of the wavelength conversion layer with the gas barrier film of the present invention.
  • 7 (A) to 7 (C) are examples of organic EL laminates in which the organic EL element is sealed by transferring the gas barrier film of the present invention.
  • An organic EL stacked body 120 a illustrated in FIG. 7A includes an element substrate 122, an organic EL element 124 formed on the element substrate 122, and a transfer layer 30 that is stacked to cover the organic EL element 124.
  • the element substrate 122 all element substrates used in various organic EL devices can be used. Specifically, an element substrate made of glass, plastic, metal, ceramic, or the like is exemplified. In order to prevent deterioration of the organic EL element 124 due to moisture or the like, it is preferable that moisture or the like can be prevented from passing through the element substrate 122 and reaching the organic EL element 124. Therefore, the element substrate 122 is preferably a substrate made of a material having a low content of moisture or the like and a low transmittance of moisture or the like, such as glass or metal.
  • gas barrier film 10 of the present invention (more specifically, the transfer layer 30) may be used as an element substrate as in the organic EL laminate 120b shown in FIG. 7B. Or what transferred the gas barrier film 10 of this invention to the resin base material may be used as an element substrate.
  • the organic EL element 124 is a known organic EL element having, for example, an organic electroluminescent layer and a transparent electrode and a reflective electrode that are an electrode pair that holds the organic electroluminescent layer. As shown in the figure, the organic EL element 124 is sealed with a transfer layer 30 transferred from the gas barrier film 10 of the present invention. Thus, by sealing the organic EL element 124 with the gas barrier film of the present invention, the thickness of the entire organic EL laminate can be reduced.
  • the organic EL laminate may be a top emission type that emits light from the transfer layer 30 side or a bottom emission type that emits light from the element substrate 122 side.
  • a passivation film 126 may be provided between the organic EL element 124 and the transfer layer 30 as in the organic EL stacked body 120c shown in FIG. That is, the organic EL element 124 may be sealed with the passivation film 126 and the transfer layer 30 may be transferred onto the passivation film 126.
  • the passivation film 126 is for preventing moisture, oxygen, and the like from reaching the organic EL element 124 and degrading the organic EL element 124.
  • various films (layers) made of a material exhibiting gas barrier properties, which are used in known organic EL devices, can be used.
  • the passivation film 126 may be formed by a known method corresponding to the film forming material.
  • RtoR means that a processed object is sent out from a roll formed by winding a long processed object, and is subjected to processing such as film formation while being conveyed in the longitudinal direction. This is a manufacturing method in which the material is wound again in a roll shape.
  • the release resin layer 20 is formed over the substrate 12 using a film formation apparatus conceptually illustrated in FIG. Specifically, for example, a coating composition containing an organic solvent and an organic compound that becomes the release resin layer 20 is prepared.
  • a substrate roll Ra obtained by winding a long substrate 12 into a roll is loaded into a predetermined position of the organic film forming apparatus.
  • the substrate 12 is sent out from the substrate roll Ra and passed through a predetermined path to the winding position.
  • a coating composition that becomes the release resin layer 20 is filled in a predetermined position of the coating unit 40.
  • the film forming apparatus includes a transport roller pair 48 for transporting the substrate 12 through a predetermined path.
  • the substrate 12 is fed out from the substrate roll Ra and conveyed in the longitudinal direction, and the prepared coating composition is applied to the substrate 12 in the coating unit 40, and then the coated coating composition is dried in the drying unit 42. Then, if necessary, the cured resin 44 is irradiated with ultraviolet rays or heated to form the release resin layer 20. Further, a long film in which the release resin layer 20 is formed on the substrate 12 is wound into a roll to obtain a base roll Rb.
  • a protective film is laminated
  • the substrate 12 on which the release resin layer 20 is formed is used as the film formation substrate Za, and the organic layer 14 is formed on the release resin layer 20 of the film formation substrate Za.
  • the formation of the organic layer 14 may be basically performed in the same manner as the formation of the release resin layer 20 using an organic film forming apparatus as shown in FIG. That is, for example, a coating composition containing an organic solvent, an organic compound that becomes the organic layer 14, and a polymerization initiator is prepared. Further, a base material roll Rb obtained by winding a long film-forming base material Za in a roll shape is loaded into a predetermined position of the organic film forming apparatus. Next, the deposition target substrate Za is sent out from the substrate roll Rb, and is passed through a predetermined path to the winding position.
  • a coating composition that becomes the organic layer 14 is filled in a predetermined position of the coating unit 40. Then, the film-forming substrate Za is sent out from the substrate roll Rb, and the prepared coating composition is applied onto the release resin layer 20 in the application unit 40 while being conveyed in the longitudinal direction, and then applied.
  • the composition is dried in the drying unit 42 and the organic compound 14 is polymerized (crosslinked) by ultraviolet irradiation or the like in the curing unit 44 to form the organic layer 14. Further, the long film-forming substrate Za on which the organic layer 14 is formed is wound into a roll shape to form a substrate roll Rc.
  • a protective film may be attached to the organic layer 14 after the organic layer 14 is formed.
  • the protective film is preferably attached before the organic layer 14 contacts another member such as a guide roller. Thereby, it is possible to prevent the organic layer 14 that is the base layer of the inorganic layer 16 from being damaged, and the inorganic layer 16 can be appropriately formed on the smooth organic layer 14, thereby obtaining a gas barrier film that exhibits high gas barrier properties. Can do.
  • the film formation of the release resin layer 20 and the film formation of the organic layer 14 are performed.
  • the present invention is not limited to this, and winding is not performed after the film formation of the release resin layer. Subsequently, the organic layer 14 may be formed.
  • the film formation of the release resin layer 20 and the film formation of the organic layer 14 may be performed continuously.
  • the deposition target substrate Zb is sent out from the substrate roll Rc, and the paper passes through a predetermined path from the supply chamber 50 to the winding chamber 54 through the deposition chamber 52.
  • the base material roll Rc is loaded so that the organic layer 14 becomes a film formation surface in the film formation chamber 52.
  • the protective film roll 26 ⁇ / b> R is loaded at a predetermined position in the film forming chamber 52.
  • the protective film 26 is sent out from the protective film roll 26 ⁇ / b> R, and the paper passes through a predetermined path from the film formation chamber 52 to the winding chamber 54.
  • the supply chamber 50 is evacuated by the vacuum evacuation means 50a
  • the film formation chamber 52 is evacuated by the vacuum evacuation means 52a
  • the take-up chamber 54 is evacuated by the vacuum evacuation means 54a.
  • the film formation substrate Zb is sent out from the substrate roll Rc, guided by the guide roller 58, and conveyed to the film formation chamber 52.
  • the film formation substrate Zb conveyed to the film formation chamber 52 is guided by the guide roller 60 and wound around the circumferential surface of the cylindrical drum 62.
  • the drum 62 also functions as an electrode in CCP-CVD.
  • the drum 62 has a temperature adjustment function as a preferred embodiment.
  • the film-forming substrate Zb is formed with the inorganic layer 16 formed by CCP-CVD while being transported along a predetermined path by the drum 62, and the substrate 12 has a release resin layer 20 and a combination of the organic layer 14 and the inorganic layer 16. Is a laminated film formed.
  • CCP-CVD is a film forming means having an electrode pair composed of a drum 62 and a shower electrode 64, a source gas supply unit 68, a high-frequency power source 70, and the like.
  • the formation of the inorganic layer 16 by plasma CVD may be performed by a known method according to the material for forming the inorganic layer 16 or the like.
  • the inorganic layer 16 can be formed by various known vapor deposition methods such as ICP-CVD (inductively coupled plasma enhanced chemical vapor deposition), sputtering, and vacuum deposition. It is.
  • the protective film 26 is sent out from the protective film roll 26R and conveyed in the longitudinal direction in synchronization with the conveyance of the film formation substrate Zb.
  • the film-forming substrate Zb on which the inorganic layer 16 is formed and the protective film 26 are laminated and pressure-bonded by the lamination roller pair 72, whereby the gas barrier film 10 is produced.
  • An adhesive layer may be formed on the surface of the protective film 26 that faces the inorganic layer 16.
  • the protective film 26 is attached after the inorganic layer 16 is formed and before the inorganic layer 16 contacts other members such as a guide roller. Thereby, the damage of the inorganic layer 16 is prevented and the gas barrier film 10 which expresses the target gas barrier property is obtained.
  • the protective film is peeled off and the inorganic layer 16 is formed before the inorganic layer 16 is formed.
  • the protective film is preferably peeled off at a position where there is no member such as a guide roller in contact with the organic layer 14 along the path to the film forming means of the inorganic layer 16.
  • the substrate 12 on which the release resin layer 20, the organic layer 14, and the inorganic layer 16 are formed is used as a film formation base material.
  • the organic film forming apparatus as shown in FIG. 5 may be used in the same manner as the release resin layer 20 and the organic layer 14.
  • Example 1 As Example 1, a gas barrier film 10a shown in FIG.
  • the coating liquid A1 to be the release resin layer 20 As the coating liquid A1 to be the release resin layer 20, a COC resin (APEL 6015T manufactured by Mitsui Chemicals, Inc.) was dissolved in cyclohexane to prepare a coating liquid having a solid content concentration of 10%.
  • the coating solution A1 was filled in the coating unit 40 of a film forming apparatus using RtoR as shown in FIG.
  • the coating unit 40 used a die coater. Further, a substrate roll Ra obtained by winding the substrate 12 in a roll shape was loaded at a predetermined position, and the substrate 12 was inserted into a predetermined transport path.
  • the coating liquid A1 is applied to the substrate 12 by the coating unit 40 so that the dry film thickness becomes 2 ⁇ m, and in the drying unit 42, the drying temperature is 100 ° C. for 3 minutes.
  • the release resin layer 20 was formed on the substrate 12 by drying. In this case, the curing part 44 was not used. That is, the material for forming the release resin layer 20 is a cycloolefin copolymer.
  • the glass transition temperature Tg of the formed release resin layer 20 was measured by a high-sensitivity differential scanning calorimeter (Hitachi High-Tech Science Co., Ltd., DSC7000X) according to JIS K 7121, and found to be 145 ° C.
  • the organic layer 14 was formed on the formed release resin layer 20 by the following procedure.
  • the coating solution B1 was filled in the coating unit 40 of a film forming apparatus using RtoR as shown in FIG.
  • the coating unit 40 used a die coater.
  • a base material roll Rb formed by winding a substrate 12 having a release resin layer 20 (hereinafter sometimes referred to as “film formation base material Za”) into a roll shape is loaded at a predetermined position to form a film.
  • the base material Za was inserted through a predetermined conveyance path.
  • the coating liquid B1 is applied onto the release resin layer 20 of the film-forming substrate Za so that the dry film thickness is 1 ⁇ m while the film-forming substrate Za is conveyed in the longitudinal direction.
  • the drying unit 42 is dried at a drying temperature of 50 ° C.
  • the curing unit 44 is irradiated with ultraviolet rays (integrated irradiation amount is about 700 mJ / cm 2 ) to be cured, and the organic layer 14 is formed on the release resin layer 20. Formed.
  • the protective film of polyethylene was affixed on the organic layer 14, and it wound up after that.
  • the glass transition temperature Tg of the formed organic layer 14 was measured according to JIS K 7121 using a high-sensitivity differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.), the measurement limit was 250 ° C. or higher.
  • the inorganic layer 16 was formed on the formed organic layer 14 by the following procedure.
  • a base material roll Rc formed by winding a certain film in a roll shape was loaded, and a protective film roll 26R was loaded at a predetermined position in the film forming chamber 52.
  • the film-forming substrate Zb was sent out from the substrate roll Rc, and passed through a predetermined conveyance path from the supply chamber 50 to the winding chamber 54 through the film-forming chamber 52.
  • the protective film 26 was sent out from the protective film roll 26 ⁇ / b> R and passed through a predetermined conveyance path from the film forming chamber 52 to the winding chamber 54. In this state, while the film-forming substrate Zb and the protective film 26 are conveyed synchronously, the protective film is peeled off from the film-forming substrate Zb after passing through the film surface touch roll immediately before film formation, A silicon nitride film was formed as the inorganic layer 16 by CCP-CVD on the surface of the organic layer 14 of the film formation substrate Zb supported / guided by the drum 62 in 52. Next, the protective film 26 was laminated and pasted on the inorganic layer 16 by the pair of laminating rollers 72 to produce a gas barrier film 10a as shown in FIG.
  • Example 2 Further, a gas barrier film 10b as shown in FIG. 2A was produced in the same manner as in Example 1 except that the organic protective layer 24 shown below was formed on the inorganic layer 16.
  • coating liquid C1 to be the organic protective layer 24 As coating liquid C1 to be the organic protective layer 24, urethane skeleton acrylic polymer (Acryt 8BR930 manufactured by Taisei Fine Chemical Co., Ltd.), photopolymerization initiator (Irg184 manufactured by BASF Japan), silane coupling agent (KBM5103 manufactured by Shin-Etsu Silicone Co., Ltd.), softening
  • the agent (Byron U1400 manufactured by Toyobo Co., Ltd.) was weighed so as to have a weight ratio of 78: 10: 10: 2, and dissolved in methyl ethyl ketone to prepare a coating solution having a solid content concentration of 15%.
  • the coating solution C1 was filled in the coating unit 40 of a film forming apparatus using RtoR as shown in FIG.
  • the coating unit 40 used a die coater.
  • a substrate roll formed by winding a substrate 12 on which the release resin layer 20, the organic layer 14, and the inorganic layer 16 are formed (hereinafter, may be referred to as “deposition substrate Zc”) in a roll shape is placed at a predetermined position.
  • the film formation substrate Zc was inserted through a predetermined transport path.
  • the coating liquid C1 is applied onto the inorganic layer 16 of the film forming substrate Zc by the coating unit 40 so that the dry film thickness is 1 ⁇ m while the film forming substrate Zc is conveyed in the longitudinal direction.
  • the drying unit 42 is dried at a drying temperature of 100 ° C.
  • the curing unit 44 is irradiated with ultraviolet rays (integrated irradiation amount of about 600 mJ / cm 2 ) to be cured and the organic protective layer 24 is formed on the inorganic layer 16. Formed.
  • Example 3 As the coating solution to be the organic protective layer 24, the following coating solution C2 was used, the thickness of the organic protective layer 24 was set to 3 ⁇ m, and after the organic protective layer 24 was formed, A gas barrier film 10c as shown in FIG. 2 (B) was produced in the same manner as in Example 2 except that a separator film (film binder BD manufactured by Fujimori Kogyo Co., Ltd.) was attached as the protective film 26.
  • the coating liquid C2 was obtained by diluting SK Dyne NT21 (manufactured by Soken Chemical Co., Ltd.) with a curing agent L-45 (manufactured by Soken Chemical Co., Ltd.) in a ratio of 100: 2, and then solid-concentrating 15%.
  • the organic protective layer 24 is an acrylic pressure-sensitive adhesive.
  • Example 4 A gas barrier film 10c was produced in the same manner as in Example 3 except that a urethane-based adhesive (No. 96 manufactured by Rock Paint Co., Ltd.) was used as the coating liquid C3 to be the organic protective layer 24.
  • the organic protective layer 24 is a urethane adhesive.
  • Example 5 A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution A2 was used as the coating solution to be the release resin layer 20.
  • the coating liquid A2 was prepared so that COC resin (APEL 6509T manufactured by Mitsui Chemicals, Inc.) was dissolved in cyclohexane and the solid content concentration was 10%. It was 70 degreeC when the glass transition temperature Tg of the formed peeling resin layer 20 was measured like the previous.
  • a gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution A3 was used as the coating solution to be the release resin layer 20.
  • Coating solution A3 was prepared by dissolving COC resin (APEL 6011T, manufactured by Mitsui Chemicals, Inc.) with cyclohexane so that the solid content concentration was 10%. It was 105 degreeC when the glass transition temperature Tg of the formed peeling resin layer 20 was measured similarly to the previous.
  • Example 7 A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution A4 was used as the coating solution to be the release resin layer 20.
  • the coating liquid A4 was prepared by dissolving COP resin (Arton D4540, manufactured by JSR Corporation) with cyclohexane so that the solid concentration was 10%. It was 128 degreeC when the glass transition temperature Tg of the formed peeling resin layer 20 was measured like the previous.
  • Example 8 A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to set the dry film thickness to 20 ⁇ m.
  • Example 9 A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to set the dry film thickness to 10 ⁇ m.
  • Example 10 A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to set the dry film thickness to 0.5 ⁇ m.
  • Example 11 A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to set the dry film thickness to 0.1 ⁇ m.
  • a gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B2 was used as the coating liquid to be the organic layer 14.
  • the coating liquid B2 was prepared by blending A-DPH (Shin Nakamura Chemical Co., Ltd., Tg 250 ° C. or higher) and A-600 (Shin Nakamura Chemical Co., Ltd., Tg-22 ° C.) at a ratio of 4: 1.
  • a photopolymerization initiator (Irg819 manufactured by BASF Japan) was weighed to a weight ratio of 97: 3, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%. It was 180 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured like the previous.
  • a gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution B3 was used as the coating solution to be the organic layer 14.
  • the coating solution B3 was prepared by blending A-DPH (Shin Nakamura Chemical Co., Ltd., Tg 250 ° C. or higher) and A-600 (Shin Nakamura Chemical Co., Ltd., Tg-22 ° C.) to 1: 1,
  • a photopolymerization initiator (Irg819 manufactured by BASF Japan) was weighed to a weight ratio of 97: 3, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%. It was 114 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured like the previous.
  • Example 14 A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution B4 was used as the coating solution to be the organic layer 14.
  • the coating solution B4 was prepared by weighing EB3702 (Tg 53 ° C.) manufactured by Daicel Ornex Co., Ltd. and a photopolymerization initiator (Irg819 manufactured by BASF Japan) at a weight ratio of 97: 3, and dissolving them in methyl ethyl ketone. The concentration was adjusted to 15%. It was 53 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured like the previous.
  • Example 15 A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution B5 was used as the coating solution to be the organic layer 14.
  • the coating solution B5 was formulated such that A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., Tg 250 ° C. or higher) and 1-ADMA (1-adamantyl methacrylate, Osaka Organic Chemical Co., Ltd. Tg 250 ° C.) were 1: 1.
  • This and a photopolymerization initiator (Irg819 manufactured by BASF Japan) were weighed to a weight ratio of 97: 3, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%. That is, the material for forming the organic layer contains one or more acrylates having an adamantane skeleton. It was 250 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured like the previous.
  • a gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B6 was used as the coating liquid to be the organic layer 14.
  • the coating liquid B6 was formulated with A-DPH (Shin Nakamura Chemical Co., Ltd. Tg 250 ° C. or higher) and EA-200 (acrylate monomer Osaka Gas Chemical Co., Ltd. Tg 211 ° C.) to a ratio of 1: 1 and light.
  • a polymerization initiator (Irg819 manufactured by BASF Japan) was weighed to a weight ratio of 97: 3, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%. That is, the material for forming the organic layer contains a bifunctional or higher acrylate having a fluorene skeleton. It was 230 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured like the previous.
  • Example 19 A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid B1 to be the organic layer 14 were changed to set the dry film thickness to 0.1 ⁇ m.
  • Example 20 A gas barrier film 10a was produced in the same manner as in Example 1 except that a silicone release film (Film Binder BD manufactured by Fujimori Kogyo Co., Ltd.) was used as the substrate 12.
  • a silicone release film Frazier BD manufactured by Fujimori Kogyo Co., Ltd.
  • Example 21 A gas barrier film 10c was produced in the same manner as in Example 3 except that the solid content concentration and the coating amount of the coating liquid C2 to be the organic protective layer 24 were changed to make the film thickness 50 ⁇ m.
  • Example 22 A gas barrier film 10c was produced in the same manner as in Example 3 except that the solid content concentration and the coating amount of the coating liquid C2 to be the organic protective layer 24 were changed to change the film thickness to 0.1 ⁇ m.
  • Example 1 A gas barrier film was produced in the same manner as in Example 1 except that the release resin layer 20 was not formed.
  • the substrate 12 was peeled as follows. First, a 200 mm square bonded film was punched into a 100 mm square using a Thomson blade so that the end face was surely peeled off. Next, with the TAC film side down, the surface of the TAC film was adsorbed and held by an adsorption plate having high flatness, and then an adhesive tape (Nitto Cello Tape (registered trademark)) for grasping the substrate 12 was attached to the end by about 2 cm. Subsequently, the adhesive tape was drawn parallel to the sample so that the substrate 12 drawn an arc as in the 180 degree peel test. In this way, the substrate 12 was peeled off. The peeling was performed in an environment with a temperature of 25 ° C. and a humidity of 50% RH.
  • Example 3 which has the organic protective layer 24 used as an adhesion layer on the inorganic layer 16, the Fujitac (made by TD80 Fuji Film Co., Ltd.) which has not bonded the adhesion film is transferred. Transfer was carried out in the same manner except that the body was used.
  • the water vapor transmission rate of the gas barrier film 10 transferred to the transfer medium and peeled off the substrate 12 was measured by a calcium corrosion method (method described in JP-A-2005-283561).
  • the conditions of the constant temperature and humidity treatment were a temperature of 40 ° C. and a relative humidity of 90% RH.
  • the water vapor permeability of Fujitac alone was 400 [g / (m 2 ⁇ day)]. Based on the measured water vapor transmission rate, evaluation was performed according to the following criteria.
  • Total light transmittance The total light transmittance of the transferred transfer layer 30 was measured using a spectrophotometer (Nippon Denshoku Co., Ltd. haze meter SH7000). Based on the measured total light transmittance, the following criteria were used for evaluation. A: Total light transmittance is 90% or more B: Total light transmittance is 88% or more and less than 90% C: Total light transmittance is 86% or more and less than 88% D: Total light transmittance is 84% or more and less than 86%
  • Retardation value The retardation value (Re value) of the transferred transfer layer 30 was measured with KOBRA-WR (manufactured by Oji Scientific Instruments). Based on the measured retardation value, the following criteria were used for evaluation. A: Retardation value is 5 nm or less B: Retardation value is more than 5 nm and less than 10 nm C: Retardation value is more than 10 nm and less than 20 nm D: Retardation value is more than 20 nm The results are shown in the following table.
  • the example of the present invention having a release resin layer between the substrate and the gas barrier layer and peeling at the interface between the release resin layer and the substrate is a gas barrier as compared with the comparative example. It can be seen that it has excellent properties and optical properties. Moreover, it turns out that it is preferable that a peeling resin layer is a cyclic olefin resin whose glass transition temperature Tg is 100 degreeC or more from the comparison of Example 1, 5 and 6. FIG. Moreover, it can be seen from the comparison between Example 1 and Example 7 that the release resin layer is preferably a cycloolefin copolymer. Further, from the comparison between Examples 1 and 8 to 11, it can be seen that the thickness of the release resin layer is preferably 0.1 to 25 ⁇ m, more preferably 0.5 to 15 ⁇ m.
  • the glass transition temperature Tg of the organic layer is preferably 200 ° C. or higher.
  • the organic layer preferably contains 5% or more and less than 50% of monofunctional or higher acrylate having an adamantane skeleton, or bifunctional or higher acrylate having a fluorene skeleton. It is understood that it is preferable to contain 5% or more and less than 50%.
  • the thickness of the organic layer is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 5 ⁇ m, and further preferably 0.2 to 3 ⁇ m. I understand that.
  • the inorganic layer is preferably silicon nitride.
  • Examples 2 to 4, 21, and 22 show that it is preferable to have the organic protective layer 24 on the inorganic layer 16. Further, it can be seen from the comparison between Example 3 and Example 4 that an acrylic adhesive is preferably used as the organic protective layer 24. Further, from the comparison with Examples 3, 21 and 22, it can be seen that the thickness of the organic protective layer 24 is preferably 0.1 to 50 ⁇ m, more preferably 0.5 to 25 ⁇ m.
  • composition for forming quantum dot layer The following quantum dot-containing polymerizable composition A was prepared, filtered through a polypropylene filter having a pore size of 0.2 ⁇ m, and then dried under reduced pressure for 30 minutes to be used as a coating composition.
  • the quantum dot concentration in the following toluene dispersion was 1% by mass.
  • Quantum dot-containing polymerizable composition A -Toluene dispersion of quantum dots 1 (emission maximum: 520 nm) 10.0 parts by mass-Toluene dispersion of quantum dots 2 (emission maximum: 630 nm) 1.0 parts by mass-80.8 parts by mass of lauryl methacrylate-Trimethylolpropane 18.2 parts by mass of triacrylate / 1.0 part by mass of photopolymerization initiator (Irgacure 819 (manufactured by BASF))
  • the coating film was sandwiched between the first film and the second film. While continuously transporting in this state, after passing through a heating zone at 60 ° C. for 3 minutes, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), curing by irradiating with ultraviolet rays, quantum dots
  • the quantum dot layer (wavelength conversion layer 102) containing was formed.
  • the irradiation amount of ultraviolet rays was 2000 mJ / cm 2 .
  • the substrate 12 was peeled from each of the first film and the second film to produce a quantum dot film (wavelength conversion film 100).
  • the luminance of the wavelength conversion film 100 immediately after production and the luminance after being left in an environment of temperature 60 ° C. and humidity 90% RH for 1000 hours (after humidification) are measured, and the durability is determined from the amount of change. evaluated.
  • the measurement of luminance was performed as follows. First, a commercially available liquid crystal display device (Amazon Kindle Kindle Fire HDX 7 ") was disassembled, and a backlight unit with a blue light source was taken out. Next, a wavelength conversion film cut into a rectangle on the light guide plate of the backlight unit The two prism sheets taken out from the liquid crystal display device were placed on top of each other so that the directions of the concavo-convex patterns on the surface were orthogonal to each other. The backlight unit was turned on, and the luminance was measured with a luminance meter (SR3 manufactured by TOPCON) installed at a position of 740 mm in the vertical direction from the front surface of the backlight unit.
  • SR3 luminance meter
  • the wavelength conversion film sealed using the gas barrier film of this invention has high durability.
  • Example 24 A retardation film 110 with a gas barrier layer as shown in FIG. 5 was produced using the produced gas barrier film 10.
  • As the retardation film 112 special polycarbonate W138 (manufactured by Teijin Limited) was used.
  • PDS1 manufactured by Panac Corporation
  • an optical adhesive film was bonded to the retardation film 112.
  • a laminator Proteus manufactured by Fellows
  • the substrate 12 of the gas barrier film 10 was peeled off to produce a retardation film 110 with a gas barrier layer.
  • the retardation film 110 with a gas barrier layer to which the gas barrier film of the present invention has been transferred has high gas barrier properties while maintaining optical characteristics.
  • Example 25 Using the produced gas barrier film 10, an organic EL laminate 120a as shown in FIG. 7A was produced.
  • a glass plate having a thickness of 500 ⁇ m and a size of 20 ⁇ 20 mm was prepared as the element substrate 122.
  • the periphery 2 mm of the element substrate 122 was masked with ceramic.
  • the element substrate subjected to masking was loaded into a general vacuum deposition apparatus, an electrode made of metal aluminum having a thickness of 100 nm was formed by vacuum deposition, and a lithium fluoride layer having a thickness of 1 nm was further formed. .
  • the following organic compound layers were sequentially formed on the element substrate 122 by vacuum deposition.
  • Tris (8-hydroxyquinolinato) aluminum film thickness 60 nm (Second hole transport layer) N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm (First hole transport layer) copper phthalocyanine: film thickness 10 nm
  • the element substrate 122 on which these layers are formed is loaded into a general sputtering apparatus, and ITO (Indium Tin Oxide indium tin oxide) is used as a target, and a 0.2 ⁇ m thick ITO film is formed by DC magnetron sputtering. A transparent electrode made of a thin film was formed. In this manner, an organic EL element 124 which is a light emitting element using an organic EL material was formed on the element substrate 122.
  • Example 26 After removing the masking, the element substrate 122 on which the organic EL element 124 is formed is loaded into a general plasma CVD apparatus, and a passivation film 126 having a thickness of 1500 nm made of silicon nitride is formed by plasma CVD (CCP-CVD). Except that was formed, an organic EL laminated body 120c as shown in FIG. 7C was produced in the same manner as in Example 25.
  • Example 27 An organic EL laminate 124 was produced in the same manner as in Example 25 except that the gas barrier film 10a of Example 1 was used as the element substrate 122. Specifically, the gas barrier film 10a of Example 1 is transferred to a TAC film with an adhesive layer in which an optical adhesive film (PDS1 Panac Co., Ltd.) is bonded to Fuji Tac (TD80 manufactured by Fuji Film Co., Ltd.), and the substrate 12 The laminate from which the substrate was peeled was used as the element substrate 122. Then, an organic EL element 124 was formed on the release resin layer 20 of the element substrate 122. Thereafter, in the same manner as above, the organic EL element 124 was sealed with another gas barrier film 10a to produce an organic EL laminate 124.
  • PDS1 Panac Co., Ltd. an optical adhesive film
  • Fuji Tac Fuji Tac
  • the produced organic EL laminate 124 was left for 200 hours in an environment of a temperature of 60 ° C. and a humidity of 90% RH. After standing, each organic EL laminated body 124 was made to emit light by applying a voltage of 7 V using a SMU2400 type source measure unit manufactured by Keithell. Observation with a microscope from the gas barrier film 10a side, the presence or absence of dark spots was confirmed, and the following criteria were used for evaluation. A: Generation of dark spots was not observed at all B: Generation of dark spots was slightly observed C: Generation of dark spots was clearly recognized D: Area ratio of dark spots was larger Evaluation As a result, the organic EL laminates of Examples 25 to 27 were all A. From the above results, the effects of the present invention are clear.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Paints Or Removers (AREA)
PCT/JP2016/060617 2015-08-28 2016-03-31 ガスバリアフィルム、ガスバリアフィルムの転写方法、波長変換フィルム、ガスバリア層付位相差フィルム、および有機ｅｌ積層体 WO2017038141A1 (ja)

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