JP2009221515A - Method for producing barrier film substrate, barrier film substrate and element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film substrate having higher barrier properties. <P>SOLUTION: A method, for producing the barrier film substrate having an organic region and an inorganic region on a support while conveying the support, comprises: a step where the organic region is provided; a step where the inorganic region is provided; and a step where a part or the whole of the support is provided with a magnetic layer. The whole or a part of a step where the support is conveyed is performed using a carriage body having a magnetic part 31 showing a magnetic pole opposite to that of the magnetic layer while allowing the magnetism of the magnetic layer and the magnetism of the magnetic part to attract each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a barrier film substrate, a barrier film substrate, and an element using the same.

  Conventionally, various methods for producing a barrier film substrate have been studied in order to improve the barrier property of the barrier film substrate (Patent Document 1, Patent Document 2). However, further improvement of the barrier property of the barrier film substrate is required.

JP 2007-204853 A JP 2004-160836 A

  The present invention aims to solve the above-described problems, and an object thereof is to provide a barrier film substrate having a high barrier property.

  As a result of the inventor's earnest study based on the above problems, a magnetic layer is provided on the barrier film substrate, and a magnetic portion is also provided on the carrier used in the production of the barrier film substrate. The magnetic force of the magnetic part and the magnetic force of the magnetic part are conveyed while attracting each other, so that the stress of the support and the organic layer and inorganic layer provided on the support is made uniform, and cracks and defects due to non-uniform stress As a result, it was found that the barrier ability was improved, and the above-mentioned problems were solved. Specifically, it has been found that the above problems can be solved by the following means.

(1) A method for producing a barrier film substrate having an organic region and an inorganic region on a support while conveying the support, the step of providing an organic region, the step of providing an inorganic region, and the support Providing a magnetic layer on a part or all of the upper part, and using a carrier having a magnetic part showing a magnetic pole opposite to the magnetic layer, all or part of the step of conveying the support, A manufacturing method, wherein the magnetic force of a magnetic layer and the magnetic force of a magnetic part are attracted to each other.
(2) The manufacturing method according to (1), wherein magnetic layers are provided at both ends of the support in the conveying direction.
(3) The manufacturing method according to (2), wherein the magnetic layer is provided in a mountain shape.
(4) The magnetic layer which shows the same magnetic pole as the magnetic part of a conveyance body is further provided in the center of the conveyance direction on a support body, The any one of (1)-(3) characterized by the above-mentioned. Production method.
(5) The manufacturing method according to any one of (1) to (4), wherein the transport body is a roller-shaped transport body.
(6) The manufacturing method according to any one of (1) to (4), wherein the transport body is a sheet-shaped transport body.
(7) The manufacturing method according to (5) or (6), wherein magnetic portions are provided at both ends of the roller-shaped transport body or at four ends of the sheet-shaped transport body.
(8) The manufacturing method according to any one of (1) to (7), wherein the magnetic layer is detachably provided.
(9) The manufacturing method according to any one of (1) to (8), wherein at least the step of providing the organic region is carried using a carrier having a magnetic part.
(10) The manufacturing method according to any one of (1) to (9), wherein at least the step of providing the inorganic region is carried using a carrier having a magnetic part.
(11) The manufacturing method according to any one of (1) to (10), wherein the manufacturing method is performed under vacuum.
(12) The method according to (11), wherein at least the organic region and / or the inorganic region is provided under vacuum.
(13) The production according to any one of (1) to (12), wherein a main component of the inorganic region is selected from a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide. Method.
(14) Any one of (1) to (13), wherein the organic region is an organic layer, the inorganic region is an inorganic layer, and the organic layer and the inorganic layer have an alternating layer structure. The production method according to item.
(15) The manufacturing method according to any one of (1) to (14), wherein the support has a thickness of 4 to 500 μm.
(16) A barrier film substrate comprising an organic region, an inorganic region, and a magnetic layer on a support.
(17) The barrier film substrate according to (16), which has magnetic layers at both ends in the longitudinal direction of the support.
(18) The barrier film substrate according to (17), wherein the magnetic layer is provided in a mountain shape.
(19) The barrier film substrate according to (17) or (18), wherein a magnetic layer showing a magnetic pole opposite to the magnetic layer is further provided at the center in the longitudinal direction of the support. .
(20) The barrier film substrate according to any one of (16) to (19), wherein the magnetic layer is detachably provided.
(21) The barrier according to any one of (16) to (20), wherein the main component of the inorganic region is selected from a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide. Film substrate.
(22) Any one of (16) to (21), wherein the organic region is an organic layer, the inorganic region is an inorganic layer, and the organic layer and the inorganic layer have an alternating layer structure. The barrier film substrate according to Item.
(23) The barrier film substrate according to any one of (16) to (22), wherein the support has a thickness of 4 to 500 μm.
(24) An element having the barrier film substrate according to any one of (16) to (23).

  According to the present invention, it is possible to provide a barrier film substrate having a high barrier property.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.

The method for producing a barrier film substrate of the present invention includes a step of providing an organic region, a step of providing an inorganic region, and a step of providing a magnetic layer on a part or all of the support, and transporting the support. All or part of the step is performed by using a carrier having a magnetic portion showing a magnetic pole opposite to the magnetic layer so that the magnetic force of the magnetic layer and the magnetic force of the magnetic portion attract each other. The barrier film substrate is usually produced by providing an organic region and an inorganic region, if necessary, a functional layer on the support while transporting the support. A magnetic part is provided on the carrier for carrying, and a magnetic layer is also provided on the support. Then, by adopting magnetic materials having opposite magnetic poles for the magnetic part and the magnetic layer, the magnetic forces of the two attract each other. Therefore, the stress applied to the support and the inorganic region, the organic region, the functional layer, and the like provided on the support in the transport process can be made uniform. Such improvement in stress uniformity prevents defects in the obtained barrier film substrate, particularly cracks and defects in the inorganic region. Furthermore, the barrier property of the barrier film substrate is improved. In addition, by improving the stress uniformity, it becomes easy to disperse the external stress. Also, it can be transported without a chuck or the like. Furthermore, by providing a magnetic layer, it is possible to eliminate static electricity, prevent foreign matter from adhering to the occurrence of static electricity, etc., prevent defects in the barrier film substrate caused thereby, and improve productivity. .
In the present specification, “all or part of the conveyance of the support” includes a case where an organic region or the like provided on the support is conveyed.

In the present invention, the magnetic layer is provided on a part or all of the support.
When the magnetic layer is provided on a part of the support, its position and shape are not particularly defined unless departing from the gist of the present invention, but it is usually provided at both ends in the transport direction of the support. Examples of the shape of the magnetic layer include a band shape and a mountain shape, but are not limited thereto. In the case of a strip shape, for example, the width of the support can be 10 to 500 cm, and the width of the magnetic layer can be 0.2 to 5 cm. In addition, the mountain shape is, for example, a configuration as shown in FIG. Specifically, the magnetic part gradually spreads in the direction of conveyance of the support (in the direction of the arrow in FIG. 1), spreads to a certain width (a in FIG. 1), and then sharply narrows (b in FIG. 1). This means repeating the shape. Here, it is preferable that the widest portion (a in FIG. 1) in the shape of a mountain is 0.5 to 10 cm, and the narrowest portion (b in FIG. 1) is 0.1 to 1 cm. Moreover, it is preferable that the space | interval (c of FIG. 1) of a mountain gap is 0.5-5 cm.
Thus, by providing the magnetic layer at both ends in the transport direction of the support, the support is pulled outward, and as a result, defects such as the support and the organic layer provided thereon are significantly reduced, As a result, the barrier property can be further improved.
As an example of a mode in which the magnetic layer is provided on the entire support, it is possible to provide a magnetic layer showing opposite magnetic poles at both ends and the center (a portion other than both ends) of the magnetic layer. In this case, the magnetic layer provided in the center of the support shows the same magnetic pole as the magnetic part of the carrier and repels the magnetic part of the carrier. For this reason, a support body will be pulled outward in the direction perpendicular | vertical to a conveyance direction, and a more uniform barrier property film substrate will be obtained. For example, as shown in FIG. 2, the width of the central magnetic layer may be narrowed, and the magnetic layer may be provided only at both ends of the support and at the center of the support. By adopting such a configuration, it is possible to adjust the stress applied to the support more finely than when the magnetic layer is provided on the entire support. Here, in FIG. 2, 21 is a conveyance body, 22 is a support body, and 23 is the barrier film substrate under manufacture. S and N indicate magnetic poles.
Needless to say, the position and shape of the magnetic layer can be appropriately adjusted by the shape and magnetic force of the magnetic portion of the carrier. In particular, by applying different widths and shapes at both ends, it is possible to adjust how stress is applied to the support and the like.
In addition, the both ends of the conveyance direction of a support body become the both ends of the longitudinal direction of the barrier film substrate finally manufactured normally.

The step of providing the magnetic layer can be arbitrarily selected in the manufacturing process of the barrier film substrate. That is, immediately after providing the support, it may be provided on the surface of the support, or after providing an organic region or the like on the support. Further, the magnetic layer may be provided on the surface opposite to the surface on which the organic region or the like is provided.
The magnetic layer may be provided so as to be peelable depending on the use of the obtained barrier film substrate. For example, when used for optical applications or transparent applications, it is preferable to provide a peelable magnetic layer. As a means for making the magnetic layer releasable, for example, a release agent made of a material that easily peels, for example, a silicone compound, a fluorine compound, and a wax described in JP-A-2002-162771, is optionally used for the magnetic layer. can do. Examples of the mold release agent include higher alkyl sodium sulfate, higher fatty acid higher alcohol ester, carbowax, higher alkyl phosphate ester, silicone compound, modified silicone, and curable silicone. Polyolefin wax, fluorine oil, fluorine wax, carnauba wax, microcrystalline wax, and silane compound are also preferably used. With respect to the release agent that can be used, U.S. Pat. Nos. 2,882,157, 3,101,060, 3,850,640, French Patent 2,180,465, British Patents 9,55061, 1,143118, 1,263,722, 1,270,578, 1,320,564, No. 1,320,757, No. 2,588,765, No. 2,738,891, No. 3,018178, No. 3,302,522, No. 3080317, No. 3030887, No. 3,212,060, No. 3,222178, No. 3,295,597, No. 3,516,883 3679411, 3870521, JP-A-49-5017, 51-141623, 54-159221, 56-81841, and Research D Closure is described in (Research Disclosure) No. 13969. Since the wax-based release agent is difficult to dissolve in an organic solvent, it is preferable to prepare an aqueous dispersion, prepare a dispersion with a thermoplastic resin solution, and apply it. In this case, the wax release agent is present in the form of fine particles in the thermoplastic resin. Moreover, as a mold release agent, a silicone type compound, a fluorine compound, a wax etc. are mentioned, for example. As the mold release agent, compounds described in “Summary of properties and application of revised wax” by Kosshobo and the silicone handbook published by Nikkan Kogyo Shimbun can be used. JP-B-59-38581, JP-B-4-32380, JP-B-2838498, JP-B-2 29558, JP-A Nos. 50-117433, 52-52640, 57-148755, and 61-62056. No. 61-62057, No. 61-118760, JP-A-2-42451, No. 3-41465, No. 4-212175, No. 4-214570, No. 4-263267, No. 5-34966 5-119514, 6-59502, 6-161150, 6-175396, 6-219040, 6-230600, 6-295093, 7-36210, 7-43940, 7-56387, 7-56390, 7-64335, 7-199682, 7-223362 7-287413, 8-184992, 8-227180, 8-248671, 8-248799, 8-248801, 8-278663, 9-152939, 9 -160278, 9-185181, 9-319139, 9-319143, 10-20549, 10-48889, 10-198069, 10-207116, 11-2917 No. 11-44969, 11-65156, 11-73049, 11-194542, and any compound used in JP-A-11-194542 can be selected. In the present invention, silicone compounds, fluorine compounds, waxes and the like are preferably used. A plurality of these compounds can be used in combination. Further, the magnetic layer may be provided via a peelable layer, for example, a layer containing a release agent composed of a silicone compound, a fluorine compound and a wax described in JP-A No. 2002-162771.
At that time, it is appropriate that the materials to be peeled have a 180 degree peel strength of 0.1 N / 25 mm or less, more preferably 0.041 N / 25 mm or less. The 180 degree peel strength can be measured according to the method described in JIS K6887 using the surface material of the production member. Further, when the magnetic layer is provided on the support and on the surface opposite to the surface on which the organic region or the like is provided, it may be preferable that it can be easily peeled off by applying physical force.
Peeling of the magnetic layer can be performed at any stage in the production process of the barrier film substrate. For example, when an inorganic region or a functional layer is provided, when performing an operation in which the magnetic field of the magnetic layer may cause a problem, such as plasma or sputtering, the magnetic layer is peeled off or cut off before the inorganic region is provided. It is preferable to provide a step of removing the magnetic layer.
Further, the magnetic layer can be cut off during use. In particular, this embodiment is preferably employed when the magnetic layer is provided at both ends of the support or when the separation of the magnetic layer is difficult.

As the composition of the magnetic layer, known materials can be used as long as they are easily magnetized, and examples thereof include ferromagnetic materials, paramagnetic materials, and diamagnetic materials. Among these, a ferromagnetic material can be mentioned as a preferable example.
Ferromagnetic materials include transition metals such as Fe, Co, Ni, and alloys thereof, rare earth metals and alloys thereof, X _a X ′ _ba MnSb (X and X ′ are Pt, Ni, Co, Fe, Ir, Rh, Os, a is 0 or 1, and b is 2.), a semimetal (half-metallic) ferromagnet such as PtMnSn, Mn ₂ Sb, VPd ₃ , or X ₂ YZ (X Is a transition metal, Y is Mn, and Z is a non-magnetic metal).
In particular, ferromagnet including Co such as simple Co or Co-based magnetic alloy, Co-doped magnetic iron oxide, or ferromagnetic such as NiFe alloy, oxidation of γ-Fe ₂ O ₃ etc. Magnetic fine particles such as iron and ferrite are preferred.
Co-based magnetic alloys include alloys in which one or more of Fe, Ni, Au, Ag, Cu, Pd, Pt, Ir, Rh, Ru, Os, Hf, etc. are added to Co. For example, an additive element such as Ti, V, Cr, Mn, Zn, Nb, Mo, Tc, Hf, Ta, W, or Re is added to an NiFe alloy, NiFeCo alloy, or an alloy having such an fcc crystal structure. Examples include alloys with high resistance.
As spinel type ferrite represented by MO.Fe ₂ O ₃ (M is a divalent metal element), Mn—Zn ferrite, Ni—Zn ferrite, Mg—Zn ferrite, Cu—Zn ferrite, Li— Examples thereof include composite ferrites such as Zn-based ferrite and Ni-Cu-Co-based ferrite, and unitary ferrites such as Mn ferrite, Co ferrite, and Ni ferrite.
The garnet type ferrite represented by 3M ₂ O ₃ .5Fe ₂ O ₃ (M is yttrium or trivalent rare earth element) includes yttrium iron garnet (YIG material), Ho substituted garnet ferrite, Gd substituted garnet ferrite, etc. Is mentioned.
Examples of the magnetoplumbite type ferrite represented by MO.6Fe ₂ O ₃ include strontium ferrite and barium ferrite.
Further, as the magnetic material, a microcrystalline precipitation type in which microcrystals are precipitated by heating from an amorphous state may be used. Examples of the microcrystalline precipitation type material include an Fe—Al—Si—Hf—C system.
Specifically, Fe, Co, γ-Fe ₂ O ₃ , Fe ₃ O ₄ , CrO ₂ , Fe, Fe—Cr, Fe—Co, MnAl, manganese / zinc ferrite, nickel ferrite, barium ferrite, strontium ferrite, Ferrite materials such as cobalt-coated ferrite, goethite, magnetite, hematite, iron, silicon steel, permalloy, sendust, nickel, nickel boron, nickel phosphorus, nickel cobalt alloy, cobalt chromium alloy, silicon steel, martensite and ferrite Magnetic alloy steels such as magnetic stainless steel, permalloy, permender, carbon steel such as SS41 and SS400, known ferromagnetic powders such as high manganese steel, metal alloy materials such as rare earth iron alloy, rare earth cobalt alloy, MO · Fe ₂ O ₃ spinel (M is a divalent metal element) is represented by _{Ferrite, 3M 2 O 3 · 5Fe 2} O 3 (M is yttrium or trivalent rare earth elements) magnetoplumbite-represented by garnet-type ferrite represented _{by, MO · 6Fe 2 O 3 (} M is a divalent metal element) And ferrite type magnetic fine particles such as type ferrite.

The magnetic layer of the present invention can be produced by using the above material as a dispersion thin film or a continuous thin film. For example, a coating solution comprising the composition of the magnetic layer can be formed by a conventionally known coating method, or a metal or an alloy can be formed on the support by a method such as vacuum deposition, sputtering, or plating. When formed by the coating method, the thickness of the magnetic layer is preferably from 0.1 to 100 μm, more preferably from 0.1 to 20 μm. Moreover, when forming by methods, such as a vacuum evaporation method, a sputtering method, and a plating method, the film thickness of a magnetic layer has preferable 100 to 1 micrometer, and 500 to 2000 micrometers is more preferable.
At the time of dispersion, a material that is insoluble in the component to be applied and does not react is used as a binder, and the material constituting the magnetic layer of the present invention is dispersed therein. The binder is not particularly limited, and for example, a known thermoplastic resin, thermosetting resin, or reactive resin (for example, an ultraviolet curable resin, an electron beam curable resin, or the like) can be used. Examples of the binder include butyral resin, vinyl chloride / vinyl acetate copolymer resin, urethane resin, polyester resin, cellulose resin, acrylic resin, epoxy resin, polyolefin resin, polyamide resin, styrene-butadiene copolymer resin, styrene. / Maleic acid copolymer resin or the like is used, and if necessary, a rubber resin such as nitrile rubber or a urethane elastomer can be added. The polyphenylene sulfide resin, which is not decomposed by contact with the oxide magnetic body and has excellent heat resistance, can be mixed while the oxide magnetic body is still at a high temperature after pulverization, and the pellets It is excellent in shielding the magnetic powder from water and carbon dioxide after the formation.

 Further, the magnetic layer of the present invention includes a surfactant, a lubricant, an antistatic agent, a silane coupling agent, a plasticizer, a wax, a silicone oil, carbon, a titanium oxide series, a tin oxide series, an oxidation, if necessary. Inorganic pigments such as metal oxides, gold, silver, nickel, aluminum, and copper, and other additives can be used. As addition amount, it is about 0.1 to 20 weight% normally.

Furthermore, commercially available ferrofluidic seals can be used as the magnetic layer of the present invention.
Moreover, it is good also as a structure which kneaded the material of the magnetic layer on the support body.

As a manufacturing apparatus used for the manufacture of the present invention, one in which a carrier of a known apparatus is replaced with one having a magnetic part can be adopted without departing from the gist of the present invention. Here, the magnetic portion is usually provided so as to correspond to the magnetic layer on the support. Here, “corresponding” does not necessarily mean that the magnetic layer of the support and the magnetic part of the carrier need to be completely matched in shape and magnetic force, but rather are usually different. For example, by making the magnetic force of the magnetic part stronger than the magnetic force of the magnetic layer, and by providing the position where the magnetic part is provided outside the position where the magnetic layer is provided, the support can be pulled more uniformly. It becomes possible.
As a conveyance body used by this invention, what used the magnet and the permanent magnet for a conventionally well-known roller-shaped conveyance body or a sheet-like conveyance body is employable. Of course, a material exhibiting magnetism may be applied.
FIG. 3 shows an example of an operational roller, and 31 indicates a magnetic part. In FIG. 3, belt-shaped magnetic portions are provided at both ends of the roller, but it is preferable to adjust appropriately in consideration of the position of the magnetic layer on the support. It is also preferable that the width of the magnetic part of the carrier is widened outward. As a result, the magnetic force tends to work in the direction perpendicular to the conveying direction of the support (the direction of the arrow in FIG. 3), and the support can be stretched more uniformly.
FIG. 4 shows an example of a non-movable roller, in which a roll-shaped transport body 41 is fixed, and a web-shaped support body 42 is transported thereon. Here, the shaded portion of the transport body 41 corresponds to a magnetic portion.
FIG. 5 and FIG. 6 are examples in which a roller-shaped transport body is viewed from the side. In FIG. 5, a particulate magnetic portion 51 is provided on the surface of a known roller via an adhesive 52. On the other hand, in FIG. 6, magnetic portions 61 are provided on the surface of a known non-movable roller via an adhesive 62 at regular intervals. In the case of a roller-shaped conveyance body, it is necessary to design in consideration of magnetically unnecessary coupling or crosstalk at adjacent locations. Crosstalk is reduced when weak magnets are used or the number of magnets is small. The place to install can be designed suitably. Of course, you may employ | adopt a thing other than FIG. 5 and FIG.
FIG. 7 shows an example of a sheet-like conveyance body, and magnetic portions 71 are provided at the four ends. In the case of such a sheet-like transport body, the magnetic part 71 is fixed to an extent that does not interfere with the transport, and the central part, that is, the part not provided with the magnetic part is structured to float by the magnetic force of the magnetic part. It is more preferable because it is possible to avoid defects such as wrinkles and scratches.

  The adsorption of the support to the manufacturing apparatus may be electrostatic adsorption or mechanically adsorbed. Mechanical adsorption is preferred when used in applications where static elimination is required or in applications where foreign matter such as dust accompanying static electricity is a problem.

 The carrier having a magnetic part may be adopted for all the carriers used in the manufacturing process of the barrier film substrate, or only for some carriers such as the step of providing an organic region and the step of providing an inorganic region. May be. In particular, when a carrier having a magnetic part is used in the step of providing any region or layer of the organic region, the inorganic region, and the functional layer, the step is preferably performed under vacuum. Under vacuum, there are few factors that reduce magnetism, such as humidity, compared to the atmosphere, and magnetism can be efficiently exhibited. That is, since a sufficient effect can be exerted if a small amount of a magnetic material is used, even if the magnetic material used for the magnetic layer of the support is colored, it can be used for transparent applications that are difficult to be colored. . Furthermore, since the manufacturing method of the present invention improves the ease of handling under vacuum, the productivity can be improved as a result.

Support In the barrier film substrate of the present invention, a plastic film is usually used as a support. The plastic film used is not particularly limited in material and thickness as long as it can hold a barrier film substrate in an organic region (for example, an organic layer) and an inorganic region (for example, an inorganic layer). Can be selected as appropriate. Examples of the plastic film include metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamide Imide resin, polyether imide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin solvent, fluorene ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds.

  When the barrier film substrate of the present invention is used as a substrate of a device such as an organic EL element described later, the plastic film is preferably made of a material having heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. Examples of such thermoplastic resins include polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, Zeonore 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Japanese Unexamined Patent Publication No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gasochemical Co., Ltd., Neoprim: 260 ° C., fluorene ring-modified polycarbonate (BCF-PC: compound described in JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: JP 2000) -227603 compound: 205 degreeC , Acryloyl compound (compound described in JP-A-2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the barrier film substrate of the present invention is used in combination with a polarizing plate, the barrier layer surface of the barrier film substrate (the surface on which the organic region or inorganic region is laminated) is directed to the inside of the cell, and the innermost (on the element) (Adjacent) is preferred. At this time, since the barrier film substrate is disposed inside the cell from the polarizing plate, the retardation value of the barrier film substrate is important. The usage form of the barrier film substrate in such an embodiment is as follows: a barrier film substrate using a support having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate) + A linear polarizing plate is used in combination with a barrier film substrate using a support having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate. preferable.

As the support having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka Corporation: Elmec Co.), cycloolefin polymer (JSR Co., Ltd.) : Arton, Nippon Zeon Co., Ltd .: ZEONOR), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd .: U100 (pellet)) ), Transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

When the barrier film substrate of the present invention is used as a device such as an organic EL element, the plastic film is preferably transparent. When used for applications requiring such transparency, the light transmittance is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the barrier film substrate of the present invention is used for display applications, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The support may have functional layers such as a transparent conductive layer and a primer layer.
The thickness of the support used for the barrier film substrate of the present invention can be appropriately selected depending on the application and is not particularly defined, but the improvement effect of the present invention is more easily exhibited at 4 to 500 μm. It is more likely to be exhibited at 200 μm.

Organic area | region The organic area | region in this invention consists of a polymer normally, and is layered (organic layer). Specifically, polyester, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetheretherketone , Polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound and other thermoplastic resin layers.

The organic layer of the present invention is preferably formed by applying a polymer precursor (for example, a monomer) that forms a polymer by polymerization. Preferred monomers that can be used in the present invention include acrylates and methacrylates. Preferable examples of acrylates and methacrylates include, for example, compounds described in US Pat. No. 6,083,628 and US Pat. No. 6,214,422.
Specific examples of acrylates and methacrylates preferably used in the present invention are shown below, but the monomers that can be used in the present invention are not limited to these.

  Examples of the method for forming the organic layer include a normal solution coating method. Examples of the solution coating method include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or US Pat. No. 2,681, It can apply | coat by the extrusion coat method using the hopper as described in 294 specification.

  The monomer polymerization method is not particularly limited, but heat polymerization, light (ultraviolet ray, visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination thereof is preferably used. Of these, photopolymerization is particularly preferred. When carrying out photopolymerization, a photopolymerization initiator is used in combination. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocur series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Esacure series (eg, Esacure TZM, Ezacur TZT, commercially available from Sartomer). Similarly, oligomer type Ezacure KIP series and the like can be mentioned.

The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more. Since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. Examples of such a method include an inert gas replacement method (nitrogen replacement method, argon replacement method, etc.) and a decompression method. Among these, the reduced pressure curing method is more preferable because it has an effect of reducing the dissolved oxygen concentration in the monomer.
When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less. Most preferably, the monomer film formed by flash vapor deposition is irradiated with energy of ² J / cm ² or more under reduced pressure to carry out ultraviolet polymerization. By taking such a method, the polymerization rate can be increased and an organic layer having high hardness can be obtained. The polymerization of the monomer is preferably performed after the monomer mixture is disposed at a target location by coating or vapor deposition. Moreover, when polymerizing the monomer of an organic layer, it is preferable to also polymerize the polymeric group (for example, ethylenic double bond) which exists in an organic coupling agent.

  The polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 92% or more. The polymerization rate here means the ratio of the reacted polymerizable groups among all the polymerizable groups (acryloyl group and methacryloyl group) in the monomer mixture. The polymerization rate can be quantified by an infrared absorption method.

  Although there is no limitation in particular about the film thickness of an organic layer, 50 nm-2000 nm are preferable and 200 nm-1500 nm are more preferable. If it is 50 nm or more, the number of defects tends to decrease and the barrier property tends to be improved, and if it is 1500 nm or less, cracks are not generated by an external force and the barrier property is not lowered.

  Two or more organic layers may be laminated. In this case, each layer may have the same composition or a different composition. Moreover, when laminating | stacking two or more layers, it is desirable to design so that each organic layer may exist in said preferable range. In addition, the barrier film substrate of the present invention has a layer having an unclear interface with the inorganic layer as disclosed in U.S. Patent Publication No. 2004-46497, and a layer whose composition changes continuously in the film thickness direction. May be present.

Inorganic region The inorganic region is usually composed of a metal compound (metal oxide, metal nitride, metal oxynitride, metal carbide, etc.), and is layered (inorganic layer). As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, there are a physical vapor deposition method (PVD) such as a vapor deposition method, a sputtering method, and an ion plating method, various chemical vapor deposition methods (CVD), and a liquid phase growth method such as plating and a sol-gel method. Among these, the physical vapor deposition method (PVD) and the like can be avoided in that the influence of heat on the base film during the formation of the inorganic layer can be avoided, the production speed is high, and a uniform thin film layer is easily obtained. It is preferable to use chemical vapor deposition (CVD).

  In the method of forming the inorganic layer of the barrier film substrate of the present invention, when the organic layer is formed by curing, the inorganic layer is formed on the cured organic layer immediately after the organic layer is cured. It is preferable. Immediately herein means that the step of forming an inorganic layer is performed immediately after the step of curing the organic layer. That is, it is preferable to form an inorganic layer on the surface of the organic layer without performing an operation of bringing something into contact with the surface of the cured organic layer.

  The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance. For example, one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like are used. An oxide, nitride, oxynitride, or the like containing can be used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride, or oxynitride of Si or Al is particularly preferable. These may contain other elements as secondary components.

  The smoothness of the inorganic layer formed according to the present invention is preferably less than 2 nm, more preferably 1 nm or less, as an average roughness (Ra value) of 10 μm square.

Although it does not specifically limit regarding the thickness of an inorganic layer, Usually, it exists in the range of 5-300 nm per layer. The thickness of the inorganic layer is preferably 20 to 200 nm, more preferably 30 to 90 nm.
In this invention, after forming an organic layer on an inorganic layer, you may form an inorganic layer further on an organic layer. Further, a plurality of inorganic layers may be formed by repeating alternate lamination of an organic layer and an inorganic layer. In these cases, each inorganic layer may have the same composition or a different composition. Incidentally, the barrier film substrate of the present invention has a layer whose interface with the organic layer as disclosed in US 2004-46497 is not clear, and a layer whose composition continuously changes in the film thickness direction. May be present.

<Element>
The barrier film substrate of the present invention can be preferably used for an element whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the element include electronic elements such as an organic EL element, a liquid crystal display element, a thin film transistor, a touch panel, electronic paper, and a solar cell, and are preferably used for the organic EL element.

  The barrier film substrate of the present invention can be used as a device substrate.

  The barrier film substrate of the present invention can also be used as a film for sealing by a solid sealing method. The solid sealing method is a method in which a protective layer is formed on an element, and then an adhesive layer and a barrier film substrate are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

(Organic EL device)
Examples of organic EL elements using a barrier film substrate are described in detail in JP-A-2007-30387.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The barrier film substrate of the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. Of these, the substrate of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably, a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, a HAN (Hybrid Aligned Nematic) type, a VA (Vertical Alignment) type, an EC type, an EC type, an EC type, an EC type, an EC type. OCB (Optically Compensated Bend) type, CPA (Continuous Pinwheel Alignment) type, and IPS (In-Plane Switching) type are preferable.

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. Electronic paper, solar cells described in Japanese Patent Application No. 7-160334, and the like.

<Optical member>
Examples of the optical member using the barrier film substrate of the present invention include a circularly polarizing plate.
(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the barrier film substrate in the present invention as a substrate. In this case, the lamination is performed so that the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1
One of the film forming apparatuses X and Y was employed as the film forming apparatus.
(Film forming device X)
A schematic diagram of the film forming apparatus X is shown in FIG. The film forming apparatus 810 includes a supply chamber 812 for supplying a long support Z (web-like support Z), a film forming chamber (chamber) 814 for forming a film on the long support Z, It has a winding chamber 816 for winding the formed long support Z, a vacuum exhaust unit 832, and a control unit 836. The operation of each element in the film forming apparatus 810 is controlled by the control unit 836.
In the film forming apparatus 810, a slit through which the support Z passes is formed in a wall 815a that partitions the supply chamber 812 and the film forming chamber 814 and a wall 815b that partitions the film forming chamber 814 and the winding chamber 816. A shaped opening 815c is formed.
In the film formation apparatus 810, a vacuum exhaust unit 832 is connected to the supply chamber 812, the film formation chamber 814, and the take-up chamber 816 through a pipe 834. This vacuum exhaust unit 832 adjusts the degree of vacuum inside the supply chamber 812, the film formation chamber 814, and the winding chamber 816.
The vacuum exhaust unit 832 exhausts the supply chamber 812, the film formation chamber 814, and the winding chamber 816 to maintain a predetermined degree of vacuum, and includes a vacuum pump. The supply chamber 812, the film formation chamber 814, and the winding chamber 816 are each provided with a pressure sensor (not shown) that measures the internal pressure. The vacuum exhaust unit 832 is controlled by the control unit 836.
The supply chamber 812 is a part that supplies a long support Z, and is provided with a support roll 820 and a transport device 850. The support roll 820 continuously feeds the long support Z, and the support Z is wound counterclockwise.
The support roll 820 is connected to a motor (not shown) as a drive source. With this motor, the support roll 820 is rotated clockwise, and the support Z is continuously fed out. The transfer device 850 guides the support Z to the film formation chamber 814 through a predetermined transfer path. As will be described later, the winding chamber 816 is a portion that winds up the support Z having a film formed on the surface Zf in the film forming chamber 814, and is provided with a winding roll 830 and a guide roller 831.
The winding roll 830 winds the film-formed support Z in a roll shape in a clockwise direction. A motor (not shown) is connected to the winding roll 830 as a drive source. The take-up roll 930 is rotated by this motor, and the film-formed support Z is taken up. In the take-up roll 830, the support Z is rotated by a motor in the winding direction R and is rotated clockwise to continuously wind the film-formed support Z in the clockwise direction.
The guide roller 831 guides the support Z transported from the film forming chamber 814 to the take-up roll 830 through a predetermined transport path.
The film forming chamber 814 functions as a vacuum chamber, and continuously forms various layers on the surface Zf of the support Z while transporting the support Z. In the film formation chamber 814, two guide rollers 824 and 828, a drum 826, and a film formation unit 840 are provided. The guide roller 824 and the guide roller 828 are arranged to face each other with a space therebetween, and the guide roller 824 and the guide roller 828 are arranged with respect to the conveyance direction D of the support Z. The longitudinal directions are arranged orthogonally. The guide roller 824 conveys the support Z conveyed from the conveying device 850 provided in the supply chamber 812 to the drum 826. The guide roller 824 has a rotation axis in a direction orthogonal to the conveyance direction D of the support Z and is rotatable, and the guide roller 824 has an axial length that is the length of the support Z (hereinafter referred to as support). Longer than the width of the body Z).
The guide roller 828 conveys the support Z wound around the drum 826 to the guide roller 831 provided in the winding chamber 816. The guide roller 828 has a rotation axis in the axial direction and is rotatable, and the guide roller 828 has an axial length longer than the width of the support Z. The drum 826 is provided below the space H between the guide roller 824 and the guide roller 828. The drum 826 is arranged with its longitudinal direction parallel to the longitudinal directions of the guide roller 824 and the guide roller 828. Furthermore, the drum 826 is grounded. The drum 826 has a cylindrical shape, has a rotation shaft in the axial direction, and is rotatable. The drum 826 is longer in the axial direction than the width of the support Z. In the drum 826, when the center in the width direction of the support Z and the center in the axial direction of the drum 826 are aligned and the support Z is wound around the surface (circumferential surface), the end portions on both sides thereof are This is a region where the support Z is not hung.
The drum 826 conveys the support Z in the conveyance direction D while holding the support Z at the film forming position by rotating the support Z around the surface (circumferential surface) and rotating the drum. .
The film forming unit 840 is provided below the drum 826, and the drum 826 rotates in a state where the support Z is wound around the drum 826, and the support Z is conveyed in the conveyance direction D while being supported. A film is formed on the surface Zf of the body Z.
The film forming unit 840 includes a film forming electrode 842, a high frequency power source 844, a source gas supply unit 846, and a partition unit 848. The control unit 836 controls the high frequency power supply 44 and the source gas supply unit 46 of the film forming unit 40. In the film formation unit 840, a film formation electrode 842 is provided below the film formation chamber 814 with a predetermined gap S facing a region where the support Z is wound around the drum 826. The film-forming electrode 842 has a plurality of holes (not shown) formed at equal intervals on a wide surface. The film forming electrode 842 is arranged with this wide surface facing the drum 826. In addition, a high frequency power supply 844 is connected to the film formation electrode 842, and a high frequency voltage is applied to the film formation electrode 842 by the high frequency power supply 844.
The source gas supply unit 846 supplies a source gas for forming a film into the gap S through the plurality of holes of the film formation electrode 842 via the pipe 847. A gap S between the drum 826 and the deposition electrode 842 becomes a plasma generation space.
The partition portion 848 (partition portion) partitions the film formation electrode 842 in the film formation chamber 814.
The partition portion 848 includes a pair of partition plates 848a, and is disposed so that the film formation electrode 842 is sandwiched between the pair of partition plates 848a.
Each partition plate 848 a is a plate-like member that extends in the length direction of the drum 826, and an end portion on the drum 826 side is bent to the opposite side to the film formation electrode 842. The partition portion 848 divides the gap S, that is, the plasma generation space, in the film formation chamber 814.

FIG. 9A is a schematic front view showing the transfer apparatus of the film forming apparatus shown in FIG. 8, and FIG. 9B is a schematic side view showing the transfer apparatus of the film forming apparatus shown in FIG. As shown to Fig.9 (a), a conveying apparatus has the stepped roller 960 and the auxiliary roller 966 (conveyance auxiliary means). The stepped roller 960 supports and conveys both sides of the end portion Ze in the width direction W of the support Z, and includes a roller portion 962 and a rotation shaft portion 964. Further, the surface Zf of the support Z is disposed and conveyed on the surface 962a side of the roller portion 962. In the stepped roller 960, the rotation shaft portion 964 is arranged in a direction in which the rotation axis A is orthogonal to the conveyance direction D of the support Z. Cylindrical roller portions 962 are provided at both ends of the rotating shaft portion 964. The end Ze of the support Z is wound around the surface 962a of the roller portion 962.
Further, the stepped roller 960 is rotated by a driving means (not shown). The driving unit is connected to the control unit, and the rotation of the stepped roller 960 is controlled by the control unit to adjust the conveyance speed of the support Z by the driving unit.
The auxiliary roller 966 temporarily assists the conveyance of the support Z when the conveyance of the support Z by the stepped roller 960 is started, and is provided so as to be able to contact and separate from the surface Zf of the support Z. . The auxiliary roller 966 is a cylindrical roller having a constant diameter, and its rotation axis (not shown) is arranged in parallel with the rotation axis A of the rotation shaft portion 964, and each roller portion 962 and the rotation shaft portion 964 are arranged. And provided above the rotating shaft portion 964.
The auxiliary roller 966 supports the central portion Zc in the width direction W of the support Z. The auxiliary roller 966 is provided with a moving mechanism (not shown) for moving itself in the vertical direction V, and this moving mechanism is connected to the control unit.
The position of the auxiliary roller 966 in the vertical direction V is controlled by the control unit via the moving mechanism. As described above, the auxiliary roller 966 can be brought into and out of contact with the surface Zf of the support Z by the moving mechanism, and the auxiliary roller 966 is moved upward to bring the peripheral surface 966a into contact with the surface Zf of the support Z. Can be made. Thereby, the conveying apparatus 950 can convey the support body Z using the auxiliary | assistant roller 966 with the stepped roller 960. FIG.
The transfer device is provided in the supply chamber 812 and is used in a vacuum environment. When the support Z is transported to the film formation chamber 814, the auxiliary roller 866 is moved in the vertical direction V so that the surface 862a of the roller portion 862 and the surface 866a of the auxiliary roller 866 are arranged on the same plane. And the support body Z sent out from the support body roll 820 is wound around the surface 862a of the roll part 862. Thereby, while supporting the edge part Ze of the both sides of the support body Z with the roller part 862, the support body Z The central portion Zc is also supported by the auxiliary roller 866 and conveyed.
Thus, the support body Z is conveyed in the state which supported the support body Z over the whole region of the width direction W. The auxiliary roller 866 temporarily holds the central portion Zc of the support Z immediately after the start of conveyance, and is separated from the support Z during conveyance.

The operation of the film forming apparatus will be described. In the film formation apparatus 810, the long support Z is passed through a predetermined path from the supply chamber 812 through the film formation chamber 814 to the take-up chamber 816, and then the supply chamber 812, the film formation chamber 814, and the take-up chamber The inside of 816 is maintained at a predetermined degree of vacuum by the vacuum exhaust unit 832, and in this state, the substrate Z is transported through the long support Z from the supply chamber 812 to the winding chamber 816, and in the film formation chamber 814, the support Z Each layer is formed. In the film formation apparatus 810, the inside of the film formation chamber 814 and the winding chamber 816 is set to a predetermined vacuum level by the vacuum exhaust unit 832.
Next, the long support Z is transferred from the support roll 820 wound in the counterclockwise direction to the film formation chamber 814 through the transfer device 850. In the film formation chamber 814, the film is transferred to the winding chamber 816 through the guide roller 824, the drum 826, and the guide roller 828. In the winding chamber 816, the long support Z is wound around the winding roll 830 through the guide roller 831.
In the transport device, the ends Ze at both ends of the support Z are supported by the roll portions 862, and the support Z is transported in a state where the central portion Zc of the support Z is supported by the auxiliary roller 866. Next, in the film forming unit 840, a high frequency voltage is applied from the high frequency power source 844 to the film forming electrode 842, and a raw material gas for forming a film is formed in the gap S from the raw material gas supply unit 846 through the pipe 847. Supply.
When electromagnetic waves are emitted around the deposition electrode 842, plasma localized in the vicinity of the deposition electrode 842 is generated in the gap S, and the source gas is excited and dissociated. Thereby, a predetermined film is formed on the surface Zf of the support Z.
Sequentially, the support roll 820 around which the long support Z is wound counterclockwise is rotated clockwise by the motor, and the long support Z is continuously fed out by the conveying device 850 and the guide roller 824. The drum 826 is rotated at a predetermined speed while the support Z is held at the position where the plasma is generated by the drum 826, and a film is continuously formed on the surface Zf of the long support Z by the film forming unit 840. To do. And the elongate support body Z formed into a film is wound up by the winding roll 830 through the guide roller 828 and the guide roller 831.

(Film forming device Y)
In the film forming apparatus X, a dry part and a cured part of an apparatus for forming an organic layer, a sputter part of an apparatus for forming an inorganic layer, and an end part of another transport roller provided with permanent magnets were used. .

As shown in Table 1, the following barrier film substrates were manufactured using either the film forming apparatus X or the film forming apparatus Y.
(Barrier film substrate A)
Polyethylene naphthalate support (PEN) with easy-adhesion layer (Teijin DuPont Films, Teonex Q65FA, width 30 cm, thickness 100 μm) on the easy-adhesion surface, a magnetic layer composed of the following composition on the entire surface of the support Was formed to be 3 μm.
[Composition of magnetic layer]
Barium ferrite 36 parts by weight Urethane resin 12 parts by weight Carbon 2 parts by weight Toluene 20 parts by weight Methyl ethyl ketone 15 parts by weight Methyl isobutyl ketone 15 parts by weight Isocyanate curing agent 2 parts by weight

Next, an organic layer having the following composition was formed on the polyethylene naphthalate support on the surface opposite to the surface on which the magnetic layer was provided, so that the dry film thickness was 1000 nm. It was cured by irradiation at 0.5 J / cm ² . On the surface of the organic layer, AlO ₃ was formed as an inorganic layer by vacuum sputtering so as to have a film thickness of 50 nm, thereby producing a barrier film substrate.
[Organic layer composition]
Daicel Cytec, aliphatic modified epoxy acrylate bifunctional, EBECRYL 3702 20 parts by weight
Made by Sartomer, Esacure KTO46 1.5 parts by weight Methyl ethyl ketone 60 parts by weight

(Barrier film substrate B)
A barrier film substrate B was produced in the same manner as the barrier film substrate A, except that the magnetic layer was provided at both ends in the width direction of the support with a width of 2 cm.

(Barrier film substrate C)
A barrier film substrate C was prepared in the same manner as the barrier film substrate A, except that polyethylene terephthalate (PET) (Toray, Lumirror T-60, thickness 100 μm) was used as the support.

(Barrier film substrate D)
A barrier film substrate D was produced in the same manner as the barrier film substrate B, except that polyethylene terephthalate (PET) (Toray, Lumirror T-60, 100 μm thick) was used as the support.

(Barrier film substrate E)
A barrier film substrate E was produced in the same manner as the barrier film substrate A, except that polyethylene terephthalate (PET) (Toray, Lumirror T-60, thickness 25 μm) was used as the support.

(Barrier film substrate F)
A barrier film substrate F was produced in the same manner as the barrier film substrate B, except that polyethylene terephthalate (PET) (Toray, Lumirror T-60, thickness 25 μm) was used as the support.

(Barrier film substrate BB)
A barrier film substrate BB was produced in the same manner as the barrier film substrate B except that the magnetic layer was not provided.

(Barrier film substrate DD)
A barrier film substrate DD was produced in the same manner as the barrier film substrate D except that the magnetic layer was not provided.

(Barrier film substrate FF)
A barrier film substrate FF was produced in the same manner as the barrier film substrate F except that the magnetic layer was not provided.

(Barrier film substrate GBB)
The magnetic layer described in the barrier film substrate A was provided on polyethylene terephthalate (PET) (manufactured by Toray, Lumirror T-60, thickness 25 μm). Moreover, the organic layer as described in the barrier film substrate A was provided on the same support as the barrier film substrate BB. These are overlapped so that their application surfaces face outward, and are bonded together with an adhesive having a peelable adhesive force (made by Shin-Etsu Silicone, X-40-3229), as described for the barrier film substrate A An inorganic layer was formed on the organic layer in the same manner as the barrier film substrate A to prepare a barrier film substrate GBB.

(Barrier film substrate GDD)
The magnetic layer described in the barrier film substrate A was provided on polyethylene terephthalate (PET) (manufactured by Toray, Lumirror T-60, thickness 25 μm). Moreover, the organic layer as described in the barrier film substrate A was provided on the same support as the barrier film substrate DD. These are overlapped so that their application surfaces face outward, and are bonded together with an adhesive having a peelable adhesive force (made by Shin-Etsu Silicone, X-40-3229), as described for the barrier film substrate A An inorganic layer was formed on the organic layer in the same manner as the barrier film substrate A to prepare a barrier film substrate GDD.

(Barrier film substrate GFF)
The magnetic layer described in the barrier film substrate A was provided on polyethylene terephthalate (PET) (manufactured by Toray, Lumirror T-60, thickness 25 μm). Moreover, the organic layer as described in the barrier film substrate A was provided on the same support as the barrier film substrate FF. These are overlapped so that their application surfaces face outward, and are bonded together with an adhesive having a peelable adhesive force (made by Shin-Etsu Silicone, X-40-3229), as described for the barrier film substrate A An inorganic layer was formed on the organic layer in the same manner as the barrier film substrate A to prepare a barrier film substrate GFF.

[Water vapor transmission rate (g / m ² / day)]
It was measured using “PERMATRAN-W3 / 31” (condition: 40 ° C., relative humidity 90%) manufactured by MOCON. Moreover, the value below 0.01 g / m < ² > / day which is the measurement limit of the said MOCON apparatus was supplemented using the following method. First, metal Ca was directly deposited on the barrier film substrate, and the measurement film was prepared by sealing the barrier film substrate and the glass substrate with a commercially available organic EL sealing material so that the deposited Ca was inside. . Next, the measurement sample was kept under the above temperature and humidity conditions, and the water vapor transmission rate was determined from the change in optical density of the metal Ca on the barrier film substrate (the metal gloss decreased due to hydroxylation or oxidation).

[defect]
The film piece after measuring the water vapor transmission rate was magnified 100 times and observed. The observation area was 4 × 4 = 16 locations at 5 mm intervals in a 25 mm square sample piece, and the number of observed dust was counted. Is 1 or less / 16 places, ◯ is 2-10 pieces / 16 places, △ is 11-20 pieces / 16 places, and more is observed when it is observed.

From the barrier film substrate 1 and the barrier film substrate 10, the barrier film substrate 2 and the barrier film substrate 12, the barrier film substrate 5 and the barrier film substrate 14, by providing a magnetic part on the transport body of the manufacturing apparatus, It was confirmed that the barrier property was improved.
Further, since the barrier film substrate 6 has a significantly improved water vapor transmission rate as compared with the barrier film substrate 15, the support having a thickness of 25 μm is more than the support having a heat of 100 μm. Also, it was confirmed that the improvement effect was high.
Further, providing a magnetic layer on the entire surface of the support opposite to the barrier layer from the barrier film substrate 7 and the barrier film substrate 11 and the barrier film substrate 9 and the barrier film substrate 15 has the same improvement effect. It was confirmed.
On the other hand, the magnetic part may be provided on the entire surface from the barrier film substrate 1 and the barrier film substrate 2, the barrier film substrate 3 and the barrier film substrate 4, the barrier film substrate 5 and the barrier film substrate 6, and the like. It was found that the barrier property was equally improved even if it was provided in the part.
In addition, the barrier property is improved regardless of whether PEN or PET is used as the support from the barrier film substrate 1 and the barrier film substrate 3, the barrier film substrate 2 and the barrier film substrate 4, etc. Confirmed to do.
Moreover, by adopting the production method of the present invention from the barrier film substrate 1 and the barrier film substrate 10, the barrier film substrate 2 and the barrier film substrate 12, the barrier film substrate 5 and the barrier film substrate 14, It was recognized that the defect also had an improvement effect.

Example 2
In Example 1 above, the organic layer was formed by flash vapor deposition, and the others were performed in the same manner. As a result, the same effect as in Example 1 was obtained.

Example 3
In the barrier film substrate 2 of Example 1, when the magnetic layer was provided on the outermost surface and the others were performed in the same manner, the same results as in Example 1 were obtained. That is, it was confirmed that the same effect can be obtained when the magnetic layer is provided at both ends of the outermost surface.

Example 4
As the conveying body of the manufacturing apparatus X of the first embodiment, a sheet-like material described in JP-A-2001-117063 is used, in which permanent magnets are provided at the four ends, and the corresponding positions are the same as in the first embodiment. It was confirmed that the same effect can be obtained even when the magnetic layer having the composition is provided.

FIG. 1 is a schematic view showing an example in which a mountain-shaped magnetic layer is provided on a support. FIG. 2 is a schematic view showing an example in which a magnetic layer showing opposite magnetic poles is provided at both ends and the center on a support. FIG. 3 is a schematic view showing an example of an operating roller. FIG. 4 is a schematic view showing an example of a non-operating roller. FIG. 5 is a schematic side view showing an example of a roller-shaped carrier. FIG. 6 is a schematic side view illustrating another example of a roller-shaped conveyance body. FIG. 7 is a schematic diagram illustrating an example of a sheet-like conveyance body. FIG. 8 is a schematic view of the film forming apparatus X used in the embodiment of the present application. FIG. 9 is a schematic front view and a schematic side view showing the transfer apparatus of the film forming apparatus shown in FIG.

Explanation of symbols

21 Carrier 22 Support 23 Barrier film substrate 31 in production 31 Magnetic part 41 Carrier 42 Support 51 Magnetic part 52 Adhesive 61 Magnetic part 62 Adhesive 71 Magnetic part 810 Film forming apparatus 812 Supply chamber 814 Film forming chamber 815a Wall 815b Wall 815c Wall 816 Winding chamber 820 Support roll 824 Guide roller 826 Drum 828 Guide roller 831 Guide roller 830 Winding roll 832 Vacuum exhaust section 834 Pipe 836 Control section 840 Film forming section 842 Film forming electrode 844 High frequency power supply 846 Raw material Gas supply unit 847 Piping 848 Partition unit 850 Conveying device 960
980 Stepped roller 962 Roller unit 964 Rotating shaft unit 966 Auxiliary roller D Conveying direction Z Support

Claims (24)

A method for producing a barrier film substrate having an organic region and an inorganic region on a support while conveying the support, the step of providing an organic region, the step of providing an inorganic region, Including a step of providing a magnetic layer on a part or all of the magnetic layer, and all or part of the step of transporting the support using a carrier having a magnetic portion showing a magnetic pole opposite to the magnetic layer. A manufacturing method, wherein the magnetic force and the magnetic force of the magnetic part are attracted to each other. The manufacturing method according to claim 1, wherein magnetic layers are provided at both ends of the support in the conveying direction. The manufacturing method according to claim 2, wherein the magnetic layer is provided in a mountain shape. The manufacturing method according to any one of claims 1 to 3, wherein a magnetic layer showing the same magnetic pole as the magnetic part of the carrier is further provided in the center of the carrier on the carrier. The manufacturing method according to claim 1, wherein the carrier is a roller-like carrier. The manufacturing method according to claim 1, wherein the carrier is a sheet-like carrier. The manufacturing method according to claim 5 or 6, wherein magnetic portions are provided at both ends of the roller-shaped conveyance body or at four ends of the sheet-shaped conveyance body. The manufacturing method according to claim 1, wherein the magnetic layer is detachably provided. The manufacturing method according to claim 1, wherein at least the step of providing the organic region is carried using a carrier having a magnetic part. The manufacturing method according to claim 1, wherein at least the step of providing the inorganic region is carried using a carrier having a magnetic part. It manufactures under a vacuum, The manufacturing method of any one of Claims 1-10 characterized by the above-mentioned. The manufacturing method according to claim 11, wherein at least the organic region and / or the inorganic region is provided under vacuum. The manufacturing method according to any one of claims 1 to 12, wherein a main component of the inorganic region is selected from a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide. 14. The production according to claim 1, wherein the organic region is an organic layer, the inorganic region is an inorganic layer, and the organic layer and the inorganic layer have an alternate layer structure. Method. The manufacturing method according to claim 1, wherein the support has a thickness of 4 to 500 μm. A barrier film substrate comprising an organic region, an inorganic region, and a magnetic layer on a support. The barrier film substrate according to claim 16, further comprising a magnetic layer at both ends in the longitudinal direction of the support. 18. The barrier film substrate according to claim 17, wherein the magnetic layer is provided in a mountain shape. The barrier film substrate according to claim 17 or 18, wherein a magnetic layer showing a magnetic pole opposite to the magnetic layer is further provided in the center in the longitudinal direction of the support. The barrier film substrate according to any one of claims 16 to 19, wherein the magnetic layer is detachably provided. The barrier film substrate according to any one of claims 16 to 20, wherein a main component of the inorganic region is selected from a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide. The organic region is an organic layer, the inorganic region is an inorganic layer, and the organic layer and the inorganic layer have an alternating layer structure, The barrier according to any one of claims 16 to 21, Film substrate. The barrier film substrate according to any one of claims 16 to 22, wherein the support has a thickness of 4 to 500 µm. An element having the barrier film substrate according to any one of claims 16 to 23.

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