JP2009090632A - LAMINATED FILM AND LIGHT EMITTING ELEMENT OR DISPLAY ELEMENT USING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light emitting element or a display element which can be formed as a passivation layer even in a single layer, has a high water vapor barrier performance and is resistant to external impact.
SOLUTION: A layer having a lower hardness than a gas barrier film and a layer having a higher hardness than a gas barrier film are provided on a surface opposite to the side on which the barrier layer is provided on a gas barrier film having a barrier layer provided on at least one side of a base film. Are laminated films in this order.
[Selection figure] None

Description

  The present invention relates to a laminated film and a light emitting device or a display device using the same.

Conventionally, a light-emitting element or a display element provided with a passivation layer (a protective film for water vapor or oxygen by a thin film) is known. In Patent Document 1, in an organic electroluminescent element, an element region having at least one organic compound layer between electrodes, a protective film formed to cover the element region, and at least two layers on the protective film An organic electroluminescent element characterized in that coating layers having different functions as described above are laminated is disclosed. Further, in Patent Document 2, an electro-optical device in which a first electrode, an element layer including at least one functional layer, and a second electrode are formed in this order on a substrate, the second electrode is covered. An electro-optical device is disclosed that includes a protective portion, and the protective portion includes at least two protective layers having different hardnesses.
However, in the light-emitting element or the display element, when it is intended to realize a high barrier property of water vapor, it is necessary to provide a plurality of passivation layers (protective films), and there is a problem that process costs increase.

JP 2003-282242 A JP 2004-127606 A

  The present invention is intended to solve the above-mentioned problems of the prior art, and even if a passivation layer (protective film) is not provided or only one layer is provided, the barrier performance of water vapor is high, and An object of the present invention is to provide a light-emitting element or a display element that is resistant to external impact.

As a result of intensive studies by the inventors under the above problems, it has been found that the above problems can be solved by the following means. Specifically, it was achieved by the following means.
(1) A layer having a hardness lower than that of the gas barrier film and a layer having a hardness higher than that of the gas barrier film are provided on the opposite surface of the gas barrier film provided with the barrier layer on at least one surface of the base film. A laminated film laminated in this order.
(2) The thickness of the gas barrier film is 25 to 4000 μm, the thickness of the layer having a lower hardness than the gas barrier film is 5 to 2000 μm, and the thickness of the layer having a higher hardness than the gas barrier film is 1 to 1000 μm. The laminated film according to (1).
(3) The laminated film according to (1) or (2), wherein the layer having a higher hardness than the gas barrier film has a circular polarization function.
(4) The laminated film according to (1) or (2), wherein the layer having a higher hardness than the gas barrier film has a light diffusion function.
(5) The method according to any one of (1) to (4), wherein an adhesive layer is provided on the outermost surface opposite to a surface provided with a layer having a higher hardness than the gas barrier film and a layer having a lower hardness than the gas barrier film. Laminated film.
(6) The gas barrier film according to any one of (1) to (5), wherein the layer having a hardness higher than that of the gas barrier film includes a hard coat material as a main component.
(7) The gas barrier film according to any one of (1) to (6), wherein the layer having a hardness lower than that of the gas barrier film includes a gel material as a main component.
(8) The laminated film according to (7), which is for a touch panel.
(9) The laminated film according to any one of (1) to (8), wherein the barrier layer has at least one organic region and at least one inorganic region.
(10) A substrate, a pair of electrodes provided on the substrate, an organic compound layer provided between the electrodes, and the electrode provided on the side opposite to the side on which the organic compound layer is provided. The laminated film according to any one of (1) to (9), and the laminated film has an electrode on a side opposite to the side provided with a layer having a higher hardness than the gas barrier film. A light-emitting element or a display element provided so as to be close to each other.
(11) The light emitting device or display device according to (10), wherein a protective layer is further provided between the electrode and the laminated film according to any one of (1) to (9).
(12) The light-emitting element or display element according to (10) or (11), wherein the light-emitting element or display element is a touch panel.
(13) The light-emitting element or display element according to (10) or (11), wherein the light-emitting element or display element is an organic EL element.
(14) A layer having a hardness lower than that of the gas barrier film and a layer having a hardness higher than that of the gas barrier film are provided on a surface opposite to the side of the gas barrier film provided with the barrier layer on at least one side of the base film. The manufacturing method of a laminated | multilayer film including laminating | stacking in this order.

  The laminated film of the present invention makes it possible to provide a light emitting element or a display element that has a high water vapor barrier performance and is resistant to external impact.

  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.

Laminated film The laminated film of the present invention is a layer having a lower hardness than the gas barrier film (hereinafter referred to as the gas barrier film) on the opposite side of the side of the gas barrier film provided with the barrier layer on at least one side of the base film. It is a laminated film in which a “low hardness layer” and a layer having a higher hardness than the gas barrier film (hereinafter also referred to as “high hardness layer”) are laminated in that order. That is, in the laminated film of the present invention, at least a barrier layer, a base film, a low hardness layer, and a high hardness layer are laminated in this order. By setting it as such a structure, the tolerance with respect to the impact from the outside can be improved. In addition, as in the prior art, if it is intended to realize a water vapor barrier function using only a passivation layer (a protective film for water vapor and oxygen by a thin film), it is necessary to perform a plurality of vacuum film formation as the passivation layer, and the process cost is increased. Although there was a problem that it becomes high, in this invention, barrier property can be improved without such a problem. Furthermore, when the gas barrier film is provided with a low hardness layer and a high hardness layer, there is an advantage that the application is easier than providing such a layer on a glass substrate or the like.

Moreover, the laminated film of this invention may be provided with other layers and films between them. For example, a gas barrier film in which a barrier layer is provided on both surfaces of a base film, that is, a gas barrier film in which a barrier layer, a base film, a barrier layer, a low hardness layer, and a high hardness layer are laminated in this order can be given. In addition to this, various functional layers and the like may be provided.
The hardness of the gas barrier film, the high hardness layer and the low altitude layer in the present invention refers to pencil hardness.

In the laminated film of the present invention, the thickness of the gas barrier film is preferably 25 to 4000 μm, more preferably 50 to 2000 μm, and further preferably 75 to 1000 μm. The thickness of the low hardness layer is preferably 5 to 2000 μm, more preferably 10 to 1000 μm, and further preferably 15 to 500 μm. The thickness of the high hardness layer is preferably 1 to 1000 μm, more preferably 1 to 500 μm, and further preferably 2 to 100 μm. Conventionally, if the film is too thin, such as when the film is transported by an automatic transport machine, troubles are likely to occur, so the thickness of the film such as a gas barrier film may be unnecessarily thickened. By providing the low-hardness layer and the high-hardness layer, the thickness of the laminated film can be adjusted, so that costs can be reduced while solving troubles caused by automatic conveyance.
In particular, when the laminated film of the present invention is used for a relatively large display such as a billboard or touch panel, the thickness of the gas barrier film is preferably 100 to 4000 μm, more preferably 150 to 1000 μm. The thickness of the low hardness layer is preferably 50 to 2000 μm, more preferably 200 to 1000 μm. The thickness of the high hardness layer is preferably 10 to 1000 μm, more preferably 20 to 100 μm.
Moreover, when using the laminated | multilayer film of this invention for comparatively small displays, such as a mobile phone and a television, the thickness of a gas barrier film becomes like this. Preferably it is 25-500 micrometers, More preferably, it is 75-150 micrometers. The thickness of the low hardness layer is preferably 5 to 500 μm, more preferably 10 to 200 μm. The thickness of the high hardness layer is preferably 1 to 50 μm, more preferably 2 to 20 μm.

Low Hardness Layer The low hardness layer in the present invention is characterized in that its hardness is lower than that of the gas barrier film, and preferably has a hardness that is one rank or more lower than that of the gas barrier film. The hardness of the low hardness layer is preferably B or less, and more preferably 2B or less.
The low hardness layer is preferably composed mainly of an organic substance, and is preferably a thermoplastic resin. Further, the main component of the low hardness layer may be a gel substance. Here, the main component means that the first component constituting the low hardness layer is a gel substance, and usually 80% by weight or more thereof is a gel substance. As a gel substance, a gelatin gel is a preferred example. By making it into a gel, the impact resistance becomes high and it is easy to use it for a touch panel or the like.

High-hardness layer The high-hardness layer in the present invention is characterized in that its hardness is higher than that of the gas barrier film. Preferably, the high-hardness layer has a hardness of one rank or more. , H or higher, preferably 3H or higher.
The high-hardness layer preferably contains an organic substance as a main component (highly hardened thermosetting resin or ultraviolet curable resin is more preferable. The high-hardness layer is mainly composed of a hard coat material. Here, the main component means that the first component constituting the high hardness layer is a hard coat material, and usually 80% by weight or more thereof is the hard coat material. As the hard coat material, a compound containing an ethylenically unsaturated group or a compound containing a ring-opening polymerizable group can be used, and these compounds can be used alone or in combination.

 As the ethylenically unsaturated group used in the present invention, a (meth) acryloyl group, a styryl group and a vinyl group are mainly preferred, and a (meth) acryloyl group is more preferred. Although the compound containing an ethylenically unsaturated group should just have two or more ethylenically unsaturated groups in a molecule | numerator, More preferably, it is three or more. Among them, a compound having a (meth) acryloyl group is preferable, and a compound called a polyfunctional (meth) acrylate monomer having 2 to 6 acryloyl groups in the molecule, urethane (meth) acrylate, or polyester (meth) acrylate. It is preferable to use a compound having several acrylate groups in the molecule called epoxy (meth) acrylate. In addition, as the compound having an acrylate group, a compound in which a part of the molecular skeleton is modified can be used.

 Preferred specific examples of the compound having two or more ethylenically unsaturated groups in the molecule include divinylbenzene, 1,6-hexanediol (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, poly Poly (meth) acrylates of polyols such as methylolpropane tri (meth) acrylate, epoxy (meth) acrylates such as di (meth) acrylate of bisphenol A diglycidyl ether, di (meth) acrylate of hexanediol diglycidyl ether, Examples thereof include urethane (meth) acrylate obtained by reaction of polyisocyanate and hydroxyl-containing (meth) acrylate such as hydroxyethyl (meth) acrylate and isocyanuric acid-modified triacrylate. Moreover, such a compound is also marketed, and EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (above, Daicel UCB ( Co., Ltd.), UV-6300, UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and the like.

 Among the compounds having two or more ethylenically unsaturated groups in the molecule mentioned above, a particularly preferred compound has three or more (meth) acryloyl groups in the molecule and has a (meth) acryloyl equivalent of 120 or less. Specific examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth). Examples include acrylate and dipentaerythritol hexa (meth) acrylate.

 The compound containing a ring-opening polymerizable group used in the present invention is a compound having a ring structure in which ring-opening polymerization proceeds by the action of a cation, an anion, a radical, etc. Among them, cationic ring-opening polymerization of a heterocyclic compound is preferable. . Examples of such compounds include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, and the like, and epoxy derivatives, oxetane derivatives, and oxazoline derivatives are particularly preferable. The number of ring-opening polymerizable groups in the same molecule is not particularly limited and may be one or more, but a compound having two or more ring-opening polymerizable groups is more preferable. Specific examples of such compounds include, for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxy as glycidyl ethers. Ethyl isocyanurate, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc. GT-401, EHPE3150CE (above, Daicel Chemical Oxetanes such as polycyclohexyl epoxy methyl ether of phenol novolac resin, OXT-121, OXT-221, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.), etc. . In addition, a glycidyl (meth) acrylate polymer or a copolymer with a monomer copolymerizable with glycidyl (meth) acrylate can be used.

 By adding crosslinkable fine particles in the hard coat layer used in the present invention, the amount of cure shrinkage of the hard coat layer can be reduced, the adhesion to the substrate is improved, or the curl of the hard coat film is reduced. Can do. Crosslinkable fine particles include inorganic fine particles such as metal oxide fine particles such as silicon, titanium, zirconium and aluminum, polyethylene, polypropylene, polytetrafluoroethylene, nylon, polyethylene terephthalate, polystyrene, poly (meth) acrylic acid esters and amides. And organic fine particles such as those obtained by crosslinking general-purpose resins such as polyvinyl chloride, acetylcellulose, nitrocellulose, and polydimethylsiloxane, and crosslinked rubber fine particles such as SBR and NBR. These crosslinkable fine particles have an average particle size of 1 nm to 20000 nm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and most preferably 10 nm to 200 nm. Further, the shape of the crosslinkable fine particles can be used without particular limitation, such as a spherical shape, a rod shape, a needle shape, or a plate shape. The addition amount of the fine particles is preferably 60% by volume or less, more preferably 40% by volume or less of the hard coat layer after curing.

 Since the inorganic fine particles described above generally have poor affinity with the binder polymer, surface treatment is performed using a surface treatment agent having a functional group such as a metal alkoxide such as silicon, aluminum or titanium, carboxylic acid, sulfonic acid or phosphonic acid group. Preferably it is done.

 The hard coat layer used in the present invention is preferably cured using heat or active energy rays, and among them, it is preferred to use active energy rays such as radiation, gamma rays, alpha rays, electron rays, ultraviolet rays, etc. In view of productivity, it is more preferable to use an electron beam or ultraviolet rays. When curing with heat, the heat resistance of the plastic itself must be considered, and the heating temperature is 140 ° C. or lower, more preferably 100 ° C. or lower. Moreover, after hardening as needed, hardening may be further advanced by heating and it can use preferably.

 The ethylenically unsaturated group used in the hard coat layer used in the present invention is a radical polymerization reaction, and the ring-opening polymerization group is reacted / cured by a cationic polymerization reaction. In any case, it is preferable to add a polymerization initiator that generates a radical generator or a cation generator (or an acid generator) by heat or active energy rays.

 Known radical generators such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide, and thioxanthone are used as radical generators that generate radicals by ultraviolet rays. It is preferable to use an agent.

 Further, a sensitizer may be used in addition to the polymerization initiator for the purpose of increasing the generation of radicals. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-brylphosphine and thioxanthone derivatives. However, sensitizers often have absorption at a wavelength of 380 nm, and the amount used is limited.

Examples of cation generators that generate cations by ultraviolet rays include ionic compounds such as triarylsulfonium salts and diaryliodonium salts, and nonionic compounds such as nitrobenzyl esters of sulfonic acids. Known photoacid generators for collecting compounds and the like described in “Organic Materials for Imaging” published by Bunshin Publishing Co., Ltd. (1997) can be used. Among these, an iodonium salt is particularly preferable, and PF ⁶⁻ , SbF ⁶⁻ , AsF ⁶⁻ , B (C6F5) ⁴⁻ , and the like are preferable as a counter ion.

 The addition amount of various polymerization initiators used in the present invention may be in the range of 0.1 to 15% by mass with respect to the total mass of the compound containing an ethylenically unsaturated group and the ring-opening polysynthetic group-containing compound. Preferably, it is more preferably used in the range of 1 to 10% by mass. In a sensitizer, 60 mass% or less is preferable with respect to the total weight of a polymerization initiator, and 50 mass% or less is more preferable.

 When the hard coat layer used in the present invention is cured with ultraviolet rays or the like, nitrogen substitution is preferably used in order to prevent radical polymerization from being inhibited by oxygen. The residual oxygen concentration during UV curing is preferably 5% by volume or less, more preferably 1% by volume or less.

 The hard coat layer used in the present invention further includes a colorant (pigment, dye), an antifoaming agent, a thickening agent, a leveling agent, an antistatic agent, a flame retardant, an ultraviolet absorber, an antioxidant and a modification agent. Conventionally known additives such as resins for use may be added.

 The hard coat layer coating solution used in the present invention is preferably prepared using an organic solvent as a medium. Examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), Aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydride) Furan), ether alcohols (e.g., 1-methoxy-2-propanol) are included. These solvents are preferably used in combination of two or more, and more preferably used in combination of three or more.

 As the coating method of the hard coat layer coating solution used in the present invention, curtain coating method, dipping method, spinner method, spray method, print coating method, roll coater method, gravure method, wire bar method, single layer or multilayer slot extrusion Known coating methods such as a coater method and a slide coater method can be used.

 For the purpose of improving the adhesion (adhesion) between the hard coat layer and the substrate used in the present invention, one or more undercoat layers can be provided as desired. The material of the undercoat layer varies depending on the material of the base material and the hard coat layer, but a copolymer such as vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, styrene, vinyl ester or latex, polyester, Examples thereof include water-soluble polymers such as polyurethane and gelatin. Further, the undercoat layer may contain a tin oxide, a metal oxide such as a tin oxide / antimony oxide composite oxide, a tin oxide / indium oxide composite oxide, or an antistatic agent such as a quaternary ammonium salt. In addition, the surface treatment method can improve adhesion by using an oxidation method or an unevenness method. Known surface treatment methods include chemical treatment, mechanical treatment, corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, high-frequency treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, and electron beam irradiation treatment. , Active plasma treatment, oxalic acid treatment, etc., and each treatment condition is preferably carried out according to the heat resistance and chemical resistance of the substrate.

 The hard coat treated article used in the present invention has a functional layer having various functions such as an ultraviolet / infrared absorbing layer, a selective wavelength absorbing layer, an electromagnetic wave shielding layer, and an antifouling layer on the front and / or back, a plastic film and a hard coat. It can be provided between the layers. Furthermore, a light reflection preventing layer and a heat ray reflection preventing layer can be provided on the surface of the hard coat treated article, and these functional layers can be prepared by a conventionally known technique. Moreover, surface treatment can be given in the meaning which improves the adhesiveness of these functional layers and the hard-coat layer used by this invention, or an undercoat layer can be provided. As the surface treatment method, the undercoat layer applied on the base material described above or the treatment described in the surface treatment can be preferably used.

Circularly polarized light function, light diffusing function The high hardness layer in the present invention may have a circularly polarized light function or a light diffusing function. Here, in order to impart the circular polarization function, for example, as the high hardness layer, for example, RD-Type manufactured by Sanlitz Co., Ltd., MCPL or MCPR manufactured by Bikan Imaging Co., Ltd., or manufactured by 3M USA HNCP37L or HNCP37R can be used. On the other hand, in order to provide the light diffusion function, for example, a UA film made by Fujifilm can be used as the high hardness layer. By adopting such means. It is not necessary to provide a high hardness layer and a circularly polarizing plate or a light diffusing plate separately, and the layer configuration can be simplified.

(Gas barrier film)
The gas barrier film in the present invention is a film having a barrier layer having a function of blocking oxygen and moisture in the atmosphere. The barrier layer in the present invention may be any layer as long as it is known to have gas barrier ability, but is preferably an organic-inorganic laminated type in which organic regions and inorganic regions or organic layers and inorganic layers are alternately laminated. . Hereinafter, a film having an organic-inorganic laminated barrier layer in which organic regions and inorganic regions or organic layers and inorganic layers are alternately laminated may be referred to as an “organic-inorganic laminated gas barrier film”.
Organic regions and inorganic regions or organic layers and inorganic layers are usually laminated alternately. In the case of an organic region and an inorganic region, a so-called gradient material layer in which each region continuously changes in the film thickness direction may be used. Examples of the gradient materials include a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. , American Vacuum Society) ”, or a continuous layer in which the organic layer and the inorganic layer do not have an interface as disclosed in US Published Patent Application No. 2004-46497. Hereinafter, for simplification, the organic layer and the organic region are described as “organic layer”, and the inorganic layer and the inorganic region are described as “inorganic layer”.
Although there is no restriction | limiting in particular regarding the number of layers which comprises a cas barrier film, Typically 2-30 layers are preferable, and 3-20 layers are more preferable. In addition, the barrier layer may be provided only on one side of the plastic film, or may be provided on both sides.

(Base film)
In the present invention, a plastic film is usually used as the base film. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specifically, as the plastic film, 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, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin Examples thereof include thermoplastic resins such as filn copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the laminated film of the present invention is used as a substrate for 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. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 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 Patent Application Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), 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 laminated film of the present invention is used in combination with a polarizing plate, the gas barrier film is preferably disposed on the innermost side (adjacent to the element) so that the barrier layer of the gas barrier film faces the inner side of the cell. At this time, since the laminated film is disposed inside the cell from the polarizing plate, the retardation value of the laminated film is important. The usage form of the laminated film in such an embodiment is that a laminated film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate) + linear polarizing plate ), Or a laminated film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate, is preferably used in combination with a linear polarizing plate.

As a base film having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR Co., Ltd.) ): Arton, Nippon Zeon Co., Ltd .: Zeonoa), 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.

Since the laminated film of the present invention is used as a device such as an organic EL element, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90% or more. It is. 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 laminated film of the present invention is used for display, 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 thickness of the plastic film used for the laminated film of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

(Inorganic layer)
The inorganic layer is usually a thin film layer made of a metal compound. 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, a coating method, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable, and specifically, Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. The described forming method can be employed.
The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but for example, one or more selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, or the like An oxide containing metal, nitride, carbide, oxynitride, oxycarbide, nitride carbide, oxynitride carbide, or the like 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.
Although it does not specifically limit regarding the thickness of the said inorganic layer, It is preferable to exist in the range of 5 nm-500 nm, More preferably, it is 10 nm-200 nm. Two or more inorganic layers may be laminated. In this case, each layer may have the same composition or a different composition. Further, as described above, a layer whose interface with the organic layer is not clear as disclosed in US Patent Publication No. 2004-46497 and whose composition changes continuously in the film thickness direction may be used.

(Organic layer)
The organic layer is usually a polymer layer. Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, polysiloxane, other organic It is a layer of a silicon compound. The organic layer may consist of a single material or a mixture. Two or more organic layers may be laminated. In this case, each layer may have the same composition or a different composition. Further, as described above, as disclosed in US 2004-46497, the interface with the inorganic layer is not clear and the layer may be a layer whose composition changes continuously in the film thickness direction.

The organic layer is preferably smooth and has a high film hardness. The smoothness of the organic layer is preferably 10 nm or less, and more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm square. The film hardness of the organic layer preferably has a pencil hardness of HB or higher, and more preferably H or higher.
The film thickness of the organic layer is not particularly limited, but if it is too thin, it will be difficult to obtain film thickness uniformity, and if it is too thick, cracks will be generated by external force and the barrier performance will deteriorate. From this viewpoint, the thickness of the organic layer is preferably 10 nm to 2000 nm, more preferably 100 nm to 1000 nm.

 Examples of the method for forming the organic layer include a normal solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294. It can apply | coat by the extrusion-coating method which uses-. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable. In the present invention, a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in Japanese Patent Application Laid-Open Nos. 2000-323273 and 2004-25732 may be used. Alternatively, a polymer layer may be formed by polymerizing a polymer precursor (for example, a polymerizable compound) and then polymerizing it.

In the present invention, the organic layer is preferably composed of a radical polymerizable compound and / or a polymer of a cationic polymerizable compound having an ether group as a functional group.
(Polymerizable compound)
The polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain and / or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds (acrylates and methacrylates are collectively referred to as (meth) acrylates), acrylamide compounds, styrene compounds, and anhydrous maleic compounds. An acid etc. are mentioned.

As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

Although the specific example of a (meth) acrylate type compound is shown below, this invention is not limited to these.

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. When performing heat polymerization, the plastic film used as a base material needs to have appropriate heat resistance. In this case, it is necessary that at least the glass transition temperature (Tg) of the plastic film is higher than the heating temperature.
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), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, commercially available from Sartomer). Etc.).
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. 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.

 At this time, the polymerization rate of the monomer is preferably 80% or more, more preferably 85% or more, and further preferably 90% 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.

(Protective layer)
The laminated film of the present invention is characterized in that barrier properties can be realized without providing a plurality of protective layers, or without providing any protective layers, but has a protective layer (passivation layer). May be. Examples of the protective layer include SiOx, SiNx, SiOxNy, SiC, AlOx and the like.
(Functional layer)
The laminated film in the present invention may have another functional layer on the barrier layer. As an example of the functional layer, a layer similar to that described in the section of the plastic film is used.

(Embodiment of laminated film)
The laminated film of the present invention can be preferably used for a light emitting device or a display device. Examples of the light emitting element or the display element include an organic EL element and a touch panel.
Hereinafter, preferred embodiments of a light emitting device or a display device using the laminated film of the present invention will be described with reference to the drawings. Needless to say, the present invention is not limited to these examples.

  FIG. 1 is an example in which the laminated film of the present invention is used for an organic EL element, wherein 1 is a gas barrier film, 2 is a low hardness layer, 3 is a high hardness layer, and 4 is an organic EL element. Yes. Conventionally, when a high hardness film is provided on the organic EL element, the organic EL element 24 and the high hardness film 23 as shown in FIG. The space 25 and the spacer 26 are provided between them. However, in the configuration as shown in FIG. 2, the entire thickness is increased, the structure for providing the space is complicated, and the component cost is increased. The space is distorted by the external pressure, and the EL element and the film are in contact with each other. As a result, there are problems such as scratches and no light emission, and the necessity of providing a hygroscopic agent to adsorb moisture in the space. The present invention is extremely significant in that this point is eliminated.

  FIG. 3 is an example in which the laminated film of the present invention is used for a touch panel, and shows a transparent substrate 36, an electrode and display material layer 37, a substrate 31, a cushion layer 32, and a substrate 33 in order from the top. Here, the touch panel element 38 is configured by the transparent electrode 36, the electrode and display material layer 37, and the substrate 31, and the organic EL element 34 is configured by the substrate 33 and the electrode. Here, the laminated film 39 in the present invention includes a touch panel element substrate 31, a cushion layer 32, and an organic EL element substrate 33. That is, the substrate 31 of the touch panel element 38 corresponds to a high hardness layer, the cushion layer 32 corresponds to a low hardness layer, and the substrate 33 of the organic EL element corresponds to a gas barrier film. In the case of this configuration, the cushion layer is usually a gel-like substance. Note that the electrodes and spacers 37 in FIG. 3 are appropriately changed according to the touch panel system.

  In addition, a film laminate in which gas barrier film / thin film transistor layer / reflecting electrode / light emitting material layer or display material layer / transparent electrode / passivation layer / adhesive layer / gas barrier film are laminated in order, or in order gas barrier film / thin film transistor layer / Low hardness layer and high hardness directly or indirectly outside the light emission side barrier film (underline) of the light emitting material layer or display material layer / reflecting electrode / adhesive layer / gas barrier film laminated film It can be set as the light emitting element or display element which provided the laminated | multilayer film which provided the layer. Such a light-emitting element or display element can significantly reduce the probability of the element breaking when an external impact is applied.

Hereinafter, the light-emitting element or display element used in the present invention will be described in more detail.
<Organic EL device>
The laminated film of the present invention can be preferably used for an organic EL device. An organic EL element has a cathode and an anode on a substrate, and an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. Due to the nature of the light emitting element, at least one of the anode and the cathode is transparent.

 As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.

Next, each element which comprises an organic EL element is demonstrated in detail.
(substrate)
The board | substrate used for the well-known organic EL element can employ | adopt widely as a board | substrate used for the organic EL element in this invention. The substrate may be a resin film or a gas barrier film. The gas barrier films described in JP-A No. 2004-136466, JP-A No. 2004-148666, JP-A No. 2005-246716, JP-A No. 2005-262529, and the like can also be preferably used.
Although the thickness of the board | substrate used by this invention is not prescribed | regulated in particular, 30 micrometers-700 micrometers are preferable, More preferably, they are 40 micrometers-200 micrometers, More preferably, they are 50 micrometers-150 micrometers. Further, in any case, the haze is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 90%. That's it.

(anode)
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode. The transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Electrode Film” published by CMC (1999). When using a substrate having low heat resistance as the substrate, ITO or IZO is used, and a transparent anode formed at a low temperature of 150 ° C. or lower is preferable.

(cathode)
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.

 Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, a material mainly composed of aluminum is preferable.
The material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The cathode material is described in detail in JP-A-2-15595 and JP-A-5-121172. Further, a dielectric layer made of a fluoride or oxide of an alkali metal or a Group 2 metal may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(Organic compound layer)
The organic EL element has at least one organic compound layer including a light emitting layer, and as the organic compound layer other than the organic light emitting layer, as described above, a hole transport layer, an electron transport layer, a charge blocking layer , Hole injection layer, electron injection layer and the like.

-Organic light emitting layer-
The organic light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, and receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines the holes and electrons. It is a layer having a function of providing light and emitting light. The light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of the fluorescent light-emitting material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyralidine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Typical examples include ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives. Various metal complexes are, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.
Although it does not specifically limit as said transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

  Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.

  Examples of the host material contained in the light emitting layer include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. And materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. In addition, the electron transport layer / electron injection layer may also function as a hole blocking layer.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
In addition, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer / hole injection layer may also serve this function.

(Protective layer)
The entire organic EL element is preferably protected by a protective layer.
As a material contained in the protective layer, a material that has a function of preventing elements such as moisture and oxygen from accelerating element deterioration from entering the element, or that imparts flatness to the surface of the organic EL element It is.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal carbides such as SiC _w and SiO _z C _w , MgF ₂ , LiF, AlF ₃ , and CaF ₂ Metal fluorides such as polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoro Copolymerization obtained by copolymerizing a monomer mixture containing ethylene and at least one comonomer , Copolymerization main chain fluorine-containing copolymer having a cyclic structure, 1% by weight of the water absorbing material water absorption, water absorption of 0.1% or less of the moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the MBE (molecular beam epitaxy) method, the cluster ion beam method, the ion plating method, the plasma polymerization method ( High frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Touch panel>
The laminated film of the present invention can be preferably used for a touch panel. The main touch panel types and features are described below.
(Resistive film type)
In this structure, a transparent conductive film is formed on the opposing surfaces of the upper film and the lower glass, and bonded through a spacer. When pressed with a finger, the upper film and the lower glass conductive film come into contact with each other to detect the position. A strip-shaped electrode is placed so that one side is perpendicular to the X-axis direction and the other side is perpendicular to the Y-axis direction. There is an “analog resistance film system” that reads an electrical change caused by conduction with a uniform resistance film.

(Optical (infrared) method)
Infrared rays are emitted from the edge of the screen at equal intervals, and an infrared net is formed on the screen. This is a method of detecting a location where light is blocked by XY coordinates. It is used in ATMs at banks and ticket machines at stations. The optical system has a high light transmittance and a long life, but due to its structure, it reacts even when it is not in direct contact with a dimension stop, or it reacts with anything other than a finger.

(Capacitance method)
A weak current is applied to the entire panel surface. When a finger touches the panel surface, electricity flows to the human body, the amount of charge changes, and this change detects the position. It is mainly used for game consoles and convenience store ticket sales terminals. The capacitance type utilizes the fact that electricity flows through the human body, so it does not react even when touched with a glove or with a pen.

(Surface acoustic wave method)
It was developed to solve the low transparency, which is a drawback of the resistive film system. A piezoelectric element is attached to a highly rigid (mainly glass) plate, and the plate is vibrated. When touching the plate, the vibration rebounds there and reaches the piezoelectric element to generate a voltage. By measuring the time when the reflected vibration returns after applying the vibration, the operated place can be detected.
The object that covers the screen is only one glass plate, and a device that is more visible than the resistive film method can be made. In addition, it is structurally more robust and has a longer life than the resistive film method.

(Ultrasonic method)
There are countless diagonal notches on the four sides of the glass, and ultrasonic waves are transmitted toward the notches, reflected by the notches on the opposing sides, and received by the receiver. The pressed position is detected by the finger absorbing this high-frequency vibration. The ultrasonic method is excellent in durability.

The touch panel is an inner touch panel, and is composed of light source / polarizer / liquid crystal / touch panel / analyzer / surface in this order, and is a resistive film type having a structure in which the position of the analyzer is changed in the liquid crystal display device to improve visibility. It is a touch panel. In addition, there is a type of touch panel configured in the order of light source / polarizer / liquid crystal / analyzer / touch panel / surface.
The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

  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
(Preparation of organic / inorganic laminated gas barrier film)
As the base film, a polyethylene naphthalate (PEN) film (thickness: 200 μm) commercially available from Teijin DuPont under the trade name Teonex Q65FA is used, and the following organic and inorganic layers are used on the smooth surface side. A gas barrier layer was applied.

Using an organic / inorganic laminated film forming apparatus (Guardian 200) manufactured by Vitex Systems, an ultraviolet-curing polymer precursor (manufactured by Vitex Systems, BRS-0101) is flash-deposited on the smooth surface side of the base film. Then, ultraviolet rays were irradiated for polymerization to form an organic layer. The film thickness was 1.1 μm. The irradiation energy of ultraviolet rays for polymerization was ² J / cm ² .
Here, Guardian 200 is an apparatus capable of producing an organic / inorganic laminated gas barrier layer. Since the organic layer and the inorganic layer are formed in a vacuum consistently, they are not released to the atmosphere until the gas barrier layer is completed.
Subsequently, an inorganic layer was formed on the organic layer using an organic / inorganic laminated film forming apparatus (Guardian 200) without removing the base film from the vacuum. The inorganic layer is an aluminum oxide film formed by a reactive sputtering method (reactive gas is oxygen) using a direct current pulse targeting aluminum. The film thickness of the obtained inorganic layer was 40 nm.
The above operation is repeated, and from the side close to the base film, an organic layer and an inorganic layer are laminated in order of four organic layers and three inorganic layers, and an organic-inorganic laminated gas barrier film (pencil hardness: H ) Was produced.

(Production of laminated film)
A thickness of the thermoplastic resin layer described in paragraph No. 0146 of JP-A-2006-208480, which is a cushioning material, as a low-hardness layer on the surface of the organic-inorganic laminated gas barrier film prepared above. However, as a high-hardness layer, an ultraviolet curable antistatic hard coat agent, SHIKO UT-3806 is used as the high hardness layer, and the thickness is 2 μm. Then, it was cured by irradiating with an ultraviolet irradiation lamp to obtain a laminated film. The pencil hardness of the low hardness layer was B, and the pencil hardness of the high hardness layer was 3H.

Example 2
(Production of organic EL element)
A hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer are sequentially provided on an ITO glass substrate subjected to oxygen plasma treatment, and the cathode is patterned with a shadow mask. Provided. Each layer was provided by resistance heating vacuum deposition.
The oxygen plasma conditions and the structure of each layer are as follows.
Oxygen plasma conditions: O ₂ flow rate = 10 sccm, RF power 200 W, treatment time 1 minute.
Hole injection layer: 4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine (abbreviated as 2-TNATA), thickness 140 nm.
Hole transport layer: N, N′-dinaphthyl-N, N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine (abbreviated as α-NPD), thickness 10 nm.
Light-emitting layer: 4,4′-bis- (9-carbazolyl) -biphenyl (abbreviated as CBP) and fac-tris (2-phenylpyridinato-N, C2 ′) iridium (III) (Ir (ppy) ₃ Abbreviated to CBP), and a thickness of 20 nm.
Hole blocking layer: bis (2-methyl-8-hydroxyquinolinato) -4-phenylphenolato aluminum (III) (abbreviated as BAlq), thickness 10 nm.
Electron transport layer: tris (8-hydroxyquinolinato) aluminum (abbreviated as Alq ₃ ), thickness 20 nm.
Electron injection layer: LiF, thickness 1 nm.
Cathode (upper electrode): Al, thickness 200 nm. The crossing area (light emitting part area) between the ITO electrode and the Al electrode is 2 mm × 2 mm.

(Attaching organic / inorganic laminated gas barrier film)
A protective film (SiN _x film, thickness 2 μm) was formed by plasma CVD (PECVD) on the cathode of the organic EL element produced above. The organic / inorganic laminated gas barrier film provided with the high hardness layer and the low hardness layer prepared above on the protective film is a thermosetting adhesive such as ThreeBond Co., Ltd. so that the base film side is in contact with the protective film side. It was pasted using an adhesive sheet made of).

Example 3
In the organic EL device produced in Example 2, the substrate of the organic EL device was changed to the organic / inorganic laminated gas barrier film produced above, and the others were carried out in the same manner to produce an organic EL device. On the obtained organic EL element, an organic-inorganic laminated gas barrier film provided with a protective film and a high hardness layer and a low hardness layer was provided in the same manner as in Example 2.

Example 4
In the laminated film produced in Example 1, a thermosetting adhesive (manufactured by ThreeBond, 20X-325C was applied to the side opposite to the side on which the high hardness layer was provided to provide an adhesive layer. A laminated film provided with a protective film and the adhesive layer in the same manner as in Example 2 was bonded onto the produced organic EL element so that the protective layer and the adhesive layer were in contact with each other.

Example 5
A laminated film was produced in the same manner as in Example 1 except that the high hardness layer was replaced with a circularly polarizing plate (MCPL, manufactured by Bikan Imaging Co., Ltd.), and an organic EL device was produced in the same manner as in Example 2. Obtained.

Example 6
A laminated film was produced in the same manner as in Example 1 except that the high-hardness layer was replaced with a light diffusion film (manufactured by Fuji Film Co., Ltd., UA film). An EL element was obtained.

(Evaluation of organic EL elements)
The device was placed on a table with the light emitting side surface of the organic EL device obtained in Examples 2 to 6 as the upper surface. The pachinko sphere was dropped 30 times from a height of about 20 cm, and after storing for 100 hours in an environment of 60 ° C. and 90% RH, the degree of change in the light emission state was visually observed.
Further, as Comparative Example 1, an organic EL element was prepared by the method described in Example 2 using the organic / inorganic laminated gas barrier film prepared in Example 1 (no high hardness layer and low altitude layer provided). The evaluation was made in the same manner as described above.
As a result, the organic EL elements of Examples 2 to 6 did not change before and after storage for 100 hours, but the light emitting state of the organic EL element of Comparative Example 1 was significantly reduced.
Further, in Example 1, an organic / inorganic laminated gas barrier film was used in which the base film was replaced with a polyethylene terephthalate (PET) film (thickness: 200 μm) marketed by Toray Industries under the trade name Lumirror T60. When the organic EL element was produced by the method described in 2, the same result as in Example 2 was obtained.

Example 7
(Production of touch panel)
Using the laminated film produced in Example 1, a touch panel was produced according to the description in JP-A No. 5-127822.

  Since the laminated film of the present invention is already provided with a low-hardness layer and a high-hardness layer, a light-emitting element or a display element can be produced using a conventional light-emitting element or display element production apparatus. That is, when a general element manufacturer provides a low-hardness layer and a high-hardness layer, it was necessary to add a new equipment for a coating machine or a laminator in addition to a normal element manufacturing apparatus. There is no problem. In addition, when the manufacturer of the device handles the gas barrier film, if the gas barrier film is too thin, there is a problem that trouble is likely to occur due to material handling (automatic conveyance) in the process equipment. Further, by providing a useful layer of a high hardness layer, there is an advantage that the thickness can be adjusted. Furthermore, since the laminated film of the present invention is strong in the film, handling properties are improved, handling by automatic conveyance is easy, yields can be improved, and process costs can be reduced.

FIG. 1 shows an example of an embodiment in which the laminated film of the present invention is used for an organic EL element. FIG. 2 shows a conventional example in which a film having high hardness is used for the organic EL element. FIG. 3 shows an example of an embodiment in which the laminated film of the present invention is used for a touch panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Low hardness layer 3 High hardness layer 4 Organic EL element 23 High hardness film 24 Organic EL element 25 Space 26 Spacer 31 Substrate 32 Cushion layer 33 Substrate 34 Organic EL element 36 Transparent substrate 38 Touch panel element 39 Multilayer film

Claims (14)

A layer having a hardness lower than that of the gas barrier film and a layer having a hardness higher than that of the gas barrier film are laminated in this order on the surface of the gas barrier film having the barrier layer provided on at least one side of the base film. Laminated film. The thickness of the gas barrier film is 25 to 4000 μm, the thickness of the layer having a lower hardness than the gas barrier film is 5 to 2000 μm, and the thickness of the layer having a higher hardness than the gas barrier film is 1 to 1000 μm. Item 2. The laminated film according to Item 1. The laminated film according to claim 1 or 2, wherein the layer having a higher hardness than the gas barrier film has a circular polarization function. The laminated film according to claim 1 or 2, wherein the layer having a higher hardness than the gas barrier film has a light diffusion function. The laminated film according to any one of claims 1 to 4, wherein an adhesive layer is provided on the outermost surface opposite to the surface provided with a layer having a higher hardness than the gas barrier film and a layer having a lower hardness than the gas barrier film. The gas barrier film according to any one of claims 1 to 5, wherein the layer having a hardness higher than that of the gas barrier film includes a hard coat material as a main component. The gas barrier film according to any one of claims 1 to 6, wherein the layer having a lower hardness than the gas barrier film has a gel-like substance as a main component. The laminated film according to claim 7, which is used for a touch panel. The laminated film according to any one of claims 1 to 8, wherein the barrier layer has at least one organic region and at least one inorganic region. A substrate, a pair of electrodes provided on the substrate, an organic compound layer provided between the electrodes, and an electrode provided on the electrode opposite to the side on which the organic compound layer is provided The laminated film according to any one of items 1 to 9, and the laminated film is provided so that a side opposite to a side on which a layer having higher hardness than the gas barrier film is provided is close to an electrode. A light emitting element or a display element. Furthermore, the light emitting element or display element of Claim 10 with which the protective layer is provided between the electrode and the laminated | multilayer film of any one of Claims 1-9. The light emitting element or the display element according to claim 10 or 11, wherein the light emitting element or the display element is a touch panel. The light emitting element or display element of Claim 10 or 11 whose said light emitting element or display element is an organic EL element. A layer having a hardness lower than that of the gas barrier film and a layer having a hardness higher than that of the gas barrier film are laminated in this order on the surface of the gas barrier film having the barrier layer provided on at least one side of the base film. The manufacturing method of laminated | multilayer film including doing.

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