KR102161963B1 - Transparent stacked film, transparent conductive film, and gas barrier stacked film - Google Patents

Abstract

A new transparent conductive film having excellent transparency and thermal dimensional stability at high temperatures (eg, 200° C. or higher) and low surface resistance value is provided. Furthermore, a new transparent laminated film and a gas barrier laminated film that can be used for the base film of the transparent conductive film and other various transparent substrates are provided.
A transparent conductive film in which a transparent conductive layer is formed on one or both of the crosslinked resin layer of a transparent laminated film having a crosslinked resin layer on at least one side of the base film, either directly or via an undercoat layer made of a resin material, wherein the transparent The laminated film is characterized by first having a heat shrinkage of 1.5% or less when heated at a temperature of 200°C for 10 minutes in a vertical direction and a horizontal direction, and the surface resistance value of the transparent conductive film is 150 Ω/□ or less. A transparent conductive film characterized by 2 is proposed.

Description

A transparent laminated film, a transparent conductive film, and a gas barrier laminated film TECHNICAL FIELD [TRANSPARENT STACKED FILM, TRANSPARENT CONDUCTIVE FILM, AND GAS BARRIER STACKED FILM}

The present invention relates to a transparent laminated film that can be used as a substrate material for, for example, a solar cell, an organic solar cell, a flexible display, an organic EL lighting, and a touch panel, and further comprises a transparent conductive film and a gas barrier layer having conductivity. It relates to a gas barrier laminated film.

Conventionally, a glass material has been used as a substrate material for various display devices such as organic EL and solar cells. However, the glass material was not only fragile, heavy, and had drawbacks such as difficulty in thinning, and it could not be said that it was a sufficient material for the recent thinning and weight reduction of the display and the flexibility of the display. Therefore, as a substitute material for glass, a thin and lightweight transparent resin film-shaped substrate is being studied.

In such applications, when a film-shaped resin substrate is used, high heat resistance is required for the film. For example, in the case of forming a circuit such as a TFT on a resin film, in order not to cause a pattern misalignment during circuit formation, the resin film used for this type of application has high dimensional stability around 200°C, which is the heat treatment temperature of the TFT. Is required.

Regarding the resin film having the gas barrier property, in order not to damage the function including the gas barrier property by destroying the functional layer as a result of cracking or wrinkling the functional layer having the gas barrier property, 150 Thermal dimensional stability under a high temperature atmosphere of ℃ or higher is required.

However, conventional conventional polyester films and the like have insufficient thermal dimensional stability in a high temperature atmosphere of 150°C or higher, specifically, a high temperature atmosphere of 150°C to 200°C. Therefore, in recent years, as a film for gas barrier processing or a film for a flexible display substrate, a resin film having high thermal dimensional stability is required.

As a means for imparting dimensional stability in a high-temperature atmosphere to a resin film, for example, in Patent Document 1, a method of adding heat relaxation treatment (also referred to as ``annealing treatment'' or ``heat set treatment'') as a final means of the film manufacturing process Is disclosed.

In addition, in Patent Documents 2 and 3, a method of forming various coating films on the surface of a film produced by a normal process is disclosed.

When a transparent conductive film, such as a metal oxide film such as ITO (indium tin oxide), is formed on a film made of a transparent resin, the film is usually sputtered at room temperature, and thus amorphous property is high. Therefore, formation of a transparent conductive film on a transparent resin film was significantly inferior in terms of surface resistance value, durability, acid resistance, and the like, as compared to that of forming a transparent conductive film such as an ITO film on a glass substrate. Therefore, in recent years, a transparent conductive film having improved crystallinity of the transparent conductive film is required.

As a means of improving the crystallinity of a transparent conductive film such as an ITO film, for example, in Patent Document 4, a method of crystallizing ITO by performing heat treatment after forming an ITO film on a polymer film substrate is disclosed. Patent Document 5 In the above, a crystallization method by irradiation of microwaves onto an ITO film is disclosed.

On the other hand, Patent Document 6 discloses a transparent electrode substrate for solar cells using a resin molded article obtained by curing a photopolymerizable composition. Since this resin molded article has high heat resistance, it is possible to increase the substrate temperature to 150°C when forming the transparent electrode layer.

In addition, Patent Document 7 discloses a transparent conductive film having an organic layer on both sides of a polymer film as a transparent conductive film, an inorganic layer on at least one side of the organic layer, and further having a transparent conductive layer on the outermost layer. have. Since this transparent conductive film has flexibility that cracking is difficult to occur even if the thickness of the conductive layer is increased, the surface resistance value can be lowered by making the thickness of the conductive layer relatively thick.

Patent Literature 8 discloses a composite film for an electronic device comprising a coated polyester substrate layer and an electrode layer containing a conductive material. This composite film has improved flexibility of the coated polyester substrate and has cracking resistance.

Patent Document 9 discloses a laminated film in which a cyclic olefin polymer layer, an anchor coating layer containing dispersed metal oxide particles, and a transparent conductive layer are laminated in this order. This laminated film has the properties that the transparent conductive layer does not generate cracks over a long period of time, maintains a low resistance value, has high strength, and is excellent in mechanical durability, and can be used for a touch panel.

In addition, as a transparent film usable for a transparent substrate, Patent Document 10 discloses a transparent laminated film having a cured layer on both the front and back sides of the base film. This transparent laminated film has properties of excellent transparency and thermal dimensionality at high temperatures, and can be used as a substrate for solar cells, organic solar cells, flexible displays, organic EL lighting, and touch panels.

In addition, as a transparent film usable for a transparent substrate, Patent Document 11 discloses a composite film having a barrier layer formed on the surface of such a coating layer as a film including a polymer substrate and a planarization coating layer. This composite film has high dimensional stability since the polymer substrate is heat set and heat stabilized.

Patent Document 12 discloses a transparent multilayer sheet comprising a layer having an average linear expansion coefficient of 50 ppm/K or less (layer A) and a layer having a tensile modulus of 1 GPa or less (layer B). More specifically, a transparent multilayer sheet composed of three layers of B layer/A layer/B layer and the like is disclosed, and such a multilayer sheet has a total light transmittance of 91% and an average coefficient of linear expansion of 43 ppm/K, and transparency and dimensional stability It is disclosed that this is excellent.

In Patent Document 13, on both surfaces of a film (I) having a cyclic olefin polymer, a particle-containing layer (II) formed by using a curable composition containing oxide particles surface-modified with a specific compound and a polymerizable unsaturated group having a specific structure is provided. It is disclosed about a laminated film obtained by laminating such a particle-containing layer (II) in the range of 0.1 to 30 with respect to the film thickness of 100 of the film (I).

Patent Document 14 discloses polyimide, polyamide, etc. having high dimensional stability at high temperatures and high transparency. Since these are formed into a film by the casting method, there is almost no orientation, so that shrinkage when heated does not occur.

As a method of improving the gas barrier property, a method of improving oxygen and water vapor permeability has been proposed by laminating a polyester film with an inorganic transparent film such as silicon oxide or an ultrathin layer by vacuum evaporation or sputtering. Yes (see, for example, Patent Document 15).

Japanese Patent Laid-Open No. 2008-265318 Japanese Patent Laid-Open No. 2001-277455 Japanese Patent No. 2952769 Japanese Patent Laid-Open No. 2-194943 Japanese Patent Publication No. 2005-141981 Japanese Patent Application Laid-Open No. 2008-85323 Japanese Patent Laid-Open No. 2000-353426 International Publication No. 09/016388 Pamphlet Japanese Patent Publication No. 2009-029108 International Publication No. 13/022011 Pamphlet Japanese Patent Publication No. 2011-518055 Japanese Patent Laid-Open No. 2007-298732 Japanese Patent Laid-Open No. 2010-23234 Japanese Patent Laid-Open Publication No. 61-141738 Japanese Patent Application Publication No. 2006-96046

As described above, in order to lower the surface resistance value of the transparent conductive film made of ITO or the like, it is necessary to increase the crystallinity of the transparent conductive film, and as one of the means for this, by forming the transparent conductive film at a high temperature, the determination of the transparent conductive film A means to increase sex is thought. For example, if the formation of a transparent conductive film by sputtering, which is usually performed at room temperature, can be formed by sputtering in a high temperature atmosphere, for example, in a temperature atmosphere of 150 to 220°C, the crystallinity of the transparent conductive film can be improved.

However, since biaxially stretched PET films or the like generally used as a base film are heat-shrinkable under such a high-temperature atmosphere, there is a problem that a transparent conductive film cannot be formed in a high-temperature atmosphere. However, if a completely new material having excellent thermal dimensional stability is used, various unexpected problems may occur, as well as problems such as an increase in cost.

Therefore, it is an object of the present invention to provide a transparent conductive film having a new configuration that can improve thermal dimensional stability in a high-temperature atmosphere, such as an atmosphere of 200° C. or higher, and further lower the surface resistance value.

Moreover, not only can it be manufactured by a simpler manufacturing process, but also under a future use environment, a thin resin film is required to have a higher heat resistance film.

Therefore, an object of the present invention is also to provide a new transparent laminated film which is excellent in transparency and thermal dimensional stability at high temperatures, such as 200°C or higher, and can, nevertheless, reduce the thickness of the film.

In addition, in the case of using a film using the gas barrier property improvement method, the polyester film as the base material shrinks in the heating annealing process required when forming a transparent electrode or element on the film, thereby reducing the gas barrier property. There was a possibility of losing it. In this way, not only can it be manufactured in a simpler manufacturing process, but also under a future use environment, development of a film having high heat resistance and excellent gas barrier properties is required.

Accordingly, an object of the present invention is also to provide a gas barrier laminated film having excellent gas barrier properties and thermal dimensional stability at a high temperature such as 150°C or higher.

The present invention is provided with a transparent laminated film having a crosslinked resin layer on both sides of a base film, and provided with a transparent conductive layer directly or via a undercoat layer on one or both sides of the front and back of the transparent laminated film, A transparent conductive film in which the total thickness of the crosslinked resin layer is 8% or more of the thickness of the base film,

The transparent laminated film is characterized in that the heat shrinkage when heated at 200°C for 10 minutes in the vertical direction and the horizontal direction is 1.5% or less, and the surface resistance value of the transparent conductive film is 150Ω/□ or less. , Propose a transparent conductive film.

The transparent conductive film proposed by the present invention has a crosslinked resin layer on both front and back sides of the base film, and the total thickness of these crosslinked resin layers is 8% or more of the thickness of the base film. Even if it tries to shrink, since the crosslinked resin layer resists this and the entire transparent conductive film can withstand the shrinkage stress, thermal dimensional stability as a transparent conductive film can be improved. Specifically, in the longitudinal direction and the transverse direction, the thermal dimensional stability of 1.5% or less of the thermal contraction rate when heated at 200°C for 10 minutes can be obtained.

Therefore, since the transparent conductive film proposed by the present invention can form a transparent conductive layer in a high temperature atmosphere such as 150 to 220°C, the crystallinity of the transparent conductive layer can be improved, and the surface resistance value of the transparent conductive film can be increased. Can be effectively lowered.

Since the transparent conductive film proposed by the present invention can obtain the above advantages, for example, display materials such as liquid crystal displays, organic light emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, and backlights. It can be suitably used for photovoltaic device substrates, in addition to substrates for solar cells and substrates for solar cells.

Further, the transparent conductive film proposed by the present invention can be used for applications requiring dimensional stability at high temperatures, such as films for electronic components. Further, by performing gas barrier processing, it can also be suitably used for semiconductor devices such as organic EL, liquid crystal display elements, and solar cells.

The present invention is also a laminate film having a crosslinked resin layer on both sides of the base film,

The first feature is that the crosslinked resin layer is formed using a curable composition containing a photopolymerizable compound, a photopolymerization initiator, and fine particles, and the thickness of the base film and the crosslinked resin layer satisfies the following (a) and (b). And

The thermal contraction rate of the laminated film in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200°C for 10 minutes is 70 of the thermal contraction rate when the base film is heated under the same conditions. % Or less, and a transparent laminated film having a total light transmittance of 80% or more of the laminated film is proposed.

(a) The thickness of the base film is 75 μm or less

(b) The total thickness of both sides of the crosslinked resin layer is 8% or more of the thickness of the base film

The transparent laminated film proposed by the present invention has a structure in which a crosslinked resin layer formed by using a curable composition containing a specific material is laminated at a specific thickness on both sides of a base film of a specific thickness, so that transparency and It has the property of extremely excellent thermal dimensional stability under high temperature (eg 200°C or higher).

In addition, in the transparent laminated film proposed by the present invention, since the crosslinked resin layers provided on both sides of the base film can withstand the stress that tends to shrink when the base film is at high temperature, dimensional change due to heat treatment while maintaining transparency. There is an advantage of less (thermal dimensional stability).

Therefore, the transparent laminated film proposed by the present invention is, for example, a substrate of a display material such as a liquid crystal display, an organic light emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, and a backlight, or a substrate of a solar cell. In addition, it can be suitably used for a photoelectric device substrate or the like.

In addition, since the transparent laminated film proposed by the present invention has the above advantages, it can be used for applications requiring dimensional stability at high temperatures, especially packaging films and films for electronic parts, and by performing gas barrier processing, thereby providing organic EL It can also be suitably used for semiconductor devices, such as a liquid crystal display element, and solar cell applications.

Further, the present invention further comprises a base film, a crosslinked resin layer on both sides of the base film, and a gas barrier layer on at least one side of the crosslinked resin layer, and the total thickness of the front and back sides of the crosslinked resin layer is As a gas barrier laminated film having a configuration of 8% or more of the thickness,

The first feature is that the crosslinked resin layer is formed using a photopolymerizable compound, a photopolymerization initiator, and a curable composition containing fine particles, and the average particle diameter of the fine particles is in the range of 1 nm to 50 nm,

The second feature is that the thickness of the gas barrier layer is in the range of 5 to 100 nm,

A gas-barrier laminated film, which is characterized in that the water vapor transmittance of the entire film is 1.0 × 10 ^-2 g/m ² /day or less, is proposed.

The gas barrier laminated film proposed by the present invention has a crosslinked resin layer and a gas barrier layer in a specific configuration, and by adjusting the thickness of the crosslinked resin layer material and the gas barrier layer, the gas barrier property and high temperature ( For example, dimensional stability at 150°C or higher) is high, and shrinkage or the like is difficult to occur even after heat treatment.

In addition, the gas barrier laminated film proposed by the present invention has a crosslinked resin layer and a gas barrier layer that improves thermal dimensional stability on both sides of the base film, thereby exhibiting high transparency and dimensional change due to heat treatment. It has the advantage of being few and also having gas barrier properties. Therefore, the gas barrier laminated film proposed by the present invention is, for example, a liquid crystal display, an organic light emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, a substrate of a display material such as a backlight, or a solar cell. In addition to the substrate of, it can be suitably used for a photoelectric device substrate or the like.

Since the gas barrier laminated film proposed by the present invention has the above advantages, applications requiring dimensional stability at high temperatures, especially packaging films, films for electronic parts, semiconductor devices such as organic EL, and liquid crystals It can be suitably used for display elements and solar cells.

Next, an example of an embodiment of the present invention will be described. However, the present invention is not limited to the following embodiments.

Transparent conductive film (referred to as ``this conductive film'') according to an example of the embodiment of the present invention, transparent laminated film (referred to as ``main laminated film''), and gas barrier laminated film (referred to as ``this gas barrier film'') ) All have a common configuration of having a crosslinked resin layer on both sides of the base film.

So, in the following, first, after explaining the constituent elements common to any of the embodiments (collectively referred to as ``the present invention film''), then, next, laminated film 1 (referred to as ``this conductive film''), laminated film Each of 2 (referred to as "this laminated film") and laminated film 3 (referred to as "this gas barrier film") is described in detail.

<Base film>

As the base film in the film of the present invention, it can be arbitrarily adopted as long as it is a transparent resin film. For example, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyphenylene sulfide resin, polyethersulfone resin, polyetherimide resin, transparent polyimide resin, polycarbonate resin, cyclic olefin homopolymer or cyclic olefin And films made of cyclic olefin resins such as copolymers. A film containing a resin composed of one type or a combination of two or more of these resins can be used.

Examples of the transparent polyimide resin described above include, for example, those in which a hexafluoroisopropylidene bond is introduced into the main chain of a polyimide resin, or a fluorinated polyimide in which hydrogen in the polyimide is substituted with fluorine, as well as cyclic contained in the structure of the polyimide resin. And alicyclic polyimides obtained by hydrogenating an unsaturated organic compound. For example, those described in JP 61-141738 A, JP 2000-292635 A, and the like can also be used.

Among the above films, a film inferior in thermal dimensional stability, for example, a substrate film that is heat-shrunk in an atmosphere at a temperature of 150 to 220°C can further enjoy the effects of the present invention. From this point of view, as the base film used for the film of the present invention, it is preferable that it is a resin film containing as a main component a resin having a glass transition temperature (Tg) of 130°C or less, and among them, preferably 50°C or more or 130°C or less, and more preferably Preferably, it is preferably a resin film containing as a main component a resin of 70°C or more or 130°C or less.

Among them, a film containing polyethylene terephthalate resin as a main component and biaxially stretched is particularly preferable from the viewpoint of being generally used as a base film for a transparent conductive film and other various transparent substrates.

<Cross-linked resin layer>

In the film of the present invention, the crosslinked resin layer means a layer formed by crosslinking a curable composition to form a crosslinked structure.

In addition, in the basic application of the priority of this application, this crosslinked resin layer is also called "cured layer". This is because it is common to form by applying and "curing" a curable composition. The "cured layer" in this basic application and the "crosslinked resin layer" in this application represent the same layer.

The curable composition may be made of a photopolymerizable compound, or may contain a photopolymerization initiator, fine particles, solvent, and other components as necessary in addition to the photopolymerizable compound.

Next, each of these components will be described.

(Photopolymerizable compound)

Examples of the photopolymerizable compound include a compound having a polymerizable unsaturated bond, specifically a monomer or oligomer having an ethylenically unsaturated bond, and more specifically, urethane (meth)acrylate, epoxy (meth)acrylate, poly In addition to (meth)acrylate monomers or oligomers such as ester (meth)acrylate, polyether (meth)acrylate, and polycarbonate (meth)acrylate, monofunctional or polyfunctional (meth)acrylate monomers or oligomers, etc. Can be mentioned. These can be used alone or in combination of two or more.

On the other hand, in the present invention, "monomer" means that there is no repetition of the structural unit having a polymerizable functional group, and "oligomer" means that the number of repetitions of the structural unit having a polymerizable functional group is 2 or more, and the molecular weight is less than 5000. Or it represents having a polymerizable functional group at the terminal.

Examples of the monofunctional or polyfunctional methacrylate monomer or acrylate monomer (hereinafter, both individually or together simply referred to as ``acrylate monomer'') include, for example, ethyl (meth)acrylate, n-butyl (meth) Acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate ) Monofunctional acrylate monomers such as acrylate and dicyclopentenyl (meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane, 2,2'-bis(4-(meth)acryloyloxypoly) Difunctional acrylate monomers such as propyleneoxyphenyl)propane, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, propoxylated glyceryl tri(meth)acrylate, etc. Functional acrylate monomers, tetrafunctional acrylate monomers such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hydroxy penta(meth)acrylate, etc. And 6-functional acrylate monomers such as dipentaerythritol hexa(meth)acrylate and the like. On the other hand, these may be used alone or in combination of two or more.

Among these, it is preferable to use a polyfunctional acrylate monomer or oligomer having two or more acryloyl groups or methacryloyl groups in one molecule from the viewpoint of being able to crosslink relatively easily when irradiated with ultraviolet rays. In this way, by having two or more functional groups, the symmetry of the molecule is increased, and as a result, the dipole moment of the molecule is lowered, and it is also possible to suppress aggregation of fine particles, particularly inorganic fine particles.

Accordingly, the crosslinked resin layer is preferably a resin layer having a crosslinked structure formed by crosslinking a polyfunctional acrylate monomer having two or more acryloyl groups or methacryloyl groups in one molecule.

Among these, further, from the viewpoint of being particularly excellent in heat shrinkage stability, an alicyclic polyfunctional acrylate monomer having an alicyclic structure, among them, an alicyclic polyfunctional acrylate monomer having at least one alicyclic structure in one molecule, or 1 Polyfunctional urethane acrylate monomers having three or more acryloyl or methacryloyl groups in the molecule are particularly preferred. These acrylate monomers may be modified with caprolactone or the like, or two or more of the above may be used in combination.

The molecular weight of the photopolymerizable compound is preferably in the range of 215 to 4000, more preferably 250 or more or 3000 or less, and even more preferably 300 or more or 2000 or less. By using a photopolymerizable compound in such a molecular weight range, the molecular weight is too low, and the possibility of the monomer being adsorbed to the inorganic fine particles in a drying process, etc. can be eliminated, while the molecular weight is too high, and the viscosity of the curable composition becomes excessively large. , Dispersion of fine particles is suppressed, and problems such as aggregation of fine particles can be eliminated. As a result, the crosslinked resin layer can effectively suppress the shrinkage of the base film at high temperature.

On the other hand, in the present invention, when the molecular weight of the photopolymerizable compound exceeds 1500, the molecular weight as a weight average molecular weight (Mw) is assumed.

In addition to the above, for example, in order to adjust physical properties such as curability, water absorption and hardness of the crosslinked resin layer, one or a combination of two or more selected from poly(meth)acrylic acid ester, epoxy resin, polyurethane resin, polyester resin, etc. It is also possible to add the resulting polymer component to the curable composition.

(Photopolymerization initiator)

Examples of the photopolymerization initiator include benzoin-based, acetophenone-based, thioxanthone-based, phosphine oxide-based and peroxide-based. Specific examples of the photopolymerization initiator include, for example, benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoyl benzoate, 4-phenyl benzophenone, t -Butyl anthraquinone, 2-ethyl anthraquinone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2 -Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenylketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butanone-1, diethyl thioxanthone, isopropyl thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-di Methoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methylbenzoyl formate, and the like can be exemplified. These can be used alone or in combination of two or more.

(Fine particles)

The crosslinked resin layer in the film of the present invention may contain fine particles as necessary.

On the other hand, in the case of including fine particles in the crosslinked resin layer, it is preferable to use a (meth)acrylate monomer having a low molecular weight, such as a weight average molecular weight of 3000 or less, as the photopolymerizable compound so that the fine particles are dispersed.

Examples of the fine particles include inorganic fine particles having transparency such as silicon oxide, aluminum oxide, titanium oxide, soda glass, and diamond.

Among these, silicon oxide fine particles are preferred from the viewpoints of coating suitability and cost. A large number of silicon oxide fine particles have been developed with a surface modified, and by using a surface-shrinkable one, the dispersibility in the curable composition is improved, and a uniform cured film can be formed.

Specific examples of the silicon oxide fine particles include dried powdery silicon oxide fine particles, colloidal silica (silica sol) dispersed in an organic solvent, and the like. Among these, it is preferable to use colloidal silica (silica sol) dispersed in an organic solvent from the viewpoint of dispersibility.

For the purpose of improving dispersibility, silicon oxide fine particles surface-treated with a silane coupling agent, titanate-based coupling agent, etc., in a range where properties such as transparency, solvent resistance, liquid crystal resistance, and heat resistance are not extremely impaired. B, the silicon oxide fine particles subjected to reverse dispersion treatment on the surface may be used.

Particularly, it is preferable to use fine particles treated with a silane coupling agent, especially a methacrylic silane coupling agent, a vinylsilane coupling agent, and a phenylsilane coupling agent.

As the methacrylic silane coupling agent, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryl And oxypropyl triethoxysilane.

Examples of the vinylsilane-based coupling agent include vinyltrimethoxysilane and vinyltriethoxysilane.

Further, examples of the phenylsilane-based coupling agent include phenyl trimethoxysilane and phenyl triethoxysilane.

Among these, fine particles treated with a methacrylic silane-based coupling agent are most preferred because they have particularly high affinity with a binder.

In the case of performing surface treatment on fine particles, the theoretical surface treatment amount is calculated by the following equation.

Addition amount (g) = weight of filler (g) × specific surface area (m ² /g)/minimum coverage area of silane coupling agent (m ² /g)

The minimum covering area referred to herein is calculated by the following equation.

Minimum coverage area (m ² /g) = 6.02×1023×13×10 ^-20 / Molecular weight of silane coupling agent

In the case of the addition amount derived by the above equation, from the viewpoint that the possibility of not being properly dispersed due to aggregation of particles, etc., and from the viewpoint of preventing rapid rise in liquid concentration or generation of bubbles, etc. when dispersed in a solvent, etc. , The amount of the surface treatment agent used is preferably within 3 times of the theoretical surface treatment amount.

By using the above-described surface-treated fine particles, it is possible to disperse fine particles uniformly at a high concentration in the crosslinked resin layer, and as a result, it is possible to prevent the occurrence of scattering phenomena and also to prevent deviation of thermal dimensional stability.

In order to reduce the amount of refractive light incident on the crosslinked resin layer, it is preferable that the refractive index of the fine particles is less than 1.6. Among them, from the viewpoint of improving transparency, it is preferable to use a resin as a reactant after curing the curable composition, particularly fine particles having a refractive index difference of less than 0.2 between the resin constituting the main component and the fine particles (fillers).

(solvent)

The curable composition may be used by adding a solvent as needed. That is, it can be used as a solution containing the curable composition, and this solution can be applied and cured on a base film to form a crosslinked resin layer as a cured coating layer.

According to various coating methods described later, the type and amount of the solvent can be appropriately selected.

Examples of the solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, aromatics such as toluene and xylene, and cyclohexanone and isopropanol. have.

The amount of use of these solvents is not particularly limited. Usually, it is 0 to 300 parts by mass with respect to 100 parts by mass of the total solid content of the curable composition.

(Other ingredients)

In addition to the above, for example, in addition to photocurable oligomers, monomers and photoinitiators other than the above examples, sensitizers, crosslinking agents, ultraviolet absorbers, polymerization inhibitors, fillers, thermoplastic resins, etc., do not interfere with physical properties such as curability, transparency, and water absorption. It can be contained in a range not included.

<Lamination structure>

In the film of the present invention, a crosslinked resin layer may be directly stacked on both sides of the base film, or another layer may be interposed between the base film and the crosslinked resin layer. For example, a primer layer or the like for improving the adhesion of the crosslinked resin layer to the base film may be interposed between the base film and the crosslinked resin layer.

<heat set processing>

In the film of the present invention, by providing a predetermined crosslinked resin layer on both sides of the base film, it has excellent transparency and thermal dimensional stability at high temperatures (e.g., 200°C or higher) even if the base film is not subjected to heat set treatment. You can do it with a film. However, the film of the present invention can also use a base film subjected to heat set treatment for alleviating shrinkage.

Before applying the curable composition on the base film, the dimensional stability of the base film and the present laminated film can be further improved by subjecting the base film to heat set treatment in advance.

Among them, a biaxially stretched polyester film subjected to a heat set treatment for alleviating shrinkage is a preferred example as a base film.

In the heat set treatment of the base film, when the glass transition temperature of the base film is Tg, it is preferable to heat the base film for 0.1 to 180 minutes at a temperature of Tg to Tg + 100°C.

The specific method of heat set treatment is not particularly limited as long as it is a method capable of maintaining the required temperature and time. For example, a method of storing in an oven or constant temperature room set to a required temperature, a method of blowing out hot air, a method of heating with an infrared heater, a method of irradiating light with a lamp, a method of directly applying heat by contacting a heating roll or a heating plate, A method of irradiating microwaves or the like can be used. Further, heat treatment may be performed after cutting the base film into a size that is easy to handle, or heat treatment may be performed while being a film roll. In addition, as long as necessary time and temperature can be obtained, a heating device may be incorporated in a part of a film production device such as a coater or a slitter, and heating may be performed during the production process.

[This conductive film]

The present conductive film according to an example of the embodiment of the present invention includes a transparent laminated film having the crosslinked resin layer on both sides of the front and back of the base film, and directly or undercoat on one or both sides of the front and back of the transparent laminated film. It is a transparent conductive film provided with a transparent conductive layer through a layer.

<Cross-linked resin layer>

The crosslinked resin layer in this conductive film is a layer which can be formed by crosslinking the curable composition.

(Fine particles)

The crosslinked resin layer in the present conductive film does not have to contain substantially fine particles, and may substantially contain fine particles. When the crosslinked resin layer contains fine particles, dimensional stability at high temperature can be further improved.

As the fine particles, it is preferable to use fine particles having an average particle diameter in the range of 1 nm to 200 nm, and particularly preferably, fine particles having an average particle diameter in the range of 1 nm or more or 10 nm or less, especially 4 nm or more or 50 nm or less. Do. By using fine particles having an average particle diameter in such a range, scattering does not occur with respect to the incident light due to Mie scattering, and transparency of the film can be ensured.

Here, ``average particle diameter'' means the number average particle diameter, and when the shape of the fine particles is spherical, it can be calculated as ``the total of the circle equivalent diameters of the measured particles / the number of measured particles'', and the shape of the fine particles is If it is not spherical, it can be calculated as "the sum of short and long diameters/number of particles to be measured".

Moreover, when it contains two or more types of fine particles, the average particle diameter of these mixed particles becomes the said "average particle diameter".

(Content ratio)

The content of the photopolymerizable compound contained in the curable composition is preferably 20 to 90% by mass (in terms of solid content when a solvent is used, the same hereinafter), and 20 to 60% by mass, based on the entire curable composition. It is more preferable, and it is most preferable to set it as 20-40 mass %. When the content of the photopolymerizable compound is small, dispersing of the fine particles becomes difficult, so that aggregation of fine particles occurs, and there is a possibility that the transparency is remarkably deteriorated. In addition, since the content of the photopolymerizable compound is not too large, the contribution of the fine particles to the thermal dimensional stability of the entire film is reduced by half, and the possibility that the excellent thermal dimensional stability of the fine particles cannot be exhibited can be eliminated.

The photoinitiator may be contained as necessary. In the case of containing a photopolymerization initiator with respect to the present conductive film, the content of the photopolymerization initiator contained in the curable composition is preferably 0.1% by mass to 10% by mass, and 0.5% by mass to 5% by mass with respect to the entire curable composition. It is more preferable to set it as %. By setting it as such a range, it becomes possible to advance the curing reaction of a curable composition reliably and efficiently.

Among the above, as the content ratio of the photopolymerizable compound and fine particles contained in the curable composition, 20 to 100% by mass of the photopolymerizable compound (hereinafter, also simply referred to as (A)) and fine particles (hereinafter, also referred to simply as (C)) ) Is preferably 0 to 80 mass%, more preferably 20 to 90 mass% for (A) and 10 to 80 mass% for (C).

In addition, as a content ratio of (A), a photoinitiator (hereinafter, also simply referred to as (B)) and (C) contained in the curable composition, (A) is 20 to 79 mass%, and (B) is 0.1 to 10 It is preferable to set the content ratio of 10 to 79 mass% for (A) or less and (C) as a content ratio, and among them, (A) is 20 to 59 mass%, (B) is 0.5 to 5 mass%, and (C) is 40 to It is more preferable to set it as 79 mass %, and especially it is most preferable to set (A) to 20-39 mass %, (B) to 0.5-5 mass %, and (C) to 60-79 mass %. By setting it as such a content ratio, it becomes possible to supply the laminated film with transparency and productivity efficiently and stably, while exhibiting to the maximum the excellent thermal dimensional stability of the fine particles.

Among them, when the present conductive film contains fine particles, the content of the fine particles contained in the curable composition is preferably 40 to 80% by mass of fine particles having an average particle diameter of 200 nm or less with respect to the entire curable composition, Especially, it is more preferable to set it as 60 mass%-80 mass %. By setting it as such a range, it becomes possible to exhibit excellent thermal dimensional stability to the maximum while maintaining transparency in a range in which fine particles can be dispersed.

(Thickness configuration)

The thickness of the base film in the present conductive film is preferably 70 μm or less, more preferably 5 μm or more and 70 μm or less, among others, more preferably 10 μm or more and 70 μm or less, and most preferably 20 μm or more and 60 μm or less. . By setting it as such a range, advantages such as an improvement in light transmittance and high handling performance can be obtained.

Resin films used as substrate materials for touch panels, organic EL displays, and organic EL lighting are required to have a thin film thickness in order to reduce the weight, thickness, and cost. In general, when a resin film is obtained by extrusion molding, in order to reduce the thickness, it is obtained by stretching a resin in a molten state to make it thin, or stretching a resin film heated to a glass transition temperature or higher.

That is, as the resin film is made thinner, external stress required for molding increases, resulting in a resin film having a large residual stress. Therefore, when a resin film having a thickness of 100 μm or less is used for a high-temperature process such as circuit formation, this residual stress is relieved at high temperature, resulting in a dimensional change.

Therefore, by providing a crosslinked resin layer having a total thickness of 8% or more of the thickness of the base film on both sides of a base film having a specific thickness, specifically, a base film of 70 μm or less, the crosslinked resin layer is at a high temperature of the base film. It becomes possible to remarkably suppress the shrinkage of and to obtain a transparent laminated film excellent in thermal dimensional stability.

In this conductive film, in order to make the heat shrinkage ratio when heated at a temperature of 200°C for 10 minutes to be 1.5% or less, a crosslinked resin layer is formed on both sides of the base film, and the total thickness of the crosslinked resin layers on both the front and back sides is It is preferable that it is 8% or more of the thickness of the base film, more preferably 10% or more of the thickness of the base film, even more preferably 15% or more or 50% or less, and among them, particularly 20% or more or 45% or less is more It is preferable, and it is most preferable that it is more than 30% and 45% or less.

When the crosslinked resin layer is thin, the rigidity as a whole laminated film becomes small, and it becomes difficult to suppress the shrinkage of the base film at high temperature. On the other hand, if the crosslinked resin layer is too thick, cracks and cracks tend to occur, which is not preferable.

<Transparent conductive layer>

This conductive film can form a transparent conductive layer directly on the transparent laminated film which has a crosslinked resin layer, or through the undercoat layer made of a resin material.

The material of the transparent conductive layer is not particularly limited. Any material capable of forming a transparent conductive film may be sufficient. For example, thin films such as indium oxide (ITO) containing tin oxide, tin oxide (ATO) containing antimony, zinc oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide may be mentioned. These compounds can make both transparency and conductivity compatible by selecting appropriate production conditions.

The thickness of the transparent conductive layer is preferably less than 100 nm, more preferably 15 nm or more or 50 nm or less, and most preferably 20 nm or more or less than 40 nm. Until now, attempts have been made to increase the thickness of the conductive layer in order to lower the surface resistance value of the transparent conductive film (for example, less than 150 Ω/□), but according to this conductive film, since it has high thermal dimensional stability under high temperature, It is possible to form a conductive layer at a high temperature, and even if the thickness of the conductive layer is not increased, a sufficiently low surface resistance value can be obtained.

As a method of forming the transparent conductive layer, a vacuum evaporation method, sputtering method, CVD method, ion plating method, spray method, and the like are known, and an appropriate method can be selected and used depending on the type of material and required film thickness. For example, in the case of the sputtering method, ordinary sputtering using a compound target, reactive sputtering using a metal target, and the like are used. At this time, a reactive gas such as oxygen, nitrogen, or water vapor may be introduced, or a means such as ozone addition or ion assist may be used in combination.

As conditions for forming the transparent conductive layer, it is preferable that the temperature is in the range of 150°C to 220°C. For example, when forming a transparent conductive layer on a film by a sputtering method, a normal sputtering temperature is about room temperature-100 degreeC. In contrast, since the transparent laminated film used for the present conductive film has excellent thermal dimensional stability as described above, it is possible to form an inorganic oxide film by sputtering even under a relatively high temperature as described above, for example, at 150°C to 220°C. Thereby, crystallization of the transparent conductive layer can be sufficiently promoted, and a transparent conductive film having a small surface resistance value can be obtained.

<Sublayer>

When forming a transparent conductive layer on a transparent laminated film, it is preferable to interpose an undercoat layer. By interposing the undercoat layer, the adhesion and crystallinity of the transparent conductive layer can be improved.

The material of the undercoat layer is not particularly limited as long as it is a resin material. For example, poly(meth)acrylic acid ester, epoxy resin, polyurethane resin, polyester resin, and the like are suitably used. In addition, a composition containing a photo- or thermally polymerizable compound may be used, and the undercoat layer may be formed by polymerizing this.

In addition, if the flatness of the undercoat layer is poor, there is a possibility that crystal growth of the transparent conductive layer may be inhibited, so that the undercoat layer is preferably substantially free of fine particles.

At this time, "substantially not containing fine particles" means that the content of the inorganic fine particles is 5% by mass or less, preferably 3% by mass or less, and particularly preferably 1% by mass or less of the entire underlying layer.

Further, in the present conductive film, when fine particles are contained in the crosslinked resin layer of the transparent laminated film, it is preferable to interpose the undercoat layer at the time of forming the transparent conductive layer on the transparent laminated film.

By interposing the undercoat layer in this manner, the surface resistance value of the present conductive film can be reduced because the surface smoothness can be increased and the continuity of the transparent conductive layer can be improved.

<physical properties>

Next, various physical properties that the present conductive film and the transparent laminated film used for the present conductive film can have will be described.

(Heat shrinkage rate)

In the transparent laminated film used for this conductive film, when heated at 200°C for 10 minutes, the shrinkage in either the vertical direction (MD direction) and the horizontal direction (TD direction) is the heat shrinkage rate of the base film measured under the same conditions. It is preferably 70% or less.

When the transparent laminated film has a shrinkage within such a range, it has the advantage of reducing the dimensional shift when forming a circuit or element, and obtaining a higher barrier property even when laminating an inorganic barrier layer.

In particular, in the case of biaxially stretched films, etc., it is possible to reduce the shrinkage rate by the transverse stiffening treatment during the film forming process, but the longitudinal stiffening treatment often requires a separate process. In general, the longitudinal shrinkage rate Is relatively large. Therefore, in this conductive film, it is particularly preferable to reduce the shrinkage in the longitudinal direction.

Moreover, it is preferable that the transparent laminated film used for this conductive film has a base film and a crosslinked resin layer, and the heat shrinkage ratio when heated at 200 degreeC for 10 minutes is 1.5% or less.

By providing a crosslinked resin layer having a thickness of 8% or more of the thickness of the base film on both sides of the front and back of the base film, the crosslinked resin layer can counteract the shrinkage stress of the base film in a high temperature region, thereby reducing shrinkage. Therefore, the thermal dimensional stability of the transparent laminated film against shrinkage at high temperature can be improved as described above.

Since this conductive film has a transparent conductive layer on a transparent laminated film having high thermal dimensional stability under such a high temperature, the formation of the transparent conductive layer in a high temperature atmosphere (specifically 150 to 220°C) is not possible. It is possible and the crystallization of the conductive layer can be sufficiently advanced, so that it can have a low surface resistance value.

(Surface resistance value)

It is preferable that it is 150 Ω/□ or less, and, as for the surface resistance value of this conductive film, it is more preferable that it is 100 Ω/□ or less. When the present conductive film has a surface resistance value in such a range, it has advantages such as reducing power transmission loss of the display device and reducing non-uniformity in response speed when the touch panel sensor is enlarged.

By forming the inorganic oxide film in a temperature atmosphere of 150 to 220°C, the crystallinity of the inorganic oxide film can be improved, and the surface resistance value can be lowered.

<Production method of this conductive film, etc.>

The transparent laminated film used for this conductive film can be produced by applying and curing a curable composition to both the front and back sides of a base film to form a crosslinked resin layer.

As a method of coating a curable composition, etc., a curable composition is applied to a base film by bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset, flexo printing, screen printing, dip coating, etc. How to do it. Moreover, after molding the crosslinked resin layer on a glass or polyester film, a method of transferring the formed crosslinked resin layer to a base film is also effective.

As a method of curing (crosslinking) the curable composition after coating the curable composition on the base film as described above, methods such as thermal curing, ultraviolet curing, and electron beam curing can be used alone or in combination. Among them, since curing can be achieved relatively easily in a short time, it is preferable to use a method by ultraviolet curing.

In the case of curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is used as a light source, and the amount of light and the arrangement of the light sources are adjusted as necessary.

Further, in the case of using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 60 m/min with respect to the first lamp having a light quantity of 80 to 160 W/cm.

On the other hand, in the case of curing with an electron beam, it is preferable to use an electron beam accelerating device having an energy of 100 to 500 eV.

<use>

As described above, the present conductive film has an advantage of having less dimensional change (thermal dimensional stability) due to heat treatment and a small surface resistance value while maintaining transparency as described above. Therefore, this conductive film can be suitably used for, for example, a substrate for a display material such as a liquid crystal display, an organic light-emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a substrate for a solar cell, or a photoelectric device substrate. .

Further, since this conductive film has the above advantages, it can be suitably used for semiconductor devices such as organic EL, liquid crystal display elements, and solar cells by performing gas barrier processing.

Moreover, this conductive film can also be used as a gas barrier film (referred to as "this barrier film") which has gas barrier properties by performing gas barrier processing on one or both of the crosslinked resin layers provided on the base film.

Conventionally, when a polyester film is used as a film for gas barrier processing, there have been problems such as cracking or wrinkles in the gas barrier layer, and the function including gas barrier properties cannot be sufficiently expressed. In contrast, this barrier film is excellent in that there is no such problem.

This barrier film is suitably used for applications requiring gas barrier properties such as solar cells, in addition to organic semiconductor devices such as organic EL, liquid crystal display elements, and the like.

On the other hand, gas barrier processing is a crosslinking of a transparent laminated film, the laminated film, and the gas barrier film using a gas barrier layer made of a material having high gas barrier properties, such as an inorganic substance such as a metal oxide or an organic substance, for the conductive film. It is a processing method formed on at least one surface of the resin layer.

At this time, as a material having high gas barrier properties, for example, silicon, aluminum, magnesium, zinc, tin, nickel, titanium, or oxides, carbides, nitrides, oxidized carbides, oxynitrides, oxidized carbonitrides, diamond-like carbons, or these Mixture, etc. are mentioned. Among them, since there is no fear of leakage of current when used in a solar cell or the like, inorganic oxides such as silicon oxide, silicon oxide carbide, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, aluminum oxide carbide and aluminum oxynitride, Nitrides such as silicon nitride and aluminum nitride, diamond-like carbon, and mixtures thereof are preferred. In particular, silicon oxide, silicon oxide carbide, silicon oxynitride, oxycarbonitride, silicon nitride, aluminum oxide, aluminum oxide carbide, aluminum oxynitride, aluminum nitride, and mixtures thereof are preferable in that they can stably maintain high gas barrier properties. Do.

As a method of forming a gas barrier layer on the present conductive film using the above material, any method such as a vapor deposition method or a coating method can be employed. The vapor deposition method is preferable in that a uniform thin film with high gas barrier properties can be obtained.

This vapor deposition method includes methods such as physical vapor deposition (PVD) or chemical vapor deposition (CVD).

Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and sputtering.

Examples of the chemical vapor deposition method include plasma CVD using plasma and catalytic chemical vapor deposition (Cat-CVD) in which a material gas is catalytically pyrolyzed using a heating catalyst.

The thickness of the gas barrier layer is preferably 10 nm to 1000 nm, particularly preferably 40 nm or more or 800 nm or less, and particularly more preferably 50 nm or more or 600 nm or less, from the viewpoint of stable gas barrier property expression and transparency. .

Further, the gas barrier layer may be a single layer or a multilayer. When the gas barrier layer is a multilayer, each layer may be made of the same material or may be made of different materials.

The water vapor transmittance at 40°C and 90% of the present barrier film is preferably less than 0.1 [g/(m ² ·day)], more preferably 0.06 [g/(m ² ·day)] or less, further Preferably it is 0.03 [g/(m ² ·day)] or less.

The measurement method of water vapor transmission rate is in accordance with various conditions of JIS Z0222 ``Moisture-proof packaging container moisture permeability test method'' and JIS Z0208 ``Moisture-proof packaging material moisture permeability test method (cup method)'', and can be specifically measured by the method described in Examples. I can.

[This laminated film]

The present laminated film according to an example of the embodiment of the present invention is a laminated film provided with a transparent laminated film having a special crosslinked resin layer on both sides of the base film as described above.

Since this laminated film has a predetermined crosslinked resin layer on both the front and back sides of the base film, the crosslinked resin layer can counteract the shrinkage stress of the base film in a high temperature region, thereby reducing shrinkage. Therefore, the dimensional stability of this laminated film against shrinkage at high temperature can be improved.

Resin films used as substrate materials for touch panels, organic EL displays, and organic EL lightings are required to have a thin film thickness in order to reduce weight, thickness, and cost. In general, when a resin film is obtained by extrusion molding, in order to reduce the thickness, it is obtained by stretching a resin in a molten state to make it thin, or stretching a resin film heated to a glass transition temperature or higher.

That is, as the resin film is made thinner, external stress required for molding increases, resulting in a resin film having a large residual stress. Therefore, when a resin film having a thickness of 100 μm or less is used for a high-temperature process such as circuit formation, this residual stress is relieved at high temperature, resulting in a dimensional change.

Therefore, in this laminated film, a crosslinked resin layer in which the total thickness is 8% or more of the thickness of the base film is provided on both sides of the base film of a specific thickness, specifically 75 μm or less, more preferably 70 μm or less. By installing, the crosslinked resin layer remarkably suppresses shrinkage of the base film at high temperature, and a transparent laminated film excellent in thermal dimensional stability can be obtained.

<Base film>

This laminated film has a property that the heat shrinkage rate when heated at a temperature of 200°C for 10 minutes is lower than that of the base film, for example, 70% or less. That is, when a base film having a high heat shrinkage under the same conditions is used, a particularly remarkable effect can be exhibited. From such a viewpoint, it is preferable to use a biaxially stretched film made of a polyethylene terephthalate resin having a relatively high shrinkage when heated at a temperature of 200°C for 10 minutes as the base film of the laminated film.

The thickness of the base film is preferably 75 μm or less, more preferably 5 μm or more or 75 μm or less, among others, more preferably 10 μm or more or 70 μm or less, and most preferably 20 μm or more or 60 μm or less. By setting it as such a range, advantages such as improved light transmittance and high handling performance can be obtained.

<Cross-linked resin layer>

The crosslinked resin layer in this laminated film can be formed using a photopolymerizable compound, a photopolymerization initiator, and a curable composition containing fine particles. As each component such as the photopolymerizable compound, it is possible to use those illustrated above. Among them, the photopolymerizable compound is preferably a photopolymerizable (meth)acrylate monomer or oligomer having two or more acryloyl groups or methacryloyl groups in one molecule, and having at least one alicyclic structure in one molecule. It is more preferable that it is an alicyclic polyfunctional acrylate monomer.

(Fine particles)

When the crosslinked resin layer in this laminated film contains fine particles, it can have excellent high temperature dimensional stability.

As the fine particles, it is preferable to use those having an average particle diameter in the range of 1 nm to 200 nm, and among them, it is particularly preferable to use fine particles having an average particle diameter in the range of 1 nm or more or 10 nm or less, especially 4 nm or more or 50 nm or less. . By using fine particles having an average particle diameter in such a range, scattering does not occur with respect to incident light due to non-scattering, and transparency of the film can be secured.

(Content ratio)

The content of the photopolymerizable compound (A) contained in the curable composition is preferably 9 to 50% by mass (in terms of solid content in the case of using a solvent, the same as hereinafter) with respect to the entire curable composition, among which 15 masses It is more preferable to set it as% or more or 45 mass% or less, and especially it is most preferable to set it as 19 mass% or more or 40 mass% or less. If the content of the photopolymerizable compound (A) is small, dispersing of the fine particles becomes difficult, so that agglomeration of the fine particles occurs, and the transparency is remarkably deteriorated. In addition, since the content of the photopolymerizable compound (A) is not too large, the contribution of the fine particles to the thermal dimensional stability of the entire film is reduced by half, thereby eliminating the possibility that the fine particles cannot exhibit excellent thermal dimensional stability. .

The content of the photopolymerization initiator (B) contained in the curable composition is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass or more or 5% by mass or less with respect to the entire curable composition. Do. By setting it as such a range, it becomes possible to advance the curing reaction of a curable composition reliably and efficiently.

The content of the fine particles (C) contained in the curable composition is preferably 10 to 90% by mass with respect to the entire curable composition, and more preferably 20% by mass or more or 84% by mass or less, and among them It is more preferably 70% by mass or more or 80% by mass or less. By setting it as such a range, it becomes possible to exhibit excellent thermal dimensional stability to the maximum while maintaining transparency in a range in which fine particles can be dispersed.

Among the above, as to the content ratio of the photopolymerizable compound and fine particles contained in the curable composition, 9 to 50% by mass of the photopolymerizable compound (A), 0.1 to 10% by mass of the photopolymerization initiator (B), and fine particles (C ) Is preferably set to a content ratio of 10 to 90% by mass, among them, 15 to 45% by mass of the photopolymerizable compound (A), 0.5 to 5% by mass of the photopolymerization initiator (B), and 20 to the fine particles (C). It is more preferable to use 84% by mass, and among them, 19 to 40% by mass of the photopolymerizable compound (A), 0.5 to 5% by mass of the photopolymerization initiator (B), and 70 to 80% by mass of the fine particles (C). More preferable. By setting it as such a content ratio, it becomes possible to supply the laminated film with transparency and productivity efficiently and stably, while exhibiting to the maximum the excellent thermal dimensional stability of the fine particles.

(Thickness of crosslinked resin layer)

The total thickness of both the front and back sides of the crosslinked resin layer in this laminated film is preferably 8% or more of the thickness of the base film, and more preferably 10% or more of the thickness of the base film. It is more preferably 12% or more or 50% or less of the thickness, more preferably 20% or more or 45% or less of the thickness, and most preferably more than 30% and 45% or less.

When the crosslinked resin layer is thin, the rigidity as a whole laminated film becomes small, and it becomes difficult to suppress the shrinkage of the base film at high temperature. On the other hand, when the hardened layer is excessively thick, cracks and cracks are liable to occur, which is not preferable.

(Physical properties of this laminated film)

Next, various physical properties that the present laminated film can have will be described.

(Total light transmittance)

The present laminated film preferably has a total light transmittance of 80% or more, and more preferably 85% or more. When the present laminated film has a total light transmittance in such a range, attenuation of light can be suppressed in lighting, a display, etc., resulting in brighter light. In addition, as a solar cell member, an advantage such as being able to introduce more light can be obtained. On the other hand, the light transmittance of the laminated film can be adjusted by adjusting the type of resin in the crosslinked resin layer, the type and particle diameter of the fine particles, and the content of the fine particles.

(Heat shrinkage rate)

For the above-described reasons, the shrinkage ratio in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200°C for 10 minutes is the heat of the base film measured under the same conditions. It is preferably 70% or less of the shrinkage rate.

When the present laminated film has a shrinkage in such a range, as described above, it has the advantage of reducing dimensional deviation when forming a circuit or element, and obtaining a higher barrier property even when an inorganic barrier layer is laminated. . Also in this laminated film, it is preferable to reduce the shrinkage ratio in the longitudinal direction especially from the above reasons.

<Production method of this laminated film>

This laminated film can be produced by applying and curing a curable composition to both the front and back sides of a base film to form a crosslinked resin layer.

The method of forming the crosslinked resin layer is the same as that of the present conductive film.

<Use of this laminated film>

As described above, the laminated film can be suitably used for the applications exemplified above, since it has the advantage of less dimensional change (thermal dimensional stability) due to heat treatment while maintaining transparency as described above. For example, a gas barrier layer can be formed on the laminated film and used as a gas barrier film (details are in accordance with the present barrier film of the conductive film).

[This gas barrier film]

The present gas barrier film according to an example of the embodiment of the present invention includes a transparent laminated film having a crosslinked resin layer as described above on both surfaces of the base film as described above, and is provided on at least one surface of the crosslinked resin layer. It is a gas barrier laminated film having a configuration having a gas barrier layer of.

This gas barrier film has a configuration in which a predetermined crosslinked resin layer is provided on both sides of the base film, and a predetermined gas barrier layer is provided on at least one side of the crosslinked resin layer. The crosslinked resin layer can counteract the shrinkage stress to relieve shrinkage. Therefore, the dimensional stability of the present gas barrier film against shrinkage at high temperature can be improved.

<Base film>

The thickness of the base film in the present gas barrier film is preferably 1 μm to 200 μm, more preferably 5 μm or more or 150 μm or less, more preferably 7 μm or more or 100 μm or less, and more preferably 10 μm or more or 100 μm or less, Most preferably, it is 12 μm or more and 100 μm or less. By setting it as such a range, advantages such as improved light transmittance and high handling performance can be obtained.

<Cross-linked resin layer>

From the viewpoint of improving the dimensional stability of the gas barrier film against shrinkage at high temperature, as described above, also in the gas barrier film, the crosslinkable resin layer is a photopolymerizable compound, a photopolymerization initiator, and a curable composition containing fine particles It is preferable that it is a layer formed by using.

As each component such as the photopolymerizable compound, it is possible to use those illustrated above. Among them, the photopolymerizable compound is preferably a photopolymerizable (meth)acrylate monomer or oligomer having two or more acryloyl groups or methacryloyl groups in one molecule, and having at least one alicyclic structure in one molecule. It is more preferable that it is an alicyclic polyfunctional acrylate monomer.

(Fine particles)

It is preferable that the crosslinked resin layer in this gas barrier film substantially contains fine particles. This is because when the crosslinked resin layer contains fine particles, excellent high temperature dimensional stability is obtained.

It is preferable that the said microparticles|fine-particles are microparticles whose average particle diameter is in the range of 1 nm-50 nm, Especially, it is especially preferable to use microparticles whose average particle diameter is 1 nm-40 nm or less, and further 4 nm or more or 30 nm or less. By using fine particles having an average particle diameter in such a range, transparency can be ensured, and damage to the smoothness of the surface of the crosslinked resin layer can be reduced.

The content rate of the fine particles is the content rate of the fine particles based on the entire crosslinked resin layer, preferably 50% by volume or more, more preferably 50% by volume or more or 90% by volume or less, and more particularly, 55% by volume or more, or It is more preferably 75% by volume or less. When 50% by volume or more of the microparticles are included in the crosslinked resin layer, the microparticles are filled in a state closer to the tightest packing, and when the amount is 72% by volume or more, theoretically, the tightest packing is achieved. By containing the fine particles in such a range, it becomes possible to reduce the dimensional change due to shrinkage caused by the orientation of the base film during heating and the like by the elastic modulus of the crosslinked resin layer.

(Content ratio)

The crosslinked resin layer in the present gas barrier film can also be formed by coating and curing a curable composition containing a photopolymerization initiator, fine particles, and optionally a solvent and other components in addition to the photopolymerizable compound as described above.

The content of the photopolymerizable compound contained in the curable composition is preferably 9 to 50% by mass, and more preferably 15% by mass or more or 45% by mass or less with respect to the entire curable composition. By setting it as such a range, the crosslinking density at the time of curing increases, and it becomes possible to impart high rigidity at high temperature.

The content of the photocuring agent, that is, the photopolymerization initiator contained in the curable composition, is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass with respect to the entire curable composition. By setting it as such a range, it becomes possible to advance a hardening reaction reliably and efficiently.

(Thickness of crosslinked resin layer)

As for the thickness of the crosslinked resin layer in this gas barrier film, it is important to make the sum of the thickness of the crosslinked resin layer on both sides of the front and back be 8% or more of the thickness of a base film. If the sum of the thicknesses of the crosslinked resin layers on both sides of the front and back is 8% or more of the thickness of the base film, the storage modulus of the gas barrier film at high temperature can be maintained high, and the laminated film can have high dimensional stability. have.

From this point of view, in particular, the total thickness of the crosslinked resin layer is preferably 8% or more and 50% or less of the thickness of the base film so that the heat shrinkage rate when heated at 180° C. for 90 minutes is 1.5% or less. It is preferably 10% or more of the thickness of the base film, particularly preferably 15% or more or 50% or less, more preferably 20% or more or 45% or less, particularly more than 30% and 45% or less Most preferred.

<Gas barrier layer>

This gas barrier film includes a gas barrier layer on at least one side of the crosslinked resin layer.

The gas barrier layer is similar to the gas barrier layer of the present barrier film, and can be formed of a material having high gas barrier properties.

Examples of materials with high gas barrier properties include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, or oxides, carbides, nitrides, oxide carbides, oxynitrides, oxycarbonitrides, diamond-like carbon, or mixtures thereof, etc. In the case of use in solar cells, etc., since there is no fear of current leakage, etc., inorganic such as silicon oxide, silicon oxide carbide, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, aluminum oxide carbide, and aluminum oxynitride Oxides, nitrides such as silicon nitride and aluminum nitride, diamond-like carbon, and mixtures thereof are preferred. In particular, silicon oxide, silicon oxide carbide, silicon oxynitride, oxycarbonitride, silicon nitride, aluminum oxide, aluminum oxide carbide, aluminum oxynitride, aluminum nitride, and mixtures thereof are preferable in that they can stably maintain high gas barrier properties. Do.

Among them, one formed of an inorganic compound composed of at least one of oxides, nitrides, and oxynitrides of silicon (Si) or aluminum (Al) is preferable.

As a method of forming the gas barrier layer using the material, any method such as a vapor deposition method or a coating method can be adopted. The vapor deposition method is preferable in that a uniform thin film with high gas barrier properties can be obtained.

This vapor deposition method includes methods such as physical vapor deposition (PVD) or chemical vapor deposition (CVD).

Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and sputtering.

Examples of the chemical vapor deposition method include plasma CVD using plasma and catalytic chemical vapor deposition (Cat-CVD) in which a material gas is catalytically pyrolyzed using a heating catalyst.

The thickness of the gas barrier layer is preferably 5 nm to 1000 nm, more preferably 800 nm or less, and particularly more preferably 100 nm or less, from the viewpoint of stable gas barrier property expression and transparency.

Further, the gas barrier layer may be a single layer or a multilayer. When the gas barrier layer is a multilayer, each layer may be made of the same material or may be made of different materials.

In the case of installing an anchor coating layer between the crosslinked resin layer and the gas barrier layer, the purpose is to smooth the surface and improve the adhesion between the crosslinked layer and the gas barrier layer, but its thickness does not impair the thermal stability of the entire film. The range is preferred. Specifically, 20 μm or less is preferable, 10 μm or less is more preferable, and 1 μm or less is more preferable.

(Physical properties of this gas barrier film)

Next, various physical properties that the present gas barrier film may have will be described.

(Total light transmittance)

Also in this gas-barrier film, from a viewpoint similar to that of the film, the total light transmittance is preferably 80% or more, and more preferably 85% or more. On the other hand, as described in the present laminated film, the light transmittance of the gas barrier film can be adjusted by adjusting the type of resin, the type and particle diameter of the fine particles, the content of the fine particles, and the like in the crosslinked resin layer.

(Heat shrinkage rate)

This gas barrier film, from the same viewpoint as the film, has a shrinkage rate in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200°C for 10 minutes, measured under the same conditions. It is preferable that it is 70% or less of the heat shrinkage ratio of the base film to be used.

In addition, it is particularly preferable that the shrinkage ratio in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 180°C for 90 minutes is 1.5% or less.

(Water vapor permeability)

The water vapor transmittance of this gas barrier film is required to be 1.0 × 10 ^-2 g/m ² /day or less, and more preferably 5 × 10 ^-3 g/m ² /day or less.

When the present gas barrier film has a water vapor transmittance within this range, when a transparent electrode or element is formed on the present gas barrier film, moisture contained in external air or other members can be sufficiently blocked. It has advantages such as that it can prevent performance degradation or deterioration of the jersey.

The measurement method of the water vapor transmission rate of this gas barrier film is evaluated by the following method according to various conditions of JIS Z0222 ``Moisture-proof packaging container moisture permeability test method'' and JIS Z0208 ``Moisture-proof packaging material moisture permeability test method (cup method)''. It becomes.

Two gas barrier laminated films with a moisture permeable area of 10.0cm×10.0cm each were used, and about 20g of anhydrous calcium chloride was added as a moisture absorbent to form a bag with four sides sealed, and the bag was placed at a temperature of 40°C and relative humidity. It is put in a 90% constant temperature and humidity device, and the weight is measured (in units of 0.1 mg) for up to 34.8 days as a standard at which the weight increase is almost constant at intervals of 48 hours or more, and the water vapor transmission rate can be calculated from the following equation.

Water vapor transmission rate (g/m ² /day) = (m/s)/t

m; Increased mass of the last two weighing intervals during the test period (g)

s; Breathable area (m ² )

t; Time (day) of the last two weighing intervals during the test period

(Arithmetic mean roughness)

It is preferable that it is 15 nm or less, and, as for the arithmetic average roughness of at least one surface of the crosslinked resin layer of this gas barrier film, it is more preferable that it is especially 10 nm or less.

When the crosslinked resin layer has an arithmetic average roughness in such a range, a uniform film with few defects can be formed when forming the gas barrier layer, and as a result, high gas barrier properties can be obtained. Further, it is possible to have advantages such as fewer element formation defects when forming an organic EL or the like on the present gas barrier film.

The arithmetic average roughness of the crosslinked resin layer is obtained by dividing the volume of a portion surrounded by the surface shape curve of the crosslinked resin layer and the average surface by the measurement area, the average surface as the XY plane, and the vertical direction as the Z axis, and the measured surface shape curve When is Z=F(x, y), it indicates what is defined by the following equation.

[Equation 1]

(Lx: measuring length in x direction, Ly: measuring length in y direction)

<Production method of this gas barrier film>

This gas barrier film can be produced by applying and curing a curable composition on both sides of a base film to form a crosslinked resin layer, and further forming a gas barrier layer by the method described above.

The method of forming the crosslinked resin layer is the same as that of the present conductive film.

<Use of this gas barrier film>

As described above, the gas barrier film can be suitably used for the applications exemplified above, since it has the advantage of little dimensional change (thermal dimensional stability) due to heat treatment while maintaining transparency as described above.

[Explanation of terms]

In the present invention, "transparent" means that what is in front of it is seen through, and the total light transmittance is preferably 80% or more.

In addition, in the present specification, when expressed as "X to Y" (X and Y are arbitrary numbers), unless otherwise noted, together with the meaning of "X or more and Y or less", "preferably greater than X" or It also includes the meaning of "preferably smaller than Y".

In addition, when expressed as ``X or more'' (X is an arbitrary number) or ``Y or less'' (Y is an arbitrary number), the intention to the effect of ``is preferably greater than X'' or ``is preferably less than Y'' Include.

Example

Hereinafter, the present invention will be described in more detail by examples and comparative examples. However, the present invention is not limited at all by these examples.

[About this conductive film]

First, the present conductive film will be described in detail below using Examples 1 to 5, Comparative Examples 1 to 2, and Reference Examples 1 to 4.

<Measurement method about the properties of this conductive film>

(Measurement method of heat shrinkage)

From the obtained transparent laminated film, the film was cut out in a strip shape of 140 mm in length and 10 mm in width, respectively, in the longitudinal direction and in the transverse direction, and a test piece with marks at intervals of 100 mm in length was put in a thermostat set at 200°C. It was suspended in a state of no load at 10 minutes, taken out, and allowed to cool at room temperature for 15 minutes or more, and the heat shrinkage rate was determined as a% value from the length between the marks before and after placing in the thermostat. On the other hand, the measurement was performed five times each, the average value was calculated, and the third decimal place was rounded off.

(Surface resistance value)

The surface resistance of the transparent conductive layer was measured using a 4-terminal method low resistivity meter "Loresta EP" manufactured by Mitsubishi Chemical.

<Example 1>

(Preparation of photocurable composition 1)

Photocurable bifunctional acrylate monomer (tricyclodecane dimethanol diacrylate, molecular weight 304, manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``A-DCP'') 22.1% by mass, fine silica particles (manufactured by Admatex Co., Ltd., brand name `` YA010C-SM1", average particle diameter 10 nm) 77.2% by mass, photopolymerization initiator A (BASF, brand name ``IRGACURE127'') 0.6% by mass, photopolymerization initiator B (BASF, brand name ``IRGACURE184'') 0.1% by mass, solvent (propylene glycol Monomethyl ether) to obtain a curable composition 1 (paint A) for forming a crosslinked resin layer.

(Preparation of transparent laminated film 1)

On one side of a 50 μm thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., brand name ``diafoil''), the above-prepared paint A was applied using a die coater so that the thickness after curing became 10 μm, and then a solvent Was dried and removed, and a high-pressure mercury lamp (160 W/cm) was irradiated on the coated surface under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side. To the side of the film on which the crosslinked resin layer is not formed, coating A was applied and cured in the same manner as described above, thereby obtaining a transparent laminated film 1 having a crosslinked resin layer formed on both surfaces thereof.

The thermal contraction rate in the longitudinal direction (MD direction) of the transparent laminated film 1 was 0.29%, and the thermal contraction rate in the transverse direction (TD direction) was 0.13%.

In addition, the value obtained by dividing the heat shrinkage rate of the transparent laminated film 1 by the heat shrinkage rate of the single base film used for the transparent laminated film 1 was 19%.

(Production of transparent conductive film 1 with transparent conductive layer)

On one side of the crosslinked resin layer of the transparent laminated film 1, an ITO film was formed as a transparent conductive layer to a thickness of 30 nm by sputtering in a 200°C atmosphere. The surface resistance value of the conductive layer of the obtained transparent conductive film 1 was measured by Loresta EP (manufactured by Mitsubishi Chemical) and found to be 119 Ω/□.

<Example 2>

(Production of transparent laminated film 2)

On one side of the transparent laminated film 1 produced in Example 1, 88% by mass of polyester resin (pesresin A-215GE manufactured by Takamatsu Oil Corporation), 12% by mass of oxazoline group-containing polymer (Epocross WS-700 manufactured by Nippon Shokubai) A coating material uniformly diluted with water was applied so that the thickness after drying became 0.5 μm, to obtain a transparent laminated film 2 in which an undercoat layer was formed on one side of the crosslinked resin layer of the transparent laminated film 1.

(Preparation of transparent conductive film 2 with transparent conductive layer)

On the undercoat surface of the transparent laminated film 2, an ITO film was formed as a transparent conductive layer in a 200°C atmosphere by sputtering to a thickness of 30 nm. The surface resistance value of the conductive layer of the obtained transparent conductive film 2 was measured by Loresta EP (manufactured by Mitsubishi Chemical) and found to be 77 Ω/□.

<Example 3>

(Production of transparent laminated film 3)

On one side of the transparent laminated film 1 produced in Example 1, a hard coating paint (NK Hard B500 manufactured by Shinnakamura Chemical Industries, Ltd.) was applied so that the thickness after drying was 3 μm, and further cured using an ultraviolet irradiation device. , The transparent laminated film 3 in which the undercoat layer was formed on one side of the crosslinked resin layer of the transparent laminated film 1 was obtained.

(Preparation of transparent conductive film 3 with transparent conductive layer)

On the undercoat of the transparent laminated film 3, an ITO film was formed as a transparent conductive layer in a 200°C atmosphere by sputtering to a thickness of 30 nm. The surface resistance value of the conductive layer of the obtained transparent conductive film 3 was measured by Loresta EP (manufactured by Mitsubishi Chemical) and found to be 75 Ω/□.

<Example 4>

(Production of transparent laminated film 4)

On one side of the transparent laminated film 1 produced in Example 1, 97% by mass of a hard coating paint (GX8801A manufactured by Daiichi Industries Pharmaceutical) and 3% by mass of a photopolymerization initiator (IRACURE184 manufactured by BASF) were uniformly mixed with toluene and isopropyl alcohol (IPA). The diluted paint was applied so that the thickness after drying became 1 μm, to obtain a transparent laminated film 4 in which an undercoat layer was formed on one side of the crosslinked resin layer of the transparent laminated film 1.

(Production of transparent conductive film 4 with transparent conductive layer)

On the bottom surface of the transparent laminated film 4, an ITO film was formed as a transparent conductive layer in a 200°C atmosphere by sputtering to a thickness of 30 nm. The surface resistance value of the conductive layer of the obtained transparent conductive film 4 was measured by Loresta EP (manufactured by Mitsubishi Chemical) and found to be 81 Ω/□.

<Example 5>

(Preparation of curable composition 2)

Photocurable 6-functional urethane acrylate (molecular weight: 800, manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``U-6LPA'') 48.5% by mass, photocurable 6-functional acrylate monomer (dipentaerythritol hexaacrylate, molecular weight 578, new Nakamura Chemical Industries Co., Ltd. make, brand name ``A-DPH'') 24.3% by mass, photocurable bifunctional acrylate monomer (tricyclodecane dimethanol diacrylate, molecular weight 304, Shinnakamura Chemical Co., Ltd. make, brand name ``A-DCP '') 24.3% by mass and 2.9% by mass of photopolymerization initiator B (made by BASF, brand name "IRGACURE184") were uniformly diluted with a solvent (propylene glycol monomethyl ether), and curable composition 2 for forming a crosslinked resin layer (paint B) Got it.

(Production of transparent laminated film 5)

On one side of a 23 μm thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., brand name ``diafoil''), the paint B prepared above was applied using a gravure coater so that the thickness after curing became 3 μm, and then a solvent Was dried and removed, and a high-pressure mercury lamp (160 W/cm) was irradiated on the coated surface under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side. To the side of the film on which the crosslinked resin layer is not formed, paint B was applied and cured in the same manner as described above to obtain a transparent laminated film 5 in which a crosslinked resin layer was formed on both sides.

As for the obtained film, the heat shrinkage was measured in the same manner as in Example 1 and found to be 1.43% in the longitudinal direction (MD direction) and 0.21% in the transverse direction (TD direction).

In addition, the value obtained by dividing the heat shrinkage rate of the transparent laminated film 5 by the heat shrinkage rate of the base film used for the transparent laminated film 5 was 67%.

(Formation of transparent conductive film)

On one side of the crosslinked resin layer of the transparent laminated film 5, an ITO film was formed as a transparent conductive layer to a thickness of 30 nm by sputtering in a 200°C atmosphere. The surface resistance value of the conductive layer of the obtained transparent conductive film 5 was measured by Loresta EP (manufactured by Mitsubishi Chemical) and found to be 68 Ω/□.

<Comparative Example 1>

For a 23 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., brand name "diafoil"), the heat shrinkage was measured in the same manner as in Example 1, and it was 2.12% in the vertical direction and 0.67% in the horizontal direction. When an attempt was made to form a transparent conductive layer on one side of the polyethylene terephthalate film in a 200°C atmosphere, the heat shrinkage was large in the sputtering device, and film formation was not possible.

<Comparative Example 2>

On one side of the transparent laminated film 1 produced in Example 1, an ITO film as a transparent conductive layer was formed at room temperature to a thickness of 30 nm by sputtering. The surface resistance value of the conductive layer of the obtained transparent conductive film 6 was measured by Loresta EP (manufactured by Mitsubishi Chemical) and found to be 257 Ω/□.

<Reference Example 1>

(Production of transparent laminated film 6)

Paint A prepared in Example 1 was cured on one side of a 100 μm-thick biaxially stretched polyethylene terephthalate film (Toyobo Corporation, brand name ``Cosmoshine'', heat shrinkage: MD direction = 4.06%, TD direction = 2.55%). After coating using a bar coater so that the thickness afterward became 1 μm, the solvent was dried and removed. Then, the film was put in a belt conveyor device while the end of the film was fixed, and a high-pressure mercury lamp (160 W/cm) was irradiated on the coated surface under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side.

Next, to the side of the film on which the crosslinked resin layer is not formed, paint A was applied and cured in the same manner as described above, thereby obtaining a transparent laminated film 6 having a crosslinked resin layer formed on both sides.

As for the transparent laminated film 6, the heat shrinkage was measured in the same manner as in Example 1, and the heat shrinkage in the longitudinal direction (MD direction) was 3.42%, and the heat shrinkage in the transverse direction (TD direction) was 1.66%.

<Reference Example 2>

(Production of transparent laminated film 7)

Paint A prepared in Example 1 was applied to one side of a 100 μm thick biaxially stretched polyethylene terephthalate film (Toyobo Corporation, brand name ``Cosmoshine'') using a bar coater so that the thickness after curing became 3 μm, The solvent was dried and removed. Then, the film was put in a belt conveyor device while the end of the film was fixed, and a high-pressure mercury lamp (160 W/cm) was irradiated on the coated surface under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side.

Next, to the side of the film on which the crosslinked resin layer is not formed, paint A was applied and cured in the same manner as described above, thereby obtaining a transparent laminated film 7 having a crosslinked resin layer formed on both sides.

As for the transparent laminated film 7, the heat shrinkage was measured in the same manner as in Example 1, the heat shrinkage in the longitudinal direction (MD direction) was 2.42%, and the heat shrinkage in the horizontal direction (TD direction) was 1.21%.

<Reference Example 3>

(Production of transparent laminated film 8)

Paint A prepared in Example 1 on one side of a 50 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., brand name ``diafoil'', heat shrinkage: MD direction = 1.51%, TD direction = 0.31%), After coating using a bar coater so that the thickness after curing became 1 μm, the solvent was dried and removed. Then, the film was put in a belt conveyor device while the end of the film was fixed, and a high-pressure mercury lamp (160 W/cm) was irradiated on the coated surface under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side.

Next, to the side of the film on which the crosslinked resin layer is not formed, paint A was applied and cured in the same manner as described above, thereby obtaining a transparent laminated film 8 having a crosslinked resin layer formed on both surfaces thereof.

For the transparent laminated film 8, the heat shrinkage was measured in the same manner as in Example 1, the heat shrinkage in the longitudinal direction (MD direction) was 1.51%, and the heat shrinkage in the horizontal direction (TD direction) was 0.42%.

<Reference Example 4>

(Preparation of photocurable composition 3)

Photocurable 6-functional urethane acrylate (molecular weight: 800, manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``U-6LPA'') 42.75% by mass, photocurable trifunctional acrylate monomer (pentaerythritol triacrylate, molecular weight 298, Shinnakamura Chemical Industry Co., Ltd. make, brand name ``ATMM-3LM-N'') 42.75 mass%, silica fine particles (Nissan Chemical Industry Co., Ltd. make, brand name ``MEK-ST-L'', average particle diameter 50 nm) in terms of solid content 12.8 mass%, photopolymerization initiator 1.7% by mass of A (manufactured by BASF, brand name "IRGACURE127") was uniformly diluted with a solvent (propylene glycol monomethyl ether and methyl ethyl ketone) to obtain curable composition 3 (paint C) for forming a crosslinked resin layer.

(Production of transparent laminated film 9)

On one side of a 23 μm thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., brand name ``diafoil''), the paint C prepared above was applied using a gravure coater so that the thickness after curing became 1 μm, and then a solvent Was dried and removed, and a high pressure mercury lamp (160 W/cm) was irradiated on the coated surface to obtain a film having a photocurable crosslinked resin layer on one side.

Next, to the side of the film on which the crosslinked resin layer is not formed, paint C was applied and cured in the same manner as described above, thereby obtaining a transparent laminated film 9 having a crosslinked resin layer formed on both sides.

As for the transparent laminated film 9, the heat shrinkage was measured in the same manner as in Example 1, the heat shrinkage in the longitudinal direction (MD direction) was 1.45%, and the heat shrinkage in the horizontal direction (TD direction) was 0.54%.

Above, the results of Reference Examples 1 to 4 are summarized in Table 2.

(Review)

From the above examples, reference examples, and test results performed by the inventors so far, it was found that thermal dimensional stability can be improved by disposing a crosslinked resin layer having a predetermined thickness on both sides of the substrate. Specifically, by designing the total thickness of the crosslinked resin layer to be 8% or more of the thickness of the base film, when the transparent conductive film is heated at 200°C for 10 minutes, the heat shrinkage in the vertical direction and the horizontal direction is It was found that all can be done below 1.50%.

Thereby, when forming a transparent conductive layer, it becomes possible to apply a process at a high temperature, specifically a film forming method in an atmosphere at a temperature of 150 to 220°C, and the surface resistance value of the transparent conductive film is reduced to 150 Ω/□ or less. I could see that I could.

[About this laminated film]

Next, the present laminated film is described in detail below using Examples 6 to 14 and Comparative Example 3.

<Measurement method about the properties of this laminated film>

(Appearance of the coating film)

The present laminated film obtained in Examples and Comparative Examples was visually observed, and the presence or absence of cracks or whitening was evaluated based on the following criteria.

(Circle): The whole is transparent, and gold, whitening, etc. are not recognized at all.

?: Either gold or white flower is confirmed.

X: Both gold and white flowers are confirmed.

(Measurement method of heat shrinkage)

From the present laminated film obtained in Examples and Comparative Examples, a film was cut out in a strip shape of 140 mm in length and 10 mm in width, respectively, in the longitudinal direction and in the transverse direction, and a test piece with marks at intervals of 100 mm in length was set at 200°C. It was suspended in a constant temperature bath for 10 minutes under no load, taken out, and allowed to cool at room temperature for 15 minutes or more, and the heat shrinkage rate was calculated as a% value from the length between the marked lines before and after placing in the thermostat. On the other hand, the measurement was performed 5 times each, the average value thereof was calculated, and the value obtained by rounding off the third decimal place was described. On the other hand, the heat shrinkage rate was measured for both the longitudinal direction (MD direction) that is the longitudinal direction of the film and the transverse direction (TD direction) orthogonal thereto. Table 3 shows the obtained heat shrinkage.

(Measurement method of total light transmittance)

The total light transmittance of this laminated film obtained in Examples and Comparative Examples was measured by a method conforming to JIS K7105 using the following apparatus.

Reflective/Transmittance Meter: Murakami Color Technology Research Institute ``HR-100''

[Example 6]

(Preparation of curable composition a)

A photocurable bifunctional acrylate monomer having a molecular weight of 304 (manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``A-DCP'', tricyclodecane dimethanol diacrylate) 22.1% by mass, silica fine particles (manufactured by Admatex Co., Ltd., brand name) ``YA010C-SM1'') 77.2% by mass, photocuring agent A (BASF product, brand name ``IRGACURE127'') 0.6% by mass, photocuring agent B (BASF product, brand name ``IRGACURE184'') 0.1% by mass, solvent (propylene glycol monomethyl ether And ethyl methyl ketone) to obtain a curable composition a (paint a) for forming a crosslinked resin layer.

(Preparation of transparent laminated film a)

On one side of a 50 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., brand name "diafoil T600E50", thermal shrinkage rate based on the measurement method described above: MD direction = 1.51%, TD direction = 0.31), the above-described The paint a prepared in was applied using a wire bar coater so that the thickness after curing became 3 μm, and then the solvent was dried and removed. Then, the film was put in a belt conveyor device while the end portion of the film was fixed, and a high pressure mercury lamp (160 W/cm) was irradiated on the coated surface under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side.

To the side of the film on which the crosslinked resin layer is not formed, a coating material a was applied and cured in the same manner as above to obtain a transparent laminated film a having a crosslinked resin layer formed on both surfaces thereof.

[Example 7]

(Production of transparent laminated film b)

It carried out similarly to Example 6 except having applied so that the thickness after hardening of one side might become 10 micrometers, and obtained the transparent laminated film b in which the crosslinked resin layer was formed on both surfaces. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 8]

(Preparation of curable composition b)

A photocurable bifunctional acrylate monomer having a molecular weight of 226 (manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``A-HD-N'') 17.7% by mass, a photocurable six-functional acrylate monomer having a molecular weight of 578 (manufactured by Shin-Nakamura Chemical Co., Ltd. , Brand name ``A-DPH'') 4.4% by mass, silica fine particles (manufactured by Admatex Co., Ltd., brand name ``YA010C-SM1'') 77.2% by mass, photoinitiator A (made by BASF, brand name ``IRGACURE127'') 0.6% by mass, photopolymerization initiator B (made by BASF, brand name "IRGACURE184") 0.1% by mass was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone) to obtain a curable composition b (paint b) for forming a crosslinked resin layer.

(Preparation of transparent laminated film c)

Except having applied the paint b, it carried out similarly to Example 6, and obtained the transparent laminated film c in which the crosslinked resin layer was formed on both surfaces. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 9]

(Preparation of transparent laminated film d)

It carried out similarly to Example 8 except having applied so that the thickness after hardening of one side might become 10 micrometers, and obtained the transparent laminated film d in which the crosslinked resin layer was formed on both sides. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 10]

(Preparation of curable composition c)

22.1 mass% of photocurable bifunctional acrylate monomer having a molecular weight of 226 (manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``A-HD-N''), 77.2 mass of silica fine particles (manufactured by Admatex Co., Ltd., brand name ``YA010C-SM1'') %, photopolymerization initiator A (BASF product, brand name ``IRGACURE127'') 0.6% by mass, photo polymerization initiator B (BASF product, brand name ``IRGACURE184'') 0.1% by mass, uniformly with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone) It diluted and obtained the curable composition c (paint c) for crosslinking resin layer formation.

(Production of transparent laminated film e)

Except having applied the paint c, it carried out similarly to Example 6, and obtained the transparent laminated film e in which the crosslinked resin layer was formed on both surfaces. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 11]

(Production of transparent laminated film f)

It carried out similarly to Example 10 except having applied so that the thickness after hardening of one side might become 10 micrometers, and obtained the transparent laminated film f in which the crosslinked resin layer was formed on both sides. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 12]

(Preparation of curable composition d)

A photocurable trifunctional acrylate monomer having a molecular weight of 537 (Shin-Nakamura Chemical Co., Ltd. make, brand name ``A-9300-1CL'') 22.1 mass%, silica fine particles (made by Admatex Co., Ltd., brand name ``YA010C-SM1'') 77.2 mass %, photocuring agent A (BASF product, brand name "IRGACURE127") 0.6% by mass, photocuring agent B (BASF product, brand name "IRGACURE184") 0.1% by mass, uniformly with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone) It diluted to obtain a curable composition d (paint d) for forming a crosslinked resin layer.

(Preparation of transparent laminated film g)

Except having applied the paint d, it carried out similarly to Example 6, and obtained the transparent laminated film g in which the crosslinked resin layer was formed on both surfaces. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 13]

(Preparation of transparent laminated film h)

It carried out similarly to Example 12 except having applied so that the thickness after hardening of one side might become 10 micrometers, and obtained the transparent laminated film h in which the crosslinked resin layer was formed on both sides. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Example 14]

(Preparation of curable composition e)

Photocurable polyfunctional acrylate oligomer with a weight average molecular weight (Mw) of 1500 (manufactured by Nippon Gosei Chemical Industries, Ltd., brand name ``UV-7640B'') 22.1% by mass, silica fine particles (manufactured by Admatex, brand name ``YA010C-SM1'') ) 77.2% by mass, photoinitiator A (BASF, brand name ``IRGACURE127'') 0.6% by mass, photo polymerization initiator B (BASF, brand name ``IRGACURE184'') 0.1% by mass, solvent (propylene glycol monomethyl ether and ethyl methyl ketone) And uniformly diluted with to obtain a curable composition e (paint e) for forming a crosslinked resin layer.

(Preparation of transparent laminated film i)

Except having applied the paint e, it carried out similarly to Example 7, and obtained the transparent laminated film i in which the crosslinked resin layer was formed on both surfaces. The values of the heat shrinkage and total light transmittance are shown in Table 3.

[Comparative Example 3]

(Production of laminated film 1)

It carried out similarly to Example 6 except having applied so that the thickness after hardening of one side might become 1 micrometer, and obtained the laminated film 1 in which the crosslinked resin layer was formed on both sides. The values of the heat shrinkage are shown in Table 3.

(Review)

From the results of the above Examples and Comparative Examples, by using a configuration in which a crosslinked resin layer having a predetermined thickness or more is disposed on a base film, it is possible to impart thermal dimensional stability at high temperatures that could not be achieved with only a base film having a thickness of 75 μm or less. I could see that it was set. In particular, as shown in Comparative Example 1, it was found that in the region where the thickness of the base film is thin, the effect of improving the thermal dimensional stability of the crosslinked resin layer cannot be obtained unless a crosslinked resin layer having a specific thickness is laminated.

[About this gas barrier film]

Finally, the present gas barrier film is described in detail below using Examples 15 to 16 and Comparative Examples 4 to 7.

<Measurement method about the properties of this gas barrier film>

About the films produced in the following Examples 15 and 16 and Comparative Examples 4 to 7, the total light transmittance, surface smoothness, and heat shrinkage were measured in accordance with the methods described below.

(Measurement of total light transmittance and haze)

The total light transmittance and haze of the films of Examples and Comparative Examples were measured by a method conforming to JIS K7105 using the following apparatus.

Apparatus: Reflective/Transmittance Meter: Murakami Color Technology Research Institute ``HR-100''

(Average particle diameter)

The average particle diameter of the fine particles was measured using TEM H-7650 manufactured by Hitachi High Technologies.

Specifically, after the acceleration voltage was set to 100 V and a digital image was acquired, the particle diameters of 200 particles were measured at random from the obtained image, and the average was determined to be the average particle diameter of the fine particles.

(Surface smoothness)

The surface smoothness, that is, the arithmetic mean roughness (Sa) of the crosslinked resin layer of the film, was determined by the optical interference method using "VertScan" (registered trademark) of Ryoka Systems Co., Ltd., and the surface shape and surface roughness in the area of 469 μm×352 μm. Was measured.

(Heating shrinkage rate)

The shrinkage ratio in the longitudinal direction (MD direction) of the film is according to JIS-C2330 7.4.6.1 (Shrink dimensional change rate: method A), the temperature of the thermostat was changed from 120°C to 150°C and 180°C, respectively, and marked The rate of dimensional change before and after heating of the strip was measured and determined.

Specifically, it measured by the following method. Three strip-shaped test pieces having a width of 10 mm and a length of 140 mm were prepared with the film flow direction as the long side, and marks with an interval of 100 mm were written around the center of each test piece. The gap between the marks was read using a vernier with an accuracy of 0.01 mm. This test piece was suspended in a constant temperature bath at a predetermined temperature for 10 minutes under no load, taken out, and allowed to cool at room temperature for 15 minutes or more, and the interval between the previously read marks was measured. The rate of change of the spacing between the marked lines before and after heating was determined, and it was set as the rate of change in dimensionality before and after heating.

[Example 15]

(Preparation of curable composition i)

Photocurable bifunctional acrylate monomer/oligomer having a tricyclodecane structure (manufactured by Shin-Nakamura Chemical Co., Ltd., brand name ``A-DCP'') 21.8% by mass, transparent fine particles A (manufactured by Admatex Co., Ltd., brand name ``YA010C- SM1'', colloidal silica, average particle diameter 10 nm) 77.5 mass%, photopolymerization initiator (BASF, 1-hydroxycyclohexyl-phenyl ketone) 0.7 mass%, solvent (Arakawa Chemical Industries, Ltd. product, propylene glycol monomethyl ether) 34.1 parts by mass was uniformly mixed to obtain a curable composition i for forming a crosslinked resin layer (hereinafter, referred to as "coating i". The solid content in the composition was 66%).

(Production of double-sided crosslinked resin layer)

As a base film, a 50 μm thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name ``P100-T50'') was used, and the coating i prepared above was applied to one side of this film, and a wire so that the thickness after curing became 10 μm. After coating with a bar coater, let stand for 2 minutes, then dry and remove the solvent by placing it in an oven set at 100°C for 10 minutes, and put it in a belt conveyor device with the end of the film fixed, and a high pressure mercury lamp on the coated surface. (160 W/cm) was irradiated to obtain a film having a photocurable crosslinked resin layer on one side. The volume ratio of colloidal silica in the crosslinked resin layer was 63.4% by volume.

Thereafter, to the side of the film on which the crosslinked resin layer was not formed, paint i was applied and cured in the same manner as described above.

(Formation of gas barrier layer)

The PET film on which the crosslinked resin layer was formed was introduced into a sputtering film forming apparatus, and on the crosslinked resin layer on one side of the PET film, by a reactive sputtering method using an Al target, a film forming pressure of 0.3 Pa, an Ar flow rate of 80 sccm, and an oxygen flow rate of 20 sccm , 20 nm of an aluminum oxide layer was formed under the conditions of input power of 4 kW, and a gas barrier laminated film 1 was obtained. Table 4 shows the results of evaluating the properties of the obtained gas barrier laminated film 1 in accordance with the above-described measurement method.

[Example 16]

(Production of double-sided crosslinked resin layer)

A 50 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name ``P100-T50'') was used as the base film, and the same coating i as in Example 15 was applied to one side of the film, and the thickness after curing was 7.5. After coating with a wire bar coater so that it becomes μm, after allowing it to stand for 2 minutes, it is then placed in an oven set at 100°C for 10 minutes to dry and remove the solvent, and the end of the film is fixed to the belt conveyor device, and the coated surface Was irradiated with a high-pressure mercury lamp (160 W/cm) to obtain a film having a photocurable crosslinked resin layer on one side. The volume ratio of colloidal silica in the crosslinked resin layer was 63.4% by volume.

Thereafter, to the side of the film on which the crosslinked resin layer was not formed, paint i was applied and cured in the same manner as above.

(Formation of gas barrier layer)

The PET film in which the crosslinked resin layer was formed was introduced into a sputtering film forming apparatus, and on one side of the crosslinked resin layer of the PET film, by a reactive sputtering method using an Al target, a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, and an oxygen flow rate An aluminum oxide layer of 20 nm was formed under the conditions of 20 sccm and an input power of 4 kW to obtain a gas barrier laminated film 2. Table 4 shows the results of evaluating the properties of the gas barrier laminated film 2 obtained in accordance with the above-described measurement method.

[Comparative Example 4]

(Formation of gas barrier layer)

As a base film, a 50 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name ``P100-T50'') was used, and a reaction sputtering method using an Al target on one side of the film, a film formation pressure of 0.3 Pa, Ar A 20 nm aluminum oxide layer was formed under conditions of a flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input power of 4 kW to obtain a laminated film 2.

Table 4 shows the results of evaluating the properties of the obtained laminated film 2 in accordance with the above-described measurement method.

[Comparative Example 5]

(Preparation of curable composition ii)

To 97% by mass of the polymerizable resin composition of urethane acrylate (manufactured by Daiichi Pharmaceutical Co., Ltd., ``New Frontier R-1302''), 3% by mass of a photopolymerization initiator (manufactured by BASF, 1-hydroxycyclohexyl-phenylketone), a solvent (Arakawa Chemical Industries, Ltd. make, methyl ethyl ketone) 34.1 parts by mass were uniformly mixed to obtain a curable composition ii for forming a crosslinked resin layer (hereinafter referred to as "paint ii". The solid content in the composition was 60%.) .

(Formation of double-sided crosslinked resin layer)

As a base film, a 50 μm thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name “P100-T50”) is used, and a wire bar coater is used so that the thickness after curing paint ii on one side of this film becomes 2 μm. After application, let stand for 2 minutes, then dry and remove the solvent by placing it in an oven set at 100°C for 10 minutes, and put it in a belt conveyor device with the end of the film fixed, and a high pressure mercury lamp (160W/cm) on the coated surface. ) Was irradiated to obtain a film having a photocurable crosslinked resin layer on one side. The volume ratio of colloidal silica in the crosslinked resin layer was 0% by volume.

Thereafter, to the side of the film on which the crosslinked resin layer was not formed, paint ii was applied and cured in the same manner as above.

(Formation of gas barrier layer)

The PET film on which the crosslinked resin layer was formed was introduced into a sputtering film forming apparatus, and on one side of the crosslinked resin layer of the PET film, by a reactive sputtering method using an Al target, a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, and an oxygen flow rate An aluminum oxide layer of 20 nm was formed under the conditions of 20 sccm and input power of 4 kW to obtain a laminated film 3. Table 4 shows the results of evaluating the properties of the obtained laminated film 3 in accordance with the measurement method described later.

[Comparative Example 6]

(Production of double-sided crosslinked resin layer)

A 50 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name “P100-T50”) was used as the base film, and the same coating i as in Example 15 was applied to one side of the film, and the thickness after curing was 10 μm. After coating with a wire bar coater so that it is applied, it is allowed to stand for 2 minutes, and then the solvent is dried and removed by placing it in an oven set at 100°C for 10 minutes, and the end of the film is fixed to the belt conveyor device, A high-pressure mercury lamp (160 W/cm) was irradiated to obtain a film having a photocurable crosslinked resin layer on one side.

Thereafter, to the side of the film on which the crosslinked resin layer was not formed, paint i was applied and cured in the same manner as above.

(Formation of gas barrier layer)

The PET film on which the crosslinked resin layer was formed was introduced into a sputtering film forming apparatus, and on one side of the crosslinked resin layer of the PET film, by a reactive sputtering method using an Al target, a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, and an oxygen flow rate An aluminum oxide layer was formed to be 4 nm under the conditions of 20 sccm and input power of 4 kW to obtain a laminated film 4. Table 4 shows the results of evaluating the properties of the obtained laminated film 4 in accordance with the above-described measurement method.

[Comparative Example 7]

(Production of double-sided crosslinked resin layer)

A 50 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name “P100-T50”) was used as the base film, and the same coating i as in Example 15 was applied to one side of the film, and the thickness after curing was 10 μm. After coating with a wire bar coater so that it is applied, it is allowed to stand for 2 minutes, and then the solvent is dried and removed by placing it in an oven set at 100°C for 10 minutes. A high-pressure mercury lamp (160 W/cm) was irradiated to obtain a film having a photocurable crosslinked resin layer on one side.

Thereafter, to the side of the film on which the crosslinked resin layer was not formed, paint i was applied and cured in the same manner as above.

(Formation of gas barrier layer)

The PET film on which the crosslinked resin layer was formed was introduced into a sputtering film forming apparatus, and on one side of the crosslinked resin layer of the PET film, by a reactive sputtering method using an Al target, a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, and an oxygen flow rate An aluminum oxide layer was formed to be 1 nm under the conditions of 20 sccm and input power of 4 kW to obtain a laminated film 5. Table 4 shows the results of evaluating the properties of the obtained laminated film 5 in accordance with the above-described measurement method.

(Review)

Since the gas barrier laminated films of Examples 15 and 16 have a predetermined crosslinked resin layer on both sides of the substrate and have a gas barrier layer with an appropriate thickness on at least one side thereof, it is highly resistant to heating while having high barrier properties. It has dimensional stability for.

On the other hand, in Comparative Example 4, since the surface was rough, high barrier properties were not exhibited, and shrinkage occurred with respect to heating. Comparative Example 5 has a barrier property because the crosslinked resin layer is provided on both sides, and the surface smoothness is improved compared to Comparative Example 4, but since the crosslinked resin layer is not filled with particles, the substrate shrinks during heating. It was overwhelmed by stress, and shrinkage occurred in the entire film, resulting in loss of performance.

In Comparative Examples 5 and 6, since the thickness of the barrier film was not appropriate, the barrier property was not exhibited.

The transparent conductive film proposed by the present invention can be most suitably used for applications requiring dimensional stability at high temperatures and excellent surface resistance values, especially for substrates of touch panels. In addition, liquid crystal displays, organic light emitting displays (OLEDs), It can also be suitably used for substrates for display materials such as electrophoretic displays (electronic paper, etc.), color filters, and backlights, substrates for solar cells, substrates for organic light emission, and optoelectronic device substrates.

The transparent laminated film proposed by the present invention can be most suitably used for applications requiring dimensional stability at high temperatures, especially for touch panel substrates, and other packaging films, liquid crystal displays, organic light emitting displays (OLEDs), and electricity It can be suitably used as a substrate for display materials such as an electrophoretic display (electronic paper, etc.), a color filter, a backlight, or a film for electronic components such as a substrate for a solar cell or a substrate for organic light emission.

The gas barrier laminated film proposed by the present invention can be most suitably used for applications requiring dimensional stability and gas barrier properties at high temperatures, substrates for organic light-emitting lighting or substrates for organic light-emitting displays (OLEDs). It can be suitably used as a substrate for display materials such as a liquid crystal display, an electrophoretic display (electronic paper, etc.), a color filter, a backlight, or a film for electronic components such as a substrate for a solar cell.

Claims (24)

A transparent laminated film having a crosslinked resin layer is provided on both sides of the base film, and a transparent conductive layer is provided on one or both sides of the front and back of the transparent laminated film directly or via an undercoat layer, and the total thickness of the crosslinked resin layer As a transparent conductive film having 8% or more of the thickness of the temporary base film,
The transparent laminated film has a heat shrinkage of 1.5% or less when heated at a temperature of 200° C. for 10 minutes in the vertical direction and the horizontal direction, and the surface resistance value of the transparent conductive film is 150 Ω/□ or less, and the substrate A transparent conductive film in which the film contains a resin having a glass transition temperature (Tg) of 130°C or lower. The method of claim 1,
A transparent conductive film, wherein the total thickness of the crosslinked resin layer on both sides of the front and back is 8% or more and 50% or less of the thickness of the base film. The method according to claim 1 or 2,
The undercoat layer is a transparent conductive film characterized in that it contains substantially no inorganic fine particles. The method according to claim 1 or 2,
The crosslinked resin layer is a resin layer having a crosslinked structure obtained by crosslinking a polyfunctional acrylate monomer having two or more acryloyl groups or methacryloyl groups in one molecule. The method of claim 4,
Transparent, characterized in that the polyfunctional acrylate monomer is an alicyclic polyfunctional acrylate monomer having an alicyclic structure, or a polyfunctional urethane acrylate monomer having three or more acryloyl groups or methacryloyl groups in one molecule Conductive film. The method according to claim 1 or 2,
The crosslinked resin layer is a transparent conductive film characterized in that it contains substantially no fine particles. The method according to claim 1 or 2,
The crosslinked resin layer contains 40 to 80 mass% of fine particles having an average particle diameter of 200 nm or less. delete The method according to claim 1 or 2,
The transparent conductive film, wherein the base film is a film containing polyethylene terephthalate resin and biaxially stretched. The method according to claim 1 or 2,
The transparent conductive film, wherein the transparent conductive layer is an inorganic oxide film formed in an atmosphere at a temperature of 150 to 220°C. The method according to claim 1 or 2,
The transparent conductive film, characterized in that the thickness of the transparent conductive layer is less than 100 nm. A laminated film having a crosslinked resin layer on both sides of a base film,
The first feature is that the crosslinked resin layer is formed using a curable composition containing a photopolymerizable compound, a photopolymerization initiator, and fine particles, and the thickness of the base film and the crosslinked resin layer satisfies the following (a) and (b). And
The thermal contraction rate of the laminated film in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200°C for 10 minutes is 70 of the thermal contraction rate when the base film is heated under the same conditions. % Or less, and the second feature is that the total light transmittance of the laminated film is 80% or more,
The transparent laminated film, wherein the base film contains a resin having a glass transition temperature (Tg) of 130°C or lower.
(a) The thickness of the base film is 75 μm or less
(b) The total thickness of both sides of the crosslinked resin layer is 8% or more of the thickness of the base film The method of claim 12,
A transparent laminated film in which the total thickness of both sides of the crosslinked resin layer is 8% or more and 50% or less of the thickness of the base film. The method of claim 12 or 13,
A transparent laminated film in which the curable composition contains 9 to 50 mass% of a photopolymerizable compound, 0.1 to 10 mass% of a photoinitiator, and 10 to 90 mass% of fine particles with respect to the entire composition. The method of claim 12 or 13,
A transparent laminated film in which the photopolymerizable compound is a photopolymerizable (meth)acrylate monomer or oligomer having two or more acryloyl groups or methacryloyl groups in one molecule. The method of claim 12 or 13,
A transparent laminated film in which the photopolymerizable compound is an alicyclic polyfunctional acrylate monomer having at least one alicyclic structure in one molecule. The method of claim 12 or 13,
A transparent laminated film in which the base film is a biaxially stretched film containing a polyethylene terephthalate resin. A structure in which a base film, a crosslinked resin layer on both sides of the base film, and a gas barrier layer on at least one side of the crosslinked resin layer, and the total thickness of both sides of the crosslinked resin layer is 8% or more of the thickness of the base film As a gas barrier laminated film having,
The first feature is that the crosslinked resin layer is formed using a photopolymerizable compound, a photopolymerization initiator, and a curable composition containing fine particles, and the average particle diameter of the fine particles is in the range of 1 nm to 50 nm,
The second feature is that the thickness of the gas barrier layer is in the range of 5 to 100 nm,
The third feature is that the water vapor transmittance of the entire film is 1.0 × 10 ^-2 g/m ² /day or less,
The gas barrier laminated film, wherein the base film contains a resin having a glass transition temperature (Tg) of 130°C or lower. The method of claim 18,
A gas-barrier laminated film in which the gas barrier layer is formed of an inorganic compound comprising at least one of oxides, nitrides, and oxynitrides of silicon (Si) or aluminum (Al). The method of claim 18 or 19,
A gas barrier laminate film having an arithmetic mean roughness (Sa) of 15 nm or less on one side of the crosslinked resin layer. The method of claim 18 or 19,
A gas barrier laminated film having a thickness of the base film of 100 μm or less. The method of claim 18 or 19,
The gas barrier laminated film, wherein the content of the fine particles is 50 to 75% by volume based on the entire crosslinked resin layer. The method of claim 18 or 19,
A gas-barrier laminated film in which the total thickness of the front and back sides of the crosslinked resin layer is 8% to 50% of the thickness of the base film. The method of claim 18 or 19,
A gas barrier laminated film in which the photopolymerizable compound is an alicyclic polyfunctional acrylate monomer having at least one alicyclic structure in one molecule.