TW201441037A - Transparent laminated film, transparent conductive film and gas-barrier laminated film - Google Patents

Abstract

The present invention provides a novel transparent conductive film, which has excellent transparency property and thermal dimensional stability at high temperature (such as 200 DEG C and above), and has lower surface resistance. The invention further provides a novel transparent laminated film and a gas-barrier laminated film that can be used on a substrate film and other kinds of transparent substrates of the transparent conductive film. The transparent conductive film contains a transparent laminated film having a cross-linked resin layer on at least one side of a substrate film, in which a transparent conductive layer is formed directly or by a underlying coating composed of a resin material on one or both sides of the cross-linked resin layer, characterized firstly in that the heat shrinkage rate of the above transparent laminated film along the vertical direction and horizontal direction is 1.5% and below when heating at a temperature of 200 DEG C for 10 minutes, and characterized secondly in that the surface resistance of the above transparent conductive film is 150 Ω / □ and below.

Description

Transparent laminated film, transparent conductive film and gas barrier laminated film

The present invention relates to a transparent laminated film which can be used as a substrate material such as a solar cell, an organic solar cell, a flexible display, an organic electroluminescence (EL), a touch panel, or the like, and further relates to a conductive film. A transparent conductive film and a gas barrier laminated film having a gas barrier layer.

It is known that a glass material has been used as a substrate material of various display elements such as organic EL or solar cells. However, the glass material is not only disadvantageous in that it is easily broken, heavy, and difficult to be thinned, and it is not a sufficient material for the thinning and weight reduction of the display or the softening of the display in recent years. Therefore, as a substitute material for glass, a thin and lightweight transparent resin film substrate has been studied.

In the above application, when a film-form resin substrate is used, high heat resistance is required for the film. For example, when a circuit such as a thin film transistor (TFT) is formed on a resin film, in order to prevent pattern shift when the circuit is formed, a resin film used for such use is required as a TFT. The dimensional stability of the heat treatment temperature is about 200 ° C.

In the resin film having gas barrier properties, in order to prevent cracks or wrinkles due to the functional layer having gas barrier properties, the functional layer is broken to impair the function including gas barrier properties, and is also required to be 150 ° C. The thermal size is stable under the above high temperature environment Sex.

However, the conventional polyester film is equivalent to a high temperature environment of 150 ° C or higher, specifically, a heat dimensional stability of a high temperature environment of 150 ° C to 200 ° C is not sufficient. 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 to a resin film in a high-temperature environment, for example, Patent Document 1 discloses a method of adding a thermal relaxation treatment (also referred to as "annealing treatment" and "heat setting treatment") as a final step of a film manufacturing step. means.

Further, Patent Documents 2 and 3 disclose a method of forming various coating films on the surface of a film produced by a usual procedure.

When a transparent conductive film such as a metal oxide film such as ITO (Indium Tin Oxide) is formed on a transparent resin film, the film is usually formed by sputtering at room temperature, and thus the amorphous property is high. Therefore, a transparent conductive film formed on a transparent resin film is significantly inferior in surface resistance value, durability, acid resistance, and the like as compared with a case where a transparent conductive film such as an ITO film is formed on a glass substrate. Therefore, in recent years, a transparent conductive film which improves the crystallinity of a transparent conductive film is required.

As a means for improving the crystallinity of a transparent conductive film such as an ITO film, for example, Patent Document 4 discloses a method in which an ITO film is formed on a polymer film substrate, and then heat treatment is performed to crystallize ITO. 5 discloses a method of crystallizing an ITO film by irradiating a microwave.

On the other hand, Patent Document 6 discloses a transparent electrode substrate for a solar cell using a resin molded body obtained by curing a photopolymerizable composition. Since the resin molded body has high heat resistance, the substrate temperature can be raised to 150 ° C when the transparent electrode layer is formed.

Further, Patent Document 7 discloses a transparent conductive film having an organic layer on both sides of a polymer film, an inorganic layer on at least one side of the organic layer, and a transparent layer on the outermost layer. Conductive layer. Since the transparent conductive film has flexibility in which cracking is less likely to occur even if the thickness of the conductive layer is made thick, the thickness of the conductive layer can be relatively increased to lower the surface resistance value.

Patent Document 8 discloses a composite film for an electronic device comprising a coated polyester substrate layer and an electrode layer containing a conductive material. The coated polyester substrate in the composite film is improved in flexibility and resistant to cracking.

Patent Document 9 discloses a laminated film in which a cyclic olefin-based polymer layer, a fixed coating layer containing metal oxide fine particles, and a transparent conductive layer are sequentially laminated. The laminated film has a property that the transparent conductive layer does not cause cracking for a long period of time, and has low resistance, high strength, and excellent mechanical durability, and can be used for a touch panel.

Further, as a transparent film which can be used for a transparent substrate, Patent Document 10 discloses a transparent laminated film having a hardened layer on both sides of a base film. The transparent laminated film is excellent in transparency and thermal dimensionality at high temperatures, and can be used as a substrate for a solar cell, an organic solar cell, a flexible display, an organic EL illumination, a touch panel, or the like.

In addition, as a transparent film which can be used for a transparent substrate, Patent Document 11 discloses a composite film which comprises a film of a polymer substrate and a planarization coating layer, and has a coating layer formed thereon. a barrier layer on the surface. The composite film has high dimensional stability due to heat setting and heat stabilization of the polymer substrate.

Patent Document 12 discloses that there is an average linear expansion coefficient of 50. A layer (layer A) of ppm/K or less and a transparent multilayer sheet of a layer (layer B) having a tensile modulus of 1 GPa or less. More specifically, a transparent multilayer sheet composed of a B layer/A layer/B layer 3 layer is disclosed, and the total light transmittance of the multilayer sheet is 91% and the average linear expansion coefficient is 43 ppm/ K, excellent in transparency and dimensional stability.

Patent Document 13 discloses a laminated film having a particle-containing layer (II) on both surfaces of a film (I) containing a cyclic olefin-based polymer, and the particle-containing layer (II) is used. It is formed by a surface-modified oxide particle of a specific compound and a curable composition having a polymerizable unsaturated group having a specific structure, and the particle-containing layer (II) is a film thickness of 100 with respect to the film (I). And layered in the range of 0.1~30.

Patent Document 14 discloses a polyimine or a polyamine which has high dimensional stability at high temperature and high transparency. Since these films are formed by the casting method, there is almost no alignment, so that shrinkage does not occur during heating.

As a method of improving the gas barrier property, there is proposed a method in which an inorganic transparent film such as ruthenium oxide is laminated on a polyester film by vacuum evaporation or sputtering, thereby improving oxygen or water vapor permeability (for example, refer to the patent document) 15).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-265318

Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-277455

Patent Document 3: Japanese Patent No. 2952769

Patent Document 4: Japanese Patent Laid-Open No. 2-194943

Patent Document 5: Japanese Patent Laid-Open Publication No. 2005-141981

Patent Document 6: Japanese Patent Laid-Open Publication No. 2008-85323

Patent Document 7: Japanese Patent Laid-Open Publication No. 2000-353426

Patent Document 8: International Publication No. 09/016388

Patent Document 9: Japanese Patent Laid-Open Publication No. 2009-029108

Patent Document 10: International Publication No. 13/022011

Patent Document 11: Japanese Patent Laid-Open Publication No. 2011-518055

Patent Document 12: Japanese Patent Laid-Open Publication No. 2007-298732

Patent Document 13: Japanese Patent Laid-Open Publication No. 2010-23234

Patent Document 14: Japanese Patent Laid-Open No. 61-141738

Patent Document 15: Japanese Patent Laid-Open Publication No. 2006-96046

As described above, in order to reduce 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. As a means for this, it is considered to improve transparency by forming a transparent conductive film at a high temperature. A means of crystallinity of a conductive film. For example, if a transparent conductive film which is usually formed by sputtering at room temperature can be formed by sputtering under a high temperature environment, for example, a temperature of 150 to 220 ° C, the crystal of the transparent conductive film can be improved. Sex.

However, a biaxially stretched polyethylene terephthalate (PET) film which is generally used as a base film is equivalent to heat shrinkage in the above high temperature environment, so that the transparent conductive film cannot be formed in a high temperature environment. problem. In this way, if a completely new material having excellent thermal dimensional stability is used, there is a possibility that various unexpected problems occur, and the cost becomes high.

Accordingly, it is an object of the present invention to provide an example that can be improved in a high temperature environment. For example, the transparent dimensionally stable film can be further improved in thermal dimensional stability in an environment of 200 ° C or higher.

Further, not only a film which can be manufactured by a simpler manufacturing process but also a thin resin film and a higher heat resistance is required in the future use environment.

Accordingly, an object of the present invention is to provide a novel transparent laminated film which is excellent in transparency and high dimensional stability at a high temperature of, for example, 200 ° C or higher, but which can also reduce the thickness of the film.

Further, in the case of using a film using a gas barrier improving method, in the heat annealing step required for forming a transparent electrode or a member on the film, the polyester film as a substrate shrinks, and thus there is a loss of gas. The possibility of barrier properties. In this way, it is required to be manufactured by a simpler manufacturing process, and it is required to develop a film having high heat resistance and excellent gas barrier properties in a future use environment.

Accordingly, an object of the present invention is to provide a gas barrier laminated film which is excellent in gas barrier properties and excellent in thermal dimensional stability at a high temperature of, for example, 150 ° C or higher.

The present invention provides a transparent conductive film which is provided with a transparent laminated film having a crosslinked resin layer on the front and back sides of the substrate film, directly or via the undercoat layer on the front side or both sides of the transparent laminated film. Further, the transparent conductive layer is provided, and the thickness of the crosslinked resin layer is 8% or more of the thickness of the base film, and the transparent laminated film is heated in the longitudinal direction and the transverse direction at a temperature of 200 ° C for 10 minutes. The heat shrinkage rate is 1.5% or less, and the surface resistivity of the transparent conductive film is 150 Ω/□ or less.

The transparent conductive film of the present invention has a crosslinked resin layer on both sides of the base film, and the thickness of the crosslinked resin layers is set to be thin. When the thickness of the film is 8% or more, the crosslinked resin layer resists the shrinkage even when the substrate film is to be shrunk in a high-temperature environment, and the shrinkable stress can be absorbed as a whole of the transparent conductive film, so that the transparent conductive film can be improved. Thermal dimensional stability. Specifically, it is possible to obtain thermal dimensional stability of 1.5% or less when heated at a temperature of 200 ° C for 10 minutes in the longitudinal direction and the transverse direction.

Therefore, since the transparent conductive film of the present invention can form a transparent conductive layer in a high-temperature environment such as 150 to 220 ° C, the crystallinity of the transparent conductive layer can be improved, thereby effectively reducing the surface of the transparent conductive film. resistance.

The transparent conductive film proposed by the present invention can obtain the advantages as described above, and thus can be preferably used for, 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 substrate of a solar cell can be preferably used for a photovoltaic element substrate or the like.

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 parts. Moreover, it can also be preferably used for a semiconductor device such as an organic EL, a liquid crystal display element, or a solar cell by performing gas barrier processing.

Moreover, the present invention provides a transparent laminated film which is a laminated film having a crosslinked resin layer on both sides of a base film, and is characterized in that the crosslinked resin layer contains a photopolymerizable compound and light. The polymerization initiator and the hardenable composition of the fine particles are formed, and the thickness of the base film and the crosslinked resin layer satisfy the following (a) and (b), and the second feature is that the temperature is heated at a temperature of 200 ° C. The thermal contraction rate of the laminated film in at least one of the longitudinal direction (MD direction) and the lateral direction (TD direction) at the time of minute is 70% or less of the heat shrinkage rate when the base film is heated under the same conditions, and The total light transmittance of the laminated film is 80% or more.

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

(b) The thickness of the front and back sides of the crosslinked resin layer is 8% or more of the thickness of the base film

The transparent laminated film of the present invention has a structure in which a crosslinked resin layer formed using a curable composition containing a specific material is laminated on a front side of a base film of a specific thickness with a specific thickness. Transparency and excellent thermal stability at high temperatures (for example, above 200 ° C).

Moreover, the transparent laminated film of the present invention can maintain the transparency and is caused by the heat treatment because the crosslinked resin layer provided on the front and back sides of the base film can withstand the stress of the base film to be shrunk at a high temperature. The advantage of small dimensional change (thermal dimensional stability).

Therefore, the transparent laminated film proposed by the present invention can be preferably used for display materials such as liquid crystal displays, organic light emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, backlights, and the like. The substrate or the substrate of the solar cell can be preferably used for a photovoltaic element substrate or the like.

Moreover, since the transparent laminated film proposed by the present invention has the advantages as described above, it can be preferably used for applications requiring dimensional stability at high temperatures, particularly for packaging films and films for electronic parts, in addition to The gas barrier processing can also be preferably used for a semiconductor device such as an organic EL, a liquid crystal display element, or a solar cell.

Furthermore, the present invention provides a gas barrier laminated film comprising a base film having a crosslinked resin layer on both surfaces of the base film and a gas barrier on at least one side of the crosslinked resin layer. In the layer, the thickness of the front and back sides of the crosslinked resin layer is 8% or more of the thickness of the base film, and the first feature is that the crosslinked resin layer contains a photopolymerizable compound and a photopolymerization initiator. And the hardenable composition of the microparticles is formed, and the average particle diameter of the microparticles is in the range of 1 nm to 50 nm, and the second characteristic is that the thickness of the gas barrier layer is in the range of 5 to 100 nm, and the third characteristic is: The water vapor permeability of the entire film is 1.0 × 10 ^-2 g / m ² /day or less.

The gas barrier laminated film according to the present invention has a crosslinked resin layer and a gas barrier layer in a specific configuration, and adjusts the thickness of the crosslinked resin layer material and the gas barrier layer, thereby maintaining transparency and gas. The barrier property and the dimensional stability at a high temperature (for example, 150 ° C or higher) are high, and the shrinkage property is hard to occur even in the subsequent heat treatment.

Moreover, the gas barrier layered film of the present invention has a high cross-linking resin layer and a gas barrier layer on both surfaces of the base film, and exhibits high transparency and is caused by heat treatment. The dimensional change is small, and thus has the advantage of gas barrier properties. Therefore, the gas barrier laminated film proposed by the present invention can be preferably used for displays such as liquid crystal displays, organic light emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, backlights, and the like. The substrate of the material or the substrate of the solar cell can be preferably used for a photovoltaic element substrate or the like.

The gas barrier laminated film of the present invention has the advantages as described above, and therefore can be preferably used for applications requiring dimensional stability at high temperatures, in particular, a film for packaging and a film for electronic parts, in addition to It is preferably used for semiconductor devices such as organic EL, liquid crystal display devices, 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.

A transparent conductive film (referred to as "this conductive film"), a transparent laminated film (referred to as "this laminated film"), and a gas barrier laminated film (referred to as "the gas barrier film" according to an embodiment of the present invention Each of them has a common structure in which a crosslinked resin layer is provided on both sides of the base film.

Therefore, the constituent elements common to any of the embodiments (these are referred to as "films of the present invention") will be described below, and then the laminated film 1 (referred to as "the present conductive film") will be described in detail next. The laminated film 2 (referred to as "this laminated film") and the laminated film 3 (referred to as "this gas barrier film").

<Substrate film>

The base film in the film of the present invention can be arbitrarily used as long as it is a transparent resin film. For example, a film containing a resin such as polyethylene terephthalate or polyethylene naphthalate, a polyphenylene sulfide resin, a polyether oxime resin, a polyether oxime resin, and a transparent film may be mentioned. A cyclic olefin resin such as a polyimine resin, a polycarbonate resin, a cyclic olefin homopolymer or a cyclic olefin copolymer. A film containing a resin composed of one or a combination of two or more of these resins can be used.

The transparent polyimine resin may, for example, be a fluorinated polyfluorene in which a hexafluoroisopropylidene bond is introduced into a main chain of a polyimide resin or a hydrogen in a polyfluorene imide is substituted with fluorine. In addition to the above, an alicyclic polyimine which is obtained by hydrogenating a cyclic unsaturated organic compound contained in the structure of a polyimide resin may be mentioned. For example, those described in JP-A-61-141738, JP-A-2000-292635, and the like can be used.

Among the above films, a film having poor thermal dimensional stability, for example, a substrate film which is heat-shrinkable in an environment of a temperature of 150 to 220 ° C can enjoy the effects of the present invention. That should In view of the above, the base film used for the film of the present invention is preferably a resin film containing a resin having a glass transition temperature (Tg) of 130 ° C or less as a main component, and more preferably 50 ° C or more. Further, a resin film having a resin of 130 ° C or lower, more preferably 70 ° C or higher and 130 ° C or lower as a main component.

Among them, in particular, from the viewpoint of generally using a base film which is a transparent conductive film and various other transparent substrates, a film which has a polyethylene terephthalate resin as a main component and which is biaxially stretched is particularly preferable. .

<Crosslinked resin layer>

In the film of the present invention, the crosslinked resin layer means a layer in which a curable composition is crosslinked to form a crosslinked structure.

Further, in the basic application of the priority of the present application, the crosslinked resin layer is also referred to as a "hardened layer". The reason for this is that it is usually formed by applying a curable composition and "hardening" it. The "hardened layer" in the basic application and the "crosslinked resin layer" in the present invention are the same layer.

The curable composition may be a photopolymerizable compound, and may be other components including a photopolymerization initiator, fine particles, and a solvent, in addition to the photopolymerizable compound.

Next, each component will be described.

(photopolymerizable compound)

The photopolymerizable compound may, for example, be a compound having a polymerizable unsaturated bond, and specific examples thereof include a monomer having an ethylenically unsaturated bond or an oligomer, and more specifically, a urethane ( Methyl) acrylate, epoxy (meth) acrylate, polyester (A a (meth) acrylate monomer or oligomer such as an acrylate, a polyether (meth) acrylate or a polycarbonate (meth) acrylate, and may be exemplified by monofunctional or polyfunctional ( A methyl acrylate monomer or oligomer or the like. These may be used alone or in combination of two or more.

In the present invention, the term "monomer" means a repeating unit of a structural unit having no polymerizable functional group, and the term "oligomer" means that the number of repeating units of a structural unit having a polymerizable functional group is Those having 2 or more and having a molecular weight of less than 5,000 or having a polymerizable functional group at the terminal.

Examples of the monofunctional or polyfunctional methacrylate monomer or acrylate monomer (hereinafter, each of them is collectively referred to as "acrylate monomer") may, for example, be ethyl (meth)acrylate or N-butyl methacrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (methyl) Phenyl acrylate, (meth) acrylate Monofunctional acrylate monomer such as ester or dicyclopentenyl (meth)acrylate, or diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexyl Diol (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, 2,2'-bis(4-(methyl)propenyloxypolyoxyphenyl)propane, 2,2'-bis(4-( a bifunctional acrylate monomer such as methyl propylene oxy oxypolypropoxy phenyl) propane, or trimethylolpropane tri(meth) acrylate or ethylene oxide modified trimethylolpropane (Meth) acrylate, caprolactone modified trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, isocyanuric acid ginate (2-hydroxyethyl) ester tris (methyl) a trifunctional acrylate monomer such as acrylate or glycerol triacrylate (meth) acrylate, or a tetrafunctional acrylic acid such as di-trimethylolpropane tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate Ester monomer, or dipentaerythritol hydroxyl (Meth) acrylate, 5 functional acrylate monomer, dipentaerythritol hexa (meth) acrylate, 6-functional acrylate monomers. In addition, these may be used alone or in combination of two or more.

Among these, it is preferred to use a polyfunctional acrylate monomer having two or more acryl fluorenyl groups or methacryl fluorenyl groups in one molecule, insofar as it is relatively easy to crosslink by irradiation with ultraviolet rays. Oligomer. As described above, 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 reduced, and aggregation of the fine particles, particularly the inorganic fine particles, can be suppressed.

Therefore, the crosslinked resin layer is preferably a resin layer having a crosslinked structure in which a polyfunctional acrylate monomer having two or more acryloyl fluorenyl groups or methacryl fluorenyl groups in one molecule is crosslinked.

Among these, an alicyclic polyfunctional acrylate monomer having an alicyclic structure and one or more alicyclic structures in one molecule are particularly preferable in terms of particularly excellent heat shrinkage stability. An alicyclic polyfunctional acrylate monomer or a polyfunctional urethane urethane monomer having three or more acryl fluorenyl groups or methacryl fluorenyl groups in one molecule. Further, these acrylate monomers may be modified by caprolactone or the like, or two or more of them may be used in combination.

The molecular weight of the photopolymerizable compound is preferably in the range of from 215 to 4,000, more preferably from 250 to 3,000, and still more preferably from 300 to 2,000. By using the photopolymerizable compound having the above molecular weight range, the possibility that the monomer is adsorbed to the inorganic fine particles in the drying step or the like due to the low molecular weight can be eliminated, and on the other hand, the hardening due to the excessive molecular weight can be eliminated. The viscosity of the sexual composition becomes too large, the dispersion of fine particles is suppressed, and the particles are agglomerated with each other. As a result, the crosslinked resin layer can effectively suppress shrinkage at a high temperature of the base film.

In the present invention, when the molecular weight of the photopolymerizable compound exceeds 1,500, the molecular weight in terms of weight average molecular weight (Mw) is used.

In addition to the above, for example, in order to adjust the physical properties such as curability, water absorbability, and hardness of the crosslinked resin layer, it is also possible to add a poly(meth)acrylate, an epoxy resin, or a polyamine group to the curable composition. A polymer component composed of one or a combination of two or more of a formate resin, a polyester resin, and the like.

(photopolymerization initiator)

Examples of the photopolymerization initiator include benzoin, acetophenone, and 9-oxosulfuric acid. System, phosphine oxide system, peroxide system, etc. Specific examples of the photopolymerization initiator include benzophenone, 4,4-bis(diethylamino)benzophenone, and 2,4,6-trimethylbenzophenone. , o-benzidine benzoic acid methyl ester, 4-phenyl benzophenone, tert-butyl hydrazine, 2-ethyl hydrazine, diethoxy acetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane 1-ketone, benzyldimethylketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl-[4-(A Thio)phenyl]-2- Lolinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1, diethyl-9-oxosulfur Isopropyl-9-oxosulfur , 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, methyl benzhydrazinecarboxylate, and the like. These may be used alone or in combination of two or more.

(microparticles)

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

Further, in the case where the crosslinked resin layer contains fine particles, it is preferred to use a (meth) acrylate monomer having a lower molecular weight such as a weight average molecular weight of 3,000 or less as a photopolymer. The compound is conjugated to disperse the microparticles.

Examples of the fine particles include transparent inorganic fine particles such as cerium oxide, aluminum oxide, titanium oxide, soda glass, and diamond.

Among these, yttrium oxide fine particles are preferred from the viewpoints of coating suitability and price. The cerium oxide microparticles have been extensively developed by surface modification, and by using a surface-shrinkage, the dispersibility in the curable composition is improved, and a uniform cured film can be formed.

Specific examples of the cerium oxide microparticles include dried powdery cerium oxide microparticles, and citric acid gel (anthraquinone sol) dispersed in an organic solvent. Among these, in terms of dispersibility, it is preferred to use a phthalic acid gel (ruthenium sol) dispersed in an organic solvent.

For the purpose of improving the dispersibility, the surface may be subjected to a decane coupling agent or a titanate coupling agent to the extent that the properties such as transparency, solvent resistance, liquid crystal resistance, and heat resistance are not impaired to the utmost. Treated cerium oxide microparticles or cerium oxide microparticles which are easily dispersible on the surface.

Among them, fine particles treated by, in particular, a decane coupling agent, further a methacryl decyl decane coupling agent, a vinyl decane coupling agent, or a phenyl decane coupling agent are preferably used.

Examples of the methacryl decyl decane coupling agent include 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, and 3-methyl. Acryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, and the like.

Examples of the vinyl decane coupling agent include vinyl trimethoxy decane and vinyl triethoxy decane.

Further, examples of the phenyl decane coupling agent include phenyltrimethoxydecane and phenyltriethoxysilane.

Among these, fine particles treated with a methacrylonitrile-based decane coupling agent are preferred because they have a high affinity especially for a binder.

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

Adding amount (g) = weight of filler (g) × specific surface area (m ² /g) / minimum coated area of decane coupling agent (m ² /g)

Here, the minimum coverage area is calculated by the following equation.

Minimum coated area (m ² /g) = 6.02 × 1023 × ¹³ × 10 ^-20 / molecular weight of decane coupling agent

In the case where the amount of addition is derived by the above formula, the particles are agglomerated or the like, and the possibility of being appropriately dispersed is low, and the liquid concentration is sharply increased when it is prevented from being dispersed in a solvent or the like. From the viewpoint of generating bubbles or the like, the amount of the surface treatment agent used is preferably within 3 times of the theoretical surface treatment amount.

By using the above-mentioned surface-treated fine particles, the fine particles can be dispersed in the crosslinked resin layer at a high concentration and uniformly, and as a result, scattering can be prevented from occurring, and variation in thermal dimensional stability can be prevented.

In order to reduce the amount of refracted light incident on the crosslinked resin layer, it is preferred that the refractive index of the fine particles is less than 1.6. Among them, from the viewpoint of improving transparency, it is preferred to use a resin which is a reaction product obtained by curing the curable composition, in particular, a particle having a refractive index difference of less than 0.2 between a resin constituting a main component and a fine particle (filler). .

(solvent)

The curable composition can be used by adding a solvent as needed. That is, it can be used in the form of a solution containing the above curable composition, which can be applied. The film is cured on the base film, and a crosslinked resin layer is formed in the form of a hard coat layer.

The type or amount of the solvent can be appropriately selected according to various coating methods described later.

Examples of the solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; aromatic acids such as toluene and xylene; and further, cyclohexanone. , isopropyl alcohol, etc.

The amount of these solvents used is not particularly limited. It is usually 0 to 300 parts by mass based on 100 parts by mass of the total solid content of the curable composition.

(other ingredients)

In addition to the above, an optically curable oligomer, a monomer or a photoinitiator other than the above-described examples may be contained in a range of physical properties such as non-destructive hardenability, transparency, and water absorbability, and other sensitizers. , a crosslinking agent, an ultraviolet absorber, a polymerization inhibitor, a filler, a thermoplastic resin, and the like.

<Laminar composition>

In the film of the present invention, the crosslinked resin layer may be directly laminated on the front and back surfaces of the base film to laminate, and another layer may be interposed between the base film and the crosslinked resin layer. For example, an undercoat layer or the like for improving the adhesion of the crosslinked resin layer to the base film may be inserted between the base film and the crosslinked resin layer.

<Heat setting processing>

In the film of the present invention, since a predetermined crosslinked resin layer is provided on both sides of the base film, the substrate film can be made transparent and at a high temperature (for example, 200 ° C or higher) even if the substrate film is not heat-set. A film with excellent thermal dimensional stability. However, the film of the present invention may also be a substrate film which is subjected to heat setting treatment for mitigating shrinkage.

Before the curable composition is applied onto the base film, the base film is previously subjected to heat setting treatment, whereby the dimensional stability of the base film and the laminated film can be further improved.

Among them, as the base film, a biaxially stretched polyester film which is heat-set for ease of shrinkage is preferably used.

The heat setting treatment of the base film is preferably performed by heating the base film at a temperature of Tg to Tg + 100 ° C for 0.1 to 180 minutes when the glass transition temperature of the base film is Tg.

The specific method of the heat setting 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 a constant temperature chamber set to a desired temperature, a method of blowing hot air, a method of heating by an infrared heater, a method of irradiating light by a lamp, and a heat roller or heat may be employed. A method in which a plate is directly contacted to impart heat, a method of irradiating microwaves, or the like. Further, the base film may be subjected to heat treatment after being cut into an easy-to-operate size, or may be heat-treated directly in the state of the film roll. Further, as long as the required time and temperature are obtained, the heating device may be incorporated in one of the film manufacturing apparatuses such as a coater or a slitter to be heated in the manufacturing process.

[This conductive film]

The conductive film according to an embodiment of the present invention includes a transparent laminated film having the crosslinked resin layer on both sides of the base film, and is on the front side or both sides of the transparent laminated film. A transparent conductive layer is provided directly or via an undercoat layer.

<Crosslinked resin layer>

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

(microparticles)

The crosslinked resin layer in the conductive film may contain substantially no fine particles or may substantially contain fine particles. By containing the fine particles in the crosslinked resin layer, the high-temperature dimensional stability can be further improved.

As the fine particles, fine particles having an average particle diameter in the range of 1 nm to 200 nm are preferably used. Among them, fine particles having an average particle diameter of 1 nm or more and 10 nm or less, and 4 nm or more and 50 nm or less are preferably used. By using fine particles having an average particle diameter in this range, scattering of the incident light is not caused by the Mie scattering phenomenon, and the transparency of the film can be ensured.

Here, the "average particle diameter" means a number average particle diameter, and when the shape of the fine particles is spherical, the calculation can be performed by "measuring the sum of the circle-equivalent diameters of the particles/the number of the measured particles", and When the shape of the microparticles is not spherical, the calculation can be performed by "the sum of the short diameter and the long diameter / the number of the measured particles".

Further, when two or more kinds of fine particles are contained, the average particle diameter of the mixed particles is the above-mentioned "average particle diameter".

(with ratio)

The content of the photopolymerizable compound contained in the curable composition is preferably 20 to 90% by mass based on the entire curable composition (in the case of using a solvent, it is converted into a solid portion, the same applies hereinafter) More preferably, it is set to 20 to 60% by mass, and most preferably set to 20 to 40% by mass. When the content of the photopolymerizable compound is small, it is difficult to disperse the fine particles, so that the fine particles are aggregated and the transparency is remarkably deteriorated. Moreover, since the content of the photopolymerizable compound is not excessive, the thermal dimensional stability of the entire film can be eliminated. The effect of sex is halved and the possibility of excellent thermal dimensional stability of the microparticles cannot be exerted.

The photopolymerization initiator may be contained as needed. In the case where the photopolymerization initiator is contained in the conductive film, the content of the photopolymerization initiator contained in the curable composition is preferably 0.1% by mass based on the entire curable composition. ~10% by mass, more preferably 0.5% by mass to 5% by mass. By setting it as the said range, the hardening reaction of a hardening composition can be performed reliably and efficiently.

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

Moreover, the content ratio of (A) and the photoinitiator (hereinafter also referred to simply as (B)) and (C) contained in the curable composition is preferably (A) 20 to 79% by mass. (B) The content ratio of 0.1 to 10% by mass and (C) 10 to 79% by mass, more preferably 20% to 59% by mass of (A), and 0.5 to 5% by mass of the photopolymerization initiator (B) And (C) 40 to 79% by mass, wherein the most preferable one is (A) 20 to 39% by mass, (B) 0.5 to 5% by mass, and (C) 60 to 79% by mass. By setting the content ratio as described above, it is possible to maximize the thermal dimensional stability of the fine particles and to efficiently and stably supply the laminated film having transparency and productivity.

In the case where the conductive film contains fine particles, the content of the fine particles contained in the curable composition is preferably such that the fine particles having an average particle diameter of 200 nm or less are contained in the entire curable composition. 80% by mass, more preferably 60% by mass to 80% by mass. By setting it as the said range, transparency can be maintained in the range which the microparticles are dispersible, and the outstanding thermal-size stability can be fully maximized.

(thickness composition)

The thickness of the base film in the conductive film is preferably 70 μm or less, more preferably 5 μm or more and 70 μm or less, and more preferably 10 μm or more and 70 μm or less, and particularly preferably 20 μm or more. 60 μm or less. By setting it as the said range, the improvement of the light transmittance, and the high processing performance are acquired.

The use of a resin film as a substrate material of a touch panel, an organic EL display, or an organic EL illumination is required to reduce the thickness of the film to make it lighter, thinner, and lower in cost. In general, when a resin film is obtained by extrusion molding, in order to reduce the thickness, the resin in a molten state is elongated and thinned, or a resin film heated to a temperature higher than the glass transition temperature is extended.

In other words, as the resin film is made thinner, the external stress applied to the molding increases, and as a result, the resin film having a large residual stress is obtained. Therefore, when a resin film having a thickness of 100 μm or less is used for a high temperature step such as circuit formation, the residual stress is moderated at a high temperature to cause a dimensional change.

Therefore, the crosslinked resin layer is remarkably suppressed by providing a crosslinked resin layer having a total thickness of 8% or more of the base film on both sides of the base film of a specific thickness, specifically, a base film of 70 μm or less. When the base film shrinks at a high temperature, a transparent laminated film excellent in thermal dimensional stability can be obtained.

In the present conductive film, in order to heat the temperature at 200 ° C for 10 minutes, the heat shrinkage ratio is 1.5% or less, and a crosslinked resin layer is formed on both sides of the front and back sides of the base film, and the front and back sides are intersected. The total thickness of the joint resin layer is preferably 8% or more of the base film, more preferably 10% or more of the thickness of the base film, and still more preferably 15% or more and 50% or less, and more preferably, especially 20% or more and 45% or less, preferably more than 30% And it is 45% or less.

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

<Transparent Conductive Layer>

The conductive film may form a transparent conductive layer directly on the transparent laminated film having the crosslinked resin layer or via a lower coating layer made of a resin material.

The material of the transparent conductive layer is not particularly limited. It suffices that it is a material which can form a transparent conductive film. For example, a film containing tin oxide-containing indium oxide (ITO), antimony-containing tin oxide (ATO), zinc oxide, a zinc-aluminum composite oxide, or an indium-zinc composite oxide may be mentioned. These compounds can have both transparency and conductivity by selecting appropriate conditions for formation.

The thickness of the transparent conductive layer is preferably less than 100 nm, more preferably 15 nm or more and 50 nm or less, and most preferably 20 nm or more and less than 40 nm. Heretofore, in order to reduce the surface resistance value of the transparent conductive film (for example, less than 150 Ω/□), it has been attempted to thicken the thickness of the conductive layer, but according to the present conductive film, it has high thermal dimensional stability at a high temperature. Therefore, the conductive layer can be formed at a high temperature, and a sufficiently low surface resistance value can be obtained without making the thickness of the conductive layer thick.

As a method of forming the transparent conductive layer, a vacuum deposition method, a sputtering method, a chemical vapor deposition (CVD) method, an ion plating method, a spray method, and the like are known, and depending on the type of material and the required material, The film thickness is selected in a suitable method. For example, in the case of a sputtering method, usual sputtering using a compound target, reactive sputtering using a metal target, or the like is employed. At this time, a reactive gas such as oxygen, nitrogen, or water vapor may be introduced, or a combination of ozone, ion assist, or the like may be used in combination.

The formation conditions of the transparent conductive layer are preferably in the range of 150 ° C to 220 ° C. For example, when a transparent conductive layer is formed on a film by sputtering, the sputtering temperature is usually about room temperature to about 100 °C. On the other hand, since the transparent laminated film used for the conductive film is excellent in thermal dimensional stability as described above, sputtering can be performed even at a relatively high temperature, for example, 150 ° C to 220 ° C. Since the inorganic oxide film is formed into a film, the crystallization of the transparent conductive layer can be sufficiently promoted, and a transparent conductive film having a small surface resistance value can be obtained.

<Under coating>

When the transparent conductive layer is formed on the transparent laminate film, it is preferably via the undercoat layer. The adhesion and crystallinity of the transparent conductive layer can be improved by the undercoat layer.

The material of the undercoat layer is not particularly limited as long as it is a resin material. For example, poly(meth)acrylate, epoxy resin, polyurethane resin, polyester resin or the like can be preferably used. In addition to this, a composition containing a light or a thermally polymerizable compound may be used and polymerized to form an undercoat layer.

Further, if the flatness of the undercoat layer is poor, the crystal growth of the transparent conductive layer may be hindered, so that the undercoat layer is preferably substantially free of fine particles.

In this case, 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.

Further, in the case where the fine conductive film is contained in the crosslinked resin layer of the transparent laminated film in the conductive film, it is preferred to insert the undercoat layer when the transparent conductive layer is formed on the transparent laminated film.

By inserting the undercoat layer as described above, the surface smoothness can be improved, and the continuity of the transparent conductive layer can be improved, so that the surface resistance value of the conductive film can be made small.

<physical property>

Next, various physical properties which the transparent laminated film used for the conductive film and the conductive film can be provided will be described.

(heat shrinkage rate)

The transparent laminated film used for the conductive film preferably has a shrinkage ratio in either of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200 ° C for 10 minutes under the same conditions. The heat shrinkage rate of the base film is 70% or less.

Since the transparent laminated film has a shrinkage ratio in the range, it has the advantage of reducing the dimensional deviation when forming a circuit or a component, and also obtaining a higher barrier property when the inorganic barrier layer is laminated.

In particular, a biaxially stretched film or the like can reduce the shrinkage rate by the relaxation treatment in the transverse direction in the film forming step, but the relaxation treatment in the longitudinal direction requires more steps, and generally the shrinkage ratio in the longitudinal direction is relatively changed. Big. Therefore, the present conductive film preferably has a reduction in the shrinkage ratio in the longitudinal direction.

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

Since the front and back sides of the base film are provided with a crosslinked resin layer having a thickness of 8% or more of the thickness of the base film, the crosslinked resin layer can withstand shrinkage stress of the base film in the high temperature region to alleviate shrinkage. Therefore, the thermal dimensional stability of the transparent laminated film with respect to shrinkage at a high temperature can be improved as described above.

Since the conductive film has a high thermal dimensional stability at a high temperature The qualitative transparent laminated film has a transparent conductive layer, so that a transparent conductive layer can be formed in a high temperature environment (specifically, 150 to 220 ° C), and the crystallization of the conductive layer can be sufficiently performed, which can be low. Surface resistance value.

(surface resistance value)

The surface resistivity of the conductive film is preferably 150 Ω/□ or less, more preferably 100 Ω/□ or less. The conductive film has the surface resistance value in the above range, and has the advantages of reducing the power transmission loss of the display device or reducing the unevenness of the response speed when the touch panel sensor is increased in size.

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

<Method for Producing the Conductive Film and the Like>

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

Examples of the method of applying the curable composition and the like include bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, lithography, and fast. Dry printing, screen printing, dip coating is a method of applying a curable composition on a substrate film. Further, the method of transferring the formed crosslinked resin layer to the base film after molding the crosslinked resin layer on the glass or polyester film is also effective.

The method of applying a curable composition to the base film as described above and then curing (crosslinking) the curable composition may be used alone or in combination of methods such as thermal curing, ultraviolet curing, and electron beam curing. Among them, in terms of achieving hardening in a short time and relatively easily, it is preferred to use a method of hardening by ultraviolet rays.

In the case where it is hardened by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal halide lamp is used as a light source, and the amount of light, the arrangement of the light source, and the like are adjusted as needed.

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

On the other hand, in the case of hardening by an electron beam, it is preferable to use an electron beam acceleration device having an energy of 100 to 500 eV.

<Use>

As described above, the conductive film has an advantage of maintaining transparency, a dimensional change (thermal dimensional stability) due to heat treatment, and a small surface resistance value. Therefore, the conductive film is preferably used for a photovoltaic element in addition to 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, or the like, or a substrate of a solar cell. Substrate, etc.

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

In addition, the conductive film may be used as a gas barrier film having gas barrier properties (referred to as "this barrier film") by performing gas barrier processing on one side or both sides of the crosslinked resin layer provided on the base film. .

When a polyester film is used as a film for gas barrier processing, there is a problem that cracks or wrinkles are formed in the gas barrier layer, and the function of containing gas barrier properties cannot be sufficiently exhibited. On the other hand, the barrier film is excellent in terms of the above problems.

The barrier film is in addition to an organic EL device such as an organic EL or a liquid crystal display element In addition to the member, it is preferably used for applications requiring gas barrier properties and conductivity such as solar cells.

Further, in the gas barrier processing, a gas such as an inorganic substance or an organic substance such as a metal oxide is formed on at least one surface of the transparent laminated film used in the conductive film, the laminated film of the laminated film and the gas barrier film. A method of processing a gas barrier layer composed of a material having a high barrier property.

In this case, examples of the material having high gas barrier properties include bismuth, aluminum, magnesium, zinc, tin, nickel, titanium, or oxides, carbides, nitrides, carbon oxides, and oxynitrides thereof. , carbon oxynitride, diamond-like carbon or a mixture of such. Among them, in the case of use in the case of solar cells or the like, there is no concern such as electric leakage, etc., preferably cerium oxide, cerium oxyhydroxide, cerium oxynitride, cerium oxycarbonate, alumina, alumina, and aluminum oxynitride. Inorganic oxides, nitrides such as tantalum nitride and aluminum nitride, diamond-like carbons and mixtures of these. In terms of stably maintaining a high gas barrier property, it is particularly preferably cerium oxide, cerium oxyhydroxide, cerium oxynitride, cerium oxynitride, cerium nitride, aluminum oxide, aluminum oxide, aluminum oxynitride, Aluminum nitride and mixtures of these.

A method of forming a gas barrier layer on the conductive film using the above material may be any method such as a vapor deposition method or a coating method. In terms of obtaining a uniform film having a high gas barrier property, a vapor deposition method is preferred.

The 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 deposition, ion plating, and sputtering.

Examples of the chemical vapor deposition method include a plasma CVD by plasma, a catalytic chemical vapor deposition (Cat-CVD) using a heating contact medium to thermally decompose a material gas, and the like.

The thickness of the gas barrier layer is preferably from 10 nm to 1000 nm from the viewpoint of exhibiting stable gas barrier properties and transparency, and more preferably 40 nm or more and 800. Below nm, it is further preferably in particular 50 nm or more and 600 nm or less.

Further, the gas barrier layer may be a single layer or a plurality of layers. In the case where the gas barrier layer is a plurality of layers, the layers may be composed of the same material or may be composed of different materials.

The water vapor transmission rate of the barrier film at a temperature of 40 ° C and a relative humidity of 90% is preferably less than 0.1 [g / (m ² .day)], more preferably 0.06 [g / (m ² .day)] Hereinafter, it is more preferably 0.03 [g/(m ² .day)] or less.

The method for measuring the water vapor transmission rate can be determined according to the conditions of JIS Z0222 "Test method for moisture permeability of moisture-proof packaging container" and JIS Z0208 "Test method for moisture permeability of moisture-proof packaging material (Kap method)", specifically The method described in the examples was carried out for measurement.

[This laminated film]

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

Since the laminated film has a predetermined crosslinked resin layer on both sides of the base film, the crosslinked resin layer can withstand shrinkage stress of the base film in the high temperature region to alleviate shrinkage. Therefore, the dimensional stability of the laminated film for shrinkage at a high temperature can be improved.

The use of a resin film which is a substrate material of a touch panel, an organic EL display, and an organic EL illumination is required to reduce the thickness of the film to make it lighter, thinner, and lower in cost. In general, when the resin film is obtained by extrusion molding, in order to reduce the thickness, the resin in a molten state is elongated and thinned, or a resin film heated to a temperature higher than the glass transition temperature is extended.

In other words, as the resin film is thinned, the external stress applied to the molding increases, and as a result, the resin film having a large residual stress is obtained. Therefore, it will have a thickness of 100 μm or less. When the resin film is used for a high temperature step such as circuit formation, the residual stress is moderated at a high temperature to cause a dimensional change.

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

<Substrate film>

The laminated film has a heat shrinkage rate at a temperature of 200 ° C for 10 minutes, and is lower than, for example, 70% or less of the base film. That is, when a base film having a high heat shrinkage ratio under the same conditions is used, a particularly remarkable effect can be exhibited. In view of the above, the base film of the laminated film is preferably a double polyethylene terephthalate resin which is relatively high in shrinkage when heated at 200 ° C for 10 minutes. Axial extension film.

The thickness of the base film is preferably 75 μm or less, and more preferably 5 μm or more and 75 μm or less, and more preferably 10 μm or more and 70 μm or less, and more preferably 20 μm or more and 60 μm or less. By setting it as the said range, the improvement of the light transmittance, and the high processing performance are acquired.

<Crosslinked resin layer>

The crosslinked resin layer in the laminated film can be formed using a curable composition containing a photopolymerizable compound, a photopolymerization initiator, and fine particles. As the respective components such as the photopolymerizable compound, those exemplified above can be used. In particular, the photopolymerizable compound is preferably a photopolymerizable (meth) acrylate monomer or oligomer having two or more acryl fluorenyl groups or methacryl fluorenyl groups in one molecule, more preferably one molecule; More than one alicyclic structure of alicyclic polyfunctional Acrylate monomer.

(microparticles)

The crosslinked resin layer in the laminated film contains fine particles, and can have excellent high-temperature dimensional stability.

As the fine particles, those having an average particle diameter of from 1 nm to 200 nm are preferably used. Among them, fine particles having an average particle diameter of 1 nm or more and 10 nm or less and 4 nm or more and 50 nm or less are preferably used. By using fine particles having an average particle diameter in this range, scattering of the incident light is not caused by the Mie scattering phenomenon, and the transparency of the film can be ensured.

(with ratio)

The content of the photopolymerizable compound (A) contained in the curable composition is preferably from 9 to 50% by mass based on the entire curable composition (in the case of using a solvent, it is converted into a solid portion) In the above, it is more preferably 15% by mass or more and 45% by mass or less, and most preferably 19% by mass or more and 40% by mass or less. When the content of the photopolymerizable compound (A) is small, the fine particles are less likely to be dispersed, and therefore the fine particles are aggregated with each other, and the transparency is remarkably deteriorated. Further, since the content of the photopolymerizable compound (A) is not excessively large, the effect of the fine particles on the thermal dimensional stability of the entire film can be eliminated, and the possibility of excellent thermal dimensional stability of the fine particles cannot be exhibited.

The content of the photopolymerization initiator (B) contained in the curable composition is preferably 0.1% by mass to 10% by mass based on the entire curable composition, and more preferably 0.5. The mass% or more and 5% by mass or less. By setting it as the said range, the hardening reaction of a hardening composition can be performed reliably and efficiently.

The content of the fine particles (C) contained in the curable composition is preferably from 10 to 90% by mass, more preferably from 20% by mass to 84% by mass, based on the total amount of the curable composition. Further, it is more preferably 70% by mass or more and 80% by mass or less. By setting it as the said range, transparency can be maintained in the range which the microparticles are dispersible, and the outstanding thermal-size stability can be fully maximized.

In the above, the content ratio of the photopolymerizable compound and the fine particles contained in the curable composition is preferably 9 to 50% by mass of the photopolymerizable compound (A), and a photopolymerization initiator (B). In the range of 0.1 to 10% by mass and 10 to 90% by mass of the fine particles (C), the photopolymerizable compound (A) is preferably 15 to 45 mass%, and the photopolymerization initiator (B) is 0.5. 5% by mass of the fine particles (C) and 20 to 84% by mass of the fine particles (C), and more preferably 19 to 40% by mass of the photopolymerizable compound (A) and 0.5 to 5% by mass of the photopolymerization initiator (B) And fine particles (C) 70 to 80% by mass. By setting the content ratio as described above, it is possible to maximize the thermal dimensional stability of the fine particles and to efficiently and stably supply the laminated film having transparency and productivity.

(thickness of crosslinked resin layer)

The total thickness of the front and back sides of the crosslinked resin layer in the 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, and further preferably In particular, the thickness of the base film is 12% or more and 50% or less, more preferably 20% or more and 45% or less, and further preferably more than 30% and 45% or less.

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

(physical properties of the laminated film)

Next, various physical properties that can be provided in the laminated film will be described.

(total light transmittance)

The total light transmittance of the laminated film is preferably 80% or more, more preferably 85% or more. Since the laminated film has a total light transmittance in the range, it is possible to suppress light attenuation in illumination, display, or the like, thereby becoming brighter. Moreover, as a solar cell member, an advantage of being able to absorb more light can be obtained. Further, the light transmittance of the laminated film can be adjusted by adjusting the kind of the resin in the crosslinked resin layer, the type and particle diameter of the fine particles, the content of the fine particles, and the like.

(heat shrinkage rate)

For the above reasons, the laminated film is preferably a substrate having a shrinkage ratio in at least one of a longitudinal direction (MD direction) and a lateral direction (TD direction) when heated at 200 ° C for 10 minutes under the same conditions. The heat shrinkage rate of the film is 70% or less.

Since the laminated film has a shrinkage ratio in this range, as described above, it has the advantage of reducing the dimensional deviation when forming a circuit or a component, and obtaining a higher barrier property when the inorganic barrier layer is laminated. The laminated film is also preferably, in particular, reduced in the longitudinal direction due to the above reasons.

<Method of Manufacturing the Multilayer Film>

The laminated film can be produced by applying a curable composition to both sides of the base film and hardening it to form a crosslinked resin layer.

The method of forming the crosslinked resin layer is the same as that of the above-described conductive film.

<Use of the laminated film>

As described above, the laminated film has an advantage of maintaining transparency and having a small dimensional change (thermal dimensional stability) caused by heat treatment, and thus can be preferably used for the above-exemplified applications. For example, a gas barrier layer can be formed on the laminated film to be used as a gas barrier film (the present barrier film according to the present conductive film is described in detail).

[This gas barrier film]

The gas barrier film of the embodiment of the present invention is a gas barrier layered film having the following structure: a transparent laminated film having the above-mentioned crosslinked resin layer on both surfaces of the base film as described above, and further At least one side of the crosslinked resin layer has a predetermined gas barrier layer.

Since the gas barrier film has a predetermined crosslinked resin layer on both surfaces of the base film and has a predetermined gas barrier layer on at least one side of the crosslinked resin layer, the crosslinked resin layer can resist high temperature regions. The shrinkage stress of the base film in the medium eases shrinkage. Therefore, the dimensional stability of the gas barrier film against shrinkage at a high temperature can be improved.

<Substrate film>

The thickness of the base film in the gas barrier film is preferably from 1 μm to 200 μm, more preferably from 5 μm to 150 μm, still more preferably from 7 μm to 100 μm, still more preferably from 10 μm to 125 μm. It is set to 12 μm or more and 100 μm or less. By setting the above range, the light transmittance can be improved and the processing performance can be improved. Etc.

<Crosslinked resin layer>

From the viewpoint of improving the dimensional stability of the gas barrier film at the time of shrinkage at a high temperature, as described above, even in the gas barrier film, it is preferred that the crosslinkable resin layer is a photopolymerizable compound. A layer formed by a photopolymerization initiator and a hardenable composition of fine particles.

As the respective components such as the photopolymerizable compound, those exemplified above can be used. In particular, the photopolymerizable compound is preferably a photopolymerizable (meth) acrylate monomer or oligomer having two or more acryl fluorenyl groups or methacryl fluorenyl groups in one molecule, more preferably one molecule; One or more alicyclic structured alicyclic polyfunctional acrylate monomers.

(microparticles)

The crosslinked resin layer in the gas barrier film preferably contains substantially fine particles. The reason for this is that the crosslinked resin layer contains fine particles and has excellent high-temperature dimensional stability.

The fine particles are preferably fine particles having an average particle diameter in the range of 1 nm to 50 nm. Among them, fine particles having an average particle diameter of 1 nm to 40 nm or less and further 4 nm or more and 30 nm or less are preferably used. By using fine particles having an average particle diameter in this range, transparency can be ensured, and damage to the surface smoothness of the crosslinked resin layer can be reduced.

The content of the fine particles is preferably 50% by volume or more, more preferably 50% by volume or more and 90% by volume or less, based on the content of the fine particles as a whole of the crosslinked resin layer. Further, among them, further preferably 55 vol% or more and 75 vol% or less. If the crosslinked resin layer contains 50% by volume or more of the above fine particles, the fine particles are closer to the most densely packed The filling is performed in the charged state, and if it is 72% by volume or more, it is theoretically the closest packing. By containing fine particles in the above range, the elastic modulus of the crosslinked resin layer can be reduced to a dimensional change caused by shrinkage due to the alignment of the base film during heating or the like.

(with ratio)

As described above, the cross-linking resin layer in the gas barrier film can also be coated with a photopolymerizable compound, and a curable composition containing other components such as a photopolymerization initiator, fine particles, and an optional solvent. Formed by hardening.

The content of the photopolymerizable compound contained in the curable composition is preferably from 9 to 50% by mass, and more preferably from 15% by mass to 45% by mass based on the entire curable composition. the following. By setting it as the said range, the bridge|crosslinking density at the time of hardening increases, and the high rigidity can be given at high temperature.

The content of the photopolymerization initiator, which is the photocuring agent contained in the curable composition, is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass based on the entire curable composition. %~5 mass%. By setting it as the said range, the hardening reaction can be performed reliably and efficiently.

(thickness of crosslinked resin layer)

The thickness of the crosslinked resin layer in the gas barrier film is such that the total thickness of the crosslinked resin layers on both sides of the front and back is 8% or more of the thickness of the base film. When the total thickness 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 a high temperature can be kept high. The laminated film has high dimensional stability.

From this point of view, in order to heat it, especially at a temperature of 180 ° C for 90 minutes The shrinkage ratio is preferably 1.5% or less, and the total thickness of the crosslinked resin layer is preferably 8% or more and 50% or less of the thickness of the base film. Among them, it is preferably 10% or more of the thickness of the base film. Further, it is more preferably 15% or more and 50% or less, and further preferably 20% or more and 45% or less, and most preferably more than 30% and 45% or less.

<Gas barrier layer>

The gas barrier film has a gas barrier layer on at least one side of the crosslinked resin layer.

The gas barrier layer is the same as the gas barrier layer of the above-mentioned barrier film, and can be formed of a material having a high gas barrier property.

Examples of the material having high gas barrier properties include ruthenium, aluminum, magnesium, zinc, tin, nickel, titanium, or oxides, carbides, nitrides, carbon oxides, nitrogen oxides, and carbon nitrogen. Oxide, diamond-like carbon, or a mixture of these, for use in the case of solar cells or the like without leakage, etc., are preferably cerium oxide, cerium oxyhydroxide, cerium oxynitride, cerium oxycarbonate, Inorganic oxides such as alumina, alumina, and aluminum oxynitride, nitrides such as tantalum nitride and aluminum nitride, diamond-like carbon, and mixtures thereof. In terms of stably maintaining a high gas barrier property, it is particularly preferably cerium oxide, cerium oxyhydroxide, cerium oxynitride, cerium oxynitride, cerium nitride, aluminum oxide, aluminum oxide, aluminum oxynitride, Aluminum nitride and mixtures of these.

Among them, an inorganic compound composed of any one or more of an oxide, a nitride, and an oxynitride of cerium (Si) or aluminum (Al) is preferable.

A method of forming a gas barrier layer using the above materials may be any method such as a vapor deposition method or a coating method. In terms of obtaining a uniform film having a high gas barrier property, a vapor deposition method is preferred.

The 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 deposition, ion plating, and sputtering.

Examples of the chemical vapor deposition method include a plasma CVD by plasma, a catalytic chemical vapor deposition (Cat-CVD) using a heating contact medium to thermally decompose a material gas, and the like.

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

Further, the gas barrier layer may be a single layer or a plurality of layers. In the case where the gas barrier layer is a plurality of layers, the layers may be composed of the same material or may be composed of different materials.

When a fixed coating layer is provided between the crosslinked resin layer and the gas barrier layer, the purpose is to improve the smoothness of the surface and the adhesion between the crosslinked layer and the gas barrier layer, and the thickness thereof is preferably such that the entire film is not damaged. The range of thermal stability. Specifically, it is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 1 μm or less.

(physical properties of the gas barrier film)

Next, various physical properties that can be provided in the gas barrier film will be described.

(total light transmittance)

In the gas barrier film, the total light transmittance is preferably 80% or more, and more preferably 85% or more, from the viewpoint of the film. Further, as described in the above laminated film, the light of the gas barrier film can be adjusted by adjusting the kind of the resin in the crosslinked resin layer, the type and particle size of the fine particles, the content of the fine particles, and the like. Penetration rate.

(heat shrinkage rate)

In the same manner as the above film, the gas barrier film preferably has a shrinkage ratio in at least one of a longitudinal direction (MD direction) and a lateral direction (TD direction) when heated at 200 ° C for 10 minutes. The substrate film measured under the same conditions has a heat shrinkage ratio of 70% or less.

Further, it is particularly preferable that the shrinkage ratio in any 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 gas barrier film of the gas barrier film must have a vapor permeability of 1.0 × 10 ^-2 g / m ² /day or less, more preferably 5 × 10 ^-3 g / m ² /day or less.

When the gas barrier film has a water vapor permeability in this range, when a transparent electrode or element is formed on the gas barrier film, the moisture contained in the external gas or other members can be sufficiently blocked, thereby preventing transparency. The performance of the electrode is reduced or the component is deteriorated.

The method for measuring the water vapor permeability of the gas barrier film is based on JIS Z0222 "Test method for moisture permeability of moisture-proof packaging containers" and JIS Z0208 "Test method for moisture permeability of moisture-proof packaging materials (Kap method)" Conditions were evaluated by the following methods.

Two gas barrier laminated films having a moisture permeability of 10.0 cm × 10.0 cm square can be used, and about 20 g of anhydrous calcium chloride is used as a moisture absorbent to prepare a sealed four-side bag, and the bag is placed at a temperature of 40 ° C. In a constant temperature and humidity apparatus with a relative humidity of 90%, the weight increase is approximately constant for 48 hours or more, and the mass is measured (unit: 0.1 mg) until 34.8 days, and the water vapor transmission rate is calculated by the following formula. .

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

m: the mass of the last two weighing intervals during the test (g)

s: moisture permeable area (m ² )

t: the time of the last 2 weighing intervals during the test (day)

(arithmetic mean thickness)

The arithmetic mean roughness of at least one side of the crosslinked resin layer of the gas barrier film is preferably 15 nm or less, more preferably 10 nm or less.

By the crosslinked resin layer having an arithmetic mean roughness of the range, a uniform film having less defects can be formed when the gas barrier layer is formed, and as a result, a gas barrier property can be obtained. Moreover, there is an advantage that the formation failure of the element is small when the organic EL or the like is formed on the gas barrier film.

The arithmetic mean roughness of the crosslinked resin layer is obtained by dividing the volume of the portion surrounded by the surface shape curved surface and the average surface by the crosslinked resin layer, and the average surface is set to the XY plane and the longitudinal direction is set. When the Z axis and the measured surface shape curve are Z=F(x, y), it is defined by the following formula.

(Lx: length is measured in the x direction, and length is measured in the Ly: y direction)

<Method for Producing the Gas Barrier Film>

The gas barrier film can be produced by applying a curable composition to both sides of the base film and hardening it to form a crosslinked resin layer, thereby forming a gas barrier layer by the above method.

The method of forming the crosslinked resin layer is the same as that of the above-described conductive film.

<Use of the gas barrier film>

As described above, the gas barrier film has an advantage of maintaining transparency and having a small dimensional change (thermal dimensional stability) due to heat treatment, and thus can be preferably used for the above-exemplified applications.

[Description of terms]

In the present invention, "transparent" means that an object located in front of it is visible through it, and preferably has a total light transmittance of 80% or more.

In the present specification, when "X~Y" (X, Y is an arbitrary number), unless otherwise specified, it means "X or more and Y or less", and also includes "better Greater than X" or "preferably less than Y".

Also, in the case of "X or above" (X is an arbitrary number) or "Y below" (Y is an arbitrary number), "preferably greater than X" or "preferably less than Y" is also included. The meaning.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. However, the present invention is not limited by any of the embodiments and the like.

[About this conductive film]

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

<Method for Measuring Characteristics of the Conductive Film> (Method for measuring heat shrinkage rate)

From the obtained transparent laminated film, the film was cut into a short strip having a length of 140 mm × a width of 10 mm in the longitudinal direction and the transverse direction, respectively, and a test mark having a length of 100 mm was interposed therebetween, and the test piece thus obtained was loaded without load. The state was suspended in a thermostat set at 200 ° C for 10 minutes, and after taking out, it was left to cool at room temperature for 15 minutes or more, and the heat shrinkage ratio was determined as a % value from the length between the marked lines before and after the thermostatic chamber. Furthermore, 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 low resistivity meter "Loresta EP" manufactured by Mitsubishi Chemical Corporation.

<Example 1> (Preparation of photocurable composition 1)

The photocurable bifunctional acrylate monomer (tricyclodecane dimethanol diacrylate, molecular weight 304, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DCP") was uniformly diluted with a solvent (propylene glycol monomethyl ether). 22.1% by mass, cerium oxide fine particles (manufactured by Admatech Co., Ltd., trade name "YA010C-SM1", average particle diameter: 10 nm), 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE 127") 0.6 The mass % and the photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE 184") were 0.1% by mass to obtain a curable composition 1 (coating material A) for forming a crosslinked resin layer.

(Production of transparent laminated film 1)

The above surface of the biaxially-oriented polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil") having a thickness of 50 μm was coated with a thickness of 10 μm after hardening using a die coater. After the prepared coating A, the solvent was dried and removed, and the coated surface was irradiated with a high pressure mercury lamp (160 W/cm) under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side. The coating material A on which the crosslinked resin layer was not formed was applied and cured in the same manner as described above, whereby a transparent laminated film 1 having a crosslinked resin layer formed on both sides thereof was obtained.

The heat shrinkage ratio in the longitudinal direction (MD direction) of the transparent laminated film 1 was 0.29%, and the heat shrinkage ratio in the transverse direction (TD direction) was 0.13%.

Further, the value obtained by dividing the heat shrinkage ratio of the transparent laminated film 1 by the heat shrinkage ratio of the base film used in the transparent laminated film 1 was 19%.

(Production of Transparent Conductive Film 1 Forming Transparent Conductive Layer)

An ITO film was formed as a transparent conductive layer on a single surface of the crosslinked resin layer of the transparent laminated film 1 by a sputtering method at a thickness of 30 nm in a 200 ° C environment. The surface resistance value of the conductive layer of the obtained transparent conductive film 1 was measured by Loresta EP (manufactured by Mitsubishi Chemical Corporation) and found to be 119 Ω/□.

<Example 2> (Production of transparent laminated film 2)

The single side of the transparent laminated film 1 produced in the first embodiment was coated with water to uniformly dilute the polyester resin (PESRESIN A-215GE manufactured by Takamatsu Oil) by 88% by mass to a thickness of 0.5 μm after drying. The oxazoline-based polymer (Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd.) was coated with 12% by mass, and the transparent laminated film 2 having the undercoat layer formed on one side of the crosslinked resin layer of the transparent laminated film 1 was obtained. .

(Production of Transparent Conductive Film 2 Forming Transparent Conductive Layer)

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

<Example 3> (Production of transparent laminated film 3)

The one surface of the transparent laminated film 1 produced in the first embodiment was applied with a hard coat layer (NK hard B500 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) so as to have a thickness of 3 μm after drying, and then hardened by using an ultraviolet irradiation device. Thus, a transparent laminated film 3 having an undercoat layer formed on one surface of the crosslinked resin layer of the transparent laminated film 1 is obtained.

(Production of Transparent Conductive Film 3 Forming Transparent Conductive Layer)

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

<Example 4> (Production of transparent laminated film 4)

One side of the transparent laminated film 1 produced in Example 1 was formed into a dried thickness. The coating of 1 μm was uniformly diluted with toluene and isopropyl alcohol (IPA) by 97% by mass of the hard coat layer (GX8801A manufactured by K.K.) and 3% by mass of the photopolymerization initiator (IRGACURE 184 manufactured by BASF). In the coating material, a transparent laminated film 4 having an undercoat layer formed on one side of the crosslinked resin layer of the transparent laminated film 1 is obtained.

(Production of Transparent Conductive Film 4 Forming Transparent Conductive Layer)

An ITO film was formed as a transparent conductive layer at a thickness of 30 nm on the undercoat surface of the transparent laminated film 4 by sputtering at 200 ° C. The surface resistance value of the conductive layer of the obtained transparent conductive film 4 was measured by Loresta EP (manufactured by Mitsubishi Chemical Corporation) and found to be 81 Ω/□.

<Example 5> (Preparation of hardenable composition 2)

The photocurable 6-functional urethane urethane (molecular weight: about 800, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "U-6LPA") was diluted with a solvent (propylene glycol monomethyl ether) by 48.5 mass%, and photohardening was carried out. A hexafunctional acrylate monomer (dipentaerythritol hexaacrylate, molecular weight 578, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DPH"), 24.3% by mass, photocurable bifunctional acrylate monomer (tricyclic ring) Hydrazine dimethanol diacrylate, molecular weight 304, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DCP") 24.3% by mass and photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE 184") 2.9 mass %, the curable composition 2 (coating B) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film 5)

The above surface of the biaxially-oriented polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil") having a thickness of 23 μm was applied by a gravure coater to a thickness of 3 μm after hardening. After the prepared coating material B, the solvent was dried and removed, and the coated surface was irradiated with a high pressure mercury lamp (160 W/cm) under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side. The coating material B on which the crosslinked resin layer was not formed was applied and cured in the same manner as described above, whereby a transparent laminated film 5 having a crosslinked resin layer formed on both sides thereof was obtained.

The heat shrinkage rate of the obtained film was measured in the same manner as in Example 1. As a result, it was 1.43% in the longitudinal direction (MD direction) and 0.21% in the transverse direction (TD direction).

Further, the value obtained by dividing the heat shrinkage ratio of the transparent laminated film 5 by the heat shrinkage ratio of the base film used in the transparent laminated film 5 was 67%.

(Formation of transparent conductive film)

An ITO film was formed as a transparent conductive layer by a sputtering method on a single side of the crosslinked resin layer of the transparent laminated film 5 at a thickness of 30 nm in a 200 ° C environment. The surface resistance value of the conductive layer of the obtained transparent conductive film 5 was measured by Loresta EP (manufactured by Mitsubishi Chemical Corporation) and found to be 68 Ω/□.

<Comparative Example 1>

The biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil") having a thickness of 23 μm was measured for heat shrinkage in the same manner as in Example 1, and as a result, it was longitudinally 2.12%, 0.67% in the horizontal direction. An attempt was made to form a transparent conductive layer on one side of the above polyethylene terephthalate film in an environment of 200 ° C. As a result, heat shrinkage was large in the sputtering apparatus, and film formation was impossible.

<Comparative Example 2>

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

<Reference Example 1> (Production of transparent laminated film 6)

Biaxially-extending polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name "COSMOSHINE", using a bar coater at a thickness of 100 μm, heat shrinkage rate: MD direction = 4.06%, TD direction = 2.55% After coating the coating material A prepared in Example 1 on one side of the hardened layer to a thickness of 1 μm, the solvent was dried and removed. Furthermore, the end surface of the film was fixed in a belt conveyor, and the coated surface was irradiated with a high-pressure mercury lamp (160 W/cm) in a nitrogen atmosphere to obtain a cross-linked resin layer having photocurability on one side. film.

Then, the coating material A on which the crosslinked resin layer was not formed was applied and cured in the same manner as described above, whereby a transparent laminated film 6 having a crosslinked resin layer formed on both sides thereof was obtained.

The heat shrinkage ratio of the transparent laminated film 6 was measured in the same manner as in Example 1. As a result, the heat shrinkage ratio in the longitudinal direction (i.e., MD direction) was 3.42%, and the transverse direction (TD direction). The heat shrinkage rate was 1.66%.

<Reference Example 2> (Production of transparent laminated film 7)

The coating was carried out by using a bar coater in a single-sided polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name "COSMOSHINE") having a thickness of 100 μm and having a thickness of 3 μm after hardening. After the coating A prepared in Example 1, the solvent was dried and removed. Furthermore, the end surface of the film was fixed in a belt conveyor, and the coated surface was irradiated with a high-pressure mercury lamp (160 W/cm) in a nitrogen atmosphere to obtain a cross-linked resin layer having photocurability on one side. film.

Then, the coating material A on which the crosslinked resin layer was not formed was applied and cured in the same manner as described above, whereby a transparent laminated film 7 having a crosslinked resin layer formed on both sides thereof was obtained.

The heat shrinkage ratio of the transparent laminated film 7 was measured in the same manner as in Example 1. As a result, the longitudinal direction (MD direction) was 2.42%, and the transverse direction (TD direction) was 1.21%. .

<Reference Example 3> (Production of transparent laminated film 8)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil") having a thickness of 50 μm using a bar coater, heat shrinkage rate: MD direction = 1.51%, TD direction = 0.31 The coating A prepared in Example 1 was applied to one side of the %) so that the thickness after hardening became 1 μm, and the solvent was dried and removed. Further, the end portion of the film is fixed in a belt conveyor, and the coated surface is irradiated under a nitrogen atmosphere. A high pressure mercury lamp (160 W/cm) was obtained, and a film having a photocurable crosslinked resin layer on one side was obtained.

Then, the coating material A on which the crosslinked resin layer was not formed was applied and cured in the same manner as described above, whereby a transparent laminated film 8 having a crosslinked resin layer formed on both sides thereof was obtained.

The heat shrinkage ratio of the transparent laminated film 8 was measured in the same manner as in Example 1. As a result, the longitudinal direction (MD direction) was 1.51%, and the transverse direction (TD direction) was 0.42%. .

<Reference Example 4> (Preparation of photocurable composition 3)

The photocurable hexafunctional urethane urethane (molecular weight about 800, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "U-6LPA") was uniformly diluted with a solvent (propylene glycol monomethyl ether and methyl ethyl ketone). 42.75 mass%, photocurable trifunctional acrylate monomer (pentaerythritol triacrylate, molecular weight 298, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "ATMM-3LM-N") 42.75 mass%, cerium oxide microparticles ( Manufactured by Nissan Chemical Industry Co., Ltd., trade name "MEK-ST-L", average particle diameter: 50 nm), 12.8% by mass in terms of solid content, and photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE 127") 1.7 mass %, and the curable composition 3 (coating C) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film 9)

A single-sided polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil") having a thickness of 23 μm was hardened by a gravure coater using a gravure coater. After coating the above-prepared coating material C with a thickness of 1 μm, the solvent was dried and removed, 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. .

Then, the coating material C on which the crosslinked resin layer is not formed is applied and cured in the same manner as described above, whereby a transparent laminated film 9 having a crosslinked resin layer formed on both sides thereof is obtained.

The heat shrinkage ratio of the transparent laminated film 9 was measured in the same manner as in Example 1. As a result, the longitudinal direction (MD direction) was 1.45%, and the transverse direction (TD direction) was 0.54%. .

If the results of the above Reference Examples 1 to 4 are summarized, they are as shown in Table 2.

(examine)

From the results of the above-described examples, reference examples, and the inventors, it has been found that the thermal dimensional stability can be improved by providing a crosslinked resin layer having a predetermined thickness on both sides of the substrate. Specifically, it is understood that the thickness of the crosslinked resin layer is designed to be 8% or more of the thickness of the base film, and the transparent conductive film can be heated in the temperature of 200 ° C for 10 minutes to obtain the longitudinal direction and the transverse direction. The heat shrinkage rate above is 1.50% or less.

It is understood that the surface resistivity of the transparent conductive film can be made 150 Ω / □ or less by applying a high temperature step, specifically, a film forming method in an environment of a temperature of 150 to 220 ° C when the transparent conductive layer is formed.

[About this laminated film]

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

<Measurement method for characteristics of the laminated film> (appearance of the film)

The laminated film obtained in the examples and the comparative examples was visually observed, and the presence or absence of crack cracking or whitening was evaluated based on the following criteria.

○: The whole was transparent and no cracks or whitening were observed at all.

△: Any one of cracks and whitening was confirmed.

×: Both cracks and whitening were confirmed.

(Method for measuring heat shrinkage rate)

The laminated film obtained in the examples and the comparative examples was cut into a short strip having a length of 140 mm × a width of 10 mm in the longitudinal direction and the transverse direction, respectively, and a mark having a length of 100 mm in the middle of the mark was obtained. The test piece was suspended in a thermostatic chamber set at 200 ° C for 10 minutes without load, and after being taken out, it was left to cool at room temperature for 15 minutes or more, and the length between the marking lines before and after being placed in the constant temperature bath was %. Form the heat shrinkage rate. In addition, the measurement was performed five times each, and the average value was calculated, and the value obtained by rounding off the third decimal place was described. Furthermore, the longitudinal direction of the film, that is, the longitudinal direction (MD direction), And the heat shrinkage ratio of both the transverse direction (TD direction) orthogonal thereto. The heat shrinkage ratio obtained is shown in Table 3.

(Method for measuring total light transmittance)

The total light transmittance of the laminated film obtained in the examples and the comparative examples was measured by the method according to JIS K7105 using the following apparatus.

reflection. Transmittance meter: "HR-100" by Murakami Color Technology Research Institute Co., Ltd.

[Embodiment 6] (Preparation of hardenable composition a)

A photocurable bifunctional acrylate monomer having a molecular weight of 304 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DCP", three rings) was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone). 22.1% by mass of decane dimethanol diacrylate), cerium oxide fine particles (manufactured by Admatech Co., Ltd., trade name "YA010C-SM1"), 77.2% by mass, and light curing agent A (manufactured by BASF, trade name "IRGACURE 127") 0.6 The mass % and the light hardener B (manufactured by BASF, trade name "IRGACURE 184") were 0.1% by mass to obtain a curable composition a (coating a) for forming a crosslinked resin layer.

(Production of transparent laminated film a)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil T600E50", manufactured by Mitsubishi Plastics Co., Ltd., using a wire bar coater, heat shrinkage rate according to the above-described measurement method: MD direction The coating material a prepared as described above was applied to the single side of the surface of the film having a thickness of 3 μm after the curing, and the solvent was dried and removed. Further, the end of the film is fixed in a belt conveyor The coated surface was irradiated with a high pressure mercury lamp (160 W/cm) under a nitrogen atmosphere to obtain a film having a photocurable crosslinked resin layer on one side.

The coating material a on which the crosslinked resin layer was not formed was applied and cured in the same manner as described above, whereby a transparent laminated film a having a crosslinked resin layer formed on both sides thereof was obtained.

[Embodiment 7] (Production of transparent laminated film b)

A transparent laminated film b having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 6 except that the thickness was 10 μm after the single-sided hardening. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Embodiment 8] (Preparation of hardenable composition b)

A photocurable bifunctional acrylate monomer having a molecular weight of 226 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-HD-N") was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone). 17.7 mass%, photo-curable 6-functional acrylate monomer having a molecular weight of 578 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DPH"), 4.4 mass%, cerium oxide microparticles (manufactured by Admatech Co., Ltd., Product name "YA010C-SM1") 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE127") 0.6% by mass, and photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE 184") 0.1 mass %, the curable composition b (coating b) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film c)

A transparent laminated film c having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 6 except that the coating material b was applied. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Embodiment 9] (Production of transparent laminated film d)

A transparent laminated film d having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 8 except that the thickness was 10 μm after the single-sided hardening. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Embodiment 10] (Preparation of hardenable composition c)

A photocurable bifunctional acrylate monomer having a molecular weight of 226 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-HD-N") was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone). 22.1% by mass, cerium oxide microparticles (manufactured by Admatech Co., Ltd., trade name "YA010C-SM1"), 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE 127"), 0.6% by mass, and photopolymerization The starting agent B (manufactured by BASF, trade name "IRGACURE 184") was 0.1% by mass, and a curable composition (coating material c) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film e)

A transparent laminated film e having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 6 except that the coating material c was applied. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Example 11] (Production of transparent laminated film f)

A transparent laminated film f having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 10 except that the thickness was 10 μm after the single-sided hardening. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Embodiment 12] (Preparation of hardenable composition d)

A photocurable trifunctional acrylate monomer having a molecular weight of 537 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-9300-1CL") was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone). 22.1% by mass, cerium oxide fine particles (manufactured by Admatech Co., Ltd., trade name "YA010C-SM1"), 77.2% by mass, light curing agent A (manufactured by BASF, trade name "IRGACURE 127"), 0.6% by mass, and light hardener B ( The resin composition ("IRGACURE 184" manufactured by BASF) was used in an amount of 0.1% by mass to obtain a curable composition d (coating material d) for forming a crosslinked resin layer.

(Production of transparent laminated film g)

A transparent laminated film g having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 6 except that the coating material d was applied. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Example 13] (Production of transparent laminated film h)

A transparent laminated film h having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 12 except that the thickness was 10 μm after the hardening of the single side. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Embodiment 14] (Preparation of hardenable composition e)

A photocurable polyfunctional acrylate oligomer having a weight average molecular weight (Mw) of 1500 (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name "UV" was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone). -2640B"), 22.1% by mass, cerium oxide microparticles (manufactured by Admatech Co., Ltd., trade name "YA010C-SM1"), 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE 127"), 0.6% by mass The photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE 184") was used in an amount of 0.1% by mass to obtain a curable composition e (coating material e) for forming a crosslinked resin layer.

(Production of transparent laminated film i)

A transparent laminated film i having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 7 except that the coating material e was applied. The values of the heat shrinkage rate and the total light transmittance are shown in Table 3.

[Comparative Example 3] (Production of laminated film 1)

A laminate film 1 having a crosslinked resin layer formed on both sides thereof was obtained in the same manner as in Example 6 except that the thickness was 1 μm after the single-sided hardening. The values of the heat shrinkage ratio are shown in Table 3.

(examine)

As a result of the above-described examples and the comparative examples, it is understood that by using a structure in which the base film is provided with a crosslinked resin layer having a predetermined thickness or more, it is possible to impart a heat temperature at a high temperature which cannot be achieved by a base film having a thickness of 75 μm or less. stability. In particular, as shown in Comparative Example 1, it is understood that the effect of improving the thermal dimensional stability of the crosslinked resin layer cannot be obtained if a crosslinked resin layer having a specific thickness is not laminated in a region where the thickness of the base film is small.

[About this gas barrier film]

Finally, the gas barrier films are described in detail below using Examples 15 to 16 and Comparative Examples 4 to 7.

<Method for Measuring Characteristics of the Gas Barrier Film>

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

(Total light transmittance, measurement of haze)

The total light transmittance and haze of the films of the examples and the comparative examples were measured by the method according to JIS K7105 using the following apparatus.

Device: reflection. Permeability meter: "HR-100" by Murakami Color Technology Research Institute Co., Ltd.

(The average particle size)

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

Specifically, the acceleration voltage was set to 100 V, and after the digital image was acquired, the particle diameter of 200 particles was randomly measured from the obtained image, and the average value thereof was determined, whereby the average particle diameter of the fine particles was determined.

(surface smoothness)

The surface smoothness, that is, the arithmetic mean roughness (Sa) of the crosslinked resin layer of the film, was measured by the optical interferometry method using the "VertScan" (registered trademark) of the MITSUBISHI Systems Co., Ltd. by the optical interference method. Surface roughness.

(heat shrinkage rate)

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

Specifically, the measurement was carried out by the following method. Set the film travel direction to the long side, Three short strip test pieces each having a width of 10 mm and a length of 100 mm were prepared, and the center portion of each test piece was set as a center, and a mark line having a spacing of 100 mm was marked. Use a vernier caliper to read the spacing between the markings with an accuracy of 0.01 mm. The test piece was suspended in a constant temperature bath at a predetermined temperature for 10 minutes without load, and after taking out, it was left 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 interval between the marking lines before and after heating was determined, and the dimensional change rate before and after heating was determined.

[Example 15] (Preparation of hardenable composition i)

2. A photocurable bifunctional acrylate monomer having a tricyclodecane structure. Oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DCP") 21.8 mass%, transparent fine particle A (manufactured by Admatechs Co., Ltd., trade name "YA010C-SM1", tannic acid gel, average particle diameter 10 nm) 77.5 mass% and a photopolymerization initiator (manufactured by BASF, 1-hydroxycyclohexyl-phenyl ketone) 0.7% by mass of a solvent (available from Arakawa Chemical Industry Co., Ltd., propylene glycol monomethyl ether) 34.1 parts by mass Further, a curable composition i for forming a crosslinked resin layer (hereinafter referred to as "coating i" was obtained. The solid content in the composition was 66%).

(Production of two-sided crosslinked resin layer)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "P100-T50") having a thickness of 50 μm was used as a base film, and a wire bar coater was used on one side of the film. After coating the above-prepared coating i to a thickness of 10 μm after hardening, it was allowed to stand for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, whereby the solvent was dried and removed to bring the end of the film. The fixed state is placed in a belt conveyor, and the coated surface is irradiated with a high-pressure mercury lamp (160 W/cm) to obtain a hard surface on one side. A film of a crosslinked resin layer. The volume ratio of the citric acid gel in the crosslinked resin layer was 63.4% by volume.

Thereafter, the coating i was applied to the surface of the film on which the crosslinked resin layer was not formed, and hardened 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 a deposition pressure of 0.3 Pa, an Ar (argon) flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input electric power of 4 kW were carried out by a reactive sputtering method using an Al target. Under the conditions, an aluminum oxide layer of 20 nm was formed on the crosslinked resin layer on one side of the PET film to obtain a gas barrier laminated film 1. The characteristics of the gas barrier laminated film 1 obtained were evaluated according to the above measurement methods, and the results are shown in Table 4.

[Example 16] (Production of two-sided crosslinked resin layer)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "P100-T50") having a thickness of 50 μm was used as a base film, and a wire bar coater was used on one side of the film. After coating the same coating material i as in Example 15 after the thickness of the hardened layer was 7.5 μm, it was allowed to stand for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, whereby the solvent was dried and removed to The end portion of the film was placed in a belt conveyor, and a high pressure mercury lamp (160 W/cm) was applied to the coated surface to obtain a film having a photocurable crosslinked resin layer on one side. The volume ratio of the citric acid gel in the crosslinked resin layer was 63.4% by volume.

Thereafter, the crosslinked resin layer is not formed on the film in the same manner as described above. The coating i is applied to the surface and hardened.

(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 under the conditions of a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input electric power of 4 kW by a reactive sputtering method using an Al target. A 20 nm aluminum oxide layer was formed on the crosslinked resin layer on either side of the PET film to obtain a gas barrier laminated film 2. The characteristics of the gas barrier laminated film 2 obtained were evaluated according to the above measurement methods, and the results are shown in Table 4.

[Comparative Example 4] (formation of gas barrier layer)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "P100-T50") having a thickness of 50 μm was used as a base film, and a film was formed by a reactive sputtering method using an Al target. Under a condition of a pressure of 0.3 Pa, an Ar flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input power of 4 kW, an aluminum oxide layer of 20 nm was formed on one surface of the film to obtain a laminated film 2.

The properties of the obtained laminated film 2 were evaluated according to the above measurement methods, and the results are shown in Table 4.

[Comparative Example 5] (Preparation of hardenable composition ii)

Polymeric resin composition of urethane urethane (manufactured by Daiichi Kogyo Co., Ltd., "New Frontier R-1302") 97% by mass and photopolymerization initiator (BASF) 34.1 parts by mass of a solvent (methyl ethyl ketone manufactured by Arakawa Chemical Industries Co., Ltd.) was uniformly mixed in a ratio of 3 mass% to be produced, and the curable property for forming a crosslinked resin layer was obtained. Composition ii (hereinafter referred to as "coating ii". The solid content in the composition was 60%).

(Formation of two-sided crosslinked resin layer)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "P100-T50") having a thickness of 50 μm was used as a base film, and a wire bar coater was used on one side of the film. After coating the coating ii with a thickness of 2 μm after hardening, it was allowed to stand for 2 minutes, and then placed in an oven set to 100 ° C for 10 minutes, thereby drying and removing the solvent to fix the end portion of the film. The film was placed in a belt conveyor, and a high pressure mercury lamp (160 W/cm) was applied to the coated surface to obtain a film having a photocurable crosslinked resin layer on one side. The volume ratio of the citric acid gel in the crosslinked resin layer was 0% by volume.

Thereafter, the coating ii is applied to the surface of the film on which the crosslinked resin layer is not formed 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 under the conditions of a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input electric power of 4 kW by a reactive sputtering method using an Al target. An aluminum oxide layer of 20 nm was formed on the crosslinked resin layer on either side of the PET film to obtain a laminated film 3. According to the above measurement method, the properties of the obtained laminated film 3 were evaluated, and the results are shown in Table 4.

[Comparative Example 6] (Production of two-sided crosslinked resin layer)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "P100-T50") having a thickness of 50 μm was used as a base film, and a wire bar coater was used on one side of the film. After coating the same coating material i as in Example 15 after the thickness was 10 μm, the mixture was allowed to stand for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, whereby the solvent was dried and removed to remove the film. The end portion was fixed in a belt conveyor, and a high pressure mercury lamp (160 W/cm) was applied to the coated surface to obtain a film having a photocurable crosslinked resin layer on one side.

Thereafter, the coating i was applied to the surface of the film on which the crosslinked resin layer was not formed, and hardened 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 under the conditions of a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input electric power of 4 kW by a reactive sputtering method using an Al target. An aluminum oxide layer of 4 nm was formed on the crosslinked resin layer on either side of the PET film to obtain a laminated film 4. The properties of the obtained laminated film 4 were evaluated according to the above measurement methods, and the results are shown in Table 4.

[Comparative Example 7] (Production of two-sided crosslinked resin layer)

A biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., product name "P100-T50") having a thickness of 50 μm was used as a base film, and a wire bar coater was used on one side of the film. After coating the same coating material i as in Example 15 after the thickness was 10 μm, the mixture was allowed to stand for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, whereby the solvent was dried and removed to remove the film. The end of the fixed state is put into the belt In the feeding device, a high pressure mercury lamp (160 W/cm) was applied to the coated surface to obtain a film having a photocurable crosslinked resin layer on one side.

Thereafter, the coating i was applied to the surface of the film on which the crosslinked resin layer was not formed, and hardened 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 under the conditions of a film formation pressure of 0.3 Pa, an Ar flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input electric power of 4 kW by a reactive sputtering method using an Al target. An aluminum oxide layer of 1 nm was formed on the crosslinked resin layer on either side of the PET film to obtain a laminated film 5. The properties of the obtained laminated film 5 were evaluated according to the above measurement methods, and the results are shown in Table 4.

(examine)

The gas barrier laminated film of Examples 15 and 16 has a predetermined crosslinked resin layer on both sides of the substrate, and has a gas barrier layer at an appropriate thickness on at least one side thereof, thereby having a high barrier property and having Dimensional stability for heating.

On the other hand, in Comparative Example 4, since the surface was rough, it was not possible to exhibit high barrier properties. And shrinkage occurs for heating. In Comparative Example 5, since the cross-linked resin layer was provided on both surfaces, the surface smoothness was improved as compared with Comparative Example 4, so that it had barrier properties. However, since the crosslinked resin layer was not filled with particles, the substrate could not withstand shrinkage upon heating. Stress, the film as a whole shrinks, resulting in loss of performance.

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

(industrial availability)

The transparent conductive film of the present invention can be optimally used for applications requiring dimensional stability at high temperatures and excellent surface resistance values, particularly substrates of touch panels, and can be preferably used for A substrate of a display material such as a liquid crystal display, an organic light emitting display (OLED), an electrophoretic display (electronic paper, etc.), a color filter, a backlight, or a substrate of a solar cell, a substrate for organic light illumination, an optoelectronic element substrate, or the like.

The transparent laminated film proposed by the invention can be optimally used for applications requiring dimensional stability at high temperatures, especially substrates of touch panels, and can also be preferably used as a film for packaging or as a liquid crystal display. A substrate for a display material such as an organic light-emitting display (OLED), an electrophoretic display (electronic paper, etc.), a color filter, a backlight, or a substrate for a solar cell, a film for an electronic component such as a substrate for an organic light-emitting illumination, or the like.

The gas barrier laminated film of the present invention can be optimally used for applications requiring dimensional stability and gas barrier properties at high temperatures, substrates for organic light-emitting illumination, or substrates for organic light-emitting displays (OLEDs), in addition to A substrate which is a display material such as a liquid crystal display, an electrophoretic display (electronic paper or the like), a color filter, a backlight, or the like, or a film for an electronic component such as a substrate of a solar cell can be preferably used.

Claims (24)

A transparent conductive film comprising a transparent laminated film having a crosslinked resin layer on both sides of a front and back of a base film, which is transparent on the front or both sides of the transparent laminated film directly or via an undercoat layer In the conductive layer, the thickness of the crosslinked resin layer is 8% or more of the thickness of the base film, and the heat shrinkage rate of the transparent laminated film is 1.5% or less when heated in the longitudinal direction and the transverse direction at a temperature of 200 ° C for 10 minutes. Further, the transparent conductive film has a surface resistance value of 150 Ω/□ or less. The transparent conductive film according to the first aspect of the invention, wherein the transparent conductive layer is an inorganic oxide film formed by forming a film at a temperature of 150 to 220 °C. The transparent conductive film of claim 1 or 2, wherein the transparent conductive layer has a thickness of less than 100 nm. The transparent conductive film according to any one of claims 1 to 3, wherein the thickness of the front and back sides of the crosslinked resin layer is 8% or more and 50% or less of the thickness of the base film. The transparent conductive film according to any one of claims 1 to 4, wherein the undercoat layer is substantially free of inorganic fine particles. The transparent conductive film according to any one of claims 1 to 5, wherein the crosslinked resin layer is provided with a polyfunctional acrylate having two or more acryl fluorenyl groups or methacryl fluorenyl groups in one molecule. A resin layer of a crosslinked structure in which a monomer is crosslinked. The transparent conductive film of claim 6, wherein the polyfunctional acrylate monomer is an alicyclic polyfunctional acrylate monomer having an alicyclic structure or three or more propylene fluorene in one molecule. A polyfunctional urethane urethane monomer based on a methacryl oxime group. The transparent conductive film according to any one of claims 1 to 7, wherein the crosslinked resin layer contains substantially no fine particles. The transparent conductive film according to any one of claims 1 to 8, wherein the crosslinked resin layer contains 40 to 80% by mass of fine particles having an average particle diameter of 200 nm or less. The transparent conductive film according to any one of the first to ninth aspects, wherein the base film is a resin film containing a resin having a glass transition temperature (Tg) of 130 ° C or less as a main component. The transparent conductive film according to any one of claims 1 to 10, wherein the base film is a film which has a polyethylene terephthalate resin as a main component and which is biaxially stretched. A transparent laminated film which is a laminated film having a crosslinked resin layer on both sides of a base film, wherein the crosslinked resin layer contains a photopolymerizable compound, a photopolymerization initiator, and The curable composition of the fine particles is formed, and the thickness of the base film and the crosslinked resin layer satisfies the following (a) and (b); and the second feature is: the longitudinal direction when heated at 200 ° C for 10 minutes ( The thermal shrinkage of the laminated film in at least one of the MD direction and the transverse direction (TD direction) is 70% or less of the heat shrinkage rate when the base film is heated under the same conditions, and the total light of the laminated film is worn. The transmittance is 80% or more, and (a) the thickness of the base film is 75 μm or less. (b) The thickness of the front and back sides of the crosslinked resin layer is 8% or more of the thickness of the base film. The transparent laminated film of claim 12, wherein the front side of the crosslinked resin layer The thickness of both sides is 8% or more and 50% or less of the thickness of the base film. The transparent laminated film of the 12th or 13th aspect of the invention, wherein the curable composition contains 9 to 50% by mass of the photopolymerizable compound, 0.1 to 10% by mass of the photopolymerization initiator, and fine particles with respect to the entire composition. 10~90% by mass. The transparent laminated film according to any one of claims 12 to 14, wherein the photopolymerizable compound is photopolymerizable (methyl) having two or more acryl fluorenyl groups or methacryl fluorenyl groups in one molecule. Acrylate monomer or oligomer. The transparent laminated film according to any one of the items 12 to 14, wherein the photopolymerizable compound is an alicyclic polyfunctional acrylate monomer having one or more alicyclic structures in one molecule. The transparent laminated film according to any one of claims 12 to 16, wherein the base film is a biaxially stretched film comprising a polyethylene terephthalate resin. A gas barrier laminated film comprising: a base film having a crosslinked resin layer on both surfaces of the base film; and a gas barrier layer provided on at least one surface of the crosslinked resin layer, the crosslinked The thickness of the front side of the resin layer is 8% or more of the thickness of the base film, and the first feature is that the crosslinked resin layer is made of a photopolymerizable compound, a photopolymerization initiator, and fine particles. The composition is formed, and the average particle diameter of the microparticles is in the range of 1 nm to 50 nm; the second characteristic is that the thickness of the gas barrier layer is in the range of 5 to 100 nm; and the third characteristic is: water vapor permeation of the entire film. The rate is 1.0 × 10 ^-2 g / m ² /day or less. The gas barrier layered film according to claim 18, wherein the gas barrier layer is an inorganic compound composed of any one or more of an oxide, a nitride or an oxynitride of cerium (Si) or aluminum (Al). form. The gas barrier laminated film according to claim 18, wherein the arithmetic mean roughness (Sa) of one surface of the crosslinked resin layer is 15 nm or less. The gas barrier laminated film according to any one of claims 18 to 20, wherein the base film has a thickness of 100 μm or less. The gas barrier laminated film according to any one of the above-mentioned claims, wherein the content of the fine particles (C) is 50 to 75% by volume based on the entire crosslinked resin layer. The gas barrier laminate film according to any one of claims 18 to 22, wherein the thickness of the front and back sides of the crosslinked resin layer is 8% or more and 50% or less of the thickness of the base film. The gas barrier layered film according to any one of claims 18 to 23, wherein the photopolymerizable compound is an alicyclic polyfunctional acrylate monomer having one or more alicyclic structures in one molecule.