TWI615273B - Transparent laminated film, transparent conductive film and gas barrier laminated film - Google Patents

Abstract

The present invention provides a new transparent conductive film which is excellent in transparency and thermal dimensional stability at high temperatures (for example, 200 ° C. or higher) and has a low surface resistance value. Furthermore, a new transparent laminated film and a gas-barrier laminated film which can be used for the base film of the transparent conductive film and various other transparent substrates are provided.

The present invention provides a transparent conductive film, which is a transparent laminated film having a crosslinked resin layer on at least one side of a substrate film, and one side or both sides of the crosslinked resin layer of the crosslinked resin layer are coated directly or through a resin material The first characteristic of those who form a transparent conductive layer is that the transparent laminated film has a thermal shrinkage of 1.5% or less when heated at a temperature of 200 ° C for 10 minutes in the longitudinal and transverse directions, and the second characteristic is that: The surface resistance value of the transparent conductive film is 150Ω / □ or less.

Description

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

The present invention relates to a transparent laminated film that can be used as a substrate material for solar cells, organic solar cells, flexible displays, organic electroluminescence (EL, Electro Luminescence) lighting, touch panels, and the like, and further relates to a conductive film having conductive properties. Transparent transparent conductive film and gas-barrier laminated film with gas-barrier layer.

Conventionally, glass materials have been used as substrate materials for various display elements such as organic EL and solar cells. However, glass materials not only have the shortcomings of being easily broken, heavy, and difficult to be thinned, but also cannot be said to be a sufficient material for the thinning and lightening of displays and the softening of displays in recent years. Therefore, as a substitute material for glass, a thin and lightweight transparent resin film substrate has been studied.

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

Regarding resin films with gas barrier properties, in order not to cause cracks or wrinkles caused by the functional layer with gas barrier properties, the functional layer is destroyed and the functions including gas barrier properties are impaired. It is also required to be at 150 ° C. Thermal dimension stability under the above high temperature environment Sex.

However, the conventionally known polyester film has a high thermal stability under 150 ° C or higher temperature, specifically, a high temperature environment of 150 ° C to 200 ° C. Therefore, in recent years, as a film for a gas barrier process 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 in which a thermal relaxation treatment (also referred to as "annealing treatment" and "heat setting treatment") is added as the final step of the film manufacturing process. means.

Further, Patent Documents 2 and 3 disclose a method in which various coating films are formed on the surface of a thin film produced by a general process.

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 therefore has high amorphousness. Therefore, those who have formed a transparent conductive film on a transparent resin film have significantly lower surface resistance, durability, and acid resistance than those who have formed a transparent conductive film such as an ITO film on a glass substrate. Therefore, in recent years, a transparent conductive thin 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 of forming an ITO film on a polymer thin film substrate and then performing heat treatment to crystallize the ITO; 5 discloses a method of crystallizing an ITO film by irradiating it with microwaves.

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 this resin molded body has high heat resistance, the substrate temperature can be increased to 150 ° C when forming a transparent electrode layer.

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. This transparent conductive film has a bending property that it is difficult to cause cracking even if the thickness of the conductive layer is increased. Therefore, the thickness of the conductive layer can be relatively increased to reduce the surface resistance value.

Patent Document 8 discloses a composite film for an electronic device. The composite film includes a coated polyester substrate layer and an electrode layer containing a conductive material. The coated polyester substrate in the composite film has improved flexibility and crack resistance.

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

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

In addition, as a transparent film that can be used for a transparent substrate, Patent Document 11 also discloses a composite film. The composite film is a thin film including a polymer substrate and a flat coating layer, and the coating film is formed on the coating layer. Barrier layer on the surface. The composite film has high dimensional stability because the polymer substrate is heat-set and thermally stabilized.

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

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

Patent Document 14 discloses a polyimide or polyimide having high dimensional stability at high temperatures and high transparency. Since these films are formed by a casting method, there is almost no alignment, and therefore no shrinkage occurs during heating.

As a method for improving gas barrier properties, a method has been proposed in which a polyester film is laminated with an inorganic transparent film such as silicon oxide by vacuum evaporation or sputtering to increase oxygen or water vapor permeability (for example, refer to Patent Documents) 15).

[Prior technical literature] [Patent Literature]

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

Patent Document 2: Japanese Patent Laid-Open 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 No. 2005-141981

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

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

Patent Document 8: International Publication No. 09/016388

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

Patent Document 10: International Publication No. 13/022011

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

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

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

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

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

As described above, in order to reduce the surface resistance value of a 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. Means of crystallinity of conductive film. For example, if the transparent conductive film formed by sputtering usually performed at room temperature can be formed by sputtering under a high temperature environment such as a temperature of 150 to 220 ° C, the crystallinity of the transparent conductive film can be improved. Sex.

However, biaxially-stretched polyethylene terephthalate (PET) film is generally used as a base film, which is equivalent to the above-mentioned high-temperature environment, which will shrink thermally. Therefore, there is a problem that a transparent conductive film cannot be formed in a high-temperature environment. problem. In this way, if a completely new material with excellent thermal dimensional stability is used, it not only has the possibility of causing various unexpected problems, but also raises problems such as higher costs.

Therefore, an object of the present invention is to provide an example which can be improved in a high temperature environment. A newly formed transparent conductive film, such as thermal dimensional stability in an environment above 200 ° C, which can further reduce the surface resistance value.

In addition, it is required not only to be able to be manufactured by simpler manufacturing steps, but also thinner resin films and films having higher heat resistance in future use environments.

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

Furthermore, in the case of using a film that uses a method of improving gas barrier properties, the polyester film as a substrate shrinks during the heating and annealing step required to form a transparent electrode or element on the film, so that there is a loss of gas. Barrier possibilities. In this way, it is not only required to be able to be manufactured by simpler manufacturing steps, but also to develop thin films with high heat resistance and excellent gas barrier properties in future use environments.

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

The invention provides a transparent conductive film, which is a transparent laminated film having a crosslinked resin layer on both sides of the front and back of a base film, and directly or through an undercoat layer on one or both sides of the front and back of the transparent laminated film A transparent conductive layer is provided, and the thickness of the cross-linked resin layer is 8% or more of the thickness of the base film, which is characterized in that the transparent laminated film is heated at a temperature of 200 ° C for 10 minutes in the vertical and horizontal directions. The thermal contraction rate is 1.5% or less, and the surface resistance value of the transparent conductive film is 150Ω / □ or less.

The transparent conductive film provided by the present invention has a crosslinked resin layer on both the front and back sides of the base film, and the total thickness of the crosslinked resin layers is set to be thin. The thickness of the film is more than 8%, so that even if the substrate film is expected to shrink in a high temperature environment, the crosslinked resin layer resists the shrinkage. The transparent conductive film as a whole can withstand the shrinkage stress, so it can be used as a transparent conductive film. Thermal dimensional stability. Specifically, thermal dimensional stability with a thermal shrinkage of 1.5% or less when heated at a temperature of 200 ° C. for 10 minutes in the longitudinal and transverse directions can be obtained.

Therefore, since the transparent conductive film proposed by the present invention can form a transparent conductive layer under a high temperature environment such as 150 to 220 ° C, the crystallinity of the transparent conductive layer can be improved, and the surface of the transparent conductive film can be effectively reduced. resistance.

The transparent conductive film proposed by the present invention can obtain the advantages as described above, and thus can be preferably used in, for example, a liquid crystal display, an organic light emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, In addition to substrates for display materials such as backlights or substrates for solar cells, they can also be preferably used for photovoltaic element substrates.

In addition, 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. Furthermore, by performing a gas barrier process, it can be preferably used for semiconductor devices such as organic EL, liquid crystal display elements, and solar cells.

In addition, the present invention provides a transparent laminated film which is a laminated film having a crosslinked resin layer on the front and back sides of a base film. The first feature is that the crosslinked resin layer contains a photopolymerizable compound, light It is formed by a hardening composition of a polymerization initiator and fine particles, and the thickness of the base film and the crosslinked resin layer satisfies the following (a) and (b), and the second characteristic is that it is heated at 200 ° C for 10 minutes. The heat shrinkage of the laminated film in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) at the minute is less than 70% of the heat shrinkage ratio when the substrate film is heated under the same conditions, and The total light transmittance of the laminated film is above 80%.

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

(b) The total thickness of the front and back sides of the crosslinked resin layer is more than 8% of the thickness of the substrate film

The transparent laminated film proposed by the present invention has a structure in which a crosslinked resin layer formed using a hardening composition containing a specific material is laminated on a front and back sides of a substrate film of a specific thickness with a specific thickness, and has a structure Excellent transparency and thermal dimensional stability at high temperature (for example, 200 ° C or higher).

In addition, since the cross-linked resin layers provided on the front and back sides of the base film can withstand the stress of the base film to shrink at high temperature, the transparent laminated film proposed by the present invention maintains transparency and is caused by heat treatment. The dimensional change (thermal dimensional stability) is small.

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 (OLED), electrophoretic displays (electronic paper), touch panels, color filters, backlights, and the like. In addition to the substrate, or the substrate of a solar cell, it can be preferably used for a photovoltaic element substrate or the like.

In addition, the transparent laminated film proposed by the present invention has the advantages as described above, so it can be preferably used for applications requiring dimensional stability at high temperatures, especially films for packaging and films for electronic parts. Gas barrier processing can also be used for semiconductor devices such as organic EL, liquid crystal display elements, and solar cells.

Furthermore, the present invention proposes a gas barrier laminated film having a structure including a base film, a crosslinked resin layer on both sides of the base film, and a gas barrier on at least one side of the crosslinked resin layer. The total thickness of the front and back sides of the crosslinked resin layer is 8% or more of the thickness of the base film. The first feature is that the crosslinked resin layer contains a photopolymerizable compound and a photopolymerization initiator. And the hardening composition of fine particles, and the average particle diameter of the fine particles 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 that: The water vapor transmission rate of the entire film is 1.0 × 10 ^-2 g / m ² / day or less.

The gas-barrier laminated film proposed by the present invention has a cross-linked resin layer and a gas-barrier layer in a specific structure, and adjusts the thickness of the cross-linked resin layer material and the gas-barrier layer, thereby maintaining transparency and gas. Barrier properties and dimensional stability at high temperatures (for example, above 150 ° C) are high, and it is difficult to cause shrinkage even in subsequent heat treatment.

In addition, the gas-barrier laminated film proposed by the present invention is provided with a cross-linked resin layer and a gas-barrier layer that improve thermal dimensional stability on both sides of the substrate film, and has high transparency and is caused by heat treatment. The dimensional change is small, and it also 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 (OLED), electrophoretic displays (electronic paper), touch panels, color filters, backlights, etc. In addition to substrates made of materials or substrates for solar cells, they can also be preferably used for photovoltaic element substrates.

The gas-barrier laminated film proposed by the present invention has the advantages as described above, so it can be preferably used for applications requiring dimensional stability at high temperatures, especially for packaging films and films for electronic parts. Ideal for semiconductor devices such as organic EL, liquid crystal display elements, and solar cell applications.

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

An example of an embodiment of the present invention is a transparent conductive film (referred to as "this conductive film"), a transparent laminated film (referred to as "this multilayer film"), and a gas barrier laminated film (referred to as "this gas barrier film" ") Have a common structure having a crosslinked resin layer on both the front and back sides of the base film.

Therefore, the following first describes components common to any embodiment (these are collectively referred to as "the film of the present invention"), and secondly, the laminated film 1 (referred to as "the conductive film"), Laminated film 2 (referred to as "this laminated film") and laminated film 3 (referred to as "this gas barrier film").

<Substrate film>

As the base film in the film of the present invention, any transparent resin film can be used arbitrarily. Examples of the film include polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyphenylene sulfide resin, polyether sulfonate resin, polyether sulfonium imine resin, and transparent Cyclic olefin-based resins such as polyimide resins, polycarbonate resins, cyclic olefin homopolymers, and cyclic olefin copolymers. Films containing a resin composed of one or a combination of two or more of these resins can be used.

Examples of the transparent polyfluorene imide resin include those in which a hexafluoroisopropylidene bond is introduced into the main chain of the polyfluorene imide resin, or a fluorinated polyfluorene which replaces hydrogen in the polyfluorene imide with fluorine. In addition to the imine, alicyclic polyimide obtained by hydrogenating a cyclic unsaturated organic compound contained in the structure of the polyimide resin may also be mentioned. For example, those described in Japanese Patent Application Laid-Open No. 61-141738 and Japanese Patent Application Laid-Open No. 2000-292635 can be used.

Among the above-mentioned films, a film having poor thermal dimensional stability, such as a substrate film that thermally shrinks in an environment of a temperature of 150 to 220 ° C, can further enjoy the effects of the present invention. Right From the viewpoint, as the base film used in the film of the present invention, a resin film containing a resin having a glass transition temperature (Tg) of 130 ° C. or lower as a main component is preferred, and 50 ° C. or higher is preferred A resin film containing 130 ° C or less, more preferably 70 ° C or more and 130 ° C or less as a main component.

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

<Crosslinked resin layer>

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

Furthermore, in the basic application of priority in this case, the crosslinked resin layer is also referred to as a “hardened layer”. The reason for this is that it is usually formed by coating and hardening a curable composition. The "hardened layer" in this base application and the "crosslinked resin layer" in this case represent the same layer.

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

Next, each of these components will be described.

(Photopolymerizable compound)

Examples of the photopolymerizable compound include a compound having a polymerizable unsaturated bond, specifically a monomer or oligomer having an ethylenically unsaturated bond, and more specifically, a urethane ( (Meth) acrylate, epoxy (meth) acrylate, polyester (formaldehyde) (Meth) acrylate, polyether (meth) acrylate, polycarbonate (meth) acrylate and other (meth) acrylate monomers or oligomers, other than monofunctional or polyfunctional ( (Meth) acrylate monomers or oligomers. These can be used singly or in combination of two or more kinds.

In addition, in the present invention, the so-called "monomer" means a repeat of a structural unit having no polymerizable functional group, and the so-called "oligomer" means a repeating number of a structural unit having a polymerizable functional group as Those having a molecular weight of less than 5,000 or having a polymerizable functional group at the terminal.

酯、(甲基)丙烯酸二環戊烯酯等單官能丙烯酸酯單體，或二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯、三環癸烷二甲醇二丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、2,2'-雙(4-(甲基)丙烯醯氧基聚乙烯氧基苯基)丙烷、2,2'-雙(4-(甲基)丙烯醯氧基聚伸丙氧基苯基)丙烷等2官能丙烯酸酯單體，或三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、異氰尿酸參(2-羥乙基)酯三(甲基)丙烯酸酯、丙氧化甘油三(甲基)丙烯酸酯等3官能丙烯酸酯單體，或二-三羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等4官能丙烯酸酯單體，或二季戊四醇羥基五(甲基)丙烯酸酯等5官能丙烯酸酯單體，或二季戊四醇六(甲基)丙烯酸酯等6官能丙烯酸酯 單體等。再者，該等可使用1種或組合2種以上使用。 Examples of the above-mentioned monofunctional or polyfunctional methacrylate monomer or acrylate monomer (hereinafter referred to as "acrylate monomer" each or in combination) are, for example, ethyl (meth) acrylate, ( N-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) Phenyl acrylate, (meth) acrylic acid

Monofunctional acrylate monomers such as esters, dicyclopentenyl (meth) acrylate, or diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane Glycol di (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol di (methyl) ) Acrylate, polypropylene glycol di (meth) acrylate, 2,2'-bis (4- (meth) acryloxypolyoxyoxyphenyl) propane, 2,2'-bis (4- ( Difunctional acrylate monomers such as (meth) acrylic acid, poly (propoxyphenyl) phenyl) propane, or trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (Meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, isocyanurate (2-hydroxyethyl) ester tri (methyl) ) Trifunctional acrylate monomers such as acrylate, glycerol tri (meth) acrylate, or 4-functional acrylic acid such as di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate Ester monomer, or dipentaerythritol hydroxyl (Meth) acrylate, 5 functional acrylate monomer, dipentaerythritol hexa (meth) acrylate, 6-functional acrylate monomers. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Among these, in terms of relatively easy cross-linking when irradiated with ultraviolet rays, it is preferable to use a polyfunctional acrylate monomer having two or more acrylfluorenyl groups or methacrylfluorenyl groups in one molecule or Oligomer. In this way, by having two or more functional groups, the symmetry of the molecule becomes high, and as a result, the dipole moment of the molecule is reduced, and the aggregation of microparticles, especially inorganic microparticles, can also 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 acrylfluorene groups or methacrylfluorene groups in one molecule is crosslinked.

Among these, in terms of particularly excellent heat shrinkage stability, an alicyclic polyfunctional acrylate monomer having an alicyclic structure is particularly preferred, and one or more of them have one or more alicyclic structures in one molecule. It is an alicyclic polyfunctional acrylate monomer, or a polyfunctional acrylic urethane monomer having 3 or more acrylfluorenyl or methacrylfluorene groups in one molecule. 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 215 to 4000. Among these, the molecular weight is more preferably 250 or more and 3000 or less, and even more preferably 300 or more and 2000 or less. By using a photopolymerizable compound in the above molecular weight range, it is possible to eliminate the possibility that a monomer is adsorbed onto the inorganic fine particles in a drying step or the like due to too low molecular weight, and on the other hand, it is possible to eliminate hardening due to excessive molecular weight. Problems such as excessive viscosity of the sexual composition, suppression of dispersion of fine particles, and aggregation of fine particles with each other. As a result, the crosslinked resin layer can effectively suppress shrinkage of the base film at high temperatures.

In addition, in this invention, when the molecular weight of a photopolymerizable compound exceeds 1500, it will be set as the thing which shows the molecular weight by weight average molecular weight (Mw).

In addition to the above, for example, in order to adjust the physical properties such as the hardenability, water absorption, and hardness of the crosslinked resin layer, a material selected from the group consisting of poly (meth) acrylate, epoxy resin, and polyamine may be added to the hardenable composition. A polymer component composed of one or a combination of two or more of formate resin, polyester resin, and the like.

(Photopolymerization initiator)

系、氧化膦系及過氧化物系等。作為上述光聚合起始劑之具體例，可例示例如：二苯甲酮、4,4-雙(二乙基胺基)二苯甲酮、2,4,6-三甲基二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯基二苯甲酮、第三丁基蒽醌、2-乙基蒽醌、二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮、苄基二甲基縮酮、1-羥基環己基-苯基酮、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、2-甲基-[4-(甲硫基)苯基]-2-

啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1、二乙基-9-氧硫

、異丙基-9-氧硫

、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、苯甲醯甲酸甲酯等。該等可單獨使用1種或將2種以上併用。 Examples of the photopolymerization initiator include benzoin-based, acetophenone-based, and 9-oxysulfur.

System, phosphine oxide system and peroxide system. Specific examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, and 2,4,6-trimethylbenzophenone. , Methyl benzophenone benzoate, 4-phenylbenzophenone, third butyl anthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl- 1-phenylpropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propanyl) -benzyl] phenyl} -2-methyl-propane 1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methyl Thio) phenyl] -2-

Phenyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-

(Phenylphenyl) -butanone-1, diethyl-9-oxysulfide

Isopropyl-9-oxysulfur

, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethylpentylphosphine oxide, Bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, methyl benzamate and the like. These can be used individually by 1 type or in combination of 2 or more types.

(Fine particles)

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

When the crosslinked resin layer contains fine particles, it is preferable to use a (meth) acrylic acid ester monomer having a low molecular weight, for example, a weight average molecular weight of 3,000 or less as the photopolymerization. Compound to disperse the fine particles.

Examples of the fine particles include inorganic fine particles having transparency such as silica, alumina, titania, soda glass, and diamond.

Among these, silicon oxide fine particles are preferred from the viewpoints of coating suitability and price. Silicon oxide microparticles have been extensively developed for surface modification. By using surface shrinkage, the dispersibility in the hardening composition is improved, and a uniform hardened film can be formed.

Specific examples of the silica fine particles include dry powdery silica fine particles, silicic acid colloid (silica sol) dispersed in an organic solvent, and the like. Among these, in terms of dispersibility, it is preferred to use a silicic acid gum (silica sol) dispersed in an organic solvent.

For the purpose of improving dispersibility, the surface may be surface-treated with a silane coupling agent, a titanate-based coupling agent, and the like within a range that does not impair transparency, solvent resistance, liquid crystal resistance, and heat resistance to the greatest extent. Treated silica particles, or silica particles with an easily dispersible surface.

Among these, it is preferable to use microparticles treated with a silane coupling agent, in particular a methacrylfluorenylsilane-based coupling agent, a vinylsilane-based coupling agent, or a phenylsilane-based coupling agent.

Examples of the methacrylic fluorenylsilane-based coupling agent include 3-methacryl methoxypropyltrimethoxysilane, 3-methacryl methoxypropylmethyldimethoxysilane, and 3-methyl Propylene ethoxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane.

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

Examples of the phenylsilane-based coupling agent include phenyltrimethoxysilane and phenyltriethoxysilane.

Among these, fine particles treated with a methacrylfluorinylsilane-based coupling agent have the highest affinity with the binder, and are therefore the best.

When the fine particles are subjected to a surface treatment, the theoretical surface treatment amount is calculated by the following formula.

Adding amount (g) = weight of filling material (g) × specific surface area (m ² / g) / minimum coating area of silane coupling agent (m ² / g)

The so-called minimum covering area is calculated by the following formula.

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

From the viewpoint of a low possibility of particles being agglomerated with each other and not being properly dispersed in the case of the amount of addition derived from the above formula, and to prevent the liquid concentration from rising sharply when dispersed in a solvent or the like From the viewpoint of generation of bubbles, the amount of the surface treatment agent used is preferably within three times the theoretical amount of the surface treatment.

By using the surface-treated fine particles, the fine particles can be dispersed in the crosslinked resin layer at a high concentration and uniformly. As a result, the occurrence of scattering phenomena can be prevented, and deviations in thermal dimensional stability can also be prevented.

In order to reduce the amount of refracted light incident on the crosslinked resin layer, the refractive index of the fine particles is preferably less than 1.6. Among these, from the viewpoint of improving transparency, it is preferable to use a resin that reacts the hardened composition with the above-mentioned hardened composition, particularly a resin having a refractive index difference between the resin constituting the main component and the fine particles (filler) of less than 0.2. .

(Solvent)

The said 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 curable composition, and the solution can be applied. It is hardened on a base film, and a crosslinked resin layer is formed in the form of a hardened coating 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; aromatics such as toluene and xylene; and cyclohexanone , Isopropanol, etc.

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

(Other ingredients)

In addition to the above, photo-curable oligomers, monomers, or photoinitiators other than those exemplified above may be contained within a range that does not impair the hardening properties, transparency, and water absorption properties. , Crosslinker, ultraviolet absorber, polymerization inhibitor, filler, thermoplastic resin, etc.

<Layer structure>

In the film of the present invention, a cross-linked resin layer can be directly laminated and laminated on the front and back surfaces of the base film, and other layers can also be inserted between the base film and the cross-linked resin layer. For example, an undercoat layer can be inserted between the base film and the crosslinked resin layer to improve the adhesion of the crosslinked resin layer to the base film.

<Heat setting treatment>

In the film of the present invention, since the predetermined cross-linked resin layers are provided on the front and back sides of the base film, the base film can be made transparent and heat-resistant at high temperatures (for example, 200 ° C or higher) without heat-setting the base film. Film with excellent thermal dimensional stability. However, the film of the present invention may be a base film that is heat-set in order to reduce shrinkage.

Prior to applying the hardening composition on the base film, the base film is heat-set in advance, thereby further improving the dimensional stability of the base film and the laminated film.

Among them, a preferred example of the base film is a biaxially stretched polyester film that is heat-set in order to reduce shrinkage.

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

The specific method of the heat setting treatment is not particularly limited as long as it can maintain the required temperature and time. For example, a method of storing in an oven or a constant temperature room set to a desired temperature, a method of blowing hot air, a method of heating by an infrared heater, a method of irradiating light with a lamp, and a method of heating it with a heat roller or heat A method of directly applying heat by contacting a plate, a method of irradiating a microwave, and the like. In addition, the substrate film may be subjected to heat treatment after being cut into a size that is easy to handle, or may be directly subjected to heat treatment in a state of a film roll. Furthermore, as long as the required time and temperature can be obtained, a heating device can be incorporated into a part of a film manufacturing apparatus such as a coating machine and a slitter to heat it during the manufacturing process.

[This conductive film]

The conductive film, which is an example of an embodiment of the present invention, is a transparent laminated film having the above-mentioned crosslinked resin layer on both sides of the front and back sides of the base film, and is on one or both sides of the front side 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 that can be formed by crosslinking the curable composition.

(Fine particles)

The crosslinked resin layer in this conductive film may not substantially contain fine particles, and may also contain substantially fine particles. When the crosslinked resin layer contains fine particles, the high-temperature dimensional stability can be further improved.

As the fine particles, it is preferable to use fine particles having an average particle diameter in a range of 1 nm to 200 nm. Among them, it is particularly preferable to use fine particles having an average particle diameter in a range of 1 nm to 100 nm, in which 4 nm to 50 nm. By using fine particles having an average particle diameter within this range, the incident light will not be scattered due to the Mie scattering phenomenon, and the transparency of the film can be ensured.

The “average particle diameter” here means an exponential average particle diameter. When the shape of the microparticles is spherical, it can be calculated by using “the sum of the circle equivalent diameter of the measured particles / the number of measured particles”. When the shape of the microparticles is not spherical, it can be calculated by using "the sum of the short and long diameters / the number of measured particles".

When two or more kinds of fine particles are contained, the average particle diameter of the mixed particles becomes the "average particle diameter" described above.

(Containing ratio)

The content of the photopolymerizable compound contained in the curable composition is preferably 20 to 90% by mass relative to the entire curable composition (when a solvent is used, it is converted to a solid content, and the same applies hereinafter). , More preferably, it is set to 20 to 60% by mass, and most preferably, it is set to 20 to 40% by mass. If the content of the photopolymerizable compound is small, since the fine particles are difficult to disperse, there is a possibility that the fine particles are aggregated with each other and the transparency is significantly deteriorated. In addition, the content of the photopolymerizable compound is not too much, and the thermal dimension stability of the fine film to the entire film can be eliminated. The effect of the nature is halved, and the possibility of the excellent thermal dimensional stability of the fine particles cannot be exhibited.

The photopolymerization initiator may be contained as necessary. When a 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 relative to the entire curable composition. ~ 10 mass%, more preferably 0.5 mass% to 5 mass%. By setting it as the said range, the hardening reaction of a hardenable composition can be performed reliably and efficiently.

Among 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 of the photopolymerizable compound (hereinafter also simply referred to as (A)) and the fine particles ( 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.

The content ratio of (A), the photoinitiator (hereinafter also simply referred to as (B)), and (C) contained in the curable composition is preferably 20 to 79% by mass of (A), (B) 0.1 to 10% by mass and (C) 10 to 79% by mass, of which (A) is preferably 20 to 59% by mass, and photopolymerization initiator (B) is 0.5 to 5% by mass And (C) 40 to 79% by mass. Among these, (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 excellent thermal dimensional stability of the fine particles, and to efficiently and stably supply a laminated film having transparency and productivity.

In the case where fine particles are contained in the conductive film, the content of the fine particles contained in the curable composition is preferably contained in the fine particles having an average particle diameter of 200 nm or less relative to the entire curable composition. 80% by mass, more preferably 60% to 80% by mass. By setting it as the said range, transparency can be maintained in the range in which microparticles can be disperse | distributed, and the outstanding thermal dimensional stability can be exhibited to the maximum.

(Thickness composition)

The thickness of the base material film in the conductive film is preferably 70 μm or less, more preferably 5 μm or more and 70 μm or less, still more preferably 10 μm or more and 70 μm or less, and particularly preferably 20 μm or more and 60 μm or less. By setting it as the said range, advantages, such as an improvement in light transmittance and high processing performance, can be obtained.

A resin film that is used as a substrate material for a touch panel, an organic EL display, or organic EL lighting is required to have a thin film thickness to reduce weight, thickness, and cost. Generally, when a resin film is obtained by extrusion molding, in order to reduce the thickness, the resin in a molten state is stretched and thinned, or the resin film heated to a temperature higher than the glass transition temperature is obtained.

That is, as the resin film is thinned, the external stress applied to the molding increases, and as a result, the resin film has a large residual stress. Therefore, when a resin film having a thickness of 100 μm or less is used for an application that undergoes a high-temperature step such as circuit formation, the residual stress is relaxed at a high temperature to cause a problem of dimensional change.

Therefore, since a cross-linked resin layer having a thickness of more than 8% of the base film is provided on both the front and back sides of a base film of a specific thickness, specifically, a base film of 70 μm or less, the cross-linked resin layer is significantly suppressed. The base film shrinks at high temperature, and a transparent laminated film with excellent thermal dimensional stability can be obtained.

In this conductive film, a crosslinked resin layer is formed on both sides of the front and back sides of the base film so that the heat shrinkage rate when heated at 200 ° C for 10 minutes becomes 1.5% or less. The total thickness of the resin layer is preferably 8% or more of the substrate film, more preferably 10% or more of the substrate film thickness, and further preferably 15% or more and 50% or less, among which, it is even more preferable. Above 20% and below 45%, preferably over 30% It is 45% or less.

If the crosslinked resin layer is thin, the rigidity of the entire laminated film becomes small, and it is difficult to suppress the shrinkage of the base film at high temperatures. On the other hand, if the crosslinked resin layer is too thick, cracks or cracks tend to occur, which is not preferable.

<Transparent conductive layer>

The conductive film can form a transparent conductive layer directly on a transparent build-up film having a crosslinked resin layer, or through an undercoat layer made of a resin material.

The material of the transparent conductive layer is not particularly limited. Any material may be used as long as it can form a transparent conductive film. Examples include thin films of tin oxide-containing indium oxide (ITO), antimony-containing tin oxide (ATO), zinc oxide, zinc-aluminum composite oxides, and indium-zinc composite oxides. These compounds can have both transparency and conductivity by selecting appropriate production conditions.

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. Hitherto, in order to reduce the surface resistance value of transparent conductive films (for example, less than 150Ω / □), attempts have been made to increase the thickness of the conductive layer. However, according to this conductive film, it has high thermal dimensional stability at high temperatures. Therefore, a conductive layer can be formed at a high temperature, and a sufficiently low surface resistance value can be obtained without increasing the thickness of the conductive layer.

As a method for forming the transparent conductive layer, a vacuum evaporation method, a sputtering method, a chemical vapor deposition (CVD) method, an ion plating method, and a spray method are known. The film thickness is selected by a suitable method. For example, in the case of a sputtering method, ordinary sputtering using a compound target, reactive sputtering using a metal target, and the like are used. In this case, a reactive gas such as oxygen, nitrogen, or water vapor may be introduced, or ozone, ion assistance, or the like may be used in combination.

As a condition for forming the transparent conductive layer, a temperature in a range of 150 ° C to 220 ° C is preferred. For example, when a transparent conductive layer is formed on a thin film by a sputtering method, the usual sputtering temperature is about room temperature to about 100 ° C. On the other hand, since the transparent laminated film used in the conductive film is excellent in thermal dimension stability as described above, it can be sputtered even at a relatively high temperature such as 150 ° C to 220 ° C. The inorganic oxide film is formed, so that 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.

<Undercoating>

When forming a transparent conductive layer on a transparent laminated film, it is preferable to pass through an undercoat layer. By passing through the undercoat layer, the adhesiveness and crystallinity of the transparent conductive layer can be improved.

The material of the undercoat layer is not particularly limited as long as it is a resin material. For example, poly (meth) acrylate, epoxy resin, polyurethane resin, polyester resin, etc. can be preferably used. Alternatively, an undercoat layer may be formed by polymerizing a composition containing a light or thermally polymerizable compound.

In addition, if the flatness of the undercoat layer is poor, crystal growth of the transparent conductive layer may be hindered. Therefore, the undercoat layer is preferably substantially free of fine particles.

At this time, "substantially free of fine particles" means that the content of the inorganic fine particles is 5 mass% or less of the entire undercoat layer, preferably 3 mass% or less, and particularly preferably 1 mass% or less.

In the case where the conductive film includes fine particles in the crosslinked resin layer of the transparent build-up film, it is preferable to insert the undercoat layer when forming a transparent conductive layer on the transparent build-up film.

By inserting the undercoat layer in this way, the surface smoothness can be improved and the continuity of the transparent conductive layer can be improved. Therefore, the surface resistance value of the conductive film can be made small.

<Physical properties>

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

(Heat shrinkage)

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

Because the transparent laminated film has a shrinkage in this range, it has the advantages of reducing the dimensional deviation when forming a circuit or an element, and also obtaining higher barrier properties when laminated with an inorganic barrier layer.

In particular, biaxially stretched films, etc., can be reduced in the film-forming step by a relaxation process in the horizontal direction, but other processes are often required for the relaxation process in the vertical direction. Generally speaking, the shrinkage rate in the vertical direction is relatively changed. Big. Therefore, the present conductive film preferably has a reduced shrinkage ratio in the longitudinal direction.

The transparent build-up film used in the conductive film preferably includes a base film and a crosslinked resin layer, and has a thermal shrinkage of 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 more than 8% of the thickness of the base film, the crosslinked resin layer can reduce the shrinkage stress of the base film in a high-temperature region and ease the shrinkage. Therefore, the thermal dimensional stability of the transparent laminated film against shrinkage at high temperatures can be improved as described above.

Because this conductive film has high thermal dimensional stability at high temperature The qualitative transparent laminated film has a structure of a transparent conductive layer, so a transparent conductive layer can be formed under a high temperature environment (specifically 150 ~ 220 ° C), which can sufficiently conduct the crystallization of the conductive layer, and can have a lower Surface resistance value.

(Surface resistance value)

The surface resistance value of this conductive film is preferably 150 Ω / □ or less, and more preferably 100 Ω / □ or less. Since the conductive film has a surface resistance value in the above-mentioned range, it 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 enlarged.

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

<Manufacturing method of the present conductive film>

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

Examples of the method for applying the hardenable composition include bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, lithography, and Dry printing, screen printing, and dip coating are equivalent to the method of coating a hardening composition on a base film. In addition, a method of transferring the molded crosslinked resin layer to a substrate film after molding the crosslinked resin layer on a glass or polyester film is also effective.

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

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

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

On the other hand, when it is hardened 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, this conductive film has the advantages of maintaining transparency, small dimensional change (thermal dimensional stability) due to heat treatment, and small surface resistance value. Therefore, the conductive film can be preferably used for photovoltaic elements in addition to substrates of display materials such as liquid crystal displays, organic light emitting displays (OLEDs), electrophoretic displays (electronic papers), and touch panels, or substrates of solar cells. Substrate, etc.

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

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

Conventionally, when a polyester film is used as a film for gas barrier processing, there are problems such as that cracks or wrinkles are generated in the gas barrier layer, and a function including gas barrier properties cannot be sufficiently expressed. On the other hand, this barrier film is excellent in the point which does not have the said problem.

Except for organic semiconductor devices such as organic EL or liquid crystal display elements of the barrier film In addition to other components, it can also be preferably used in applications requiring gas barrier properties and electrical conductivity, such as solar cells.

In addition, the gas barrier processing is formed on the at least one side of the transparent laminated film, the laminated film, and the crosslinked resin layer of the gas barrier film used in the conductive film by forming a gas such as an inorganic substance such as a metal oxide or an organic substance Processing method of gas barrier layer made of high barrier material.

In this case, examples of the material having high gas barrier properties include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, and oxides, carbides, nitrides, carbon oxides, and nitrogen oxides. , Carbonitrides, diamond-like carbon or mixtures of these. Among them, silicon oxide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, aluminum oxide, aluminum oxide and the like are preferred in terms of no concerns about leakage when used in solar cells and the like. Inorganic oxides, nitrides such as silicon nitride and aluminum nitride, diamond-like carbon and mixtures thereof. In terms of stably maintaining high gas barrier properties, particularly preferred are silicon oxide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, silicon nitride, aluminum oxide, aluminum oxide, aluminum nitride, Aluminum nitride and mixtures of these.

As a method for forming a gas barrier layer on the conductive thin film by using the above materials, a method such as a vapor deposition method and a coating method can be arbitrarily adopted. In terms of obtaining a uniform thin film having a high gas barrier property, a vapor deposition method is preferred.

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

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

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

The thickness of the gas barrier layer is preferably from 10 nm to 1000 nm from the viewpoint of showing stable gas barrier properties and transparency, and more preferably from 40 nm to 800 Among them, nm is preferably at least 50 nm and at most 600 nm.

The gas barrier layer may be a single layer or a multilayer. When the gas barrier layer is a multilayer, each layer 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. Days)] or less.

The measurement method of water vapor transmission rate can be based on each condition of 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)". The measurement was carried out by the method described in the examples.

[This laminated film]

This laminated film, which is an example of an embodiment of the present invention, is a laminated film provided with a transparent laminated film having a special crosslinked resin layer on the front and back sides of the substrate film as described above.

The laminated film has predetermined crosslinked resin layers on the front and back sides of the base film, so the crosslinked resin layer can reduce the shrinkage stress of the base film in a high temperature region. Therefore, the dimensional stability of the laminated film against shrinkage at high temperatures can be improved.

Resin films that are used as substrate materials for touch panels, organic EL displays, and organic EL lighting are required to be thinner to reduce weight, thickness, and cost. Generally, when a resin film is obtained by extrusion molding, in order to reduce the thickness, the resin in a molten state is stretched and thinned, or the resin film heated to a temperature higher than the glass transition temperature is obtained.

That is, as the resin film is thinned, the external stress applied to the molding increases, and as a result, the resin film has a large residual stress. Therefore, in the case of having a thickness of 100 μm or less When the resin film is used in applications where a high-temperature step such as circuit formation is required, the residual stress is relaxed at high temperatures to cause a problem of dimensional change.

Therefore, in this laminated film, the substrate film of a specific thickness is specifically 75 μm or less, and more preferably 70 μm or less. The front and back sides of the substrate film are set so that the total thickness becomes more than 8% of the substrate film. By cross-linking the resin layer, the cross-linked resin layer significantly suppresses shrinkage of the base film at high temperatures, and a transparent laminated film having excellent thermal dimensional stability can be obtained.

<Substrate film>

This laminated film has a property that the heat shrinkage rate when heated at 200 ° C. for 10 minutes is lower than the base film by 70% or less, for example. That is, when a base film having a high thermal shrinkage under the same conditions is used, a particularly remarkable effect can be exhibited. From the viewpoints described above, as the base film of the laminated film, it is preferable to use a double polyethylene terephthalate resin composed of a polyethylene terephthalate resin having a relatively high shrinkage when heated at 200 ° C for 10 minutes. Shaft extension film.

The thickness of the substrate film is preferably 75 μm or less, more preferably 5 μm or more and 75 μm or less, still more preferably 10 μm or more and 70 μm or less, and most preferably 20 μm or more and 60 μm or less. By setting it as the said range, advantages, such as an improvement in light transmittance and high processing performance, can be obtained.

<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 components such as the photopolymerizable compound, those exemplified above can be used. Among these, the photopolymerizable compound is preferably a photopolymerizable (meth) acrylate monomer or oligomer having two or more acrylfluorenyl groups or methacrylfluorenyl groups in one molecule, and more preferably one having 1 or more alicyclic polyfunctional alicyclic structure Acrylic monomer.

(Fine particles)

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

As the fine particles, those having an average particle diameter in a range of 1 nm to 200 nm are preferably used. Among them, fine particles having an average particle diameter in a range of 1 nm to 100 nm, and 4 nm to 50 nm are particularly preferred. By using fine particles having an average particle diameter within this range, the incident light will not be scattered due to the Mie scattering phenomenon, and the transparency of the film can be ensured.

(Containing ratio)

The content of the photopolymerizable compound (A) contained in the curable composition is preferably 9 to 50% by mass based on the entire curable composition (converted to a solid content when a solvent is used). , The same applies hereinafter), among which it is more preferably set to 15% by mass or more and 45% by mass or less, and most preferably set to 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 difficult to disperse, so that the fine particles are aggregated with each other, and the transparency is significantly deteriorated. In addition, by not containing too much the content of the photopolymerizable compound (A), it is possible to eliminate the possibility that the effect of the fine particles on the overall thermal dimensional stability of the film is halved and the 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% to 10% by mass based on the entire curable composition, and more preferably 0.5%. Above mass% and below 5 mass%. By setting it as the said range, the hardening reaction of a hardenable composition can be performed reliably and efficiently.

The content of the fine particles (C) contained in the hardenable composition is preferably 10 to 90% by mass based on the entire hardenable composition, and more preferably 20 to 84% by mass. Among them, 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 in which microparticles can be disperse | distributed, and the outstanding thermal dimensional stability can be exhibited to the maximum.

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

(Thickness of the crosslinked resin layer)

The total thickness of the front and back sides of the crosslinked resin layer in the laminated film is preferably more than 8% of the thickness of the substrate film, and more preferably, it is more than 10% of the thickness of the substrate film. In particular, the thickness of the base film is 12% or more and 50% or less. Among these, the thickness is more preferably 20% or more and 45% or less, and the most preferable is more than 30% and 45% or less.

If the crosslinked resin layer is thin, the rigidity of the entire laminated film becomes small, and it is difficult to suppress the shrinkage of the base film at high temperatures. 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 this laminated film)

Next, the various physical properties which this laminated film can have are demonstrated.

(Total Light Transmission)

The total light transmittance of the laminated film is preferably 80% or more, and more preferably 85% or more. Since this laminated film has a total light transmittance in this range, it can suppress the attenuation of light in lighting or displays, and thus become brighter. Further, as a solar cell member, advantages such as being able to absorb more light can be obtained. Furthermore, the light transmittance of the laminated film can be adjusted by adjusting the type of resin in the crosslinked resin layer, the type and particle size of the particles, and the content of the particles.

(Heat shrinkage)

For the above reasons, it is preferable that the shrinkage of the laminated film in at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200 ° C for 10 minutes is the substrate measured under the same conditions. The thermal shrinkage of the film is less than 70%.

Since the laminated film has a shrinkage in this range, as described above, it has the advantages of reducing the dimensional deviation when forming a circuit or an element, and obtaining higher barrier properties when laminated with an inorganic barrier layer. The laminated film is also preferred to reduce the shrinkage in the longitudinal direction, especially for the reasons described above.

<Manufacturing method of this laminated film>

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

The method for forming a crosslinked resin layer is the same as the above-mentioned conductive film.

<Application of this laminated film>

As described above, this laminated film has the advantages of maintaining transparency and having a small dimensional change (thermal dimensional stability) due to heat treatment. Therefore, it can be preferably used for the applications exemplified above. For example, a gas barrier layer can be formed on the laminated film and used as a gas barrier film (details are based on the barrier film of the conductive film).

[This gas barrier film]

This gas barrier film, which is an example of an embodiment of the present invention, is a gas barrier laminate film having the following structure: a transparent laminate film having a crosslinked resin layer as described above on both sides of the substrate film as described above, and further At least one side of the crosslinked resin layer is provided with a predetermined gas barrier layer.

This gas barrier film has a structure having a predetermined crosslinked resin layer on both sides of the base film and a predetermined gas barrier layer on at least one side of the crosslinked resin layer, so the crosslinked resin layer can resist high temperature regions. The shrinkage stress of the substrate film reduces the shrinkage. Therefore, the dimensional stability of the gas barrier film against shrinkage at high temperatures can be improved.

<Substrate film>

The thickness of the base film in this gas-barrier film is preferably 1 μm to 200 μm, more preferably 5 μm or more and 150 μm or less, still more preferably 7 μm or more and 100 μm or less, and still more preferably 10 μm or more and 100 μm or less, most preferably It is 12 μm or more and 100 μm or less. By setting the above range, it is possible to obtain improved light transmittance and high processing performance. Etc.

<Crosslinked resin layer>

From the viewpoint of improving the dimensional stability of the gas-barrier film with respect to shrinkage at high temperatures, as described above, even in the gas-barrier film, it is preferred that the crosslinkable resin layer contains a photopolymerizable compound. A layer formed by a photopolymerization initiator and a curable composition of fine particles.

As the components such as the photopolymerizable compound, those exemplified above can be used. Among these, the photopolymerizable compound is preferably a photopolymerizable (meth) acrylate monomer or oligomer having two or more acrylfluorenyl groups or methacrylfluorenyl groups in one molecule, and more preferably one having One or more alicyclic polyfunctional acrylate monomers having an alicyclic structure.

(Fine particles)

The crosslinked resin layer in the present gas barrier film preferably contains fine particles substantially. This is because the crosslinked resin layer contains fine particles, and thus has excellent high-temperature dimensional stability.

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

The content rate of the fine particles is based on the content rate of the fine particles using the entire crosslinked resin layer as a reference, and is preferably 50% by volume or more, more preferably 50% by volume or more and 90% by volume or less, and further more preferably 55% by volume to 75% by volume. If the crosslinked resin layer contains more than 50% by volume of the fine particles, the fine particles are closer to the closest packing. Filling is performed in a filled state. If it is 72% by volume or more, theoretically, it becomes the densest filling. Since the fine particles are contained in the above range, the elastic modulus of the crosslinked resin layer can reduce the dimensional change caused by the shrinkage caused by the orientation of the substrate film during heating and the like.

(Containing ratio)

The crosslinked resin layer in this gas barrier film is also as described above, and a hardening composition containing other components such as a photopolymerization initiator, fine particles, and optionally a solvent in addition to the photopolymerizable compound can be applied and made. Formed by hardening.

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

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

(Thickness of the crosslinked resin layer)

The thickness of the crosslinked resin layer in this gas barrier film is important to set the total thickness of the crosslinked resin layers on both sides of the front and back to 8% or more of the thickness of the base film. If the total thickness of the crosslinked resin layers on both sides of the front and back is set to more than 8% of the thickness of the base film, the storage modulus of the gas barrier film at high temperature can be kept high, so that the Laminated films have high dimensional stability.

From this viewpoint, in order to make the heat especially when heated at a temperature of 180 ° C for 90 minutes, The shrinkage rate is 1.5% or less. The total thickness of the above-mentioned crosslinked resin layer is preferably 8% or more and 50% or less of the thickness of the substrate film. Among them, 10% or more of the thickness of the substrate film is preferred. It is more preferably 15% or more and 50% or less, and more preferably 20% or more and 45% or less, and most preferably 30% or more and 45% or less.

<Gas barrier layer>

This gas barrier film is provided with a gas barrier layer on at least one side of a crosslinked resin layer.

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

Examples of materials having high gas barrier properties include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, and oxides, carbides, nitrides, carbon oxides, nitrogen oxides, and carbon nitrogen. Oxide, diamond-like carbon, or a mixture of these is preferably silicon oxide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, Inorganic oxides such as aluminum oxide, aluminum carbonate and aluminum nitride, nitrides such as silicon nitride and aluminum nitride, diamond-like carbon, and mixtures thereof. In terms of stably maintaining high gas barrier properties, particularly preferred are silicon oxide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, silicon nitride, aluminum oxide, aluminum oxide, aluminum nitride, Aluminum nitride and mixtures of these.

Among these, an inorganic compound composed of any one or more of silicon (Si) or aluminum (Al) oxides, nitrides, and oxynitrides is preferred.

As a method for forming a gas barrier layer using the above materials, a method such as a vapor deposition method and a coating method can be arbitrarily adopted. In terms of obtaining a uniform thin film having a high gas barrier property, a vapor deposition method is preferred.

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

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

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

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

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

When a fixed coating 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. The thickness is preferably not to damage the entire film. 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 this gas barrier film)

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

(Total Light Transmission)

In this gas barrier film, also from the same viewpoint as the above-mentioned film, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Furthermore, as described in the above-mentioned laminated film, the light of the gas-barrier film can be adjusted by adjusting the type of resin, the type and particle size of the particles in the crosslinked resin layer, and the content of the particles. Penetration.

(Heat shrinkage)

From the same viewpoint as the above film, the gas barrier film preferably has a shrinkage ratio of at least one of the longitudinal direction (MD direction) and the transverse direction (TD direction) when heated at 200 ° C for 10 minutes. The thermal shrinkage of the substrate film measured under the same conditions is less than 70%.

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

(Water vapor permeability)

The water vapor transmission rate of the gas barrier film must be 1.0 × 10 ^-2 g / m ² / day or less, and more preferably 5 × 10 ^-3 g / m ² / day or less.

Since the gas barrier film has a water vapor transmission rate in this range, when a transparent electrode or element is formed on the gas barrier film, it can sufficiently block the moisture contained in the external gas or other members, so it can prevent transparency. The performance of the electrode is reduced or the element is deteriorated.

The method for measuring the water vapor transmission rate of this gas barrier film is based on each of 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)" The conditions were evaluated by the following methods.

You can use 2 pieces of gas barrier laminate films with a moisture permeability of 10.0cm × 10.0cm square, put about 20g of anhydrous calcium chloride as a hygroscopic agent, make a sealed four-sided bag, and put the bag at a temperature of 40 ° C In a constant-temperature and constant-humidity device with a relative humidity of 90%, the weight increase is roughly fixed as the standard after an interval of 48 hours or more. The mass measurement (unit: 0.1 mg) is performed until 34.8 days have passed. .

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

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

s: moisture permeability area (m ² )

t: time between the last two weighing intervals during the test (day)

(Arithmetic mean thickness)

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

Since the crosslinked resin layer has an arithmetic average thickness in this range, a uniform film with fewer defects can be formed when the gas barrier layer is formed, and as a result, it can have higher gas barrier properties. In addition, when forming an organic EL or the like on the gas-barrier film, there are advantages such that there are fewer element formation defects.

The arithmetic average thickness of the cross-linked resin layer is obtained by dividing the volume of the portion surrounded by the surface shape curved surface and the average surface of the cross-linked resin layer by the measurement area, and setting the average surface to the XY plane and the vertical direction to When the Z-axis and the measured surface shape curve are set to Z = F (x, y), it is defined by the following formula.

(Lx：x方向測定長度，Ly：y方向測定長度)

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

<Manufacturing method of this gas barrier film>

The present gas barrier film can be produced by coating a hardening composition on both the front and back sides of a base film and curing them to form a crosslinked resin layer, and further forming a gas barrier layer by the method described above.

The method for forming a crosslinked resin layer is the same as the above-mentioned conductive film.

<Applications of this gas barrier film>

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

[Explanation of terms]

In the present invention, the so-called "transparent" means that an object located in front of it can be seen through it, and the total light transmittance is preferably 80% or more.

In addition, in this specification, when it is expressed as "X ~ Y" (X and Y are arbitrary numbers), unless otherwise specified, it means "above X and below Y" and also includes "preferably Meaning "greater than X" or "preferably less than Y".

In addition, when the expression is "above X" (X is an arbitrary number) or "below Y" (Y is an arbitrary number), it also includes "preferably greater than X" or "preferably less than Y" Meaning.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited in any way by these examples and the like.

[About this conductive film]

First, about this conductive film, Examples 1-5, Comparative Examples 1-2, and Reference Examples 1-4 will be described in detail below.

<Method for measuring characteristics of this conductive film> (Measurement method of thermal shrinkage)

From the obtained transparent laminated film, the film was cut into short strips with a length of 140 mm × width of 10 mm in the longitudinal and transverse directions, and a marking line with a length of 100 mm was marked in the middle, and the test piece thus obtained was subjected to no load. The state is suspended in a thermostatic bath set at 200 ° C for 10 minutes. After being taken out, it is left to cool at room temperature for more than 15 minutes. The heat shrinkage rate is calculated from the length between the marked lines before and after the thermostatic bath is placed. The measurement was performed five times each, the average value was calculated, and the decimal point was rounded to the third place.

(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.

<Example 1> (Preparation of photocurable composition 1)

The solvent (propylene glycol monomethyl ether) is used to uniformly dilute the photocurable bifunctional acrylate monomer (tricyclodecane dimethanol diacrylate, molecular weight 304, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DCP" ) 22.1% by mass, silicon dioxide fine particles (manufactured by Admatechs Co., Ltd., trade name "YA010C-SM1", average particle size 10nm) 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE127") 0.6 The mass% and the photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE184") were 0.1 mass%, and a curable composition 1 (coating A) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film 1)

Using a die coater, apply the above on one side of a biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., trade name "Diafoil") with a thickness of 50 μm so that the thickness after curing becomes 10 μm. After the prepared coating material A was dried and removed, the coated surface was irradiated with a high-pressure mercury lamp (160 W / cm) under a nitrogen environment to obtain a thin film of a crosslinked resin layer having photocurability on one side. In the same manner as described above, the surface of the above-mentioned film on which the crosslinked resin layer is not formed is coated with a coating material A and cured, whereby a transparent laminated film 1 having a crosslinked resin layer formed on both sides is obtained.

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

The value obtained by dividing the thermal shrinkage of the transparent laminated film 1 by the thermal shrinkage of the base film monomer used in the transparent laminated film 1 was 19%.

(Fabrication of transparent conductive film 1 with transparent conductive layer formed)

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

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

唑啉基之聚合物(日本觸媒製造之Epocros WS-700)12質量%而成之塗料，而獲得於透明積層薄膜1之交 聯樹脂層之單面形成有下塗層的透明積層薄膜2。 One side of the transparent laminated film 1 prepared in Example 1 was coated so that the thickness after drying became 0.5 μm. Polyester resin (PESRESIN A-215GE manufactured by Takamatsu Oil and Fat Co., Ltd.) was evenly diluted with water. 88% by mass and

A coating made of 12% by mass of an oxazoline-based polymer (Epocros WS-700 manufactured by Japan Catalysts), and a transparent build-up film 2 having an undercoat layer formed on one side of a cross-linked resin layer of the transparent build-up film 1 .

(Fabrication of transparent conductive film 2 with a transparent conductive layer)

An ITO film was formed as a transparent conductive layer with a thickness of 30 nm on the coating surface under the transparent laminated film 2 by a sputtering method under a 200 ° C environment. The surface resistance value of the conductive layer of the obtained transparent conductive film 2 was measured with Loresta EP (manufactured by Mitsubishi Chemical), and it was 77 Ω / □.

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

A hard coat coating (NK hard B500 manufactured by Shin Nakamura Chemical Industry Co., Ltd.) was applied on one side of the transparent laminated film 1 prepared in Example 1 so that the thickness became 3 μm after drying, and was further hardened using an ultraviolet irradiation device. Thus, a transparent laminated film 3 having an undercoat layer formed on one side of the crosslinked resin layer of the transparent laminated film 1 is obtained.

(Fabrication of transparent conductive film 3 with a transparent conductive layer)

An ITO film was formed as a transparent conductive layer with a thickness of 30 nm on the coating surface under the transparent laminated film 3 by a sputtering method under a 200 ° C environment. The surface resistance value of the conductive layer of the obtained transparent conductive film 3 was measured with Loresta EP (manufactured by Mitsubishi Chemical), and it was 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 thickness after drying. A 1 μm coating was applied with toluene and isopropyl alcohol (IPA) to evenly dilute the hard coat coating (GX8801A manufactured by Daiichi Kogyo) 97% by mass and the photopolymerization initiator (IRGACURE184 manufactured by BASF) at 3% by mass. The transparent coating film 4 is obtained by forming an undercoat layer on one side of the crosslinked resin layer of the transparent multilayer film 1.

(Fabrication of transparent conductive film 4 with a transparent conductive layer)

An ITO film was formed as a transparent conductive layer with a thickness of 30 nm on the coating surface under the transparent laminated film 4 by a sputtering method under a 200 ° C environment. The surface resistance value of the conductive layer of the obtained transparent conductive film 4 was measured with Loresta EP (manufactured by Mitsubishi Chemical), and it was 81 Ω / □.

<Example 5> (Preparation of hardening composition 2)

The solvent (propylene glycol monomethyl ether) was used to uniformly dilute the photo-curable 6-functional acrylic urethane (molecular weight of about 800, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "U-6LPA") 48.5 mass%, photo-hardening 6-functional acrylate monomer (dipentaerythritol hexaacrylate, molecular weight 578, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DPH") 24.3% by mass, photocurable bifunctional acrylate monomer (tricyclic Decane dimethanol diacrylate, molecular weight 304, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DCP") 24.3% by mass and photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE184") 2.9 mass %, And a curable composition 2 (paint B) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film 5)

Using a gravure coater, apply the above on one side of a biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resins Co., Ltd., trade name "Diafoil") with a thickness of 23 μm so that the thickness after curing becomes 3 μm. After the coating B prepared, the solvent was dried and removed, and the coated surface was irradiated with a high-pressure mercury lamp (160 W / cm) under a nitrogen environment to obtain a thin film of a crosslinked resin layer having photocurability on one side. In the same manner as described above, the coating B is applied to the side of the film on which the crosslinked resin layer is not formed and cured, thereby obtaining a transparent laminated film 5 having a crosslinked resin layer formed on both sides.

With respect to the obtained film, the thermal shrinkage 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).

The value obtained by dividing the thermal shrinkage of the transparent laminated film 5 by the thermal shrinkage of the base film monomer used in the transparent laminated film 5 is 67%.

(Formation of transparent conductive film)

An ITO film was formed as a transparent conductive layer with a thickness of 30 nm on one side of the crosslinked resin layer of the transparent build-up film 5 by a sputtering method under a 200 ° C environment. The surface resistance value of the conductive layer of the obtained transparent conductive film 5 was measured with Loresta EP (manufactured by Mitsubishi Chemical), and it was 68 Ω / □.

<Comparative example 1>

Regarding a biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., trade name "Diafoil") with a thickness of 23 μm, the thermal shrinkage was measured in the same manner as in Example 1. As a result, it was 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 under a 200 ° C environment. As a result, the thermal shrinkage was large in the sputtering apparatus, and film formation could not be performed.

<Comparative example 2>

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

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

A biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd. under the trade name "COSMOSHINE") with a thickness of 100 μm using a bar coater, thermal shrinkage: MD direction = 4.06%, TD direction = 2.55% After the coating A prepared in Example 1 was coated on one side of the film so that the thickness after curing became 1 μm, the solvent was dried and removed. Furthermore, the end of the film is fixed in a belt conveyer, and the coated surface is irradiated with a high-pressure mercury lamp (160 W / cm) under a nitrogen environment to obtain a cross-linked resin layer having photocurability on one side. film.

Next, in the same manner as described above, the surface of the film not formed with the crosslinked resin layer is coated with a coating material A and cured, thereby obtaining a transparent laminated film 6 having a crosslinked resin layer formed on both sides.

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

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

A 100-m-thick biaxially-stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name "COSMOSHINE") was applied using a bar coater so that the thickness after curing was 3 μm After the coating material A prepared in Example 1, the solvent was dried and removed. Furthermore, the end of the film is fixed in a belt conveyer, and the coated surface is irradiated with a high-pressure mercury lamp (160 W / cm) under a nitrogen environment to obtain a cross-linked resin layer having photocurability on one side. film.

Next, in the same manner as described above, the surface of the film not formed with the crosslinked resin layer is coated with a coating material A and cured, whereby a transparent laminated film 7 having a crosslinked resin layer formed on both sides is obtained.

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

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

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resins Co., Ltd., trade name “Diafoil”, using a bar coater, heat shrinkage: MD direction = 1.51%, TD direction = 0.31 %) On one side, the coating A prepared in Example 1 was applied so that the thickness after curing became 1 μm, and then the solvent was dried and removed. Furthermore, the film end was fixed in a belt conveyor and the coated surface was irradiated in a nitrogen environment. A high-pressure mercury lamp (160 W / cm) to obtain a thin film of a crosslinked resin layer having photocurability on one side.

Next, in the same manner as described above, the surface of the film not formed with the crosslinked resin layer is coated with a coating material A and cured, thereby obtaining a transparent laminated film 8 having a crosslinked resin layer formed on both sides.

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

<Reference Example 4> (Preparation of Photocurable Composition 3)

Solvent (propylene glycol monomethyl ether and methyl ethyl ketone) was used to uniformly dilute the photocurable 6-functional acrylic urethane (molecular weight approximately 800, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "U-6LPA") 42.75 mass%, photocurable trifunctional acrylate monomer (pentaerythritol triacrylate, molecular weight 298, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "ATMM-3LM-N"), 42.75 mass%, silicon dioxide fine particles ( Manufactured by Nissan Chemical Industry Co., Ltd., trade name "MEK-ST-L", average particle size 50 nm) 12.8% by mass in terms of solid content and photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE127") 1.7 mass %, And a curable composition 3 (coating C) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film 9)

A gravure coater was used to harden one side of a biaxially stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., trade name "Diafoil") with a thickness of 23 μm. After the coating C prepared above was applied to 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 of a crosslinked resin layer having photocurability on one side. .

Next, in the same manner as described above, the surface of the film not formed with the crosslinked resin layer is coated with a coating material C and cured, whereby a transparent laminated film 9 having a crosslinked resin layer formed on both sides is obtained.

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

The results of the above reference examples 1 to 4 are summarized as shown in Table 2.

(Inspection)

From the above examples, reference examples, and test results conducted by the present inventors, it can be known that the thermal dimensional stability can be improved by providing a cross-linked resin layer of a predetermined thickness on both sides of the substrate. Specifically, it can be seen that by designing the total thickness of the crosslinked resin layer to be 8% or more of the thickness of the substrate film, the transparent conductive film can be heated in the vertical direction and the horizontal direction for 10 minutes at a temperature of 200 ° C. The thermal shrinkage ratios are all below 1.50%.

It can be known that by applying the step under high temperature when forming the transparent conductive layer, specifically, the film formation method in an environment with a temperature of 150 to 220 ° C, the surface resistance value of the transparent conductive film can be made 150 Ω / □ or less.

[About this laminated film]

Next, about this laminated film, Examples 6-14 and Comparative Example 3 are used and it demonstrates in detail below.

<Method for measuring characteristics of the laminated film> (Appearance of coating film)

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

(Circle): The whole was transparent, and cracks, whitening, etc. were not recognized at all.

(Triangle | delta): Either a crack or whitening was recognized.

×: Both cracks and whitening were confirmed.

(Measurement method of thermal shrinkage)

From the laminated films obtained in the examples and comparative examples, the films were cut into short strips with a length of 140 mm x a width of 10 mm in the longitudinal and transverse directions, and the ruled lines with a length of 100 mm were marked in the middle. The test piece was suspended in a thermostatic bath set at 200 ° C for 10 minutes without load. After being taken out, it was left to cool at room temperature for more than 15 minutes. The length between the marked lines before and after being placed in the thermostatic bath was expressed in%. Find the heat shrinkage ratio. In addition, the measurement was performed 5 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 thermal contraction rate in the transverse direction (TD direction) orthogonal to it. The obtained thermal shrinkage is shown in Table 3.

(Measurement method of total light transmittance)

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

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

[Example 6] (Preparation of hardening composition a)

A solvent (propylene glycol monomethyl ether and ethyl methyl ketone) was used to uniformly dilute a photo-curable bifunctional acrylate monomer (manufactured by Shin Nakamura Chemical Industry Co., Ltd., with a molecular weight of 304, trade name "A-DCP", tricyclic Decane dimethanol diacrylate) 22.1% by mass, silica fine particles (manufactured by Admatechs, Inc., trade name "YA010C-SM1") 77.2% by mass, light hardener A (manufactured by BASF, trade name "IRGACURE127") 0.6 A mass hardening agent B (manufactured by BASF, trade name "IRGACURE184") was 0.1 mass%, and a curable composition a (paint a) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film a)

Using a wire rod coater on a 50-m-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resins Co., Ltd., trade name "Diafoil T600E50", according to the measurement method described above) Thermal shrinkage: MD direction = 1.51%, TD direction = 0.31%), after the coating a prepared above is applied so that the thickness after curing becomes 3 μm, the solvent is dried and removed. And put the film end into the belt conveyor In a nitrogen atmosphere, the coated surface was irradiated with a high-pressure mercury lamp (160 W / cm) to obtain a thin film of a crosslinked resin layer having photocurability on one side.

In the same manner as described above, the coating a is applied to the side of the film on which the crosslinked resin layer is not formed and cured, thereby obtaining a transparent laminated film a having a crosslinked resin layer formed on both sides.

[Example 7] (Fabrication of transparent laminated film b)

A transparent laminated film b having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 6 except that the thickness after curing on one side became 10 μm. Table 3 shows the values of thermal shrinkage and total light transmittance.

[Example 8] (Preparation of hardening composition b)

The solvent (propylene glycol monomethyl ether and ethyl methyl ketone) was used to uniformly dilute the photocurable bifunctional acrylate monomer having a molecular weight of 226 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-HD-N") 17.7 mass%, photocurable 6-functional acrylate monomer (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DPH") with a molecular weight of 578, 4.4 mass%, silicon dioxide fine particles (manufactured by Admatechs Co., Ltd., Trade 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 "IRGACURE184") 0.1 mass % To obtain a curable composition b (paint b) for forming a crosslinked resin layer.

(Production of transparent laminated film c)

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

[Example 9] (Fabrication of transparent laminated film d)

A transparent laminated film d having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 8 except that the thickness after curing on one side became 10 μm. Table 3 shows the values of thermal shrinkage and total light transmittance.

[Example 10] (Preparation of hardening composition c)

The solvent (propylene glycol monomethyl ether and ethyl methyl ketone) was used to uniformly dilute the photocurable bifunctional acrylate monomer having a molecular weight of 226 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-HD-N") 22.1% by mass, silicon dioxide fine particles (manufactured by Admatechs, Inc., trade name "YA010C-SM1") 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name "IRGACURE127"), 0.6% by mass, and photopolymerization The initiator B (manufactured by BASF, trade name "IRGACURE184") was 0.1% by mass to obtain a curable composition (coating c) for forming a crosslinked resin layer.

(Fabrication of transparent laminated film e)

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

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

A transparent laminated film f having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 10 except that the thickness after curing on one side became 10 μm. Table 3 shows the values of thermal shrinkage and total light transmittance.

[Example 12] (Preparation of hardening composition d)

The solvent (propylene glycol monomethyl ether and ethyl methyl ketone) was used to uniformly dilute the photocurable trifunctional acrylate monomer with a molecular weight of 537 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-9300-1CL") 22.1% by mass, silica fine particles (manufactured by Admatechs, Inc., trade name "YA010C-SM1") 77.2% by mass, light hardener A (manufactured by BASF, trade name "IRGACURE127") 0.6% by mass, and light hardener B ( Made by BASF, trade name "IRGACURE184") 0.1% by mass, and a curable composition d (paint d) for forming a crosslinked resin layer was obtained.

(Production of transparent laminated film g)

A transparent build-up film g having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 6 except that the coating material d was applied. Table 3 shows the values of thermal shrinkage and total light transmittance.

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

A transparent laminated film h having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 12 except that the thickness after curing on one side became 10 μm. Table 3 shows the values of thermal shrinkage and total light transmittance.

[Example 14] (Preparation of hardening composition e)

A photo-curable polyfunctional acrylate oligomer having a weight-average molecular weight (Mw) of 1500 was uniformly diluted with a solvent (propylene glycol monomethyl ether and ethyl methyl ketone) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd. under the trade name "UV -7640B ") 22.1% by mass, silicon dioxide fine particles (manufactured by Admatechs Corporation, trade name" YA010C-SM1 ") 77.2% by mass, photopolymerization initiator A (manufactured by BASF, trade name" IRGACURE127 ") 0.6% by mass And a photopolymerization initiator B (manufactured by BASF, trade name "IRGACURE184") of 0.1% by mass, to obtain a curable composition e (paint e) for forming a crosslinked resin layer.

(Fabrication of transparent laminated film i)

A transparent build-up film i having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 7 except that the coating material e was applied. Table 3 shows the values of thermal shrinkage and total light transmittance.

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

Except that coating was performed so that the thickness after curing on one side became 1 μm, a laminated film 1 having a crosslinked resin layer formed on both sides was obtained in the same manner as in Example 6. Table 3 shows the values of the thermal shrinkage.

(Inspection)

From the results of the above examples and comparative examples, it can be seen that by employing a structure in which a base film is provided with a crosslinked resin layer having a predetermined thickness or more, it is possible to provide a thermal dimension at a high temperature that cannot be achieved only with a base film having a thickness of 75 μm or less. stability. In particular, as shown in Comparative Example 1, it can be seen that in a region where the thickness of the base film is thin, if a crosslinked resin layer having a specific thickness is not laminated, the effect of improving the thermal dimensional stability of the crosslinked resin layer cannot be obtained.

[About this gas barrier film]

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

<Method for measuring characteristics of this gas barrier film>

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

(Measurement of total light transmittance and haze)

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

Device: reflection. Transmittance 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 obtaining a digital image, the particle diameters of 200 particles were randomly measured from the obtained images, and the average value was calculated to obtain the average particle diameter of the fine particles.

(Surface smoothness)

The surface smoothness is the arithmetic average roughness (Sa) of the crosslinked resin layer of the film. The surface shape and the area in the area of 469μm × 352μm were measured by the optical interference method using "VertScan" (registered trademark) of Linghua Systems Co., Ltd. Surface roughness.

(Heat shrinkage)

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

Specifically, it measured by the following method. Set the film travel direction to the long side. Three short strip-shaped test pieces with a width of 10 mm and a length of 140 mm were prepared. The center of each test piece was set to the center, and a marking line with a distance of 100 mm was marked. Use a vernier caliper to read the interval between the marked lines with an accuracy of 0.01mm. The test piece was suspended in a constant temperature bath at a predetermined temperature in a load-free state for 10 minutes. After being taken out, it was left to cool at room temperature for more than 15 minutes, and the interval between the previously read marks was measured. The change rate of the interval between the graticule lines before and after heating is obtained, and it is set as the dimensional change rate before and after heating.

[Example 15] (Preparation of hardening composition i)

Photocurable bifunctional acrylate monomer with tricyclodecane structure. Oligomer (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name "A-DCP") 21.8% by mass, transparent microparticles A (manufactured by Admatechs Co., Ltd., trade name "YA010C-SM1", silica gel, average particle size 10nm) 77.5% by mass and a photopolymerization initiator (manufactured by BASF, 1-hydroxycyclohexyl-phenyl ketone) 0.7% by mass uniformly mixed with a solvent (manufactured by Arakawa Chemical Industry Co., Ltd., propylene glycol monomethyl ether) 34.1 parts by mass Then, a curable composition i for forming a crosslinked resin layer (hereinafter referred to as "coating i" is obtained. The solid content in the composition is 66%).

(Production of double-sided crosslinked resin layer)

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name "P100-T50") was used as a base film, and a wire rod coater was used on one side of the film to After coating the coating material i prepared above with a thickness of 10 μm, it was allowed to stand for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, thereby drying and removing the solvent to remove the end of the film. The fixed state is put into a belt conveyor, and the coated surface is irradiated with a high-pressure mercury lamp (160W / cm), and the light is hardened on one side. Thin film of chemically crosslinked resin layer. The volume ratio of the silicic acid glue in the crosslinked resin layer was 63.4% by volume.

Thereafter, in the same manner as described above, the surface of the thin film on which the crosslinked resin layer is not formed is coated with a coating material i and cured.

(Formation of gas barrier layer)

The PET film formed with the above-mentioned crosslinked resin layer was introduced into a sputtering film forming apparatus, and the reaction sputtering method using an Al target was used to form a film at a pressure of 0.3 Pa, an Ar (argon) flow rate of 80 sccm, an oxygen flow rate of 20 sccm, and an input power of 4 kW. Under the conditions, a 20 nm alumina layer was formed on the cross-linked resin layer on one side of the PET film to obtain a gas-barrier laminated film 1. The characteristics of the obtained gas-barrier laminated film 1 were evaluated according to the above measurement method, and the results are shown in Table 4.

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

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name "P100-T50") was used as a base film, and a wire rod coater was used on one side of the film to After coating the same coating material i as in Example 15 so that the thickness after curing became 7.5 μm, it was left for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, thereby drying and removing the solvent to remove the solvent. The end of the film was fixed in a belt conveyor, and the coated surface was irradiated with a high-pressure mercury lamp (160 W / cm) to obtain a film having a photo-curable crosslinked resin layer on one side. The volume ratio of the silicic acid glue in the crosslinked resin layer was 63.4% by volume.

Thereafter, in the same manner as described above, the above-mentioned film was not formed with the crosslinked resin layer. Coating i is applied and hardened.

(Formation of gas barrier layer)

The PET film having the above-mentioned crosslinked resin layer was introduced into a sputtering film forming apparatus, and a reaction sputtering method using an Al target was used under conditions of a film forming 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 A 20-nm alumina layer was formed on the cross-linked resin layer on any one side of the PET film to obtain a gas-barrier laminated film 2. The characteristics of the obtained gas-barrier laminated film 2 were evaluated according to the above measurement method, and the results are shown in Table 4.

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

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resins Co., Ltd., product name "P100-T50") was used as a base film, and a reactive sputtering method using an Al target was used to form the film. Under the conditions 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 alumina layer of 20 nm was formed on one side of the film to obtain a laminated film 2.

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

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

97% by mass of a polymerizable resin composition in acrylic urethane (manufactured by Daiichi Kogyo Co., Ltd., "New Frontier R-1302") and a photopolymerization initiator (BASF Production, 14.1 hydroxycyclohexyl-phenyl ketone) was mixed uniformly with 34.1 parts by mass of a solvent (manufactured by Arakawa Chemical Industry Co., Ltd., methyl ethyl ketone) in 3% by mass to obtain hardenability for forming a crosslinked resin layer. Composition ii (hereinafter referred to as "coating ii". The solid content in the composition is 60%).

(Formation of two-sided crosslinked resin layer)

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name "P100-T50") was used as a base film, and a wire rod coater was used on one side of the film to After the coating ii was applied so that the thickness after curing became 2 μm, it was left for 2 minutes, and then placed in an oven set at 100 ° C for 10 minutes, thereby drying and removing the solvent to fix the end of the film. The film was placed in a belt conveyor, and the coated surface was irradiated with a high-pressure mercury lamp (160 W / cm) to obtain a film of a crosslinked resin layer having photocurability on one side. The volume ratio of the silica gel in the crosslinked resin layer is 0% by volume.

Thereafter, in the same manner as described above, the surface of the thin film on which the crosslinked resin layer is not formed is coated with a coating material ii and cured.

(Formation of gas barrier layer)

The PET film having the above-mentioned crosslinked resin layer was introduced into a sputtering film forming apparatus, and a reaction sputtering method using an Al target was used under conditions of a film forming 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. A 20 nm alumina layer was formed on the cross-linked resin layer on any one side of the PET film to obtain a laminated film 3. The characteristics of the obtained laminated film 3 were evaluated according to the above measurement method, and the results are shown in Table 4.

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

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name "P100-T50") was used as a base film, and a wire rod coater was used on one side of the film to After coating the same coating material i as in Example 15 in a thickness of 10 μm after curing, it was left for 2 minutes, and then placed in an oven set at 100 ° C. for 10 minutes, thereby drying and removing the solvent to remove the film. A state where the end portion was fixed was put into a belt conveyor, and a high-pressure mercury lamp (160 W / cm) was irradiated on the coated surface to obtain a film of a crosslinked resin layer having photocurability on one side.

Thereafter, in the same manner as described above, the surface of the thin film on which the crosslinked resin layer is not formed is coated with a coating material i and cured.

(Formation of gas barrier layer)

The PET film having the above-mentioned crosslinked resin layer was introduced into a sputtering film forming apparatus, and a reaction sputtering method using an Al target was used under conditions of a film forming 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 A 4 nm alumina layer was formed on the cross-linked resin layer on any one side of the PET film to obtain a laminated film 4. The characteristics of the obtained laminated film 4 were evaluated according to the above-mentioned measurement method, and the results are shown in Table 4.

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

A 50 μm-thick biaxially-stretched polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., product name "P100-T50") was used as a base film, and a wire rod coater was used on one side of the film to After coating the same coating material i as in Example 15 in a thickness of 10 μm after curing, it was left for 2 minutes, and then placed in an oven set at 100 ° C. for 10 minutes, thereby drying and removing the solvent to remove the film. The end of the fixed state into the belt input In the feeding device, a high-pressure mercury lamp (160 W / cm) was irradiated on the coating surface to obtain a thin film of a crosslinked resin layer having photocurability on one side.

Thereafter, in the same manner as described above, the surface of the thin film on which the crosslinked resin layer is not formed is coated with a coating material i and cured.

(Formation of gas barrier layer)

The PET film having the above-mentioned crosslinked resin layer was introduced into a sputtering film forming apparatus, and a reaction sputtering method using an Al target was used under conditions of a film forming 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 A 1 nm alumina layer was formed on the cross-linked resin layer on any one side of the PET film to obtain a laminated film 5. The characteristics of the obtained laminated film 5 were evaluated according to the above measurement method, and the results are shown in Table 4.

(Inspection)

The gas-barrier laminated films of Examples 15 and 16 have a predetermined cross-linked resin layer on both sides of the substrate, and have a gas-barrier layer at an appropriate thickness at least on one side thereof, and therefore have high barrier properties and have For heating dimensional stability.

On the other hand, Comparative Example 4 cannot exhibit high barrier properties due to its rough surface. In addition, shrinkage occurs when heated. Comparative Example 5 has barrier properties compared to Comparative Example 4 because it has a crosslinked resin layer on both sides, and it has barrier properties. However, since the crosslinked resin layer is not filled with particles, it cannot withstand the shrinkage of the substrate during heating. Stress causes shrinkage of the entire film, which results in loss of performance.

Comparative Examples 5 and 6 did not exhibit barrier properties because the thickness of the barrier film was inappropriate.

(Industrial availability)

The transparent conductive film proposed by the present invention can be optimally used for applications requiring dimensional stability at high temperatures and excellent surface resistance values, especially substrates for touch panels. In addition, it can also be preferably used for Liquid crystal display, organic light-emitting display (OLED), electrophoretic display (electronic paper, etc.), substrates for display materials such as color filters, backlights, etc., or substrates for solar cells, substrates for organic light-emitting lighting, substrates for optoelectronic components, etc.

The transparent laminated film proposed by the present invention can be optimally used for applications requiring dimensional stability at high temperatures, especially substrates for touch panels. In addition, it can also be preferably used as a packaging film or as a liquid crystal display. , Organic light-emitting displays (OLED), electrophoretic displays (electronic paper, etc.), substrates for display materials such as color filters, backlights, or solar cell substrates, organic light-emitting substrates, and other thin films for electronic components.

The gas-barrier laminated film proposed by the present invention can be optimally used for applications that require dimensional stability and gas-barrier properties at high temperatures, substrates for organic light-emitting lighting, or substrates for organic light-emitting displays (OLEDs). A substrate for a display material such as a liquid crystal display, an electrophoretic display (electronic paper, etc.), a color filter, a backlight, 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 is provided with a transparent laminated film having a crosslinked resin layer on both sides of the front and back of the base film. The transparent laminated film is provided with transparency on one or both sides of the front and back directly or through an undercoat layer. The thickness of the conductive layer, the total thickness of the crosslinked resin layer is 8% or more of the thickness of the base film, and the transparent laminated film has a thermal shrinkage of 1.5% or less when heated at 200 ° C for 10 minutes in the longitudinal and transverse directions. And the surface resistance value of the transparent conductive film is 150 Ω / □ or less. For example, the transparent conductive thin film of the scope of application for the first item, wherein the transparent conductive layer is an inorganic oxide film formed by forming a film in an environment at a temperature of 150 to 220 ° C. For example, the transparent conductive film according to item 1 or 2 of the patent application scope, wherein the thickness of the transparent conductive layer is less than 100 nm. For example, if the transparent conductive film of the first or second patent application scope, the thickness of the front and back sides of the crosslinked resin layer is 8% to 50% of the thickness of the base film in total. For example, the transparent conductive film according to item 1 or 2 of the patent application scope, wherein the undercoating layer does not substantially contain inorganic fine particles. For example, the transparent conductive film according to item 1 or 2 of the patent application range, wherein the crosslinked resin layer is provided with a polyfunctional acrylate monomer having two or more acrylfluorene groups or methacrylfluorene groups in one molecule for cross-linking. A resin layer with a cross-linked structure. For example, the transparent conductive film according to item 6 of the patent application, wherein the polyfunctional acrylate monomer is an alicyclic polyfunctional acrylate monomer having an alicyclic structure, or 3 or more propylene in one molecule. Multifunctional acrylic urethane monomer based on methacrylic acid or methacryl group. For example, the transparent conductive film according to item 1 or 2 of the patent application scope, wherein the above-mentioned crosslinked tree The lipid layer is substantially free of fine particles. For example, the transparent conductive film according to item 1 or 2 of the patent application range, wherein the crosslinked resin layer contains 40 to 80% by mass of fine particles having an average particle diameter of 200 nm or less. For example, the transparent conductive film according to item 1 or 2 of the patent application range, wherein the base film is a resin film containing a resin having a glass transition temperature (Tg) of 130 ° C. or lower as a main component. For example, the transparent conductive film according to item 1 or 2 of the patent application range, wherein the base film is a film having polyethylene terephthalate resin as a main component and biaxially extending. A transparent laminated film is a laminated film having a crosslinked resin layer on the front and back sides of a base film. The first feature is that the above-mentioned crosslinked resin layer uses a photopolymerizable compound, a photopolymerization initiator, and The microparticles are formed of a hardenable composition, and the thickness of the base film and the crosslinked resin layer satisfy the following (a) and (b); its second characteristic is that it is longitudinally heated at 200 ° C for 10 minutes ( MD direction) and transverse direction (TD direction) of at least one of the laminated film's thermal shrinkage is less than 70% of the thermal shrinkage of the substrate film when heated under the same conditions, and the total light of the laminated film passes through The transmittance is 80% or more, (a) the thickness of the base film is 75 μm or less, and (b) the thicknesses of the front and back sides of the crosslinked resin layer total 8% or more of the thickness of the base film. For example, the transparent laminated film of item 12 of the patent application scope, wherein the thicknesses of the front and back sides of the crosslinked resin layer total 8% to 50% of the thickness of the base film. For example, the transparent laminated film of the scope of patent application No. 12 or 13, wherein the hardening composition The system contains 9 to 50% by mass of a photopolymerizable compound, 0.1 to 10% by mass of a photopolymerization initiator, and 10 to 90% by mass of fine particles with respect to the entire composition. For example, the transparent laminated film of the scope of application for the patent No. 12 or 13, wherein the photopolymerizable compound is a photopolymerizable (meth) acrylate monomer having two or more acrylfluorenyl groups or methacrylfluorenyl groups in one molecule. Or oligomers. For example, the transparent laminated film according to item 12 or 13 of the application scope, wherein the photopolymerizable compound is an alicyclic polyfunctional acrylate monomer having one or more alicyclic structures in one molecule. For example, the transparent laminated film with the scope of application patent No. 12 or 13, wherein the base film is a biaxially stretched film made of polyethylene terephthalate resin. A gas-barrier laminated film having a structure including a base film, a cross-linked resin layer on both sides of the base film, and a gas-barrier layer on at least one side of the cross-linked resin layer, the cross-linking The total thickness of the front and back sides of the resin layer is 8% or more of the thickness of the base film. The first characteristic is that the crosslinked resin layer uses a hardening property containing a photopolymerizable compound, a photopolymerization initiator, and fine particles. The composition is formed, and the average particle diameter of the fine particles 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. The third characteristic is that the entire film is penetrated by water vapor. The rate is 1.0 × 10 ^-2 g / m ² / day or less. For example, the gas-barrier laminated film of the scope of application for patent No. 18, wherein the gas-barrier layer is an inorganic compound composed of any one or more of silicon (Si) or aluminum (Al) oxides, nitrides, and oxynitrides. form. For example, the gas-barrier laminated film according to item 18 or 19 of the scope of patent application, wherein the arithmetic average roughness (Sa) of one surface of the crosslinked resin layer is 15 nm or less. For example, the gas-barrier laminated film with the scope of patent application No. 18 or 19, wherein the thickness of the substrate film is 100 μm or less. For example, the gas-barrier laminated film according to item 18 or 19 of the patent application range, wherein the content of the fine particles (C) is 50 to 75% by volume based on the entire crosslinked resin layer. For example, the gas-barrier laminated film of the scope of patent application No. 18 or 19, wherein the thicknesses of the front and back sides of the crosslinked resin layer total 8% to 50% of the thickness of the substrate film. For example, the gas-barrier laminated film according to item 18 or 19 of the scope of patent application, wherein the photopolymerizable compound is an alicyclic polyfunctional acrylate monomer having one or more alicyclic structures in one molecule.