JP2006088538A - Gas-barrier film, organic electroluminescent element, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film which is light in weight and high in gas-barrier properties. <P>SOLUTION: In the gas-barrier film, at least one barrier layer containing an inorganic substance and at least one organic layer are formed alternately on a support, and at least one layer selected from the group consisting of an antistatic layer, cured resin layer, reflection preventing layer, easy adhesion layer, glare shielding layer, and optical compensation layer is formed on at least one surface of the support. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gas barrier film having an ultra-high gas barrier property, and particularly to a substrate suitable for coating substrates of various devices and the substrate. The present invention also relates to an organic electroluminescence element (hereinafter referred to as “organic EL element”) and a liquid crystal display element excellent in durability and flexibility.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used to wrap an article that needs to block various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. Moreover, it is used with a liquid crystal display element, a solar cell, an electroluminescence (EL) substrate, etc. besides the packaging use. In particular, transparent substrates that have been applied to liquid crystal display elements, EL elements, etc. have recently been required to be lighter and larger, have long-term reliability and a high degree of freedom in shape, and can display curved surfaces. With the addition of high demands such as that, film substrates such as transparent plastics have begun to be used instead of glass substrates that are heavy, fragile and difficult to increase in area. A plastic film not only meets the above requirements, but also has a roll-to-roll system, and is more advantageous than glass in terms of productivity and cost reduction.

However, a film substrate such as a transparent plastic has a problem that gas barrier properties are inferior to glass. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, causing deterioration of the liquid crystal in the liquid crystal cell, for example, resulting in display defects and deterioration of display quality. In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a gas barrier film substrate. Gas barrier films used for packaging materials and liquid crystal display elements are known in which silicon oxide is vapor-deposited on a plastic film (Patent Document 1) and in which aluminum oxide is vapor-deposited (Patent Document 2). It has a water vapor barrier property of about 1 g / m ² / day. In recent years, the demand for gas barrier performance on a film substrate has increased to about 0.1 g / m ² / day for a gas substrate due to the development of large-sized liquid crystal displays, high-definition displays, and the like. Furthermore, development of organic EL displays and high-definition color liquid crystal displays that require further barrier properties in recent years has progressed, and while maintaining the transparency that can be used for these, it is possible to achieve further high barrier properties (particularly in the case of a water vapor barrier. Substrates having a performance of less than 1 g / m ² / day) have been required.

  In order to realize high barrier performance that meets such demands, studies are being made on film formation by sputtering or CVD, in which a thin film is formed using plasma generated by glow discharge under low pressure conditions. In addition, a technique for producing a barrier film having an alternately laminated structure of organic layers / inorganic layers by a vacuum deposition method has been proposed (Patent Document 3 and Non-Patent Document 1).

Japanese Patent Publication No.53-12953 JP 58-217344 A US Pat. No. 6,413,645 Thin Solid Film, 290-291 (1996)

However, in these thin film formation methods, the organic matter ejected as high-temperature vapor aggregates on the film to form a thin film, so that the film is temporarily heated to cause partial deformation, and the subsequent lamination process is non-uniform. Thus, there is a problem that sufficient barrier ability cannot be obtained. In addition, since the thin layer structure is adopted in order to achieve compatibility with the flexibility, there is a problem that the barrier property is impaired even if a minute amount of foreign matter is present.
Thus, if organic EL etc. are designed with a plastic substrate, a significant weight reduction can be promoted with respect to the conventional glass, but on the other hand, there is a problem that the element deterioration caused by the above-mentioned permeation gas occurs. there were. For this reason, the expression of the technology that achieves both durability and light weight of the element has been desired.

As a result of intensive studies, the present inventors have found that the following technique can solve the problem, and have provided the present invention.
(1) A barrier layer and an organic layer containing an inorganic substance are alternately provided on the support, and at least one layer of the support is provided with an antistatic layer, a cured resin layer, and a reflection on at least one surface of the support. A gas barrier film having at least one layer selected from the group consisting of a prevention layer, an easy adhesion layer, an antiglare layer and an optical compensation layer.
(2) The gas barrier film according to (1), wherein the support has a thermal expansion coefficient of 30 ppm / ° C. or less.
(3) An organic electroluminescence device using the gas barrier film according to (1) or (2).
(4) A liquid crystal display device using the gas barrier film according to (1) or (2).

  The gas barrier film of the present invention is characterized by extremely high gas barrier properties while being lightweight. For this reason, the organic EL element and liquid crystal display element which use the gas barrier film of this invention are excellent in optical performance, and its durability is high.

  Hereinafter, the gas barrier film of the present invention and its use will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Gas barrier film]
The gas barrier film of the present invention has a barrier layer containing an inorganic substance and an organic layer alternately on the support at least one layer at a time. The number of barrier layers and organic layers is preferably 10 or less, more preferably one each. The barrier layer and the organic layer are preferably adjacent to each other, but other layers may exist between the barrier layer and the organic layer. As for the gas barrier property of the gas barrier film of the present invention, the value obtained by the Ca method published by G. NISTOTO et al. In IDW'01 is 10 ⁻⁴ or less.
Below, the barrier layer containing an inorganic substance and the organic layer will be described in order.

(Barrier layer containing inorganic substances)
In the gas barrier film of the present invention, the barrier layer containing an inorganic substance may be directly formed on the support, or may be formed on an undercoat layer or an organic layer described later.
The kind of inorganic substance contained in the barrier layer is not particularly limited. For example, an oxide or nitride or oxynitride containing one or more inorganic elements such as Si, Al, In, Sn, Zn, Ti, Cu, Ce, and Ta. Things can be used. In order to achieve both water vapor barrier properties and high transparency, it is preferable to use silicon oxide or silicon oxynitride for the barrier layer. In the case of using silicon oxide (SiOx), it is desirable to satisfy 1.6 <x <1.9 in order to achieve both good water vapor barrier properties and high light transmittance. When silicon oxynitride (SiOxNy) is used, it is preferable to use an oxygen-rich film with 1 <x <2 and 0 <y <1 when importance is placed on improving adhesion, and when importance is placed on improving water vapor barrier properties. Is preferably a nitrogen-rich film with 0 <x <0.8 and 0.8 <y <1.3. These can be appropriately determined according to the purpose of use of the gas barrier film.

The barrier layer may be formed by any method as long as it can be formed in the intended manner. For example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable. Can be membrane.
Although it does not specifically limit about the thickness of a barrier layer, The range of 5 nm-1000 nm is preferable, More preferably, it is 10 nm-1000 nm, Most preferably, it is 10 nm-200 nm. When the gas barrier film of the present invention has a plurality of barrier layers, the total thickness of the barrier layers is preferably within the above range. If the barrier layer is too thick, cracks due to bending stress may occur. If the barrier layer is too thin, the film may be distributed in an island shape.
The gas barrier film of the present invention may have two or more barrier layers, and in that case, each layer may have the same composition or different compositions.

(Organic layer)
The gas barrier film of the present invention has an organic layer. In order to improve the brittleness and barrier properties of the barrier layer, an organic layer is preferably formed adjacent to the gas barrier layer. It does not specifically limit about the thickness of an organic layer, 10 nm-5000 nm are preferable, More preferably, it is 10-2000 nm, Most preferably, it is 10 nm-5000 nm. When the gas barrier film of the present invention has a plurality of organic layers, the total thickness of these organic layers is preferably within the above range. If the thickness of the organic layer is too thin, it will be difficult to obtain thickness uniformity, and structural defects in the inorganic layer may not be efficiently filled with the organic layer, and the barrier property may not be improved. . On the other hand, if the organic layer is too thick, the organic layer is likely to crack due to an external force such as bending, which may cause a problem that the barrier property is lowered.
The method for forming the organic layer in the gas barrier film of the present invention is not particularly limited. For example, (1) a method of forming using an inorganic oxide layer prepared using a sol-gel method, After laminating by a film method, a method of curing with ultraviolet rays or an electron beam can be used. (1) and (2) may be used in combination. For example, after forming a thin film by the method of (1) on a resin film as a support, a barrier layer containing an inorganic oxide is formed, and then Alternatively, the organic layer may be formed by the method (2). Moreover, you may form the multilayer structure which has a barrier layer and an organic layer alternately by repeating these.

(1) Sol-gel method When the sol-gel method is used, a dense thin film can be obtained by preferably hydrolyzing and polycondensing a metal alkoxide in a solution or in a coating film. At this time, an organic-inorganic hybrid material may be used in combination with a resin.
Examples of the metal alkoxide used in the sol-gel method include alkoxysilane and / or metal alkoxide other than alkoxysilane. As the metal alkoxide other than alkoxysilane, zirconium alkoxide, titanium alkoxide, aluminum alkoxide and the like are preferable.

  The polymer used in combination during the sol-gel reaction preferably has a hydrogen bond forming group. Examples of resins having hydrogen bond-forming groups include hydroxyl group-containing polymers and derivatives thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymers, phenol resins, methylol melamine, and derivatives thereof); carboxyl groups Polymers and derivatives thereof (mono or copolymers containing units of polymerizable unsaturated acids such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, and esterified products of these polymers (vinyl esters such as vinyl acetate, Homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate)); polymers having an ether bond (polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, silicon resin, etc.); amide bond Having a polymer (> N COR) -bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent) N- of polyoxazoline or polyalkyleneimine Acylated product);> polyvinylpyrrolidone having a NC (O) -bond and derivatives thereof; polyurethane having a urethane bond; polymer having a urea bond, and the like.

Further, an organic-inorganic hybrid material can also be formed by using a monomer in combination during the sol-gel reaction and polymerizing during or after the sol-gel reaction.
During the sol-gel reaction, the metal alkoxide is hydrolyzed and polycondensed in water and an organic solvent. At this time, it is preferable to use a catalyst. As the hydrolysis catalyst, an acid (organic or inorganic acid) is generally used.
The amount of the acid used is preferably 0.0001 to 0.05 mol, more preferably 1 mol per 1 mol of metal alkoxide (alkoxysilane and other metal alkoxide in the case of containing alkoxysilane and other metal alkoxide). Is 0.001 to 0.01 mol. After hydrolysis, a basic compound such as an inorganic base or an amine may be added to bring the pH of the solution to near neutrality to promote condensation polymerization.
In addition, other sol-gel catalysts such as metal chelate compounds having Al, Ti, and Zr as the central metal, organometallic compounds such as tin compounds, and metal salts such as alkali metal salts of organic acids can be used in combination.

  The proportion of the sol-gel catalyst compound in the composition is preferably 0.01 to 50% by weight, more preferably 0.1 to 50% by weight, and still more preferably 0.5 to 0.5% with respect to the alkoxysilane that is the raw material of the sol liquid. 10% by weight.

  Solvents used in the sol-gel reaction can be applied to various coating methods at the same time that the components of the sol solution are uniformly mixed and the solid content of the composition of the present invention is prepared. It is preferable to improve storage stability. Preferable examples of the solvent include water and an organic solvent that is highly miscible with water.

For the purpose of adjusting the speed of the sol-gel reaction, an organic compound capable of multidentate coordination may be added to stabilize the metal alkoxide. Examples thereof include β-diketones and / or β-ketoesters, and alkanolamines.
Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-tert-butyl, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione, 5-methyl Examples thereof include hexanedione. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.
These compounds capable of multidentate coordination can also be used for the purpose of adjusting the reaction rate when the metal chelate compound is used as a sol-gel catalyst.

  Next, a method for applying the sol-gel reaction composition will be described. The sol solution can form a thin film on the transparent film by a coating method such as curtain flow coating, dip coating, spin coating or roll coating. In this case, the hydrolysis may be performed at any time during the production process. For example, a solution of a required composition is hydrolyzed and partially condensed to prepare a desired sol solution, which is applied and dried, and a solution of the required composition is prepared and dried while hydrolyzing and partially condensing simultaneously. Method, application-After primary drying, a method of applying a water-containing liquid necessary for hydrolysis repeatedly and applying hydrolysis can be suitably employed. In addition, the coating method can take various forms. However, when productivity is important, each of the lower layer coating solution and the upper layer coating solution is required on a slide Geyser having a multistage discharge port. A method (simultaneous multi-layer method) is preferably used in which the discharge flow rate is adjusted so that the coating amount is obtained, and the formed multilayer flow is continuously placed on a support and dried.

  The drying temperature is preferably 150 to 350 ° C, more preferably 150 to 250 ° C, and further preferably 150 to 200 ° C.

In order to make the film after coating and drying more dense, irradiation with energy rays may be performed. Although there is no restriction | limiting in particular in the kind of irradiation radiation, In consideration of the influence with respect to a deformation | transformation and modification | denaturation of a support body, irradiation of an ultraviolet-ray, an electron beam, or a microwave can be used especially preferable. The irradiation intensity is preferably from ^{30mJ / cm 2 ~500mJ / cm 2} , particularly preferably ^{50mJ / cm 2 ~400mJ / cm 2} . The irradiation temperature can be employed without limitation between room temperature and the deformation temperature of the support, and is preferably 30 ° C to 150 ° C, particularly preferably 50 ° C to 130 ° C.

(2) A method in which an organic substance is applied or laminated by a vacuum film formation method, and then cured by ultraviolet light or electron beam. After an organic substance is laminated by application or vapor deposition, the monomer is crosslinked by a method that is cured by ultraviolet ray or electron beam. An organic layer mainly composed of the obtained polymer can be formed.
The monomer to be used is not particularly limited as long as it contains a group that can be cross-linked by ultraviolet rays or electron beams, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxetane group. For example, epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester (meth) acrylate, etc. Among these, it is preferable that a polymer obtained by crosslinking a monomer having a bifunctional or higher functional acryloyl group or methacryloyl group as a main component. These monomers having a bifunctional or higher functional acryloyl group or methacryloyl group may be used as a mixture of two or more kinds, or as a mixture of monofunctional (meth) acrylates. Moreover, as a monomer which has oxetane group, it is preferable to use what has a structure described in Unexamined-Japanese-Patent No. 2002-356607 General formula (3)-(6). In this case, these may be arbitrarily mixed and used.
In addition, from the viewpoint of heat resistance and solvent resistance required for display applications, it is mainly composed of isocyanuric acid acrylate, epoxy acrylate, urethane acrylate having a high degree of crosslinking and a glass transition temperature of 200 ° C. or higher. Further preferred.

  Examples of the method for forming the organic layer include a coating method and a vacuum film forming method. When forming by a coating method, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used. When forming by a vacuum film-forming method, there is no particular limitation, but a film-forming method such as vapor deposition or plasma CVD is preferable, and a resistance heating vapor-deposition method that can easily control the film formation rate of the organic substance monomer is more preferable. There is no limitation on the monomer crosslinking method, but crosslinking with an electron beam or ultraviolet rays is desirable in that it can be easily mounted in a vacuum chamber and the high molecular weight can be increased by a crosslinking reaction.

(Configuration of functional layer)
The gas barrier film of the present invention has at least one functional layer. Examples of the functional layer include an antireflection layer, a polarizing layer, a color filter layer, an ultraviolet absorption layer, a light extraction efficiency improving layer, an antiglare layer, an optical compensation layer, an orientation control layer, a refractive index control layer, a liquid crystal layer, and the like. Optical functional layer; Mechanical functional layer such as cured resin layer (hard coat layer) and stress relaxation layer; Electrical functional layer such as antistatic layer and conductive layer; Antifogging layer; Easy adhesion layer; Adhesive layer; Antifouling layer A printing layer and the like. Preferred as the functional layer are an antistatic layer, a cured resin layer (particularly a transparent cured resin layer), an antireflection layer, an easy adhesion layer, an antiglare layer, an optical compensation layer, an alignment layer, and a liquid crystal layer, and more preferably a charging layer. An antistatic layer, a cured resin layer (particularly a transparent cured resin layer), an antireflection layer, an easy adhesion layer, an antiglare layer, and an optical compensation layer, more preferably an antistatic layer and a cured resin layer. In particular, the antistatic layer is excellent in that it stably imparts a high barrier ability.

  These functional layers are preferably formed on the laminate of the barrier layer and the organic layer, or on the surface (back surface) opposite to the surface on which the laminate is formed. . The functional layer is preferably the outermost layer.

  In the gas barrier film of the present invention, only one functional layer may be formed, or two or more functional layers may be formed. When two or more layers are formed, a plurality of the same type of functional layers may be formed, or different types of functional layers may be formed. Examples of the case where two or more functional layers are formed include a combination of an antistatic layer and a cured resin layer, a combination of an antistatic layer and an easily adhesive layer, an easily adhesive layer, an antistatic layer, and a cured resin layer. Can be mentioned.

  In these functional layers, materials that exhibit various functions can be used in appropriate combinations as needed. By selecting these materials according to the purpose, a functional layer having a desired function can be formed. In the following, typical materials such as surfactants, slip agents, and matting agents will be described, and further details of the antistatic layer and the cured resin layer will be described.

(Surfactant)
First, surfactants are classified into dispersants, coating agents, wetting agents, antistatic agents, and the like, depending on the purpose of use, but these purposes can be achieved by appropriately using the surfactants described below. In the present invention, any nonionic or ionic (anion, cation, betaine) surfactant can be used. Further, a fluorosurfactant is also preferably used as a coating agent in an organic solvent or an antistatic agent. For example, a layer can be formed by applying and applying in a cellulose acylate solution.

When the gas barrier film of the present invention is used for optical applications, a surfactant can be used for functional layers such as an orientation control layer, a refractive index control layer, an antifouling layer, and an adhesive layer. Further, it can be used for an undercoat layer, an intermediate layer, a protective layer, a back undercoat layer, a back layer, and the like. The amount of the surfactant used is not particularly limited as long as it is an amount necessary for achieving the purpose, but generally 0.0001 to 5% by mass is preferable with respect to the mass of the layer to be added, and further 0.0005 to 2% by mass is preferred. In this case, the coating amount is preferably 0.02 to 1000 mg, more preferably 0.05 to 200 mg per 1 m ² .

  Preferred nonionic surfactants are surfactants having nonionic hydrophilic groups such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl and sorbitan, specifically, polyoxyethylene alkyl ethers, polyoxyethylenes. Ethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine fatty acid Mention may be made of partial esters.

  Preferred anionic surfactants are carboxylate, sulfate, sulfonate, and phosphate ester salt, and representative examples include fatty acid salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, and alkyl sulfonate. , Α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyl taurine, petroleum sulfonate, alkyl sulfate, sulfated oil and fat, polyoxyethylene alkyl ether sulfate, Polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, naphthalene sulfonate formaldehyde condensate and the like can be mentioned.

  Examples of the cationic surfactant include amine salts, quaternary ammonium salts, pyridinium salts, and the like. More specifically, primary to tertiary fatty amine salts, quaternary ammonium salts (tetraalkylammonium salts, trimethylammonium salts). Alkyl benzyl ammonium salt, alkyl pyridium salt, alkyl imidazolium salt, etc.).

  Examples of amphoteric surfactants include carboxybetaine and sulfobetaine, and specific examples include N-trialkyl-N-carboxymethylammonium betaine and N-trialkyl-N-sulfoalkyleneammonium betaine. Can do.

These surfactants are described in Application of Surfactants (written by Koshobo, Takao Karie, published on September 1, 1980). The amount of the surfactant used is not particularly limited as long as the desired surface active characteristics can be obtained. Specific examples of the surfactant are described below, but the surfactant that can be used in the present invention is not limited to these (herein, —C ₆ H ₄ — represents a phenylene group).

WA-1: C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₁₀ OH
_{WA-2: C 9 H 19} -C 6 H 4 - (OCH 2 CH 2) 12 OH
WA-3: Poly (degree of polymerization 20) oxyethylene sorbitan monolaurate ester WA-4: Sodium dodecylbenzenesulfonate WA-5: Sodium tri (isopropyl) naphthalenesulfonate WA-6: Sodium dodecyl sulfate WA-7: α- Surufakohaku di (2-ethylhexyl) ester sodium salt WA-8: cetyltrimethylammonium chloride _{WA-9: C 11 H 23} CONHCH 2 CH 2 N (+) (CH 3) 2 -CH 2 COO (-)
_{WA-10: C 8 F 17} SO 2 N (C 3 H 7) (CH 2 CH 2 O) 16 H

WA-11: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK
WA-12: C ₇ F ₁₅ COONH ₄
WA-13: C ₈ F ₁₇ SO ₃ K
_{WA-14: C 8 F 17} SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 SO 3 Na
_{WA-15: C 8 F 17} SO 2 N (C 3 H 7) - (CH 2) 3 -N (+) (CH 3) 3 · I (-)
_{WA-16: C 8 F 17} SO 2 N (C 3 H 7) CH 2 CH 2 CH 2 N (+) (CH 3) 2 -CH 2 CO O (-)
_{WA-17: C 8 F 17} CH 2 CH 2 O (CH 2 CH 2 O) 16 H
_{WA-18: C 8 F 17} CH 2 CH 2 O (CH 2) 3 -N (+) (CH 3) 3 · I (-)
_{WA-19: H (CF 2} ) 8 CH 2 CH 2 OCOCH 2 CH (SO 3 Na) COOCH 2 CH 2 CH 2 CH 2 (CF 2) 8 H
_{WA-20: H (CF 2} ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 16 H

WA-21: H (CF ₂ ) ₈ CH ₂ CH ₂ O (CH ₂ ) ₃ —N ⁽⁺⁾ (CH ₃ ) ₃ · I ⁽⁻⁾
_{WA-22: H (CF 2} ) 8 CH 2 CH 2 OCOCH 2 CH (SO 3 K) COOCH 2 CH 2 CH 2 CH 2 C 8 F 17
_{WA-23: C 9 F 17} -C 6 H 4 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 16 H
_{WA-24: C 9 F 17} -C 6 H 4 CSO 2 N (C 3 H 7) - (CH 2) 3 -N (+) (CH 3) 3 · I (-)

(Slip agent)
In the gas barrier film of the present invention, a slip agent can be contained in any layer on the support, and is particularly preferably contained in the outermost layer. Examples of the slip agent used include polyorganosiloxanes disclosed in Japanese Patent Publication No. 53-292, higher fatty acid amides disclosed in US Pat. No. 4,275,146, Higher fatty acid esters (having 10 to 24 carbon atoms) such as those disclosed in JP-A-58-33541, British Patent No. 927,446, JP-A-55-126238 and JP-A-58-90633. Esters of fatty acids and alcohols having 10 to 24 carbon atoms), and higher fatty acid metal salts such as those disclosed in U.S. Pat. No. 3,933,516, and also disclosed in JP-A-58-50534 Such esters of linear higher fatty acids and linear higher alcohols are known.

  Among these, as polyorganosiloxane, in addition to polyalkylsiloxanes such as polydimethylsiloxane polydiethylsiloxane and polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, which are generally known, JP-B 53-292 No. 5, JP-B-55-49294, JP-A-60-140341, etc., an organopolysiloxane having an alkyl group of C5 or more, an alkylpolysiloxane having a polyoxyalkylene group in the side chain, A modified polysiloxane such as an organopolysiloxane having an alkoxy, hydroxy, hydrogen, carboxyl, amino, or mercapto group in the side chain can also be used. Also, block copolymers having siloxane units and compounds described in JP-A-60-19124 can be used.

  Specific examples of the polyorganosiloxane that can be used as a slipping agent in the present invention are shown below, but the range of the slipping agent that can be used in the present invention is not limited to these specific examples.

_{(S-1) (CH 3} ) 3 SiO- (Si (CH 3) 2 O) a -Si (CH 3) 3
a = 5 to 1000
_{(S-2) (C 6} H 5) 3 SiO- (Si (CH 3) 2 O) a -Si (CH 3) 3
a = 5 to 1000
_{(S-3) (CH 3} ) 3 SiO- (Si (C 5 H 11) (CH 3) -O) a -Si (CH 3) 3
a = 10
_{(S-4) (CH 3} ) 3 SiO- (Si (C 12 H 25) (CH 3) -O) 10 -
_{(Si (CH 3) 2 O} ) 18 -Si (CH 3) 30
_{(S-5) (CH 3} ) 3 SiO- (Si (CH 3) 2 O) x -
_{(Si (CH 3) ((} CH 2) 3 -O (CH 2 CH 2 O) 10 H) -O) y -
_{(Si (CH 3) 2 O} ) z -Si (CH 3) 3
x + y + z = 30
_{(S-6) (CH 3} ) 3 SiO- (Si (CH 3) 2 O) x - (Si (CH 3)
{(CH ₂ ) ₃ —O (CH ₂ CH (CH ₃ ) —O) _{10
(CH 2 CH 2 O) 10} C 3 H 7} O) y - (Si (CH 3) 2 O) z -
Si (CH ₃ ) ₃
x + y + z = 35

  In addition, higher fatty acids and derivatives thereof, higher alcohols and derivatives thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters, and the like. Use of monoalkyl phosphite, dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, amide compound or salt thereof of aliphatic alcohol Can do.

  Specific examples of higher fatty acids, higher alcohols and derivatives thereof are shown below, but the range of the slipping agent that can be used in the present invention is not limited to these specific examples.

(S-7) n-C 15 H 31 COOC 30 H 61 -n
(S-8) n-C 17 H 35 COOC 30 H 61 -n
(S-9) n-C 15 H 31 COOC 50 H 101 -n
(S-10) n-C 21 H 43 COO- (CH 2) 7 CH (CH 3) -C 9 H 19
(S-11) n-C 21 H 43 COOC 24 H 49 -iso
(S-12) n-C 18 H 37 OCO (CH 2) 4 COOC 40 H 81 -n
(S-13) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₅ H
(S-14) n-C 4 0H 81 OCOCH 2 CH 2 COO (CH 2 CH 2 O) 16 H
(S-15) n-C ₂₁ H ₄₁ CONH ₂
(S-14) Liquid paraffin H
(S-15) Carnauba wax

By using such a slipping agent, it is possible to obtain an excellent film that has excellent scratch strength and does not cause repelling or the like on the undercoat surface. The amount of slip agent to be used is not particularly limited, but the content is preferably 0.0005 to ² g / m ² , more preferably 0.001 to 1 g / m ² , and particularly preferably 0.002 to 0.5 g / m ² . m ² . Although it does not specifically limit as an additive layer of the slip agent of this technique, It is preferable to make it contain in the outermost layer of a back surface. The surface layer containing the above-mentioned slipping agent is formed by applying a coating solution obtained by dissolving this in a suitable organic solvent on a support or a support provided with another layer on the back layer, and drying. Can do. The slipping agent can also be added in the form of a dispersion in the coating solution. Solvents used include water, alcohols (such as methanol, ethanol, isopropanol), ketones (such as acetone, methyl ethyl ketone, cyclohexanone), esters (methyl such as acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, Ethyl, propyl, butyl ester, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.) and amides (dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.) are preferred.

In coating the slip agent, it can be used together with a binder having a film forming ability. As such a polymer, known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, mixtures thereof, and hydrophilic binders such as gelatin can be used.
The sliding performance is preferably a static friction coefficient of 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less. Further, it is preferable that the coefficient of static friction with the mating material to be contacted is small, which also helps prevent scratches. In this case, the coefficient of static friction with the mating material is preferably 0.3 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less. In many cases, it is preferable to reduce the static friction coefficient between the front and back surfaces of the film or optical film. The static friction coefficient between them is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less. The coefficient of dynamic friction is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.15 or less. The coefficient of dynamic friction with the mating material is preferably 0.3 or less, more preferably 0.25 or less, and particularly preferably 0.15 or less. In many cases, it is preferable to reduce the dynamic friction coefficient of the front and back surfaces of the film or optical film. The dynamic friction coefficient between them is preferably 0.30 or less, more preferably 0.25 or less, and particularly preferably 0.13 or less.

(Matting agent)
In the functional layer of the film of the present technology, it is preferable to use a matting agent in order to improve the slipperiness of the film and the adhesion resistance under high humidity. In that case, the average height of the protrusions on the surface is preferably 0.005 to 10 μm, more preferably 0.01 to 5 μm. Further, it is better that there are a large number of protrusions on the surface. If the preferred protrusions are in the range having the average height of the protrusions, for example, when the protrusions are formed with a spherical or irregular matting agent, the content is preferably 0.5 to 600 mg / m ² , More preferred is 1 to 400 mg / m ² . At this time, as the matting agent used, fine particles added to the above-described film can be used, and the composition thereof is not particularly limited, and may be an inorganic material, an organic material, or a mixture of two or more.

  Examples of the matting agent include fine powders of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. Furthermore, for example, silicon dioxide such as synthetic silica obtained by a wet method or gelation of silicic acid, titanium dioxide (rutile type or anatase type) produced by titanium slug and sulfuric acid, and the like can be mentioned. It can also be obtained by pulverizing from an inorganic substance having a relatively large particle size (for example, 20 μm or more), followed by classification (vibration filtration, wind classification, etc.). In addition, polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine resin, polyolefin powder Further, there may be mentioned pulverized and classified products of organic polymer compounds such as polyester resins, polyamide resins, polyimide resins, polyfluorinated ethylene resins and starch. Alternatively, a high molecular compound synthesized by a suspension polymerization method, a high molecular compound made spherical by a spray drying method or a dispersion method, or an inorganic compound can be used. Moreover, it is also possible to form an antiglare layer by adding 0.1 to 10 μm particles having the same material and a larger particle size and / or the aforementioned fine particles. At this time, it is preferable to add fine particles of 0.5 to 20% by mass of the total mass of the layer. These fine particles are preferably silicon dioxide such as silica, for example, Silicia manufactured by Fuji Silysia Chemical Co., Ltd. and Nippon Sil E manufactured by Nippon Silica Co., Ltd.

As these fine particles of the present technology, it is also preferable to use fine particles having an alkyl group or aryl group having 2 to 20 carbon atoms on the surface. The alkyl group preferably has 4 to 12 carbon atoms, and more preferably has 6 to 10 carbon atoms. The smaller the number of carbons, the better the dispersibility, and the larger the number of carbons, the less reaggregation when mixed with the dope.
Examples of inorganic compounds among the fine particles having an alkyl group having 2 to 20 carbon atoms and the fine particles having an aryl group on the surface used in the present technology include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and calcium carbonate. Calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Silicon dioxide, titanium dioxide and zirconium oxide are preferred, and among them, a compound containing a silicon atom, particularly silicon dioxide is preferred. Silicon dioxide fine particles are commercially available under trade names such as Aerosil 130, Aerosil 200, Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.). Further, silicon dioxide fine particles whose surfaces are modified with silicone oil and spherical monodispersed silicon dioxide fine particles are also preferably used.

Fine particles of an inorganic compound having an alkyl group having 2 to 20 carbon atoms on the surface can be obtained, for example, by treating the fine particles of silicon dioxide with octylsilane. Moreover, it is marketed by the brand name of Aerosil R805 (made by Nippon Aerosil Co., Ltd.) which has an octyl group on the surface, and can be used.
The fine particles of an inorganic compound having a phenyl group on the surface can be obtained, for example, by treating the fine particles of silicon dioxide with trichlorophenylsilane.

Among the materials of fine particles having an alkyl group having 2 to 20 carbon atoms and fine particles having a phenyl group on the surface, examples of the polymer include silicone resin, fluorine resin and acrylic resin, and polymethyl methacrylate is particularly preferable. . As described above, a compound containing silicon is preferable, but silicon dioxide or a silicone resin having a three-dimensional network structure is particularly preferable, and silicon dioxide is most preferable.
These fine particles are preferably used at 0.005 to 0.3% by weight, more preferably 0.01 to 0.1% by weight. Thus, by using the fine particles according to the present technology, it is possible to obtain a film having a very excellent fine particle dispersibility in which aggregated particles having a particle size of 10 μm or more are contained at 10 particles / m ² or less. These are described in JP-A-2001-2788.

(Antistatic agent)
The antistatic agent can be effectively used for imparting a function of preventing the resin film from being charged when the resin film is handled. Specifically, it is possible to prevent charging by providing a layer containing an ion conductive substance or conductive fine particles. Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples include ionic polymer compounds.

Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-B-49-23827, JP-B-47-28937, and the like; In the main chain as seen in JP-A-50-54772, JP-B-59-14735, JP-B-57-18175, JP-B-57-18176, JP-B-57-56059, etc. Ionene type polymer having a dissociating group: JP-B 53-13223, JP-B 57-15376, JP-B 53-45231, JP-B 55-145783, JP-B 55-65950, JP-B 55-67746, JP-B-57-11342, JP-B-57-19735, JP-B-58-56858, JP-A-61-27853, JP-B-62-9346, etc. As seen in JP, mention may be made of cationic pendant polymers having a cationic dissociative group in the side chain.
Of these, the conductive material is preferably in the form of fine particles, and these are finely dispersed and added to the resin. Preferred conductive materials used for these include conductive fine particles composed of metal oxides and composite oxides thereof, and ionene conductive polymers or intermolecular crosslinks as described in JP-A-9-203810. A quaternary ammonium cation conductive polymer particle etc. can be mentioned. The preferred particle size depends on the type of fine particles, but is, for example, in the range of 5 nm to 10 μm.

Examples of the metal oxide which is a conductive fine particle include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof. Are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sb, Nb and halogen elements to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.
Further, the volume resistivity of these conductive metal oxide powders is 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less, the primary particle size is 100 μm to 0.2 μm, and the major structure has a major axis. It is preferable that the conductive layer contains 0.01% to 20% by volume of the powder having a specific structure of 30 nm to 6 μm.

  In addition, the crosslinked cationic conductive polymer as a dispersible granular polymer can have a high concentration and high density of the cation component in the particles, and thus has not only excellent conductivity but also low conductivity. Even under relative humidity, there is no deterioration in conductivity, and even though the particles are well dispersed in a dispersed state, the film strength is strong due to good adhesion between the particles in the film formation process after coating. Furthermore, it has the characteristic that it has excellent adhesiveness to other substances (for example, a support) and is excellent in chemical resistance.

  The dispersible granular polymer, which is a crosslinked cationic conductive polymer used in the antistatic layer, generally has a particle size of about 10 nm to 1000 nm, preferably in the range of 0 nm to 300 nm. As used herein, a dispersible particulate polymer is a polymer that appears as a transparent or slightly turbid solution by visual observation, but appears as a particulate dispersion under an electron microscope. By using a coating composition that does not substantially contain dust (foreign matter) larger than the particle size corresponding to the film thickness of the upper layer in the lower layer coating composition, failure of the upper layer foreign matter can be prevented.

  The ratio of the fine particles to the resin is preferably 0.5 to 4 parts by mass of the resin with respect to 1 part by mass of the fine particles, and particularly the adhesion after ultraviolet irradiation is 1 to 1 part by mass of the fine particles with respect to 1 part by mass of the resin. It is preferable that it is -2 mass parts. Furthermore, a conductive organic compound can also be used. For example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphosphazene and the like. These are preferably used in a complex with polystyrene sulfonic acid, perchloric acid or the like as an acid donor.

  The resin used here is, for example, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, or cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate, or copolybutylene / terephthalate. / Polyesters such as isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene-based polymers containing norbornene compounds, polymethyl methacrylate, polyethyl methacrylate, polypropylyl methacrylate, Polybutyl methacrylate, polymethyl acrylate, etc. Can be used a copolymer of Lil resin or acrylic resin and other resin is not particularly limited thereto. Among these, cellulose derivatives or acrylic resins are preferable, and acrylic resins are most preferably used.

As a resin used for a resin layer such as an antistatic layer, the above-mentioned thermoplastic resin having a weight average molecular weight exceeding 400,000 and a glass transition point of 80 to 110 ° C. is used in terms of optical properties and surface quality of the coating layer. preferable.
The glass transition point can be determined by the method described in JIS K7121. The resin used here is 60% by mass or more, more preferably 80% by mass or more of the entire resin used in the lower layer, and an active ray curable resin or a thermosetting resin can be added as necessary. These resins are coated as a binder in a state dissolved in the above-mentioned appropriate solvent.

In the coating composition for coating the antistatic layer, hydrocarbons, alcohols, ketones, esters, glycol ethers and the like can be appropriately mixed and used as a solvent. It is not limited to.
Among these solvents, a solvent having a low boiling point is likely to condense moisture in the air by evaporation, and easily incorporates moisture into the coating composition in the liquid preparation step and the coating step. In particular, it is easily affected by an increase in external humidity during rainfall, and the effect becomes significant in an environment where the relative humidity is 65% or more. Especially when the dissolution time of the resin is long in the liquid preparation process, the time that the coating composition is exposed to air in the coating process is long, or the contact area between the coating composition and air is large. Becomes bigger.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, Examples include pentanol, 2-methyl-2-butanol, and cyclohexanol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, and methyl acetate. , Ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, methyl lactate and the like. Examples of glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether. (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters include propylene glycol monomethyl ether Examples of acetate, propylene glycol monoethyl ether acetate, and other solvents include N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

  As a method of applying the coating composition in the present technology, doctor coating, extrusion coating, slide coating, roll coating, gravure coating, wire bar coating, reverse coating, curtain coating, extrusion coating, or U.S. Pat. No. 2,681,294 Examples include an extrusion coating method using the hopper described in the specification. By appropriately using these methods, the coating can be applied so that the dry film thickness is preferably 0.1 to 10 μm, more preferably 0.1 to 1 μm.

(Cured resin layer)
Next, the cured resin layer that can be provided as a functional layer on the gas barrier film of the present invention will be described.
When the gas barrier film of the present invention is used as an optical film, it is preferable to provide a transparent cured resin layer. An actinic radiation curable resin or a thermosetting resin is preferably used as the transparent curable resin layer. The actinic radiation curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an actinic ray other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. (Only acrylate is shown), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate, and is described in, for example, JP-A-59-151110.

The UV curable polyester acrylate resin can be easily obtained by reacting a polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer. ing.
Specific examples of the ultraviolet curable epoxy acrylate resins include those obtained by reacting epoxy acrylate with an oligomer and adding a reactive diluent and a photoinitiator to the oligomer. It is described in the gazette. As the photoinitiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.
Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. These resins are usually used together with known photosensitizers.

Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying is particularly preferably 2.5 to 6% by mass of the composition. If it is less than 2.5%, the plasticizer and / or ultraviolet absorber eluted from the resin film may be inhibited by curing, resulting in a decrease in scratch resistance. Conversely, if it exceeds 6% by mass, it is a relatively ultraviolet curable resin. On the contrary, the surface quality of the coating film may be deteriorated due to the decrease in the scratch resistance and the applicability due to the decrease in the components.

Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.
The solid concentration of the coating composition for the actinic radiation curable resin layer is preferably 10 to 95% by mass, and an appropriate concentration is selected depending on the coating method.

As the light source for forming the cured film layer of the actinic radiation curable resin by photocuring reaction, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any 20~10000mJ / cm ^2, preferably 50~2000mJ / cm ^2. From the near ultraviolet region to the visible light region, it can be used by using a sensitizer having an absorption maximum in that region. The ultraviolet irradiation may be performed once or twice or more.

  As a solvent for coating the actinic radiation curable resin layer, a solvent for coating the above resin layer, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents as appropriate. Can be selected or mixed for use. Preferably, a solvent containing 5% by mass or more, more preferably 5 to 80% by mass or more of propylene glycol mono (C1-C4) alkyl ether or propylene glycol mono (C1-C4) alkyl ether ester is used.

As a coating device for the ultraviolet curable resin composition coating solution, a known device such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, or an air doctor coater can be used. The coating amount is suitably 0.1 to 200 μm, preferably 0.5 to 100 μm in terms of wet film thickness. The coating speed is preferably 5 to 200 m / min. When the film thickness is thick, it may be divided and applied twice or more to form a transparent cured resin layer. The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.
The thickness of the resulting barcode layer upon drying is preferably 02 to 100 μm, more preferably 1 to 50 μm, and particularly 2 to 45 μm.

In order to impart slipperiness to such a coating layer, the aforementioned inorganic or organic fine particles may be added.
These may use the matting agent described above. Further, as described above, these actinic radiation curable resin layers can be provided on a resin layer such as an antistatic layer. The antistatic layer or the transparent curable resin layer can be provided alone or in layers. Specifically, either side of the optical film with antistatic, polarizing plate protective film, cellulose acylate film, etc. of JP-A-6-123806, JP-A-9-113728, JP-A-9-203810, etc. It can be provided directly or via an undercoat layer.

(Antireflection layer)
The gas barrier film of the present invention can be provided with an antireflection layer. Various configurations of the antireflection layer are known, such as a single layer and a multilayer. The multilayer structure generally has a structure in which high refractive index layers and low refractive index layers are alternately laminated.
Examples of the configuration of the antireflection layer include those laminated in the order of the high refractive index layer / low refractive index layer from the transparent base material side, or three layers having different refractive indices, the medium refractive index layer (transparent base material or There are layers in which the refractive index is higher than that of the cured resin layer and the refractive index is lower than that of the high refractive index layer) / high refractive index layer / low refractive index layer. Laminates have also been proposed. Among them, in view of durability, optical characteristics, cost, productivity, etc., an antireflection layer is formed by applying a high refractive index layer / a middle refractive index layer / a low refractive index layer in this order on a substrate having a cured resin layer. It is preferable.
A high refractive index layer / low refractive index layer (in some cases, a middle refractive layer may be provided) are laminated on the support in order, and the optical film thickness of the high refractive index layer and the low refractive index layer is set to a certain value with respect to the wavelength of light. Thus, it is particularly preferable as the antireflection layer that an optical interference layer is formed to form an antireflection laminate. The refractive index and the film thickness can be calculated and calculated by measuring the spectral reflectance.

The level of refractive index is almost determined by the metal or compound contained in the layer. For example, Ti is high, Si is low, and F-containing compounds are even lower. The refractive index can be appropriately adjusted by a combination of these materials.
As a method for producing an antireflection layer by sequentially laminating a multilayer antireflection layer on a transparent support, a compound selected from metal alkoxides such as titanium and zirconium and hydrolysates thereof, an active energy ray reactive compound and an organic material A composition containing a solvent is applied, an active energy ray is irradiated to form a high refractive index layer, and a low refractive index layer composition containing a low refractive material and an organic solvent is further applied thereon to form a low refractive index layer. A method of forming a low refractive index layer by applying active energy after forming a refractive index coating film can be mentioned. At this time, an intermediate refractive layer may be provided between the high refractive index layer and the low refractive index layer.

  The high refractive index layer comprises at least one compound selected from the group consisting of a metal alkoxide having no active energy ray reactive group and a hydrolyzate thereof, an active energy ray reactive metal alkoxide compound, and preferably an active energy ray. It is preferable to form the composition by irradiating the coating film with active energy rays after coating a high refractive index composition containing a reactive compound on the transparent support. As a result, a high refractive index layer having an arbitrary refractive index can be formed.

As the metal constituting the metal alkoxide used in the high refractive index layer, a partially hydrolyzed product thereof, and the active energy ray reactive metal alkoxide compound of the general formula (II) described later, Al, Si, Ti, V, Ni, Cu , Zn, Y, Ga, Ge, Zr, In, Sn, Sb, Sr, La, Ta, Tl, W, Ce and Nd. The active energy ray-reactive metal alkoxide compound is useful for changing the refractive index of the layer containing these, particularly by ultraviolet irradiation. Preferred metals are Al, Si, Ti, V, Zn, Y, Zr, In, Sn, Sr, Ta, Tl, W, and Ce. Particularly preferred metals that can easily change the refractive index are Ti, Zr, Tl, (as in-Sn complex) an in, a Sr (as Sr-TiO ₂ complex). In the case of Ti, it is known to react to light, but it is not known to change the refractive index of a layer containing a Ti compound by light.

The metal alkoxide having no active energy ray reactive group is preferably a compound having 1 to 10 carbon atoms, preferably a compound having 1 to 4 carbon atoms. The hydrolyzate of metal alkoxide reacts like -metal atom-oxygen atom-metal atom when the alkoxide group is hydrolyzed to form a crosslinked structure and form a hardened layer.
Examples of the metal alkoxide having no active energy ray reactive group include Al (O—CH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , and Al (Oi—C ₃ H ₇ ). _{3, Al (O-n-} C 4 H 9) 3; examples of _{Si, Si (OCH 3) 4,} Si (OC 2 H 5) 4, Si (O-i-C 3 H 7) 4, Si (O-tert-C ₄ H ₉ ) ₄ ; Examples of Ti include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti ( O-i-C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ di- to 10-mer, Ti (O-i-C ₃ H ₇ ) ₄ di- to 10-mer, Ti (On-C ₄ H ₉ ) ₄ di- to 10-mer, examples of V include VO (OC ₂ H ₅ ) ₃ ; _{is, Zn (OC 2 H 5)} 2; and examples of Y Y (OC ₄ H _{9) 3} is Te; examples of Zr _{is, Zr (OCH 3) 4,} Zr (OC 2 H 5) 4, Zr (O-n-C 3 H 7) 4, Zr (O- i-C ₃ H ₇ ) ₄ , Zr (O-i-C ₄ H ₉ ) ₄ , Zr (On-C ₄ H ₉ ) ₄ dimer to 10-mer; Examples of In include In (O -N-C ₄ H ₉ ) ₃ ; Examples of Sn include Sn (On-C ₄ H ₉ ) ₄ , Examples of Ta include Ta (OCH ₃ ) ₅ , Ta (On-C ₃ H _{7) 5, Ta (O-} i-C 3 H 7) 5, Ta (O-n-C 4 H 9) 5; examples of W _{are, W (OC 2 H 5)} 6; examples of Ce is , Ce (OC ₃ H ₇ ) _{3 and the} like. These can be used alone or in combination of two or more. Among them, Ti (O-n-C 3 H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H _{7) 4} 2-10 mer, Ti (O-n-C 4 H 9) 4 2-10 mer; Zr (O-i-C 3 H 7) 4, Zr (O-n-C 4 _{H 9) 4; Si (OC} 2 H 5) 4, Si (O-i-C 3 H 7) 4 are particularly preferred.

The metal alkoxide may be used after hydrolysis (partial or complete hydrolysis). Further, for example, the above metal alkoxide may be hydrolyzed in an organic solvent in the presence of an acidic catalyst or a basic catalyst. Examples of the acidic catalyst include mineral acids such as nitric acid and hydrochloric acid, and organic acids such as oxalic acid and acetic acid, and examples of the basic catalyst include ammonia.
The layer containing the metal alkoxide compound is one in which the metal alkoxide itself is self-condensed and crosslinked to form a network bond. Catalysts and curing agents can be used to accelerate the reaction, and include metal chelate compounds, organometallic compounds such as organic carboxylates, organosilicon compounds having amino groups, photoacid generators, and the like. is there. Particularly preferable among these catalysts or curing agents are an aluminum chelate compound and an acid generator (photoacid generator) by light. Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate and aluminum trisethyl. Acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetonate, etc. Examples of other photoacid generators include benzyltriphenylphosphonium hexafluorophosphate and other Examples thereof include phosphonium salts and salts of triphenylphosphonium hexafluorophosphate.

A coating composition containing a metal alkoxide having no active energy ray reactive group and / or a hydrolyzate thereof used is reacted with a β-diketone and added with a chelate compound in order to stabilize the storage of the coating solution. Thus, a more stable coating composition can be obtained.
The active energy ray reactive compound preferably used for the high refractive index layer has two or more polymerizable groups such as a polymerizable vinyl group, allyl group, acryloyl group, methacryloyl group, isopropenyl group, and epoxy group. Those that form a crosslinked structure or a network structure by irradiation with active energy rays are preferred. Among these active groups, an acryloyl group, a methacryloyl group or an epoxy group is preferable from the viewpoint of polymerization rate and reactivity, and are described in, for example, JP-A-59-151110 and JP-A-59-151112. Yes. Among these, a polyfunctional monomer or oligomer is more preferable.

  An active energy ray reactive epoxy resin is also preferably used. As the active energy ray-reactive epoxy resin, an aromatic epoxy compound (polyglycidyl ether of polyhydric phenol) is preferable. The active energy ray-reactive compound epoxy resin can be used by blending monoepoxide in accordance with desired performance in addition to those having two or more epoxy groups in the molecule. The active energy ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is not affected by oxygen in the reaction system, and is therefore a preferred active energy ray reactive resin.

  Aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, etc., JP-A-50-151997, JP-A 52-30899, JP-A-59-55420, VIA group aromatic onium salts described in JP-A-55-125105, JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc. An oxosulfonium salt, an aromatic diazonium salt described in JP-B-49-17040, a thiopyrylium salt described in US Pat. No. 4,139,655, and the like can be preferably used. Moreover, an aluminum complex, a photodegradable silicon compound polymerization initiator, etc. can also be used. Further, the cationic polymerization initiator may be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  Specific examples of active energy ray-reactive metal alkoxides include vinyltrimethoxytitanium, vinyltri (β-methoxy-ethoxy) titanium, divinyloxydimethoxytitanium, glycidyloxyethyltriethoxytitanium, γ-acryloyloxypropyltri-n. -Propyltitanium, gamma-methacryloyloxy-n-propyltri-n-propyltitanium, di (gamma-acryloyloxy-n-propyl) di-n-propyltitanium, acryloyloxydimethoxyethyltitanium, vinyltrimethoxyzircon, divini Loxodimethoxyzircon, acryloyloxyethyltriethoxyzircon, γ-acryloyloxy-n-propyltri-n-propylzircon, γ-methacryloyloxy-n-propyltri-n-propylzircon, di (γ-a Liloyloxy-n-propyl) di-n-propylzircon, acryloyloxydimethoxyethylzircon, vinyldimethoxythallium, vinyldi (β-methoxy-ethoxy) thallium, divinyloxymethoxythallium, acryloyloxyethyldiethoxythallium, γ-acryloyloxy N-propyldi-n-propylthallium, γ-methacryloyloxy-n-propyldi-n-propylthallium, di (γ-acryloyloxy-n-propyl) -n-propylthallium, acryloyloxymethoxyethylthallium, vinyltrimethoxy Silane, vinyltri (β-methoxy-ethoxy) silane, divinyloxydimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, acryloyloxyethylate Liethoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy-n-propyltri-n-propylsilane, γ-methacryloyloxy-n-propyltri-n-propylsilane, di (γ-acryloyloxy-n- Propyl) di-n-propylsilane, acryloyloxydimethoxyethylsilane and the like.

The behavior of photopolymerization by active energy rays with respect to the active energy ray reactive group used in the high refractive index layer and the reactive group of the active energy ray reactive compound preferably used is almost the same, and the light of the aforementioned active energy ray compound is not changed. Similar sensitizers and photoinitiators are used.
The active energy ray can be used without limitation as long as it is an energy source that activates the compound by ultraviolet rays, electron rays, γ rays, etc., but ultraviolet rays and electron rays are preferable, and handling is particularly simple and high energy can be easily obtained. In this respect, ultraviolet rays are preferable. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 50 mJ / m ² or more, more preferably 100 mJ / cm ² or more, and further preferably 400 mJ / cm ² or more. The ultraviolet rays may be irradiated to the multilayer antireflection layer one by one or after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers. In this case, it is efficient to carry out under the condition that the oxygen concentration is 0.5% or less, which is preferable in terms of curing speed.
Moreover, an electron beam can be used similarly. The electron beam is preferably emitted from various electron beam accelerators such as Cockloft Walton type, Bande graph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc., preferably 50 to 1000 keV, more preferably Can include an electron beam having an energy of 100 to 300 keV.

The low refractive index layer as the outermost layer preferably contains a low refractive index substance containing a fluorine atom or a silicon atom in order to lower the refractive index of the layer. Examples of the low refractive index substance include at least one compound selected from a fluorine-containing resin, a compound formed from a silicate oligomer, and a compound formed from a SiO ₂ sol and a reactive organosilicon compound. No. 126552, JP-A-7-188582, JP-A-8-48935, JP-A-8-100136, JP-A-9-220791, JP-A-9-272169, and the like are preferably used. It is done.

Examples of the fluorine-containing resin that can be preferably used in the present technology include a polymer mainly containing a fluorine-containing unsaturated ethylenic monomer component and a fluorine-containing epoxy compound.
Examples of the fluorine-containing unsaturated ethylenic monomer include a fluorine-containing alkene, a fluorine-containing acrylic ester, a fluorine-containing methacrylate ester, a fluorine-containing vinyl ester, and a fluorine-containing vinyl ether. For example, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, trifluoropropylene, heptafluoropropylene, hexafluoropropylene, 3,3,4,4,5,5,6,6,6-nonafluoro- 1-hexene, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene, 4-ethoxy-1,1,1-trifluoro -3-buten-2-one, pentadecafluorooctyl acrylate, tetrafluoro-3- (pentafluoroethoxy) propyl acrylate, tetrafluoro-3-trifluoromethoxypropyl acrylate, undecafluorohexyl acrylate, nonafluoropentyl acrylate, Octafluoropentyl acrylate, pentafluoropi Pyracrylate, 2-heptafluorobutoxyethyl acrylate, 2,2,3,4,4,4-hexafluorobutoxy acrylate, trifluoroethyl acrylate, 2- (1,1,2,2-tetrafluoroethoxy) ethyl acrylate , Trifluoroisopropyl methacrylate, (2,2,2-trifluoro-1-methyl) ethyl methacrylate, 3-trifluoromethyl-4,4,4-trifluorobutyl acrylate, 1-methyl-2,2,3, 3,3-pentafluoropropyl acrylate, 1-methyl-2,2,3,3,4,4,4-heptaurourobutyl acrylate, 2,2,2-trifluoroethyl acrylate, pentafluoropropyl acrylate, 1 , 1,1,3,3,3-Hexafluoroisopropyl Acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, nonafluoropentyl acrylate, Undecafluorohexyl acrylate, tridecafluoroheptyl acrylate, pentadecafluorooctyl acrylate, tridecafluorooctyl acrylate, nonadecafluorodecyl acrylate, heptadecafluorodecyl acrylate, hexafluoroisopropyl acrylate, tetrafluoropropyl acrylate, hexafluorobutyl acrylate (The above acrylate may be methacrylate or α-fluoro acrylate), vinyl trifluoroacetate, vinyl-2 2,2-trifluoropropionate, vinyl-3,3,3,2,2-heptabtylate, 2,2,2-trifluoroethyl vinyl ether, 1- (trifluoromethyl) ethenyl acetate, allyl trifluoro Acetate, allyl-1,1,2,2-tetrafluoroethyl ether, allyl-1,2,3,3,3-hexafluoropropyl ether, ethyl-4,4,4-trifluorocrotonate, isopropyl-2 , 2,2-trifluoroethyl fumarate, isopropyl-pentafluoropropyl fumarate, isopropyl-2,2,3,3,4,4,4-heptafluorobutyl fumarate, isopropyl-2,2,3,3 , 4,4,5,5,5-nonapropylpentyl fumarate, isopropyl-2,2,3,3,4,4,5 5,6,6,6-undecafluorohexyl fumarate, isopropyl-tridecafluoroheptyl fumarate, isopropyl-pentadecafluorooctyl fumarate, isopropyl-tridecafluorooctyl fumarate, isopropyl-nonadecafluorodecyl fumarate Isopropyl-heptadecafluorodecyl fumarate, isopropyl-2-trifluoromethyl-3,3,3-trifluoropropyl fumarate, isopropyl-3-trifluoromethyl-4,4,4-trifluorobutyl fumarate, Isopropyl-1-methyl-2,2,3,3,3-pentafluoropropyl fumarate, isopropyl-1-methyl-heptafluorooctyl fumarate, tert-butyl-pentylfluoropropyl fumarate, tert Fluorine-containing unsaturated ethylenic monomers such as -butyl-heptafluorobutyl fumarate can be mentioned, but the compounds that can be used in the present invention are not limited to these. Further, the copolymerization partner monomer may or may not contain fluorine.

  Monomers that can be copolymerized with the fluorine-containing monomer include, for example, ethylene, propylene, butene, vinyl acetate, vinyl ethyl ether, vinyl ethyl ketone, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl-α-fluoroacrylate, ethyl-α-fluoroacrylate, propyl-α-fluoroacrylate, butyl-α-fluoroacrylate, cyclohexyl-α-fluoroacrylate, hexyl- α-fluoroacrylate, benzyl-α-fluoroacrylate, acrylic acid, methacrylic acid, α-fluoroacrylic acid, styrene, styrenesulfonic acid, etc. I can make it.

  The refractive index of the single resin of the fluorine-containing ethylenically unsaturated monomer is in the range of about 1.33 to 1.42, and the refraction of the single resin limer of the monomer not containing fluorine that can be copolymerized. The ratio is 1.44 or more, and these can be copolymerized at an arbitrary ratio and used as a fluorine-containing resin having a desired refractive index. Further, the fluorine-containing resin of the present technology and a resin not containing fluorine may be mixed at an arbitrary ratio and used as those having a target refractive index. The fluorine content of the low refractive index material is preferably 50% by mass or more, and varies depending on the material, but is particularly preferably 60 to 90% by mass. In the case of a fluorine-containing polymer, if the fluorine content is in such a range, it has good solubility in an organic solvent and thus is easy to process, and has excellent adhesion to the underlying substrate and layer, and is high. A layer with transparency and a low refractive index can be obtained.

  As the polymerization initiator for polymerizing the fluorine-containing alkene, acrylate, vinyl ester, vinyl ether or the like to be used, a normal radical polymerization initiator can be used. Specific examples of the polymerization initiator include azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobisvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene peroxide , Organic peroxide radical polymerization initiators such as diacyl peroxide, inorganic radical polymerization initiators such as ammonium persulfate and potassium persulfate, redox such as hydrogen peroxide-ferrous ammonium sulfate, ammonium persulfate-sodium metasulfite Various radical polymerization initiators such as system polymerization initiators can be used, and known radical polymerization such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or radiation polymerization can be performed using these. At this time, the reaction temperature is preferably 10 to 100 ° C., and the reaction time is preferably 1 to 100 hours. The number average molecular weight of the fluorine-containing resin thus obtained is desirably 1000 to 300,000. The fluorine-containing epoxy resin as the fluorine-containing resin can be obtained, for example, by reacting the following epoxy compound by a conventional method.

  As the fluorine-containing epoxy compound, mono-, di-, tri- and oligoglycidyl ethers of fluorinated alcohols are preferable. Among them, examples of the fluorine-containing alkane-terminated diol glycidyl ether include 2,2,3,3-tetrafluoro-1,4-butanediol diglycidyl ether, 2,2,3,3,4,4,5,5-octa Examples include fluoro-1,6-hexanediol diglycidyl ether, but are not limited thereto. In addition to these, a small amount of an epoxy compound containing no fluorine may be used so that the refractive index does not increase so much. Although there is no restriction | limiting in the structure of the fluorine-containing epoxy compound used here, it is better that there is little use of the epoxy compound which has a benzene nucleus which raises a refractive index, or an alicyclic epoxy compound.

  Another preferred low refractive index material is a compound formed from a silicate oligomer. Examples of the silicate oligomer used for the compound formed from the silicate oligomer include tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and tetra-2,2,2-trifluoroethoxysilane. , Tetra-2-fluoroethoxysilane, tetra-2,2,3,3-tetrafluoro-1-propoxysilane, tetra-1,1,1,3,3,3-hexafluoro-2-propoxysilane , Tetra-2,2,3,3,3-pentafluoro-1-propoxysilane, tetra-1,3-difluoro-2-propoxysilane, tetra-2,2,3,3,4,4, 4-heptafluoro-1-butoxysilane, tetra-2,2,3,4,4,4-hexafluoro-1 Butoxysilane, it can be mentioned tetra-cyclohexyloxy silane or tetraphenoxysilane like, silicate oligomer is obtained by these hydrolysis.

As described above, a hydrolyzate cured by a method such as adding a solvent to a hydrolyzate obtained by adding a catalyst and water to tetraalkoxysilane and then adding a curing catalyst and water is obtained. As such a solvent, it is preferable to use one or two kinds of methanol and ethanol because it is inexpensive and the properties of the resulting film are excellent and the hardness is good. Although isopropanol, n-butanol, isobutanol, octanol, and the like can be used, the hardness of the obtained film tends to be low. The amount of the solvent is 50 to 400 parts by mass, preferably 100 to 250 parts by mass with respect to 100 parts by mass of the partial hydrolyzate. Examples of the curing catalyst include acids, alkalis, organic metals, metal alkoxides, and the like, and acids such as acetic acid, maleic acid, oxalic acid, and fumaric acid are preferably used. The SiO ₂ content in the silicate oligomer is 1 to 100%, preferably 10 to 99%. If the SiO ₂ content is less than 1%, the durability is not improved.

  The method for forming a silicon layer from these silicate oligomers is not particularly limited, but for example, a solvent that does not inhibit the optical performance of the silicate oligomer such as alcohol (methanol, ethanol, isopropanol, etc.), ethyl acetate, butyl acetate, acetic acid. Cellosolve, methyl glycol acetate, methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylene chloride, toluene, xylene, mineram spirit, cresol, xylenol, furfural, etc., dilute silicate oligomer with these, bar coater, roll What is necessary is just to apply | coat and heat-process a base material with well-known apparatuses, such as a coater, a gravure coater, a reverse coater, a lip coater.

Yet another preferred low refractive index material, a compound formed from the reactive organic silicon compound SiO ₂ sol, using a sol solution containing a reactive organic silicon compound SiO ₂ sol, the SiO ₂ gel film A low refractive index layer is formed. The SiO ₂ sol is prepared by dissolving silicon alkoxide in an organic solvent suitable for coating and adding a certain amount of water for hydrolysis. Preferred silicon alkoxides used to form the SiO ₂ sol are, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra -Tert-butoxysilane, tetrapentaethoxysilane, tetrapentaisopropoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane , Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethylmethoxysilane, dimethyldiethoxysilane, dimethylmethoxysilane, Methyl silane, dimethyl propyl silane, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane and the like.

A SiO ₂ sol can be obtained by dissolving the alkyl silicon alkoxide or silicon alkoxide in a suitable solvent. Examples of the solvent used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate, and butyl acetate, and aromatic hydrocarbons such as ketones, esters, halogenated hydrocarbons, toluene, xylene, and the like. Or a mixture thereof. Alkyl silicon alkoxide or silicon alkoxide is added to the above solvent so that the concentration is 0.1% by mass or more, preferably 0.1 to 10% by mass in terms of SiO ₂ produced as a result of 100% hydrolysis and condensation. Dissolve. If the concentration of the SiO ₂ sol is less than 0.1% by mass, the formed sol film cannot sufficiently exhibit the desired characteristics, while if it exceeds 10% by mass, it becomes difficult to form a transparent homogeneous film. Moreover, in this technique, if it is less than the above solid content, it is also possible to use an organic substance and an inorganic binder together.

Water more than the amount necessary for hydrolysis is added to this solution, and preferably stirred at a temperature of 15 to 35 ° C., more preferably 22 to 28 ° C., preferably 0.5 to 10 hours, more preferably 2 to 5 hours. I do. In the hydrolysis, it is preferable to use a catalyst. As these catalysts, acids such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid are preferable. These acids are preferably added as an aqueous solution of about 0.001 to 40.0 mol / L, more preferably about 0.005 to 10.0 mol / L, and the water in the aqueous solution is used as water for hydrolysis. it can.
Although the gel film finally obtained is used as a low refractive index layer of an antireflection film, it may be necessary to adjust the refractive index. For example, a fluorine-based organosilicon compound can be added to lower the refractive index, an organosilicon compound can be added to increase the refractive index, and a boron-based organic compound can be added to further increase the refractive index. Specifically, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, alkyltrialkoxysilane, Colcoat 40 (manufactured by Colcoat), MS51 (manufactured by Mitsubishi Chemical Corporation), Snowtex (manufactured by Nissan Chemical Industries, Ltd.) ), Etc., ZAFLON FC-110, 220, 250 (manufactured by Toa Gosei Chemical Co., Ltd.), sexual coat A-402B (manufactured by Central Glass Co., Ltd.), heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane And fluorine compounds such as trifluorooctyltrimethoxysilane and trifluoropropyltrimethoxysilane, and boric acid compounds such as triethyl borate, trimethyl borate, tripropyl borate and tributyl borate. These additives may be added during the preparation of the sol, or may be added after the formation of the sol. By using these additives, during the hydrolysis of the alkyl silicon alkoxide or silicon alkoxide, or after that, it reacts with the silanol group, and more uniformly reacts to obtain and form a more uniform and transparent sol solution. The refractive index of the gel film can be changed within a certain range.

Next, a low refractive index layer containing at least one low refractive index material selected from the fluorine-containing resin, a compound formed from a silicate oligomer, and a compound formed from a SiO ₂ sol and a reactive organosilicon compound (the above-mentioned (Provided on the high refractive index layer) may be added with the active energy ray-reactive compounds mentioned above for the high refractive index layer. Of these, epoxy active energy ray reactive compounds are preferably used. The epoxy-based active energy ray-reactive compound is a compound having two or more epoxy groups in the molecule and capable of releasing cationic polymerization as an initiator by irradiation with active energy rays as described above. Examples of the epoxy-based active energy ray-reactive compound include (a) glycidyl ether of bisphenol A (this compound is obtained by reaction of epichlorohydrin and bisphenol A, and is obtained as a mixture having different degrees of polymerization); A compound having a glycidyl ether group at the terminal by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A can be exemplified. The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy-based active energy ray-reactive compound is a compound capable of releasing a cationic polymerization initiator by irradiation with active energy rays, and particularly preferably a cation by irradiation. A group of double salts of onium salts that release Lewis acids capable of initiating polymerization. Since these are the same as those in the general formula (I), they are omitted here. These active energy ray-reactive compounds are cured by application of ultraviolet rays, active energy rays such as electron beams, plasma treatment, or thermal energy similar to those described for the high refractive index layer. Is the same.

(Anti-glare layer)
The gas barrier film of the present invention may be provided with an antiglare layer. In particular, when used as an optical film, it may be preferable to form an antiglare layer. The anti-glare layer has a structure having irregularities on the surface, and the anti-glare function is expressed by scattering light on the anti-glare layer surface or inside the anti-glare layer. It has a configuration. What is preferable as these layers is a layer containing one or more fine particles having a film thickness of 0.5 to 5.0 μm and an average particle size of 0.25 to 10 μm, and the average particle size is the film thickness. 1 to 2 times the silicon dioxide particles and silicon dioxide fine particles having an average particle size of 0.005 to 0.1 μm in a binder such as diacetyl cellulose. Examples of the “particle” here include inorganic particles and organic particles. Examples of inorganic particles that can be used in the present technology include silicon dioxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. Organic particles include poly (meth) acrylate resins, silicone resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used.

Among these, silicon dioxide such as silica is particularly preferably used to achieve the antiglare property applied in the present technology. As the silicon dioxide particles preferably used here, ultrafine hydrated silicic acid produced by a wet method among synthetic amorphous silicas is preferable because of its great effect of reducing the glossiness. The wet method is a method in which sodium silicate is reacted with a mineral acid and salts in an aqueous solution. Examples thereof include silicia manufactured by Fuji Silysia Chemical Co., Ltd. and Nippon Sil E manufactured by Nippon Silica Co., Ltd.
In the antiglare layer, it is particularly preferable to use an actinic radiation curable resin as a binder, and the actinic radiation curable resin layer containing silicon dioxide particles or silicon dioxide fine particles is formed by irradiation with actinic radiation after coating. In view of increasing the mechanical strength of the polarizing plate surface, an antiglare layer using an actinic radiation curable resin as a binder is more preferable.
The actinic radiation curable resin that can be used here refers to a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams.

  Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may be used. Examples of UV curable resins include UV curable polyester acrylate resins, UV curable acrylic urethane resins, UV curable acrylate resins, UV curable methacrylate resins, UV curable polyester acrylate resins and Examples include ultraviolet curable polyol acrylate resins.

  Examples of ultraviolet curable polyol acrylate resins that can be used in this technology include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Photopolymerized monomer oligomer such as alkyl-modified dipentaerythritol pentaerythritol. These polyol acrylate resins are characterized by high crosslinkability, high curability, high hardness, low cure shrinkage, low odor, low toxicity and relatively high safety.

  The ultraviolet curable polyol acrylate resin may contain other ultraviolet curable resins, for example, an ultraviolet curable epoxy resin as long as the effect is not impaired. A cured coating film obtained by coating a thick film of an acrylate resin has strong curling due to curing shrinkage, which may cause trouble in handling work. Epoxy resins generally have less cure shrinkage and less curling of cured coatings than acrylate resins. The ultraviolet curable epoxy resin as used herein is a compound containing two or more epoxy groups in the molecule, is an epoxy resin that contains a cationic polymerization initiator and undergoes a crosslinking reaction when irradiated with ultraviolet rays.

  Examples of the electron beam curable resin that can be used are preferably those having an acrylate functional group, such as a polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd having a relatively low molecular weight. Examples include resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like.

Among these, it is preferable to use an ultraviolet curable resin. The actinic radiation curable resin can be cured by irradiation with actinic rays such as an electron beam or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 keV emitted from various electron beam accelerators such as a Cochloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 keV is used. In the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. .
The thickness of the antiglare layer is preferably 0.5 to 5.0 μm, more preferably 2.0 to 4.0 μm.

Instead of active radiation used for curing each component layer of an optical film having an anti-reflection layer or an anti-glare layer and an easy-adhesion layer on the opposite side of the substrate, plasma treatment, Such a method is also preferable. As the plasma treatment, a method described in JP 2000-327310 A can be preferably used. Further, as the heat treatment for imparting active energy, it is also effective to perform heat treatment after coating and drying of the antireflection layer or the antiglare layer. It is preferable to heat at 70 ° C. or higher for 30 seconds to 10 minutes, more preferably 30 seconds to 5 minutes. By providing these antiglare layers, it is desirable that the visible light transmittance does not decrease, and the haze value is preferably 3% or more. Further, the transmittance at that time is preferably 90% or more in terms of transmittance at 550 nm. The surface layer of the antiglare layer preferably has a critical surface tension of 20 × 10 ⁻⁶ N / cm or less. When the critical surface tension is larger than 20 × 10 ⁻⁶ N / cm, it becomes difficult to remove the dirt attached to the surface layer. A fluorine-containing fluorine material is preferable in terms of preventing contamination.

As fluorine-containing materials, vinylidene fluoride copolymers, fluoroolefin / hydrocarbon olefin copolymers, fluorine-containing epoxy resins, fluorine-containing epoxy acrylates, fluorine-containing silicones, which are soluble in organic solvents and are easy to handle , Fluorine-containing alkoxysilane, TEFRON (registered trademark) AF1600 (DuPont, n = 1.30), CYTOP (Asahi Glass Co., Ltd., n = 1.34), 17FM (Mitsubishi Rayon Co., Ltd.) Product, refractive index n = 1.35), LR201 (manufactured by Nissan Chemical Industries, Ltd., n = 1.38), and the like. These can be used alone or in combination.
Further, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-9-methyldecyl) ) Fluorinated methacrylate such as ethyl methacrylate, 3- (perfluoro-8-methyldecyl) 2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (per Fluorine-containing acrylates such as fluoro-9-methyldecyl) ethyl acrylate, epoxides such as 3-perfluorodecyl 1,2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2-epoxypropane, It can be exemplified port carboxymethyl radiation-curable fluorine-containing monomers such as acrylates, oligomers, prepolymers, and the like. These can be used alone or in combination.

(Anti-curl layer)
The film of the present technology can be anti-curled. Anti-curl processing gives the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film, When surface treatments of different degrees and types are applied, it functions to prevent curling with the surface facing inward.
The anti-curl layer may be provided on the side opposite to the side having the anti-glare layer or anti-reflection layer of the base material, or for example, an easy-adhesion layer may be coated on one side of the transparent resin film, and the anti-curl processing is performed on the opposite side. The mode which coats is mentioned.

  Specific examples of the anti-curl processing include solvent coating, and a method of applying a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate. The method using a solvent is specifically performed by applying a composition containing a solvent for dissolving or swelling a cellulose acylate film used as a protective film for a polarizing plate. Accordingly, the coating solution for the layer having a function of preventing curling preferably contains a ketone-based or ester-based organic solvent. Examples of preferred ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, Examples thereof include methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, etc. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, acetic acid Examples include butyl, methyl lactate, and ethyl lactate. However, as a solvent to be used, in addition to a solvent mixture to be dissolved and / or a solvent to be swollen, it may further contain a solvent that does not dissolve, and a composition in which these are mixed at an appropriate ratio depending on the curl degree of the transparent resin film and the type of resin This is done using the product and the coating amount. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

In the gas barrier film of the present invention, a layer having a function of preventing curling can be preferably provided on the side opposite to the side having the antiglare layer or antireflection layer of the substrate. The film thus produced preferably has a curl degree of −10 to +10 at 23 ° C. and a relative humidity of 60%.
The curl degree is measured by the following method. The film sample is allowed to stand for 48 hours in an environment of 80 ° C. and a relative humidity of 90%, and then the film is cut into a width direction of 50 mm and a longitudinal direction of 2 mm. Further, the film piece is conditioned for 24 hours in an environment of 23 ° C. ± 2 ° C. and a relative humidity of 55%, and the curl value of the film is measured using a curvature scale.

  The curl value is represented by 1 / R, where R is a radius of curvature and the unit is m. As for the curl value, a film with little deformation of the film is preferable, and the deformation direction may be the + direction or the-direction. That is, it is sufficient that the absolute value of the curl value is small. Specifically, when the absolute value of the curl value of the film is greater than 10, when a polarizing plate or the like is produced using the film, Left at 48C for 90 hours at 80 ° C and 90% relative humidity). If the curl value of the film is 10 or less, when a polarizing plate or the like is produced using the film, deformation such as warpage is caused even under high temperature and high humidity (for example, left at 80 ° C. and 90% relative humidity for 48 hours). Can be used small.

Despite the coating of these anti-curl layers and other layers, when the gas barrier film of the present invention is used as an optical film, the haze value is 3% or more and the transmittance at 550 nm is 90% or more. Is preferred.
In addition, these outermost surface layers have a certain degree of hydrophilicity because they are used by bonding an easy-adhesion layer to a polarizer or by attaching an antireflection layer surface to a protective layer film surface. In particular, the contact angle of water at 23 ° C. and a relative humidity of 60% of the easy-adhesion layer described below is preferably 50 degrees or less.

(Easily adhesive layer)
An easy-adhesion layer can also be applied to the gas barrier film of the present invention. An easy-adhesion layer means the layer which provides the function which makes it easy to adhere | attach a protective film for polarizing plates and its adjacent layer, typically a polarizing film, for example.
Examples of the easy adhesion layer preferably used in the present technology include a layer containing a polymer compound having a -COOM (M represents a hydrogen atom or a cation) group, and a more preferable embodiment is a film substrate. A layer containing a polymer compound having a —COOM group is provided on the side, and a layer containing a hydrophilic polymer compound as a main component is provided on the polarizing film side adjacent to the layer. Examples of the polymer compound having -COOM group herein include styrene-maleic acid copolymer having -COOM group, vinyl acetate-maleic acid copolymer having -COOM group, and vinyl acetate-maleic acid-maleic anhydride. For example, a vinyl acetate-maleic acid copolymer having a -COOM group is preferably used. These polymer compounds are used alone or in combination of two or more, and the preferred weight average molecular weight is preferably about 500 to 500,000. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

  The hydrophilic polymer compound is preferably a hydrophilic cellulose derivative (eg, methyl cellulose, carboxymethyl cellulose, hydroxy cellulose, etc.), a polyvinyl alcohol derivative (eg, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal). , Polyvinyl benzal, etc.), natural polymer compounds (eg, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (eg, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (eg, poly -N-vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), and may be used alone or in combination of two or more.

(Support)
Next, the resin used for the support of the gas barrier film of the present invention will be described.
The resin used for the support is preferably a thermoplastic resin, such as methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification Examples thereof include polycarbonate resins and acryloyl compounds.

  The resin used for the support is preferably one having a thermal expansion coefficient of 30 ppm / ° C. or less. The thermal expansion coefficient in this specification is measured with TMA8310 (manufactured by Rigaku Corporation, Thermo Plus series). Examples of the resin having a coefficient of thermal expansion of 30 ppm / ° C. or less include PET (manufactured by Torel Miller, 15 ppm / ° C.), PEN (manufactured by DuPont-Teijin, Q65A, 20 ppm / ° C.), PI (manufactured by Ube Industries, Upilex, 20 ppm / ° C), aramid resin (manufactured by Teijin, 2 ppm / ° C), and the like.

  The resin having a thermal expansion coefficient of 30 ppm / ° C. or less used in the present invention is obtained by adding an inorganic substance such as a sol-gel method, glass cloth, glass fiber or the like to a resin having a glass transition point (Tg) of 150 ° C. or more. May be adjusted to 30 ppm or less. As the resin having a glass transition point (Tg) of 150 ° C. or higher used here (Tg is shown in parentheses), polycarbonate resin (PC: 140 ° C.), alicyclic polyolefin resin (for example, manufactured by Nippon Zeon Co., Ltd.) ZEONOR 1600: 160 ° C., JSR Corporation Arton: 170 ° C., polyarylate resin (PAr: 210 ° C.), polyethersulfone resin (PES: 220 ° C.), polysulfone resin (PSF: 190 ° C.), polyester resin ( For example, Kanebo Co., Ltd. O-PET: 125 ° C., polyethylene terephthalate, polyethylene naphthalate), cycloolefin copolymer (COC: compound of Example 1 of JP 2001-150584 A: 162 ° C.), fluorene ring-modified polycarbonate resin (BCF-PC: JP 2000-227603 A Compound of Example 4 of the publication: 225 ° C., alicyclic modified polycarbonate resin (IP-PC: compound of Example 5 of JP 2000-227603 A: 205 ° C.), acryloyl compound (JP 2002-80616) Compound of Example-1 of the publication No .: 300 ° C. or higher).

  A polycarbonate resin containing bisphenol represented by the following formula (A) as a bisphenol component is also a preferred example of a resin having a thermal expansion coefficient of 30 ppm / ° C. or less.

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group or an aryl group, and X is a cycloalkylene group having 5 to 10 carbon atoms and an aralkylene group having 7 to 15 carbon atoms. , A haloalkylene group having 1 to 5 carbon atoms. Preferable specific examples of the cycloalkylene group which X can take include 1,1-cyclopentylene group, 1,1-cyclohexylene group, 1,1- (3,3,5-trimethyl) cyclohexylene group, norbornane-2 , 2-diyl group, tricyclo [5.2.1.0 ^2,6 ] decane-8,8'-diyl group, especially 1,1-cyclohexylene group, 1,1- (3,3,5-trimethyl ) Cyclohexylene group. Preferred specific examples of the aralkylene group that X can take include a phenylmethylene group, a diphenylmethylene group, a 1,1- (1-phenyl) ethylene group, and a 9,9-fluorenylene group. Furthermore, preferred specific examples of the haloalkylene group which X can take include a 2,2-hexafluoropropylene group and a 2,2- (1,1,3,3-tetrafluoro-1,3-dichloro) propylene group. It is done.

  The structural unit of the resin used as the support in the present invention may be composed of only one type, or may be composed of two or more types. Moreover, in the range which does not impair the effect of this invention, you may include structural units other than having illustrated above. The substitution amount is usually 50 mol% or less, preferably 10 mol% or less. In addition, the resin used as the support in the present invention may be a blend of two or more resins, in which case it may be blended with a resin other than those exemplified above.

  The molecular weight of the resin used as the support in the present invention is preferably 10,000 to 300,000 (polystyrene equivalent) in terms of number average molecular weight, more preferably 20,000 to 200,000, and most preferably 30,000 to 150,000. When the molecular weight is low, the mechanical strength becomes insufficient when used as a plastic substrate.

  As the support in the present invention, a crosslinked resin can also be preferably used from the viewpoint of solvent resistance, heat resistance and the like. As the kind of the cross-linked resin, various known ones can be used without any particular limitation as the thermosetting resin and the radiation curable resin. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin and the like. As a crosslinking method, any reaction that forms a covalent bond can be used without any particular limitation, and a system in which a reaction proceeds at room temperature using a polyalcohol compound and a polyisocyanate compound to form a urethane bond is not particularly limited. Can be used. However, such a system often has a problem of pot life before film formation, and is usually used as a two-component mixed type in which a polyisocyanate compound is added immediately before film formation. On the other hand, when used as a one-component type, it is effective to protect the functional group involved in the crosslinking reaction, and it is also commercially available as a block type curing agent. As commercially available block type curing agents, B-882N manufactured by Mitsui Takeda Chemical Co., Ltd., Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd. (above block polyisocyanate), Cymel 303 manufactured by Mitsui Cytec Co., Ltd. (methylated melamine resin) ) Etc. are known. Further, a blocked carboxylic acid such as the following B-1 that protects a polycarboxylic acid that can be used as a curing agent for an epoxy resin is also known.

  Radiation curable resins are roughly classified into radical curable resins and cationic curable resins. As the curable component of the radical curable resin, a compound having a plurality of radical polymerizable groups in the molecule is used. As a typical example, a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule And compounds having a plurality of acrylate groups in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. As a typical curing method of the radical curable resin, there are a method of irradiating an electron beam and a method of irradiating ultraviolet rays. Usually, in the method of irradiating with ultraviolet rays, a polymerization initiator that generates radicals upon irradiation with ultraviolet rays is added. In addition, if the polymerization initiator which generate | occur | produces a radical by heating is added, it can also be used as a thermosetting resin. As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used. As a typical curing method, a photoacid generator that generates an acid upon irradiation with ultraviolet rays is added, and ultraviolet rays are added. And a method of curing by irradiation. Examples of the cationically polymerizable compound include a compound containing a ring-opening polymerizable group such as an epoxy group and a compound containing a vinyl ether group.

In the support of the present invention, a plurality of the thermosetting resins and radiation curable resins mentioned above may be mixed and used, or a thermosetting resin and a radiation curable resin may be used in combination. Moreover, you may mix and use a crosslinkable resin and the polymer which does not have a crosslinkable group.
It is preferable to mix these crosslinkable resins with the resin because the solvent resistance, heat resistance, optical properties, and toughness of the obtained support can be improved. Moreover, it is also possible to introduce a crosslinkable group into the resin, and it may have a crosslinkable group at any site in the polymer main chain terminal, the polymer side chain, or the polymer main chain. In this case, you may produce a support body, without using together general purpose crosslinking | crosslinked resin quoted above.
When the gas barrier film of the present invention is used for a liquid crystal display element or the like, the support for the gas barrier film is preferably an amorphous polymer in order to achieve optical uniformity. Furthermore, for the purpose of controlling retardation (Re) and its wavelength dispersion, it is possible to combine resins having different signs of intrinsic birefringence of resins, or to combine resins having large (or small) wavelength dispersion.
The gas barrier film of the present invention can be suitably laminated with different resins for the purpose of controlling retardation (Re) and improving gas permeability and mechanical properties.
There is no restriction | limiting in particular as a preferable combination of different resin, Any resin mentioned above can be used.

The support constituting the gas barrier film of the present invention may be stretched. By stretching, mechanical strength such as folding strength is improved, and there is an advantage that handling property is improved. In particular, those having an orientation release stress in the stretching direction (ASTM D1504, hereinafter abbreviated as ORS) of 0.3 to 3 GPa are preferred because the mechanical strength is improved. ORS is the internal stress caused by stretching that is frozen in a stretched film or sheet.
For stretching, a known method can be used. For example, a roll uniaxial stretching method, a tenter uniaxial stretching method, a simultaneous biaxial stretching at a temperature between 10 ° C. and 50 ° C. higher than the glass transition temperature (Tg) of the resin. The film can be stretched by a method, a sequential biaxial stretching method, or an inflation method. The draw ratio is preferably 1.1 to 3.5 times.

The resin used for the support may be a plasticizer, dye / pigment, antistatic agent, ultraviolet absorber, antioxidant, inorganic fine particles, release accelerator, leveling agent, and lubrication as necessary, as long as the effects of the present invention are not impaired. A resin modifier such as an agent may be added.
Moreover, when forming a layer on a support body, you may perform an activation process to the surface of a support body. By activating the surface, the adhesion with the layer formed thereon can be improved. Specific examples of the surface activation treatment include corona treatment, glow discharge treatment, electron beam irradiation treatment, and plasma treatment.

  The thickness of the gas barrier film of the present invention is not particularly defined, but is preferably 30 μm to 700 μm, more preferably 40 μm to 200 μm, and still more preferably 50 μm to 150 μm. Further, in any case, the haze is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 90%. That's it.

(Arbitrary layer)
In the gas barrier film of the present invention, for example, the following layers can be arbitrarily formed.
(1) Undercoat layer In order to improve the adhesion between the support and the layer formed thereon, an undercoat layer (adhesive layer) may be provided on the support. Prior to forming the undercoat layer, the support may be subjected to some surface treatment.
The undercoat layer may be a single layer (single layer method) or a plurality of layers (multilayer method). In the case of consisting of a plurality of layers, for example, a layer that adheres well to the support can be provided as the first undercoat layer, and a layer that adheres well to the layer formed thereon can be provided thereon as the second undercoat layer.

  In the single layer method, good adhesion is often achieved by expanding the support and interfacial mixing with the material of the undercoat layer. Examples of the polymer for the undercoat layer used in the present technology include water-soluble polymers, cellulose acylates, latex polymers, and water-soluble polyesters. Examples of water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, and cellulose acylates include carboxymethyl cellulose, hydroxy Examples include ethyl cellulose. Examples of the latex polymer include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylate ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer.

  As the material for the first undercoat layer in the multi-layer method, for example, a co-polymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Starting with coalescence, oligomers or polymers such as polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose and the like can be mentioned. These materials are described in detail in E.H. Immergut, Polymer Handbook, IV187-231, Interscience Pub. New York 1966, and the like.

The undercoat layer can contain inorganic or organic fine particles as a matting agent to such an extent that the transparency of the functional layer is not substantially impaired. Examples of the inorganic fine particle matting agent include silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, and magnesium carbonate. Examples of the organic fine-particle matting agent include polymethyl methacrylate, cellulose acetate propionate, polystyrene, a treatment solution-soluble one described in US Pat. No. 4,142,894, US Pat. Examples thereof include polymers described in 396,706. The average particle size of these fine particle matting agents is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm. Moreover, the content is preferably 0.5 to 600 mg / m ² , more preferably 1 to 400 mg / m ² .
The undercoating liquid is generally a well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or US Pat. , 681,294 specification, and can be applied by an extrusion coating method using a hopper.

(2) Layer containing water absorbent It is particularly preferred to use a water absorbent in the gas barrier film of the present invention. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. Examples thereof include BaO, SrO, CaO, and MgO. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.
The layer containing these water absorbents may be prepared by using a vacuum deposition method or the like in the same manner as the barrier layer described above, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing the water absorbent is between the support and the laminate (a laminate of the barrier layer and the organic layer), between the uppermost layer of the laminate, between the laminates, or in the organic layer or barrier layer in the laminate. It may be added. When added to the barrier layer, a co-evaporation method is preferably used.

(3) Primer Layer / Inorganic Thin Film Layer In the gas barrier film of the present invention, a known primer layer or inorganic thin film layer can be installed between the support and the laminate. As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin or the like can be used. In the present invention, an organic-inorganic hybrid layer is used as the primer layer, an inorganic vapor deposition layer or a sol-gel is used as the inorganic thin film layer. A dense inorganic coating thin film by the method is preferred. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

[Image display element]
Although the use of the gas barrier film of the present invention is not particularly limited, it can be suitably used as a transparent electrode substrate of an image display element because it is excellent in optical properties and mechanical properties. The term “image display element” as used herein means a circularly polarizing plate / liquid crystal display element, a touch panel, an organic EL element, or the like.

(Circularly polarizing plate)
A circularly polarizing plate can be prepared by laminating a λ / 4 plate and a polarizing plate on the gas barrier film of the present invention (in particular, one provided with an antistatic layer). In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used, and for example, the one described in JP-A-2002-865554 can be suitably used. .

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film of the present invention can be used as the transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has a structure consisting of a film. Among these, the gas barrier film of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
The liquid crystal cell is not particularly limited, but more preferably TN (Twisted Nematic) type, STN (Supper Twisted Nematic) type or HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB type (Electrically Controlled Birefringence), OCB A type (Optically Compensatory Bend) and a CPA type (Continuous Pinwheel Alignment) are preferable.

(Touch panel)
The gas barrier film of the present invention can be applied to touch panels described in JP-A-5-127822 and JP-A-2002-48913.

(Organic EL device)
The gas barrier film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.
When the film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776, etc. The contents described in each publication can be applied. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

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

<1. Preparation of support>
After drying 100 parts by weight of polyethylene-2,6-naphthalate polymer (manufactured by Dupont-Teijin, Q65A) and 2 parts by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals, Tinuvin P. 326), the mixture was heated to 300 ° C. After melting and extruding from a T-shaped die, 3.3 times longitudinal stretching is performed at 140 ° C, then 3.3 times transverse stretching is performed at 130 ° C, and heat setting is further performed at 250 ° C for 6 seconds. A 90 μm thick PEN film was obtained. This PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I- 27, II-5) was added in an appropriate amount. Furthermore, it was wound around a stainless steel core having a diameter of 20 cm and given a thermal history of 48 hours at 110 ° C., thereby providing a support that was difficult to curl.

<2. Formation of functional layer>
(Coating the undercoat layer)
After corona discharge treatment, UV irradiation treatment, and glow discharge treatment on both sides of the support, gelatin 0.1 g / m ² , α-sulfodi-2-ethylhexyl sodium cinnamate 0.01 g / m ^{2 on one side} , Salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ ═CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate A primer solution of 0.02 g / m ² was applied at 10 mL / m ² using a bar coater. Drying was performed for 6 minutes under the condition that all rollers and transporting devices in the drying zone were controlled at 115 ° C. to form an undercoat layer.

(Coating of antistatic layer)
A dispersion of fine particles of tin oxide-antimony oxide composite having an average particle size of 0.005 μm (specific resistance 5 Ω · cm, secondary aggregated particle size of about 0.08μm) 0.2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02g / m 2, polyoxyethylene -p- nonylphenol (polymerization 10) 0.005 g / m ² and resorcin 0.22 g / m ² were applied and dried to form an antistatic layer.

(Coating of sliding layer)
On the antistatic layer, diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O ) A ₁₆ H (9 mg / m ² ) mixture was applied. This mixture was melted in xylene / propylene glycol monomethyl ether (1/1) at 105 ° C., poured and dispersed in normal temperature propylene glycol monomethyl ether (10-fold amount), and then dispersed in acetone (average The particle size was 0.01 μm) and then added. Silicon dioxide particles (0.3 μm) were added as a matting agent so as to be 15 mg / m ² . After coating, the roller and the conveying device in the drying zone were dried for 6 minutes under the condition where the temperature was controlled at 115 ° C. to form a sliding layer. The sliding layer has a dynamic friction coefficient of 0.06 (measured at 5 mmφ stainless hard ball, load 100 g, speed 6 cm / min), static friction coefficient 0.07 (measured by the clip method), and dynamic friction between the outermost layer on the surface and the sliding layer on the back surface. The coefficient was 0.12, indicating excellent characteristics.

(Formation of cured resin layer)
Furthermore, after applying a methyl ethyl ketone solution containing 20 to 30% by mass of an acrylate derivative with a polymerization initiator added on the sliding layer in a nitrogen atmosphere in which the oxygen concentration is controlled to 3% or less, the thickness is 1 to 40 μm, A cured resin layer was formed by irradiation with UV light.

<3. Formation of barrier layer and organic layer>
(Formation of barrier layer)
A barrier layer was formed on the primer layer. For forming the barrier layer, a roll-to-roll sputtering apparatus (1) shown in FIG. 1 was used. This apparatus has a vacuum chamber (2), and a drum (3) for cooling the plastic film (6) in contact with the surface is disposed at the center thereof. In addition, a delivery roll (4) and a take-up roll (5) for winding the plastic film (6) are disposed in the vacuum chamber (2). The plastic film (6) wound around the feed roll (4) is wound around the drum (3) via the guide roll (7), and further the plastic film (6) is rolled (5) via the guide roll (8). Wrapped around. As a vacuum exhaust system, the exhaust in the vacuum chamber (2) is always performed from the exhaust port (9) by the vacuum pump (10). As a film forming system, a target (not shown) is mounted on a cathode (12) connected to a DC-type discharge power source (11) to which pulse power can be applied. The discharge power source (11) is connected to a controller (13), and the controller (13) adjusts the gas flow rate to be supplied to the vacuum chamber (2) through the pipe (15) while adjusting the reaction gas introduction amount. Connected to the unit (14). The vacuum chamber (2) is configured to be supplied with a discharge gas at a constant flow rate (not shown).

Si was set as a target, and a pulse application type DC power source was prepared as a discharge power source (11). The film prepared above was placed on a feed roll (4) as a plastic film (6) and passed to a take-up roll (5). After completing the preparation of the base material to the sputtering apparatus (1), the door of the vacuum chamber (2) was closed, the vacuum pump (10) was started, and vacuuming and cooling of the drum were started. When the ultimate pressure reached 4 × 10 ⁻⁴ Pa and the drum temperature reached 5 ° C., the plastic film (6) started to run. Argon was introduced as a discharge gas, the discharge power source (11) was turned on, plasma was generated on the Si target at a discharge power of 5 kW and a film formation pressure of 0.3 Pa, and pre-sputtering was performed for 3 minutes. Thereafter, oxygen was introduced as a reaction gas. After the discharge was stabilized, the amounts of argon and oxygen gas were gradually reduced to lower the film forming pressure to 0.1 Pa. After confirming the stability of discharge at 0.1 Pa, a silicon oxide film was formed for a certain period of time. After completion of the film formation, the vacuum chamber (2) was returned to atmospheric pressure to form a silicon oxide film, which was taken out as a barrier layer.

(Formation of organic layer)
To a solution in which tetraethylene glycol diacrylate, caprolactone acrylate, and tripropylene glycol monoacrylate are mixed at a weight ratio of 7: 1.2: 1.4, a radical initiator (Irgacure 651, manufactured by Ciba Specialty Chemicals) is added. 1% by mass was added and dissolved in a solvent, and the resulting coating solution was applied onto the barrier layer of the film prepared above, dried and then cured by UV irradiation to form an organic layer having a thickness of about 1 μm. .

(Lamination of barrier layer and organic layer)
The above-described barrier layer forming step and organic layer forming step were alternately repeated to prepare a gas barrier film 3 in which three layers each of a barrier layer and an organic layer were laminated.
Gas barrier films 1, 2, 4 to 10 were prepared by the same method by changing the material of the support and the presence or absence of the antistatic layer as shown in Table 1.

<4. Manufacture of organic EL elements>
Using each of the gas barrier films 1 to 10, organic EL elements were produced according to the following procedure.
A gas barrier film was introduced into the vacuum chamber, and a transparent electrode made of an IXO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering using an IXO target. Aluminum lead wires were connected from the transparent electrode (IXO) to form a laminated structure.
The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: solid content 1.3 mass%), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thick A hole-transporting organic thin film layer having a thickness of 100 nm was formed and used as a substrate X.
On the other hand, using a spin coater, a coating solution for a light-emitting organic thin film layer having the following composition was formed on one side of a temporary support made of polyethersulfone (Sumitomo Bakelite Co., Ltd., Sumilite FS-1300) having a thickness of 188 μm. By coating and drying at room temperature, a 13 nm thick luminescent organic thin film layer was formed on the temporary support. This was designated as transfer material Y.
Polyvinylcarbazole (Mw = 63000, manufactured by Aldrich) 40 parts by mass Tris (2-phenylpyridine) iridium complex (orthometalated complex) 1 part by mass Dichloroethane 3200 parts by mass

The luminescent organic thin film layer side of the transfer material Y is superimposed on the upper surface of the organic thin film layer of the substrate X, heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and the temporary support is attached. By peeling off, a light-emitting organic thin film layer was formed on the upper surface of the substrate X. This was designated as substrate XY.
Further, a patterned evaporation mask (a mask with a light emission area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) having a thickness of 50 μm cut into 25 mm square. Al was evaporated in a reduced pressure atmosphere of 1 mPa to form an electrode having a film thickness of 0.3 μm. Using an Al ₂ O ₃ target by DC magnetron sputtering, the Al ₂ O ₃ was deposited in the same pattern as the Al layer and the thickness of 3 nm. An aluminum lead wire was connected from the Al electrode to form a laminated structure. A coating solution for an electron transporting organic thin film layer having the following composition is coated on the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours to thereby transport an electron having a thickness of 15 nm. An organic thin film layer was formed on LiF. This was designated as substrate Z.
Polyvinyl butyral 2000L (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.) 10 parts by mass Electron transporting compound having the following structure 20 parts by mass

１−ブタノール： ３５００質量部

1-butanol: 3500 parts by mass

  Using the substrates XY and Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL element was obtained by bonding.

When the obtained organic EL element was made to emit light by applying a direct current using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.), the light emission was good.
After the device was created, it was left to stand at 25 ° C. and 75% relative humidity for 1 month, and light was emitted in the same manner. The area ratio of the entire light emitting portion (non-light emitting portion was a dark spot) was measured using a microanalyzer manufactured by Pola Digital Japan. Asked. The results were as shown in the following table.

ＰＥＴ＝（東レ製、ルミラー：熱膨張係数１５ｐｐｍ／℃）
ＰＥＮ＝（DuPont-Teijin製、Ｑ６５Ａ：熱膨張係数２０ｐｐｍ／℃）
ポリイミド＝（宇部興産製、ユーピレックス：熱膨張係数２０ｐｐｍ／℃）
ポリエステル＝（ユニチカ製、Ｕ−１００：熱膨張係数８０ｐｐｍ／℃）
ＰＣ＝（帝人、ピュアエース：熱膨張係数７０ｐｐｍ／℃）

PET = (Toray, Lumirror: thermal expansion coefficient 15ppm / ° C)
PEN = (DuPont-Teijin, Q65A: coefficient of thermal expansion 20 ppm / ° C.)
Polyimide = (Ube Industries, Upilex: coefficient of thermal expansion 20ppm / ° C)
Polyester = (Unitika, U-100: coefficient of thermal expansion of 80 ppm / ° C.)
PC = (Teijin, Pure Ace: coefficient of thermal expansion 70 ppm / ° C)

  As is clear from Table 1, the organic EL device using the gas barrier film satisfying the conditions of the present invention showed good performance even after being stored under high humidity.

  The gas barrier film of the present invention has extremely high gas barrier properties while being lightweight. For this reason, the gas barrier film of this invention can be effectively used for an organic EL element and a liquid crystal display element. In addition, the gas barrier film of the present invention has excellent optical performance and high durability. For this reason, this invention has high industrial applicability.

It is a schematic explanatory drawing of the sputtering apparatus of a roll to roll system.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sputtering apparatus 2 Vacuum tank 3 Drum 4 Delivery roll 5 Take-up roll 6 Plastic film 7 Guide roll 8 Guide roll 9 Exhaust port 10 Vacuum pump 11 Discharge power supply 12 Cathode 13 Controller 14 Gas flow rate adjustment unit 15 Piping

Claims (4)

On the support, the barrier layer and the organic layer containing an inorganic substance are alternately provided at least one layer at a time, and on at least one surface of the support, an antistatic layer, a cured resin layer, an antireflection layer, A gas barrier film having at least one layer selected from the group consisting of an easy adhesion layer, an antiglare layer and an optical compensation layer. The gas barrier film according to claim 1, wherein the support has a thermal expansion coefficient of 30 ppm / ° C. or less. The organic electroluminescent element using the gas barrier film of Claim 1 or 2. A liquid crystal display element using the gas barrier film according to claim 1.

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