JP2011143550A - Gas-barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic lamination layer type gas-barrier film that is superior in water vapor-barrier properties and has good adhesion between an organic layer and an inorganic layer. <P>SOLUTION: The gas-barrier film includes a gas-barrier layer having the inorganic layer made of silicon oxide, which is obtained by applying and curing at least two polysilazane layers, and the organic layer of at least one layer on at least one side of a plastic film, wherein the difference in film density of each layer of the inorganic layer is 0.15-0.80, and the organic layer contains nano-particles. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a gas barrier film, in particular, to a gas barrier film having excellent barrier layer adhesion and low water vapor and transmittance, and further to an environmentally sensitive device using this gas barrier film, particularly an organic EL element (organic electroluminescent element). The present invention relates to a gas barrier film used for the image display element.

  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 film is used for wrapping articles, food, It has been widely used as a packaging application for preventing alteration of industrial articles and pharmaceuticals.

  In recent years, in the fields of liquid crystal display elements, organic EL elements, and the like, plastic film substrates are being used instead of glass substrates that are heavy and easily broken. Since the plastic film substrate can be applied to a roll-to-roll method, it is advantageous in terms of cost. However, there is a problem that the plastic film substrate is inferior in water vapor barrier property as compared with the glass substrate. For this reason, when a plastic film substrate is used for a liquid crystal display element, water vapor enters the liquid crystal cell and a display defect occurs.

In order to solve this problem, it is known to use a gas barrier film in which a water vapor barrier layer is formed on a plastic film. As gas barrier films, there are known those obtained by vapor-depositing silicon oxide on a plastic film (for example, see Patent Document 1) and those obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). It has a barrier property that the permeability is about 1 g / m ² / day.

However, a substrate for use in solar cells or the like is required to have a higher water vapor barrier property. As a means for meeting this requirement, a technique for realizing a water vapor transmission rate of less than 0.1 g / m ² / day by using a laminate of an organic layer and an inorganic layer as a gas barrier layer (for example, Patent Documents 3 to 5) And a technique (Patent Document 6) that realizes excellent gas barrier properties by laminating a plurality of organic / inorganic gas barrier layers (barrier stacks). However, the organic-inorganic laminated gas barrier film disclosed here has problems that the gas barrier property is not always sufficient and that the organic layer and the inorganic layer are easily peeled off by mechanical stress.

Japanese Examined Patent Publication No. 53-12953 (pages 1 to 3) JP 58-217344 A (pages 1 to 4) JP 2003-335880 A JP 2003-335820 A JP 2003-327718 A US Pat. No. 6,413,645

  As described above, a technique for achieving both high gas barrier properties and sufficient adhesion of the gas barrier layer has not been provided, and it has been desired to provide a gas gas barrier film in which these are compatible.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic / inorganic laminate type gas barrier film having excellent water vapor barrier properties and good adhesion between an organic layer and an inorganic layer. There is to do.

  The above object of the present invention can be achieved by the following constitution.

1. A gas barrier film comprising an inorganic layer composed of silicon oxide and at least one organic layer coated with at least two layers of polysilazane and cured on at least one surface of the plastic film, wherein the inorganic layer comprises: A gas barrier film, wherein the difference in film density of each layer is 0.15 to 0.80 (g / cm ³ ), and the organic layer contains nanoparticles.

2. Among the inorganic layers, at least one inorganic layer has a film density of 1.40 to 2.05 (g / cm ³ ), and at least one other inorganic layer has a film density of 1. 55~2.20 (g / cm ³⁾ in and, and, on the one difference in film density of each layer of the inorganic layer is characterized in that it is a 0.15~0.80 (g / cm ³⁾ The gas barrier film as described.

  3. 3. The gas barrier film as described in 1 or 2 above, wherein the inorganic layer has a single layer thickness of 10 nm to 1000 nm.

4). Any one of the above 1-3, wherein the nanoparticles are metal compounds composed of at least one selected from Al ₂ O ₃ , CaO, SrO, BaO and MgO particles having a sphere equivalent diameter of 1 to 100 nm. The gas barrier film according to Item.

  5. The gas barrier film according to any one of 1 to 4, wherein a plurality of the gas barrier layers are formed.

  ADVANTAGE OF THE INVENTION According to this invention, the water-vapor barrier property is excellent and the organic-inorganic laminated | stacked gas barrier film with the favorable adhesiveness between an organic layer and an inorganic layer can be provided.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.

The present invention relates to a gas barrier film comprising, on at least one surface of a plastic film, a gas barrier layer having an inorganic layer made of silicon oxide coated with at least two layers of polysilazane and cured, and at least one organic layer. The difference in film density of each layer of the inorganic layer is 0.15 to 0.80 (g / cm ³ ), and the organic layer contains nanoparticles.

In the present invention, in particular, the difference in film density between the inorganic layers is 0.15 to 0.80 (g / cm ³ ), and by containing nanoparticles in the organic layer, the water vapor barrier property is excellent. In addition, an organic / inorganic laminate type gas barrier film having good adhesion between the organic layer and the inorganic layer can be obtained.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail.
[Layer structure of gas barrier film]
The gas barrier film of the present invention has the organic layer of the present invention and the inorganic layer of the present invention on at least one surface of a plastic film. The inorganic layer of the present invention is composed of an inorganic layer made of silicon oxide obtained by applying and curing at least two layers of polysilazane. The difference in film density between the two inorganic layers is 0.15 to 0.80 (g / cm ³ ).

  The order of lamination of the organic layer of the present invention and the inorganic layer of the present invention constituting the gas barrier film of the present invention may be configured in any order. The gas barrier layer having such characteristics may be provided only on one side of the plastic film, or may be provided on both sides. When provided on both sides, the two gas barrier layers may have the same configuration or different configurations. Further, a gas barrier layer may be further laminated.

  The organic layer of the present invention has a defect such as crystal grain boundaries, pinholes, cracks (microcracks), etc. of the inorganic layer of the present invention and prevention of diffusion after the formation of the gas dissolved in the polymer of the organic layer of the present invention. The nanoparticles of the present invention are contained in the organic layer. This pore phenomenon can be eliminated by “filling in” pinholes, cracks and the like in the inorganic layer of the present invention using the nanoparticles of the present invention. The nanoparticle of the present invention has two roles, and not only plugs cracks and pinholes, but also reacts with moisture and oxygen to be taken into its own particles, and it is presumed that gas barrier performance is improved.

Below, the plastic film and each layer which comprise a gas barrier film are demonstrated in detail.
[Plastic film]
The plastic film (also referred to as a resin film) of the present invention is preferably a plastic film having a smooth layer.

  Next, the plastic film having a smooth layer used in the present invention will be described.

  The plastic film (support) of the plastic film having a smooth layer is not particularly limited as long as it is formed of an organic material capable of holding a gas barrier layer having a gas barrier property described later.

  For example, acrylic ester, methacrylate ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP) , Polystyrene (PS), nylon (registered trademark) (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide and other resin films, silsesquioxy having an organic-inorganic hybrid structure A heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having Sun as a basic skeleton, and a resin film formed by laminating two or more layers of the above resin can be used. In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, inorganic layer, In terms of adhesion to the gas barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  The resin film support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, it is possible to make a transparent back sheet for a solar cell, so that it can be a transparent substrate such as a solar cell element. Because it becomes.

  Moreover, the unstretched film may be sufficient as the resin film support body using the resin etc. which were mentioned above, and a stretched film may be sufficient as it.

  The resin film support used in the present invention can be produced by a conventionally known general method. For example, an unstretched support that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the support, it is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  In the resin film support according to the present invention, corona treatment may be performed before forming the gas barrier film.

Furthermore, an anchor coat agent layer may be formed on the surface of the support according to the present invention for the purpose of improving the adhesion with the gas barrier film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).
(Smooth layer)
The smooth layer of the present invention flattens the rough surface of the transparent resin film support with protrusions or the like, or fills the irregularities and pinholes generated in the transparent inorganic compound layer with the protrusions present on the transparent resin film support. Provided for flattening. Such a smooth layer is basically formed by curing a photosensitive resin.

  As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  The composition of the photosensitive resin contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, mihi -Ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, Examples include a combination of a photoreducible dye such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  Solvents used when forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. When the value is larger than the lower limit of this range, the coating property is improved when the coating means comes into contact with the surface of the smooth layer in a coating method such as a wire bar or a wireless bar at the stage of coating a silicon compound described later. It is preferable that it is not damaged. Moreover, when smaller than the upper limit of this range, it is preferable from a viewpoint which can uneven | corrugate after apply | coating a silicon compound.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

Additive to smooth layer One of the preferred embodiments is a reactive silica particle (hereinafter, also simply referred to as “reactive silica particle”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin. ). Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm. The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. Addition of 20% or more improves adhesion with the gas barrier layer. Further, if it is 60% or less, the viewpoint of suppressing the occurrence of cracks when the film is bent or heat-treated, and the influence on the optical properties such as transparency and refractive index of the back sheet for solar cells. To preferred.

  In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

The thickness of the smooth layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer has a high transparency. When the film is provided only on one surface of the molecular film, curling of the smooth film can be easily suppressed.
(Bleed-out prevention layer)
The bleed-out prevention layer is for the purpose of suppressing the phenomenon that when the plastic film having a smooth layer is heated, unreacted oligomers migrate to the surface from the plastic film support and contaminate the contact surface. And provided on the opposite surface of the support having a smooth layer.

  The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  The unsaturated organic compound having a polymerizable unsaturated group as a hard coat agent that can be included in the bleed-out prevention layer is a polyunsaturated organic having two or more polymerizable unsaturated groups in the molecule. Examples thereof include a compound, or a unitary unsaturated organic compound having one polymerizable unsaturated group in the molecule.

  Examples of polyunsaturated organic compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropante La (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of the monounsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxy) Ethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than mass parts, more preferably not more than 16 mass parts.

  The bleed-out preventing layer of the present invention may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicone resin etc. are mentioned.

  Moreover, as ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material which mixed 1 type (s) or 2 or more types, such as a photopolymerizable prepolymer or a photopolymerizable monomer. Things can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  As photopolymerization initiators, acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) Examples include -1-propane, α-acyloxime ester, and thioxanthone.

  The bleed-out prevention layer as described above is mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. It becomes possible to make it easy to suppress curling when the surface is provided.
<Gas barrier layer>
The gas barrier layer of the present invention has an inorganic layer of the present invention composed of silicon oxide obtained by applying and curing at least two layers of polysilazane and at least one organic layer of the present invention.
[Inorganic layer]
The inorganic layer of the present invention is an inorganic layer made of silicon oxide obtained by applying and curing at least two layers of polysilazane, and the difference in film density between the inorganic layers is 0.15 to 0.80 (g / cm ^3). ). It is preferable that it is 0.40-0.80 (g / cm < ³ >).

Among the inorganic layers, at least one inorganic layer has a film density of 1.40 to 2.05 (g / cm ³ ), and at least one other inorganic layer has a film density of 1. It is preferable that it is 55-2.20 (g / cm < ³ >), and the difference of the film density of each layer of the said inorganic layer is 0.15-0.80 (g / cm < ³ >).

  The inorganic layer of the present invention is an inorganic layer made of silicon oxide coated with polysilazane and cured, and is obtained by dissolving polysilazane in a solvent to prepare a coating composition, which is coated and then cured. As the polysilazane, a commercially available product such as ALCEDAR COAT manufactured by Clariant Japan Co., Ltd. may be used, or it may be appropriately diluted with a solvent.

  The film density of the inorganic layer of the present invention is adjusted by controlling conditions such as thermal reaction, photoreaction, reaction rate acceleration by a catalyst, etc. from the properties of polysilazane. For example, it describes as an example in photoreaction.

Curing of polysilazane (enhancement of density) is achieved by successful conversion in a very short time in a single step by initiating the oxidative conversion of the polysilazane skeleton into a three-dimensional SiO _x network directly with VUV photons. Is called. The mechanism of this conversion process is that in the range of penetration depth of VUV photons, the Si—N bond is broken and the -SiH ₂ —NH— component is so strong that layer conversion occurs in the presence of oxygen and water vapor. This can be explained by being excited by absorption of VUV photons.

  Suitable radiation sources in the present invention include an excimer radiator having a maximum emission at about 172 nm, a low pressure mercury vapor lamp having an emission line at about 185 nm, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and about 222 nm. Excimer lamp with maximum emission.

Using a radiation source having a radiation component with a wavelength of 180 nm or less, for example a Xe ₂ ^* excimar radiator having a maximum emission at about 172 nm, a high absorption of these gases in the above wavelength range in the presence of oxygen and / or water vapor. Ozone and oxygen and hydroxyl radicals are generated very efficiently by photolysis because of the modulus, which promotes the oxidation of the polysilazane layer. However, both mechanisms, i.e., the cleavage of Si-N bonds and the action of ozone, oxygen radicals and hydroxyl radicals, can only occur after VUV radiation reaches the surface of the polysilazane layer.

  Therefore, in order to apply the highest possible dose of VUV radiation on the surface of the layer, in some cases the VUV treatment path is replaced by nitrogen and by supplying oxygen and water vapor in a tunable manner as described above. It is necessary for the above wavelength range to reduce the oxygen and water vapor concentrations of the radiation path length accordingly.

  Solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon hydrocarbon solvents, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, aliphatic ethers, and alicyclic ethers. The concentration of the solution is preferably 1 to 50% by mass in terms of solid content.

  As a coating method, general solution coating methods such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and slide coating can be used.

  A cured silica film (inorganic layer) is obtained by applying heat treatment after applying polysilazane, and the temperature of the heat treatment is preferably 120 ° C. or lower. When the heat treatment is performed at 120 ° C. or lower, it is preferable from the viewpoint of preventing the plastic film from being deformed or the strength of the plastic film from being deteriorated. However, the heat treatment temperature can be appropriately set depending on the heat resistance of the plastic film to be used. The heating atmosphere may be either oxygen or air.

The polysilazane is preferably cured in a moist heat atmosphere. The humidity is not particularly limited, but is preferably 10 to 100%, more preferably 50 to 90%, and particularly preferably 60 to 80% in terms of relative humidity. The temperature is effective at room temperature or higher, but room temperature to 120 ° C is preferable, and 50 to 100 ° C is particularly preferable. Although heat processing time is not specifically limited, 10 minutes-6 hours are preferable, and 30 minutes-4 hours are especially preferable. When the curing is sufficient, it is preferable from the viewpoint that the conversion from the Si—N bond in the polysilazane to the Si—O bond proceeds sufficiently and a function as a barrier property is exhibited. The bond number ratio (Si—O / Si—N) of Si—O bonds and Si—N bonds in the cured film is preferably 2.0 or more, and more preferably 5.0 or more. Incidentally, Si-O bonds and Si-N bonds is a chemical bond constituting a cured film can be confirmed by infrared absorption spectrum, the specific absorption peaks around 1080 cm ^-1 and 860 cm ^-1, respectively can be seen , Each peak intensity ratio can be calculated.

As thickness of the inorganic layer (polysilazane cured film) of this invention, 10-2000 nm is preferable and 10-1000 nm is more preferable. This range is preferable from the viewpoint of preventing the occurrence of cracks.
(First inorganic layer, second inorganic layer)
In the present invention, at least two inorganic layers of the present invention included in the gas barrier layer have a difference in film density of each layer of 0.15 to 0.80 (g / cm ³ ).

In the inorganic layer of the present invention, for example, when having a first inorganic layer and a second inorganic layer, the second inorganic layer is composed of an inorganic substance (polysilazane cured film) whose film density is higher than the film density of the first inorganic layer. ing. If the film density is low, sufficient gas barrier properties cannot be obtained. By increasing the film density, the film becomes dense and the gas barrier properties are improved. The inorganic material (polysilazane cured film) of the second inorganic layer is not particularly limited as long as it satisfies the film density condition. The film density difference between the first inorganic layer and the second inorganic layer of the inorganic layer of the present invention is 0.15 to 0.80 (g / cm ³ ), and is 0.40 to 0.80 (g / cm ³ ). Preferably there is. If the film density difference is too small, the gas barrier property of the inorganic layer itself may not be sufficiently obtained. Conversely, if the film density difference is too large, peeling or cracking between the inorganic layers tends to occur. The film density of the second inorganic layer is preferably 2.20 (g / cm ³ ) or less, and more preferably 2.10 (g / cm ³ ) or less. In addition, the film density said here is measured by the X-ray reflectivity measuring method. Specifically, the X-ray generation source targets copper and operates at 50 kV-300 mA. X-rays monochromatized with a multilayer mirror and a Ge (111) channel cut monochromator are used. The measurement was performed using the software ATX-Crystal Guide Ver. 6.5.3.4, halved, after alignment adjustment, 2θ / ω = 0 ° to 1 ° from 0.002 ° / step to 0.05 ° / min. Scan with. After measuring the reflectance curve under the above measurement conditions, GXRR Ver. It can be determined using 2.1.0.0 analysis software.

  The thickness of the second inorganic layer is preferably 10 to 1000 nm, and more preferably 20 to 200 nm.

The thickness of the single layer of the inorganic layer of the present invention is preferably 10 nm to 1000 nm, and more preferably 150 nm to 200 nm. If it is said range, it will be hard to be influenced by a defect part and the part with the low density between crystals, and high gas barrier property will be acquired. Further, even when it is deformed, the destruction of the inorganic layer can be reduced, which is preferable in practice.
[Functional layer]
Furthermore, the gas barrier film of the present invention may be provided with various functional layers in addition to the inorganic layer of the present invention and the organic layer of the present invention. Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and a light extraction efficiency improving layer; a mechanical functional layer such as a hard coat layer and a stress relaxation layer; an antistatic layer and a conductive layer. An electric functional layer such as: an antifogging layer; an antifouling layer; a layer to be printed, and the like. These functional layers do not impair the effects of the present invention between the plastic film, the inorganic layer of the present invention, the organic layer of the present invention, or the opposite surface of the plastic film on which the inorganic layer of the present invention is installed. You may install in the range and may include the heat processing process before film-forming hardening similarly to the organic layer of this invention.

  Furthermore, the gas barrier having the gas barrier layer of the present invention in which at least the inorganic layer of the present invention and the organic layer of the present invention are laminated on the surface of the plastic film opposite to the surface on which the gas barrier layer satisfying the conditions of the present invention is formed. A conductive laminate layer can also be provided. The gas barrier laminate layer prevents stress concentration and breakage to the barrier layer by suppressing the dimensional change of the gas barrier film by preventing the intrusion of water molecules from the opposite surface of the film, resulting in increased durability. It has the characteristics.

The organic layer of the present invention described above, the first inorganic layer of the present invention, the second inorganic layer of the present invention, the functional layer and other thicknesses are all arbitrarily adjusted by adjusting the coating solution concentration and coating speed. Can do.
[Organic layer]
The organic layer of the present invention is preferably composed of a curable resin.

  A curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays or electron beams. Specifically, it is an unsaturated double bond such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a single structure. Or a polymerizable functional group such as an epoxy group. Among these, an acrylic resin containing an acryloyl group is particularly preferable. The radiation curable resin may be one kind of resin or a mixture of several kinds of resins, but an acrylic resin having two or more acryloyl groups in a molecule or unit structure may be used. preferable. Examples of such polyfunctional acrylate resins include, but are not limited to, urethane acrylates, ester acrylates, epoxy acrylates, and the like.

  When using the ultraviolet curing method, a known photopolymerization initiator is used in combination with the aforementioned radiation curable resin. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959 Irgacure 907, Irgacure 369, Irgacure, commercially available from Ciba Japan. 379, Irgacure 819, etc.), Darocur series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, commercially available from Sartomer) And Ezacure TZT).

The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more. Since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. In addition, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

  In order to further strengthen the interaction with the polymer molecule, a hydrolyzate of alkoxysilane or a silane coupling agent may be mixed with the radiation curable resin. As the silane coupling agent, one having a hydrolyzable reactive group such as a methoxy group, an ethoxy group, or an acetoxy group and the other having an epoxy group, a vinyl group, an amino group, a halogen group, or a mercapto group. Preferably, in this case, those having a vinyl group having the same reactive group are particularly preferably used for fixing to the main component resin. For example, KBM-503, KBM-803 of Shin-Etsu Chemical Co., Ltd., Nippon Unicar Co., Ltd. A-187 made by) or the like is used. These addition amounts are preferably 0.2 to 3% by mass.

  Furthermore, for the purpose of improving the adhesion with the inorganic layer of the present invention, it is desirable to mix an acrylate or methacrylate having a phosphate group or a phosphate ester group with the curable resin constituting monomer. The amount to be mixed is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass. Examples of acrylates or methacrylates having phosphoric acid groups or phosphoric acid ester groups include KAYAMER series manufactured by Nippon Kayaku Co., Ltd., Phosmer series manufactured by Unichemical Co., Ltd., and light ester P- manufactured by Kyoeisha Chemical Co., Ltd. 1M, P-2M and the like.

  As a coating method of the organic layer, a normal solution coating method can be exemplified. Examples of the solution coating method include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or US Pat. No. 2,681,294. It can apply | coat by the extrusion coat method which uses the hopper as described in above.

  Examples of the method for forming the organic layer include a vacuum film forming method. Although there is no restriction | limiting in particular as a vacuum film-forming method, The flash evaporation as described in each specification, such as US Patent 4,842,893, 4,954,371, 5,032,461, etc. The method is preferred.

The film thickness of the organic layer of the present invention is not particularly limited, but if it is too thin, it will be difficult to obtain film thickness uniformity, and if it is too thick, cracks will be generated due to external forces and the barrier properties will tend to decrease. . From this viewpoint, the thickness of the organic layer is preferably 10 nm to 2000 nm, and more preferably 20 nm to 1000 nm.
<Nanoparticles>
The nanoparticles of the present invention can be appropriately selected from compounds having a water absorption function centering on alkaline earth metals. The water absorbent is preferably at least one selected from, for example, TiO ₂ , Al ₂ O ₃ , ZrO ₂ , ZnO, BaO, SrO, CaO, MgO, VO, CrO, MoO ₂ and LiMn ₂ O. Further, the water absorbent can be selected from metal elements such as Ti, Mg, Ba, and Ca.

  The particle size is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 1 to 10 nm in terms of a sphere equivalent diameter. If the particle size of the water absorbent is 1 to 100 nm in terms of a sphere equivalent diameter, it is preferable because transparency can be maintained and the amount of water absorption per unit mass is increased.

  Here, the “sphere equivalent diameter” means the diameter of a sphere when the particle size of the water absorbent is converted to a sphere having the same volume as that of the water absorbent.

The organic layer of the present invention described above, the first inorganic layer of the present invention, the second inorganic layer of the present invention, the functional layer and other thicknesses are all arbitrarily adjusted by adjusting the coating solution concentration and coating speed. Can do.
[Performance of gas barrier film]
The gas barrier film of the present invention exhibits excellent gas barrier properties. Water vapor permeability of the gas barrier film of the present invention can achieve the following 0.01g ^/ m 2 · day, preferably 0.005g ^/ m 2 · day or less, more preferably 0.003g ^/ m 2 · day Hereinafter, it is more preferably 0.001 g / m ² · day or less. In the gas barrier film of the present invention, the gas barrier layer exhibits excellent adhesion. That is, the adhesion between the organic layer of the present invention constituting the gas barrier layer and the inorganic layer of the present invention is excellent. Such excellent water vapor transmission rate and adhesion are maintained even after the gas barrier film is bent a plurality of times. Therefore, the gas barrier film of the present invention is suitably used for a flexible image display element and the like.
[Environmentally sensitive devices]
(Use of gas barrier film)
The gas barrier film of the present invention can be used for various applications. Especially, it can use preferably for an environmentally sensitive device.

The environment-sensitive device in the present invention refers to a device whose performance changes under the influence of substances present in the environment, such as oxygen and moisture, such as an image display element, an organic memory, an organic battery, and an organic solar battery. Can be mentioned. The image display element in the present invention means a circularly polarizing plate / liquid crystal display element, a touch panel, an organic EL element and the like. Details of each environmentally sensitive device will be described below.
(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film of the present invention as a substrate. In this case, the lamination is performed so that the slow axis of the λ / 4 plate 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. For example, those 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 substrate 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 the structure which consists of a film | membrane. Among these, the substrate of the present invention can be used as the upper transparent electrode substrate 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 type of the liquid crystal cell is not particularly limited, but more preferably a TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, VA (Vertical Aligned) type, EC type, Bt type, EC type, Br type. OCB type (Optically Compensated Bend) and CPA type (Continuous Pinwheel Alignment) are preferable.
(Touch panel)
The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.
(Organic EL device)
An organic EL element means an organic electroluminescence element. The gas barrier film of the present invention is useful as a sealing film for organic EL devices. The organic EL element has a cathode and an anode on a substrate, and an organic compound layer including a light emitting layer between both electrodes. Due to the nature of the light emitting element, at least one of the anode and the cathode is transparent.

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

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “part” or “%” in the examples represents “part by mass” or “% by mass”.

Example 1
(Support)
As the thermoplastic resin support, a 50 μm-thick polyester film (Tetron O3, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides was annealed at 170 ° C. for 30 minutes and used.
(Film having smooth layer and bleed-out preventing layer: production of support)
A bleed-out prevention layer was formed on one side and a smooth layer was formed on the opposite side of the polyester film by the following forming method to prepare a support.

(Formation of bleed-out prevention layer)
A UV curing organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the support, and the coating was applied with a wire bar so that the film thickness after drying was 4 μm, followed by curing conditions: 1.0 J / cm ² under air, a high pressure mercury lamp used, drying conditions; 80 ° C., subjected to cure for 3 minutes to form a bleedout-preventing layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the support, and the film was dried with a wire bar so that the film thickness after drying was 4 μm, and then drying conditions; After drying at 80 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 1.0 J / cm ² curing was performed to form a smooth layer.

  The maximum cross-sectional height Rt (p) representing the surface roughness at this time was 16 nm.

The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.
(Production of gas barrier film)
Next, on the smooth layer of the support sample provided with the smooth layer and the bleed out prevention layer obtained above (in the case of Sample 1-17, on the smooth layer and the bleed out prevention layer, both) The gas barrier layer is formed by performing the following formation of the low film density inorganic layers a to c, formation of the high film density inorganic layers D to G, and formation of the organic layer so as to have the layer configuration shown in Table 1. Gas barrier film samples 1-1 to 1-19 shown in Table 1 were prepared.
(1) Formation of low film density inorganic layers a to c <Formation of low film density inorganic layers a>
A silica film with a film thickness of 200 nm is obtained by applying a polysilazane coating solution (manufactured by Clariant Japan Co., Ltd., L110) with a wire bar and curing at 120 ° C. for 1 hour and at 95 ° C. and a relative humidity of 80% for 3 hours. And a low film density inorganic layer a was formed. The ratio of the number of Si—O bonds / the number of Si—N bonds determined from the intensity ratio of the infrared absorption spectrum was 8.5.
<Low film density inorganic layer b>
In the formation of the low film density inorganic layer a, the low film density inorganic layer b was formed by changing only the point that the curing treatment condition of the polysilazane coating film was 1 hour at 80 ° C. The ratio of the number of Si—O bonds / the number of Si—N bonds determined from the intensity ratio of the infrared absorption spectrum was 3.2.
<Low film density barrier layer c>
In the formation of the low film density inorganic layer a, the low film density inorganic layer c was formed by changing only the point that the curing condition of the polysilazane coating film was 1 hour at 65 ° C. The ratio of the number of Si—O bonds / the number of Si—N bonds determined from the intensity ratio of the infrared absorption spectrum was 1.7.
(2) Formation of high film density inorganic layers D to G <Formation of high film density inorganic layer D>
A 20% by weight dibutyl ether solution of perhydroxypolysilazane (PHPS) as a high-film density inorganic layer coating solution was dried at AZ Electronic Materials Co., Ltd. Aquamica NAX120-20 wireless bar, resulting in a film thickness of 300 nm after drying. Thus, a sample coated and dried was obtained.

(Plasma treatment)
The sample obtained above was treated in an atmosphere of a temperature of 85 ° C. and a humidity of 55% RH for 30 minutes, and then plasma treatment was performed under the following conditions to form a high film density inorganic layer D.

  The support holding temperature during film formation was 120 ° C.

  The treatment was performed using a roll electrode type discharge treatment apparatus. A plurality of rod-shaped electrodes opposed to the roll electrode were installed in parallel with the sample (film) transport direction, power was applied to each electrode portion, and the coated surface was plasma-treated as follows.

  Here, the dielectric is a ceramic sprayed one (coated with 1 mm) together with the opposing electrodes. The electrode gap was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (80 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used.

Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 80 kHz, 3 W / cm ²
High frequency side power supply power: 13.56 MHz at 9 W / cm ²
The maximum cross-sectional height Rt (p) after the plasma treatment was 12 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

  The gas barrier film obtained as described above is etched in the depth direction from the surface of the high-density inorganic layer using a sputtering method, and the barrier layer is used using an XPS surface analyzer (X-ray electron spectroscopy). The atomic composition ratio of the high film density inorganic layer was measured every 10 nm with the outermost surface being 0 nm.

  There is no particular limitation on the XPS surface analyzer, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

  The ratio of Si and O from the surface of the high film density inorganic layer to the smooth layer was the following value. In addition, an average value is the value which averaged the measured value for every 10 nm from the high film density inorganic layer outermost surface to the interface of a smooth layer, and rounded off the 2nd decimal place.

Minimum: 2.2, Maximum: 2.5, Average: 2.4
A high-density inorganic layer D having a thickness of 200 nm was formed.
<Formation of high film density inorganic layers E, F, G>
Further, in the formation of the high film density inorganic layer D, the plasma treatment is changed to UV ozone treatment, and the treatment time is 12, 24, 48 hours while heating to 90 ° C., and the high film density inorganic having a film thickness of 200 nm is performed. Layers E, F, and G were formed, respectively.
<Formation of organic layer>
2-butyl-2-ethyl-propanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate BEPG-A), caprolactone 2-hydroxyethyl methacrylate phosphate (manufactured by Nippon Kayaku Co., Ltd., KAYAMER PM-21) ) 4.5 g, Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) 0.5 g, UV polymerization initiator (manufactured by Ciba Japan, trade name: Ciba Irgacure 907) 0.6 g, 2 -A mixed solution of 190 g of butanone and 3 g of nanoparticles of the type shown in Table 1 was applied using a wire bar so that the liquid thickness was 5 μm. After drying at room temperature for 2 hours, it is cured by irradiating with UV light from a high-pressure mercury lamp (accumulated dose of about ² J / cm ² ) in a chamber where the oxygen concentration is 0.45% by the nitrogen substitution method. A layer was formed. At this time, the film thickness was 500 nm ± 50 nm.
<Measurement of film density and film thickness of inorganic layer>
The film density and film thickness of the low film density inorganic layer (first inorganic layer) and the high film density inorganic layer (second inorganic layer) of each sample are measured by the X-ray reflectivity measurement method. Rigaku Co., Ltd.), using X-ray reflectivity analysis software GXRR, using interference of reflection at the interface with a difference in density between the surface of the layer and film thickness, film density, and surface / interface roughness Was measured.
<Evaluation>
<Evaluation of water vapor barrier properties>
Using a vacuum deposition device (JEOL-made vacuum deposition device JEE-400) on the inorganic layer side surface of each gas barrier film sample that has been bent 100 times at an angle of 180 degrees in advance so as to have a radius of curvature of 10 mm, A portion of the film sample other than the portion to be deposited (9 locations of 12 mm × 12 mm) was masked to deposit metallic calcium. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the gas barrier film sample. After sealing with aluminum, the vacuum state is released, and in a dry nitrogen gas atmosphere, the silica sealing side (through Nagase Chemtex Co., Ltd.) is sealed on quartz glass with a thickness of 0.2 mm via a sealing UV curable resin (manufactured by Nagase ChemteX). An evaluation cell was produced by facing and irradiating with ultraviolet rays.

  The obtained sample with both sides sealed was stored under high temperature and high humidity of 60 ° C. and 90% RH, and entered through the barrier defect of the plastic film with a barrier film based on the method described in JP-A-2005-283561. This is a measurement method that utilizes the reaction between moisture and calcium.Place a film specimen with a metallic calcium film on the inside in a constant temperature and humidity environment, and image the amount of calcium corroded by reaction with water vapor that permeated through the film. By measuring the water vapor permeation amount of the film by measuring the treatment, etc.), calculating the amount of water permeated into the cell from the corrosion amount of the calcium metal, and an index representing the water vapor barrier property based on the following evaluation criteria As shown.

In addition, in order to confirm that there is no permeation of water vapor other than from the gas barrier film sample surface, instead of the gas barrier film sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm was used as a comparative sample. The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.
(Evaluation criteria)
Less than 5: 1 × 10 ⁻⁵ g / m ² / day 4: 1 × 10 ⁻⁵ g / m ² / day or more, less than 1 × 10 ⁻⁴ g / m ² / day 3: 1 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g ^/ m 2 / day or more.
<Adhesion>
Bending test Each gas barrier film sample was formed into a cylindrical shape by bonding both ends with the gas barrier layer-formed side facing outside, and then a laminated film with two conveying rollers having a diameter of 12 mm applied with a tension of about 1 N between the two rollers. The roller film was rotated and conveyed for 60 minutes at 30 cm / min while paying attention so that the roller part completely contacted and the laminated film did not slip.
Measurement and evaluation of adhesion The adhesion of the barrier layer after the bending test described above was examined by a cross-cut peeling method in accordance with JIS (Japanese Industrial Standards) K5600-5-6 (ISO 2409). The evaluation value of adhesion is expressed as a ratio (percentage%) of the area where film destruction did not occur and is shown as an index representing adhesion. The larger the evaluation value, the higher the adhesion.

  As can be seen from Table 1, the barrier film of the present invention has excellent water vapor barrier properties, and further has excellent adhesion, and hardly deteriorates in performance under harsh environments.

  In the case of this invention, it turns out that the water vapor | steam barrier property is excellent and the organic-inorganic laminated | stacked gas barrier film with the favorable adhesiveness between an organic layer and an inorganic layer can be provided.

Example 2
(Production of gas barrier film)
On the support sample provided with the smooth layer and the bleed-out prevention layer obtained in Example 1, formation of the low film density barrier layer a described in Example 1 so as to have the layer structure described in Table 2, Formation of the low film density barrier layers d and e, formation of the high film density barrier layer D described in Example 1, formation of the following high film density barrier layers H and I, and formation of the organic layer described in Example 1. Then, gas barrier film samples 2-1 to 2-11 shown in Table 2 were produced.
<Formation of low-density inorganic layer d>
A silica film having a film thickness of 500 nm is obtained by applying a polysilazane coating solution (manufactured by Clariant Japan Co., Ltd., L110) with a wire bar and curing at 120 ° C. for 1 hour and at 95 ° C. and a relative humidity of 80% for 3 hours. The low-density inorganic layer d was formed. The ratio of the number of Si—O bonds / the number of Si—N bonds determined from the intensity ratio of the infrared absorption spectrum was 8.5.
<Formation of low-density inorganic layer e>
A silica film having a film thickness of 1060 nm was formed in the same manner as described above, and a low film density inorganic layer e was formed. The ratio of the number of Si—O bonds / the number of Si—N bonds determined from the intensity ratio of the infrared absorption spectrum was 8.4.
<Formation of high film density inorganic layers H and I>
The high film density inorganic layer H and the high film density inorganic layer I were formed in the same manner as the production of the high film density inorganic layer D except that the film thickness was 500 nm and 1060 nm.

  Table 2 shows the results of film thickness, film density, film density difference, water vapor barrier property, and adhesion obtained for the obtained gas barrier film sample in the same manner as in Example 1.

  As can be seen from Table 2, the barrier film of the present invention is excellent in water vapor barrier properties, and further has excellent adhesion and is less susceptible to performance degradation under harsh environments.

  In the case of this invention, it turns out that the water vapor | steam barrier property is excellent and the organic-inorganic laminated | stacked gas barrier film with the favorable adhesiveness between an organic layer and an inorganic layer can be provided.

Claims (5)

A gas barrier film comprising an inorganic layer composed of silicon oxide and at least one organic layer coated with at least two layers of polysilazane and cured on at least one surface of the plastic film, wherein the inorganic layer comprises: A gas barrier film, wherein the difference in film density of each layer is 0.15 to 0.80 (g / cm ³ ), and the organic layer contains nanoparticles. Among the inorganic layers, at least one inorganic layer has a film density of 1.40 to 2.05 (g / cm ³ ), and at least one other inorganic layer has a film density of 1. 55~2.20 (g / cm ³⁾ in and, and, according to claim 1, the difference in film density of each layer of the inorganic layer is characterized in that it is a 0.15~0.80 (g / cm ³⁾ The gas barrier film according to 1.   The gas barrier film according to claim 1, wherein the inorganic layer has a single layer thickness of 10 nm to 1000 nm. Wherein the nanoparticles, _Al 2 _O 3 equivalent spherical diameter 1~100nm, CaO, SrO, any one of the preceding claims, characterized in that a metal compound comprising at least one selected from BaO and MgO particles The gas barrier film according to one item.   The gas barrier film according to claim 1, wherein a plurality of the gas barrier layers are formed.