JP2014019056A - Film roll package and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide means for preventing moisture from being adsorbed onto a gas barrier film with time.SOLUTION: A film roll package comprises: a film roll including a winding core and a gas barrier film wound around by the winding core; and a packaging part including a wrapping material for wrapping the film roll. The gas barrier film includes a base material and a gas barrier layer and has a water vapor permeability of 1×10g/m/day or less.

Description

  The present invention relates to a film roll package and a manufacturing method thereof.

  Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for. By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.

  In recent years, such a gas barrier film that prevents permeation of water vapor, oxygen, and the like is being used in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL). In order to apply a gas barrier film to an electronic device, it is necessary to have flexibility, transparency, heat resistance, and the like. In addition, since electronic devices are particularly susceptible to moisture and the like, a high gas barrier property, for example, a gas barrier property comparable to a glass substrate is required.

As a gas barrier film that can be applied to an electronic device, for example, in Patent Document 1, a gas barrier layer having a laminated structure composed of a plurality of layers is laminated on one side or both sides of a base sheet. A gas barrier film is described in which at least a layer in contact with the base material sheet is an inorganic compound layer made of silicon oxycarbide or silicon oxynitride carbide among a plurality of constituent layers. Since the gas barrier film described in Patent Document 1 has high gas barrier performance (for example, the water vapor permeability of Examples 1 to 6 is 0.005 to 0.013 g / m ² / day), a transparent touch panel, It is described that it can be applied to electronic devices such as liquid crystal display elements, organic or inorganic EL display elements.

JP-A-2005-324406

  The gas barrier film is usually shipped as a product in the form of a film roll in which the gas barrier film is wound around a core. At this time, since the gas barrier film that can be applied to the electronic device has high gas barrier properties, it has been considered that the gas barrier film itself is hardly affected by moisture or the like. Therefore, until now, the gas barrier film has not been particularly studied for the influence of the storage environment.

  However, as a result of intensive studies by the present inventors, it has surprisingly been found that even gas barrier films having high gas barrier properties can adsorb moisture onto the gas barrier films over time. If such a gas barrier film adsorbing moisture is applied to an electronic device as it is, it may adversely affect the performance of the electronic device.

  Therefore, the present invention provides means for preventing the adsorption of moisture that may occur over time in the gas barrier film.

  As a result of diligent research, the present inventor has solved the above problems by forming a gas barrier film having a high gas barrier property into a film roll form and further packaging the film roll with a packaging material to form a film roll package. As a result, the present invention has been completed.

  That is, the said subject of this invention is achieved by the following means.

1. A film roll package including a roll and a film roll including a gas barrier film wound around the roll, and a packaging unit including a packaging material for wrapping the film roll, wherein the gas barrier film includes: A film roll package comprising a substrate and a gas barrier layer and having a water vapor transmission rate of 1 × 10 ⁻² g / m ² / day or less;
2. 2. The film roll according to 1, wherein the gas barrier film further has a resin layer having releasability, and the base material, the gas barrier layer, and the resin layer having releasability are arranged in this order. Packing body;
3. The film roll package according to 1 or 2, wherein the packaging material has a water vapor permeability of 1 g / m ² / day or less;
4). The film roll package according to any one of 1 to 3, wherein the dew point in the packing part is 10 ° C. or lower;
5. The film roll package according to any one of 1 to 4, wherein the packing section is packaged with two or more packaging materials;
6). The film roll package according to any one of 1 to 5, further comprising a hygroscopic material, wherein the hygroscopic material is packaged together with the film roll;
7). The film roll package according to any one of 1 to 6, wherein the core has hygroscopicity;
8). The film roll package according to any one of 1 to 7, wherein the material of the core is paper;
9. A step (1) for producing a gas barrier film by forming a gas barrier layer on a substrate, a step (2) for producing a film roll by winding the gas barrier film around a core, and the film roll And a step (3) of forming a packing part by packaging with a packaging material, wherein the gas barrier film has a water vapor transmission rate of 1 × 10 ⁻² g / m ^2. / Day or less, the manufacturing method;
10. The manufacturing method according to 9, wherein the winding in the step (2) is performed at a winding tension of 30 to 300 N / m;
11. The manufacturing method according to 9 or 10, wherein the step (1) further includes forming a resin layer having releasability on the surface of the gas barrier film.

  ADVANTAGE OF THE INVENTION According to this invention, the adsorption | suction of the water | moisture content which can arise in a gas barrier film over time can be prevented.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

According to an aspect of the present invention, there is provided a film roll package including a core and a film roll including a gas barrier film wound around the core, and a packing unit including a packaging material for packaging the film roll. Provided. In this case, the gas barrier film includes a base material and a gas barrier layer, and has a water vapor transmission rate of 1 × 10 ⁻² g / m ² / day or less.

  As described above, conventionally, gas barrier films have been thought to be less susceptible to moisture and the like. However, even if the gas barrier film has a high gas barrier property, moisture in the air may penetrate into the gas barrier layer over a long period of time, which may have an adverse effect when applied to an electronic device. is there.

  Generally, when moisture is adsorbed on a film or the like, the moisture can be removed by heating and drying. However, if the gas barrier film has a high gas barrier property, it is difficult to penetrate moisture into the gas barrier layer, but it may be difficult to remove the penetrated moisture. That is, it is considered that moisture is difficult to enter and difficult to escape. In addition, when the gas barrier film includes a resin having no heat resistance as a base material, baking performed at a high temperature cannot be applied. Furthermore, it is known that there are multiple moisture adsorption states (N. Hirashita et al., JJAP 32, 1787 (1993)), and moisture adsorbed by wet cleaning, etc. is easily adsorbed but easily desorbed. On the other hand, it is considered that moisture adsorbed over time cannot be easily desorbed by adsorbing to the film in a stable state that is more difficult to desorb.

  Therefore, in order to remove the water that has once entered the gas barrier layer, a heat-resistant substrate to which baking or the like can be applied is used, or the substrate is dried for a long time at a temperature that does not affect the performance. A heat-resistant substrate is generally expensive, and the types of applicable substrates are limited. Moreover, performing a long time drying before use has a problem from a viewpoint of productivity. From such a point of view, a means for preventing in advance the adsorption of moisture that may occur in the gas barrier film during storage or transportation is desired.

  On the other hand, according to the film roll package according to the present embodiment, it is possible to prevent moisture adsorption that may occur over time in the gas barrier film even when long-term storage or transportation is performed. .

<Film roll>
The film roll includes a core and a gas barrier film wound around the core.

[Core]
The winding core serves as a core for winding the gas barrier film, and has a function of preventing wrinkles of the wound gas barrier film.

  The material of the core that can be used is not particularly limited, and examples thereof include paper, wood, metal, resin, and fiber reinforced resin. Examples of the metal include iron, aluminum, copper, titanium, lead, zinc, gold, nickel, chromium, tin, silver, palladium, and platinum. Examples of the resin include polyethylene, polypropylene, vinyl chloride, ABS resin, epoxy resin, polyester resin, butadiene rubber, polystyrene, polyimide resin, polyamide resin, polyamideimide resin, acrylic resin, vinyl chloride, polyvinylidene chloride, and polyurethane resin. Can be mentioned. Examples of the fiber reinforced resin include glass fiber, carbon fiber, metal fiber, polyimide fiber, and aramid fiber. Of these, the core material is preferably hygroscopic (paper, wood, carbon fiber, etc.), and more preferably paper. As the paper tube, it is preferable to use a dust-proof treated paper tube with less fuzz that may cause foreign matters. The said material may be used independently or may be used in combination of 2 or more type.

  The shape of the core is not particularly limited, but is preferably cylindrical or columnar. Moreover, the level | step difference according to the thickness of the gas barrier film mentioned later may be provided in the surface of the said core. By having the step, it is possible to prevent the occurrence of winding deviation, film loss, and the like when the gas barrier film is wound.

  The size (outer diameter) of the core is not particularly limited, but is preferably 25 to 400 mm, more preferably 70 to 300 mm, and further preferably 150 to 200 mm.

  The moisture content of the core is preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and further preferably 0.3% by mass or less. A moisture content of 0.5% by mass or less is preferable because the humidity inside the package can be reduced. In the present specification, a value measured by a coulometric titration method using the Karl Fischer method is adopted as the moisture content value. More specifically, the moisture content is measured using a moisture measuring device CA-200 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) as the amount of water evaporated from the substrate when the substrate is heated from room temperature to 200 ° C. It is the value.

Modulus of the core is preferably at 200 kgf / mm ² or more, more preferably 500~7000kgf / mm ^2, further preferably 1500~7000kgf / mm ^2. When the elastic modulus of the core is 200 kgf / mm ² or more, the core is less likely to be deformed when the gas barrier film is wound, and the residual stress in the circumferential direction is reduced and the film surface is less likely to be wrinkled. To preferred. In this specification, the value measured by the three-point bending method of JIS K7171: 2008 is adopted as the value of the elastic modulus.

Linear expansion coefficient of the core is preferably less ^{10 × 10 -6 cm / cm /} ℃, more preferably not more than ^{5 × 10 -6 cm / cm /} ℃, 2 × 10 -6 cm / More preferably, it is not more than cm / ° C. A linear expansion coefficient of 10 × 10 ⁻⁶ cm / cm / ° C. or less is preferable because the film winding can be prevented from shifting. In addition, in this specification, the value measured by the following method shall be employ | adopted for the value of a linear expansion coefficient. Specifically, using EXSTAR TMA / SS6000 type thermal stress strain measuring device (manufactured by Seiko Instruments Inc.), the substrate to be measured was heated to 30-50 ° C. at 5 ° C./min in a nitrogen atmosphere, Maintain a temporary temperature. Then, it heats again to 30-150 degreeC at 5 degree-C / min, and measures the dimensional change of a base material by the tension mode (load 5g) at this time. A linear expansion coefficient is calculated | required from the said value.

[Gas barrier film]
The gas barrier film has a function of preventing gas permeation. In the present invention, the gas barrier film has a water vapor permeability of 1 × 10 ⁻² g / m ² / day or less, preferably 1 × 10 ⁻³ g / m ² / day or less, more preferably 5 × 10 ⁻⁴ g. / M ² / day or less. The gas barrier film includes a substrate and a gas barrier layer. The gas barrier layer is usually disposed on a substrate. Moreover, the said gas barrier layer may be arrange | positioned at both surfaces of the base material. In the present specification, “gas” mainly means water vapor. The “water vapor transmission rate” is a value measured based on JIS K7129: 2008 (temperature 40 ° C., relative humidity (RH) 90%) using PERMATRAN-W3 / 33 (manufactured by MOCON) according to the Mocon method. Shall be adopted.

(Base material)
The substrate has a function of holding the gas barrier layer.

  Although the base material which concerns on this invention is not specifically limited, It is preferable that it is a foldable film base material which has flexibility and permeability | transmittance.

  Specific examples of the substrate include polyolefin (PO) resins that are homopolymers or copolymers such as ethylene, propylene, and butene, non-quality polyolefin resins (APO) such as cyclic polyolefin, polyethylene terephthalate (PET), polyethylene- Polyester resins such as 2,6-naphthalate (PEN), nylon-6, nylon-12, polyamide (PA) resins such as copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) ) And the like, polyimide (pI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) Resin, Polyvinyl Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), Examples thereof include fluorine resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA).

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical reactive unsaturated compound, a resin composition comprising the acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as urethane acrylate, polyester acrylate, or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a laminate coating, as a resin base material.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON Corporation), ARTON of non-quality cyclopolyolefin resin film (manufactured by JSR Corporation), Pure Ace of polycarbonate film (manufactured by Teijin Limited), Konica Minolta of cellulose triacetate film Commercially available products such as Tack KC4UX, KC8UX (manufactured by Konica Minolta Opto), and polyethylene terephthalate film with clear hard coat layer (manufactured by Kimoto) can be preferably used.

  Moreover, the base material using the resin film may be an unstretched film or a stretched film.

  The base material using the resin film can be produced by a conventionally known general method. For example, an unstretched film 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. In addition, the unstretched film is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like in the flow (vertical axis) direction of the substrate or the base. A stretched film can be produced by stretching in the direction perpendicular to the flow direction of the material (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  The thickness of the substrate used in the present invention is preferably 5 to 500 μm, and more preferably 25 to 250 μm.

  Moreover, it is preferable that the base material used for this invention is transparent. If the substrate is transparent, it can be made a transparent functional film, and can be applied to substrates of electronic devices such as photoelectric conversion elements (solar cells).

  The substrate used in the present invention preferably has a linear expansion coefficient of 50 ppm / ° C. or less, and preferably 1 to 50 ppm / ° C. When the functional barrier film is applied to an electronic device such as a liquid crystal display (LCD) panel when the linear expansion coefficient of the base material is 50 ppm / ° C. or less, color misregistration or deformation of the base material due to environmental temperature changes, etc. Is preferable because it can be suppressed.

  The substrate according to the present invention preferably has a visible light (400 nm to 700 nm) light transmittance of 80% or more, and more preferably 90% or more. When the light transmittance is 80% or more, when a functional barrier film is applied to an electronic device such as a liquid crystal display (LCD) panel, it is preferable because high luminance can be obtained. In this specification, the value of the light transmittance is the incidence of visible light using a spectrophotometer (visible ultraviolet spectrophotometer UV-2500PC: manufactured by Shimadzu Corporation) in accordance with ASTM D-1003 standard. The average transmittance value in the visible light range calculated by measuring the total transmitted light amount with respect to the light amount is adopted.

  The substrate according to the present invention may be subjected to corona treatment.

  Moreover, the base material which concerns on this invention may form another layer (intermediate layer) suitably. For example, an anchor coat layer (an easy-adhesion layer) may be formed for the purpose of improving the adhesion of a hybrid layer or the like to the substrate surface. The anchor coating agent that can be used is not particularly limited, but a silane coupling agent is used from the viewpoint of obtaining a high adhesion by forming a thin film at a monomolecular level to a nano level and forming a molecular bond at the layer interface. Is preferred. In addition, a stress relaxation layer made of a resin or the like, a smoothing layer for smoothing the surface of the substrate, a bleedout prevention layer for preventing bleedout from the substrate or the like can be provided.

  Furthermore, a back coat layer may be provided on the substrate for the purpose of improving the curl balance of the gas barrier layer, device fabrication process resistance, handling suitability, and the like.

  When the intermediate layer is provided on the substrate, the gas barrier layer is usually disposed on the intermediate layer.

(Gas barrier layer)
The gas barrier layer has a function of imparting gas barrier performance to the gas barrier film.

Any gas barrier layer may be used as long as the water vapor permeability of the obtained gas barrier film is 1 × 10 ⁻² g / m ² / day or less.

  A specific example of the gas barrier layer is preferably a layer containing an inorganic substance. Examples of the inorganic substance include zinc disulfide, aluminum oxide, indium oxide, tin oxide, gallium oxide, indium tin oxide (ITO), aluminum-added zinc oxide (AZO), zinc-tin composite oxide (ZTO), aluminum nitride, carbonized Examples thereof include silicon, silicon oxide, silicon nitride, and silicon oxynitride. Of these, the inorganic material is preferably silicon oxide, silicon nitride, or silicon oxynitride.

  The inorganic material may be formed by modifying an inorganic precursor. The modification can be performed, for example, by irradiating the inorganic precursor with energy rays such as vacuum ultraviolet light. However, in this case, unmodified inorganic precursors and by-products may be contained together with the inorganic substance. Therefore, when forming an inorganic substance by modification | reformation of an inorganic precursor, it may become difficult to define uniquely the component contained in a gas barrier layer.

  The gas barrier layer may be a single layer or a laminate of two or more layers. When two or more layers are laminated, each layer may be composed of the same component or a layer composed of different components.

  When the gas barrier layer has a structure in which two or more layers are stacked, the gas barrier layer may have a layer containing an organic substance together with a layer containing an inorganic substance. When the layer containing an organic substance is disposed in contact with the layer containing an inorganic substance, defects such as micropores, minute cracks, and cracks that can occur in the layer containing the inorganic substance can be prevented.

  Examples of the organic material include acrylate-containing polymers and methacrylate-containing polymers.

  The thickness of the gas barrier layer is preferably 1 nm to 10 μm, more preferably 2 nm to 1 μm, and further preferably 5 to 600 nm. It is preferable that the gas barrier layer has a thickness of 1 nm or more because sufficient gas barrier properties can be obtained. On the other hand, it is preferable that the gas barrier layer is 10 μm or less because cracks are hardly generated in the gas barrier layer. In addition, when two or more gas barrier layers are laminated, it is preferable that the total film thickness (including a layer containing an organic substance) is within the above range. Moreover, when a gas barrier layer is formed in both surfaces, it is preferable that each film thickness exists in the said range.

(Protective layer)
You may provide a protective layer in a gas barrier film as needed.

  The protective layer has a function of imparting high gas barrier properties to the gas barrier film by protecting the gas barrier layer. A protective layer is normally arrange | positioned on the surface opposite to the base material of a gas barrier layer. A preferred form of the gas barrier film is a form in which a substrate, a gas barrier layer, and a protective layer are laminated in this order.

  The protective layer includes polysiloxane and / or a product obtained by modifying polysiloxane.

Polysiloxane The polysiloxane is not particularly limited, and known ones can be used. Among these, it is preferable to use an organopolysiloxane represented by the following general formula (1).

In the said General formula (1), R < ¹ > -R < ⁶ > represents a C1-C8 organic group each independently. At this time, at least one of the R ^{1 to} R ⁶ is an alkoxy group or a hydroxyl group, and m is an integer of 1 or more. The C1-C8 organic group is not particularly limited, but is a halogenated alkyl group such as a γ-chloropropyl group or 3,3,3-trifluoropropyl group; an alkenyl group such as a vinyl group; an aryl group such as a phenyl group. A (meth) acrylic acid ester group such as γ-methacryloxypropyl group; an epoxy-containing alkyl group such as γ-glycidoxypropyl group; a mercapto-containing alkyl group such as γ-mercaptopropyl group; a γ-aminopropyl group; Aminoalkyl group; isocyanate-containing alkyl group such as γ-isocyanatopropyl group; linear or branched alkyl group such as methyl group, ethyl group, propyl group and isopropyl group; alicyclic alkyl group such as cyclohexyl group and cyclopentyl group; Linear or branched group such as ethoxy group, propyloxy group, isopropyloxy group, etc. Jo alkoxy group; an acetyl group, a propionyl group, a butyryl group, valeryl group, and an acyl group such as caproyl.

  Of the organopolysiloxanes represented by the general formula (1), it is more preferable to use an organopolysiloxane having m of 1 or more and a weight average molecular weight (polystyrene conversion) of 1000 to 20000. It is preferable that the weight average molecular weight of the organopolysiloxane is 1000 or more because cracks are unlikely to occur in the formed protective layer and the gas barrier property can be maintained. On the other hand, when the weight average molecular weight of the organopolysiloxane is 20000 or less, the protective layer to be formed is sufficiently cured and sufficient hardness as the protective layer can be obtained.

Product formed by modifying polysiloxane A product formed by modifying polysiloxane can be formed by modifying the above-described polysiloxane with vacuum ultraviolet light or the like. The specific composition of the product obtained by modifying the polysiloxane is not clear.

  The protective layer may be a single layer or a laminate of two or more layers. When two or more layers are laminated, each layer may be composed of the same component or different components.

  The thickness of the protective layer can be appropriately set according to the desired performance. For example, the thickness of the protective layer is preferably 50 nm to 10 μm, and more preferably 100 nm to 1 μm. It is preferable that the thickness of the protective layer is 50 nm or more because sufficient gas barrier properties can be obtained. On the other hand, it is preferable that the thickness of the protective layer is 10 μm or less because high light transmittance can be realized and stable coating can be performed when the protective layer is formed.

(Resin layer with releasability)
The gas barrier film may be provided with a resin layer having releasability as required.

  The releasable resin layer prevents moisture from adsorbing from the surface of the gas barrier film, and also reduces the damage to the gas barrier layer and the entry of foreign objects when the gas barrier film is wound around the core. Have In addition, about the side surface of a gas-barrier film, since the area which contacts air is small, it is hardly influenced by the water | moisture content etc. in air. In the present specification, the “release property” means that it can be adhered to any element constituting the gas barrier film and can be peeled by arbitrarily applying predetermined energy.

  The resin layer having the releasability is usually bonded to the surface of the gas barrier layer. A preferred form of the gas barrier film is a form in which a substrate, a gas barrier layer, and a resin layer having releasability are laminated in this order. In addition, when the gas barrier film includes a protective layer, a preferable form of the gas barrier film is a form in which a base material, a gas barrier layer, a protective layer, and a resin layer having releasability are laminated in this order. The resin layer having releasability may be disposed on the surface opposite to the gas barrier layer of the substrate. In this case, a preferable form of the gas barrier film is a form in which a releasable resin layer, a base material, and a gas barrier layer are laminated in this order.

  Although there is no restriction | limiting in particular in the resin layer which has mold release property, It is preferable that it consists of a board | substrate and the adhesion layer containing the adhesive formed in the single side | surface of the said board | substrate.

Substrate The substrate has a function of holding the adhesive layer.

  Although it does not restrict | limit especially as a board | substrate which can be used, Polyolefin-type films, such as a polyethylene film and a polypropylene film; Polyester films, such as a polyethylene terephthalate and a polybutylene terephthalate; Polyamide-type films, such as a hexamethylene adipamide; Polyvinyl chloride, Polyvinylidene And halogen-based films such as chloride and polyfluoroethylene; vinyl acetate such as polyvinyl acetate, polyvinyl alcohol, and ethylene vinyl acetate copolymer; and their derivative films. Among these, it is preferable to use a polyethylene film, a polypropylene film, or a polyethylene terephthalate film from the viewpoint of availability.

  The thickness of the substrate is not particularly limited, but is preferably 10 to 300 μm, and more preferably 25 to 150 μm. It is preferable that the thickness of the substrate is 10 μm or more because handling becomes easy. On the other hand, it is preferable that the thickness of the substrate is 300 μm or less because the resin layer having releasability does not become excessively hard.

Adhesive layer The adhesive layer contains an adhesive. The adhesive is not particularly limited, and for example, acrylic adhesive, rubber adhesive, urethane adhesive, silicone adhesive, ultraviolet curable adhesive, polyolefin adhesive, ethylene vinyl acetate copolymer (EVA) system An adhesive etc. can be mentioned and at least 1 sort (s) can be used. Moreover, it is preferable that the adhesive force of an adhesive is 1 mN / cm-2 N / cm, It is more preferable that it is 1-200 mN / cm, More preferably, it is 1-80 mN / cm. If the adhesive strength of the pressure-sensitive adhesive is 1 mN / cm or more, sufficient adhesion between the gas barrier film and the resin layer having releasability can be obtained, and no peeling occurs during continuous conveyance. It is possible to prevent the influence on the already formed gas barrier film or the like due to contact of the roll or the like at the time. If the adhesive force is 2 N / cm or less, when the resin material is peeled off, the gas barrier film may be destroyed or the adhesive may remain on the gas barrier film without applying excessive force to the gas barrier film. It is preferable in terms of few points.

  The adhesive strength of the pressure-sensitive adhesive can be determined by measuring 20 minutes after the resin material is pressure-bonded to the test plate using Corning 1737 as a test plate according to a measurement method based on JIS Z 0237.

  Further, the thickness of the adhesive layer is preferably 0.1 to 30 μm. When the thickness of the pressure-sensitive adhesive layer is 0.1 μm or more, sufficient adhesion between the gas barrier film and the resin layer having releasability can be obtained, and peeling during continuous conveyance does not occur. It is possible to prevent the gas barrier film from being affected by the contact of the roll or the like. Further, when the thickness of the adhesive layer is 30 μm or less, when the resin material is peeled off, an excessive force is not applied to the gas barrier film, and the gas barrier film is destroyed or the adhesive on the gas barrier film is excessive. There is no residue.

  As the acrylic pressure-sensitive adhesive, for example, a homopolymer of (meth) acrylic acid ester or a copolymer with another copolymerizable monomer is used. Furthermore, examples of monomers or copolymerizable monomers constituting these copolymers include alkyl esters of (meth) acrylic acid (for example, methyl esters, ethyl esters, butyl esters, 2-ethylhexyl esters, octyl esters, isoforms). Nonyl esters, etc.), hydroxyalkyl esters of (meth) acrylic acid (eg, hydroxyethyl ester, hydroxybutyl ester, hydroxyhexyl ester), (meth) acrylic acid glycidyl ester, (meth) acrylic acid, itaconic acid, maleic anhydride Acid, (meth) acrylic acid amide, (meth) acrylic acid N-hydroxymethylamide, (meth) acrylic acid alkylaminoalkyl ester (for example, dimethylaminoethinomethacrylate, t-butanolenoaminoethino Methacrylate), acetic pinyl, styrene, and acrylonitrile. As the monomer of the main component, an alkyl acrylate ester having a homopolymer glass transition point of 500 ° C. or lower is usually used.

  As the curing agent for the acrylic pressure-sensitive adhesive, for example, an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used. As the isocyanate curing agent, an aromatic type such as tonoleylene diisocyanate (TDI) can be preferably used in order to obtain a stable adhesive force even after long-term storage and to form a harder adhesive layer.

  Examples of the rubber-based pressure-sensitive adhesive include polyisobutylene rubber, butyl rubber and a mixture thereof, or these rubber-based pressure-sensitive adhesives such as apinic acid rosin ester, terpene / phenol copolymer, terpene / indene copolymer, etc. Those containing a tackifier are used.

  Examples of the rubber-based adhesive base polymer include natural rubber, isoprene-based rubber, styrene-tadiene rubber, recycled rubber, polyisobutylene rubber, styrene-isoprene styrene rubber, styrene butadiene styrene rubber, and the like. It is done.

  Among these, the block rubber-based pressure-sensitive adhesive is a block copolymer represented by a general formula A-B-A or a block copolymer represented by a general formula A-B (where A is a styrene-based polymer block, B is a butadiene polymer block, an isoprene polymer block, or an olefin polymer block obtained by hydrogenation of these, and includes a tackifying resin, a softener, etc. Composition.

  In the block rubber adhesive, the styrene polymer block A preferably has an average molecular weight of about 4,000 to 120,000, and more preferably about 10,000 to 60,000. The glass transition temperature is preferably 150 ° C. or higher. Further, the butadiene polymer block, the isoprene polymer block, or the olefin polymer block B obtained by hydrogenating them is preferably one having an average molecular weight of about 30,000 to 400,000, more preferably 60,000 to 200, About 000 is more preferable. The glass transition temperature is preferably -150 ° C or lower. A preferable mass ratio of the A component and the B component is A / B = 5/95 to 50/50, and more preferably A / B = 10/90 to 30/70. When the value of A / B is 50/50 or less, the rubber elasticity of the polymer becomes high at normal temperature, and the tackiness tends to be manifested, and when it is 5/95 or more, the styrene domain becomes dense and due to sufficient cohesive force. The desired adhesive strength can be obtained, and problems such as the tearing of the pressure-sensitive adhesive layer during peeling are less likely to occur.

  Furthermore, the release property from a release paper or a release film can be improved by adding a polyolefin resin to the adhesive layer. Examples of the polyolefin resin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene α-olefin copolymer, propylene α-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene -Vinyl acetate copolymer, ethylene methyl methacrylate copolymer, ethylene n-butyl acrylate copolymer, and mixtures thereof.

  The polyolefin-based resin preferably has a low molecular weight, and specifically, the low molecular weight extracted by boiling boiling with n-pentane is preferably less than 1.0% by mass. When the low molecular weight component is small, it is preferable because the adhesive property is less likely to be adversely affected and the adhesive force is less likely to be lowered according to a change in temperature or a change with time.

  Moreover, the affinity with the white back surface provided with the coating film which has polyvinyl alcohol as a main component can further be reduced by adding silicone oil to the said adhesive. This silicone oil is a polymer compound with a polyalkoxysiloxane chain in the main chain, which increases the hydrophobicity of the adhesive layer and further bleeds to the adhesive interface, that is, the surface of the adhesive layer. There is a function that makes it difficult for a phenomenon to occur.

  A cross-linking agent is added to the rubber-based pressure-sensitive adhesive to cross-link to form a pressure-sensitive adhesive layer.

  As the crosslinking agent, for example, sulfur, a vulcanization aid, and a vulcanization accelerator (typically, dibutylthiocarbamate zinc, etc.) are used for crosslinking of the natural rubber-based pressure-sensitive adhesive. Polyisocyanates are used as a cross-linking agent capable of cross-linking an adhesive made from natural rubber and carboxylic acid copolymerized polyisoprene at room temperature. Polyalkylphenol resins are used as cross-linking agents that have heat-resistant and non-fouling characteristics in cross-linking agents such as butyl rubber and natural rubber. There are organic peroxides such as benzoyl peroxide and dicumyl peroxide in the crosslinking of pressure-sensitive adhesives made from butadiene rubber, styrene-butadiene rubber and natural rubber, and non-fouling pressure-sensitive adhesives can be obtained. Polyfunctional methacrylic esters are used as a crosslinking aid. There is also the formation of pressure-sensitive adhesives by crosslinking such as ultraviolet crosslinking and electron beam crosslinking.

  Silicone adhesives include addition reaction curable silicone adhesives and condensation polymerization curable silicone adhesives. In the present invention, addition reaction curable adhesives are preferably used.

  As the composition of the addition reaction curable silicone pressure-sensitive adhesive composition, those listed below are preferably used.

(A) Polydiorganosiloxane having two or more alkenyl groups in one molecule (B) Polyorganosiloxane containing SiH group (C) Control agent (D) Platinum catalyst (E) Conductive fine particles.

  Here, the component (A) is a polydiorganosiloxane having two or more alkenyl groups in one molecule, and examples of such alkenyl group-containing polydiorganosiloxane include those represented by the following general formula (2). It can be illustrated.

In the general formula (2), R ⁷ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is an alkenyl group-containing organic group. a is an integer of 0 to 3, preferably 1, and m is 0 or more, but when a = 0, m is 2 or more, and m and n are numbers satisfying 100 ≦ m + n ≦ 20,000, respectively. And p is 2 or more.

R ⁷ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, or tolyl. An aryl group such as a group is exemplified, and a methyl group and a phenyl group are particularly preferable.

  X is an alkenyl group-containing organic group, preferably having 2 to 10 carbon atoms, specifically pinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclohexenylethyl group. Group, pinyloxypropyl group, and the like, among which vinyl group and hexenyl group are particularly preferable.

  The polydiorganosiloxane may be in the form of oil or raw rubber, and the viscosity of the component (A) is preferably 100 mPa · s or more, particularly 1,000 mPa · s or more at 250 ° C. The upper limit is not particularly limited, but is preferably selected so that the degree of polymerization is 20,000 or less because of easy mixing with other components. Moreover, (A) component may be used individually by 1 type, and may use 2 or more types together.

  The polyorganosiloxane containing SiH groups as the component (B) is a crosslinking agent, and is an organohydropolysiloxane having at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule. , Branched, annular, etc. can be used.

  (B) As a component, although the compound represented by following General formula (3) can be mentioned, it is not limited to these.

In the general formula (3), R ⁸ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond having 1 to 6 carbon atoms. b is an integer of 0 to 3, and x and y are integers, respectively, and indicate the number at which the viscosity of this organohydropolysiloxane at 250 ° C. is 1 to 5,000 mPa · s.

  The viscosity of this organohydropolysiloxane at 250 ° C. is preferably 1 to 5,000 mPa · s, particularly preferably 5 to 1000 mPa · S, and may be a mixture of two or more.

  Crosslinking by addition reaction occurs between the component (A) and the component (B) of the crosslinking agent, and the gel fraction of the adhesive layer after curing is determined by the proportion of the crosslinking component. It is preferable to blend so that the molar ratio of the SiH group in the component (B) to the alkenyl group in the component) is in the range of 0.5 to 20, particularly 0.8 to 15. If it is 0.5 or more, the crosslinking density is maintained, and a holding force can be obtained accordingly. On the other hand, if it is 20 or less, adhesive force and tack can be obtained.

  In addition, in order to improve the heat resistance such as heat resistance and solvent resistance such as suppression of solvent penetration, the proportion of the cross-linking component in the composition may be increased. There may be effects such as reduced flexibility. From such a point, the blending mass ratio of the component (A) / (B) may be 20/80 to 80/20, and is particularly preferably 45/55 to 70/30. If the blending ratio of component (A) is 20/80 or more, sufficient adhesive properties such as adhesive strength and tack can be obtained, and if it is 80/20 or less, sufficient heat resistance is obtained.

  Component (C) is an addition reaction control agent, so that when a silicone pressure-sensitive adhesive composition is prepared and applied to a substrate, the treatment liquid does not thicken or gel before heat curing. It is to be added.

  Specific examples of the component (C) include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl. Cyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethyl Siloxycyclohexane, pis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetrapinylcyclotetrasiloxane, 1,1,3 Examples include 3-tetramethyl-1,3-divinyldisiloxane.

  The amount of component (C) is preferably in the range of 0 to 5.0 parts by weight, particularly 0.05 to 2.0 parts by weight, based on a total of 100 parts by weight of components (A) and (B). Is preferred. When it is in the above range, a decrease in curability can be suppressed.

  Component (D) is a platinum catalyst, containing chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and containing chloroplatinic acid and a vinyl group A reaction product with siloxane can be used.

  The amount of component (D) added is preferably 1 to 5,000 ppm, more preferably 5 to 2,000 ppm in terms of platinum relative to the total amount of components (A) and (B). If it is 1 ppm or more, sufficient curability is obtained, the crosslinking density is high, and the holding power can be maintained.

  The pressure-sensitive adhesive layer containing the above-mentioned pressure-sensitive adhesive can contain a stabilizer, an ultraviolet absorber, a flame retardant, and an antistatic agent as additives.

  For example, the antistatic agent is not particularly limited, and those containing a quaternary ammonium ion such as an alkyltrimethylammonium salt can be used. In the case where the adhesive layer contains an antistatic agent, the resin layer having releasability exhibits an antistatic function, and when applied to the film roll according to the present invention, it is preferable because the handleability is improved.

  In addition, in order to impart removability to the adhesive layer or to keep the adhesive force low and stable, an organic resin such as wax, silicon, fluorine, etc. A component having a low surface energy may be added. For example, in an organic resin such as wax, a higher fatty acid ester or a low molecular weight phthalate ester may be used.

  Moreover, as for the length of the film roll which concerns on this form, it is preferable that width | variety is 20-400 cm, and it is more preferable that it is 50-250 cm. Moreover, it is preferable that it is 20-10000m in length, and it is more preferable that it is 100-4000m. It is preferable that the length of the film roll is within the above range because productivity is increased.

<Packing part>
The packaging unit has a function of packaging the film roll. By packaging the film roll by the packaging unit, the chance that the gas barrier film comes into contact with moisture in the air can be reduced, and adsorption of moisture that may occur over time in the gas barrier film can be prevented. In this specification, “packaging” means packaging so as not to come into contact with outside air.

  The packaging unit includes a packaging material.

[Packaging materials]
The packaging material has a function of preventing permeation of moisture in the air.

  The material of the packaging material that can be used is not particularly limited, and examples thereof include resin materials such as polyethylene, polypropylene, and polyethylene terephthalate, and metals such as paper, glass, aluminum, iron, and stainless steel (SUS). Among these, as the packaging material, a resin material and paper are preferable from the viewpoint of weight reduction. Further, from the viewpoint of moisture resistance, a resin material and paper that have been moisture-proofed are more preferable. The resin material and paper subjected to moisture-proof treatment indicate those obtained by laminating aluminum foil or those subjected to vapor deposition of aluminum or silicon oxide.

  The packaging material may have a configuration in which two or more packaging materials are packaged. In this case, the material of each packaging material may be the same or different. When packaged with two or more packaging materials, the permeation of moisture in the air can be further suppressed.

The packaging material preferably has a water vapor permeability of 1 g / m ² / day or less.

  Advantages of packing the film roll in the packing part include that the moisture content in the air can be prevented and that the moisture content inside the packing part can be kept low.

  The atmosphere in the packing part is preferably an inert gas (a rare gas such as nitrogen gas, helium, neon, argon, krypton, or xenon) atmosphere or a vacuum atmosphere.

  Moreover, it is preferable that it is 10 degrees C or less, and, as for the dew point inside a packing part, it is more preferable that it is 5 degrees C or less. In the present specification, “dew point” is measured using a commercially available dew point meter. The dew point can also be a value calculated from temperature and relative humidity.

<Hygroscopic material>
The film roll package may further include a hygroscopic material. In this case, the hygroscopic material is packaged together with the film roll. The hygroscopic agent has a function of absorbing moisture that may be present in the packaging part.

  The hygroscopic material that can be used is not particularly limited, but clay, zeolite, silica gel, calcium chloride, zinc chloride, calcium sulfate, montmorillonite, aluminum oxide, activated carbon, barn clay, barium oxide, calcium oxide, calcium bromide, chlorine Examples thereof include magnesium acid, copper sulfate, molecular sieve, and phosphorous pentoxide. Of these, clay, zeolite, and silica gel are preferably used.

  According to the film roll package according to this embodiment, it is possible to prevent the adsorption of moisture that may occur over time in the gas barrier film even when storage or transportation for a long period of time is performed. More specifically, the long period is preferably 2 months or longer, more preferably 3 months or longer, and even more preferably 6 months or longer.

  The gas barrier film of the film roll package can be used by opening the packing portion and pulling out the wound gas barrier film from the roll. At this time, when a resin layer having releasability is attached to the gas barrier film, it can be removed by peeling off by hand, winding up and peeling off the releasable resin film in-line. In addition, when it is considered that a very small amount of moisture is attached to the gas barrier film, the moisture may be removed by heating or the like as necessary.

<Method for producing film roll package>
According to one aspect of the present invention, a step (1) of producing a gas barrier film by forming a gas barrier layer on a substrate, and a step of producing a film roll by winding the gas barrier film around a core. (2) and the manufacturing method of a film roll package body including the process (3) which wraps the said film roll with a packaging material and forms a packaging part are provided. At this time, the water vapor permeability of the gas barrier film is 1 × 10 ⁻² g / m ² / day or less.

[Step (1)]
Step (1) is a step of producing a gas barrier film by forming a gas barrier layer on a substrate.

(Formation of gas barrier layer)
The method for producing the gas barrier film is not particularly limited as long as the water vapor permeability of the gas barrier film is 1 × 10 ⁻² g / m ² / day or less. Examples of the method for producing the gas barrier film include a dry film forming method and a wet film forming method.

Dry film forming method Examples of the dry film forming method include physical vapor deposition and chemical vapor deposition. The physical vapor deposition method is a method in which a thin film of a target substance is deposited on the surface of the substance by a physical method in a gas phase, and a vapor deposition method (resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method). , Ion plating method, sputtering method and the like. On the other hand, the chemical vapor deposition method (chemical vapor deposition method, CVD method) is a method in which a source gas containing a target thin film component is supplied onto a base material and a film is deposited by a chemical reaction on the substrate surface or in the gas phase. This method includes a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, a vacuum plasma CVD method, and an atmospheric pressure plasma CVD method. Of these, the sputtering method, the vacuum plasma CVD method, and the atmospheric pressure plasma CVD method are preferably used, and the atmospheric pressure plasma CVD method is more preferably used.

  Hereinafter, the atmospheric pressure plasma CVD method will be described as an example.

  The atmospheric pressure plasma CVD method is a method of forming a gas barrier layer using charged particles, active radicals, and the like that are generated with high density and generated when a decomposition gas is irradiated with plasma near atmospheric pressure. The charged particles, active radicals, and the like cause a very fast chemical reaction with an inorganic precursor (hereinafter, the inorganic precursor used in the atmospheric pressure plasma CVD method is also referred to as “first inorganic precursor”). 1 inorganic substance precursor etc. can be converted into a thermodynamically stable compound (inorganic substance) in a short time. The atmospheric pressure plasma CVD method is excellent in productivity because it is not necessary to use a reduced pressure environment. Moreover, since the plasma density is high, the film forming speed is high. Furthermore, since the mean free path of the cracked gas is very short, a homogeneous film can be obtained. In the present specification, “near atmospheric pressure” usually means a pressure of 20 to 110 kPa, preferably 93 to 104 kPa.

  Although it does not restrict | limit especially as a 1st inorganic substance precursor which can be used, An organometallic compound is mentioned. Examples of the organometallic compound include silicon compounds such as silane, tetramethoxysilane, and tetraethoxysilane; titanium compounds such as titanium methoxide, titanium ethoxide, and titanium isopropoxide; zirconium-n-propoxide, zirconium-n-butoxide. Zirconium compounds such as zirconium-t-butoxide; aluminum compounds such as aluminum ethoxide and aluminum triisopropoxide; boron compounds such as diborane, boron chloride and borane-THF complex; tin compounds such as tetraethyltin and tetramethyltin Is mentioned. These first inorganic precursors may be used alone or in admixture of two or more.

  The cracked gas that can be used is not particularly limited, but hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen Gas, water vapor, fluorine gas, hydrogen fluoride gas, trifluoroalcohol gas, trifluorotoluene gas, hydrogen sulfide gas, sulfur dioxide gas, carbon disulfide gas, chlorine gas, helium gas, neon gas, argon gas, krypton gas, xenon Gas, radon gas, etc. are mentioned. These cracked gases may be used alone or in combination of two or more.

A method of generating plasma is not particularly limited, but a method of forming electric fields of different frequencies (first high frequency electric field and second high frequency electric field) is used as described in the pamphlet of International Publication No. 2007/026545. It is preferable. More specifically, the frequency of the first high-frequency electric field is ω1, the intensity is V1, the frequency of the second high-frequency electric field is ω2, the intensity is V2, the output density is S2, and the intensity of the discharge start electrolysis is IV (1 / 2Vp-p), the following conditions (1) to (3):
(1) ω1 <ω2
(2) V1 ≧ IV> V2 or V1> IV ≧ V2
(3) S2 ≧ 1 W / cm ²
It is preferable to satisfy at least one of the following. The first high-frequency electric field has a function of generating plasma of decomposition gas, and the second high-frequency electric field can contribute to the plasma density. Therefore, by generating plasma under such conditions, it is possible to generate a discharge even with a cracked gas having a high discharge starting electric field strength such as nitrogen gas. In addition, a high-density and stable plasma state can be maintained, and a high-performance thin film can be formed.

  The frequency ω1 of the first high-frequency electric field is preferably 1 kHz or more, and more preferably 1 to 200 kHz.

  The frequency ω2 of the second high frequency electrolysis is preferably 800 kHz or more, and more preferably 800 kHz to 200 MHz.

  The electric field waveform of the first or second high frequency electric field may be a continuous wave or a pulse wave.

Wet film-forming method The wet film-forming method refers to a so-called coating method in which a coating liquid is applied and the resulting coating film is dried to form a film.

  The coating method is not particularly limited, and a known method can be used. Among them, a coating liquid (hereinafter also referred to as “first coating liquid”) containing an inorganic precursor (hereinafter, the inorganic precursor used in the coating method is also referred to as “second inorganic precursor”) is applied onto the substrate. After drying, it is preferable that the obtained coating film is irradiated with vacuum ultraviolet rays to modify the second inorganic precursor into an inorganic substance.

As the second inorganic precursor, polysilazane is preferably used. Polysilazane is a polymer having a bond such as Si—N, Si—H, or N—H in its structure, and is an inorganic precursor such as SiO ₂ , Si ₃ N ₄ , or an intermediate solid solution thereof such as SiO _x N _y. Function as.

  The polysilazane is not particularly limited, but it is preferable that the polysilazane is a compound that is converted to silica by being ceramicized at a relatively low temperature in consideration of performing a modification treatment described later. For example, it is described in JP-A-8-112879. It is preferable that it is a compound which has the main frame | skeleton which consists of a unit represented by following General formula (4).

In the general formula (4), R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. Represents a group.

The polysilazane is particularly preferably perhydropolysilazane (hereinafter also referred to as “PHPS”) in which all of R ⁹ , R ¹⁰ , and R ¹¹ are hydrogen atoms, from the viewpoint of the denseness of the resulting gas barrier layer.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and can be a liquid or solid substance (depending on the molecular weight). As the perhydropolysilazane, a commercially available product may be used. Examples of the commercially available product include Aquamica NN120, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (manufactured by AZ Electronic Materials Co., Ltd.) and the like. Can be mentioned.

  As another example of the polysilazane that is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a polysilazane represented by the above general formula with a silicon alkoxide (for example, JP-A-5-238827), glycidol is reacted. Glycidol-added polysilazane (for example, JP-A-6-122852) obtained by reaction, alcohol-added polysilazane (for example, JP-A-6-240208) obtained by reacting alcohol, and metal carboxylate Metal silicic acid salt-added polysilazane (for example, JP-A-6-299118), acetylacetonate complex-added polysilazane (for example, JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal Add fine particles Are fine metal particles added polysilazane (e.g., JP-A-7-196986 JP), and the like.

  The content of polysilazane in the first coating liquid varies depending on the desired film thickness of the gas barrier layer, the pot life of the coating liquid, etc., but is 0.2% by mass to 35% by mass with respect to the total amount of the coating liquid. Preferably there is.

  The first coating liquid may further contain a solvent, an amine catalyst, and a metal catalyst.

  The solvent is not particularly limited as long as it does not react with polysilazane, and a known solvent can be used. Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; ether solvents such as aliphatic ethers and alicyclic ethers. More specifically, examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like. Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran. These solvents can be used alone or in admixture of two or more.

  The amine catalyst and the metal can promote the conversion of polysilazane to a silicon oxide compound in the modification treatment described later.

  The amine catalyst that can be used is not particularly limited, but N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N ′. -Tetramethyl-1,3-diaminopropane, N, N, N ', N'-tetramethyl-1,6-diaminohexane.

  The metal catalyst that can be used is not particularly limited, and examples thereof include platinum compounds such as platinum acetylacetonate, palladium compounds such as palladium propionate, and rhodium compounds such as rhodium acetylacetonate.

  It is preferable to contain 0.1-10 mass% of an amine catalyst and a metal catalyst with respect to polysilazane. Especially about an amine catalyst, it is more preferable to contain 0.5-5 mass% with respect to polysilazane from a viewpoint of improvement of applicability | paintability and shortening of reaction time.

  A coating film is obtained by apply | coating and drying the said 1st coating liquid on a base material.

  As a coating method of the first coating solution, a known method can be adopted as appropriate. Examples of the coating method include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, casting film formation, bar coating, and gravure printing.

  The coating amount of the first coating liquid is not particularly limited, but can be appropriately adjusted in consideration of the thickness of the gas barrier layer.

  After apply | coating a 1st coating liquid, a coating film is obtained by making it dry. By the drying, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained. The remaining solvent can be removed at the time of vacuum ultraviolet irradiation described later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  Moreover, you may anneal from a viewpoint of obtaining a uniform coating film.

  The annealing temperature is not particularly limited, but is preferably 60 to 200 ° C, and more preferably 70 to 160 ° C. The annealing temperature may be constant, may be changed stepwise, or may be continuously changed (temperature increase and / or temperature decrease).

  The annealing time is not particularly limited, but is preferably 5 seconds to 24 hours, and more preferably 10 seconds to 2 hours.

  By irradiating the obtained coating film with vacuum ultraviolet light, the polysilazane constituting the coating film is modified into an inorganic substance. Here, the modification of polysilazane means that polysilazane is converted into a silicon oxide compound and / or a silicon oxynitride compound. In this specification, “vacuum ultraviolet light” means ultraviolet light including electromagnetic waves having a wavelength of 10 to 200 nm, preferably 100 to 200 nm, and more preferably 100 to 195 nm.

  Polysilazane modification treatment, that is, formation of silicon oxide and / or silicon oxynitride by substitution reaction of polysilazane usually requires a high temperature of 450 ° C. or more, and the modification treatment by heating is based on a resin film. It is difficult to apply it to Thus, modification by irradiation with vacuum ultraviolet light that can be modified at a lower temperature is applied. When polysilazane is irradiated with vacuum ultraviolet light, polysilazane is directly oxidized without passing through silanol (photon process called photon process). Films and / or silicon oxynitride films can be obtained. Further, in vacuum ultraviolet light, ozone or active oxygen having high oxidation ability is generated from oxygen or the like present in the reaction atmosphere, and polysilazane reforming treatment can be performed by the ozone or active oxygen. As a result, a denser silicon oxide film and / or silicon oxynitride film can be obtained. Therefore, the gas barrier layer obtained by modifying polysilazane by irradiation with vacuum ultraviolet light can have high barrier properties.

  The light source of the vacuum ultraviolet light is not particularly limited, and a known light source can be used. For example, a low pressure mercury lamp, an excimer lamp, an amalgam lamp, etc. are mentioned. Of these, it is preferable to use an excimer lamp, particularly a xenon (Xe) excimer lamp.

A rare gas excimer lamp such as the xenon excimer lamp can irradiate vacuum ultraviolet rays. A rare gas atom such as Xe, Kr, Ar, Ne or the like is called an inert gas because the outermost electrons are closed and are chemically very inert. However, noble gases (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. For example, when the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
It becomes. At this time, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light (vacuum ultraviolet light) of 172 nm emits light. The excimer lamp uses the excimer light. Examples of the method for generating the excimer light include a method using dielectric barrier discharge and a method using electrodeless field discharge. Dielectric barrier discharge means that a gas space is disposed between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp), and a high frequency high voltage of several tens of kHz is applied to the electrode. It is a very thin discharge called micro discharge similar to the lightning that occurs. The electrodeless field discharge is an electrodeless field discharge due to capacitive coupling, and is also called an RF discharge. Specifically, this is a spatially and temporally uniform discharge obtained when a lamp, an electrode, and the like are arranged in the same manner as the dielectric barrier discharge and a high frequency voltage of several MHz is applied to the electrode.

  The excimer lamp is characterized in that the excimer light is concentrated at one wavelength, and only the necessary light is hardly emitted, and is highly efficient. Moreover, since excess light is not radiated | emitted, the temperature of a target object can be kept low. Further, since no time is required for starting and restarting, lighting and blinking can be performed instantaneously. In particular, the Xe excimer lamp is excellent in luminous efficiency because it emits short wavelength 172 nm vacuum ultraviolet light at a single wavelength. Since the Xe excimer lamp has a short wavelength of 172 nm and a high energy, it is known that the bond breaking ability of organic compounds is high. In addition, since the Xe excimer lamp has a large oxygen absorption coefficient, it can efficiently generate active oxygen and ozone even with a very small amount of oxygen. Therefore, for example, in contrast to a low-pressure mercury lamp that emits vacuum ultraviolet light having a wavelength of 185 nm, the Xe excimer lamp has a high bond breaking ability of organic compounds, can efficiently generate active oxygen and ozone, and has a low temperature. In addition, the polysilazane can be modified in a short time. In addition, since the Xe excimer lamp has high light generation efficiency, it can be turned on and off instantaneously with low power and can emit a single wavelength. Therefore, it is preferable also from the viewpoint of application to a gas barrier film using a base material that is easily damaged by heat, such as a reduction in process time and a reduction in equipment area associated with high throughput.

  Thus, since the excimer lamp has high light generation efficiency, it can be turned on with low power, and an increase in the surface temperature of the irradiation object can be suppressed. In addition, since the number of photons penetrating into the interior increases, the modified film thickness can be increased and / or the film quality can be increased.

  The conditions of vacuum ultraviolet light irradiation are generally examined for the conversion reaction using the integrated light amount represented by the product of irradiation intensity and irradiation time as an index, but there are various conditions even if the composition is the same as in silicon oxide. When using a material having a structural form, the absolute value of the irradiation intensity may be important.

The irradiation intensity of the vacuum ultraviolet radiation, the composition of the base material and the polysilazane layer used, varies depending on the concentration and the ^like, it is preferably from ^{1mW / cm 2 ~100kW / cm 2} , at 1mW / cm ² ~10W / cm 2 More preferably.

  Although the time of vacuum ultraviolet light irradiation changes also with the composition, density | concentration, etc. of a base material to be used or a polysilazane layer, it is preferable that it is 0.1 second-10 minutes, and it is more preferable that it is 0.5 second-3 minutes. preferable.

Integrated light quantity of vacuum ultraviolet light is not particularly limited, is preferably from 1000~10000mJ / cm ^2, more preferably 1000~5000mJ / cm ^2. It is preferable that the accumulated amount of vacuum ultraviolet light is 1000 mJ / cm ² or more because high barrier properties can be obtained by sufficient modification. On the other hand, when the cumulative amount of vacuum ultraviolet light is 10,000 mJ / cm ² or less, it is preferable because a gas barrier layer having high smoothness can be formed without deformation of the substrate.

  Moreover, the irradiation temperature of vacuum ultraviolet light changes with base materials to apply, and can be suitably determined by those skilled in the art. The irradiation temperature of the vacuum ultraviolet light is preferably 50 to 200 ° C, and more preferably 80 to 150 ° C. It is preferable for the irradiation temperature to be within the above-mentioned range since deformation of the base material, deterioration of strength, etc. are unlikely to occur and the characteristics of the base material are not impaired.

  Furthermore, the irradiation atmosphere of the vacuum ultraviolet light is not particularly limited, but it is preferably performed in an atmosphere containing oxygen from the viewpoint of generating active oxygen and ozone and efficiently modifying. The oxygen concentration in the vacuum ultraviolet irradiation is preferably 300 to 10,000 ppm (0.03 to 1%), more preferably 500 to 5000 ppm. It is preferable that the oxygen concentration is 300 ppm or more because the reforming efficiency becomes high. On the other hand, when the oxygen concentration is 10,000 ppm or less, the substitution time between the atmosphere and oxygen can be shortened, which is preferable.

  The coating film to be irradiated with ultraviolet rays is mixed with oxygen and a small amount of moisture at the time of application, and adsorbed oxygen and adsorbed water may also exist in the base material and adjacent layers. If oxygen or the like is used, the oxygen source required for generation of active oxygen or ozone for performing the reforming process may be sufficient without newly introducing oxygen into the irradiation chamber. In addition, since 172 nm vacuum ultraviolet rays such as Xe excimer lamps are absorbed by oxygen, the amount of vacuum ultraviolet rays reaching the coating film may decrease. Therefore, when irradiating vacuum ultraviolet rays, the oxygen concentration is set low, It is preferable that the vacuum ultraviolet rays can reach the coating film efficiently.

  The gas other than oxygen in the atmosphere irradiated with vacuum ultraviolet light is preferably a dry inert gas, and more preferably a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas, inert gas, or the like introduced into the irradiation chamber and changing the flow rate ratio.

  From the viewpoint of improving the irradiation efficiency and achieving uniform irradiation, the generated vacuum ultraviolet light may be applied to the polysilazane layer before modification after reflecting the vacuum ultraviolet light from the generation source with a reflector. Moreover, the irradiation of vacuum ultraviolet light can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, when the substrate is in the form of a long film, it is preferable to perform the modification by continuously irradiating the vacuum ultraviolet light while transporting the substrate.

  The film thickness, density, and the like of the gas barrier layer obtained by the above-described modification treatment can be controlled by appropriately selecting application conditions, vacuum ultraviolet light irradiation conditions, and the like. For example, the film thickness and density of the gas barrier layer can be controlled by appropriately selecting the irradiation method of vacuum ultraviolet light from continuous irradiation, irradiation divided into a plurality of times, and so-called pulsed irradiation, etc. in which the plurality of times of irradiation is short. Can be done.

  As for the degree of the modification treatment, the formed functional inorganic layer is subjected to XPS surface analysis to obtain each atomic composition ratio of silicon (Si) atoms, nitrogen (N) atoms, oxygen (O) atoms, etc. I can confirm.

(Formation of protective layer)
The protective layer can be formed by applying and drying a coating liquid containing polysiloxane (hereinafter also referred to as “second coating liquid”) on the gas barrier layer obtained above.

  Since the polysiloxane may be the same as described above, the description thereof is omitted here.

  The second coating liquid may further contain a solvent and appropriately known components.

  Examples of the solvent include, but are not limited to, water, alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, and the like. Examples of alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, and triethylene. Examples include glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of ether solvents include tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Examples of the ketone solvent include cyclohexanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include methyl acetate, ethyl acetate, ethoxyethyl acetate and the like. In addition to these, solvents such as dichloroethane and acetic acid may be used. These solvents may be used alone or in combination of two or more.

  Examples of the known components include aminosilane compounds, epoxysilane compounds, colloidal silica, and curing catalysts.

  A protective layer is obtained by applying the second coating liquid to the gas barrier layer and drying it.

  As the coating method of the second coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating, dipping, roller blades, and spraying methods.

  The coating amount of the second coating solution is not particularly limited, but can be appropriately adjusted in consideration of the thickness of the protective layer.

  After applying the second coating solution, the protective layer is obtained by drying. By the drying, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable protective layer can be obtained. As the drying method, a method similar to the wet film forming method in the formation of the gas barrier layer described above can be applied.

  The protective layer containing polysiloxane thus obtained may be further irradiated with vacuum ultraviolet light. By performing the vacuum ultraviolet light irradiation, the polysiloxane is modified to obtain a product obtained by modifying the polysiloxane. For the vacuum ultraviolet light irradiation, the same method as the wet film forming method in the formation of the gas barrier layer described above is applied, and the irradiation conditions can be appropriately set according to the desired performance.

  In the present invention, a resin layer having releasability may be provided on the surface of the gas barrier film before the gas barrier film produced in the step (2) is wound around the core.

  As a method of providing a resin layer having releasability on the surface of the gas barrier film, a conventionally known method can be used. Specific examples include a roll laminator, a vacuum laminator, co-extrusion, and winding with a winding shaft at the same time as winding.

[Step (2)]
Step (2) is a step of winding the gas barrier film produced in step (1) around a core to produce a film roll.

  Since the same core as that described above can be used, the description thereof is omitted here.

  The method for winding the gas barrier film is not particularly limited, and a known method can be used. Specifically, a method of winding the film from the winding core is used.

  The winding tension at the time of winding the gas barrier film is preferably 20 to 350 N / m, more preferably 30 to 300 N / m, and still more preferably 40 to 300 N / m. When the winding tension is 20 N / m or more, it is preferable because a decrease in gas barrier properties due to winding deviation and a deterioration in storage stability of the gas barrier film can be prevented. On the other hand, when the winding tension is 350 N / m or less, it is preferable because it is possible to prevent the gas barrier property from being lowered and the storage stability of the gas barrier film from being deteriorated due to winding.

[Step (3)]
Step (3) is a step of wrapping the film roll manufactured in step (2) with a packaging material to form a packing part.

  Since the same packaging material as that described above can be used, the description thereof is omitted here.

  The method for packaging the film roll is not particularly limited, and a known method can be used. For example, when the packaging material is a thermoplastic resin, the film roll and any material (such as a hygroscopic agent) are covered with the packaging material, and then a part of the packaging material (opening) is heated and pressure is applied. Then, a method of cooling and sealing (a packaging method by heat sealing) is mentioned.

  Before packaging a film roll or the like with a packaging material, it is preferable to perform deaeration or replacement with an inert gas. By performing deaeration or replacement with an inert gas, the internal environment (dew point, etc.) of the formed packing part can be adjusted.

  When packaging two or more packaging materials, a packaging part can be formed by repeating the packaging method by heat seal etc. for every packaging material.

<Application of film roll packaging>
According to one embodiment of the present invention, an electronic device including a gas barrier film included in the film roll package described above or the film roll package manufactured by the method described above is provided.

  At this time, the gas barrier film can be prepared by opening the film roll package, cutting off the gas barrier film, peeling the resin layer having releasability, and the like as described above.

[Electronic device]
The electronic device is not particularly limited, and includes a known electronic device body to which a gas barrier film can be applied. For example, a solar cell (PV), a liquid crystal display element (LCD), an organic electroluminescence (EL) element, etc. are mentioned. Hereinafter, an organic EL element will be described as an example.

(Organic EL device)
The organic EL element is not particularly limited, but can usually have the following layer structure.

(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (6) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / Electron transport layer / cathode buffer layer (electron injection layer) / cathode.

  Various layers conventionally used can be used for the layers used in the above-mentioned respective layer configurations.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

<Manufacture of film roll packaging>
Example 1
On a polyethylene terephthalate (PET) film with a clear hard coat (CHC) layer (CHC layer thickness: 6 μm, PET layer thickness: 125 μm, manufactured by Kimoto Co., Ltd.), the first gas barrier layer and 2 gas barrier layer is formed, and a resin material NBO-0424 (acrylic adhesive containing an antistatic agent, manufactured by Fujimori Kogyo Co., Ltd. containing an antistatic agent) having a releasability is laminated on the second gas barrier layer and wound up in a roll shape It was. The winding tension at that time was 150 N / m, and the core was clean core S100 (material: paper, Sankyo Paper Industry Co., Ltd.). Next, the wound film roll is MZ-TB which is a barrier bag (polyethylene terephthalate (PET) / biaxially stretched nylon (ONY) / polyethylene (PE), water vapor transmission rate: 0.15 g / m ² / day), Thickness: 87 μm, manufactured by Maruai Co., Ltd., and hygroscopic care dry CT-100 (manufactured by Oe Chemical Co., Ltd.), deaeration treatment, and the barrier bag inlet is heat sealed The film roll package was manufactured by closing and packaging.

[Formation of first gas barrier layer]
Using an atmospheric pressure plasma film forming apparatus (a roll-to-roll type atmospheric pressure plasma CVD apparatus shown in FIG. 3 of Japanese Patent Laid-Open No. 2008-56967), silicon oxide is formed under the following thin film formation conditions by an atmospheric pressure plasma method. A first gas barrier layer (50 nm) of (SiO ₂ ) was formed.

[Composition of mixed gas]
Discharge gas: Nitrogen gas (94.9% by volume)
Gas barrier layer forming gas: tetraethoxysilane (0.1% by volume)
Additive gas: Oxygen gas (5.0% by volume)
[Film forming conditions]
(First electrode)
Power supply: PHF-6k (manufactured by HEIDEN Laboratory)
Frequency: 100 kHz (continuous mode)
Output density: 10 W / m ²
Electrode temperature: 120 ° C
(Second electrode)
Power supply: CF-5000-13M (manufactured by Pearl Industry Co., Ltd.)
Frequency: 13.56MHz
Output density: 10 W / m ²
Electrode temperature: 90 ° C
[Formation of second gas barrier layer]
On the 1st gas barrier layer formed by the said method, the 2nd gas barrier layer was formed with the following method. The film thickness of the obtained second gas barrier layer was 300 nm.

(Application)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20: manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass (solid content) of amine catalyst (N, N, N ′, N And a 20 mass% dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20: manufactured by AZ Electronic Materials Co., Ltd.) containing '-tetramethyl-1,6-diaminohexane), and the first coating solution 1 was prepared. In the obtained first coating liquid 1, the amine catalyst was 1% by mass (solid content).

  Next, the first coating solution 1 was applied onto the first gas barrier layer using a die coater and dried at 80 ° C. for 3 minutes to form a polysilazane-containing layer. The polysilazane-containing layer is not completely solidified.

(Vacuum ultraviolet light irradiation)
Subsequent to the formation of the polysilazane layer, vacuum ultraviolet light irradiation (excimer irradiation) and gas injection were continuously performed by a vacuum ultraviolet light irradiation device. The excimer lamp is used under the conditions of a wavelength of 172 nm, an integrated light quantity of 3 J / cm ² , and an oxygen concentration of 0.1% or less using a xenon excimer irradiation apparatus MODEL: METH-1-400 (manufactured by M.D.Com). It was.

About the obtained gas-barrier film, the water-vapor-permeation rate was measured based on JISK7129: 2008 (temperature 40 degreeC, relative humidity (RH) 90%) using PERMATRAN-W3 / 33 (made by MOCON). However, the water vapor transmission rate was less than 1 × 10 ⁻² g / m ² / day.

(Example 2)
A film roll package was produced in the same manner as in Example 1 except that the resin material was changed to Sanitect PAC3-50THK (polyolefin adhesive, manufactured by Sanei Kaken Co., Ltd.).

(Example 3)
A film roll package was produced in the same manner as in Example 1 except that the winding tension was changed to 40 N / m.

Example 4
A film roll package was produced in the same manner as in Example 1 except that the winding tension was changed to 300 N / m.

(Example 5)
A resin layer having releasability is not provided, the winding tension is changed to 20 N / m, and a polyethylene film (water vapor transmission rate: 10 g / m ² / day, film thickness: 50 μm, product name: MZ as a packaging material) A film roll package was produced in the same manner as in Example 1 except that the change was made to -PE, manufactured by Maruai Co., Ltd.

(Example 6)
A film is formed in the same manner as in Example 1 except that a resin layer having releasability is not provided and a polyethylene film is used as a packaging material so that the entire film roll is covered without being deaerated. A roll package was produced.

(Example 7)
A film roll package was produced in the same manner as in Example 1 except that the winding tension was changed to 20 N / m.

(Example 8)
A film roll package was produced in the same manner as in Example 1 except that the winding tension was changed to 310 N / m.

Example 9
A film roll package was produced in the same manner as in Example 1 except that the resin layer having releasability was not formed.

(Example 10)
A film roll package was produced in the same manner as in Example 1 except that a polyethylene film was used as the packaging material and the film roll was covered so as not to be deaerated.

(Example 11)
On a polyethylene terephthalate (PET) film with a clear hard coat (CHC) layer (CHC layer thickness: 6 μm, PET layer thickness: 125 μm, manufactured by Kimoto Co., Ltd.), the first gas barrier layer, 2 gas barrier layer and protective layer are formed, and a resin material NBO-0424 (acrylic adhesive containing an antistatic agent, manufactured by Fujimori Kogyo Co., Ltd. containing an antistatic agent) having release properties is laminated on the protective layer and wound into a roll I took it. The winding tension at that time was 150 N / m, and the core was clean core S100 (material: paper, Sankyo Paper Industry Co., Ltd.). Next, the wound film roll is placed in MZ-TB (PET / ONY / PE, water vapor transmission rate: 0.15 g / m ² / day, film thickness: 87 μm, manufactured by Maruai Co., Ltd.) which is a barrier bag, and removed. The barrier bag was closed by heat sealing and packaging was performed. Furthermore, it puts into MZ-AL which is a barrier bag (PET / aluminum / ONY / PE, water vapor transmission rate: 0.1 g / m ² / day, film thickness: 94 μm, manufactured by Maruai Co., Ltd.), deaeration treatment, and barrier A film roll package was manufactured by closing the bag slot with heat sealing and packaging.

[Formation of first gas barrier layer]
(Application)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20: manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass (solid content) of amine catalyst (N, N, N ′, N And 20% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20: manufactured by AZ Electronic Materials Co., Ltd.) containing '-tetramethyl-1,6-diaminohexane) A first coating solution 2 was prepared by diluting with dibutyl ether so as to be 5% by mass. In the obtained first coating liquid 2, the amine catalyst was 1% by mass (solid content).

  Next, the said 1st coating liquid 2 was apply | coated using the die-coater on the base material, and it was made to dry at 80 degreeC for 3 minute (s), and the polysilazane content layer was formed. The polysilazane-containing layer is not completely solidified.

(Vacuum ultraviolet light irradiation)
Subsequent to the formation of the polysilazane layer, vacuum ultraviolet light irradiation (excimer irradiation) and gas injection were continuously performed by a vacuum ultraviolet light irradiation device. The excimer lamp is used under the conditions of a wavelength of 172 nm, an integrated light quantity of 3 J / cm ² , and an oxygen concentration of 0.1% or less using a xenon excimer irradiation apparatus MODEL: METH-1-400 (manufactured by M.D.Com). It was. The film thickness of the obtained second gas barrier layer was 150 nm.

[Formation of second gas barrier layer]
(Application)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20: manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass (solid content) of amine catalyst (N, N, N ′, N And 20% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20: manufactured by AZ Electronic Materials Co., Ltd.) containing '-tetramethyl-1,6-diaminohexane) A first coating solution 3 was prepared by diluting with dibutyl ether to 1.7% by mass. In the obtained first coating liquid 3, the amine catalyst was 1% by mass (solid content).

  Next, the said 1st coating liquid 3 was apply | coated using the die-coater on the base material, and it was made to dry at 80 degreeC for 3 minute (s), and the polysilazane content layer was formed. The polysilazane-containing layer is not completely solidified.

(Vacuum ultraviolet light irradiation)
Subsequent to the formation of the polysilazane layer, vacuum ultraviolet light irradiation (excimer irradiation) and gas injection were continuously performed by a vacuum ultraviolet light irradiation device. The excimer lamp is used under the conditions of a wavelength of 172 nm, an integrated light quantity of 3 J / cm ² , and an oxygen concentration of 0.1% or less using a xenon excimer irradiation apparatus MODEL: METH-1-400 (manufactured by M.D.Com). It was. The film thickness of the obtained second gas barrier layer was 50 nm.

[Formation of protective layer]
A protective layer was formed on the second gas barrier layer formed by the above method by the following method. In addition, the film thickness of the obtained protective layer was 500 nm.

(Application)
A dibutyl ether solution of organopolysiloxane (Glaska HPC7003: manufactured by JSR Corporation) was diluted with butanol until the total solid content was 10% by mass to prepare a second coating solution.

  Next, the second coating solution was applied onto the second gas barrier layer using a die coater and dried at 120 ° C. for 2 minutes to form a polysiloxane-containing layer. The polysiloxane-containing layer is not completely solidified.

(Vacuum ultraviolet light irradiation)
Subsequent to the formation of the polysiloxane-containing layer, vacuum ultraviolet light irradiation (excimer irradiation) and gas injection were continuously performed by a vacuum ultraviolet light irradiation device. An excimer lamp is used under the conditions of a wavelength of 172 nm, an integrated light quantity of 1 J / cm ² , and an oxygen concentration of 0.1% or less using a xenon excimer irradiation apparatus MODEL: METH-1-400 (manufactured by M.D.Com). It was.

About the obtained gas-barrier film, the water-vapor-permeation rate was measured based on JISK7129: 2008 (temperature 40 degreeC, relative humidity (RH) 90%) using PERMATRAN-W3 / 33 (made by MOCON). However, the water vapor transmission rate was less than 1 × 10 ⁻² g / m ² / day.

(Comparative Example 1)
A film roll was produced in the same manner as in Example 6 except that the resin layer having releasability was not formed and the resin layer was not packaged with a packaging material.

(Comparative Example 2)
A film roll was produced in the same manner as in Comparative Example 1 except that the winding tension was changed to 400 N / m.

(Comparative Example 3)
A film roll was produced in the same manner as in Comparative Example 1 except that the winding tension was changed to 20 N / m.

(Comparative Example 4)
A first gas barrier layer is formed on a polyethylene terephthalate (PET) film with a clear hard coat (CHC) layer (CHC layer thickness: 6 μm, PET layer thickness: 125 μm, manufactured by Kimoto Co., Ltd.) under the following conditions. Then, a resin material NBO-0424 (an acrylic pressure-sensitive adhesive containing an antistatic agent, manufactured by Fujimori Kogyo Co., Ltd. containing an antistatic agent) having releasability was laminated on the first gas barrier layer and wound into a roll. The winding tension at that time was 150 N / m, and the core was clean core S100 (material: paper, Sankyo Paper Industry Co., Ltd.). Next, the wound film roll is placed in MZ-TB (PET / ONY / PE, water vapor transmission rate: 0.15 g / m ² / day, film thickness: 87 μm, manufactured by Maruai Co., Ltd.) which is a barrier bag, and removed. The barrier bag was closed by heat sealing and packaging was performed. Further, it is put into a barrier bag MZ-AL (PET / Al / ONY / PE, water vapor transmission rate: 0.1 g / m ² / day, film thickness: 94 μm, manufactured by Maruai Co., Ltd.), deaeration treatment, and barrier A film roll package was manufactured by closing the bag slot with heat sealing and packaging.

[Formation of first gas barrier layer]
(Sputtering method)
The base material was set in a sputtering apparatus and vacuum deaerated up to 1 × 10 ⁻⁴ Pa level. After the inside of the vacuum chamber was set to 90 ° C., argon was introduced as a discharge gas at a partial pressure of 0.1 Pa, and oxygen gas was introduced as a reaction gas at a partial pressure of 0.008 Pa. When the atmospheric pressure and temperature were stabilized, discharge was started at a sputtering power of 2 W / cm ² and plasma was generated on the Si target to start the sputtering process. When the process was stabilized, the shutter was opened and sputtering was started to form a gas barrier layer made of silicon nitride having a thickness of 100 nm.

About the obtained gas-barrier film, the water-vapor-permeation rate was measured based on JISK7129: 2008 (temperature 40 degreeC, relative humidity (RH) 90%) using PERMATRAN-W3 / 33 (made by MOCON). The water vapor transmission rate was 8 × 10 ⁻² g / m ² / day.

  The composition of each film roll package manufactured in Examples 1 to 11 and Comparative Examples 1 to 4 is shown in Table 1 below.

<Performance evaluation of film roll package>
(Evaluation of organic EL elements)
After the film roll package manufactured in Examples 1 to 11 and Comparative Examples 1 to 4 was stored at 30 ° C. and 80% RH for 6 months, the film roll was taken out from the packing portion and part of the wound gas barrier film Cut out. An organic EL device was prepared and evaluated using the gas barrier film (gas barrier film after 6 months of storage) thus obtained and the gas barrier film immediately after production.

Production of Organic EL Element A pixel electrode made of ITO was formed on the gas barrier layer (or protective layer) of the gas barrier film, and a vertical polyimide alignment layer was formed on the pixel electrode.

  On the other hand, a common electrode was formed on the gas barrier layer (or protective layer) of the gas barrier film, and a vertical polyimide alignment layer was formed on the common electrode.

  The two films obtained above are opposed so that the electrode layers (polyimide alignment layers) face each other, and the positions of the two substrates are kept constant by using spacer beads, and an opening for liquid crystal injection The periphery was sealed with a sealant so as to leave Next, VA liquid crystal MLC-6610 (manufactured by Merck & Co., Inc.) was injected from the opening between the polyimide alignment layers, and the opening was sealed to produce a simple organic EL device.

[Evaluation of organic EL elements]
The black spots were evaluated for each of the produced organic EL elements.

Specifically, a current of 1 mA / cm ² was applied to the sample to emit light, and a 100-fold microscope MS-804 (Mortex Co., Ltd.) and lens MP-ZE25-200 (Mortex Co., Ltd.) were used. A part of the panel was enlarged, and the situation of black spots (DS) was examined. The gas barrier film immediately after production and the gas barrier film after 6 months of storage were evaluated according to the following criteria.

(Immediately after manufacture)
A: Black spot generation area is less than 0.1% B: Black spot generation area is 0.1% or more and less than 0.5% Δ: Black spot generation area is 0.5% or more, 2.0 X: The area where black spots are generated is 2.0% or more.

(Gas barrier film after 6 months storage)
A: The amount of increase in the black spot generation area is less than 0.1% compared to immediately after the manufacture. ○: The amount of increase in the black spot generation area is 0.1% or more and less than 0.3% compared to that immediately after the manufacture. Δ: The amount of increase in black spot generation area is 0.3% or more and less than 1.0% compared to immediately after production. ×: The amount of increase in black spot generation area is 1.0% or more compared to immediately after production. .

  The obtained results are shown in Table 2 below.

  From the results of Comparative Examples 1 to 4, it was found that the gas barrier film was affected by moisture when stored for a long period of time.

  And from the result of Examples 1-11, even if it used the gas-barrier film stored for a long time by using a film roll as a package, it turned out that it has little influence on the performance of an organic EL element.

  Moreover, it turned out that the influence with respect to the water | moisture content of a gas barrier film changes with the resin material which has the release property to be applied, and the form of packaging from the result of Example 1 and 2 and Example 1 and 10.

  In addition, when the film roll package manufactured in Examples 1 to 11 was transported back and forth between Japan and Los Angeles by sea, the organic EL device was evaluated in the same manner as described above. Equivalent results were obtained. On the other hand, when the film roll package manufactured in Comparative Examples 1 to 4 was transported back and forth between Japan and Los Angeles by sea, and the organic EL device was evaluated in the same manner as described above, the preservation of Table 2 was performed. Obviously, the amount of increase in the black spot generation area compared with the case immediately after production increased more than when the gas barrier film after 6 months was used. From the above results, it is considered that the gas barrier film was affected by moisture in the air.

Claims (11)

A film roll comprising a core and a gas barrier film wound around the core;
A packaging unit including a packaging material for packaging the film roll;
A film roll package comprising:
The film roll packaging body in which the gas barrier film includes a base material and a gas barrier layer and has a water vapor transmission rate of 1 × 10 ⁻² g / m ² / day or less.   2. The gas barrier film according to claim 1, wherein the gas barrier film further includes a resin layer having releasability, and the base material, the gas barrier layer, and the resin layer having releasability are arranged in this order. Film roll package. The film roll package of Claim 1 or 2 whose water vapor permeability of the said packaging material is 1 g / m < ² > / day or less.   The film roll package of any one of Claims 1-3 whose dew point in the said packaging part is 10 degrees C or less.   The film roll package according to any one of claims 1 to 4, wherein the packing part is packaged with two or more packaging materials.   The film roll package according to any one of claims 1 to 5, further comprising a hygroscopic material, wherein the hygroscopic material is packaged together with the film roll.   The film roll package according to claim 1, wherein the core has hygroscopicity.   The film roll package according to any one of claims 1 to 7, wherein a material of the core is paper. Forming a gas barrier layer on the substrate to produce a gas barrier film (1);
Step (2) of winding the gas barrier film around a core to produce a film roll;
A step (3) of wrapping the film roll with a packaging material to form a packing portion;
A method for producing a film roll package comprising:
The manufacturing method whose water vapor transmission rate of the said gas-barrier film is 1 * 10 ^<-2 > g / m ^{< 2} > / day or less.   The manufacturing method according to claim 9, wherein the winding in the step (2) is performed at a winding tension of 30 to 300 N / m.   The manufacturing method according to claim 9 or 10, wherein the step (1) further includes forming a resin layer having releasability on the surface of the gas barrier film.