JP5927943B2 - GAS BARRIER FILM, MANUFACTURING METHOD THEREOF, AND DEVICE USING GAS BARRIER FILM - Google Patents

Description

  The present invention relates to a gas barrier film exhibiting good gas barrier properties and weather resistance, a method for producing the same, and an apparatus using the gas barrier film.

  The gas barrier film is preferably applied to devices such as organic EL elements, liquid crystal display elements, thin film transistors, solar cells, touch panels, electronic papers and the like in order to prevent permeation of chemical components such as oxygen or water vapor that degrade their performance. Yes. In particular, with high performance and high quality of recent electronic devices, high gas barrier properties are also required for gas barrier films.

  Some recent gas barrier films include a plastic film, an organic layer provided on the plastic film, and an inorganic layer provided on the organic layer. The organic layer is provided under the inorganic layer to play a role of enhancing the gas barrier property.

  Patent Document 1 is a gas barrier film having a barrier layer including an organic layer and an inorganic layer on at least one surface of a plastic film, the barrier layer being an organic layer, a first inorganic layer having a film density of 1.7 or more, And the invention regarding the gas barrier film comprised from the 2nd inorganic layer whose film density is 0.5-1.5 higher than the 1st inorganic layer is described.

  According to the document, in a gas barrier film having a barrier layer including an organic layer and an inorganic layer, by introducing another inorganic underlayer having different physical properties from the inorganic layer between the organic layer and the inorganic layer, The barrier property of the inorganic layer formed in the upper layer is increased.

JP 2009-95989 A

  The recent demand for higher performance is the same for gas barrier films. In addition to ensuring the necessary and sufficient gas barrier properties, not only the durability against heat and humidity (humidity heat resistance) is increased, but also against light. It is desired to increase durability (light resistance). Specifically, according to the study of the present inventor, the technique described in the above-mentioned Patent Document 1 shows that the transparency and gas barrier properties after the initial and wet heat resistance tests are good, but the ultraviolet rays from the outside are not good. Irradiation caused the organic layer to deteriorate over time, the organic layer yellowed and the transparency deteriorated, or the adhesion between the organic layer and the inorganic layer was lowered to lower the gas barrier property.

  As described above, the gas barrier film is expected to expand in the future while being used in various applications, and is expected to be maintained in various harsh environments. Therefore, improving the weather resistance such as moisture and heat resistance and light resistance of the gas barrier film is a serious problem in obtaining a gas barrier film that can be actually used.

  This invention solves the said subject, The objective is to provide the gas-barrier film which shows favorable gas-barrier property and a weather resistance, and its manufacturing method. Another object of the present invention is to provide an apparatus using a gas barrier film exhibiting good gas barrier properties and weather resistance.

  The present inventor has intensively studied the above problems, and the reason why the organic layer of the gas barrier film deteriorates with time due to external ultraviolet irradiation is that an oxidation reaction occurs in the organic layer due to external ultraviolet irradiation. Presumed to be. The present inventor has found that when the organic layer contains an ultraviolet absorber and a light stabilizer, the organic layer is prevented from being deteriorated by irradiation with ultraviolet rays from the outside. Specifically, even when the gas barrier film is held under ultraviolet irradiation from the outside, the organic layer is not yellowed, and the adhesion between the organic layer and the inorganic layer is reduced. The present inventors have found that good gas barrier properties can be maintained without any problem.

  However, when the organic layer is composed of an ultraviolet curable resin, which is a conventional constituent material of the organic layer, there has been a problem that the curing of the organic layer becomes insufficient. The present inventor presumed that the cause of such a problem was that the organic layer forming coating solution for forming the organic layer contained an ultraviolet absorber and a light stabilizer. That is, when an organic layer is formed by curing a coating solution for forming an organic layer containing an ultraviolet absorber and a light stabilizer, the ultraviolet absorber is formed when the coating solution for forming an organic layer is composed of an ultraviolet curable compound. Absorbs ultraviolet rays for curing UV curable compounds, and this light stabilizer traps radicals for curing UV curable compounds, so that the curing reaction of UV curable compounds does not proceed. Estimated. Therefore, as a result of further intensive studies by the present inventors, it has been found that the problem in forming such an organic layer can be solved by configuring the organic layer with an electron beam curable resin, and the present invention has been completed.

  The gas barrier film according to the present invention for solving the above-mentioned problems has a base material, an organic layer provided on the base material, and an inorganic layer provided on the organic layer, and the organic layer However, it is characterized by containing one or more kinds of electron beam curable resins, ultraviolet absorbers and light stabilizers.

  According to this invention, since the organic layer contains the ultraviolet absorber and the light stabilizer, it is possible to suppress the ultraviolet rays irradiated to the organic layer from being absorbed by the ultraviolet absorber and generating free radicals in the organic layer. Even if free radicals are generated in the organic layer, the light stabilizer can capture and stabilize the free radicals. Therefore, even when the organic layer is irradiated with ultraviolet rays from the outside, the oxidation reaction of the organic layer based on free radicals can be suppressed, so that the organic layer can be prevented from being oxidized and yellowed. Moreover, since it can prevent that an organic layer oxidizes and changes in quality, it can prevent that the adhesiveness of an organic layer and an inorganic layer falls, and can prevent that gas barrier property falls. As a result, a gas barrier film exhibiting good gas barrier properties and weather resistance can be provided. In addition, since the organic layer contains an electron beam curable resin, even if the organic layer contains an ultraviolet absorber and a light stabilizer, the organic layer does not cause a problem that the curing reaction of the resin does not proceed when forming the organic layer. Layers can be formed.

  In the gas barrier film according to the present invention, the organic layer contains 0.1% by mass or less of a polymerization initiator or does not contain a polymerization initiator.

  In the gas barrier film according to the present invention, the electron beam curable resin is an acrylic resin.

  In the gas barrier film according to the present invention, the ultraviolet absorber is a triazine-based ultraviolet absorber.

  In the gas barrier film according to the present invention, the light stabilizer is a hindered amine light stabilizer.

  In the gas barrier film according to the present invention, a protective layer containing the ultraviolet absorber is provided on the inorganic layer.

  According to this invention, since the protective layer containing the ultraviolet absorber is provided on the inorganic layer, the protective layer absorbs the ultraviolet rays from the outside, and the organic layer is irradiated with the ultraviolet rays from the outside. Can be prevented. As a result, the weather resistance of the gas barrier film can be further improved.

  An apparatus according to the present invention for solving the above-described problems is a display device or a power generation device using the gas barrier film according to the present invention.

  According to this invention, since the gas barrier film exhibiting good gas barrier properties and weather resistance is used, it is possible to provide an apparatus that is excellent in gas barrier properties and requires weather resistance.

  The method for producing a gas barrier film according to the present invention for solving the above problems is for forming an organic layer containing one or more electron beam curable compounds, ultraviolet absorbers and light stabilizers on a substrate. A step of applying a coating solution, a step of irradiating the coating solution for forming an organic layer applied on the substrate with an electron beam to form an organic layer, and a step of forming an inorganic layer on the organic layer. It is characterized by having.

  According to this invention, since the organic layer forming coating solution contains an electron beam curable compound and irradiates an electron beam to form an organic layer, the organic layer forming coating solution contains an ultraviolet absorber and a light stabilizer, respectively. Even if it is a case where 1 type or 2 types or more are included, an organic layer can be formed without a problem. In the gas barrier film thus produced, the organic layer contains an ultraviolet absorber and a light stabilizer, so that the ultraviolet ray irradiated to the organic layer is absorbed by the ultraviolet absorber and free radicals are generated in the organic layer. Can be suppressed. Even if free radicals are generated in the organic layer, the light stabilizer can capture and stabilize the free radicals. Therefore, even when the organic layer is irradiated with ultraviolet rays from the outside, the oxidation reaction of the organic layer based on free radicals can be suppressed, so that the organic layer can be prevented from being oxidized and yellowed. Moreover, since it can prevent that an organic layer oxidizes and changes in quality, it can prevent that the adhesiveness of an organic layer and an inorganic layer falls, and can prevent that gas barrier property falls. As a result, a method for producing a gas barrier film exhibiting good gas barrier properties and weather resistance can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the gas-barrier film which shows favorable gas-barrier property and a weather resistance, and its manufacturing method can be provided. Moreover, the apparatus using the gas-barrier film which shows favorable gas-barrier property and a weather resistance can be provided.

It is a typical sectional view showing an example of a gas barrier film concerning the present invention. It is typical sectional drawing which shows another example of the gas barrier film which concerns on this invention. It is typical sectional drawing which shows another example of the gas barrier film which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

[Gas barrier film and gas barrier layer]
As shown in FIGS. 1 and 2, the gas barrier film 10 according to the present invention includes a base material 1, an organic layer 2 provided on the base material 1, and an inorganic layer 3 provided on the organic layer 2. Have The organic layer 2 is characterized in that it contains one or more types of electron beam curable resins, ultraviolet absorbers, and light stabilizers.

  According to such a gas barrier film 10, it is possible to suppress generation of free radicals in the organic layer 2 by absorbing the ultraviolet rays irradiated to the organic layer 2 by the ultraviolet absorbent. Even if free radicals are generated in the organic layer 2, the light stabilizer can capture and stabilize the free radicals. Therefore, even when the organic layer 2 is irradiated with ultraviolet rays from the outside, the oxidation reaction of the organic layer 2 based on free radicals can be suppressed, so that the organic layer 2 is prevented from being oxidized and yellowing. it can. Moreover, since it can prevent that the organic layer 2 oxidizes and changes in quality, it can prevent that the adhesiveness of the organic layer 2 and the inorganic layer 3 falls, and can prevent that gas barrier property falls. As a result, it is possible to provide the gas barrier film 10 exhibiting good gas barrier properties and weather resistance. In addition, since the organic layer 2 contains an electron beam curable resin, even when the organic layer 2 contains an ultraviolet absorber and a light stabilizer, a problem that the resin curing reaction does not proceed when forming the organic layer 2 is caused. The organic layer 2 can be formed without

  The organic layer 2 and the inorganic layer 3 (these two layers are also referred to as “gas barrier layer 4”) are provided at least in that order on one surface S1 of the substrate 1 as shown in FIG. As shown in FIG. 5, the organic layer 2 ′ and the inorganic layer 3 ′ (also referred to as “gas barrier layer 4 ′”) may be provided in this order on the other surface S2. Further, as shown in FIG. 1, neither the organic layer 2 'nor the inorganic layer 3' may be provided on the other surface S2, or the inorganic layer 3 'may be provided without providing the organic layer 2'. The gas barrier property may be further improved by providing an inorganic layer 3 ′ on the other surface S <b> 2 or providing a gas barrier layer 4 ′ (organic layer 2 ′ and inorganic layer 3 ′).

  The achievement of good gas barrier properties and weather resistance in the gas barrier film 10 and the gas barrier layer 4 is based on the knowledge obtained from the following examination process.

  Specifically, in the process of earnestly examining the gas barrier film, the inventor of the present invention has a gas barrier film having a conventional organic layer, which has a gas barrier property immediately after production (initial) and adhesion between the organic layer and the inorganic layer. It was found that the organic layer deteriorates with time due to irradiation with ultraviolet rays from the outside even if the film is good. Specifically, in order to test the light resistance of the gas barrier film in an accelerated manner, the light resistance test for holding the gas barrier film under ultraviolet irradiation is performed, whereby yellowing occurs in the organic layer and the transparency deteriorates. In addition, the present inventors have found that the problem that the organic barrier layer is oxidized and deteriorated, the adhesiveness between the organic layer and the inorganic layer is reduced, and the gas barrier property is deteriorated.

  The present inventor considered the phenomenon that the organic layer deteriorates with time due to the irradiation of ultraviolet rays from the outside, and estimated the following deterioration mechanism. That is, when the organic layer is irradiated with ultraviolet rays in the light, the organic compound in the organic layer absorbs the ultraviolet rays and generates free radicals in the molecular chain. This free radical causes the organic layer oxidation reaction to proceed continuously while inducing a hydrogen abstraction reaction from other molecules and a decomposition reaction of a hydroperoxide group (—OOH). As a result, the organic layer is oxidized and deteriorated, and the organic layer is deteriorated.

  In order to solve these problems, the present inventor prevents the generation of free radicals in the organic layer and stabilizes the free radicals generated in the organic layer, thereby suppressing the oxidation reaction of the organic layer, The organic layer was proposed to contain an ultraviolet absorber that absorbs ultraviolet rays and a light stabilizer that traps and stabilizes free radicals. Such an organic layer does not cause yellowing in the organic layer because the oxidation reaction of the organic layer is suppressed even when the gas barrier film is held under ultraviolet irradiation from the outside. It has been found that good gas barrier properties can be maintained without deteriorating the adhesion between the organic layer and the inorganic layer, since it can be prevented from oxidizing and deteriorating.

  However, when an organic layer is composed of an ultraviolet curable resin, which is a general constituent material of an organic layer, although the organic layer can be provided with light resistance by containing an ultraviolet absorber and a light stabilizer in the organic layer. The problem of insufficient curing of the organic layer occurred. This is because when the coating solution for forming an organic layer made of an ultraviolet curable compound contains an ultraviolet absorber and a light stabilizer, the ultraviolet absorber absorbs ultraviolet rays for curing the ultraviolet curable compound and is also light stable. This is thought to be because the agent traps and stabilizes radicals for curing the ultraviolet curable compound.

  Therefore, as a result of further earnest studies, the present inventor made the constituent material of the organic layer not an ultraviolet curable resin, but an electron beam curable resin cured by an electron beam that is not absorbed by an ultraviolet absorber, The present inventors have found that the above-mentioned curing problem at the time of forming the organic layer can be solved, and have completed the present invention. The electron beam curable resin is a resin obtained by curing an electron beam curable compound with an electron beam, and the ultraviolet curable resin is a resin obtained by curing an ultraviolet curable compound with ultraviolet rays.

  Here, whether the resin constituting the organic layer is an electron beam curable resin or an ultraviolet curable resin is specified as follows. Both the electron beam curable resin and the ultraviolet curable resin are ionizing radiation curable compounds. In general, it is difficult because it is an ionizing radiation curable resin cured in step (b). However, both can be identified by quantifying the contents of the ultraviolet absorber and the light stabilizer contained in the organic layer. That is, when an organic layer is formed with a coating solution for forming an organic layer containing an ultraviolet curable compound and an ultraviolet absorber, the ultraviolet absorber also absorbs ultraviolet rays for curing, and the curing reaction of the ultraviolet curable compound. Will not proceed and the organic layer will be insufficiently cured. In addition, when an organic layer is formed with a coating solution for forming an organic layer containing an ultraviolet curable compound and a light stabilizer, the light stabilizer also captures and stabilizes radicals for curing, resulting in ultraviolet curable properties. The curing reaction of the compound does not proceed and the organic layer is not sufficiently cured. Therefore, when the organic layer is analyzed and a predetermined amount of ultraviolet absorber or light stabilizer is detected from the organic layer, the organic layer is not composed of an ultraviolet curable resin, but is composed of an electron beam curable resin. I can say that. The ionizing radiation is an electron beam and an ultraviolet ray, an electromagnetic wave such as a visible ray, an X-ray and a γ ray, and a charged particle beam such as an α ray.

  Examples of a method for quantifying the ultraviolet absorber and the light stabilizer in the organic layer include gas chromatography mass spectrometry. Specifically, the organic layer component is volatilized by putting the gas barrier film in a vial, sealing it, and heating it. After the vial was brought into an equilibrium state according to the distribution ratio of the gas phase to the solid phase at that temperature, a part of the head space part (gas phase part) was led to gas chromatography, and the individual separated by gas chromatography The component can be qualitatively measured by measuring a mass spectrum of the component, and further quantified by the detected ion intensity.

  Next, the components of the gas barrier film 10 and the gas barrier layer 4 will be described in more detail.

<Base material>
Although the material of the base material 1 is not particularly limited, it is preferable to use a base material made of a plastic material (hereinafter sometimes referred to as “plastic base material”) from the viewpoint of versatility and industrial property. As the plastic material, a polyester resin can be preferably mentioned from the viewpoint of actual use. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), copolymers thereof, and polycyclohexanedimethylene terephthalate (PCT). Among the polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and copolymers thereof are preferable. Particularly preferably, the plastic substrate 1 is a polyethylene naphthalate film or a polyethylene terephthalate film.

  When a polyester-based resin is applied as the material of the plastic substrate 1, the whole may be a film-like substrate made of a polyester-based resin, or the side on which the organic layer 2 is formed (one side S <b> 1 or FIG. 1 in FIG. 1). 2 may be a film-like laminated base material in which at least a polyester-based resin layer is formed on both surfaces S1, S2). In this film-like laminated substrate, layers other than the polyester resin layer on which the organic layer 2 is formed may not be a polyester resin layer. In selecting a layer type other than the polyester-based resin layer, various resin layers are arbitrarily selected in consideration of heat resistance, thermal expansion, light transmittance, and the like.

  Although the thickness of the plastic base material 1 is not specifically limited, It is preferable that it is about 10 micrometers or more and 500 micrometers or less.

  The surface of the plastic substrate 1 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, and easy adhesion treatment as necessary. . As a specific method of such surface treatment, a conventionally known method can be appropriately used. Moreover, you may provide another functional layer in the surface where the organic layer 2 is not directly formed. Examples of functional layers include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, antifouling layers, coatings. A printing layer, an easily bonding layer, etc. are mentioned.

<Organic layer>
The organic layer 2 is provided on a base material (plastic base material) 1 and constitutes a gas barrier layer 4 together with an inorganic layer 3 described later. Regarding the organic layer 2, a part of the description has already been described, but will be described in more detail below. The gas barrier film 10 is an example in which the plastic substrate 1 and the organic layer 2 are in contact with each other. However, in the present invention, they do not necessarily have to be in contact with each other, and other layers may be interposed between them if necessary. It may be provided.

  The organic layer 2 is composed of an electron beam curable resin. Such an electron beam curable resin is obtained by curing an electron beam curable compound with an electron beam. The electron beam curable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated double bond, but is preferably an acrylic resin. The acrylic resin is composed of a resin having an acrylic monomer as a main component. Specific examples of the resin having the acrylic monomer as a main component include those having an acrylate functional group, for example, a polyester resin having a relatively low molecular weight, a polyester resin, and the like. Ether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols, reactive diluents Etc. Of these, polyester acrylate is preferred in view of industrial production and the like. More specifically, monofunctional monomers and polyfunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, such as polymethylolpropane tri (meth) acrylate, hexanediol (Meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonylphenol EO modified acrylate, bisphenol AEO modified diacrylate, polypropylene glycol diacrylate, dipenta Risuri penta acrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, ditrimethylolpropane tetraacrylate, urethane acrylate, 2-hydroxy-3-phenoxypropyl acrylate and the like. In the present specification, “(meth) acrylate” means acrylate or methacrylate.

  The ultraviolet absorber (UVA) is for absorbing and shielding ultraviolet rays contained in electrical or electronic devices, natural light, and the like. As the UV absorber, any known UV absorber can be used as long as it can achieve these purposes. Examples thereof include organic UV absorbers and inorganic UV absorbers (also referred to as “UV scattering agents”). be able to. Either one of these may be contained in the organic layer 2, or both may be contained.

  Examples of organic ultraviolet absorbers include triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, and acrylonitrile ultraviolet absorbers. Among them, a triazine-based ultraviolet absorber that has a high ultraviolet-absorbing ability and hardly deteriorates even with high energy such as ultraviolet rays can be given.

  Specific examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tri [[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] and A benzotriazole type ultraviolet absorber etc. can be mentioned. Specific examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, Examples include 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol.

  Examples of the inorganic ultraviolet absorber include metal oxide particles having an average particle diameter of about 5 nm to 120 nm. Such metal oxide particles are not particularly limited, and examples thereof include titanium dioxide, cerium oxide, zinc oxide, iron oxide, and barium sulfate.

  The ultraviolet absorber is preferably contained in an amount of 0.1% to 25% by mass, more preferably 0.5% to 25% by mass with respect to the resin forming the organic layer 2. It is particularly preferable to contain 5% by mass or more and 20% by mass or less.

  The light stabilizer is for capturing and stabilizing free radicals catalytically. As the light stabilizer, any known one can be used as long as such an object can be achieved. Among them, a hindered amine light stabilizer (HALS) is preferable from the viewpoints of solubility in various organic solvents and synergistic effect with the ultraviolet absorber. Can be mentioned.

  Specifically, the hindered amine light stabilizer is 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2,6,6). -Pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl ( 1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4- Yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraca Bokishireto, it can be mentioned 1,2,2,6,6-pentamethyl-4-piperidinyloxy methacrylate.

  The light stabilizer is preferably contained in an amount of 0.05% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less with respect to the resin forming the organic layer 2. The content is more preferably from 1% by mass to 15% by mass, and particularly preferably from 1% by mass to 10% by mass.

  As UV absorbers and light stabilizers, reactive UV absorption having reactive functional groups such as (meth) acryloyl groups in the molecule, or reactivity having reactive functional groups such as (meth) acryloyl groups in the molecule Light stabilizers can also be used. In the present specification, “(meth) acryloyl” means acryloyl or methacryloyl.

  Examples of the reactive ultraviolet absorber include (2-hydroxy-4- (methacryloyloxyethoxy) benzophenone) methyl methacrylate copolymer. Examples of the reactive light stabilizer include N-methyl-2,2,6,6-tetramethylpiperidyl methacrylate.

  In addition, in order to harden an electron beam curable compound, since polymerization initiators, such as a photoinitiator, are unnecessary, the organic layer 2 comprised with the electron beam curing resin normally does not contain a polymerization initiator. On the other hand, since a photopolymerization initiator is usually required to cure the ultraviolet curable compound, the organic layer 2 made of an ultraviolet curable resin contains a photopolymerization initiator. Therefore, when the organic layer 2 is composed of an ionizing radiation curable resin such as an electron beam curable resin or an ultraviolet curable resin, and the organic layer 2 does not contain or substantially does not contain a polymerization initiator, the organic layer 2 It can be said that it is composed of an electron beam curable resin. Further, when the organic layer 2 is made of an ionizing radiation curable resin and the organic layer 2 contains, for example, more than 0.1% by mass of a photopolymerization initiator, the organic layer 2 is made of an ultraviolet curable resin. Can be said to have been. The method for quantifying the polymerization initiator in the organic layer 2 can be performed by the same method as the method for quantifying the ultraviolet absorber and the light stabilizer described above.

  Examples of the polymerization initiator include acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones. Examples of the photopolymerization initiator include An oligo [2-hydroxy-2-methyl- [1- (methylvinyl) phenyl] propanone] can be mentioned.

  Although there is no restriction | limiting in particular in the formation method of the organic layer 2, Usually, it is performed using the coating liquid for organic layer formation. The coating solution for forming an organic layer contains one or more electron beam curable compounds, ultraviolet absorbers, and light stabilizers. The coating solution for forming an organic layer may contain a polymerizable compound other than the above.

  The organic layer forming coating solution may contain a solvent from the viewpoint of adjusting the viscosity of the coating solution. Solvents include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic carbonization such as toluene and xylene Mention may be made of hydrogen; or mixtures thereof. These solvents may be mixed and used at an arbitrary ratio within the scope of the gist of the present invention.

  If necessary, an additive may be added to the organic layer forming coating solution within a range that does not impair the effects of the present invention. Examples of the additive include a heat stabilizer, a plasticizer, a surfactant, an antistatic agent, an antioxidant, an infrared absorber, a dye (colored dye, colored pigment), an extender pigment, and a light diffusing agent. .

  When the organic layer forming coating solution is used, the organic layer 2 is formed by applying the organic layer forming coating solution on the plastic substrate 1, and irradiating the coated film with an electron beam to cause cross-linking polymerization. . The application method can be selected and applied from the application methods described in the “Manufacturing method” section below. The electron beam irradiation at this time may be performed using a conventionally known method and apparatus. In addition, since such a coating liquid for organic layer formation does not contain a polymerization initiator substantially, it can be said that it is a coating liquid for organic layer formation for electron beam curing. On the other hand, the organic layer forming coating solution substantially containing the photopolymerization initiator can be said to be an organic layer forming coating solution for ultraviolet curing.

  The organic layer 2 may be a single layer formed by one film formation, or two or more layers formed by two or more film formations. In the case of two or more layers, as long as the constituent elements of the present invention are satisfied, each layer may use the same organic layer forming coating solution or different organic layer forming coating solutions. The thickness of the organic layer 2 is preferably 0.1 μm or more and 20 μm or less from the viewpoint of substrate deflection, regardless of whether it is a single layer or two or more layers, and 0.5 μm from the viewpoint of surface properties and productivity. More preferably, it is 10 μm or less.

  When the organic layer 2 is formed by curing with an electron beam, the temperature of the organic layer forming coating solution does not rise, so the ultraviolet absorber and the light stabilizer contained in the organic layer forming coating solution are heated. It does not volatilize or decompose. On the other hand, when the organic layer 2 is formed by being cured by heat, the ultraviolet absorber and the light stabilizer contained in the organic layer forming coating liquid are volatilized or decomposed in the course of thermal curing. Therefore, the organic layer obtained by thermosetting the organic layer forming coating solution for thermosetting is inferior in weather resistance. In addition, the coating liquid for organic layer formation for thermosetting is a coating liquid for organic layer formation which consists of a thermosetting compound.

<Inorganic layer>
The inorganic layer 3 is formed on the organic layer 2 as a functional layer that blocks gas such as water vapor, and constitutes a gas barrier layer 4 together with the organic layer 2. Examples of the material for forming the inorganic layer 3 include one or more inorganic compounds selected from inorganic oxides, inorganic oxynitrides, inorganic nitrides, inorganic oxide carbides, inorganic oxycarbonitrides, silicon zinc oxides, and the like. Can be mentioned. Specific examples include inorganic compounds containing one or more elements selected from silicon, aluminum, magnesium, titanium, tin, indium, cerium, and zinc, and more specifically, silicon. Inorganic oxides such as oxides, aluminum oxides, magnesium oxides, titanium oxides, tin oxides, silicon zinc alloy oxides and indium alloy oxides, inorganics such as silicon nitrides, aluminum nitrides and titanium nitrides Inorganic silicon oxynitride such as nitride and silicon oxynitride can be given. Particularly preferably, the inorganic layer 3 is a layer made of one or more selected from silicon oxide, silicon nitride, silicon oxynitride, and silicon zinc oxide. The inorganic layer 3 may use the said material independently, and may mix and use the said material in arbitrary ratios within the range of the summary of this invention.

  The thickness of the inorganic layer 3 varies depending on the inorganic compound used, but is usually 5 nm or more, preferably 10 nm or more from the viewpoint of securing gas barrier properties, and usually 5000 nm or less from the viewpoint of suppressing the occurrence of cracks and the like. , Preferably 500 nm or less, more preferably 300 nm or less. Further, the inorganic layer 3 may be a single layer or two or more inorganic layers 3 having a total thickness within the above range. In the case of two or more inorganic layers 3, the same materials may be combined or different materials may be combined.

<Other configurations>
As described above, the gas barrier film 10 includes the base material 1, the organic layer 2, and the inorganic layer 3. For example, as shown in FIG. 3, the primer layer is further formed on one surface S1 of the base material 1. 5 and the protective layer 6 may be provided in that order. Further, for example, a primer layer 5 and a protective layer 6 may be further provided in this order on the organic layer 2 ′ and the inorganic layer 3 ′ on the other surface S2 of the gas barrier film 10B shown in FIG. 2 (not shown). ).

  The primer layer 5 is not essential, but is preferably provided in order to improve the adhesion between the inorganic layer 3 and the protective layer 6. Such a primer layer 5 is composed of a polymerizable compound. The polymerizable compound is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyester resins. Examples thereof include resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, urethane-acrylic copolymer resins, and the like. These resins can be used alone or as a mixture of two or more. Of these, urethane-acrylic copolymer resin is particularly preferable because it combines flexibility, toughness, and elasticity. In consideration of the environment, it is preferable not to use a resin system containing chlorine.

  Examples of the urethane-acrylic copolymer resin contained in the primer layer 5 include polycarbonate-based urethane- (meth) acrylic copolymer resin, polyester-based urethane- (meth) acrylic copolymer resin, polycarbonate-based urethane (meth) acrylate, A resin composed of an acrylic polyol is preferable, and a polycarbonate-based urethane- (meth) acrylic copolymer resin is more preferable. By forming the primer layer 5 containing these resins, stress relaxation properties are imparted, and those having excellent weather resistance are obtained.

  The primer layer 5 may contain one or both of an ultraviolet absorber and a light stabilizer. Since the primer layer 5 containing the ultraviolet absorber absorbs ultraviolet rays from the outside, the organic layer 2 can be prevented from being irradiated with ultraviolet rays from the outside, and the light resistance of the gas barrier film 10 can be further improved. it can. Moreover, the primer layer 5 containing a light stabilizer can improve the light resistance of the primer layer 5 itself. In addition, each kind of ultraviolet absorber and light stabilizer to be contained may be one kind or two or more kinds. Since the specific contents of the ultraviolet absorber and the light stabilizer are as described in the explanation section of the above “organic layer”, the explanation is omitted here.

  The thickness of the primer layer 5 is preferably 1 μm or more and 10 μm or less, and more preferably 3 μm or more and 6 μm or less. The primer layer 5 in this range can exhibit sufficient weather resistance and is advantageous in terms of economy. If the thickness of the primer layer 5 is less than 1 μm, sufficient weather resistance may not be obtained, and if the thickness of the primer layer 5 is more than 10 μm, it is disadvantageous in terms of economy. The primer layer 5 can be formed by using the resin composition as it is or by dissolving or dispersing it in a solvent. As a method for forming the primer layer 5, a known printing method or coating method is applied. For example, a knife coat, a comma coat, a gravure coat, a roll coat, etc. can be mentioned. Further, when the primer layer 5 is laminated on the inorganic layer 3, the surface of the inorganic layer 3 is subjected to so-called corona discharge treatment, plasma treatment, ozone treatment or ultraviolet ray in order to ensure adhesion between the inorganic layer 3 and the primer layer 5. It may be processed. Thereby, the adhesiveness of the inorganic layer 3 and the primer layer 5 can further be improved.

  Although the protective layer 6 is not an essential component, it is preferably provided in order to improve the weather resistance of the gas barrier film 10 and also imparts hard coat properties such as scratch resistance, solvent resistance, and antifouling properties. Are preferably provided. As illustrated in FIG. 3, the protective layer 6 may be provided on the surface of the gas barrier film 10, and another layer may be provided on the protective layer 6 (not shown). Examples of such other layers include an antistatic layer, a light shielding layer, an antireflection layer, a hard coat layer, an antifogging layer, an antifouling layer, and a printing layer.

  The protective layer 6 is made of an ionizing radiation curable resin. Such an ionizing radiation curable resin is obtained by curing an ionizing radiation curable compound with ionizing radiation. As the ionizing radiation curable compound, an ionizing radiation curable compound having a (meth) acryloyl group is preferable, and a polymerizable oligomer or prepolymer conventionally used as an ionizing radiation curable compound, particularly a polyfunctional compound. It can be suitably selected from polymerizable oligomers or prepolymers.

  Examples of such polyfunctional polymerizable oligomers or prepolymers include polymerizable oligomers or prepolymers having a radical polymerizable unsaturated group in the molecule. Examples of the polymerizable oligomer or prepolymer include epoxy (meth) acrylate, urethane (meth) acrylate, polyether urethane (meth) acrylate, caprolactone urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meta ) Polyfunctional polymerizable oligomers or prepolymers such as acrylate are preferred. Among these, polyfunctional urethane (meth) acrylate is preferable in terms of achieving both weather resistance and hard coat properties, and in particular, a tetrafunctional or higher urethane (meth) acrylate oligomer is preferable from the viewpoint of enhancing hard coat properties. As the urethane (meth) acrylate oligomer, an oligomer of caprolactone-based urethane (meth) acrylate is preferable. By improving the hard coat properties, it is possible to prevent scratches and suppress deterioration of visibility due to scratches.

  In addition to the above polymerizable oligomer, the ionizing radiation curable compound is used in combination with a polymer urethane (meth) acrylate such as a highly hydrophobic polybutadiene (meth) acrylate having a (meth) acrylate group in the side chain of the polybutadiene oligomer. be able to. The weather resistance can be further improved by using such a polymer urethane (meth) acrylate in combination. Among these polymer urethane (meth) acrylates, caprolactone-based ones are more preferable in terms of improving weather resistance.

  The protective layer 6 may contain one or both of an ultraviolet absorber and a light stabilizer. The protective layer 6 containing the ultraviolet absorber can absorb the ultraviolet rays from the outside and prevent the organic layer 2 from being irradiated with the ultraviolet rays from the outside, thereby further improving the weather resistance of the gas barrier film 10. Can do. Moreover, the protective layer 6 containing a light stabilizer can improve the light resistance of the protective layer 6 itself. In addition, 1 type may be sufficient as each kind of ultraviolet absorber and light stabilizer to contain, and 2 or more types may be sufficient as it. Since the specific contents of the ultraviolet absorber and the light stabilizer are as described in the explanation section of the above “organic layer”, the explanation is omitted here. The protective layer 6 containing an ultraviolet absorber is preferably composed of an electron beam curable resin.

  In addition, for the purpose of adjusting the viscosity of the protective layer 6 with a multifunctional urethane (meth) acrylate, a diluent such as a monofunctional (meth) acrylate such as methyl (meth) acrylate, They can be used in combination as long as the object of the present invention is not impaired. A monofunctional (meth) acrylate may be used individually by 1 type, may be used in combination of 2 or more type, and may use low-molecular-weight polyfunctional (meth) acrylate together. Moreover, as a diluent, the applicability | paintability of a resin composition can also be ensured using a normal organic solvent other than said monomer.

  The protective layer 6 may be added with a water-repellent additive such as a silicone-based surfactant and a fluorine-based surfactant. By adding such a water repellent additive, the moisture barrier property of the gas barrier film 10 can be improved. Moreover, the antifouling property of the gas barrier film 10 can be improved, and the visibility can be prevented from being lowered due to contamination. In addition, the protective layer 6 can contain a scratch-resistant filler in order to further improve the hard coat properties. The protective layer 6 may contain known additives other than those described above.

  The thickness of the protective layer 6 is preferably 3 μm or more and 15 μm or less, and more preferably 3 μm or more and 10 μm or less. The protective layer 6 in this range can sufficiently exhibit the function as the protective layer 6, and is also economical. If the thickness of the protective layer 6 is less than 3 μm, the function as the protective layer 6 may not be sufficiently exhibited, and if the thickness of the protective layer 6 is more than 15 μm, it is disadvantageous in terms of economy.

  The gas barrier film 10 is not limited to the structure of the primer layer 5 and the protective layer 6 described above, and other layers may be appropriately inserted between the organic layer 2 and the substrate 1, or the organic layer 2 of the plastic substrate 1 may be You may laminate | stack on the surface S2 of the side which is not formed, or may laminate | stack on the inorganic layer 3 or inorganic layer 3 '. As an arbitrary layer, as long as the characteristics of the present invention are not inhibited, for example, a conventionally known primer layer, matting agent layer, antistatic layer, smoothing layer, adhesion improving layer, light shielding layer, antireflection layer, hard coat layer , A stress relaxation layer, an antifogging layer, an antifouling layer, a printing layer, and an easy adhesion layer.

  The thus configured gas barrier film 10 according to the present invention has good gas barrier properties and weather resistance.

[Production method]
The manufacturing method of the gas-barrier film 10 which concerns on this invention is the process of apply | coating the coating liquid for organic layer formation which contains 1 type (s) or 2 or more types of electron beam curable resin, a ultraviolet absorber, and a light stabilizer on the base material 1 ( Coating step), a step of forming an organic layer 2 by irradiating the coating liquid for forming an organic layer applied on the substrate 1 with an electron beam (an organic layer forming step), and an inorganic layer on the organic layer 2 And the step of forming 3 (inorganic layer forming step).

  According to such a method for producing the gas barrier film 10, the organic layer 2 can be formed without any problem even when the organic layer forming coating solution contains one or more ultraviolet absorbers and light stabilizers. Can do. The gas barrier film 10 manufactured in this way can suppress the generation of free radicals in the organic layer 2 by absorbing the ultraviolet rays applied to the organic layer 2 by the ultraviolet absorber. Even if free radicals are generated in the organic layer 2, the light stabilizer can capture and stabilize the free radicals. Therefore, even when the organic layer 2 is irradiated with ultraviolet rays from the outside, the oxidation reaction of the organic layer 2 based on free radicals can be suppressed, so that the organic layer 2 is prevented from being oxidized and yellowing. it can. Moreover, since it can prevent that the organic layer 2 oxidizes and changes in quality, it can prevent that the adhesiveness of the organic layer 2 and the inorganic layer 3 falls, and can prevent that gas barrier property falls. As a result, the manufacturing method of the gas barrier film 10 which shows favorable gas barrier property and a weather resistance can be provided. Hereinafter, each step will be described.

(Coating process)
The coating process is a process of coating an organic layer forming coating solution containing one or more electron beam curable compounds, ultraviolet absorbers, and light stabilizers on the plastic substrate 1. The organic layer forming coating solution is as described in the explanation section of the above “organic layer”, and therefore the description thereof is omitted here.

  Examples of the coating method for the organic layer forming coating solution include a roll coating method, a gravure roll coating method, a kiss roll coating method, a reverse roll coating method, a Miya bar coating method, a gravure coating method, a spin coating method, and a die coating method. Can be mentioned.

  After applying the organic layer forming coating solution, drying is performed as necessary. The drying temperature may be room temperature, but when the organic layer forming coating solution contains a solvent, it is preferable to perform drying to remove the solvent at a temperature equal to or higher than the boiling point of the solvent.

(Organic layer formation process)
The organic layer forming step is a step of forming the organic layer 2 by irradiating the organic layer forming coating solution applied on the substrate 1 with an electron beam. As an electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The acceleration voltage of the electron beam is usually 100 keV or more and 1000 keV or less, and preferably 100 keV or more and 300 keV or less. The irradiation amount of the electron beam is usually 1 Mrad or more and 30 Mrad or less.

(Inorganic layer forming process)
The inorganic layer forming step is a step of depositing an inorganic layer material (inorganic layer forming material) on the organic layer 2 to form the inorganic layer 3. Since the inorganic layer material is as described in the explanation section of the “inorganic layer”, the description thereof is omitted here.

  As a method for forming the inorganic layer 3, for example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, or a plasma chemical vapor deposition method can be preferably exemplified. The film forming conditions in these various forming methods may be adjusted by appropriately adjusting conventionally known film forming conditions in consideration of the physical properties and thickness of the inorganic layer to be obtained.

  More specifically, (1) a vacuum vapor deposition method in which a raw material such as an inorganic oxide, inorganic nitride, inorganic oxynitride, or metal is heated and deposited on a substrate, and (2) oxygen gas is introduced into the raw material. Oxidation reaction vapor deposition method to oxidize and deposit on the substrate, (3) Sputtering method to deposit on the substrate by introducing argon gas and oxygen gas into the target material and sputtering, (4) Generate the material with plasma gun Using an ion plating method in which the plasma beam is heated and deposited on the substrate, and (5) a plasma chemical vapor deposition method in which an organic silicon compound or the like is used as a raw material and a silicon oxide film is deposited on the substrate. Can do.

  In addition, when the gas barrier film 10 has the other functional layer mentioned above, the formation process of those layers is included arbitrarily.

[apparatus]
The device according to the present invention is a display device or a power generation device using the gas barrier film 10 of the present invention. Thereby, since the gas barrier film 10 which shows favorable gas barrier property and a weather resistance was used, the apparatus which is excellent in a gas barrier property and a weather resistance is requested | required can be provided. More specifically, it is possible to reduce the influence of ultraviolet rays and the like that degrade the quality characteristics of the apparatus.

  Examples of the display device include an organic EL element, a liquid crystal display element, a touch panel, and electronic paper. A thin film transistor that drives these display devices in an active matrix is also included in the display device. In addition, the configuration of each of these display devices is not particularly limited, and a conventionally known configuration can be appropriately employed, and the sealing means by the gas barrier film 10 applied to each of such display devices is not particularly limited. It can be a known means.

  Specifically, for example, as an organic EL element, a cathode and an anode are provided on the gas barrier film 10 according to the present invention, and an organic light emitting layer (also simply referred to as “light emitting layer”) is provided between both electrodes. The thing which has an organic layer to include can be mentioned. As a lamination | stacking aspect of the organic layer containing a light emitting layer, the aspect laminated | stacked in order of the positive hole transport layer, the light emitting layer, and the electron carrying layer from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. Further, a hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be only one layer, or the light emitting layer may be divided like a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers. Since the organic EL element is a light emitting element, at least one of the anode and the cathode is preferably transparent.

  Examples of the power generation device include a solar cell element (solar cell module). The configuration of the power generation device is not particularly limited, and a conventionally known configuration can be appropriately employed. Furthermore, the sealing means by the gas barrier film 10 applied to such a power generator is not particularly limited, and can be a conventionally known means. For example, the gas barrier film 10 can be used as a back surface protection sheet for solar cell elements.

  Specifically, for example, as a solar cell module, an example in which the gas barrier film 10 according to the present invention is used as a solar cell back sheet can be given. Such solar cell modules are, in order from the sunlight side in the thickness direction, a front substrate (having high light transmittance such as glass or film), filler, solar cell element, lead wire, terminal, terminal box, solar In the configuration of the battery back sheet, they are fixed to exterior materials (such as aluminum frames) at both ends via a sealing material. Examples of the solar cell backsheet include an example in which the gas barrier film 10 according to the present invention is sandwiched between the back surface sealing film and the film disposed on the outer layer side. As the back surface sealing film, for example, a white polyester film having a high reflectivity is used so as to reflect sunlight on the solar cell module side and increase the conversion efficiency. Moreover, as a film arrange | positioned at the outer layer side, a weather resistance, a hydrolysis resistance film, etc. are used.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
As a plastic substrate, an organic layer-forming coating solution A for electron beam curing prepared on the one side of a 100 μm-thick polyethylene terephthalate film (trade name: Cosmo Shine A-4300, manufactured by Toyobo Co., Ltd.) Was applied by die coating, dried at 70 ° C. for 1 minute, and then irradiated with an electron beam under the conditions of 165 keV and 5 Mrad (50 kGy) to form an organic layer having a thickness of 5 μm. In addition, the coating liquid A for organic layer formation does not contain a polymerization initiator.

(Composition of coating solution A for organic layer formation)
-Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass-Methyl ethyl ketone: 17 parts by mass-Toluene: 18 parts by mass-Hydroxyphenyltriazine-based ultraviolet absorber (BASF Japan Ltd.) Product name: Tinuvin 479): 3 parts by mass Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., Product name: Sanol LS-3410): 3 parts by mass

The inorganic layer was formed on the organic layer. Specifically, the plastic substrate on which the organic layer was formed was set in a hollow cathode type ion plating apparatus so that the organic layer side was oriented to form a film. Then, silicon oxide (manufactured by High Purity Chemical Research Laboratories), which is an evaporation source material, was put into a crucible in a hollow cathode type ion plating apparatus and then evacuated. After the degree of vacuum reached 5 × 10 ⁻⁴ Pa, 15 sccm of argon gas was introduced into the plasma gun, and plasma with a current of 110 A and a voltage of 90 V was generated. Plasma was bent in a predetermined direction by maintaining the inside of the chamber at 1 × 10 ⁻¹ Pa and magnetic force, and the evaporation source material was irradiated. It was confirmed that the evaporation source material in the crucible sublimates through a molten state. Ion plating was performed for 15 seconds to deposit on the substrate, thereby forming a silicon oxide layer having a thickness of 100 nm.

  The layer structure of the gas barrier film of Example 1 obtained as described above is plastic base material / organic layer / inorganic layer.

[Example 2]
A gas barrier film of Example 2 was produced in the same manner as in Example 1 except that the coating solution B for forming an organic layer for electron beam curing prepared in the following composition was used. The organic layer forming coating solution B is the same as the organic layer forming coating solution A except that the type of the UV absorber is changed. In addition, the coating liquid B for organic layer formation does not contain a polymerization initiator.

(Composition of coating liquid B for organic layer formation)
-Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass-Methyl ethyl ketone: 17 parts by mass-Toluene: 18 parts by mass-Hydroxyphenyltriazine-based ultraviolet absorber (BASF Japan Ltd.) Product name: Tinuvin 400): 3 parts by mass Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., Product name: Sanol LS-3410): 3 parts by mass

[Example 3]
A gas barrier film of Example 3 was produced in the same manner as Example 1 except that the coating solution C for forming an organic layer for electron beam curing prepared in the following composition was used. The organic layer forming coating solution C is the same as the organic layer forming coating solution A except that the type of the UV absorber is changed. In addition, the coating liquid C for organic layer formation does not contain a polymerization initiator.

(Composition of coating liquid C for organic layer formation)
Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass Methyl ethyl ketone: 17 parts by mass Toluene: 18 parts by mass Benzotriazole ultraviolet absorber (BASF Japan, Inc. , Trade name: Tinuvin 328): 3 parts by mass Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., product Name: Sanol LS-3410): 3 parts by mass

[Example 4]
A gas barrier film of Example 4 was produced in the same manner as in Example 1 except that the coating solution D for forming an organic layer for electron beam curing prepared in the following composition was used. The organic layer forming coating solution D is the same as the organic layer forming coating solution A except that the type of the light stabilizer is changed. In addition, the coating liquid D for organic layer formation does not contain a polymerization initiator.

(Composition of organic layer forming coating solution D)
Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass Methyl ethyl ketone: 17 parts by mass Toluene: 18 parts by mass Benzotriazole ultraviolet absorber (BASF Japan, Inc. , Trade name: Tinuvin 328): 3 parts by mass Hindered amine light stabilizer (manufactured by BASF Japan Ltd., trade name: Tinuvin 123): 3 parts by mass

[Example 5]
A gas barrier film of Example 5 was produced in the same manner as in Example 1 except that the coating solution E for forming an organic layer for electron beam curing prepared in the following composition was used. The organic layer forming coating solution E is the same as the organic layer forming coating solution A except that the type of the electron beam curable compound is changed. In addition, the coating liquid E for organic layer formation does not contain a polymerization initiator.

(Composition of coating solution E for organic layer formation)
-Urethane acrylate oligomer (polymerizable compound, manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: UV-7600B): 65 parts by mass-Methyl ethyl ketone: 17 parts by mass-Toluene: 18 parts by mass-Hydroxyphenyltriazine-based UV absorber (BASF Japan) Product name: Tinuvin 479): 3 parts by mass-Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, Nippon Emulsifier Co., Ltd.) Product name: Sanol LS-3410): 3 parts by mass

[Example 6]
A gas barrier film of Example 6 was produced in the same manner as in Example 1 except that the coating solution F for forming an organic layer for electron beam curing having the following composition was used. The organic layer forming coating solution F is the same as the organic layer forming coating solution A except that the type of the electron beam curable compound is changed. In addition, the coating liquid F for organic layer formation does not contain a polymerization initiator.

(Composition of coating solution F for organic layer formation)
-Bifunctional caprolactone-based urethane acrylate oligomer: 65 parts by mass-Methyl ethyl ketone: 17 parts by mass-Toluene: 18 parts by mass-Hydroxyphenyltriazine-based ultraviolet absorber (trade name: Tinuvin 479 manufactured by BASF Japan Ltd.): 3 parts by mass Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass

[Comparative Example 1]
A gas barrier film of Comparative Example 1 was produced in the same manner as in Example 1 except that the coating solution a for forming an organic layer for ultraviolet curing prepared in the following composition was irradiated with ultraviolet rays instead of an electron beam. . The organic layer forming coating solution a is the same as the organic layer forming coating solution A except that it contains a photopolymerization initiator and does not contain an ultraviolet absorber and a light stabilizer. Irradiation with ultraviolet rays was performed under the conditions of a wavelength in the range of 260 nm to 400 nm and an integrated light amount of 300 mJ / cm ² .

(Composition of coating solution a for organic layer formation)
Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass Methyl ethyl ketone: 17 parts by mass Toluene: 18 parts by mass Oligo [2-hydroxy-2-methyl- [1 -(Methylvinyl) phenyl] propanone] (photopolymerization initiator, manufactured by Lamberti, trade name: ESACURE ONE): 2 parts by mass

[Comparative Example 2]
A gas barrier film of Comparative Example 2 was produced in the same manner as Comparative Example 1 except that the coating solution b for forming an organic layer for ultraviolet curing prepared in the following composition was used. The organic layer forming coating solution b is the same as the organic layer forming coating solution a except that it contains an ultraviolet absorber.

(Composition of coating liquid b for organic layer formation)
Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass Methyl ethyl ketone: 17 parts by mass Toluene: 18 parts by mass Oligo [2-hydroxy-2-methyl- [1 -(Methylvinyl) phenyl] propanone] (photopolymerization initiator, manufactured by Lamberti, trade name: ESACURE ONE): 2 parts by mass-Hydroxyphenyltriazine-based ultraviolet absorber (BASF Japan, trade name: Tinuvin 479) : 3 parts by mass

  The gas barrier film of Comparative Example 2 could not be evaluated because the curing reaction of the coating liquid b for forming an organic layer did not proceed due to ultraviolet irradiation, and the curing of the organic layer was insufficient.

[Comparative Example 3]
A gas barrier film of Comparative Example 3 was produced in the same manner as Comparative Example 1, except that the coating solution c for forming an organic layer for ultraviolet curing prepared in the following composition was used. The organic layer forming coating solution c is the same as the organic layer forming coating solution a except that it contains a light stabilizer.

(Composition of coating solution c for forming an organic layer)
Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass Methyl ethyl ketone: 17 parts by mass Toluene: 18 parts by mass Oligo [2-hydroxy-2-methyl- [1 -(Methylvinyl) phenyl] propanone] (photopolymerization initiator, manufactured by Lamberti, trade name: ESACURE ONE): 2 parts by mass A hindered amine light stabilizer having a reactive functional group (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., trade name: SANOL LS-3410): 3 parts by mass

[Comparative Example 4]
A gas barrier film of Comparative Example 4 was produced in the same manner as in Example 1 except that the coating solution d for forming an organic layer for electron beam curing having the following composition was used. The organic layer forming coating solution d is the same as the organic layer forming coating solution A except that it does not contain an ultraviolet absorber and a light stabilizer.

(Composition of coating liquid d for organic layer formation)
Polyester acrylate (polymerizable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 65 parts by mass Methyl ethyl ketone: 17 parts by mass Toluene: 18 parts by mass

[Comparative Example 5]
A gas barrier film of Comparative Example 5 is produced in the same manner as in Example 1 except that the coating liquid e for forming an organic layer for thermosetting prepared in the following composition is used and heat curing treatment is performed instead of electron beam irradiation. did. The organic layer forming coating solution e is the same as the organic layer forming coating solution A except that the electron beam curable compound is changed to a thermosetting compound. The heat curing treatment was performed by holding at 160 ° C. for 1 hour.

(Composition of organic layer forming coating solution e)
-Cardo polymer (manufactured by Nippon Steel Chemical Co., Ltd., trade name: V-259-EH): 65 parts by mass-Methyl ethyl ketone: 17 parts by mass-Toluene: 18 parts by mass-Hydroxyphenyltriazine-based ultraviolet absorber (BASF Japan Ltd.) Product name: Tinuvin 479): 3 parts by mass Hindered amine light stabilizer having a reactive functional group (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by Nippon Emulsifier Co., Ltd., Product name: Sanol LS-3410): 3 parts by mass

[Evaluation and results]
For the gas barrier films of Examples 1 to 6 and Comparative Examples 1 to 5, (a) measurement of water vapor transmission rate immediately after production (initial), (b) measurement of water vapor transmission rate after light resistance test, and (c) light resistance test. After the color inspection, (d) the adhesion test after the light resistance test was conducted.

The water vapor transmission rate was measured using a water vapor transmission rate measuring device (trade name: PERMATRAN-W3 / 31, manufactured by MOCON) in an atmosphere of a temperature of 37.8 ° C. and a humidity of 100% RH. The measurement limit of this device is 0.05 g / m ² / day.

The light resistance test was performed by repeating the following (A), (B), and (C) on the gas barrier film with one cycle using an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.) and repeating this 21 times. .
(A) Irradiation with ultraviolet rays having an illuminance of 65 mW / cm ² and a wavelength of 365 nm in an atmosphere of temperature: 63 ° C. and humidity: 50% RH for 20 hours.
(B) Watering treatment is performed for 30 seconds.
(C) Hold for 4 hours in an atmosphere of temperature: 63 ° C. and humidity: 98% RH (no UV irradiation).

  The color inspection was performed by visually observing the gas barrier film and confirming the presence or absence of yellowing.

  The adhesion test was performed by a cross cut test. The cross-cut test was performed in accordance with the description in 8.5.1 of JIS-K5400. Specifically, using a cutter guide with a gap interval of 2 mm, the cuts reaching the plastic substrate through the inorganic layer are made vertically and horizontally to form 100 squares, and cellophane adhesive tape (Nichiban 405 No. 24 mm) Width) was attached to the cut surface of the mass and rubbed with an eraser to completely adhere, and then peeled off vertically. And the surface after peeling was observed visually and the presence or absence of peeling was confirmed.

  The results are shown in Table 1.

  In addition, the component contained in the organic layer of the gas barrier film of Examples 1-6 was analyzed. This analysis was performed using gas chromatography (manufactured by Shimadzu Corporation, trade name: GC-2025). The gas barrier films of Examples 1 to 6 were placed in a vial and sealed, and kept at 160 ° C. for 30 minutes to volatilize the organic layer components to achieve an equilibrium state, and then a part of the headspace part was subjected to gas chromatography. A qualitative analysis and a quantitative analysis were performed on each component that was introduced and separated by gas chromatography. It was confirmed that the organic layers of the gas barrier films of Examples 1 to 6 contained the electron beam curable resin, the ultraviolet absorber, and the light stabilizer at the same ratio as the blending ratio. Moreover, the organic layer of the gas-barrier film of Examples 1-6 did not contain a polymerization initiator substantially.

  From Table 1, the gas barrier films of Examples 1 to 6 can maintain a high water vapor transmission rate even after the light resistance test, the yellowing does not occur in the organic layer, and the organic layer and the organic layer are tested by the adhesion test. It was found that no separation occurred between the inorganic layer and the inorganic layer.

1 Base material (plastic base material)
2, 2 'organic layer 3, 3' inorganic layer 4, 4 'gas barrier layer 5 primer layer 6 protective layer 10, 10A, 10B, 10C gas barrier film S1 one side of plastic substrate S2 other side of plastic substrate

Claims (8)

A base material, an organic layer provided on the base material, and an inorganic layer provided on the organic layer,
The organic layer includes an electron beam curable resin, an ultraviolet absorber of 0.1% by mass to 25% by mass with respect to the resin, and a light stabilizer of 0.05% by mass to 15% by mass with respect to the resin. A gas barrier film characterized by containing one or more of each.   The gas barrier film according to claim 1, wherein the organic layer contains 0.1% by mass or less of a polymerization initiator or does not contain a polymerization initiator.   The gas barrier film according to claim 1 or 2, wherein the electron beam curable resin is an acrylic resin.   The gas barrier film according to any one of claims 1 to 3, wherein the ultraviolet absorber is a triazine-based ultraviolet absorber.   The gas barrier film according to any one of claims 1 to 4, wherein the light stabilizer is a hindered amine light stabilizer.   The gas barrier film according to any one of claims 1 to 5, wherein a protective layer containing an ultraviolet absorber is provided on the inorganic layer.   An apparatus, which is a display apparatus or a power generation apparatus using the gas barrier film according to claim 1. Applying a coating solution for forming an organic layer containing one or more electron beam curable compounds, ultraviolet absorbers, and light stabilizers on the substrate; and
Irradiating an electron beam to the organic layer forming coating solution applied on the substrate to form an organic layer;
And a step of forming an inorganic layer on the organic layer.

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