JP4624894B2 - Gas barrier structure and method for producing the same - Google Patents

Description

  The present invention relates to a gas barrier structure. More specifically, the present invention relates to a structure requiring barrier properties against permeation of oxygen or water vapor, for example, a structure having excellent gas barrier properties suitable as a film-like substrate such as an organic EL device, and a method for producing the same. It is about.

  A gas barrier film used for a substrate such as a packaging for foods and pharmaceuticals is required to have a barrier property against permeation of oxygen and water vapor. This is because in food packaging, it is important to maintain the taste and freshness by suppressing oxidation and alteration of proteins and fats and oils, and in pharmaceutical packaging, it is important to maintain the efficacy by inhibiting alteration of active ingredients.

  Conventionally, polyvinyl alcohol (PVA) and ethylene vinyl acetate copolymer (EVOH) have been widely used as gas barrier films. However, these gas barrier films have a large temperature-humidity dependency on gas barrier properties, so There was a problem that the gas barrier property was lowered under humidity. Particularly, the water vapor barrier property is remarkably lowered, and it is not suitable for use in boiling sterilization treatment or retort sterilization treatment or for food packaging with high water activity in which a large amount of water is contained in the contents. In addition, in the case of a gas barrier film made of polyvinylidene chloride (PVDC), the humidity dependency is small, but it is difficult to obtain a high gas barrier property. There are problems in terms of waste disposal such as cycling.

On the other hand, a gas barrier film obtained by forming an inorganic compound thin film such as SiO _x has a better gas barrier property than that using a gas barrier polymer and has a low temperature and humidity dependency, and is now widely used.

SiN _x and SiO _x N _y are used as sealing films in liquid crystal display elements, organic EL elements, and the like, and are currently mainly used for glass substrates. However, such a glass substrate has not been satisfactory in terms of weight reduction and impact resistance. Moreover, since the glass substrate has poor flexibility, it could not be used as a flexible substrate.

  In a flexible substrate, if the gas barrier film cannot follow the substrate, cracks and peeling occur, causing deterioration of the barrier properties. However, when the gas barrier film is formed on the flexible substrate with a sufficient thickness to ensure a predetermined barrier property, the followability of the gas barrier film may be reduced and cracks and peeling may occur. Therefore, there is a demand for a barrier film that is excellent in terms of flexibility and bonding strength in addition to gas barrier properties.

Japanese Patent Application Laid-Open No. 2001-205743 discloses an example in which a plastic substrate having a multilayer structure and having a layer containing a layered compound is used for a liquid crystal display device. The use of the layered compound provides heat resistance, hardness, and air resistance. It is described that it is improved. However, this plastic substrate does not seem to have sufficient gas barrier properties depending on the application.
JP 2001-205743 A

  In view of these problems of the prior art, an object of the present invention is to provide a structure excellent in heat resistance and gas barrier properties. In particular, an object of the present invention is to provide a gas barrier structure that can be used for an organic EL device using a flexible support.

  The present invention achieves the above object.

  The method for producing a gas barrier structure according to the present invention is a method for producing a gas barrier structure having at least one photocurable resin layer and an inorganic compound layer, and is formed on at least one surface of a support substrate. A first curing step of producing a semi-cured photo-curable resin layer by irradiating the photo-curable resin layer with ultraviolet rays, and an inorganic compound layer was formed on the semi-cured photo-curable resin layer by vacuum deposition Thereafter, the second curing step of further irradiating ultraviolet rays to further cure the semi-cured photocurable resin layer is performed.

Such a method for producing a gas barrier structure according to the present invention includes, as a preferred specific example, the first curing step, the dynamic elasticity measured by the dynamic viscoelasticity measurement method for the photocurable resin layer. This is performed until the value of E ′ (E ₁ ′) shown is 30 to 70% of the value of E ′ (E ₂ ′) after the second curing step.

  Such a method for producing a gas barrier structure according to the present invention includes, as a preferred specific example, that the photocurable resin is made of polyacrylate or acrylic.

  In a preferred specific example of the method for producing a gas barrier structure according to the present invention, the inorganic compound layer is made of aluminum oxide, silicon oxide, silicon oxynitride, silicon oxide carbide, silicon oxycarbonitride, or silicon dioxide. Which is either.

  As a preferable specific example of the method for producing a gas barrier structure according to the present invention, the vacuum vapor deposition method is any one of a plasma PVD method, a sputtering method, an ion plating method, and a CVD method. Include.

  Such a method for producing a gas barrier structure according to the present invention includes, as a preferred specific example, a method in which at least one layer of a photocurable resin layer or an inorganic compound layer is further formed on the inorganic compound layer. .

The gas barrier structure according to the present invention has an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 h or less and a water vapor permeability of 0.5 g / m ² · 24 h or less. To do.

  The method for producing a gas barrier structure according to the present invention is a method for producing a gas barrier structure having at least one photocurable resin layer and an inorganic compound layer, and is formed on at least one surface of a support substrate. A first curing step of producing a semi-cured photo-curable resin layer by irradiating the photo-curable resin layer with ultraviolet rays, and an inorganic compound layer was formed on the semi-cured photo-curable resin layer by vacuum deposition After that, it is characterized by performing the second curing step of further irradiating ultraviolet rays to further cure the semi-cured photo-curable resin layer, and has excellent gas barrier properties and durability. It is possible to produce a gas barrier structure having excellent properties.

Such a gas barrier structure obtained by the present invention has remarkably low gas permeability of gas (for example, oxygen, water vapor, etc.), and the bonding strength of each layer constituting the gas barrier structure is high. Therefore, the gas barrier property is prevented from being deteriorated by ambient temperature, humidity, mechanical shock, bending when used as a flexible substrate, and the like.
Therefore, the gas barrier structure according to the present invention maintains a sufficient gas barrier property for a long time even if it is thinner than the conventional structure, so that it is light in weight, thinned, reduced in manufacturing cost, high light transmittance, transparency, etc. It is particularly suitable for particularly required applications (for example, laminated films for displays, organic EL elements, etc.).

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
1 to 3 are sectional views showing preferred specific examples of the gas barrier structure of the present invention.

  A gas barrier structure 10 according to the present invention shown in FIG. 1 includes a photocurable resin layer 11 and an inorganic compound layer 12 laminated on one surface of the photocurable resin layer 11 / inorganic compound layer 12 layer. It is a thing of composition.

  The gas barrier structure according to the present invention has at least one photocurable resin layer and an inorganic compound layer. Therefore, two or more photocurable resin layers and inorganic compound layers can exist.

  The gas barrier structure 20 according to the present invention shown in FIG. 2 includes a photocurable resin layer 11 (first photocurable resin layer), an inorganic compound layer 12 laminated on one surface thereof, and a photocurable resin layer 21. The layer configuration of “photocurable resin layer 11 / inorganic compound layer 12 / photocurable resin layer 21” in which (second photocurable resin layer) is laminated.

  The gas barrier structure 30 according to the present invention shown in FIG. 3 includes a photocurable resin layer 11 and an inorganic compound layer (first inorganic compound layer) 12 laminated on one surface thereof, and the photocurable resin layer described above. 11 is a layer configuration of “inorganic compound layer 12 / photo-curing resin layer 11 / inorganic compound layer 13” in which an inorganic compound layer 13 (second inorganic compound layer) is laminated on the opposite surface.

  Below, the manufacturing method of the gas-barrier structure of this invention is demonstrated.

(1) Method for Producing Gas Barrier Structure The method for producing a gas barrier structure according to the present invention is a method for producing a gas barrier structure having at least one photocurable resin layer and an inorganic compound layer, each comprising a supporting group. A first curing step of producing a semi-cured photocurable resin layer by irradiating the photocurable resin layer formed on at least one surface of the material with ultraviolet rays; and on the semi-cured photocurable resin layer After the inorganic compound layer is formed by a vacuum deposition method, the second curing step of further irradiating ultraviolet rays to further cure the semi-cured photocurable resin layer is performed.

  In the gas barrier structure according to the present invention, it is sufficient that at least one layer of the photocurable resin layer and the inorganic compound layer exist. Therefore, the photocurable resin layer and the inorganic compound layer can each be present in one layer or two or more layers. Moreover, in this invention, layers or materials other than a photocurable resin layer and an inorganic compound layer may be formed in the whole surface or a part of gas barrier structure by this invention.

  When producing the gas barrier structure according to the present invention, the photocurable resin layer is formed on at least one surface of the support substrate, and the support substrate is peeled off after the photocurable resin layer is cured. Alternatively, it may exist in the gas barrier structure as a layer constituting the gas barrier structure according to the present invention without peeling.

  In addition, when the gas barrier structure according to the present invention is applied to an application requiring light transmittance, for example, a laminated film for a display, etc., when the support substrate is present in the gas barrier structure, the support is used. The substrate needs to be light transmissive. Further, in the first curing step and / or the second curing step in the present invention, when the supporting substrate is present on the ultraviolet irradiation surface side of the photocurable resin layer, the supporting substrate is UV transmissive. Need to be.

(I) Support base material The support base material used when producing the gas barrier structure according to the present invention is preferably made of a resin material having high heat resistance and transparency and a small linear expansion coefficient. In this invention, the resin material conventionally used in the electronic component use and the laminated film use for a display can be used.

  Among such resin materials, particularly preferred as the support substrate of the present invention include, for example, poly (meth) acrylate, poly (meth) arylate (PAR), polyimide (PI), polyamideimide (PAI), poly Ether sulfone (PES), polycarbonate (PC), polynorbornene which is a cyclic polyolefin copolymer, cyclic polyolefin resin, polycyclohexene, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide (PEI) , Polysiloxane, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF), Vinyl fluoride (PVF), Over fluoroethylene - perfluoro propylene - perfluoro ether - can be exemplified a fluorine-based resin such as copolymer (EPA). Examples thereof include a resin composition containing a (meth) acrylate compound having a cycloalkyl skeleton and a derivative thereof as disclosed in JP-A-11-222508.

  Examples of preferable cyclic polyolefin include cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd., trade name: “Zeonor”), norbornene resin (manufactured by JSR Corporation, trade name: “Arton”) and the like. More preferable examples include a resin composition containing a (meth) acrylate compound having a cycloalkyl skeleton and a derivative thereof described in JP-A-11-222508.

  When the support substrate is required to be transparent, it is preferable that the light transmittance in the wavelength region of 400 to 800 nm is 80% or more. And when it is exposed to a relatively high temperature (for example, a temperature of 150 ° C. or higher) in the production process, for example, for electronic parts and display laminated films, the linear expansion coefficient is 15 to 100 ppm / K. Particularly preferred are those having a glass transition temperature (Tg) of 150 to 300 ° C.

  The thickness of the supporting substrate is about 5 to 220 μm, preferably 10 to 50 μm. If it is less than this range, pinholes are likely to be generated due to electrostatic discharge, and the gas barrier properties may be deteriorated by the pinholes, which is not preferable. On the other hand, if the above range is exceeded, even if the same gas barrier performance can be maintained, the quantity that can be input to the production machine at a time is limited, and the production amount of one lot is small, resulting in high costs.

  And the supporting substrate is, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties as required. Various plastic compounding agents, additives and the like can be added for the purpose of improving and modifying electrical characteristics, strength, and the like. The addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. If necessary, other general additives such as lubricants, plasticizers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, dyes, pigments A colorant such as the above can be used, and a modifying resin can also be used.

(B) Photocurable resin layer The resin material for forming the photocurable resin layer 11 of the gas barrier structure according to the present invention is preferably one having an acrylate functional group, for example, a relatively low molecular weight polyester. Resins, polyether 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 and reactions Monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and other polyfunctional monomers such as hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, acrylic acid, methacrylic acid, itaconic acid, maleic Acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isooctyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate, Cyclohexyl acrylate, t-butylaminoethyl methacrylate, 2-cyanoethyl Acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-ethoxyethyl methacrylate, 2 (2-ethoxyethoxy) ethyl acrylate, nonylphenoxy polyethylene glycol acrylate, nonyl Phenoxy polypropylene glycol acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, phenoxy ethyl acrylate, benzyl acrylate, benzyl methacrylate, 2-ethylhexyl carbitol acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, perfluoro Octylethyl methacrylate, iso Anate ethyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, cyclohexyl methacrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate (Tg = 107 ° C.), N-methylol methacrylamide, acrylamide, Tetrahydrofurfuryl methacrylate, diacetone acrylamide, N-vinyl pyrrolidone, isobornyl methacrylate, isobornyl acrylate and the like can be mentioned.

  Further, when the above-mentioned resin material is made photocurable, the photopolymerization initiator includes acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthone. In addition, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be used as a photosensitizer. In particular, in the present invention, it is preferable to mix urethane acrylate as an oligomer and dipentaerythritol hexaacrylate as a monomer.

The amount of the active energy ray to be irradiated, 0.1~100J / cm ² ultraviolet rays 200 to 400 nm, preferably in the range of 1~30J / cm ^2. Specific examples of the lamp to be used include a metal halide lamp, a high pressure mercury lamp, and the like.

  The thickness of the photocurable resin layer in the gas barrier structure can be appropriately set in the range of about 200 to 3000 nm, preferably 500 to 1500 nm. When the thickness is less than 200 nm, protrusions such as waviness of the supporting substrate cannot be filled, and the surface cannot be flattened. When the thickness exceeds 3000 nm, the stress of the film increases, and the supporting substrate becomes The flexible case is not preferable because cracks are likely to occur and the time required for film formation becomes long.

(C) Inorganic compound layer The inorganic compound layer 12 can form a thin film on the photocurable resin layer by a vacuum deposition method, and has a predetermined barrier property against a gas (for example, a gas such as oxygen or water vapor). In addition, any inorganic compound can be used as long as it transmits ultraviolet light sufficient to cure the photocurable resin layer in the second curing step. In particular, when the gas barrier structure is required to have a high degree of transparency, such as when applied to a laminated film for a display, one having a high transmittance for both ultraviolet light and visible light is preferable.

  Particularly preferable inorganic compounds in the present invention are, for example, oxides such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. From the viewpoint of production efficiency, aluminum oxide, silicon oxide, silicon oxynitride, silicon oxide carbide, and silicon dioxide can be mentioned.

  As a method for forming the inorganic compound layer 12, a sputtering method, an ion plating method, a plasma PVD method, a plasma CVD method, an ion beam assisted CVD method, or the like can be applied. These methods can be appropriately selected in consideration of the type of base film or inorganic oxide film forming material, easiness of film formation, process efficiency, and the like.

  The thickness of the inorganic compound layer 12 can be appropriately selected depending on the type and configuration of the inorganic compound used. Generally, 5 to 300 nm is preferable. If it exceeds 300 nm, the flexibility of the thin film is lowered, and there is a possibility that the thin film may be cracked by an external force such as bending or pulling after film formation. In addition, coloring, transparency may be reduced, or the stress of the material itself may increase and flexibility may be impaired. Also, productivity may be significantly reduced, and protrusions may be formed from abnormal grain growth to produce Rz (maximum This is not preferable because the height roughness tends to increase. On the other hand, when the thickness of the inorganic compound layer 12 is less than 5 nm, although it is preferable in terms of transparency, it is difficult to obtain a uniform film, and it is difficult to sufficiently achieve the gas barrier function. From the above points, the thickness of the inorganic compound layer 12 is particularly preferably 10 to 100 nm. In addition, the thickness of an inorganic compound layer is a thing when it measures using the fluorescence X-ray-analysis apparatus: RIX-3000 by Rigaku Corporation.

(D) Curing Step In the method for producing a gas barrier structure according to the present invention, a first curing step for producing a semi-cured photocurable resin layer by irradiating the photocurable resin layer with ultraviolet rays, and this semicured step After forming an inorganic compound layer on the photocurable resin layer, it is important to perform a second curing step of further irradiating ultraviolet rays to further cure the semi-cured photocurable resin layer. . If the number of times of irradiation with ultraviolet rays is one and ultraviolet rays are not irradiated again after the formation of the inorganic compound layer, it is difficult to obtain the high gas barrier property and strong bonding strength of the inorganic compound layer as in the present invention.

  Although the present invention is not restricted by any theory, it is considered as follows that excellent gas barrier properties and bonding strength were obtained by the present invention.

  Normally, when the photocurable resin is cured by irradiating it with ultraviolet rays, shrinkage of the photocurable resin is observed as the curing reaction proceeds. As in the conventional method, when UV irradiation is performed once and the curing of the photocurable resin is substantially completed by this single UV irradiation, the shrinkage of the photocurable resin is almost completed. Thus, the inorganic compound layer is formed on the surface of the photo-curing resin layer in which the shrinkage is almost completed.

  On the other hand, in the method for producing a gas barrier structure according to the present invention, after the inorganic compound layer is formed on the semi-cured photocurable resin layer formed by the first curing step, the ultraviolet ray is irradiated again to form the above-mentioned A second curing step for further curing the semi-cured photocurable resin layer is performed. Since the semi-cured photocurable resin layer formed by the first curing step has not yet been contracted due to the curing reaction, the inorganic compound layer is a photocurable resin layer that has not yet been contracted. Formed on the surface. And this inorganic compound layer reduces the area so that it may accompany the shrinkage | contraction of the photocurable resin layer accompanying a 2nd hardening process. By reducing the area of the inorganic compound layer, the inorganic compound layer is densified, and at the same time, the curing and shrinkage of the photocurable resin layer proceeds or is completed during the formation of the inorganic compound layer, whereby the inorganic compound layer and the photocurable resin layer are formed. It is considered that the layers are closely integrated with each other, and this contributes to the improvement of the bonding strength at the interface between the photocurable resin layer and the inorganic compound layer.

In the present invention, the photocurable resin layer is cured by performing the first curing step and the second curing step over time. The extent to which the photocurable resin layer is cured in the first curing step is arbitrary as long as the effect of the present invention is recognized. Usually, in the first curing step, the value of E ′ (E ₁ ′) indicating the dynamic elasticity measured by the dynamic viscoelasticity measurement method for this photocurable resin layer is the value of E ′ after the second curing step. 30% to 70% of _{(E 2} '), in particular 40% to 60%, it is preferably performed until the. When the first curing step is performed until (E ₁ ′) exceeds 70% of (E ₂ ′) after the second curing, the shrinkage during the second curing step hardly occurs, and the inorganic compound layer adheres. The effect of improving the property becomes poor On the other hand, if it is less than 30%, the photocurable resin layer is not sufficiently cured in the first curing step, the shrinkage or deformation of the photocurable resin layer in the second curing step is large, and the inorganic compound layer is cracked. It may be a cause.

Note that E ′ ((E ₁ ′) and (E ₂ ′)) indicating dynamic elasticity is measured with a dynamic viscoelasticity measuring device Rheogel E-4000 (manufactured by UBM Co., Ltd.).

(2) Gas barrier structure The gas barrier structure according to the present invention has an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 h or less and a water vapor permeability of 0.5 g / m ² · 24 h or less. Is. Such a gas barrier structure can be produced by the above method.

  The gas barrier structure according to the present invention has such an excellent gas barrier property, and the bonding strength of the gas barrier layer is improved. Further, the deterioration of gas barrier properties due to changes in temperature and humidity, impact, and bending when applied to a flexible substrate are effectively prevented.

  Therefore, the gas barrier structure according to the present invention can be used for various applications. The gas barrier structure according to the present invention is particularly suitable for, for example, a use that is thin and light in addition to high barrier properties, and further requires transparency, in particular, a display laminate and an organic EL element.

  As a preferred specific example of the gas barrier structure according to the present invention, there can be mentioned a gas barrier structure 10 having a layer configuration of “photocured resin layer 11 / inorganic compound layer 12” as shown in FIG.

  As another preferred specific example of the gas barrier structure according to the present invention, at least one photocurable resin layer or inorganic compound layer is further formed on the inorganic compound layer 12 of the gas barrier structure 10 shown in FIG. What is formed can be mentioned.

  As another preferred specific example of such a gas barrier structure according to the present invention, as shown in FIG. 2, “photo-curing resin layer (first photo-curing resin layer) 11 / inorganic compound layer 12 / photo-curing resin” A gas barrier structure 20 having a layer configuration of a layer (second photo-curing resin layer) 21 "may be mentioned. In this gas barrier structure 20, since the second photo-curing resin layer 21 is further formed on the inorganic compound layer 12 and the inorganic compound layer 12 is protected, the gas barrier property can be maintained more stably for a long period of time. Is. Here, the 1st photocurable resin layer 11 and the 2nd photocurable resin layer 21 can be formed with the same or different kind of photocurable resin.

  Further, as another preferred specific example of the gas barrier structure according to the present invention, “inorganic compound layer (second inorganic compound layer) 31 / photocurable resin layer 11 / inorganic compound layer (first) as shown in FIG. A gas barrier structure 30 having a layer structure of “one inorganic compound layer) 12” can be mentioned. In such a gas barrier structure 30, the inorganic compound layers 12 and 31 are formed so that the front and back surfaces are symmetrical about the photocurable resin layer 11, and therefore the inorganic compound layer is formed only on one side. The stress generated in this case is offset or relaxed, and the occurrence of distortion and warping (also referred to as bending or curling) in post-processing steps including heating is prevented. Therefore, the right-angle accuracy, dimensional accuracy, and dimensional accuracy at the partial location are improved, and the problem of alignment required at the time of patterning, for example, in the post-process such as electrode formation is eliminated. There is no bias and convenience in use is improved. Here, the first inorganic compound layer 12 and the second inorganic compound layer 31 can be formed of the same or different types of inorganic compounds.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

<Example 1>
Formation of photocurable resin layer 94 parts of hydroxymethyltricyclodecane dimethacrylate, 6 parts of hydroxymethyltricyclodecane monomethacrylate, 6 parts of β-thiopropionate, photoinitiator ("Lucirin TPO" manufactured by BASF) 1 part and 0.1 part of benzophenone were uniformly stirred and mixed to obtain an acrylic composition.
After coating this acrylic composition on a polyethylene terephthalate (PET) film (supporting base material), the PET film was covered also on the coated surface and the resin layer was sandwiched between the PET films.

First curing step The photocurable resin layer was semi-cured by irradiating it with ultraviolet rays having an irradiation energy of 2.5 J / cm ² using a conveyor-conveying ultraviolet irradiation device. The two-layer PET film was peeled off to obtain a semi-cured photocurable resin layer having a thickness of 100 μm.

Formation of inorganic compound layer In the chamber of a batch type sputtering apparatus in which a target material is made of silicon nitride having a sintered density of 60%, the semi-cured photocurable resin layer is placed at a distance of 50 mm from the target material. It was mounted to become.

Next, the inside of the chamber was depressurized to an ultimate vacuum of 5.0 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Next, oxygen gas is introduced into the chamber at 9 sccm, argon gas is introduced at a flow rate of 6 sccm, and the opening / closing degree of the valve between the vacuum pump and the chamber is controlled to maintain the pressure in the chamber at 0.25 Pa, A layer (inorganic compound layer) made of silicon oxynitride having a thickness of 80 nm was formed on the laminate with an input power of 1.2 kw by RF magnetron sputtering (where sccm is an abbreviation for standard cubic centimeter per minute) The same applies to the following).

After taking out the semi-cured photocurable resin layer on which the inorganic compound layer is formed from the vacuum curing apparatus in the second curing process , ultraviolet light is irradiated with an irradiation energy of 2.5 J / cm ² by a conveyor-conveying ultraviolet irradiation apparatus. Irradiation was performed again to obtain a gas barrier structure of Example 1.

<Example 2>
The gas barrier property of Example 2 was the same as Example 1 except that the irradiation energy amount in the first curing step was 2.0 J / cm ² and the irradiation energy amount in the second curing step was 3.0 J / cm ² . A laminate was obtained.

<Example 3>
The gas barrier property of Example 3 was the same as Example 1 except that the irradiation energy amount in the first curing step was 3.5 J / cm ² and the irradiation energy amount in the second curing step was 1.5 J / cm ² . A laminate was obtained.

< Comparative Example 1 >
The irradiation energy amount in the first curing step was 4.5 J / cm ^2, except that the amount of irradiation energy in the second curing step was 0.5 J / cm ² in the same manner as in Example 1, the gas barrier properties of Comparative Example 1 A laminate was obtained.

<Comparative example 2 >
The gas barrier laminate of Comparative Example 2 was obtained in the same manner as in Example 1 except that the irradiation energy amount in the first curing step was 5.0 J / cm ² and the second curing step was not performed.

<Evaluation method>
The water vapor transmission rate was measured using a water vapor transmission rate measuring device Permatran 3/31 (trade name, manufactured by MOCON, USA) under the conditions of 40 ° C. and 100% Rh.
The oxygen permeability was measured under the condition of 23 ° C. and 90% Rh using an oxygen excess rate measuring device Oxytran 3/31 (trade name, manufactured by MOCON, USA).
The unit of oxygen permeability is (cc / m ² · day · atm), and the unit of water vapor permeability is (g / m ² · day).
The above evaluation results (measurement results) are shown in the following table.

In all of Examples 1 to 3, the oxygen permeability was 0.5 cc / m ² · 24 h · atm or less, and the water vapor permeability was 0.5 g / m ² · 24 h or less. In Comparative Example 2 , oxygen permeability and water vapor permeability were worse than those in Examples 1-3.
Separately, the inorganic compound layer is not formed, only ultraviolet radiation is performed, and the dynamic viscoelasticity measurement of the photocured resin layer is performed under the conditions of the measurement temperature of 30 ° C. and the frequency of 40 Hz, It was measured.
The above evaluation results (measurement results) are shown in the following table.

Sectional drawing which shows one preferable specific example of the gas-barrier structure by this invention Sectional drawing which shows one preferable specific example of the gas-barrier structure by this invention Sectional drawing which shows one preferable specific example of the gas-barrier structure by this invention

Explanation of symbols

10, 20, 30 Gas barrier structure 11, 21 Photo-curing resin layer 12, 31 Inorganic compound layer

Claims (5)

A method for producing a gas barrier structure having at least one photocurable resin layer and an inorganic compound layer,
A first curing step of producing a semi-cured photocurable resin layer by irradiating the photocurable resin layer formed on at least one surface of the support substrate with ultraviolet rays;
A second curing step in which an inorganic compound layer is formed on the semi-cured photocurable resin layer by a vacuum vapor deposition method, and then irradiated with ultraviolet rays again to further cure the semi-cured photocurable resin layer. Consists of
In the first curing step, the value of E ′ (E ₁ ′) indicating the dynamic elasticity measured by the dynamic viscoelasticity measurement method for this photocurable resin layer is E ′ after the second curing step. value 'went until 30 to 70 percent (wherein, _{E 1 (E 2)'} and _{E 2} 'are each, by a dynamic viscoelasticity measuring apparatus, measurement temperature 30 ° C., at a frequency of 40Hz Measured)),
A gas barrier structure characterized by producing a gas barrier structure having an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 h or less and a water vapor permeability of 0.5 g / m ² · 24 h or less. Body manufacturing method. The method for producing a gas barrier structure according to claim 1 , wherein the photocurable resin has an acrylic functional group . The method for producing a gas barrier structure according to claim 1 or 2 , wherein the inorganic compound layer is any one of aluminum oxide, silicon oxide, silicon oxynitride, silicon oxide carbide, silicon oxycarbonitride, and silicon dioxide. The method for producing a gas barrier structure according to any one of claims 1 to 3 , wherein the vacuum deposition method is any one of a plasma PVD method, a sputtering method, an ion plating method, and a CVD method. The method for producing a gas barrier structure according to any one of claims 1 to 4 , wherein at least one layer of a photocurable resin layer or an inorganic compound layer is further formed on the inorganic compound layer.

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