JP5966293B2 - Gas barrier film, gas barrier layer, and apparatus - Google Patents

Description

  The present invention relates to a gas barrier film, a gas barrier layer, an apparatus, and a method for producing a gas barrier film.

  The gas barrier film is permeable to chemical components such as oxygen or water vapor that degrade the performance of various devices such as organic EL elements, liquid crystal display elements, touch panels, electronic paper, and other power generation devices such as solar cell elements. It is preferably applied to prevent. With recent high performance of various devices, high transparency is demanded particularly for gas barrier films used on the display surface side of display devices and the light receiving surface side of power generation devices.

  Some gas barrier films in recent years are composed of a plastic substrate, an organic layer provided on the plastic substrate, and an inorganic layer provided on the organic layer. The organic layer is provided as a layer for flattening the base of the gas barrier inorganic layer, and plays a role of increasing the gas barrier property by reducing defects generated in the inorganic layer.

  For example, Patent Document 1 proposes a gas barrier film in which a first inorganic film, an organic film, and a second inorganic film are sequentially provided on a base material. In this document, a cardo polymer containing a resin having a fluorene skeleton derived from a bisphenol compound is proposed as a preferable constituent material of the organic film.

JP-A-2005-96108

  In the example of Patent Document 1, a gas barrier film having a total light transmittance of 92% is obtained. However, due to the recent demand for higher performance, the gas barrier film is required to have further transparency, and it is difficult for the inventor to improve the transparency when an inorganic layer is provided on the plastic substrate. I encountered the problem of being.

  This invention solves the said problem, The objective is to provide the gas-barrier film and gas-barrier layer which show favorable transparency. Another object of the present invention is to provide an apparatus using a gas barrier film or gas barrier layer exhibiting good transparency. Still another object of the present invention is to provide a method for producing a gas barrier film exhibiting good transparency.

  The present inventor has completed the present invention by examining and demonstrating why the transparency is not improved in the research process for the above problem. That is, as a factor that hinders the transparency of the gas barrier film, when light enters from a layer having a high refractive index toward a layer having a low refractive index, all the light incident at an incident angle greater than the critical angle is The effect of so-called total reflection phenomenon reflected at the interface of these layers was considered to be large. In addition, it is preferable to use a high-speed film forming means such as an ion plating method or a reactive sputtering method from the viewpoint of obtaining a high film forming speed for forming the inorganic layer. It was considered that the transparency of the plastic substrate may be reduced by damaging the plastic substrate due to the reduced pressure environment, thermal environment or plasma environment. And under these considerations, as a result of earnest studies to achieve suppression of total reflection phenomenon and suppression of damage to the plastic substrate, it was proved that good transparency can be obtained, and the present invention was completed. It was. That is, the present invention for solving the above problems is as follows.

（上記一般式（１）におけるｎ ₁ ＋ｎ ₂ は１〜２０の整数であり、Ｒ ₁ ，Ｒ ₂ は水素原子又はメチル基であり、Ｒ ₃ ，Ｒ ₄ は水素原子、メチル基又はエチル基であり、Ｒ ₅ ，Ｒ ₆ は水素原子、メチル基又はエチル基である。）
Gas barrier film according to the first invention includes a plastic substrate, and the plastic substrate on the provided organic layer on the inorganic provided in contact organic layer layer, refraction of the inorganic layer The refractive index difference obtained by subtracting the refractive index of the organic layer from the refractive index is 0.15 or less, and the refractive index difference obtained by subtracting the refractive index of the plastic substrate from the refractive index of the organic layer is 0.15 or less. The total light transmittance is 90% or more, and the organic layer is a layer in which the compound represented by the general formula (1) is crosslinked with an alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure. Features.

(In the general formula (1), n ₁ + n ₂ is an integer of 1 to 20, R ₁ and R ₂ are hydrogen atoms or methyl groups, and R ₃ and R ₄ are hydrogen atoms, methyl groups, or ethyl groups. R ₅ and R ₆ are a hydrogen atom, a methyl group or an ethyl group.)

  According to the first invention, since the refractive index difference obtained by subtracting the refractive index of the organic layer from the refractive index of the inorganic layer is 0.15 or less, and the organic layer and the plastic substrate are in contact, the inorganic layer side When the light is incident from the surface, even if the total reflection phenomenon does not occur or does not occur at the interface between the inorganic layer and the organic layer and the interface between the organic layer and the base material, the influence on the decrease in the total light transmittance is small. Furthermore, since the inorganic layer is provided on the plastic substrate via the organic layer, even if the inorganic layer is formed by a high-speed film forming means such as an ion plating method or a reactive sputtering method, the plastic substrate is used. The gas barrier film showing good transparency can be obtained.

According to the first aspect of the present invention, since the alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group that easily adsorbs other components in the structure is crosslinked, an inorganic layer is formed on the organic layer. Even so, a gas barrier film capable of stably realizing good gas barrier properties can be obtained. The reason for this is that the layer in which the alkylene oxide-modified fluorene acrylate is crosslinked has high resistance to a reduced pressure environment, a thermal environment or a plasma environment at the time of film formation. In addition, since the structure of the alkylene oxide-modified fluorene acrylate does not contain a hydroxyl group that easily adsorbs other components, adsorption of low molecular components such as moisture is suppressed. The low molecular component does not escape from the organic layer during the formation of the inorganic layer and does not hinder the formation of the inorganic layer. As a result, it is assumed that the inorganic layer with few defects can be formed.

According to the second invention, the gas barrier film according to the first invention, the also the other surface of the plastic substrate, and the organic layer and the inorganic layer is provided in contact in that order.

According to the second invention, since the organic layer and the inorganic layer are provided in contact with the opposite surface of the plastic base material, the inorganic layer on the light incident surface side even when light is incident from any surface side. Even if the total reflection phenomenon does not occur or does not occur at the interface between the organic layer and the interface between the organic layer and the base material, the influence on the decrease in the total light transmittance is small. Moreover, a total light transmittance can be improved by providing an organic layer and an inorganic layer in contact with the opposite surface of a base material. The reason is that the total reflection phenomenon that occurs at the interface between the organic layer and the inorganic layer on the light-emitting surface side and the interface between the inorganic layer and air did not provide the organic layer and the inorganic layer on the opposite surface of the substrate. In this case, it is assumed that the influence on the decrease in the total light transmittance is less than the total reflection phenomenon that occurs at the interface between the base material and air.

A gas barrier layer according to a third invention includes the organic layer according to any one of the first to second inventions and the inorganic layer provided in contact with the organic layer. .

According to the third invention, since the refractive index difference obtained by subtracting the refractive index of the organic layer from the refractive index of the inorganic layer is 0.15 or less, when the light enters from the inorganic layer side, Even if the total reflection phenomenon does not occur or does not occur at the interface, there is little influence on the decrease in the total light transmittance, so that a gas barrier layer exhibiting good transparency can be obtained.

A device according to a fourth invention is a display device or a power generator using the gas barrier film according to any one of the first to second inventions or the gas barrier layer according to the third invention. To do.

According to the fourth invention, since the gas barrier film or gas barrier layer exhibiting good transparency is used, it is possible to provide a display device or a power generator that requires high performance.

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier film and gas barrier layer which show favorable transparency can be provided. Moreover, the apparatus using the gas barrier film or gas barrier layer which shows favorable transparency can be provided. Moreover, the manufacturing method of the gas-barrier film which shows favorable transparency 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.

  Although embodiments of the present invention will be described in detail below, 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 is provided with a plastic substrate 1, an organic layer 2 provided in contact with the plastic substrate 1, and a contact with the organic layer 2. Inorganic layer 3 formed. The refractive index difference obtained by subtracting the refractive index of the organic layer 2 from the refractive index of the inorganic layer 3 is 0.15 or less.

  Further, as shown in FIGS. 1 and 2, the gas barrier layer 4 according to the present invention has an organic layer 2 and an inorganic layer 3 provided in contact with the organic layer 2, and the refractive index of the inorganic layer 3. The difference in refractive index obtained by subtracting the refractive index of the organic layer 2 from the organic layer 2 is 0.15 or less.

  The organic layer 2 and the inorganic layer 3 (these two layers are also referred to as “gas barrier layer 4”) are provided in contact with at least one surface S1 of the plastic substrate 1 in that order as shown in FIG. However, as shown in FIG. 2, an organic layer 2 ′ and an inorganic layer 3 ′ (these two layers are also referred to as “gas barrier layer 4 ′”) may be provided in contact with each other 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'.

  By providing the organic layer 2 'and the inorganic layer 3' in contact with the other surface S2 in that order, the inorganic layer and the organic layer on the light incident surface side can be obtained from any surface side. Even if the total reflection phenomenon does not occur or does not occur at the interface between and the interface between the organic layer and the substrate, the influence on the decrease in the total light transmittance is small. Further, the total light transmittance can be improved by providing the organic layer 2 'and the inorganic layer 3' on the other surface S2. The reason is that the total reflection phenomenon that occurs at the interface between the organic layer and the inorganic layer on the light-emitting surface side and the interface between the inorganic layer and air did not provide the organic layer and the inorganic layer on the opposite surface of the substrate. In this case, it is assumed that the influence on the decrease in the total light transmittance is less than the total reflection phenomenon that occurs at the interface between the base material and air.

  Below, the component of a gas barrier film and a gas barrier layer is demonstrated in detail.

(Plastic substrate)
The material of the plastic substrate 1 is not particularly limited, optical characteristics such as light transmittance and refractive index, thermal characteristics such as heat deformation temperature and glass transition temperature, mechanical characteristics such as Young's modulus and rigidity, cost, etc. In consideration of the above, various resins suitable for the application of the gas barrier film are arbitrarily selected. For example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cycloolefin resins such as polycarbonate resin (PC), cycloolefin polymer (COP) and cycloolefin copolymer (COC), polyacrylic acid Acrylic resins such as methyl (PMA) and polymethyl methacrylate (PMMA), polyamide resins such as nylon; cellulose resins such as polyvinyl alcohol resin (PVA) and triacetyl cellulose (TAC), and polypropylene (PP) And olefin-based resins. As the material of the plastic substrate 1, one type of resin may be used alone, or two or more types of resins may be used in combination as a copolymer, a mixture, and a laminate.

  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 in contact with the plastic substrate 1 and constitutes a gas barrier layer 4 together with an inorganic layer 3 described later. In the present invention, the organic layer 2 is a layer formed mainly of a resin (“resin” means “organic polymer compound”). In the present invention, the refractive index difference obtained by subtracting the refractive index of the organic layer 2 from the refractive index of the inorganic layer 3 is 0.15 or less. That is, whether the refractive index of the organic layer 2 is higher than the refractive index of the inorganic layer 3, is the same as the refractive index of the inorganic layer 3, or is lower than the refractive index of the inorganic layer 3 within a range of 0.15 or less. Either. Thereby, even if the total reflection phenomenon occurs or does not occur at the interface between the inorganic layer 3 and the organic layer 2 on the light incident surface side, the influence on the decrease in the total light transmittance can be reduced. The refractive index of the organic layer 3 can be adjusted by appropriately selecting the type of resin to be used or by adding a known refractive index adjusting agent such as extender pigments or hollow particles. In addition, since both the plastic base material 1 and the organic layer 2 use resin as a main component, these refractive index differences are usually small, and the influence of the interface between them on the decrease in the total light transmittance is Although considered to be small, when considering the relationship between the refractive index of the plastic substrate 1 and the organic layer 2, the difference in refractive index obtained by subtracting the refractive index of the plastic substrate 1 from the refractive index of the organic layer 2 is 0.15. By making it as follows, even if the total reflection phenomenon does not occur at the interface between the organic layer 2 and the base material 1 on the light incident surface side, the influence on the decrease in the total light transmittance is reduced. Can do.

  The resin for forming the organic layer 2 is not particularly limited, and examples thereof include various resins described in the above “plastic substrate”.

  The resin of the organic layer 2 is preferably a resin in which a curable compound is crosslinked. This is because the resin in which the curable compound is cross-linked has a three-dimensional network structure, and therefore has high resistance to a reduced pressure environment, a thermal environment, or a plasma environment when the inorganic layer 3 is formed on the organic layer 2. . The resin in which the curable compound is crosslinked can be obtained, for example, by irradiating the composition for organic layer containing the ionizing radiation curable compound with ionizing radiation to crosslink the curable compound. The ionizing radiation is typically ultraviolet rays or electron beams, but other examples include electromagnetic waves such as visible rays, X rays and γ rays, and charged particle rays such as α rays. Alternatively, the resin in which the curable compound is cross-linked is, for example, a composition for an organic layer containing a cross-linking agent such as an isocyanate type, an amine type, or a silane coupling type and a thermosetting compound having a reactive group for these. It can be obtained by applying heat to the product to crosslink the curable compound. Irradiating ionizing radiation to crosslink the curable compound is preferable to crosslinking the curable compound by applying heat because it can be cured in a short time.

  As the organic layer 2, a layer in which an acrylate is crosslinked can be preferably used. Specific examples of acrylates include alkylene oxide modified fluorene acrylate, alkylene oxide modified acrylate, phenol EO modified acrylate, nonylphenol EO modified acrylate, nonylphenol PO modified acrylate, 2-ethylhexyl EO modified acrylate, N-acryloyloxyethyl hexahydrophthalimide, bisphenol. F EO modified diacrylate, bisphenol A EO modified diacrylate, isocyanuric acid EO modified diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolprohan triacrylate, trimethylolpropane PO modified triacrylate, trimethylolpropane EO modified tri Acrylate, isocyanuric acid EO-modified di and triacrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, pentaerythritol tri and tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate, ω-carboxy-polycaprolactone monoacrylate, Examples include phthalic acid monohydroxyethyl acrylate and polyester acrylate. Moreover, these acrylates may be used alone or in combination of two or more. As commercial products of these acrylates, for example, Aronix series manufactured by Toagosei Co., Ltd. can be used.

  As the organic layer 2, a layer in which an alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure is crosslinked can be particularly preferably used. The alkylene oxide-modified fluorene acrylate has a fluorene skeleton derived from a bisphenol compound and may be included in a group collectively referred to as a cardo polymer, but the alkylene oxide-modified fluorene acrylate that is particularly preferably used contains other components. Even when the inorganic layer 3 is formed on the organic layer 2 formed of the compound by the high-speed film forming means such as the ion plating method or the reactive sputtering method. It can be set as the gas barrier film 10 or the gas barrier layer 4 which can implement | achieve favorable gas barrier property stably. Adoption of alkylene oxide-modified fluorene acrylate having no hydroxyl group suppresses the adsorption of low-molecular components such as moisture, so that the low-molecular components are gasified from the organic layer 2 by heat or plasma during the formation of the inorganic layer 3. As a result, it is presumed that the inorganic layer 3 with few defects could be formed.

As the alkylene oxide-modified fluorene acrylate having no hydroxyl group in the structure (hereinafter, also simply referred to as “modified fluorene acrylate”), a compound represented by the general formula (1) can be preferably used. In this general formula (1), n ₁ + n ₂ is an integer of 1 to 20, R ₁ and R ₂ are hydrogen atoms or methyl groups, and R ₃ and R ₄ are hydrogen atoms, methyl groups or ethyl groups. R ₅ and R ₆ are a hydrogen atom, a methyl group or an ethyl group. In particular, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are preferably hydrogen atoms or methyl groups, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same. And more preferably a hydrogen atom or a methyl group.

The organic layer 2 in which the modified fluorene acrylate having n ₁ + n ₂ of 1 to 20 is crosslinked is effective for forming the gas barrier layer 4 having preferable gas barrier properties. When the organic layer 2 is formed of a modified fluorene acrylate having n ₁ + n ₂ of less than 1 (that is, 0), it becomes difficult to dissolve due to high crystallinity, making it difficult to make an ink or coating. May end up. On the other hand, when the organic layer 2 is formed of a modified fluorene acrylate with n ₁ + n ₂ exceeding 20, since the number of linear alkylene-modified sites increases in the organic layer, low molecular components are incorporated into the molecular chain. There is a risk that.

When n ₁ + n ₂ increases, the glass transition temperature (Tg) of the formed organic layer 2 decreases, and the organic layer 2 is affected by heat and plasma when the inorganic layer 3 is formed on the organic layer 2. There is a possibility that the crystallization of the organic layer 2 proceeds and the organic layer 2 is whitened. When the organic layer 2 is whitened, the surface of the organic layer 2 is rough, so that the inorganic layer 3 formed on the organic layer 2 is likely to be cracked, and the gas barrier property may be lowered. Moreover, since the cloudiness of the organic layer 2 falls even if gas barrier property does not fall, it is unpreferable. For such problems, it is preferable to form the organic layer 2 with a modified fluorene acrylate having n ₁ + n ₂ of 1 to 6, and the glass transition temperature Tg of the organic layer 2 can be increased. As a result, it is possible to prevent the organic layer 2 from being whitened and to form a gas barrier layer 4 that is transparent and has good gas barrier properties.

The number of n ₁ and n ₂ may or may not be the same, as long as the total is within the above range.

  The compound represented by the general formula (1) can be synthesized by a known method. For example, (meth) acrylic acid or (meth) acrylic acid chloride is used for (meth) acrylic esterification of an alcohol having a fluorene ring or a compound containing a fluorene ring-substituted -OH group. Examples of the compound containing an alcohol having a fluorene ring or a fluorene ring-substituted -OH group used here include 9-fluorenemethanol, 9,9-bis (4-hydroxyethyloxyphenyl) fluorene, and 9,9- Bis (3-methyl-4-hydroxyethyloxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyethyloxyphenyl) fluorene, 9,9-bis (3,3′-dimethyl-4-hydroxy) Ethyloxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) ) Fluorene, etc.

  As a commercial item of the compound represented by the general formula (1), for example, NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd. or Ogsol EA series manufactured by Osaka Gas Chemical Co., Ltd. can be used.

  When using an alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure, the composition for an organic layer may contain only an alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure as a curable compound, Other curable compounds may also be included. As the other curable compound that can be used in combination with the alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure, an acrylate that does not contain a hydroxyl group in the structure can be preferably used, but it does not depart from the spirit of the present invention. If it is a range, the acrylate which contains a hydroxyl group in a structure may be sufficient. However, the mixing ratio of the organic layer composition in that case is such that the mass ratio of the compound not containing a hydroxyl group to the compound containing the hydroxyl group is about 100: 0 to 50:50, preferably 100: 0 to 75: 25. Within this range, the intended purpose can be achieved within the scope of using the alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure, and the gas barrier film 10 or the gas barrier layer 4 having good gas barrier properties can be obtained. Can be obtained.

  The ultraviolet curable organic layer composition usually contains a polymerization initiator. As the polymerization initiator, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones, and the like can be used. Although the compounding quantity of a polymerization initiator is not specifically limited, From a viewpoint that favorable bridge | crosslinking is performed, it is preferable to add about 0.1-5 mass parts with respect to 100 mass parts of curable compounds.

  A solvent can be arbitrarily mixed according to the composition for organic layers from the viewpoint of viscosity adjustment of a coating liquid. 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.

  Additives can be appropriately added to the composition for an organic layer as needed within a range not impairing the effects of the present invention. Examples of additives include photosensitizers, heat stabilizers, radical scavengers, plasticizers, surfactants, antistatic agents, antioxidants, ultraviolet absorbers, infrared absorbers, and pigments (colored dyes and colored pigments). ), Extender pigments, hollow particles, light diffusing agents and the like. As a photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.

  The organic layer 2 is obtained by applying a composition for an organic layer on the plastic substrate 1 and, if necessary, irradiating the coating film after application with ionizing radiation or applying heat to crosslink the coating film. Can be formed. The application method can be selected and applied from the application methods described in the “Manufacturing method” section below.

  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, each layer may use the same organic layer composition or different organic layer compositions. 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.

(Inorganic layer)
The inorganic layer 3 is provided in contact with the organic layer 2 as a functional layer that blocks gas such as water vapor, and constitutes the gas barrier layer 4 together with the organic layer 2. The inorganic layer 3 is a layer formed mainly of a gas barrier inorganic compound. In the present invention, the refractive index difference of the organic layer 3 is 0.15 or less obtained by subtracting the refractive index of the organic layer 2 therefrom. That is, whether the refractive index of the inorganic layer 3 is lower than the refractive index of the organic layer 2, is the same as the refractive index of the organic layer 2, or is higher within the range of 0.15 than the refractive index of the organic layer 2. Either. Thereby, even if the total reflection phenomenon occurs or does not occur at the interface between the inorganic layer 3 and the organic layer 2 on the light incident surface side, the influence on the decrease in the total light transmittance can be reduced. The refractive index of the inorganic layer 3 can be adjusted by appropriately selecting the kind of the inorganic compound or adding a known refractive index adjusting agent such as extender pigments and hollow particles within a range in which necessary gas barrier properties can be secured. it can.

  The gas barrier inorganic compound for forming the inorganic layer 3 is not particularly limited. For example, one or more elements selected from silicon, aluminum, magnesium, zinc, titanium, tin, zirconium and indium are used. The inorganic compound to contain is mentioned. From the viewpoint of transparency, an inorganic compound containing silicon is preferable. These elements may be used alone or as a composite inorganic compound combined with other elements. Examples of the composite oxide include inorganic oxides, inorganic nitrides, and inorganic oxynitrides. However, a composite inorganic compound containing nitrogen as a main component is not preferable because it may be colored to impair the transparency of the inorganic layer 3. Therefore, from the viewpoint of transparency, inorganic oxides are preferable, and specifically, one or more inorganic compounds selected from silicon oxide, silicon aluminum oxide, and silicon zinc oxide are most preferable. The inorganic layer 3 may use one kind of inorganic compound alone, may use two or more kinds of inorganic compounds together, and uses both inorganic compounds and organic compounds within the scope of the present invention. Also good.

  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 plastic substrate 1, the organic layer 2, and the inorganic layer 3. For example, the organic layer 2 of the plastic substrate 1 is formed of layers other than these. It may be laminated on the non-side surface S2, or may be laminated on the inorganic layer 3 or the inorganic layer 3 ′. As an optional layer, as long as the characteristics of the present invention are not impaired, for example, a conventionally known primer layer, matting agent layer, protective layer, antistatic layer, smoothing layer, adhesion improving layer, light shielding layer, antireflection layer, Examples include a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer, a printing layer, and an easy adhesion layer.

[Production method]
The method for producing a gas barrier film 10 according to the present invention includes a step of forming an organic layer 2 in contact with the plastic substrate 1, and a step of forming an inorganic layer 3 in contact with the organic layer 2, The refractive index difference obtained by subtracting the refractive index of the organic layer from the refractive index of the inorganic layer is set to 0.15 or less. Note that the difference in refractive index obtained by subtracting the refractive index of the organic layer from the refractive index of the inorganic layer is 0.15 or less, as described above in the description section of the “organic layer” and “inorganic layer”. The description is omitted here.
Below, each process is demonstrated.

(Organic layer formation process)
The organic layer forming step is a step of forming the organic layer 2 with the organic layer composition on the plastic substrate 1. Usually, the organic layer composition is applied onto the plastic substrate 1, and the coating film is irradiated with ionizing radiation or heat is applied to cure the curable compound contained in the organic layer composition to form an organic material. Layer 2 is formed. In addition, since it is as having demonstrated in the description column of the said "organic layer" about the composition for organic layers, the description is abbreviate | omitted here.

  Examples of the coating method for the organic layer composition 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 apply | coating the composition for organic layers, it dries as needed. The drying temperature may be room temperature, but when the organic layer composition contains a solvent, the drying for removing the solvent may be performed at a temperature equal to or higher than the temperature at which evaporation of the solvent is promoted. preferable. The ionizing radiation applied to the organic layer composition is as described above. However, when ultraviolet rays are applied as the ionizing radiation, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a black light fluorescence A light source such as a lamp or a metal halide lamp is used.

(Inorganic layer forming process)
The inorganic layer forming step is a step of forming the inorganic layer 3 by depositing an inorganic layer material on the organic layer 2. 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 3 to be obtained.

  More specifically, (1) a vacuum vapor deposition method in which a raw material is heated and vapor-deposited on a base material, (2) an oxidation reaction vapor deposition method in which oxygen gas is introduced into the raw material to be oxidized and vapor-deposited on the base material, (3) a target Sputtering method in which argon gas and oxygen gas are introduced into the raw material and sputtering to deposit on the base material, (4) Ion plating method in which the raw material is heated with a plasma beam generated by a plasma gun and deposited on the base material (5) A plasma chemical vapor deposition method using an organic silicon compound or the like as a raw material and depositing a silicon oxide film or the like on a substrate can be used.

  In the present invention, since the inorganic layer 3 is provided on the plastic substrate 1 via the organic layer 2, damage to the plastic substrate 1 due to heat or plasma applied during the formation of the inorganic layer can be suppressed. In addition, when the organic layer 2 is formed of an alkylene oxide-modified fluorene acrylate that does not contain a hydroxyl group in the structure, there are few low molecular components contained in the organic layer, and the organic layer 2 is also formed by heat and plasma applied during the formation of the inorganic layer. The low molecular component in the layer is discharged as a gas and does not hinder the formation of the inorganic layer 3.

  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 or the gas barrier layer 4 of the present invention. Since both the gas barrier film 10 and the gas barrier layer 4 described above exhibit good transparency, the use of the gas barrier film 10 or the gas barrier layer 4 can contribute to the enhancement of the functions of the display device and the power generation device.

  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 adopted, and the sealing means by the gas barrier film 10 or the gas barrier layer 4 applied to each of such display devices is also particularly limited. Instead, a conventionally known means can be used.

  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 or the gas barrier layer 4 applied to such a power generator is not particularly limited, and may be a conventionally known means.

  Specifically, for example, an example in which the gas barrier film 10 according to the present invention is used as a member of a front sheet or a back sheet of a solar cell element can be given. Such a solar cell element is composed of a front sheet, a filler, a solar cell element, a lead wire, a terminal, a terminal box, and a back sheet in order from the sunlight side in the thickness direction. It is fixed to the material. Examples of the front sheet include an example in which a transparent film disposed on the outer layer side and the gas barrier sheet 10 according to the present invention are bonded together. As the film disposed on the outer layer side, a weather resistance, hydrolysis resistance film or the like is used. As the back sheet, an example in which the gas barrier sheet 10 according to the present invention is sandwiched between the back sealing film and the film disposed on the outer layer side can be given. 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 1, an ultraviolet curable type of 100 μm thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark) A-4300, refractive index 1.58) adjusted to the following composition was used. The organic layer composition (ultraviolet curable organic layer ink A) is applied by die coating, dried at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays under the condition of an integrated light quantity of 300 mJ / cm ² in a wavelength range of 260 nm to 400 nm. Irradiation was performed to form an organic layer 2 having a thickness of 5 μm.

(Composition of UV-curable organic layer ink A)
Compound of general formula (1): R _{1 to} R ₄ = hydrogen atom, n ₁ + n ₂ = 2 (curable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-BPEF): 19 mass Part Polyester acrylate (curable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 19 parts by mass Toluene: 60 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

The inorganic layer 3 was set in a hollow cathode ion plating apparatus so that a film in which the organic layer 2 was formed on one side of a polyethylene terephthalate film having a thickness of 100 μm was formed on the organic layer side. Then, silicon oxide (manufactured by High Purity Chemical Research Laboratory), 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 10 of Example 1 obtained as described above is plastic base material / organic layer / inorganic layer.

[ Reference Example 1 ]
A gas barrier film 10 of Reference Example 1 was produced in the same manner as in Example 1 except that an ultraviolet curable organic layer composition (ultraviolet curable organic layer ink B) adjusted to the following composition was used.

(Composition of UV-curable organic layer ink B)
-Ethoxylated bisphenol A diacrylate (curable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., ABE-300): 19 parts by mass-Polyester acrylate (curable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 19 parts by mass Toluene: 60 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 Part

[ Reference Example 2 ]
A gas barrier film 10 of Reference Example 2 was produced in the same manner as in Example 1 except that an ultraviolet curable organic layer composition (ultraviolet curable organic layer ink C) adjusted to the following composition was used.

(Composition of UV-curable organic layer ink C)
Polyethylene glycol # 200 diacrylate (curable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., A-200A): 19 parts by mass Polyester acrylate (curable compound, manufactured by Toagosei Co., Ltd., trade name: M-8030): 19 parts by mass Toluene: 60 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 Part

[ Example 2 ]
A gas barrier film 10 of Example 2 was produced in the same manner as in Example 1 except that an ultraviolet curable organic layer composition (ultraviolet curable organic layer ink D) adjusted to the following composition was used.

(Composition of UV-curable organic layer ink D)
Compound of general formula (1): R _{1 to} R ₄ = hydrogen atom, n ₁ + n ₂ = 2 (polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-BPEF): 38 parts by mass Toluene: 60 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

[ Example 3 ]
A gas barrier film 10 of Example 3 was produced in the same manner as in Example 1 except that an ultraviolet curable organic layer composition (ultraviolet curable organic layer ink E) adjusted to the following composition was used.

(Composition of UV-curable organic layer ink E)
Compound of general formula (1): R _{1 to} R ₄ = hydrogen atom, n ₁ + n ₂ = 2 (polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-BPEF): 35 parts by mass Compound of the following general formula (2) (polymerizable compound, R _{1 to} R ₃ = hydrogen atom): 3 parts by mass Toluene: 60 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

  The fluorene acrylate represented by the general formula (2) was synthesized as follows. First, 231 g of bisphenolfluorene type epoxy polymer (epoxy equivalent 231), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-di-isobutylphenol, and 72.0 g of acrylic acid are mixed in a 500 mL four-necked flask. Then, it was dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 25 mL per minute. Although this solution was cloudy, the temperature was gradually raised as it was, and the solution was heated to 120 ° C. to be completely dissolved. Although the solution gradually became transparent and viscous, the stirring was continued as it was, and during this time, the acid value was measured, and this heating and stirring was continued until the acid value became less than 2.0 mgKOH / g. After 8 hours when the acid value reached the target (acid value 0.8), the solution was cooled to room temperature to obtain a fluorene acrylate of the general formula (2), which was a colorless and transparent solid.

[ Reference Example 3 ]
A gas barrier film of Reference Example 3 was produced in the same manner as in Example 1 except that the ultraviolet curable organic layer composition (ultraviolet curable organic layer ink F) adjusted to the following composition was used.

(Composition of UV-curable organic layer ink F)
Compound of the above general formula (2): (polymerizable compound, R _{1 to} R ₃ = hydrogen atom): 38 parts by mass Toluene: 60 parts by mass Oligo [2-hydroxy-2-methyl- [1- (methyl) Vinyl) phenyl] propanone] (photopolymerization initiator, manufactured by Lamberti, trade name: ESACURE ONE): 2 parts by mass

[ Example 4 ]
A silicon oxide zinc layer is formed by using a mixture of 100 parts by mass of silicon oxide (manufactured by Kojundo Chemical Laboratories Co., Ltd.) and 30 parts by mass of zinc oxide (manufactured by Canon Optron Co., Ltd.) as a vapor deposition raw material for the inorganic layer 3. A gas barrier film of Example 4 was produced in the same manner as in Example 1 except that.

[ Example 5 ]
A silicon oxide aluminum layer is formed using a mixture of 50 parts by mass of silicon oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and 50 parts by mass of aluminum oxide (manufactured by Canon Optron Co., Ltd.) as a raw material for vapor deposition of the inorganic layer 3. A gas barrier film of Example 5 was produced in the same manner as in Example 1 except that.

[ Example 6 ]
The gas barrier properties of Example 6 were the same as Example 1 except that zirconium oxide-aluminum oxide (Canon Optron Co., Ltd., OM-4) was used as the vapor deposition raw material for inorganic layer 3 and an aluminum zirconium oxide layer was formed. A film was produced.

[Comparative Example 1]
A gas barrier film of Comparative Example 1 was produced in the same manner as in Example 1 except that an aluminum oxide layer was formed using aluminum oxide (manufactured by Canon Optron Co., Ltd.) as a vapor deposition raw material for the inorganic layer 3.

[Comparative Example 2]
A gas barrier film of Comparative Example 2 was produced in the same manner as in Example 1 except that zinc oxide (manufactured by Canon Optron Co., Ltd.) was used as a vapor deposition raw material for the inorganic layer 3 and a zinc oxide layer was formed.

[ Example 7 ]
Example 7 was the same as Example 1 except that a 100 μm thick polyethylene naphthalate film (manufactured by Teijin DuPont, Teonex (registered trademark) Q65F, refractive index 1.64) was used as the plastic substrate 1. A gas barrier film was produced.

[ Example 8 ]
Example 8 is the same as Example 1 except that a polycarbonate film having a thickness of 100 μm (Pure Ace (registered trademark) C110, refractive index 1.59) manufactured by Teijin Chemicals Limited is used as the plastic substrate 1. A gas barrier film was produced.

[ Example 9 ]
As the plastic substrate 1, cycloolefin polymer film having a thickness of 100μm except for using (Nippon Zeon Co., Ltd., ZEONOR (registered trademark) ZD-12, refractive index 1.53), the same procedure as in Example 1 carried out The gas barrier film of Example 9 was produced.

[ Example 10 ]
On the other side of the polyethylene terephthalate film of the gas barrier film 10 of Example 1 in which the organic layer 2 and the inorganic layer 3 are formed on one side, the organic layer 2 ′ and the inorganic layer 3 ′ are formed in the same manner as in Example 1. The gas barrier film of Example 10 was produced. The layer structure of the gas barrier film 10 of Example 10 is inorganic layer / organic layer / plastic substrate / organic layer / inorganic layer.

[ Example 11 ]
The other side of the polycarbonate film of the gas barrier film 10 of Example 8 to form an organic layer 2 and the inorganic layer 3 on one side, to form an organic layer 2 'and the inorganic layer 3' in the same manner as in Example 7, performed The gas barrier film of Example 11 was produced. The layer structure of the gas barrier film 10 of Example 11 is inorganic layer / organic layer / plastic substrate / organic layer / inorganic layer.

[Evaluation and results]
(Measurement method of refractive index, transparency and gas barrier properties)
About the gas barrier film of Examples 1-11 , Comparative Examples 1-2, and Reference Examples 1-3 , the refractive index of each layer, the total light transmittance, and the water-vapor-permeation rate were measured. The refractive index of each layer was measured using a spectroscopic ellipsometer (manufactured by JOBIN YVON, UVISEL), and a value of 589 nm was adopted. Measurement of the total light transmittance was carried out by entering light from the inorganic layer surface side using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000, D65 light source) in accordance with JIS K7361-1 (1997). . The water vapor transmission rate was measured using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W3 / 31) under conditions of a temperature of 37.8 ° C. and a humidity of 100% RH. These results are shown in Table 1.

(result)
As shown in Table 1, Examples 1 to 11 in which the difference in refractive index obtained by subtracting the refractive index of the organic layer from the refractive index of the inorganic layer is 0.15 or less, the total light transmittance is 90% or more, and good However, Comparative Examples 1 and 2 having a refractive index difference of more than 0.15 were inferior in transparency. Moreover, by comparing Examples 1 and 8 with Examples 10 and 11 , it can be seen that the total light transmittance is improved by providing the organic layer and the inorganic layer on both surfaces of the substrate. Examples 1 to 11 in which the organic layer is a layer in which an alkylene oxide-modified fluorene acrylate having no hydroxyl group in the structure is crosslinked have a water vapor transmission rate of less than 0.1 g / m 2 / day and a good gas barrier. Showed sex. Reference Examples 1 to 3 were inferior in water vapor transmission rate.

DESCRIPTION OF SYMBOLS 1 Plastic base material 2, 2 'Organic layer 3, 3' Inorganic layer 4, 4 'Gas barrier layer 10, 10A, 10B Gas barrier film S1 One side of a plastic base material S2 Other side of a plastic base material

Claims (4)

Includes a plastic substrate and an inorganic layer in contact the plastic base on the provided organic layers in the organic layer,
The refractive index difference obtained by subtracting the refractive index of the organic layer from the refractive index of the inorganic layer is 0.15 or less, and the refractive index difference obtained by subtracting the refractive index of the plastic substrate from the refractive index of the organic layer is 0. .15 or less,
The total light transmittance is 90% or more,
The gas barrier film , wherein the organic layer is a layer in which a compound represented by the general formula (1) is crosslinked with an alkylene oxide-modified fluorene acrylate having no hydroxyl group in the structure .

(In the general formula (1), n ₁ + n ₂ is an integer of 1 to 20, R ₁ and R ₂ are hydrogen atoms or methyl groups, and R ₃ and R ₄ are hydrogen atoms, methyl groups, or ethyl groups. R ₅ and R ₆ are a hydrogen atom, a methyl group or an ethyl group.)   The gas barrier film according to claim 1, wherein the organic layer and the inorganic layer are also provided in contact with each other on the other surface of the plastic substrate. It has the said organic layer of any one of Claims 1-2 , and the said inorganic layer provided in contact with the said organic layer, The gas barrier layer characterized by the above-mentioned . A device comprising the gas barrier film according to claim 1 or the display device or the power generation device using the gas barrier layer according to claim 3 .

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