WO2018207508A1 - Film barrière contre les gaz et procédé de fabrication de film barrière contre les gaz - Google Patents

Film barrière contre les gaz et procédé de fabrication de film barrière contre les gaz Download PDF

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Publication number
WO2018207508A1
WO2018207508A1 PCT/JP2018/014506 JP2018014506W WO2018207508A1 WO 2018207508 A1 WO2018207508 A1 WO 2018207508A1 JP 2018014506 W JP2018014506 W JP 2018014506W WO 2018207508 A1 WO2018207508 A1 WO 2018207508A1
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Prior art keywords
layer
gas barrier
inorganic layer
barrier film
inorganic
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PCT/JP2018/014506
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English (en)
Japanese (ja)
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英二郎 岩瀬
泰雄 江夏
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富士フイルム株式会社
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Publication of WO2018207508A1 publication Critical patent/WO2018207508A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges

Definitions

  • the present invention relates to a gas barrier film having excellent gas barrier properties and a production method for producing the gas barrier film.
  • gas barrier films to protect materials that are sensitive to oxygen and water.
  • a self-luminous material such as organic EL (Electro Luminescence) deteriorates due to moisture.
  • organic EL Electro Luminescence
  • Such an organic EL can have flexibility by replacing a conventionally used glass substrate with a gas barrier film.
  • a gas barrier film having flexibility As a substitute for a glass substrate, the added value of the product is improved. Therefore, the expectation for the gas barrier film which has flexibility and can express high gas barrier performance is high.
  • Gas barrier films are also used in such industrial equipment. For example, by replacing the glass portion of a conventionally used solar cell module (solar cell panel) with a gas barrier film, in addition to light weight and flexibility, flexibility and weight reduction can be achieved. Furthermore, the gas barrier film can be applied to building materials. Gas barrier films have a wide range of applications and are expected to be used in many ways.
  • a gas barrier film used for such applications is required to have a high gas barrier property such as a water vapor transmission rate of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ day) or less.
  • a laminated gas barrier film is known.
  • the laminated gas barrier film is a gas barrier film having at least one combination of an inorganic layer that mainly exhibits gas barrier properties and a base organic layer that serves as a base layer (undercoat layer) of the inorganic layer.
  • a gas barrier film having a high gas barrier property can be obtained by sufficiently exhibiting the gas barrier property of the inorganic layer.
  • the base organic layer In a laminated gas barrier film, in order to obtain a high gas barrier property, the base organic layer properly covers the foreign matter adhering to the support and the unevenness of the support, and the base organic layer is damaged. It is important that there is no.
  • the base organic layer serving as a smooth layer cannot cover the foreign matter or the like adhering to the support, irregularities are formed on the formation surface of the inorganic layer.
  • the thin inorganic layer cannot cover the entire surface due to the foreign matter or the like to form a film, and the inorganic layer cannot be formed in the shadowed portion of the unevenness.
  • the inorganic layer is formed by, for example, plasma CVD (Chemical Vapor Deposition).
  • plasma CVD Chemical Vapor Deposition
  • the surface of the organic layer is exposed to the surface of the organic layer after the formation of the base organic layer and before the inorganic layer is formed. May cause minor damage (micro-scratch failure). Even when the organic layer has such damage, the thin inorganic layer cannot cover the entire damaged portion of the organic layer, as in the case of the unevenness due to the above-mentioned foreign matter, and similarly, it has a high gas barrier property. Can't get.
  • Patent Document 1 prepares a coating liquid containing an organic compound and an organic solvent having a glass transition temperature of 100 ° C. or higher when producing a laminated type functional film.
  • the coating was applied so that the thickness of the underlying organic layer was 0.05 to 3 ⁇ m at a coating amount of 5 cc / m 2 or more, and the coating solution was a viscosity of 20 cP or more and a surface tension of 34 dyn / cm or less in a reduced rate dry state.
  • the method for producing a functional film is described in which the organic compound is cured to form a base organic layer after being dried.
  • the base organic layer that efficiently covers the foreign matter is formed by controlling the coating state of the coating liquid that forms the base organic layer in this way.
  • Patent Document 2 a support is continuously fed from a film roll, a coating film (underlying organic layer) is formed on the support, and then a laminate film is applied to the surface of the coating film to form a film roll.
  • the winding process and the wound film roll are loaded into a vacuum film forming apparatus, the support to which the laminated film is continuously applied is sent from the film roll, the laminated film is peeled off, and the inorganic layer is formed on the coating film.
  • a process for producing a functional film comprising the steps of forming and winding on a film roll.
  • the underlying organic layer is prevented from being damaged, and an appropriate inorganic layer can be formed on the intact underlying organic layer.
  • an inorganic layer can be formed on a proper underlying organic layer that covers the entire surface of the support foreign matter and the like and is not damaged. Therefore, the gas barrier property of the inorganic layer is fully expressed, and the gas barrier has a high water vapor permeability of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ day) or less, such as a device using an organic EL or a solar cell. Therefore, a gas barrier film that can be suitably used for applications requiring high performance can be obtained.
  • An object of the present invention is to solve such problems of the prior art, and to provide a gas barrier film having a high gas barrier property and a method for producing the gas barrier film.
  • the gas barrier film of the present invention comprises a support and at least one combination of an inorganic layer containing silicon and an underlayer of the inorganic layer provided on at least one surface of the support.
  • the underlayer includes a polymer of alkoxysilane
  • the present invention provides a gas barrier film comprising a mixed layer containing components of both the inorganic layer and the base layer between the inorganic layer and the base layer.
  • the alkoxysilane polymer preferably contains a tri- to hexafunctional alkoxysilane polymer.
  • the inorganic layer preferably contains one or more of silicon nitride, silicon oxide, and silicon oxynitride. Further, the thickness of the underlayer is preferably 0.05 to 3 ⁇ m.
  • the polymer of alkoxysilane is preferably a polymer of plural types of alkoxysilane.
  • a combination of an inorganic layer and an underlayer is formed only on one side of the support, and an adhesion layer is formed on the other side of the support.
  • the method for producing a gas barrier film of the present invention is a method for producing a gas barrier film having one or more combinations of an inorganic layer and an underlayer of the inorganic layer, A preparation step for preparing a coating solution containing alkoxysilane, Applying the prepared coating liquid on the formation surface of the base layer, heating the coating liquid to polymerize alkoxysilane, thereby forming a base layer forming step, and There is provided an inorganic layer forming step of forming an inorganic layer containing silicon on the surface of a base layer by plasma CVD while applying a bias potential to the base layer.
  • the coating liquid containing alkoxysilane prepared preferably contains water as a solvent.
  • the method for producing a gas barrier film preferably further includes a step of sticking the base layer protective film on the surface of the base layer and a step of peeling the base layer protective film attached to the surface of the base layer.
  • the process of sticking an inorganic layer protective film on the surface of an inorganic layer, the liquid preparation process which prepares the coating liquid of a protective organic layer, and peeling the inorganic layer protective film stuck on the surface of an inorganic layer, and protecting organic It is preferable to further include a step of applying a layer coating solution on the surface of the inorganic layer, and drying and curing the protective organic layer coating solution.
  • a gas barrier film having high gas barrier properties and a method for producing the gas barrier film are provided.
  • gas barrier film of the present invention and the method for producing the gas barrier film will be described in detail.
  • the gas barrier film 10 which is the 1st Embodiment of this invention is shown notionally.
  • the gas barrier film 10 is formed on the surface of the base layer 14 using the support 12, the base layer 14 formed on one surface of the support 12 (the upper surface in FIG. 1), and the base layer 14 as a base.
  • an inorganic layer 16 is formed between the inorganic layer 16 and the base layer 14 that is the base of the inorganic layer 16.
  • the surface is the main surface, that is, the maximum surface of the sheet-like material and the layer (film).
  • the upper side in the figure is also simply referred to as “upper”.
  • the material for forming the support 12 is not limited, and various resin materials can be used as long as the base layer 14 and the inorganic layer 16 can be formed.
  • Examples of the material for forming the support 12 include polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacrylonitrile ( PAN), polyimide (PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), acrylonitrile / butadiene / styrene copolymer ( ABS), cyclic olefin copolymer (COC), cycloolefin polymer (COP), and triacetyl cellulose (TAC).
  • PE polyethylene
  • PEN polyethylene naphthalate
  • PA polyamide
  • PET poly
  • the thickness of the support 12 can be appropriately set according to the application, the forming material, and the like.
  • the thickness of the support 12 is from the viewpoint of sufficiently securing the mechanical strength of the gas barrier film 10, and from the viewpoint of ensuring the flexibility (flexibility) of the gas barrier film 10, and reducing the weight and thickness. 5 to 150 ⁇ m is preferable, and 10 to 100 ⁇ m is more preferable.
  • the support 12 is preferably transparent. Specifically, the support 12 preferably has a total light transmittance of 85% or more, and preferably 88% or more. Thereby, the gas barrier film 10 with high transparency is obtained.
  • the total light transmittance may be measured in accordance with JIS K 7361 using a commercially available measuring apparatus such as NDH5000 and SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the support 12 may have an easy adhesion layer, a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, a stress relaxation layer, and the like on at least one surface. Good. These layers may have a plurality of types.
  • the support 12 has an easy adhesion layer on at least one surface, preferably both surfaces.
  • an easily bonding layer Various well-known easily bonding layers formed in the surface of various resin films can be utilized.
  • an easy-adhesion layer the easy-adhesion layer etc. which are formed as an example using a urethane compound and an isocyanate compound are illustrated.
  • the easy-adhesion layer provided on the surface of the support 12 contains a matting agent such as colloidal silica, methyl (meth) acrylate polymer, butyl (meth) acrylate polymer, oleic acid amide, and silicon oxide particles (silica particles). May be.
  • a matting agent such as colloidal silica, methyl (meth) acrylate polymer, butyl (meth) acrylate polymer, oleic acid amide, and silicon oxide particles (silica particles). May be.
  • the easy-adhesion layer contains a matting agent, the roll-to-roll described later becomes easy to roll, the roll-to-roll roll is beautifully rolled, and the roll-to-roll roll is being transported. It is preferable in that it can prevent a scratch failure due to slippage.
  • the formation of the base layer 14 is performed.
  • a matting agent having a small average particle size is preferable so as not to affect the above.
  • the size of the matting agent is preferably 0.2 ⁇ m or less.
  • the formation surface of the base layer 14 may be the surface of the support 12 or the surface of the inorganic layer 16.
  • the gas barrier film 10 having two or more combinations of the inorganic layer 16 and the base layer 14 includes the base layer 14 formed on the surface of the support 12 and the base layer 14 formed on the surface of the inorganic layer 16.
  • the base layer 14 is provided on one surface of the support 12.
  • An inorganic layer 16 is provided on the base layer 14. That is, the gas barrier film 10 shown in FIG. 1 has one set of a combination of a base layer 14 and an inorganic layer 16 having the base layer 14 as a base (undercoat).
  • the gas barrier film of this invention is not limited to what has only one set of the combination of the base layer 14 used as a base, and the inorganic layer 16, as shown in FIG. That is, the gas barrier film of the present invention may have two combinations of the inorganic layer 16 and the base layer 14 as a base, like the gas barrier film 20 conceptually shown in FIG. Alternatively, the gas barrier film of the present invention may have three or more combinations of the inorganic layer 16 and the base layer 14 serving as the base. A gas barrier film having higher gas barrier properties can be obtained as the number of combinations of the base layer 14 and the inorganic layer 16 serving as the base increases. On the other hand, the greater the number of combinations of the base layer 14 and the inorganic layer 16 that are the base, the more disadvantageous in terms of thinning, lightening, and flexibility of the gas barrier film.
  • the gas barrier film of the present invention is not limited to the gas barrier film having a combination of the base layer 14 and the inorganic layer 16 on only one surface of the support 12 as shown in FIGS. That is, the gas barrier film of the present invention may have one or more combinations of the base layer 14 and the inorganic layer 16 on both surfaces of the support 12.
  • the foundation layer 14 is a layer (undercoat layer) that serves as a foundation for the inorganic layer 16. That is, the underlayer 14 is a layer that embeds irregularities on the surface of the support 12 and / or foreign matters attached to the surface and smoothes the surface on which the inorganic layer 16 is formed.
  • the gas barrier film 10 of the present invention has such an underlayer 14, thereby enabling the inorganic layer 16 that mainly exhibits gas barrier properties to be appropriately formed on the entire surface without any gaps. Yes.
  • the base layer of the inorganic layer 16 is a base organic layer obtained by polymerizing a (meth) acrylate compound or the like.
  • the underlayer 14 of the gas barrier film 10 of the present invention includes a polymerized product (condensed polymer) of alkoxysilane.
  • the inorganic layer 16 contains silicon.
  • the gas barrier film 10 of the present invention is a mixture containing both the components of the inorganic layer 16 and the component of the base layer 14 between the inorganic layer 16 and the base layer 14 serving as the base of the inorganic layer 16. It has a layer 18. The present invention realizes a gas barrier film having more excellent gas barrier properties by having such a configuration.
  • a coating liquid containing an organic compound that becomes an organic layer such as a (meth) acrylate monomer, a photopolymerization initiator, and an organic solvent is prepared.
  • the base organic layer is formed by polymerizing (crosslinking / curing) the organic compound by applying the coating liquid onto the surface of the support and drying it, and then irradiating the coating film with ultraviolet rays.
  • the laminated gas barrier film it is possible to obtain a gas barrier film having a high gas barrier property such that the water vapor transmission rate is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ day) or less. Furthermore, as described in Patent Document 2, after forming the base organic layer, by sticking a laminate film on the surface of the base organic layer, the organic layer is prevented from being damaged until the inorganic layer is formed. it can.
  • the present inventors have found that in a gas barrier film having a base organic layer, defects in the inorganic layer occur due to the unreacted organic compound, the remaining polymerization initiator, and the remaining organic solvent. Thus, it was found that this hinders further improvement in gas barrier properties.
  • the base organic layer is formed by preparing a coating solution using an organic solvent, coating and drying, and then polymerizing the organic compound. Here, it is difficult to completely remove the solvent of the coating solution, and some organic solvent remains in the underlying organic layer. Similarly, it is difficult to completely react the organic compound and the polymerization initiator in the coating solution, and some organic compounds and the polymerization initiator remain in the underlying organic layer.
  • an unreacted organic compound tends to remain in an intermediate region in the thickness direction of the base organic layer.
  • the inorganic layer having the base organic layer as a base layer is preferably formed by plasma CVD.
  • the underlying organic layer is etched to some extent by the plasma irradiation during the formation of the inorganic layer by plasma CVD. Since the organic solvent, the organic compound, and the polymerization initiator are highly volatile, they are vaporized and released by this etching. Since the release of such a substance inhibits the deposition of the inorganic layer, it causes a defective film formation of the inorganic layer, and hinders further improvement in the performance of the laminated gas barrier film having the base organic layer and the inorganic layer. It has become.
  • the present inventors have made extensive studies on a base layer formed of a material that is dense and has high hardness and in which an unreacted material does not affect the formation of the inorganic layer 16 by plasma CVD. .
  • the underlayer 14 containing a polymer of alkoxysilane as the underlayer of the inorganic layer 16 containing silicon, the inorganic layer 16 is formed with high density and high hardness, and the unreacted material is formed by plasma CVD. It was found that a gas barrier film having better gas barrier properties and the like can be obtained by forming the underlayer 14 that does not affect the above.
  • a polymer of alkoxysilane forms a bond of “—O—Si—O—” by hydrolysis and polymerization (condensation polymerization) of alkoxysilane. Therefore, since the base layer 14 containing the polymer of alkoxysilane has a very high density and a hard film, after the base layer 14 is formed, damage to the base layer 14 due to transportation or the like can be largely prevented. .
  • the base layer 14 made of a polymer of alkoxysilane dissolves alkoxysilane in a solvent, and forms the base layer 14 to which a curing agent, a surfactant and the like are added as necessary. It forms using a coating liquid.
  • the underlayer 14 having excellent support and embedding of foreign matter and the like and having a smooth surface, that is, the surface on which the inorganic layer 16 is formed.
  • alkoxysilane can be dissolved in water, it is not necessary to use an organic solvent in the coating solution, it can be formed with a film-forming apparatus that does not consider explosion-proof properties, and also in terms of preventing environmental pollution. It is advantageous.
  • the hydrolysis of the alkoxysilane, that is, the polymerization reaction also proceeds favorably.
  • the underlayer 14 contains a polymerized alkoxysilane.
  • the base layer 14 may be a polymer of alkoxysilane as a main component, but 50% by mass or more is preferably a polymer of alkoxysilane, and 60% by mass or more is a polymer of alkoxysilane. More preferably, 70% by mass or more is a polymer of alkoxysilane.
  • a main component means the component with the largest containing mass ratio among the components which a layer contains.
  • the underlayer 14 is prepared by preparing a coating solution containing the alkoxysilane and forming the underlayer 14, and applying the coating solution to the support 12 (the surface on which the underlayer 14 is formed). By heating the film, the alkoxysilane is hydrolyzed and polymerized (condensation polymerization) (by curing the alkoxysilane) to form.
  • the coating liquid for forming the base layer 14 is also referred to as “underlayer coating liquid”.
  • alkoxysilane used as the base layer 14
  • a well-known various alkoxysilane can be utilized.
  • silazane is also regarded as alkoxysilane.
  • examples of the alkoxysilane include compounds represented by the following general formula (1).
  • General formula (1) R 1 is an organic group having 1 to 10 carbon atoms
  • R 2 is an alkyl group having 1 to 3 carbon atoms
  • a is 0 or 1.
  • the alkoxysilane includes methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, and n-propyl.
  • Triethoxysilane isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexylmethyldimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, tetra Examples include ethoxysilane (TEOS) and hexamethyldisilazane. Of these, tri- to hexa-functional alkoxysilanes are preferably used.
  • tetraethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like are preferably used.
  • an alkoxysilane having a radical polymerizable group is used and curing is performed with the radical polymerizable group, uneven distribution of the curing in the thickness direction may increase.
  • the underlayer 14 is etched by plasma during the formation of the inorganic layer 16 described later, a portion of the unpolymerized radical polymerizable group is exposed from the inside, resulting in a defect failure that impairs the gas barrier performance. sell.
  • a plurality of alkoxysilanes serving as the underlayer 14 may be used in combination, for example, a combination of tetraethoxysilane and 3-glycidoxypropyltriethoxysilane.
  • a plurality of alkoxysilanes are used in combination, it is preferable to use at least one alkoxysilane having a straight chain (which may have a side chain) having 3 or more carbon atoms.
  • the use of a straight-chain alkoxysilane having 3 or more carbon atoms is preferable in that the curl of the gas barrier film 10 can be suitably prevented and sufficient polymerizability can be secured.
  • the underlayer 14, that is, the underlayer coating solution may contain colloidal silica, if necessary.
  • the underlayer 14 contains colloidal silica, it imparts slidability and facilitates conveyance and roll-up in roll-to-roll described later.
  • the rolled form of roll-to-roll is beautiful. It is preferable in that the hardness of the underlayer 14 can be improved.
  • colloidal silica content in the underlayer 14 increases, the gas galliarity tends to decrease. Therefore, colloidal silica is preferably added to the underlayer 14 when emphasis is placed on transportability, winding property, and the like rather than gas barrier properties.
  • the content of colloidal silica in the underlayer 14 is preferably 1 to 40% by mass, and more preferably 5 to 20% by mass.
  • the thickness of the underlayer 14 is not limited. Therefore, the thickness capable of embedding irregularities on the surface of the support 12 can be appropriately set according to the alkoxysilane or the like that forms the base layer 14.
  • the thickness of the underlayer 14 is preferably 0.03 to 3 ⁇ m, more preferably 0.05 to 3 ⁇ m, further preferably 0.1 to 2.5 ⁇ m, and particularly preferably 0.5 to 2 ⁇ m.
  • the thickness of the underlayer 14 By setting the thickness of the underlayer 14 to 0.03 ⁇ m or more, the surface of the underlayer 14 can be flattened by embedding irregularities on the surface of the support 12 and foreign matters attached to the surface of the support 12. This is preferable.
  • By setting the thickness of the underlayer 14 to 3 ⁇ m or less it is preferable in that cracks of the underlayer 14 can be prevented, the flexibility of the gas barrier film 10 can be increased, and the gas barrier film 10 can be reduced in thickness and weight. .
  • each base layer 14 may be the same or different.
  • the underlayer 14 can be formed by a known method corresponding to the forming material.
  • the base layer 14 is prepared by preparing a base layer coating solution containing alkoxysilane to be the base layer 14 (a coating solution for forming the base layer 14), and applying the coating solution to the surface of the support 12. It can be formed by a so-called coating method in which it is applied and heated (dried).
  • the undercoat layer coating liquid may contain colloidal silica, and may contain a curing agent and / or a surfactant as necessary.
  • the underlayer 14 can be formed by so-called roll-to-roll.
  • roll-to-roll is also referred to as “RtoR”.
  • RtoR is a roll formed by winding a long film formation target sheet, the film formation target sheet is sent out, the film formation target sheet is conveyed in the longitudinal direction, and film formation is performed in a roll shape. It is a manufacturing method wound around. By using RtoR, high productivity and production efficiency can be obtained.
  • the inorganic layer 16 is provided on the surface of the base layer 14.
  • the inorganic layer 16 is a layer mainly composed of a compound containing silicon, and is preferably a layer made of a compound containing silicon except for inevitable impurities.
  • the inorganic layer 16 exhibits gas barrier properties.
  • the inorganic layer 16 is appropriately formed by being provided on the surface of the underlayer 14.
  • the support 12 has regions where it is difficult for the inorganic compound to deposit, such as surface irregularities and shadows of foreign matter. By providing the base layer 14 on the support 12, a region where the inorganic compound is difficult to deposit is covered. Therefore, the inorganic layer 16 can be formed on the entire surface of the support 12 without any gaps.
  • the material for forming the inorganic layer 16 include silicon oxides such as silicon oxide, silicon oxynitride, silicon oxycarbide, and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide These hydrides; mixtures of these two or more; and inorganic compounds such as these hydrogen-containing materials. A mixture of two or more of these can also be used.
  • silicon nitride, silicon oxide, and silicon oxynitride are preferably used because they are highly transparent and can exhibit excellent gas barrier properties.
  • silicon nitride is preferably used because it can exhibit excellent gas barrier properties.
  • the thickness which can express the target gas barrier property can be set suitably.
  • the thickness of the inorganic layer 16 is preferably 10 to 200 nm, more preferably 15 to 100 nm, and further preferably 20 to 75 nm. By setting the thickness of the inorganic layer 16 to 10 nm or more, it is preferable in that the inorganic layer 16 that stably exhibits sufficient gas barrier properties can be formed.
  • the inorganic layer 16 is generally brittle, and if it is too thick, there is a possibility of causing cracks, cracks, peeling, etc.
  • the thickness of the inorganic layer 16 is 200 nm or less, cracks will occur. Can be prevented. Further, by setting the thickness of the inorganic layer 16 to 150 nm or less, when the gas barrier film 10 is bent, the inorganic layer 16 is prevented from being cracked and peeled, and the highly flexible gas barrier film 10 can be obtained. However, it is preferable.
  • each inorganic layer 16 may be the same or different.
  • the inorganic layer 16 can be formed by a known method according to the forming material.
  • plasma CVD such as CCP (Capacitively Coupled Plasma) -CVD and ICP (Inductively Coupled Plasm) -CVD, atomic layer deposition (ALD), sputtering such as magnetron sputtering and reactive sputtering, and vacuum
  • plasma CVD particularly plasma CVD for applying a bias potential to the underlayer 14 is preferably used.
  • the inorganic layer 16 is also preferably formed of RtoR.
  • the gas barrier film 10 of the present invention includes a mixed layer 18 between an inorganic layer 16 and a base layer 14 that is a base of the inorganic layer 16.
  • the mixed layer 18 is a layer containing both the component for forming the underlayer 14, that is, the component derived from alkoxysilane, and the component derived from the inorganic layer 16, that is, silicon nitride.
  • the mixed layer 18 can be formed by forming the inorganic layer 16 by plasma CVD and forming the inorganic layer 16 under conditions such that the plasma sufficiently etches the underlayer 14.
  • the inorganic layer 16 is a layer containing an inorganic compound containing silicon
  • the underlayer 14 is a layer mainly composed of a polymer of alkoxysilane
  • the mixed layer 18 is used when the inorganic layer 16 is formed. It is formed by etching the underlayer 14. Therefore, a bond of “—O—Si—O—” is formed between the inorganic layer 16 and the mixed layer 18 by the formation component of the inorganic layer 16 and the formation component of the underlayer 14, and the mixed layer 18 and the underlayer Similarly, a bond of “—O—Si—O—” is formed by the component for forming the inorganic layer 16 and the component for forming the underlayer 14.
  • the mixed layer 18 is not simply a layer in which the components of the inorganic layer 16 and the base layer 14 are mixed, but a layer that bonds the inorganic layer 16 and the base layer 14 by chemical bonding. Become. Therefore, by having the mixed layer 18, the adhesion between the underlayer 14 and the inorganic layer 16 can be greatly increased.
  • the mixed layer 18 is a layer in which the components of the inorganic layer 16 and the components of the base layer 14 are mixed, the optical characteristics, particularly the refractive index, are between the base layer 14 and the inorganic layer 16. Moreover, the mixed layer 18 is formed by etching the base layer 14 when the inorganic layer 16 is generated. Therefore, the mixed layer 18 has, in order from the inorganic layer 16 side to the base layer 14 side, a region in which the inorganic layer 16 component is large and the base layer 14 component is small, and the inorganic layer 16 component and base layer 14 component. And a region where the components of the inorganic layer 16 are small and the component of the base layer 14 is large, and the balance of the components gradually changes, that is, the optical characteristics also gradually change.
  • the mixed layer 18 is a region having both components of the inorganic layer 16 and the base layer 14 located between the inorganic layer 16 and the base layer 14. Therefore, when elemental analysis is performed from the inorganic layer 16 side to the base layer 14 side in the thickness direction (stacking direction of each layer), the component derived from the inorganic layer 16 is detected and then the component derived from the base layer 14 Is detected. As the elemental analysis proceeds to the base layer 14 side, components derived from the inorganic layer 16 are gradually not detected, and only components derived from the base layer 14 are detected.
  • elemental analysis is performed in the thickness direction from the inorganic layer 16 side to the base layer 14 side, and only the inorganic layer 16 is detected from the position where the component contained only in the base layer 14 starts to be detected.
  • the mixed layer 18 is formed up to the position where the component contained in is not detected.
  • the inorganic layer 16 is a silicon nitride film and the base layer 14 is a film obtained by polymerizing tetraethoxysilane
  • elemental analysis is performed from the inorganic layer 16 side to the base layer 14 side in the thickness direction, and carbon From the position at which nitrogen is detected to the position at which nitrogen is no longer detected, the mixed layer 18 is formed. Therefore, the film thickness of the mixed layer 18 can be measured using this.
  • the thickness of the mixed layer 18 is not limited. Here, in order to obtain sufficient effects such as improvement in adhesion and optical characteristics by having the mixed layer 18, it is preferable that the mixed layer 18 has a certain thickness. On the other hand, the thicker the mixed layer 18 is, the thinner the inorganic layer 16 is. However, since the mixed layer 18 does not have the same gas barrier properties as the inorganic layer, the thicker the mixed layer 18 is, the more disadvantageous in terms of gas barrier properties. Considering this point, the thickness of the mixed layer 18 is preferably 1 to 30 nm, more preferably 3 to 15 nm, and further preferably 5 to 10 nm.
  • the thickness of the thickest portion of the mixed layer 18 is preferably within the above range, and the thickness of the entire region is more preferably within the above range.
  • the thickness of the mixed layer 18 is measured at 10 arbitrarily selected points. If the thickness of the mixed layer 18 is within the above range at all measurement points, the mixed layer 18 is measured. Can be considered that the thickness of the entire region falls within the above range.
  • the thickness of the mixed layer 18 is detected by performing elemental analysis in the thickness direction as described above using a cross-sectional TEM (Transmission Electron Microscope). To measure.
  • Such a mixed layer 18 forms the inorganic layer 16 under the condition that the inorganic layer 16 is formed by plasma CVD, and when the inorganic layer 16 is formed by this plasma CVD, the underlayer 14 is strongly etched. By doing so, it can be formed. Specifically, when the inorganic layer 16 is formed by plasma CVD, a bias potential is applied to the base layer 14, and the bias potential applied to the base layer 14 can be sufficiently etched by the plasma. By setting the height, the mixed layer 18 can be formed. Further, the mixed layer 18 can be made thicker by increasing the bias potential applied to the base layer 14, and the mixed layer 18 can be made thinner by lowering the bias potential.
  • the thicknesses of the inorganic layer 16 and the mixed layer 18 are, for example, from the start of film formation by experiments or simulations in which the formation conditions (film formation conditions) of the inorganic layer 16 such as a bias potential applied to the base layer 14 are changed in advance.
  • the time until the formation of the inorganic layer 16 is started, the thickness of the formed mixed layer 18, the deposition rate of the inorganic layer 16, etc. are known and can be controlled using this.
  • the gas barrier film 10 of the present invention preferably has a total light transmittance of 85% or more, and preferably 88% or more. In this regard, the same applies to the gas barrier film of another embodiment described later.
  • the gas barrier film 24 which is the 2nd Embodiment of this invention is shown notionally.
  • the gas barrier film 24 shown in FIG. 3 is composed of the same members as the gas barrier film 10 shown in FIG. 1 except that the protective organic layer 26 is provided. Mainly do different parts.
  • the protective organic layer 26 is a layer made of an organic compound, which is formed on the surface of the inorganic layer 16 that is farthest from the support 12 in the stacking direction of the layers. That is, the protective organic layer 26 is a layer laminated on the surface of the uppermost inorganic layer 16. By having such a protective organic layer 26, it is possible to prevent damage to the inorganic layer 16 that exhibits gas barrier properties, such as cracks and cracks, and to obtain a gas barrier film having high gas barrier properties.
  • the protective organic layer 26 is formed, for example, by curing a coating solution containing an organic compound (monomer, dimer, trimer, oligomer, polymer, etc.).
  • the coating liquid for forming the protective organic layer 26 may contain only one type of organic compound or two or more types.
  • the coating solution preferably contains an organic solvent, a surfactant, a silane coupling agent, and the like.
  • the protective organic layer 26 contains, for example, a thermoplastic resin and an organosilicon compound.
  • the thermoplastic resin include polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, and polyurethane.
  • the organosilicon compound include polysiloxane.
  • the protective organic layer 26 preferably contains a polymer of a radical curable compound and / or a cationic curable compound having an ether group from the viewpoint of excellent strength and a glass transition temperature. From the viewpoint of lowering the refractive index of the protective organic layer 26, the protective organic layer 26 preferably contains a (meth) acrylic resin mainly composed of a (meth) acrylate monomer or oligomer polymer.
  • the protective organic layer 26 is more preferably bifunctional such as dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), and the like. It contains a (meth) acrylic resin whose main component is the above (meth) acrylate monomer or oligomer polymer, more preferably a trifunctional or higher functional (meth) acrylate monomer or oligomer polymer as the main component. (Meth) acrylic resin is included. A plurality of these (meth) acrylic resins may be used. A main component means a component with the largest containing mass ratio among the components to contain.
  • the silane coupling agent includes various compounds produced from the silane coupling agent, such as a hydrolyzate of the silane coupling agent, a hydrogen bond of the silane coupling agent, and a dehydrated condensate of the silane coupling agent. including. In this regard, the same applies to layers containing other silane coupling agents.
  • the protective organic layer 26 includes a graft copolymer having a main chain of an acrylic polymer and at least one of a urethane polymer having an acryloyl group and a urethane oligomer having an acryloyl group as a side chain.
  • the coating liquid containing the above (meth) acrylate monomer, (meth) acrylate polymer, and silane coupling agent is coated on the inorganic layer 16 and dried, and the coating liquid is polymerized (cured).
  • the layer is
  • the protective organic layer 26 may have a polymer (cured product) of urethane acrylate oligomer. That is, the coating liquid for forming the protective organic layer 26 may contain a urethane acrylate oligomer as necessary.
  • a graft copolymer having an acrylic polymer as a main chain and a side chain as a urethane polymer having an acryloyl group at the end and a urethane oligomer having an acryloyl group at the end is simply referred to as “graft copolymer”. Also called “polymer”.
  • the graft copolymer used for the protective organic layer 26 is a graft copolymer having an acrylic polymer as a main chain and a urethane polymer having an acryloyl group at the end and / or a urethane oligomer having an acryloyl group at the end as a side chain.
  • the graft copolymer may be a copolymer having a structure in which urethane monomer units are arranged as side chains at the monomer units of the main acrylic main chain, and is generally a structure formed by graft copolymerization. As long as it has.
  • the acrylic main chain of the graft copolymer may be formed by individually polymerizing an acrylate monomer, an ethyl acrylate monomer, etc., and any of these copolymers or any of these and a copolymer of other monomers. It may be a polymer. For example, a copolymer obtained from (meth) acrylic acid ester and ethylene is also preferable. At least a part of the side chain bonded to the acrylic main chain is a side chain containing a urethane polymer unit or a urethane oligomer unit.
  • the graft copolymer may have a plurality of urethane polymer units having different molecular weights and / or a plurality of urethane oligomer units having different molecular weights.
  • the graft copolymer preferably has a weight average molecular weight of 10,000 or more.
  • the weight average molecular weight of the graft copolymer is preferably 10,000 to 300,000, the molecular weight of the graft copolymer is more preferably 10,000 to 2500,000, and further preferably 12,000 to 200,000.
  • the weight average molecular weight (Mw) of various polymers can be measured as a molecular weight in terms of polystyrene (PS) by gel permeation chromatography (GPC). Good. More specifically, the weight average molecular weight is HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID ⁇ 15.0 cm) as a column, and 10 mmol / L as an eluent. It may be obtained by using a lithium bromide NMP (N-methylpyrrolidinone) solution. As the weight average molecular weight of a polymer or the like, a numerical value described in a catalog or the like may be used.
  • the graft copolymer preferably has a double bond equivalent (acryl equivalent) of 500 g / mol or more, more preferably 550 g / mol or more, and still more preferably 600 g / mol or more.
  • the double bond equivalent of the graft copolymer is preferably 2000 g / mol or less.
  • the double bond equivalent is a weight average molecular weight (polymer mass) per mole of polymerizable double bonds (that is, (meth) acryloyl groups) contained in the graft copolymer.
  • the double bond equivalent of the urethane polymer of a graft copolymer may utilize the numerical value described in the catalog etc.
  • Such a graft copolymer may be a commercially available product such as Acryt 8BR series such as Acryt 8BR-930 which is an ultraviolet curable urethane acrylic polymer manufactured by Taisei Fine Chemical Co., Ltd.
  • a plurality of graft copolymers may be used in combination.
  • Trifunctional or higher (meth) acrylate monomer As the trifunctional or higher functional (meth) acrylate monomer, various known ones can be used. Specifically, TMPTA, DPHA, epichlorohydrin (ECH) modified glycerol tri (meth) acrylate, ethylene oxide (EO) modified glycerol tri (meth) acrylate, propylene oxide (PO) modified glycerol tri (meth) acrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, EO-modified phosphoric acid triacrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified TMPTA, PO-modified TMPTA, tris (acryloxyethyl) isocyanurate, dipentaerythritol penta (meta) ) Acrylate, caprolactone-modified DPHA, dipentaeryth
  • the trifunctional or higher functional (meth) acrylate monomer in the compound represented by the general formula (1) can be obtained as a commercial product. Further, the trifunctional or higher functional (meth) acrylate monomer in the compound represented by the general formula (1) can be synthesized by a known method.
  • the (meth) acrylate polymer may be an acrylate polymer, a methacrylate polymer, or a mixture of an acrylate polymer and a methacrylate polymer.
  • the methacrylate polymer is preferably used in that the protective organic layer 26 having high hardness can be obtained.
  • the molecular weight of the (meth) acrylate polymer is not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 40,000 or more.
  • the weight average molecular weight of the (meth) acrylate polymer is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 40,000 or more.
  • ⁇ Silane coupling agent having one or more (meth) acryloyl groups Various known silane coupling agents can be used as long as they have one or more (meth) acryloyl groups. Specifically, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Etc. are exemplified.
  • silane coupling agent having one or more (meth) acryloyl groups examples include KBM-5103, KBM-502, KBM-503, KBE-502, and KBE-503 manufactured by Shin-Etsu Silicone.
  • the urethane acrylate oligomer As the urethane acrylate oligomer, various types of urethane oligomers that can be cured by ultraviolet rays and have an acrylate terminal can be used.
  • the urethane acrylate oligomer is a urethane acrylate molecule having a molecular weight of 1000 to 10,000.
  • the molecular weight intends the molecular weight calculated from the chemical structural formula.
  • the urethane acrylate oligomer has a molecular weight distribution, the molecular weight intends the above-mentioned weight average molecular weight. To do.
  • urethane acrylate oligomer a commercially available product can be suitably used.
  • examples of commercially available urethane acrylate oligomers include functional oligomer CN series manufactured by Sartomer, and photocurable oligomer NK series manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the protective organic layer 26 may contain a slipping agent as necessary. That is, the coating liquid for forming the protective organic layer 26 may contain a slip agent as necessary.
  • the protective organic layer 26 is also preferably formed by RtoR. When the protective organic layer 26 contains a slipping agent, it is possible to perform winding and unwinding in RtoR stably and smoothly, and the rolled form of the roll is also beautiful.
  • the thickness of the protective organic layer 26 is preferably 3 to 30 ⁇ m, and more preferably 5 to 15 ⁇ m.
  • the thickness of the protective organic layer 26 is preferably 3 to 30 ⁇ m, and more preferably 5 to 15 ⁇ m.
  • the gas barrier film 30 which is the 3rd Embodiment of this invention is shown notionally.
  • the gas barrier film 30 shown in FIG. 4 consists of the same member as the gas barrier film 10 shown in FIG. 1 except having the contact
  • the gas barrier film of the present invention may have both the protective organic layer 26 and the adhesion layer 32 described above.
  • the gas barrier film 30 has an adhesion layer 32 on the surface of the support 12 opposite to the surface on which the base layer 14 and the inorganic layer 16 are formed.
  • the formation surface of the base layer 14 and the inorganic layer 16 is also referred to as “upper surface” and the opposite surface is also referred to as “rear surface”.
  • the adhesion layer 32 may be directly formed on the back surface of the support 12 or may be formed on the above-described easy adhesion layer formed on the support 12.
  • the adhesion layer 32 is, for example, an adhesion layer that also serves as a sliding layer.
  • an adhesion layer By having such an adhesion layer, it is easy to roll up in RtoR, the roll form of roll by RtoR is beautiful, the handling property of the gas barrier film can be improved, and damage to the back surface can be prevented. It is preferable in terms of easy bonding.
  • adherence layer in various sheet-like materials can be utilized.
  • an adhesive layer containing, as a sliding particle, the matting agent exemplified in the above-mentioned easy adhesion layer using urethane and polyolefin as a binder is exemplified.
  • the adhesion layer 32 may be formed by a known method according to the material for forming the adhesion layer, such as a coating method.
  • the adhesion layer 32 (sliding layer described later) is preferably formed using a coating solution containing water as a solvent. Thereby, when forming the underlayer 14 using water as a solvent, it is possible to form the underlayer 14 and the adhesion layer 32 with the same film forming apparatus. It is also advantageous in terms of preventing environmental pollution.
  • the layer formed on the back surface of the support 12 is not limited to the adhesion layer 32.
  • a sliding layer is illustrated.
  • various known sliding layers can be used.
  • a binder made of urethane, acrylate, epoxy resin, or the like contains particles that may be any of organic and inorganic substances such as silica and polymethyl methacrylate. Examples include matted layers.
  • the apparatus shown in FIG. 5 is a coating film forming apparatus 36 that forms the underlayer 14.
  • the coating film forming apparatus 36 forms an organic layer by RtoR, and while transporting the long support 12 in the longitudinal direction, a coating solution for forming a base layer (a coating solution for forming the base layer 14 (polymerizable composition). After applying ()), the alkoxysilane contained in the undercoat layer coating solution is hydrolyzed and polymerized by heating to form the undercoat layer 14.
  • the coating film forming apparatus 36 in the illustrated example includes, as an example, a coating unit 37, a heating unit 38, a rotating shaft 40, a winding shaft 42, and conveyance roller pairs 46 a and 46 b.
  • the apparatus shown in FIG. 6 is an inorganic film forming apparatus 50 that forms the inorganic layer 16.
  • the inorganic film forming apparatus 50 also forms the inorganic layer 16 by RtoR, and the base layer 14 formed on the support 12 is transported in the longitudinal direction while the long support 12 on which the base layer 14 is formed is transported in the longitudinal direction.
  • An inorganic layer 16 is formed thereon.
  • the illustrated inorganic film forming apparatus 50 includes a supply chamber 51, a film forming chamber 52, and a winding chamber 54.
  • the supply chamber 51 and the film formation chamber 52 are separated by a partition wall 76 having an opening 76a
  • the film formation chamber 52 and the winding chamber 54 are separated by a partition wall 78 having an opening 78a.
  • the underlayer 14 is formed on the surface of the support 12.
  • the inorganic layer 16 is formed (inorganic layer forming step) and manufactured.
  • a support roll 12Ra formed by winding a long support 12 is loaded on the rotary shaft 40 of the coating film forming apparatus 36. Then The support 12 drawn out from the support roll 12Ra is passed through a predetermined transport path that reaches the winding shaft 42 through the transport roller pair 46a, the coating unit 37, the heating unit 38, and the transport roller pair 46b. .
  • the support 12 is transported to the coating unit 37 by a pair of transport rollers 46a, and a base layer coating solution obtained by dissolving alkoxysilane in a solvent is coated on the surface.
  • a known curing agent and surfactant may be added to the undercoat layer coating solution depending on the alkoxysilane used.
  • the undercoat layer coating liquid preferably contains water, not an organic solvent.
  • the underlayer 14 is formed by hydrolysis and polymerization (condensation polymerization) of alkoxysilane. Accordingly, by using water as a solvent, the hydrolysis and polymerization reaction of alkoxysilane can be more suitably advanced. Further, by using water as a solvent, it is not necessary to take an explosion-proof measure for the film forming apparatus, the apparatus can be simplified, and it is advantageous in terms of preventing environmental pollution. In addition, it is preferable to use pure water, distilled water, ion-exchanged water, or the like as water as the solvent.
  • Various known methods such as a die coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a bar coating method, and a gravure coating method can be used for applying the undercoat layer coating solution in the coating unit 37. It is.
  • the heating unit 38 includes an upper surface side heating unit 38a that heats and dries the upper surface side (the coating surface side of the base layer coating solution) of the support 12, and a back surface side that heats and dries from the back surface side of the support 12
  • a heating unit 38b is provided, and the undercoat layer coating solution is heated from both the upper surface side and the back surface side.
  • the heating in the heating unit 38 may be performed by a known method for heating the sheet-like material.
  • the upper surface side heating unit 38a on the upper surface side is a warm air heating unit
  • the back surface side heating unit 38b on the back surface side is a heat roller (pass roller having a heating mechanism).
  • the protective film Ga (undercoat layer protective film) fed from the supply roll 47 is adhered to the surface of the underlayer 14 in the pair of conveyance rollers 46b (underlayer). Step of attaching a protective film). Next, the support 12 is wound around the winding shaft 42 to obtain a roll 12Rb.
  • the support 12 on which the base layer 14 is formed can be supplied to the inorganic film forming apparatus 50 shown in FIG.
  • the protective film Ga for protecting the underlayer 14 and the protective film Gb for protecting the inorganic layer 16 to be described later are not limited, and are known protective films used for protecting sheet-like materials such as polyolefin films such as polyethylene films. Various types of (laminate film) can be used.
  • the roll 12 ⁇ / b> Rb is loaded on the rotation shaft 56 of the supply chamber 51.
  • the support 12 (the support 12 on which the underlayer 14 is formed) is pulled out, and the take-up shaft of the take-up chamber 54 is drawn from the supply chamber 51 through the film forming chamber 52.
  • a predetermined route to 58 is taken.
  • the vacuum evacuation means 61 of the supply chamber 51, the vacuum evacuation means 74 of the film forming chamber 52, and the vacuum evacuation means 82 of the winding chamber 54 are driven to form an inorganic film forming apparatus.
  • the inside of 50 is set to a predetermined pressure.
  • the support 12 delivered from the roll 12Rb is guided by the pass roller 60 and conveyed to the film forming chamber 52.
  • the support 12 conveyed to the film forming chamber 52 is guided by the pass roller 68 and wound around the drum 62, supported by the drum 62 and conveyed along a predetermined path, while the inorganic layer 16 is formed by the film forming means 64. It is formed.
  • the protective film Ga is stuck on the underlayer 14, it is preferable to peel off the protective film Ga (underlayer protective film) in the pass roller 68.
  • the peeled protective film Ga can be recovered by the recovery roll 70.
  • the film forming unit 64 is a known film forming unit that forms the inorganic layer 16 by CCP-CVD using the drum 62 as an electrode, for example.
  • the film forming means 64 includes a shower electrode 64a (shower plate 64a) constituting an electrode pair with the drum 62, a high frequency power source 64b for supplying plasma excitation power to the shower electrode 64a, and a gas for supplying a film forming gas to the shower electrode 64a. It has a supply means 64c.
  • the inorganic layer 16 is formed by CCP-CVD while applying a bias potential to the underlayer 14.
  • a bias power source 64 d is connected to the drum 62, and bias power is supplied to the drum 62 constituting the electrode pair with the shower electrode 64 a, so that a bias potential is applied to the base layer 14.
  • the inorganic layer 16 is formed by CCP-CVD.
  • the bias potential applied to the underlayer 14, that is, the bias power supplied to the drum 62, is set to a potential at which the plasma by CCP-CVD sufficiently etches the underlayer 14.
  • the bias power source 64d is not limited, and various known bias power sources that are used in a plasma CVD apparatus or the like, such as a high-frequency power source, an AC or DC pulse power source, can be used.
  • the inorganic layer 16 is formed by a known vapor deposition method according to the inorganic layer 16 to be formed, such as plasma CVD such as CCP-CVD or ICP-CVD, sputtering such as magnetron sputtering or reactive sputtering, or vacuum deposition. What is necessary is as described above. Therefore, the source gas (film forming gas / process gas) to be used, film forming conditions, and the like may be set and selected as appropriate according to the inorganic layer 16 to be formed, the film thickness, and the like. For example, when a silicon nitride film is formed as the inorganic layer 16 by CCP-CVD, for example, silane gas, nitrogen gas, ammonia gas, and hydrogen gas may be used as the source gas.
  • the protective film Gb inorganic layer protective film fed from the supply roll 73 is preferably attached to the surface of the inorganic layer 16. (The process of sticking an inorganic layer protective film).
  • the gas barrier film 10 is conveyed to the winding chamber 54.
  • the gas barrier film 10 conveyed to the take-up chamber 54 is taken up by a take-up shaft 58 to form a gas barrier film roll 10R formed by winding the gas barrier film 10.
  • the gas barrier film 10 preferably further has a protective organic layer on the inorganic layer 16.
  • the gas barrier film roll 10 ⁇ / b> R may be loaded again on the rotating shaft 40 of the coating film forming apparatus 36, and the protective organic layer may be formed on the gas barrier film 10 in the same manner as the underlayer forming process.
  • the protective film Gb is stuck on the inorganic layer 14, it is preferable to peel off the protective film Gb (inorganic layer protective film) in the transport roller pair 46a.
  • the peeled protective film Gb can be recovered by the recovery roll 48.
  • the formation of the base layer 14 (underlayer forming step)
  • the formation with the inorganic layer 16 may be repeated according to the number of combinations of the inorganic layer 16 and the base layer 14 to be formed.
  • the protective film Gb laminated on the inorganic layer 16 is peeled off by the transport roller pair 46 a prior to the application of the foundation layer coating solution in the coating section 37, and the recovery roll Wind up to 48.
  • the formation timing is not limited. Therefore, for example, after the adhesion layer 32 is formed on the back surface of the support 12, the underlayer 14 and the inorganic layer 16 may be formed on the opposite surface of the support 12, or the support 12 After forming the underlayer 14 on one surface of the substrate, the adhesion layer 32 may be formed on the back surface of the support 12 and then the inorganic layer 16 may be formed. Alternatively, the bottom surface may be formed on one surface of the support 12. After forming the base layer 14 and the inorganic layer 16, the adhesion layer 32 may be formed on the back surface of the support 12.
  • Example 1 ⁇ Production of support> A PET resin having an intrinsic viscosity of 0.66, polycondensed using an antimony compound as a catalyst, was dried to a water content of 50 ppm or less and melted in an extruder set at a heater temperature of 280 to 300 ° C. The melted PET resin was discharged from a die part onto a chill roll electrostatically applied to obtain an amorphous PET film. The obtained amorphous PET film was stretched 3.1 times in the film running direction. Thereafter, the following easy-adhesion layer coating solution A is applied to one surface of the PET film obtained by stretching, and the following easy-adhesion layer coating solution B is applied to the opposite surface thereof (in-line coating).
  • the coating solution After drying the coating solution, it was stretched 3.8 times in the width direction to obtain a support 12 made of PET with an easy-adhesion layer subjected to in-line coating.
  • the thickness of the support 12 was 100 ⁇ m.
  • the easy-adhesion layer coating solution A and the easy-adhesion layer coating solution B were both applied so that the thickness after drying and stretching was 75 nm.
  • ⁇ Coating liquid A for easy adhesion layer >> A composition containing the following components was prepared.
  • ⁇ Self-crosslinkable urethane (Daiichi Kogyo Seiyaku Co., Ltd., Elastolon H-3-DF) 164.9 parts by mass
  • Catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Elastolon CAT-21) 3.3 parts by mass
  • Block polyisocyanate Asahi Kasei Chemicals, Duranate WM44-L70G) 7.7 parts by mass Anionic surfactant (manufactured by NOF Corporation, Lapisol A-90)
  • 0.4 parts by mass Water-containing amorphous silicon dioxide (matting agent) (Tosoh Silica, NIPGEL AZ-204, particle size 0.1 ⁇ m) 0.1 parts by mass Colloidal silica (manufactured by Fuso Chemical Industries, PL-3-D) 7.4 parts by mass Carnauba
  • ⁇ Coating liquid B for easy adhesion layer >> A composition containing the following components was prepared.
  • Block polyisocyanate Asahi Kasei Chemicals Co., Ltd., Duranate WM44-L70G) 7.7 parts by mass Anionic surfactant (manufactured by NOF Corporation, Lapisol A-90) 0.4 parts by mass Colloidal silica (manufactured by Fuso Chemical Industries, PL-3- D) 7.4 parts by mass-Carnauba wax dispersion (manufactured by Chukyo Yushi Co., Ltd., cellosol 524DK) 4.9 parts by mass After adjusting the pH of the composition
  • the acetic acid aqueous solution is an acetic acid aqueous solution having an acetic acid concentration of 1% by mass.
  • tetraethoxysilane was added to the acetic acid aqueous solution with vigorous stirring over 5 minutes, and then stirring was continued at 40 ° C. for 3 hours to prepare a silanol aqueous solution.
  • a curing agent (aluminum chelate (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate D)) and a surfactant (manufactured by NOF Corporation, Rapisol a90, and Sanyo Kasei Kogyo Co., Ltd., NAROACTI cl-95) are sequentially added to prepare an aqueous undercoat layer coating solution (a coating solution for forming the underlayer 14).
  • the addition amount of 3-glycidoxypropyltriethoxysilane is 67.5 parts by mass
  • the addition amount of tetraethoxysilane is 22.5 parts by mass
  • the addition amount of the curing agent is 9 parts by mass.
  • the addition amount of the surfactant was 1 part by mass (0.5 parts by mass added).
  • the hydrolysis rate of alkoxysilane was 99.4%.
  • the base layer coating solution is applied to one surface of the support 12 by a general coating film forming apparatus that forms a film by RtoR as shown in FIG.
  • the base layer 14 having a thickness of 1 ⁇ m was formed by heating and drying.
  • a bar coater was used to apply the underlayer coating solution.
  • the heating temperature of the underlayer coating solution was 175 ° C., and the heating time was 2 minutes.
  • the underlayer 14 was formed on the surface of the support 12 on which the easy-adhesion layer was formed with the easy-adhesion layer coating liquid B (a coating liquid not containing water-containing amorphous silicon dioxide (matting agent)). Therefore, the surface on which the underlayer 14 is formed becomes the upper surface of the support 12.
  • the easy-adhesion layer coating liquid B a coating liquid not containing water-containing amorphous silicon dioxide (matting agent)
  • a silicon nitride film (SiN) is formed as an inorganic layer on the surface of the underlayer using a general inorganic film forming apparatus for forming a film by CCP-CVD using RtoR as shown in FIG.
  • a gas barrier film 10 as shown was produced.
  • Silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm), hydrogen gas (flow rate 590 sccm), and nitrogen gas (flow rate 240 sccm) were used as source gases for forming the inorganic layer 16.
  • the high frequency power source 64b was a high frequency power source having a frequency of 13.56 MHz, and the plasma excitation power was 2 kW.
  • the film forming pressure was 40 Pa.
  • As the bias power source 64 d a high frequency power source of 0.4 MHz was used, a bias power of 0.2 kW was supplied to the support 12, and a bias potential was applied to the base layer 14.
  • the thickness of the inorganic layer 16 was 20 nm
  • the thickness of the mixed layer 18 was 10 nm
  • the thickness of the underlayer 14 was 0.99 ⁇ m (990 nm).
  • Example 2 In the formation of the underlayer 14, the gas barrier film 10 was produced in the same manner as in Example 1 except that the coating amount of the underlayer coating solution to be applied was changed and the thickness of the underlayer 14 to be formed was changed to 3 ⁇ m. When measured in the same manner as in Example 1, the thickness of the inorganic layer 16 was 20 nm, the thickness of the mixed layer 18 was 10 nm, and the thickness of the underlayer 14 was 2.99 ⁇ m (2990 nm). [Example 3] In the formation of the underlayer 14, the gas barrier film 10 was produced in the same manner as in Example 1 except that the coating amount of the underlayer coating solution to be applied was changed and the thickness of the underlayer 14 to be formed was changed to 0.2 ⁇ m. . When measured in the same manner as in Example 1, the thickness of the inorganic layer 16 was 20 nm, the thickness of the mixed layer 18 was 10 nm, and the thickness of the underlayer 14 was 0.19 ⁇ m (190 nm).
  • Example 4 Similar to the coating film forming apparatus shown in FIG. 5, after forming the base layer 14, a polyethylene (PE) protective film is laminated on the surface of the base layer 14, and similarly to the inorganic film forming apparatus shown in FIG. A gas barrier film 10 was produced in the same manner as in Example 1 except that the protective film was peeled off before the inorganic layer 16 was formed.
  • Example 5 Similar to the inorganic film forming apparatus shown in FIG. 6, after forming the inorganic layer 16, a gas barrier film 10 was produced in the same manner as in Example 1 except that a protective film made of polyethylene was laminated on the surface of the inorganic layer 16.
  • Example 6 After forming the underlayer 14, a protective film made of polyethylene is laminated on the surface of the underlayer 14 similarly to the film forming apparatus shown in FIG. 5, and the inorganic layer 16 is formed as in the inorganic film forming apparatus shown in FIG.
  • the gas barrier film 10 was produced in the same manner as in Example 1 except that the protective film was peeled off before forming the inorganic layer 16 and then a polyethylene protective film was laminated on the surface of the inorganic layer 16.
  • Example 7 ⁇ Preparation of coating solution for forming protective organic layer 26>
  • ACRYT 8BR-930 UV curable urethane acrylic polymer having a weight average molecular weight of 16000 manufactured by Taisei Fine Chemical Co., Ltd. was prepared.
  • As a (meth) acrylate polymer Dainal BR83 (polymethyl methacrylate (PMMA) having a weight average molecular weight of 40000) manufactured by Mitsubishi Rayon Co., Ltd. was prepared.
  • A-DPH dipentaerythritol hexaacrylate (DPHA)) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • a tri- or higher functional (meth) acrylate monomer was prepared as a tri- or higher functional (meth) acrylate monomer.
  • silane coupling agent having one or more (meth) acryloyl groups KBM5103 manufactured by Shin-Etsu Silicone Co., Ltd. was prepared.
  • ESACURE KTO46 manufactured by Lamberti was prepared as a photopolymerization initiator. These materials were weighed so that the mass ratio of graft copolymer: PMMA: acrylate monomer: silane coupling agent: photopolymerization initiator was 35: 22: 30: 10: 3, and these were dissolved in methyl ethyl ketone.
  • a coating solution for forming the protective organic layer 26 having a solid content concentration of 30% was prepared.
  • a gas barrier film was produced in the same manner as in Example 6. Thereafter, the protective organic layer 26 is formed on the surface of the inorganic layer 16 with a coating liquid for forming the prepared protective organic layer 26 using a general film forming apparatus that forms an ultraviolet curable organic layer by a coating method using RtoR. did. Thereby, a gas barrier film 24 having a protective organic layer 26 as shown in FIG. 3 was produced. Prior to the application of the coating liquid in the formation of the protective organic layer 26, the protective film laminated on the inorganic layer 16 was peeled off. A die coater was used to apply the coating solution for forming the protective organic layer 26.
  • the drying temperature of the coating solution was 130 ° C., and the drying time was 3 minutes. Thereafter, while heating from the back side of the support 12 to 80 ° C., the coating solution is irradiated with ultraviolet rays (integrated irradiation amount of about 600 mJ / cm 2 ) to cure the coating solution to form the protective organic layer 26, and gas barrier Film 24 was produced.
  • the thickness of the protective organic layer 26 was 5 ⁇ m.
  • Example 8 An easy adhesion layer was formed on both surfaces of the support 12 using the coating liquid A for an easy adhesion layer.
  • a gas barrier film 10 was produced in the same manner as in Example 1 except that this support 12 was used. That is, in the gas barrier film 10, the easy-adhesion layer on the upper surface (formation surface of the base layer 14) of the support 12 also contains water-containing amorphous silicon dioxide (mat agent).
  • Example 9 ⁇ Formation of adhesion layer>
  • the coating liquid for forming the adhesion layer shown below on the surface on which the easy-adhesion layer was formed with the coating liquid A for easy-adhesion layer was applied at a thickness of 10 cc / m 2 with a bar coater. This was applied and dried at 150 ° C. for 2 minutes to form an adhesion layer 32 having a thickness of 1.5 ⁇ m.
  • the adhesion layer 32 was formed by a general coating film forming apparatus for forming a film by a coating method using RtoR as shown in FIG.
  • a crosslinking agent 15.07% by mass of a water-soluble oxazoline-based crosslinking agent (Nippon Shokubai Co., Ltd., Epocros WS-700), As a binder, 59.27% by mass of a polyolefin resin (manufactured by Unitika, Arrow Base SE-1013N), and 24.79% by mass of a polyurethane resin (manufactured by Mitsui Chemicals, Takelac S-5100), Fluorosurfactant (manufactured by FUJIFILM Fine Chemical Co., Ltd., bis (3,3,4,4,5,5,6,6,6-nonafluorohexyl) sulfosuccinate sodium salt, solid content 2 mass%) 0.09 mass%, and nonionic surfactant (manufactured by Sanyo Chemical Industries, NAROACTY CL95, solid content 1 mass%) 0.18 mass%, and As a matting agent, 0.6%
  • the base layer 14 and the inorganic layer 16 are formed on the surface of the support 12 on which the adhesion layer 32 is formed, on which the adhesion layer 32 is not formed, as in Example 1, and the adhesion layer 32 as shown in FIG. A gas barrier film 30 having the same was produced.
  • Example 10 In the preparation of the undercoat layer coating solution, acetone was used as a solvent instead of water.
  • a gas barrier film 10 was prepared in the same manner as in Example 1 except that the base layer 14 was formed using a base layer coating solution containing acetone as a solvent.
  • the inorganic layer 16 had a thickness of 12 nm
  • the mixed layer 18 had a thickness of 18 nm
  • the underlayer 14 had a thickness of 0.982 ⁇ m (982 nm).
  • Example 11 In the formation of the inorganic layer 16, the gas barrier film 10 was produced in the same manner as in Example 1 except that the bias power supplied to the support 12 was changed from 0.2 kW to 0.02 kW. When measured in the same manner as in Example 1, the thickness of the inorganic layer 16 was 29.5 nm, the thickness of the mixed layer 18 was 0.5 nm, and the thickness of the underlayer 14 was 0.9995 ⁇ m (999.5 nm). .
  • TMPTA manufactured by Daicel Cytec Co., Ltd.
  • a photopolymerization initiator manufactured by Lamberti Co., ESACURE KTO46
  • MEK methyl ethyl ketone
  • a general coating film forming apparatus for forming an ultraviolet curable organic layer by a coating method using RtoR was used, and the base organic layer was formed in place of the base layer 14 with the prepared coating liquid for forming the base organic layer. Except for this, a gas barrier film was produced in the same manner as in Example 1.
  • a die coater was used to apply the coating solution for forming the base organic layer.
  • the drying temperature of the coating solution was 50 ° C., and the drying time was 3 minutes.
  • the base organic layer was formed by irradiating with ultraviolet rays (accumulated dose of about 600 mJ / cm 2 ) to cure the coating solution (TMPTA).
  • the thickness of the formed base organic layer was 1 ⁇ m.
  • the thickness of the inorganic layer 16 was 15 nm
  • the thickness of the mixed layer 18 was 15 nm
  • the thickness of the underlayer 14 was 0.985 ⁇ m (985 nm).
  • Example 2 In the formation of the inorganic layer 16, a gas barrier film was produced in the same manner as in Example 1 except that no bias power was supplied to the drum, that is, no bias potential was applied to the base layer 14. When measured in the same manner as in Example 1, the thickness of the inorganic layer 16 was 30 nm, the thickness of the underlayer 14 was 1 ⁇ m, and the mixed layer 18 was not formed.
  • a gas barrier film was produced in the same manner as in Example 1 except that an aluminum oxide film (alumina) was formed by reactive sputtering. Aluminum was used as the target. Oxygen and argon were used as process gases.
  • As the film forming apparatus a general sputtering apparatus that performs film formation by sputtering with RtoR was used. The vacuum evacuation means is driven to start evacuation of the film forming chamber, and when the pressure in the film forming chamber reaches 5 ⁇ 10 ⁇ 4 Pa, introduction of the process gas into the film forming chamber is started. Was set to 1 ⁇ 10 ⁇ 3 Pa.
  • the support 12 is started to be transported.
  • the pressure in each chamber is stabilized at 5 ⁇ 10 ⁇ 4 Pa
  • the supply of power to the film formation cathode is started.
  • An aluminum oxide film was formed on the surface of the base layer 14 by reactive sputtering.
  • the thickness of the inorganic layer was 30 nm
  • the thickness of the underlayer 14 was 1 ⁇ m
  • the mixed layer 18 was not formed.
  • the gas barrier film thus produced was evaluated for gas barrier properties, optical properties, and adhesion.
  • the protective film protecting the inorganic layer 16 was peeled off.
  • ⁇ Gas barrier properties> Water vapor transmission rate (WVTR) [g / (m 2 ⁇ day) of the gas barrier film under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH by a calcium corrosion method (a method described in JP-A-2005-283561). ] was measured.
  • the total light transmittance of the gas barrier film was measured based on JIS K 7361 using NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • ⁇ Adhesion> The adhesion between the underlayer 14 and the inorganic layer 16 was evaluated by a cross-cut peel test in accordance with JIS K5400. Using a cutter knife, 90 ° cuts were made at 1 mm intervals on the surface of each gas barrier film on which the inorganic layer 16 was formed, and 100 grids with 1 mm intervals were created. On top of this, the tape affixed with a 2 cm wide Mylar tape (Nitto Denko, polyester tape, No. 31B) was peeled off. Adhesiveness was evaluated by the number of cells in which the inorganic layer 16 remained (maximum 100). The results are shown in the table below.
  • the gas barrier film of the invention is excellent in gas barrier properties and transparency, and has high adhesion between the inorganic layer 16 and the underlayer 14. Further, as shown in Examples 4 to 7, higher gas barrier properties can be obtained by attaching a protective film after forming the base layer 14 and the inorganic layer 16. In addition, as shown in Example 10 and Examples 1 to 9, more excellent gas barrier properties can be obtained by using water as a solvent for the undercoat layer coating solution for forming the undercoat layer 14.
  • Example 11 and Examples 1 to 9 when the thickness of the mixed layer 18 is 1 nm or more, more excellent gas barrier properties and adhesion between the inorganic layer 16 and the underlayer 14 can be obtained. can get.
  • Comparative Example 1 in which an organic layer is formed as a base layer is slightly inferior in gas barrier properties and adhesion between the base layer and the inorganic layer as compared with the Examples.
  • Comparative Example 2 and Comparative Example 3 that do not have the mixed layer 18 have good gas barrier properties and transparency, but poor adhesion between the underlayer and the inorganic layer. From the above results, the effects of the present invention are clear.

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Abstract

L'invention concerne: un film barrière contre les gaz qui a d'excellentes propriétés de barrière contre les gaz; et un procédé de fabrication d'un tel film barrière contre les gaz. Ce film barrière contre les gaz comprend: un corps de support; et une ou plusieurs combinaisons d'une couche inorganique contenant du silicium et d'une couche de base pour la couche inorganique. La couche de base contient un produit polymérisé d'un alcoxysilane; et une couche mixte qui contient des composants à la fois de la couche inorganique et de la couche de base est disposée entre la couche inorganique et la couche de base. Un procédé de production d'un film barrière contre les gaz selon la présente invention comprend: une étape consistant à former une couche de base par application et chauffage d'un liquide de revêtement qui contient un alcoxysilane; et une étape consistant à former une couche inorganique sur la couche de base au moyen d'un CVD par plasma, tout en appliquant un potentiel de polarisation à la couche de base.
PCT/JP2018/014506 2017-05-12 2018-04-05 Film barrière contre les gaz et procédé de fabrication de film barrière contre les gaz WO2018207508A1 (fr)

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WO2016190053A1 (fr) * 2015-05-22 2016-12-01 コニカミノルタ株式会社 Film barrière contre les gaz et procédé de production de film barrière contre les gaz
WO2016190284A1 (fr) * 2015-05-22 2016-12-01 コニカミノルタ株式会社 Film barrière contre les gaz et son procédé de production
WO2017013980A1 (fr) * 2015-07-23 2017-01-26 コニカミノルタ株式会社 Film barrière contre les gaz

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JP2005324469A (ja) * 2004-05-14 2005-11-24 Keiwa Inc 高バリア性シート
JP2009220342A (ja) * 2008-03-14 2009-10-01 Oike Ind Co Ltd ガスバリアフィルムの製造方法及びガスバリアフィルム
JP2011162851A (ja) * 2010-02-10 2011-08-25 Fujifilm Corp ガスバリアフィルムの製造方法
JP2014091057A (ja) * 2012-10-31 2014-05-19 Sekisui Chem Co Ltd ガスバリア性フィルムの製造方法
WO2014109231A1 (fr) * 2013-01-11 2014-07-17 東レ株式会社 Film de barrière contre les gaz
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WO2016190284A1 (fr) * 2015-05-22 2016-12-01 コニカミノルタ株式会社 Film barrière contre les gaz et son procédé de production
WO2017013980A1 (fr) * 2015-07-23 2017-01-26 コニカミノルタ株式会社 Film barrière contre les gaz

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JPWO2020196607A1 (fr) * 2019-03-27 2020-10-01
WO2020196607A1 (fr) * 2019-03-27 2020-10-01 富士フイルム株式会社 Film fonctionnel et procédé de production de film fonctionnel
JP7132431B2 (ja) 2019-03-27 2022-09-06 富士フイルム株式会社 機能性フィルムおよび機能性フィルムの製造方法

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