WO2014050918A1 - Film fonctionnel - Google Patents

Film fonctionnel Download PDF

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Publication number
WO2014050918A1
WO2014050918A1 PCT/JP2013/075967 JP2013075967W WO2014050918A1 WO 2014050918 A1 WO2014050918 A1 WO 2014050918A1 JP 2013075967 W JP2013075967 W JP 2013075967W WO 2014050918 A1 WO2014050918 A1 WO 2014050918A1
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WO
WIPO (PCT)
Prior art keywords
layer
organic layer
film
substrate
gas barrier
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PCT/JP2013/075967
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English (en)
Japanese (ja)
Inventor
謙一 梅森
英二郎 岩瀬
藤縄　淳
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富士フイルム株式会社
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Publication of WO2014050918A1 publication Critical patent/WO2014050918A1/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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • B32B5/145—Variation across the thickness of the layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable

Definitions

  • the present invention relates to an organic / inorganic laminated functional film in which an organic layer and an inorganic layer are formed on a substrate.
  • optical devices such as gas barrier films, protective films, optical filters and antireflection films, etc. for optical devices
  • display devices such as organic EL displays (OLEDs) and liquid crystal displays
  • functional films functional sheets
  • a plastic film such as a polyethylene terephthalate (PET) film is used as a substrate, and an inorganic layer (a layer made of an inorganic compound) that exhibits a desired function is formed thereon. It has the composition which becomes.
  • PET polyethylene terephthalate
  • a gas barrier film in which a layer (film) made of silicon nitride or silicon oxynitride charcoal that exhibits gas barrier properties is formed on the surface of a plastic film.
  • a layer (film) made of silicon nitride or silicon oxynitride charcoal that exhibits gas barrier properties is formed on the surface of a plastic film.
  • an organic layer made of an organic compound is provided as a base layer (undercoat layer) on the surface of the substrate, and the organic layer is made of an inorganic compound that exhibits gas barrier properties.
  • An organic / inorganic laminated type gas barrier film having an inorganic layer is known.
  • higher gas barrier properties can be obtained by having a plurality of laminated structures of an organic layer and an inorganic layer.
  • Patent Document 1 has a structure in which an easy adhesion layer, an organic layer, and an inorganic layer are sequentially laminated on the surface of a plastic film, and the center line average roughness Ra of the inorganic layer side surface of the organic layer.
  • a gas barrier film comprising a resin obtained by curing, as a polymerization component, an acrylic monomer having an organic layer having an acryloyl group having two or more acryloyl groups and two or more urethane groups in the same molecule. ing.
  • Patent Document 2 includes a gas barrier layer having an organic layer and an inorganic oxide layer, and the organic layer in contact with the inorganic oxide layer includes a compound containing a silicon atom or a fluorine atom, Further, a gas barrier film is described in which the organic layer has a thickness of 10 nm to 1 ⁇ m and the inorganic oxide layer has a thickness of 5 to 500 nm.
  • Patent Document 1 and Patent Document 2 after forming an organic layer as an underlayer, by forming an inorganic layer that exhibits gas barrier properties, the surface of the organic layer is used for cracking. And a uniform inorganic layer free from defects such as peeling. Therefore, according to such a laminated gas barrier film, 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 gas barrier film when used for an application requiring optical characteristics such as an organic EL display and a liquid crystal display, it is necessary to satisfy both optical characteristics such as high light transmittance and high gas barrier performance.
  • the inorganic layer with a high refractive index that causes a decrease in light transmittance is thinned. It is necessary to cover the surface of the organic layer appropriately and form an inorganic layer.
  • An object of the present invention is to solve the above-mentioned problems of the prior art.
  • the inorganic layer is the surface of the organic layer.
  • a functional film satisfying high optical properties and high functionality that has a high optical property by thinning the inorganic layer and excellent adhesion between the organic layer and the substrate. It is to provide.
  • the functional film of the present invention includes a substrate, an organic layer on the substrate, an inorganic layer on the organic layer, and a particle dispersed between the substrate and the organic layer. And the content of particles derived from the easy adhesion layer in a region of 10% thickness on the inorganic layer side of the organic layer is 15% or less. Provide functional film.
  • the particle diameter of the particles contained in the easy adhesion layer is preferably 0.01 to 0.1 ⁇ m.
  • the inorganic layer is preferably made of silicon nitride.
  • the inorganic layer preferably has a thickness of 10 to 100 nm.
  • the organic layer preferably has a thickness of 0.5 to 5 ⁇ m.
  • the water vapor transmission rate is preferably 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)] or less.
  • an organic / inorganic laminated type comprising an organic layer as a base layer on a substrate and an inorganic layer exhibiting a desired function is formed thereon.
  • the inorganic layer can be thinned to obtain high optical characteristics, and the inorganic layer that properly covers the organic layer exhibits high performance, and also has excellent adhesion between the organic layer and the substrate.
  • a functional film having both optical properties and high functions can be obtained.
  • (A) And (B) is a figure which shows notionally an example of the gas barrier film using the functional film of this invention. It is a figure which shows notionally an example of the manufacturing apparatus which manufactures the gas barrier film shown in FIG. 1, (A) is an organic film-forming apparatus, (B) is an inorganic film-forming apparatus.
  • FIG. 1A conceptually shows an example of a gas barrier film using the functional film of the present invention.
  • a gas barrier film 10 using the functional film of the present invention shown in FIG. 1A (hereinafter also referred to as “gas barrier film 10” or “gas barrier film of the present invention”) has an organic layer 14 on a substrate 12. And an inorganic layer 16 on the organic layer 14. Further, the gas barrier film 10 has an easy adhesion layer 20 between the substrate 12 and the organic layer 14 for improving the adhesion between the substrate 12 and the organic layer 14. Furthermore, the gas barrier film 10 has the protective organic layer 18 for protecting the inorganic layer 16 on the inorganic layer 16 as a preferable aspect.
  • gas barrier film (functional film) of this invention is not limited to the structure shown by FIG. 1 (A), has the organic layer 14 on the board
  • the easy-adhesion layer 20 and the organic layer 14 are formed on the substrate 12 as in the gas barrier film 28 shown in FIG.
  • the organic layer 14 has the inorganic layer 16, the inorganic layer 16 has the intermediate organic layer 24, the intermediate organic layer 24 has the inorganic layer 16, and the inorganic layer 16 has The structure which has the protective organic layer 18 on top may be sufficient.
  • the organic layer acts as an underlayer for properly forming an inorganic layer that exhibits gas barrier properties. That is, in the present invention, as long as necessary optical characteristics such as light transmittance can be secured, a plurality of combinations of an organic layer serving as a base and an inorganic layer thereon may be provided.
  • the organic layer 14 formed on the substrate 12 has particles derived from the easy adhesion layer 20 (before the organic layer 14 is formed).
  • the particles 20a) contained in the easy-adhesion layer 20 are dispersed.
  • the content rate of the particles 20a in the region of 10% thickness on the inorganic layer 16 side (upper side) of the organic layer 14 is 15% or less.
  • the gas barrier film 10 of the present invention is a laminated type gas barrier film formed by laminating an organic layer 14 and an inorganic layer 16, and the inorganic layer 16 is thinned in order to improve optical characteristics such as light transmittance.
  • the functional film of the present invention is not limited to a gas barrier film. That is, the present invention can be used in various known functional films such as various optical films such as an optical filter and an antireflection film.
  • various optical films such as an optical filter and an antireflection film.
  • the present invention is suitably used for a gas barrier film in which performance deterioration due to defects or the like of the inorganic layer 16 is large and excellent optical characteristics such as light transmittance are often required.
  • the substrate 12 (base material or support) is not limited, and various known sheet-like materials that are used as substrates in the gas barrier film (functional film) can be used. is there.
  • a long and flexible sheet-like substrate 12 (having flexibility so that the organic layer 14 and the inorganic layer 16 can be formed by roll-to-roll described later.
  • a web-like substrate 12) is used.
  • Suitable examples include plastic films made of various plastics (polymer materials).
  • a plastic film is used as a support, and 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, etc. are provided on the surface.
  • a substrate (layer 12) on which layers (films) for obtaining various functions are formed may be used.
  • the gas barrier film 10 has an organic layer 14 on a substrate 12.
  • the gas barrier film 10 has an easy adhesion layer 20 between the organic layer 14 and the substrate 12. That is, the organic layer 14 is formed (formed) on the substrate 12 via the easy-adhesion layer 20.
  • the easy-adhesion layer 20 is provided to improve the easy-adhesion property when a hard coat layer or the like is formed on the surface of a general optical film.
  • a known easy-adhesion layer can be used. By having this easy-adhesion layer 20, adhesion between the substrate 12 and the organic layer 14 can be secured.
  • the easy-adhesion layer 20 is a known easy-adhesion layer provided on a general optical film, and is a polymer material (resin material / polymer) that acts as a binder.
  • Particles 20a contained in the easy-adhesion layer 20 have a particle size (diameter: minor axis) of 0.1 ⁇ m or less. It is preferable to do this.
  • the particle size of the particles 20a derived from the easy-adhesion layer 20 is set to 0.1 ⁇ m or less. It is possible to prevent problems such as a decrease in light transmittance of the gas barrier film 10 due to light scattering caused by the particles 20a. Thus, the gas barrier film 10 having excellent optical properties can be obtained.
  • the lower limit of the particle 20a is not particularly limited. However, too fine particles 20a are difficult to manufacture and handle, and the cost increases.
  • the particle diameter of the particles 20a is preferably 0.01 ⁇ m or more.
  • the particle diameter of the particle in the present invention means an average value of particle diameters of 50 particles arbitrarily selected.
  • the particle size of the particles can be measured by cross-sectional SEM observation. In detail, using NOVA200 (scanning electron microscope) manufactured by FEI, the gas barrier film is processed by FIB (focused ion beam) to create a section, and the particle size of the particles appearing in the cross section is measured and obtained. Can do.
  • the easy-adhesion layer in the gas barrier film of the present invention preferably contains 0.1% or more and 10% or less of particles, and more preferably contains 1% or more and 5% or less before the formation of the organic layer.
  • the gas barrier film 10 of the present invention various commercially available plastic films having the easy-adhesion layer 20 (applied with an easy-adhesion process) can be suitably used as the substrate 12.
  • an optical plastic film (highly light-transmitting plastic film) having the easy-adhesion layer 20 is suitable.
  • the easy adhesion layer 20 may be formed by a known method such as the method described in Patent Document 1 described above using a plastic film or the like that does not have an easy adhesion layer as the substrate 12.
  • An organic layer 14 is formed on the substrate 12 (easily adhesive layer 20).
  • FIG. 1A an interface is shown between the easy-adhesion layer 20 and the organic layer 14 in order to clarify the configuration of the gas barrier film 10.
  • the surface of the easy-adhesion layer 20 formed on the substrate 12 is dissolved by the paint that becomes the organic layer 14 when the organic layer 14 is formed.
  • the organic layer 14 and the easy-adhesion layer 20 are compatible, there is no clear interface between them.
  • the particles 20 a in the easy-adhesion layer 20 are mixed and dispersed in the organic layer 14.
  • the organic layer 14 is a layer made of an organic compound (a layer (film) containing an organic compound as a main component) and is basically a monomer and / or oligomer crosslinked (polymerized).
  • the organic layer 14 functions as a base layer for properly forming an inorganic layer 16 that exhibits gas barrier properties, which will be described later. In this way, it is possible to obtain a flattened surface by embedding irregularities on the surface of the substrate 12 or foreign matters adhering to the surface of the substrate 12.
  • the planarized organic layer surface there are irregularities on the surface of the substrate 12 and foreign substances on the surface of the substrate 12, so that an area in which the inorganic compound that becomes the inorganic layer 16 is difficult to deposit does not occur.
  • the inorganic layer 16 can be appropriately formed on the entire surface of the organic layer 14.
  • the thickness of the organic layer 14 is not limited, but is preferably 0.5 to 5 ⁇ m. By setting the thickness of the organic layer 14 to 0.5 ⁇ m or more, unevenness on the surface of the substrate 12 and foreign matters attached to the surface of the substrate 12 are suitably embedded, so that the surface of the planarized organic layer 14 is Can be obtained. In addition, by setting the thickness of the organic layer 14 to 5 ⁇ m or less, cracks in the organic layer 14, curling of the gas barrier film 10, and the like caused by the organic layer 14 being too thick increases the internal stress of the film. The occurrence of problems can be suitably suppressed. Considering the above points, the thickness of the organic layer 14 is more preferably 1 to 3 ⁇ m.
  • the material for forming the organic layer 14 is not limited, and various known organic compounds (resins / polymer compounds) can be used. Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc.
  • An organosilicon compound is preferably exemplified.
  • the organic layer 14 composed of a polymer of a cationically polymerizable compound having a functional group having a radically polymerizable compound and / or an ether group is preferable from the viewpoint of excellent Tg and strength.
  • acrylic resins and methacrylic resins mainly composed of acrylate and / or methacrylate monomers and oligomer polymers,
  • the organic layer 14 is preferably exemplified.
  • DPGDA dipropylene glycol di (meth) acrylate
  • TMPTA trimethylolpropane tri (meth) acrylate
  • DPHA dipentaerythritol hexa (meth) acrylate
  • Acrylic resins and methacrylic resins whose main component is a polymer of acrylate and / or methacrylate monomers or oligomers are preferably exemplified.
  • the description regarding the above organic layer 14 is applicable similarly to the intermediate
  • the gas barrier film of the present invention has a plurality of organic layers, such as when the protective organic layer 18 and the intermediate organic layer 24 are included, the thickness of each organic layer may be the same or different.
  • Such an organic layer 14 is usually formed by a coating method. That is, an organic compound (monomer / oligomer) is dissolved in an organic solvent such as MEK (methyl ethyl ketone), and if necessary, a coating material to be an organic layer 14 is prepared by adding a surfactant, a silane coupling agent, or the like. To do.
  • This paint is applied to the surface of the substrate 12 having the easy-adhesion layer 20 (the surface of the easy-adhesion layer 20), and dried with warm air, a heater, or the like. When the paint is dried, the organic layer 14 is formed by crosslinking the organic compound by irradiation with light such as ultraviolet rays or visible light, heating with a heater, or the like.
  • the coating material to be the organic layer 14 is applied to the substrate 12, the surface of the easy-adhesion layer 20 is dissolved and compatible with the paint, and the particles 20a dispersed in the easy-adhesion layer 20 are contained in the coating material. Mixed in.
  • convection occurs inside the paint due to heating when the paint is dried.
  • the particles 20 a flowing into the coating material are dispersed (so-called migration occurs), and as a result, the particles 20 a derived from the easy adhesion layer 20 are dispersed in the organic layer 14.
  • the region of 10% thickness on the inorganic layer 16 side of the organic layer 14 in the thickness direction of the layer (film) is a particle 20a derived from the easy adhesion layer 20.
  • the content of is 15% or less. That is, as shown in FIG. 1A, in the organic layer 14 having a thickness L, the region of the thickness L / 10 on the inorganic layer 16 side has a content ratio of the particles 20a in the organic layer 14 of 15% or less.
  • the inorganic layer 16 side is also referred to as the upper side and the opposite substrate 12 side is also referred to as the lower side.
  • the present invention makes it possible to achieve both optical properties such as light transmittance and gas barrier properties (target performance) in a laminated gas barrier film in which an organic layer 14 and an inorganic layer 16 are laminated.
  • the inorganic layer 16 can be appropriately formed and high gas barrier properties can be obtained.
  • a gas barrier film used for an organic EL display or the like needs not only high gas barrier performance but also excellent optical characteristics such as high light transmittance.
  • the inorganic layer 16 is made thin in order to ensure light transmittance and the like, the inorganic layer 16 cannot be properly formed, and the target gas barrier property cannot be obtained in many cases.
  • the present inventor has conducted extensive studies on this cause. As a result, defects in the inorganic layer 16 occur due to the presence of the particles 20a included in the easy adhesion layer 20 and dispersed in the organic layer 14 on the surface (upper surface) of the organic layer 14 or in the vicinity of the surface. I found out.
  • the inorganic layer 16 made of silicon nitride film made of silicon nitride
  • plasma CVD is often used.
  • the particles 20a derived from the easy-adhesion layer 20 are present on the surface of the organic layer 14 or in the vicinity of the surface, the particles 20a are released by etching of the organic layer 14 by plasma inevitably generated in film formation by plasma CVD. Is done. As a result, the portion of the organic layer 14 from which the particles 20a are released is in a state where a hole is opened.
  • the holes by the particles 20a are not a big problem.
  • the inorganic layer 16 is made thin in order to improve the optical characteristics of the gas barrier film 10 such as when the inorganic layer 16 is 100 ⁇ m or less, an inorganic compound such as silicon nitride can be sufficiently deposited on the hole. Therefore, it becomes a defective portion of the inorganic layer 16. When such a defective portion is present, moisture or the like passes from here, and the gas barrier property is lowered.
  • the region of 10% on the upper side (inorganic layer 16 side) of the organic layer 14 has a content ratio of particles 20a derived from the easy adhesion layer 20 to 15%. % Or less. That is, in the organic layer 14 having a thickness L, the upper region of the thickness L / 10 sets the content ratio of the particles 20a in the organic layer 14 to 15% or less.
  • the present invention greatly reduces defects in the inorganic layer 16 caused by the particles 20a derived from the easy-adhesion layer 20, even when the inorganic layer 16 is a thin film of 100 nm or less. Thus, a high gas barrier property can be obtained.
  • the present invention excellent optical characteristics such as a high light transmittance due to the thin inorganic layer 16 and a high water vapor transmittance of 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)] or less.
  • a high-performance gas barrier film 10 having both gas barrier performance can be obtained.
  • the adhesion between the substrate 12 and the organic layer 14 can be sufficiently ensured by having the easy adhesion layer 20.
  • the content of the particles 20a in the region of 10% thickness on the upper side of the organic layer 14 exceeds 15%, defects in the inorganic layer 16 due to the particles 20a can be sufficiently suppressed. Therefore, the target gas barrier performance cannot be obtained stably.
  • the content of the particles 20a in the region of 10% thickness on the upper side of the organic layer 14 is preferably 10% or less, particularly preferably 5% or less. Thereby, generation of defects in the inorganic layer 16 due to the particles 20a is sufficiently suppressed, and a high gas barrier performance such that the water vapor transmission rate is 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)] or less is obtained. It becomes possible to obtain the gas barrier film which has it more stably.
  • the easy-adhesion layer 20 and the organic layer 14 are compatible with each other, and thus there is no clear interface. Therefore, in the present invention, in the calculation of the content rate, the surface of the substrate 12 is set as the lower end (end surface on the substrate 12 side) of the organic layer 14 in the cross section. Further, as described above, when the inorganic layer 16 is formed by plasma CVD, the organic layer 14 is etched. By this etching, a layer like a mixed layer in which a component derived from the organic layer 14 and a component derived from the inorganic layer 16 are mixed may be formed between the organic layer 14 and the inorganic layer 16. is there.
  • the mixed layer is regarded as the organic layer 14, and in the thickness direction, the position where the component derived from the organic layer 14 disappears in the entire area in the plane direction (that is, all in the entire area in the plane direction becomes the inorganic layer 16).
  • the position where the component is derived is defined as the upper end (end surface on the inorganic layer 16 side) of the organic layer 14 in the cross section.
  • the content rate of the particles 20a in the region of 10% thickness on the upper side of the organic layer 14 is, as will be described later, in the film formation of the organic layer 14, the drying control of the paint (particularly during constant rate drying), the organic layer 14 It can be controlled by, for example, irradiating the coating material with light before drying.
  • the gas barrier film 10 has an inorganic layer 16 on the organic layer 14.
  • the inorganic layer 16 is a layer made of an inorganic compound, and the gas barrier film 10 mainly exhibits gas barrier properties.
  • metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Films made of inorganic compounds such as these hydrogen-containing materials are preferably exemplified.
  • silicon nitride, silicon oxide, silicon oxynitride, and aluminum oxide are suitably used for the gas barrier film because they are highly transparent and can exhibit excellent gas barrier properties.
  • silicon nitride is particularly suitable for its excellent gas barrier properties and high transparency.
  • the thickness of the inorganic layer 16 is preferably 10 to 100 nm. If the thickness of the inorganic layer 16 is 10 nm or less, it may be difficult to stably obtain the target gas barrier property. In addition, the inorganic layer 16 has a high refractive index and causes a decrease in light transmittance. By setting the thickness of the inorganic layer 16 to 100 nm or less, a gas barrier film having high light transmittance and excellent optical characteristics is obtained. It can be obtained stably. Furthermore, since the inorganic layer 16 is hard and brittle, as it becomes thicker, cracks, cracks, peeling, and the like are more likely to occur. However, if the thickness is 100 nm or less, these disadvantages can be more suitably prevented. In consideration of such points, the thickness of the inorganic layer 16 is more preferably 15 to 100 nm, and particularly preferably 20 to 75 nm.
  • the formation material of each inorganic layer may be the same or different.
  • the thickness of the plurality of inorganic layers 16 may be the same or different. However, in view of productivity, production facilities, and the like, when the plurality of inorganic layers 16 are provided, it is preferable that all the inorganic layers be the same inorganic compound.
  • the method for forming the inorganic layer 16 is not limited, and a known film forming method such as plasma CVD, sputtering, or vacuum deposition may be used depending on the inorganic compound that forms the inorganic layer 16.
  • a silicon nitride film is formed as the inorganic layer 16
  • the inorganic layer 16 may be formed using plasma CVD.
  • plasma CVD is preferably exemplified from the viewpoint that when the inorganic layer 16 is thinned, the effect of suppressing a decrease in gas barrier properties is greatly obtained.
  • the gas barrier film 10 of the example of illustration has the protective organic layer 18 for protecting the inorganic layer 16 in the uppermost layer (on the inorganic layer 16) as a preferable aspect.
  • the gas barrier film 10 shown to FIG. 1 (A) has the protective organic layer 18 which protects the inorganic layer 16 in a top layer as a preferable aspect. By having such a protective organic layer 18, damage to the inorganic layer 16 can be prevented, and a desired gas barrier property can be stably exhibited.
  • the protective organic layer 18 (and the gas barrier film 28 shown in FIG. 1B also includes the intermediate organic layer 24) basically has no particle 20a derived from the easy-adhesion layer 20.
  • the organic layer 14 may be the same as described above.
  • FIG. 2 shows an example of a manufacturing apparatus for manufacturing the gas barrier film 10 (gas barrier film 28) by forming the organic layer 14 by the coating method as described above and forming the inorganic layer 16 by plasma CVD.
  • the manufacturing apparatus includes an organic film forming apparatus 30 that forms the organic layer 14 and an inorganic film forming apparatus 32 that forms the inorganic layer 16.
  • 2A shows the organic film forming apparatus 30, and
  • FIG. 2B shows the inorganic film forming apparatus 32. 2 illustrates the production of the gas barrier film 10 shown in FIG. 1A, which has the organic layer 14 on the substrate 12 and the inorganic layer 16 thereon.
  • the organic film forming apparatus 30 and the inorganic film forming apparatus 32 illustrated in FIG. 2 are apparatuses that perform film formation by so-called roll-to-roll (hereinafter also referred to as “RtoR”).
  • RtoR is a substrate on which a film is formed by feeding a substrate from a roll formed by winding a long substrate (web-shaped substrate) 12 and transporting the substrate in the longitudinal direction. Is a manufacturing method in which the material is wound into a roll again. By using such RtoR, it becomes possible to manufacture the gas barrier film 10 with high production efficiency.
  • the gas barrier film of this invention can be manufactured also with the manufacturing method of what is called a batch type (sheet format) using the cut sheet-like board
  • FIG. even when a cut sheet-like substrate is used, the method of forming each layer is basically the same as the manufacturing method using RtoR described below.
  • the organic film forming apparatus 30 shown in FIG. 2A applies a coating material that becomes the organic layer 14 while transporting the long substrate 12 having the easy adhesion layer 20 in the longitudinal direction, and after drying, by light irradiation.
  • This is an apparatus for forming an organic layer 14 by crosslinking and curing an organic compound contained in the coating film.
  • the substrate having the easy-adhesion layer 20 on the surface is also simply referred to as the substrate 12 when it is not particularly necessary to touch the easy-adhesion layer 20.
  • the organic film forming apparatus 30 includes a coating unit 36, a drying unit 38, a light irradiation unit 40, a rotating shaft 42, a winding shaft 46, and conveyance roller pairs 48 and 50.
  • the organic film forming apparatus 30 is provided in a known apparatus that performs film formation by coating while conveying a long film forming material such as a guide member such as the substrate 12 and various sensors. Various members may be included.
  • the substrate roll R formed by winding the long substrate 12 is loaded on the rotating shaft 42.
  • the substrate 12 is pulled out from the substrate roll R, passes through the conveying roller pair 48, passes through the lower part of the coating unit 36, the drying unit 38, and the light irradiation unit 40, It passes through a predetermined conveying path that reaches the winding shaft 46 through the conveying roller pair 50.
  • the feeding of the substrate 12 from the substrate roll R and the winding of the substrate 12 on which the organic layer 14 is formed on the winding shaft 46 are performed in synchronization.
  • the coating material that forms the organic layer 14 is applied by the coating unit 36, the coating material is dried by the drying unit 38, and cured by the light irradiation unit 40. By doing so, the organic layer 14 is formed.
  • the coating means 36 is for applying a coating material prepared in advance to form the organic layer 14 on the surface of the substrate 12 (easily adhesive layer 20).
  • the coating material to be the organic layer 14 is crosslinked and polymerized to convert an organic compound (monomer / oligomer), for example, an acrylate and / or methacrylate monomer or oligomer into an organic solvent such as MEK or cyclohexanone. Dissolved (dispersed).
  • various additives necessary for forming the organic layer 14 such as a surfactant (surface modifier), a silane coupling agent, and a polymerization initiator (crosslinking agent) are appropriately added to this coating material. Is done.
  • the application of the paint is all known coating methods such as die coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, etc. Is available.
  • the substrate 12 is then transferred to the drying means 38 and dries the paint applied by the applying means 36.
  • the method of drying the paint by the drying means 38 there is no limitation on the method of drying the paint by the drying means 38 as long as the paint can be dried (the organic solvent is removed) before the substrate 12 reaches the light irradiation means 40 so that crosslinking can be performed.
  • Any known drying means can be used. As an example, heat drying with a heater, heat drying with warm air, and the like are exemplified.
  • the paint When the paint is applied to the substrate 12 (the easy-adhesion layer 20), the surface of the easy-adhesion layer 20 is dissolved, and the particles 20a contained in the easy-adhesion layer 20 are mixed in the paint that becomes the organic layer 14. To do. Further, when the paint is dried, the particles 20 a are dispersed (migrated) by convection generated in the paint, and as a result, the particles 20 a derived from the easy adhesion layer 20 are dispersed in the organic layer 14.
  • the distribution of the particles 20a in the organic layer 14 is controlled by controlling the processing from application of the paint forming the organic layer 14 to drying of the paint (coating film), and in the thickness direction of the layer.
  • the content ratio of the particles 20a derived from the easy-adhesion layer 20 in the 10% thick region on the upper side of the organic layer 14 can be 15% or less.
  • the drying temperature of the coating material for forming the organic layer 14 it is possible to suppress the particles 20a riding on the convection and reaching the surface or the vicinity of the surface (hereinafter, also referred to as “expression”).
  • a method of controlling the content of the particles 20a in the region of 10% thickness on the upper side of the organic layer 14 to 15% or less is exemplified.
  • a method of drying the coating material for forming the organic layer 14 in a drying atmosphere in a low temperature / low humidity state with the viscosity of the coating material being low can be suitably used.
  • the drying temperature or further the drying humidity of the paint that becomes the organic layer 14 is used as a method for controlling the content ratio of the particles 20a in the region of 10% thickness on the upper side of the organic layer 14 to 15% or less.
  • the method of suppressing the convection in the coating film to suppress the expression of the particles 20a and the method of adjusting the viscosity of the coating film to suppress the expression of the particles 20a are used. Is possible.
  • a light irradiation unit similar to the light irradiation unit 40 described later is provided between the coating unit 36 and the drying unit 38, and ultraviolet rays (UV light), visible light, etc. are applied to the applied coating prior to drying the coating. It is also possible to use a method in which the organic compound contained in the paint is slightly cross-linked by irradiation. Thereby, the viscosity of the paint is improved, the appearance of the particles 20a is suppressed, and the content of the particles 20a in the region of 10% thickness on the upper side of the organic layer 14 is controlled to be 15% or less. it can.
  • the method of suppressing the exposure of the particles 20a by adding a high-viscosity material to the paint, and the amount of particles contained in the easy-adhesion layer to the extent that the adhesion between the organic layer 14 and the substrate 12 is not deteriorated can also be used.
  • the substrate 12 from which the paint has been dried is conveyed to the light irradiation means 40.
  • the light irradiation means 40 irradiates the coating material applied by the coating means 36 and dried by the drying means 38 with ultraviolet rays or visible light to crosslink (polymerize) organic compounds (monomers or oligomers of organic compounds) contained in the coating material.
  • the coating film is cured to form the organic layer 14.
  • the light irradiation area by the light irradiation means 40 on the substrate 12 may be an inert atmosphere (oxygen-free atmosphere) by nitrogen substitution or the like, if necessary.
  • the crosslinking of the organic compound contained in the coating film to be the organic layer 14 is not limited to photopolymerization. That is, various methods according to the organic compound, such as heat polymerization, electron beam polymerization, and plasma polymerization, can be used for crosslinking of the organic compound.
  • various methods according to the organic compound such as heat polymerization, electron beam polymerization, and plasma polymerization, can be used for crosslinking of the organic compound.
  • an acrylic resin such as an acrylic resin or a methacrylic resin is preferably used as the organic layer 14
  • photopolymerization is preferably used.
  • substrate 12o The substrate 12 on which the organic layer 14 is formed in this manner (hereinafter, the substrate 12 on which the organic layer 14 is formed is referred to as “substrate 12o”) is nipped and conveyed by the conveying roller pair 50 and is taken up. 46, and is taken up again by the take-up shaft 46 into a roll shape to obtain a roll 12 o R formed by winding the substrate 12 o.
  • This roll 12oR is supplied to the inorganic film forming apparatus 32 shown in FIG.
  • the inorganic film forming apparatus 32 shown in FIG. 2B forms the inorganic layer 16 by plasma CVD.
  • the vacuum chamber 60 and the unwind chamber 62 and the film forming in the vacuum chamber 60 are formed.
  • a chamber 64 and a drum 68 are included.
  • a part of the shower electrode 80 disposed in the film formation chamber 64 is shown in cross section.
  • the inorganic film forming apparatus 32 is known to perform film formation by a vapor deposition method while conveying a long film-forming material such as a pair of conveying rollers, a guide member, and various sensors. You may have the various members provided in an apparatus.
  • a roll 12 oR formed by winding the substrate 12 o is loaded into the unwind chamber 62.
  • the substrate 12o is pulled out from the roll 12oR in the unwinding chamber 62, and is transported in the longitudinal direction while being wound around the drum 68, while the inorganic layer 16 is formed in the film forming chamber 64, and then unwound again. It is conveyed to the chamber 62 and wound around the winding shaft 74 (wound in a roll shape).
  • the drum 68 is a cylindrical member that rotates counterclockwise in the drawing around the center line.
  • the drum 68 wraps a substrate 12o guided by a guide roller 76a of the unwind chamber 62, which will be described later, on a predetermined area of the peripheral surface and conveys it in the longitudinal direction while holding it at a predetermined position. It is conveyed into the film chamber 64 and sent again to the guide roller 76b in the unwind chamber 62.
  • the drum 68 also functions as a counter electrode of a shower electrode 80 (film formation electrode) of the film formation chamber 64 described later. That is, in the illustrated inorganic film forming apparatus 32, the drum 68 and the shower electrode 80 constitute an electrode pair. Therefore, in the illustrated example, the drum 68 is grounded.
  • a bias power source for applying a bias to the drum 68 may be connected to the drum 68 as necessary. Alternatively, the connection between the ground and the bias power source may be switchable.
  • the drum 68 may also serve as temperature adjusting means for the substrate 12o during film formation (that is, the film formation temperature). Therefore, it is preferable that the drum 68 includes a known temperature adjusting means.
  • the vacuum chamber 60 includes the unwinding chamber 62 and the film forming chamber 64.
  • the unwinding chamber 62 and the film forming chamber 64 are arranged in the vertical direction (vertical direction) with the unwinding chamber 62 facing upward.
  • the unwinding chamber 62 and the film forming chamber 64 are (almost) hermetically separated by the drum 68 and the partition walls 70a and 70b extending from the inner wall surface 60a on the side surface side of the vacuum chamber 60 to the vicinity of the peripheral surface of the drum 68. Is done.
  • the tips of the partition walls 70a and 70b may not come into contact with the substrate 12o to be transported. It is preferable to be close to the peripheral surface of the drum 68 to the position.
  • the unwinding chamber 62 includes a rotating shaft 72, a winding shaft 74, guide rollers 76a and 76b, and a vacuum exhaust means 78.
  • the rotating shaft 72 is a known object that rotates while supporting the roll 12oR.
  • the take-up shaft 74 is a well-known long take-up shaft for taking up the film-formed substrate 12o.
  • the guide rollers 76a and 76b are ordinary guide rollers that guide the substrate 12o along a predetermined transport path.
  • the roll 12oR is attached to the rotation shaft 72.
  • the substrate 12o is passed through a predetermined path that reaches the winding shaft 74 through the guide roller 76a, the drum 68, and the guide roller 76b.
  • the feeding of the substrate 12o from the roll 12oR and the winding of the film-formed substrate 12o on the winding shaft 74 are performed in synchronization, and the long substrate 12o is moved along a predetermined transport path.
  • the film is formed in the film formation chamber 64 while being conveyed in the longitudinal direction.
  • the vacuum exhaust means 78 is for depressurizing the inside of the unwinding chamber 62 to a predetermined degree of vacuum.
  • the evacuation unit 78 is also provided in the unwinding chamber 62, and the inside of the unwinding chamber 62 is maintained at a predetermined degree of vacuum, whereby the pressure in the unwinding chamber 62 is reduced in the film forming chamber 64. The film 16 is prevented from being affected.
  • the vacuum exhaust means 78 is not particularly limited, and vacuum pumps such as turbo pumps, mechanical booster pumps, rotary pumps, and dry pumps, further auxiliary means such as cryocoils, the degree of ultimate vacuum and the amount of exhaust.
  • vacuum pumps such as turbo pumps, mechanical booster pumps, rotary pumps, and dry pumps
  • auxiliary means such as cryocoils, the degree of ultimate vacuum and the amount of exhaust.
  • Various known (vacuum) evacuation means used in a vacuum film forming apparatus using an adjusting means or the like can be used. In this regard, the same applies to the vacuum exhaust means 92 described later.
  • the film forming chamber 64 is provided under the unwinding chamber 62 (under the partition walls 70 a and 70 b).
  • the film forming chamber 64 includes a shower electrode 80, a source gas supply unit 86, a high frequency power supply 90, and a vacuum exhaust unit 92.
  • the inorganic layer 16 is formed on the surface of the substrate 12o, that is, on the organic layer 14, by CCP-CVD (Capacitively Coupled Plasma Capacitive Coupled Plasma CVD).
  • the shower electrode 80 is a film-forming electrode and constitutes an electrode pair in CCP-CVD together with the drum 68 (counter electrode) described above.
  • the shower electrode 80 has, for example, a substantially rectangular parallelepiped shape made of aluminum and having a maximum surface facing the peripheral surface of the drum 68.
  • the shower electrode 80 is a curved surface shape so that the opposing surface with the drum 68 may become a parallel surface spaced apart from the surrounding surface of the drum 68 as a preferable aspect.
  • a hollow portion 80 a is formed inside the shower electrode 80.
  • a large number of gas supply holes 80b are formed to communicate from the hollow portion 80a to the surface facing the drum 68 (substrate 12o) to supply the source gas.
  • the gas supply hole 80 b is formed entirely on the surface facing the drum 68.
  • the shower electrode 80 a known shower electrode (shower plate) used in an apparatus for performing film formation by plasma CVD or the like can be used. Further, the surface of the shower electrode 80 facing the drum 68 may be roughened by depositing a sprayed film, blasting or the like in order to prevent the deposited film from being peeled off.
  • the source gas supply unit 86 is a known gas supply unit used in a plasma CVD apparatus for supplying source gas (process gas / film formation gas).
  • the source gas may be appropriately selected from known gases capable of forming a target film by plasma CVD according to the inorganic layer 16 to be formed.
  • the inorganic layer 16 may be formed using silane gas, ammonia gas, and hydrogen gas (and / or nitrogen gas) as a source gas.
  • the source gas supply unit 86 supplies source gas to the hollow portion 80 a of the shower electrode 80.
  • the source gas flows into the gas supply hole 80b from the hollow portion 80a, and is supplied from the gas supply hole 80b between the shower electrode 80 and the drum 68 (substrate 12o), that is, between the electrode pair in CCP-CVD. .
  • the high-frequency power supply 90 is also a known high-frequency power supply used in a plasma CVD apparatus.
  • the high frequency power supply 90 supplies plasma excitation power (film formation power) to the shower electrode 80 that is a film formation electrode.
  • the source gas is supplied from the source gas supply unit 86 to the hollow portion 80a of the shower electrode 80, and the source gas is discharged from the gas supply hole 80b communicating with the hollow portion 80a.
  • a source gas is supplied between the drum 68 (substrate 12o) and plasma excitation power is supplied from the high-frequency power source 90 to the shower electrode 80, whereby an inorganic surface is formed on the surface of the substrate 12o (organic layer 14) by CCP-CVD.
  • Layer 16 is deposited.
  • the film formation conditions are appropriately set according to the thickness of the inorganic layer 16, the type of the inorganic layer 16 to be formed, the target film formation speed, the film thickness of the inorganic layer 16, the source gas used, and the like. That's fine.
  • the substrate 12o on which the inorganic layer 16 has been formed in the film formation chamber 64 is again conveyed to the unwind chamber 62, guided by the guide roller 76b, conveyed to the take-up shaft 74, and wound into a roll.
  • the operation of the inorganic film forming apparatus 32 will be described.
  • the roll 12oR formed by winding the substrate 12o formed with the organic layer 14 on the substrate 12 is loaded on the rotating shaft 72, the substrate 12o is pulled out from the roll 12oR, and the guide roller A predetermined conveyance path that reaches the take-up shaft 74 through 76a, the drum 68, and the guide roller 76b is inserted.
  • the vacuum chamber 60 is closed, and the evacuation means 78 and 92 are driven to start evacuation of each chamber.
  • the source gas supply unit 86 is then driven to supply the source gas to the film forming chamber 64.
  • the drum 68 and the like are started to rotate, the conveyance of the substrate 12o is started, and the high frequency power supply 90 is driven to convey the substrate 12o in the longitudinal direction.
  • Film formation of the inorganic layer 16 on the substrate 12o in the film formation chamber 64 is started, and the inorganic layer 16 is continuously formed on the long substrate 12o.
  • the organic layer 14 is controlled so that the content of the particles 20a derived from the easy-adhesion layer 20 in the region of 10% thickness on the upper side of the organic layer 14 is 15% or less.
  • the inorganic layer 16 exhibiting high gas barrier properties with few defects can be formed.
  • the protective organic layer 18 (intermediate organic layer 24) is formed on the inorganic layer 16 like the gas barrier film 10, a roll formed by winding the substrate 12o on which the inorganic layer 16 is formed is again Then, the protective organic layer 18 may be formed on the inorganic layer 16 by loading it on the rotating shaft 42 of the organic film forming apparatus 30 in the same manner as described above.
  • the protective organic layer 18 it is not necessary to control the distribution of the particles 20 a in the organic layer 14 (suppressing the rise of the particles 20 a) as described above.
  • Example 1 As a functional film, a gas barrier film 10 having an organic layer 14 and an inorganic layer 16 on the surface of a substrate 12 as shown in FIG.
  • a long PET film having a width of 1000 mm and a thickness of 100 ⁇ m (Cosmo Shine A8300 manufactured by Toyobo Co., Ltd.) was used.
  • An easy adhesion layer 20 in which particles 20a having a particle diameter of about 50 nm are dispersed is formed on this PET film.
  • An organic compound was charged into an organic solvent and stirred to prepare a coating material for the organic layer 14.
  • DPHA manufactured by Daicel-Cytec
  • MEK was used as the organic solvent.
  • a photopolymerization initiator (Irgacure manufactured by Ciba Geigy) was added to the paint. The paint was prepared so that the organic compound was 20 parts by mass, the organic solvent was 79 parts by mass, and the photopolymerization initiator was 1 part by mass.
  • the substrate roll R formed by winding the substrate 12 is loaded on the rotating shaft 42 of the organic film forming apparatus 30 shown in FIG. 2A, and the prepared paint is applied / dried on the surface of the substrate 12 by the applying means 36.
  • crosslinking / curing with the light irradiation means 40 was obtained.
  • the coating means 36 used a die coater.
  • the coating amount of the paint was set so that the dry film thickness was 3 ⁇ m. That is, the film thickness of the organic layer 14 is approximately 3 ⁇ m. Drying by the drying means 38 was performed at 30 ° C. using warm air.
  • the light irradiation means 40 was irradiated with ultraviolet rays of 1000 mJ / cm 2 using an ultraviolet irradiation device.
  • the roll 12oR is loaded in the inorganic film forming apparatus 32 shown in FIG. 2B, and the surface of the substrate 12o on which the organic layer 14 is formed is formed on the surface of the substrate 12o by CCP-CVD to form a 40 nm-thick silicon nitride film as the inorganic layer 16
  • a roll 10aR formed by forming a film and winding the gas barrier film 10 having the inorganic layer 16 formed on the organic layer 14 was produced.
  • the drum 68 is made of stainless steel and has a diameter of 1000 mm.
  • the high frequency power supply 90 was a 13.5 MHz high frequency power supply, and the plasma excitation power supplied to the shower electrode 80 was 3 kW.
  • silane gas (SiH 4 ), ammonia gas (NH 3 ), and hydrogen gas (H 2 ) were used as a film forming gas.
  • Supply amounts are 8.45 ⁇ 10 ⁇ 2 Pa ⁇ m 3 / s for silane gas, 1.69 ⁇ 10 ⁇ 2 Pa ⁇ m 3 / s for ammonia gas, and 2.54 ⁇ 10 ⁇ 2 Pa ⁇ m for hydrogen gas. 3 / s.
  • the film forming pressure was 100 Pa.
  • a gas barrier film similar to the gas barrier film 10 shown in FIG. 1 (A) except for not having the protective organic layer 18 was produced to 200 m.
  • the produced gas barrier film is cut in the width direction, the cross section is observed with a scanning electron microscope (manufactured by FEI, NOVA200), morphological analysis is performed, and a region of 10% thickness on the upper side of the organic layer 14 in this cross section
  • the area ratio of the particles 20a derived from the easy adhesion layer 20 therein was calculated.
  • the area ratio was calculated at 10 arbitrary cross sections, the average was calculated, and the content ratio of particles in the 10% thick region on the upper side of the organic layer 14 was calculated. As a result, the content ratio of the particles in the 10% thick region on the upper side of the organic layer 14 was 0.2%.
  • Example 2 A gas barrier film was produced in the same manner as in Example 1 except that the drying temperature of the paint in forming the organic layer 14 was 40 ° C. In the same manner as in Example 1, the particle content in the 10% thick region on the upper side of the organic layer 14 was calculated and found to be 5%.
  • Example 3 A gas barrier film was produced in the same manner as in Example 1 except that the drying temperature of the paint in forming the organic layer 14 was 60 ° C. In the same manner as in Example 1, the content ratio of the particles in the 10% thick region on the upper side of the organic layer 14 was calculated to be 12%.
  • Example 1 A gas barrier film was produced in the same manner as in Example 1 except that the drying temperature of the paint in forming the organic layer 14 was 80 ° C. In the same manner as in Example 1, the content of the particles in the 10% thick region on the upper side of the organic layer 14 was calculated and found to be 20%.
  • Example 1 is less than 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)]
  • Example 2 is less than 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)]
  • Example 3 is less than 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)]
  • Comparative Example 1 is 1 ⁇ 10 ⁇ 3 [g / (m 2 ⁇ day)]
  • Comparative Example 2 is less than 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)], Met.
  • Each of the gas barrier films of the present invention having a water content of 15% or less has a high gas barrier property such that the water vapor transmission rate is less than 1 ⁇ 10 ⁇ 4 [g / (m 2 ⁇ day)]. It also has excellent adhesion to the layer 14.
  • Comparative Example 1 in which the content of particles derived from the easy-adhesion layer 20 in the region of 10% thickness on the upper side of the organic layer 14 is 20%, the adhesion between the substrate 12 and the organic layer 14 is Is good, but it is considered that many defects of the inorganic layer 16 are generated due to the particles present on the surface (near the surface) of the organic layer 14, and the gas barrier property is lower than that of the present invention.
  • Comparative Example 2 that does not have the easy-adhesion layer 20 is excellent in gas barrier properties but has low adhesion between the substrate 12 and the organic layer 14. From the above results, the effects of the present invention are clear.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film fonctionnel comprenant, sur un substrat, une couche organique, une couche inorganique, et une couche hautement adhésive qui contient des particules et qui est disposée entre la couche organique et le substrat. Une région côté couche inorganique de la couche organique, ladite région occupant 10 % de l'épaisseur de la couche organique par rapport à la surface côté couche inorganique, contient des particules provenant de la couche hautement adhésive en une quantité de 15 % ou moins.
PCT/JP2013/075967 2012-09-27 2013-09-26 Film fonctionnel WO2014050918A1 (fr)

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JP2012213770A JP2015231667A (ja) 2012-09-27 2012-09-27 機能性フィルム

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015186507A1 (fr) * 2014-06-04 2015-12-10 日東電工株式会社 Film conducteur transparent
WO2016152488A1 (fr) * 2015-03-20 2016-09-29 コニカミノルタ株式会社 Film barrière contre les gaz
WO2019044473A1 (fr) * 2017-08-31 2019-03-07 富士フイルム株式会社 Stratifié formant barrière aux gaz et cellule photovoltaïque

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI708680B (zh) * 2019-01-08 2020-11-01 穎華科技股份有限公司 高分子塑膠前面板及其製法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002347161A (ja) * 2000-05-31 2002-12-04 Nitto Denko Corp 粒子分散系樹脂シートおよび液晶表示装置
JP2004034399A (ja) * 2002-07-01 2004-02-05 Nitto Denko Corp ハードコートフィルム、その製造方法、光学素子および画像表示装置
JP2004322489A (ja) * 2003-04-25 2004-11-18 Pioneer Electronic Corp ガスバリア基材およびその製造方法
JP2006018233A (ja) * 2004-05-31 2006-01-19 Fuji Photo Film Co Ltd 光学フイルム、偏光板、及びそれを用いた画像表示装置
JP2007152932A (ja) * 2005-07-04 2007-06-21 Teijin Dupont Films Japan Ltd ガスバリア加工用ポリエステルフィルム及びそれからなるガスバリア性積層ポリエステルフィルム
JP2008152120A (ja) * 2006-12-19 2008-07-03 Nippon Zeon Co Ltd 光学フィルム
JP2009237160A (ja) * 2008-03-26 2009-10-15 Konica Minolta Opto Inc 樹脂フィルムの製造方法、樹脂フィルム、積層フィルム、偏光板及び液晶表示装置
JP2010020268A (ja) * 2008-06-09 2010-01-28 Sony Corp 光学フィルムおよびその製造方法、防眩性フィルム、光学層付偏光子、ならびに表示装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002347161A (ja) * 2000-05-31 2002-12-04 Nitto Denko Corp 粒子分散系樹脂シートおよび液晶表示装置
JP2004034399A (ja) * 2002-07-01 2004-02-05 Nitto Denko Corp ハードコートフィルム、その製造方法、光学素子および画像表示装置
JP2004322489A (ja) * 2003-04-25 2004-11-18 Pioneer Electronic Corp ガスバリア基材およびその製造方法
JP2006018233A (ja) * 2004-05-31 2006-01-19 Fuji Photo Film Co Ltd 光学フイルム、偏光板、及びそれを用いた画像表示装置
JP2007152932A (ja) * 2005-07-04 2007-06-21 Teijin Dupont Films Japan Ltd ガスバリア加工用ポリエステルフィルム及びそれからなるガスバリア性積層ポリエステルフィルム
JP2008152120A (ja) * 2006-12-19 2008-07-03 Nippon Zeon Co Ltd 光学フィルム
JP2009237160A (ja) * 2008-03-26 2009-10-15 Konica Minolta Opto Inc 樹脂フィルムの製造方法、樹脂フィルム、積層フィルム、偏光板及び液晶表示装置
JP2010020268A (ja) * 2008-06-09 2010-01-28 Sony Corp 光学フィルムおよびその製造方法、防眩性フィルム、光学層付偏光子、ならびに表示装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015186507A1 (fr) * 2014-06-04 2015-12-10 日東電工株式会社 Film conducteur transparent
JP2015230785A (ja) * 2014-06-04 2015-12-21 日東電工株式会社 透明導電性フィルム
WO2016152488A1 (fr) * 2015-03-20 2016-09-29 コニカミノルタ株式会社 Film barrière contre les gaz
JPWO2016152488A1 (ja) * 2015-03-20 2017-12-28 コニカミノルタ株式会社 ガスバリアーフィルム
WO2019044473A1 (fr) * 2017-08-31 2019-03-07 富士フイルム株式会社 Stratifié formant barrière aux gaz et cellule photovoltaïque

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