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WO2017033665A1 - Film barrière contre les gaz, son procédé de fabrication et film optique - Google Patents

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

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Publication number
WO2017033665A1
WO2017033665A1 PCT/JP2016/072272 JP2016072272W WO2017033665A1 WO 2017033665 A1 WO2017033665 A1 WO 2017033665A1 JP 2016072272 W JP2016072272 W JP 2016072272W WO 2017033665 A1 WO2017033665 A1 WO 2017033665A1
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WIPO (PCT)
Prior art keywords
gas barrier
adhesive layer
layer
barrier film
film
Prior art date
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Ceased
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PCT/JP2016/072272
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English (en)
Japanese (ja)
Inventor
晃矢子 和地
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Konica Minolta Inc
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Konica Minolta Inc
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Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2017536707A priority Critical patent/JPWO2017033665A1/ja
Publication of WO2017033665A1 publication Critical patent/WO2017033665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters

Definitions

  • the present invention relates to a gas barrier film, a production method thereof, and an optical film. More specifically, the present invention relates to a gas barrier film having a high gas barrier property and heat resistance, and the gas barrier film having the gas barrier film, and adhesion to the phosphor particle-containing layer in a high temperature and high humidity environment, The present invention relates to an optical film containing phosphor particles having excellent side leak resistance.
  • a gas barrier layer that prevents the permeation of water vapor, oxygen, etc. by providing a deposition film made of an inorganic compound such as a metal oxide or a coating film of a resin on the surface of a resin substrate A gas barrier film provided with is known.
  • liquid crystal display elements LCD
  • solar cells PV
  • organic electroluminescence elements hereinafter also referred to as “organic EL elements”
  • QD quantum dots
  • phosphor particles Also in the field of electronic devices using QD films having QD particles ”), there is an increasing demand for gas barrier films using a resin base material for the purpose of providing lightness, resistance to cracking, and flexibility. Yes.
  • a quantum dot-containing layer containing quantum dots that emit light at various wavelengths is made transparent.
  • An optical film (hereinafter also referred to as “QD film”) that has been formed into a sheet by being sandwiched by a conductive sheet member has been studied. Since the QD particles used in this QD film are not sufficiently resistant to moisture, oxygen, etc., the translucent sheet that sandwiches the QD particle-containing layer in order to protect the QD particle-containing layer from deterioration due to moisture or oxygen As a member, it is necessary to laminate with a gas barrier film.
  • a gas barrier layer composed of an inorganic material and an ultraviolet curable resin layer containing an ultraviolet curable resin that is cured by irradiating with ultraviolet rays (UV) are provided adjacent to the gas barrier layer.
  • an ultraviolet curable resin layer include a protective layer (hard coat layer) for protecting the surface of the gas barrier layer.
  • a gas barrier film is disposed so as to sandwich a quantum dot layer (light emitting layer) in which phosphor particles functioning as quantum dots (QD) are dispersed in an ultraviolet curable resin or a thermosetting resin. A configuration is disclosed.
  • the problem that the adhesiveness deteriorates has appeared.
  • the QD particle-containing layer needs to have a thickness of several tens of ⁇ m, even if the upper or lower surface of the QD particle-containing layer is protected with a gas barrier film, the QD particle-containing layer has a thick film structure. Since moisture and oxygen penetrate from the side surface (also referred to as a cross section or edge) of the layer, the QD particles located at the end are damaged, so that the QD particle-containing layer itself However, a certain level of gas barrier resistance is required.
  • an inorganic oxide thin film is provided on one surface of a flexible resin substrate, and the inorganic oxide is further provided.
  • a method for forming a thin film containing a silane coupling agent and adhering the QD particle-containing layer is disclosed (for example, see Patent Document 2).
  • silane coupling agents those modified with a vinyl group, a methacryloxy group (methacryloyl group), an amino group, an epoxy group, a mercapto group or the like are disclosed.
  • a thin film composed of a silane coupling agent by providing a thin film composed of a silane coupling agent, adhesion between a thin layer of inorganic oxide (inorganic barrier layer) and a heat-meltable heat-sealable resin is improved. We are trying to improve.
  • the adhesion between the QD particle-containing layer and the inorganic oxide layer is improved by the effect of the silane coupling agent.
  • the gas barrier film is subjected to thermal deformation, the gas barrier property is improved.
  • the refractive index difference between the gas barrier film and the QD particle-containing layer is increased, and the efficiency of taking out light emitted by the QD particles is reduced due to optical loss.
  • the present invention has been made in view of the above-described problems and situations, and the solution is to use a gas barrier film having high gas barrier properties and heat resistance, and a phosphor particle-containing layer using the gas barrier film.
  • the present invention provides a phosphor particle-containing optical film that is excellent in adhesion and side leak resistance in a high-temperature and high-humidity environment with excellent luminous efficiency.
  • the resin base material has a gas barrier layer and an adhesive layer in this order, and the gas barrier layer contains at least silicon atoms.
  • a gas barrier film having high gas barrier properties and heat resistance can be realized by the film, and the gas barrier film has a gas barrier layer and an adhesive layer in this order on a resin substrate, and the gas barrier layer Contains an inorganic oxide containing at least a silicon atom, and the adhesive layer is an adhesive layer 1 satisfying a specific condition (1) or an adhesive layer 2 satisfying a condition (2),
  • the phosphor film-containing layer and the adhesive layer are disposed adjacent to each other to suppress deterioration of the QD particles due to moisture and oxygen and to increase the temperature of the phosphor particle-containing layer at a high temperature. It has been found that a phosphor particle-containing optical film can be obtained that has excellent adhesion in a wet environment and resistance to side leaks, as well as excellent luminous
  • a gas barrier film having a gas barrier layer and an adhesive layer in this order on a resin substrate,
  • the gas barrier layer contains an inorganic oxide containing at least silicon atoms,
  • the gas barrier property wherein the adhesive layer contains at least a compound containing an unreacted acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer is in the range of 100 to 1000 nm. the film.
  • Item 4 The gas barrier film according to any one of Items 1 to 3, wherein the adhesive layer contains organic fine particles having an average particle diameter in the range of 300 to 1000 nm.
  • a method for producing a gas barrier film for producing the gas barrier film according to any one of items 1 to 4 After forming a gas barrier layer composed of an inorganic oxide containing at least a silicon atom on a resin substrate, a compound containing at least an unreacted acryloyl group and a compound containing a silicon atom are formed on the gas barrier layer.
  • An optical film including a gas barrier film having a gas barrier layer and an adhesive layer in this order on a resin substrate,
  • the gas barrier layer contains an inorganic oxide containing at least silicon atoms
  • the adhesive layer is an adhesive layer 1 that satisfies the condition (1) defined below or an adhesive layer 2 that satisfies the condition (2), Condition (1):
  • the adhesive layer 1 contains at least a compound containing an acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer is in the range of 100 to 1000 nm.
  • the adhesive layer 2 contains inorganic fine particles having an average primary particle size in the range of 30 to 100 nm, organic fine particles having an average primary particle size in the range of 300 to 1000 nm, and a binder component.
  • An optical film characterized in that a phosphor particle-containing layer is disposed adjacent to the adhesive layer.
  • Item 9 The optical film according to Item 7 or 8, wherein the thickness of the adhesive layer 1 is in the range of 100 to 500 nm.
  • Item 11 The optical film according to any one of Items 7 to 10, wherein the adhesive layer 1 contains organic fine particles having an average particle diameter in the range of 300 to 1000 nm.
  • Item 9 The optical film according to Item 7 or 8, wherein the inorganic fine particles contained in the adhesive layer 2 are silica particles.
  • Item 17 The optical film as described in Item 16, wherein the silane coupling agent is a polymer type silane coupling agent.
  • Item 17 The optical film as described in Item 16, wherein the acryloyl group-containing compound is an acrylic polymer.
  • a gas barrier film having high gas barrier properties and heat resistance and the gas barrier film, adhesion with a phosphor particle-containing layer in a high temperature and high humidity environment, and side leak resistance
  • the gas barrier film of the present invention contains a compound containing an acryloyl group and a compound containing a silicon atom together with a gas barrier layer containing an inorganic oxide containing a silicon atom on a resin substrate, and the layer thickness is 100.
  • an adhesive layer in the range of ⁇ 1000 nm, a gas barrier film having high gas barrier properties and heat resistance can be realized, and the gas barrier film can be used as an optical film having a phosphor particle-containing layer. By applying, both adhesiveness and the side leak resistance of the phosphor particle-containing layer can be improved.
  • an unreacted acryloyl group (hereinafter also simply referred to as an acryloyl group) is formed on a gas barrier layer composed of an inorganic oxide containing a silicon atom.
  • an adhesive layer containing a compound containing silicon and a compound containing silicon atoms By providing an adhesive layer containing a compound containing silicon and a compound containing silicon atoms, the silicon atoms contained in the gas barrier layer interact with the silicon atoms contained in the adhesive layer, and the gas barrier layer is formed inside the adhesive layer.
  • a concentration gradient structure of silicon atoms is formed, and the hardness in the adhesive layer has a gradient structure in conjunction therewith.
  • the hardness pattern having this inclined structure can effectively relieve stress, resulting in excellent heat resistance and It is speculated that gas barrier properties can be obtained.
  • the phosphor particle-containing layer is formed by forming an adhesive layer containing inorganic fine particles and organic fine particles having different average particle diameters and refractive indexes at positions adjacent to the phosphor particle-containing layer. It has been found that the light emitted from can be efficiently extracted to the outside and the luminous efficiency can be increased.
  • inorganic fine particles with a small average particle diameter have the effect of scattering the light emitted from the phosphor particle-containing layer inside the adhesive layer, and the average particle diameter of the organic fine particles constitutes the adhesive layer. Since the refractive index is averaged by the uneven portions formed at the interface between the phosphor particle-containing layer and the adhesive layer, the optical component is estimated to be improved optically. .
  • the anchoring effect due to the resin component constituting the phosphor particle-containing layer entering the gap portion of the concavo-convex structure is exhibited.
  • adhesion can be improved by forming a strong bond with the phosphor particle-containing layer. It is.
  • a silane coupling agent or the like as a binder component on a gas barrier layer composed of an inorganic oxide containing silicon atoms, a silicon atom contained in the gas barrier layer and an adhesive layer are formed. By interacting with the silicon atoms contained, many silicon atoms are oriented on the gas barrier layer interface side inside the adhesive layer, thereby forming a concentration gradient structure of silicon atoms. Regarding the hardness, it is presumed that the adhesion can be improved by having an inclined structure.
  • Schematic sectional view showing an example of the configuration of the gas barrier film Schematic sectional view showing an example of the orientation state of the acryloyl group in the adhesive layer of the gas barrier film
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer and an adhesive layer in this order on a resin substrate, wherein the gas barrier layer contains an inorganic oxide containing at least silicon atoms. And the adhesive layer contains at least a compound containing an acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer is in the range of 100 to 1000 nm. This feature is a technical feature common to or corresponding to the claimed invention.
  • the present invention from the standpoint that the effects of the present invention can be further manifested, it is possible to maintain good adhesion and to prevent side leakage when the thickness of the adhesive layer is in the range of 100 to 500 nm. This is preferable in that the resistance can be further improved.
  • an acryloyl group-containing silane coupling polymer as the compound containing the acryloyl group contained in the adhesive layer in terms of further improving the adhesion, which is an object effect of the present invention.
  • the adhesive layer contains organic fine particles having an average particle size in the range of 300 to 1000 nm from the viewpoint that heat resistance can be further improved.
  • a gas barrier layer composed of an inorganic oxide containing at least silicon atoms is formed on a resin substrate, and then at least an acryloyl group is formed on the gas barrier layer.
  • An adhesive layer containing a compound containing a compound containing a silicon atom and a compound containing a silicon atom is formed in a thickness range of 100 to 1000 nm. Furthermore, it is a preferable embodiment that the adhesiveness and side leak resistance can be further improved when the gas barrier film is not subjected to a curing treatment by irradiation with actinic rays such as ultraviolet rays.
  • the optical film of the present invention comprises a gas barrier film on at least one surface side of the phosphor particle-containing layer, and the gas barrier film has a gas barrier layer and an adhesive layer on the resin substrate.
  • the gas barrier layer contains an inorganic oxide containing at least a silicon atom, and the adhesive layer satisfies the specific condition (1) or the adhesive layer 1 that satisfies the condition (2) 2 and the phosphor particle-containing layer and the adhesive layer are disposed adjacent to each other.
  • the adhesive layer constituting the gas barrier film contains at least a compound containing an acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer is from 100 to 100.
  • the adhesive layer 1 is in the range of 1000 nm.
  • the adhesive layer constituting the gas barrier film includes an inorganic fine particle having an average primary particle size in the range of 30 to 100 nm and an average primary particle size in the range of 300 to 1000 nm. It is characterized by being the adhesive layer 2 containing the organic fine particles and the binder component.
  • the phosphor particle-containing layer is a quantum dot-containing layer containing quantum dots as phosphor particles, so that more excellent emission characteristics are obtained. It is preferable in that it can be obtained.
  • the inorganic fine particles contained in the adhesive layer are silica particles, have a refractive index approximate to the binder component constituting the adhesive layer, and can exhibit an efficient light scattering effect in the adhesive layer, This is preferable from the viewpoint of realizing higher luminous efficiency.
  • the adhesive layer is formed at the interface between the phosphor particle-containing layer and the adhesive layer by setting the layer thickness to be equal to or greater than the average primary particle size of the inorganic fine particles and less than the average primary particle size of the organic fine particles. It is preferable from the viewpoint that higher luminous efficiency can be realized by averaging the refractive index by the uneven structure.
  • a silane coupling agent or a polymer-type silane coupling agent as a binder component constituting the adhesive layer, adhesion between the phosphor particle-containing layer and the adhesive layer, or an adhesive layer and a gas barrier. This is preferable from the viewpoint of improving the adhesion between the layers.
  • the adhesiveness between the phosphor particle-containing layer and the adhesive layer, or the adhesiveness between the adhesive layer and the gas barrier layer is included.
  • the gas barrier film of the present invention has a gas barrier layer and an adhesive layer in this order on a resin substrate, the gas barrier layer contains an inorganic oxide containing at least silicon atoms, and the adhesive layer 1 includes a compound containing at least an acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer 1 is in the range of 100 to 1000 nm.
  • the “gas barrier film” as used in the present invention is a water vapor permeability measured by a method in accordance with JIS K 7129-1992 (abbreviation: WVTR, temperature: 38 ° C., relative humidity (RH): 100%). Of 1.0 g / m 2 ⁇ 24 h or less.
  • the water vapor permeability can be measured, for example, with a water vapor permeability measuring device (trade name: Permatran, manufactured by Mocon) in an atmosphere of 38 ° C. and 100% RH.
  • a water vapor permeability measuring device (trade name: Permatran, manufactured by Mocon) in an atmosphere of 38 ° C. and 100% RH.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a gas barrier film.
  • a gas barrier film (1) comprises a gas barrier layer (3) composed of an inorganic oxide containing at least silicon atoms on a resin substrate (2), and an adhesive layer 1 ( 4).
  • the adhesive layer 1 contains at least a compound containing an unreacted acryloyl group and a compound containing a silicon atom, and the layer thickness is in the range of 100 to 1000 nm.
  • the thickness of the adhesive layer 1 is in the range of 100 to 500 nm, or the compound containing an acryloyl group contained in the adhesive layer 1 is an acryloyl group-containing silane coupling polymer. is there.
  • FIG. 2 is a schematic cross-sectional view showing an example of the orientation state of the acryloyl group in the adhesive layer 1 of the gas barrier film.
  • the gas barrier film (1) shown in FIG. 2 is composed of a resin substrate (2), a gas barrier layer (3), and an adhesive layer 1 (4), and contributes to improving heat resistance and adhesion.
  • a state in which (5) is oriented in the surface region of the adhesive layer 1 is shown as a schematic diagram.
  • acryloyl group is an acyl group derived from acrylic acid represented by the structure shown below.
  • the amount of acryloyl group (mol / m 2 ) in the surface region of the adhesive layer 1 can be determined by the following method.
  • the surface region of the adhesive layer 1 in the present invention refers to a region from the outermost surface part to 10 nm in the depth direction, and the amount of acryloyl group (mol / m 2) with respect to the surface region according to the following measurement method. ) Can be obtained by measuring.
  • the ratio of the amount of Br on the surface is quantified to determine the unreacted acrylate group Can be quantified.
  • the acryloyl group content in the surface region of the adhesive layer 1 is preferably 0.1 mol / m 2 or more, more preferably 0.5 mol / m 2 or more.
  • a gas barrier layer and an adhesive layer 2 are provided in this order on a resin substrate, and the gas barrier layer is an inorganic material containing at least silicon atoms.
  • the gas barrier layer is an inorganic material containing at least silicon atoms.
  • FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a gas barrier film having a second configuration having a gas barrier layer and an adhesive layer 2 containing inorganic fine particles and organic fine particles.
  • a gas barrier layer (103) composed of an inorganic oxide containing at least silicon atoms is formed on a resin substrate (102), and a second barrier film is formed thereon. It is the structure which has the contact bonding layer 2 (104) which is embodiment.
  • the adhesive layer 2 (104) includes inorganic fine particles (106) having an average primary particle diameter in the range of 30 to 100 nm and an average primary particle diameter in the range of 300 to 1000 nm. It consists of organic fine particles (107) and a binder component (105) inside.
  • the inorganic fine particles (106) contained in the adhesive layer 2 (104) are silica particles.
  • the layer thickness of the adhesive layer 2 (104) is not less than the average primary particle size of the inorganic fine particles (106) and less than the average primary particle size of the organic fine particles (107).
  • the layer thickness of the binder component satisfying the above conditions is 30 nm or more and less than 1000 nm, but the practical layer thickness is 100 nm or more and less than 1000 nm, more preferably in the range of 100 to 800 nm, particularly preferably. Is in the range of 200 to 500 nm.
  • the layer thickness of the adhesive layer 2 (104) referred to in the present invention is, as shown in FIG. 3, when the organic fine particles (107) which are large particles protrude from the upper surface to form a concavo-convex structure.
  • the interface with the gas barrier layer (103) is A and the bottom surface of the concave structure on the surface of the adhesive layer (4) is B, the average thickness (Ad) from A to B is the adhesive layer 2 ( 104).
  • the optical film of the present invention has a gas barrier film having a structure defined in the present invention and a phosphor particle-containing layer containing phosphor particles, and a surface region constituting the gas barrier film of the present invention.
  • An adhesive layer having an acryloyl group and a phosphor particle-containing layer are disposed adjacent to each other, and the adhesive layer contains at least a compound containing an acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer
  • the adhesive layer 1 in the range of 100 to 1000 nm, or the adhesive layer has inorganic fine particles having an average primary particle size in the range of 30 to 100 nm, and an average primary particle size of 300 to It is an adhesive layer 2 (second embodiment) containing organic fine particles within a range of 1000 nm and a binder component.
  • the adhesive layer contains at least a compound containing an acryloyl group and a compound containing a silicon atom as the adhesive layer, and the thickness of the adhesive layer is in the range of 100 to 1000 nm.
  • One feature is that 1 is applied.
  • 4A and 4B are schematic cross-sectional views illustrating an example of a first configuration of an optical film including a gas barrier film having an adhesive layer 1 (4, 4A, 4B) and a phosphor particle-containing layer. .
  • the gas barrier layer (3) a compound containing at least an acryloyl group, a compound containing a silicon atom, and a layer thickness are formed on the resin substrate (2).
  • the gas barrier film (1) having a structure in which the adhesive layer 1 (4) within the range of 100 to 1000 nm is laminated and the position facing the adhesive layer 1 (4).
  • An example of a configuration in which a phosphor particle-containing layer (6) configured by dispersing phosphor particles (7, QD particles) is arranged is shown.
  • a structure in which a sealing member (9) or the like is provided on the opposite surface of the phosphor particle-containing layer (6) provided with the gas barrier film to prevent the phosphor particles from being affected by moisture, oxygen, or the like. preferable.
  • the phosphor particle-containing layer (6) containing the phosphor particles (7) is sandwiched between gas barrier films (1A and 1B) having a pair of adhesive layers 1.
  • the configuration is shown.
  • the adhesive layer 1 (4A and 4B) having an acryloyl group in the surface region constituting each gas barrier film and the phosphor particle-containing layer (6) are adjacent to each other. Has been placed.
  • optical film of the second configuration In the optical film of the present invention having the second configuration, as the adhesive layer, inorganic fine particles having an average primary particle size in the range of 30 to 100 nm, organic fine particles having an average primary particle size in the range of 300 to 1000 nm, and One feature is to apply the adhesive layer 2 containing a binder component.
  • FIG. 5A and FIG. 5B are schematic cross-sectional views showing an example of the configuration of the optical film (F) of the second configuration configured by the gas barrier film having the adhesive layer 2 and the phosphor particle-containing layer.
  • 5A contains a gas barrier layer (103A), inorganic fine particles (106A), organic fine particles (107A), and a binder component (105A) on the resin substrate (102A).
  • Gas barrier film (101A) having a structure in which adhesive layer 2 (104A) is laminated, and phosphor particles (109, QD particles) in resin binder (110) at a position adjacent to adhesive layer 2 (104A).
  • distributing is shown.
  • a sealing member (111) is used to prevent the phosphor particles (109) from being affected by moisture, oxygen, or the like. Etc.) is preferable.
  • FIG. 5B is a schematic cross-sectional view showing an example of an optical film having a structure in which a phosphor particle-containing layer is sandwiched between gas barrier films having an adhesive layer 2 according to a pair of second embodiments.
  • both sides of the phosphor particle-containing layer (108) containing the phosphor particles (109) are formed on the gas barrier films (101A and 101B) according to the second configuration of the present invention.
  • the adhesive layers 2 (104A and 104B) of the gas barrier films (101A and 101B) are disposed at positions adjacent to both surfaces of the phosphor particle-containing layer (8).
  • the gas barrier films (101A and 101B) may be gas barrier films having the same structure that satisfies the conditions defined in the present invention.
  • the gas barrier films (101A and 101B) are gas barrier films having different structures, at least one of the gas barrier films (1A and 1B) has the adhesive layer 2 defined in the present invention. Any gas barrier film may be used.
  • the resin base material applicable to the gas barrier film of the present invention is not particularly limited as long as it can hold the gas barrier layer and the adhesive layer.
  • a flexible plastic film or sheet is usually used, and a film or sheet made of a colorless and transparent resin is preferably used.
  • the resin base material used includes various functional layers (hard coat layer, etc.) provided as appropriate according to the purpose, and phosphor particle-containing layers constituting the optical film.
  • the material, thickness, and the like are not particularly limited and can be appropriately selected depending on the purpose of use.
  • Examples of the resin substrate applicable to the present invention include poly (meth) acrylate, polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC), Polyarylate, polyvinyl chloride (abbreviation: PVC), polyethylene (abbreviation: PE), polypropylene (abbreviation: PP), polystyrene (abbreviation: PS), nylon (abbreviation: Ny), aromatic polyamide, polyetheretherketone, polysulfone Resin film composed of resin components such as polyethersulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, etc., and heat-resistant transparent with silsesquioxane having organic-inorganic hybrid structure as the basic skeleton Film (e.g., product name Sila-DEC, manufactured by Chisso Corporation), and
  • the thickness of the resin substrate is not particularly limited, but is preferably 5 to 300 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • various functional layers such as a transparent conductive layer, a primer layer, and a clear hard-coat layer, as needed.
  • functional layers described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be appropriately selected and employed depending on the purpose. .
  • the resin base material according to the present invention is preferably transparent. Since the resin base material is transparent and the layer formed on the resin base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it can be used as a transparent substrate such as an organic EL element. Because it becomes.
  • “Transparent” in the present invention means that the visible light transmittance measured by a method in accordance with JIS S3107 (2013) is 50% or more, preferably 65% or more, more preferably 80% or more, More preferably, it is 90% or more.
  • the resin base material preferably has high surface smoothness.
  • the surface smoothness those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the resin substrate, at least the side on which the gas barrier layer is provided, may be polished to improve smoothness.
  • various known treatments for improving adhesion such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, Layers may be stacked or the above treatments may be combined.
  • gas barrier layer One feature of the gas barrier film of the present invention is that it has a gas barrier layer composed of an inorganic oxide containing at least one silicon atom on a resin substrate.
  • the gas barrier layer according to the present invention has an undercoat layer (for example, a smooth layer, a primer layer), an anchor coat between the resin substrate and the gas barrier layer, in addition to an embodiment in which the gas barrier layer is directly formed on the resin substrate surface.
  • Various functional layers such as layers (anchor layers) may be provided as necessary.
  • the gas barrier layer is composed of an inorganic compound containing at least silicon atoms. That is, it is an inorganic oxide containing silicon atoms (composition: SiO x ).
  • the chemical composition in the gas barrier layer can be determined by measuring the atomic composition ratio using an XPS surface analyzer (for example, QUANTERASXM manufactured by ULVAC-PHI). It can also be determined by cutting the side surface of the gas barrier layer and measuring the exposed cut surface by measuring the atomic composition ratio with an XPS surface analyzer.
  • the chemical composition in the gas barrier layer can be controlled by the type and amount of raw materials used when forming the gas barrier layer, the formation conditions during film formation, the modification treatment conditions after formation, and the like.
  • the content of the inorganic compound containing a silicon atom constituting the gas barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more based on the total mass of the gas barrier layer.
  • the content is more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass, that is, the gas barrier layer is most preferably composed only of an inorganic compound.
  • the gas barrier layer By constituting the gas barrier layer from an inorganic compound containing a silicon atom as a main component, it has high density and can exhibit excellent gas barrier properties.
  • the gas barrier property of the gas barrier layer is, as described above, the water vapor permeability (abbreviation: WVTR, temperature: 38 ° C., relative humidity (RH)): 100 measured by a method according to JIS K 7129-1992. %) Is 1.0 g / (m 2 ⁇ 24 h) or less, preferably 0.1 g / (m 2 ⁇ 24 h) or less, and 0.01 g / (m 2 ⁇ 24 h) or less. It is more preferable that
  • the method for forming the gas barrier layer is not particularly limited.
  • the gas barrier layer is formed by a vapor deposition method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) using a silicon-containing compound.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • a coating film containing a precursor for forming a gas barrier layer by applying a coating solution containing a silicon compound (for example, polysilazane, etc.)
  • a gas barrier layer is formed by performing a modification treatment using vacuum ultraviolet rays or the like. And the like (hereinafter also referred to as a coating method).
  • the physical vapor deposition method is a method in which a target substance, for example, a thin film such as a silicon atom-containing film is deposited on the surface of a substrate in the gas phase by physical means.
  • the physical film forming means includes, for example, a sputtering method (for example, a DC sputtering method, an RF sputtering method, an ion beam sputtering method, a magnetron sputtering method), a vacuum deposition method, an ion plating method, and the like.
  • a target is placed in a vacuum chamber, a high-voltage ionized rare gas element (usually argon) is collided with the target, and silicon atoms are ejected from the target surface to adhere to the resin substrate. It is a method of depositing. At this time, by flowing nitrogen gas or oxygen gas into the chamber, the silicon atoms ejected from the target by argon gas react with nitrogen and oxygen to form an inorganic oxide layer containing silicon atoms. A sputtering method may be used.
  • the chemical vapor deposition method (Chemical Vapor Deposition, CVD method) is a method of supplying a raw material gas containing silicon atoms as a target thin film component onto a resin base material, on the surface of the resin base material or in the gas phase.
  • CVD method is a method of supplying a raw material gas containing silicon atoms as a target thin film component onto a resin base material, on the surface of the resin base material or in the gas phase.
  • an inorganic oxide film containing silicon atoms is deposited by a chemical reaction.
  • Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned.
  • the gas barrier layer obtained by the vacuum plasma CVD method or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure is based on conditions such as the silicon-containing compound, decomposition gas, decomposition temperature, and input power that are raw materials (also referred to as raw materials) Is preferable because a silicon atom-containing oxide having a desired composition can be produced.
  • the conditions for forming the barrier layer by the plasma CVD method for example, by appropriately adopting the conditions described in paragraphs (0033) to (0051) of International Publication No. 2012/067186, an inorganic oxide containing a silicon atom is used.
  • a gas barrier layer containing an object can be formed.
  • the gas barrier layer according to the present invention is, for example, a coating film formed by applying a coating solution for forming a gas barrier layer containing an inorganic compound containing a silicon atom on a resin base material. You may form by the method (application
  • an inorganic compound containing a silicon element according to the present invention hereinafter referred to as a silicon compound
  • a silicon compound an inorganic compound containing a silicon element according to the present invention
  • the silicon compound according to the present invention is not particularly limited as long as a coating solution containing a silicon compound can be prepared.
  • a coating solution containing a silicon compound can be prepared.
  • polysilazane compounds, silazane compounds, aminosilane compounds, silylacetamide compounds, silylimidazole compounds, and other silicon compounds containing nitrogen are used.
  • the polysilazane compound (hereinafter also simply referred to as polysilazane) preferably used in the present invention is a polymer having a silicon-nitrogen bond.
  • Examples of polysilazane used in the present invention are not particularly limited and include known ones.
  • compounds specifically described in paragraphs (0043) to (0058) of JP2013-022799A and paragraphs (0038) to (0056) of JP2013-226758A are appropriately employed. can do.
  • Polysilazane is also commercially available in a solution in an organic solvent.
  • examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, manufactured by AZ Electronic Materials Co., Ltd. NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 and the like.
  • a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide see, for example, JP-A-5-238827)
  • glycidol A glycidol-added polysilazane obtained (for example, see JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (for example, see JP-A-6-240208), and a metal carboxylate are reacted.
  • Metal carboxylate-added polysilazane for example, see JP-A-6-299118
  • acetylacetonate complex-added polysilazane for example, JP-A-6-306329 obtained by reacting a metal-containing acetylacetonate complex.
  • Polysilazane added with metal fine particles for example, see JP-A-7-196986
  • silazane compounds that are monomers preferably used in the present invention include dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, and 1,3-divinyl-1,1. , 3,3-tetramethyldisilazane and the like, but not limited thereto.
  • aminosilane compounds preferably used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-arylaminopropyltrimethoxysilane, propylethylenediaminesilane, N- [3- (trimethoxysilyl) ) Propyl] ethylenediamine, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, and bis (butylamino) dimethylsilane.
  • silylacetamide compounds preferably used in the present invention include N-methyl-N-trimethylsilylacetamide, N, O-bis (tert-butyldimethylsilyl) acetamide, N, O-bis (diethylhydrogensilyl) trifluoroacetamide , N, O-bis (trimethylsilyl) acetamide, N-trimethylsilylacetamide and the like, but are not limited thereto.
  • silylimidazole compounds preferably used in the present invention include 1- (tert-butyldimethylsilyl) imidazole, 1- (dimethylethylsilyl) imidazole, 1- (dimethylisopropylsilyl) imidazole, and N-trimethylsilylimidazole. However, it is not limited to these.
  • ⁇ Other nitrogen-containing silicon compounds in addition to the above silicon compound containing nitrogen, for example, bis (trimethylsilyl) carbodiimide, trimethylsilyl azide, N, O-bis (trimethylsilyl) hydroxylamine, N, N′-bis (trimethylsilyl) urea, 3 -Bromo-1- (triisopropylsilyl) indole, 3-bromo-1- (triisopropylsilyl) pyrrole, N-methyl-N, O-bis (trimethylsilyl) hydroxylamine, 3-isocyanatopropyltriethoxysilane, and silicon Although tetraisothiocyanate etc. are used, it is not limited to these.
  • polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane and the like are preferable from the viewpoints of film formation, few defects such as cracks, and small amount of residual organic matter, and high gas barrier performance.
  • Polysilazane is more preferred, and perhydropolysilazane (PHPS) is particularly preferred because gas barrier performance is maintained even when bent and under high temperature and high humidity conditions.
  • PHPS perhydropolysilazane
  • the content of polysilazane in the gas barrier layer before the modification treatment is 100% by mass when the total mass of the gas barrier layer is 100% by mass, that is, the entire layer is formed of polysilazane. Can do.
  • the polysilazane content in the layer is preferably in the range of 10 to 99% by mass, and in the range of 40 to 95% by mass. More preferably, it is particularly preferably in the range of 70 to 95% by mass.
  • the formation method by the coating method of the gas barrier layer as described above is not particularly limited, and a known method can be applied. However, a coating solution for forming a gas barrier layer containing a silicon compound and, if necessary, a catalyst in an organic solvent is used. It is preferable to apply a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.
  • the modification treatment of the gas barrier layer formed by the coating method in the present invention refers to a conversion reaction of a silicon compound to silicon oxide, silicon oxynitride, or the like.
  • the gas barrier film as a whole has gas barrier properties. This refers to a process for forming an inorganic oxide thin film containing a silicon element at a level that can contribute to the development of (water vapor permeability is preferably 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ day or less).
  • the conversion reaction of the silicon compound as a precursor to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method.
  • Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment (for example, excimer irradiation treatment), and heat treatment.
  • the modification treatment include plasma treatment, ultraviolet irradiation treatment (for example, excimer irradiation treatment), and heat treatment.
  • the formation of a silicon oxide layer or silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or higher, so that it can be applied to flexible substrates such as plastics. difficult. For this reason, it is preferable to perform heat treatment in combination with other reforming treatments by limiting the upper limit temperature to be applied.
  • the modification treatment from the viewpoint of adapting to a plastic substrate, a conversion method using a plasma treatment or an ultraviolet irradiation treatment capable of a conversion reaction at a lower temperature is preferable.
  • a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used.
  • the atmospheric pressure plasma CVD method which performs plasma CVD processing near atmospheric pressure, does not require a reduced pressure environment and does not require a large vacuum facility.
  • the deposition rate is high, and the average free path of gas is very high under high pressure conditions under atmospheric pressure compared to the conditions of normal CVD. Since it is short, a very homogeneous film can be obtained.
  • nitrogen gas or a gas containing Group 18 atoms of the long-period periodic table specifically helium, neon, argon, krypton, xenon, radon, or the like is used.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • the modification treatment can be efficiently performed by heat-treating the coating film containing the silicon compound in combination with another modification treatment, preferably an excimer irradiation treatment described later.
  • the gas barrier layer is formed using a sol-gel method
  • the heating temperature is preferably in the temperature range of 50 to 300 ° C., more preferably in the temperature range of 70 to 200 ° C.
  • the heating time is preferably in the range of 0.005 to 60 minutes, more preferably.
  • Heat treatment methods include, for example, a method in which a resin substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, a method in which the atmosphere is heated by an external heater such as a resistance wire, and a red color such as an IR heater.
  • a heating element such as a heat block
  • the coating film is heated by heat conduction
  • a method in which the atmosphere is heated by an external heater such as a resistance wire
  • a red color such as an IR heater.
  • UV irradiation treatment As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable.
  • Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.
  • the resin base material is heated, and O 2 and H 2 O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated, so that polysilazane is excited and polysilazane is excited.
  • the formation of ceramics is promoted, and the resulting gas barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.
  • any commonly used ultraviolet ray generator can be used.
  • the ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength in the range of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, preferably 210. Ultraviolet light in the wavelength range of ⁇ 375 nm is used.
  • the ultraviolet irradiation it is preferable to set the irradiation intensity and the irradiation time within a range in which the resin base material carrying the irradiated gas barrier layer is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the irradiation intensity of the resin substrate surface is 20 to 300 mW / cm 2 , preferably 50 to
  • the distance between the resin substrate and the ultraviolet irradiation lamp can be set to 200 mW / cm 2 and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the temperature of the resin base material during the ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the resin base material are impaired, such as the plastic base material being deformed or its strength deteriorated in the case of a plastic film or the like. In many cases. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit as the temperature of the resin substrate at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of resin substrate. Moreover, there is no restriction
  • ultraviolet ray generating means examples include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by MD Excimer Co., Ltd.), UV light laser, and the like.
  • excimer lamps single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by MD Excimer Co., Ltd.
  • UV light laser and the like.
  • UV irradiation can be performed either batchwise or continuously, and can be selected as appropriate depending on the shape of the resin substrate used.
  • a laminate having a gas barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above.
  • the ultraviolet baking furnace itself is generally known.
  • an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used.
  • the ceramic is obtained by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while transporting the laminate.
  • the time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the resin substrate and gas barrier layer used.
  • the most preferable modification treatment method in forming the gas barrier layer is treatment by vacuum ultraviolet irradiation (also referred to as excimer irradiation treatment).
  • the treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C.
  • the radiation source in the excimer irradiation treatment may be any radiation source that generates light having a wavelength in the range of 100 to 180 nm, and preferably an excimer radiator having a maximum emission at about 172 nm (for example, an Xe excimer lamp). ), Low pressure mercury vapor lamps having an emission line at about 185 nm, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having a maximum emission at about 222 nm.
  • the Xe excimer lamp is excellent in luminous efficiency because it can emit ultraviolet light having a short wavelength of 172 nm as a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power.
  • light having a long wavelength that causes a temperature rise due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, a short wavelength, so that the rise in the surface temperature of the object to be fired is suppressed.
  • a gas barrier film using a flexible film material such as polyethylene terephthalate (abbreviation: PET) that is easily affected by heat as a resin base material.
  • PET polyethylene terephthalate
  • Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably in the range of 10 to 20000 ppm by volume, and more preferably in the range of 50 to 10,000 ppm by volume. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.
  • a gas used for vacuum ultraviolet irradiation and satisfying the irradiation atmosphere is preferably a dry inert gas, and particularly preferably a dry nitrogen gas from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and controlling the flow rate ratio.
  • the illuminance of the vacuum ultraviolet rays on the coating surface received by the polysilazane coating is preferably in the range of 1 mW / cm 2 to 10 W / cm 2 , and in the range of 30 to 200 mW / cm 2. More preferably, it is more preferably in the range of 50 to 160 mW / cm 2 . If the illuminance of the vacuum ultraviolet ray is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, the coating film is less likely to be ablated and the resin substrate is less likely to be damaged.
  • the amount of irradiation energy (integrated light amount) of vacuum ultraviolet rays on the coating surface is preferably within the range of 10 to 10000 mJ / cm 2 , more preferably within the range of 100 to 8000 mJ / cm 2 , and 200 to 6000 mJ. More preferably within the range of / cm 2 . If the amount of irradiation energy of vacuum ultraviolet rays is 10 mJ / cm 2 or more, the modification can be sufficiently advanced. If it is 10,000 mJ / cm ⁇ 2 > or less, the generation
  • the vacuum ultraviolet light used for the modification may be generated by plasma formed of a gas containing at least one of CO, CO 2 and CH 4 .
  • a gas containing at least one of CO, CO 2 and CH 4 hereinafter also referred to as carbon-containing gas
  • a carbon-containing gas may be used alone, but a rare gas or H 2 is used as a main gas. It is preferable to add a small amount of the contained gas.
  • plasma generation methods include capacitively coupled plasma.
  • the film composition of the gas barrier layer can be determined by measuring the atomic composition ratio using an XPS surface analyzer. It can also be determined by cutting the gas barrier layer and measuring the cut surface with an XPS surface analyzer to measure the atomic composition ratio.
  • the film density of the gas barrier layer can be appropriately set according to the purpose.
  • the film density of the gas barrier layer is preferably in the range of 1.5 to 2.6 g / cm 3 . If it is in this range, the density of the film will be higher, and it will be difficult for the gas barrier property to deteriorate and the film to be oxidized by humidity.
  • the gas barrier layers may have the same composition or different compositions.
  • the gas barrier layer may consist only of a layer formed by a vacuum film-forming method or only a layer formed by a coating method.
  • a combination of a layer formed by a vacuum film forming method and a layer formed by a coating method may be used.
  • the gas barrier layer preferably contains a nitrogen element or a carbon element from the viewpoints of stress relaxation and absorption of ultraviolet rays used in forming a metal atom-containing layer described later.
  • a nitrogen element or a carbon element from the viewpoints of stress relaxation and absorption of ultraviolet rays used in forming a metal atom-containing layer described later.
  • it has properties such as stress relaxation and ultraviolet absorption, and by improving the adhesion between the gas barrier layer and the metal atom-containing layer, effects such as improved gas barrier properties are obtained. It is preferable.
  • the chemical composition of the gas barrier layer can be controlled by the type and amount of the silicon compound and the like when forming the gas barrier layer, and the conditions when modifying the layer containing the silicon compound.
  • the gas barrier film constituting the optical film of the present invention has a gas barrier layer and an adhesive layer on the resin substrate, and the adhesive layer 1 satisfies the condition (1) defined below or The adhesive layer 2 satisfies the condition (2).
  • Adhesive layer 1 containing a compound containing at least an acryloyl group and a compound containing a silicon atom, and the thickness of the adhesive layer is in the range of 100 to 1000 nm.
  • Adhesive layer 2 containing inorganic fine particles having an average primary particle size in the range of 30 to 100 nm, organic fine particles having an average primary particle size in the range of 300 to 1000 nm, and a binder component.
  • the gas barrier film (1) of the present invention has a gas barrier layer (3) on the resin base material (2), and further has at least unreacted acryloyl thereon.
  • An adhesive layer 1 (4) containing a compound containing a group and a compound containing a silicon atom and having a layer thickness in the range of 100 to 1000 nm is provided.
  • a specific amount of unreacted acryloyl group (CH 2 ⁇ CH—C ( ⁇ O) —) is present in the surface region of the adhesive layer 1 (4). It is preferable.
  • the acryloyl group here is an acyl group derived from acrylic acid.
  • FIG. 2 there is no particular limitation on the form in which a specific amount of acryloyl group (5) is present in the surface region of adhesive layer 1 (4).
  • the adhesive layer 1 (4) according to the present invention is formed as a thick film having a thickness of 100 to 1000 nm, and the layer thickness of the adhesive layer 1 can be confirmed by an observation means such as TEM.
  • a compound containing an acryloyl group and a compound containing a silicon atom may be individually contained, or a compound containing an acryloyl group and a silicon atom in the same structure may be used. Also good.
  • the compound containing an acryloyl group include an acryloyl group-containing compound (including an acryloyl group-containing polymer) such as an acrylate compound, an acrylsilane coupling agent containing an acryloyl group, and the like.
  • a silane coupling agent, a silicon dioxide particle (silica particle), etc. can be mentioned.
  • the compound containing an acryloyl group is not particularly limited, but an acryloyl group-containing compound (including an acryloyl group-containing polymer) such as an acrylate compound or an acrylsilane coupling agent containing an acryloyl group is preferably used. Can do.
  • acryloyl group-containing compound examples include a polymer type and a monomer type, and examples thereof include polyol polyacrylate, epoxy acrylate, urethane acrylate, and acrylic monomer.
  • Polyol polyacrylate is an ester compound of polyol and acrylic acid.
  • the polyol selected here is not particularly limited.
  • polyester polyols such as succinate and polycaprolactone, and ⁇ , ⁇ -poly (1,6-hexylene carbonate) diol, ⁇ , ⁇ -poly (3-methyl-1,5- Styrene carbonate) diol, ⁇ , ⁇ -poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, ⁇ , ⁇ -poly [(1,9-nonylene: 2-methyl-1,8 (Octylene) carbonate] (poly) carbonate diols such as diols. These may be used alone or in combination of two or more.
  • Epoxy acrylate is a compound obtained by adding acrylic acid to the terminal epoxy group of an epoxy resin.
  • an epoxy resin There is no restriction
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.
  • Urethane acrylate is a compound obtained by reacting polyol, polyisocyanate, and hydroxyl group-containing acrylate, or polyol and isocyanato group-containing acrylate. At this time, there is no particular limitation on the polyol, polyisocyanate, hydroxyl group-containing acrylate, and isocyanate group-containing acrylate to be selected.
  • the polyol is the same as the polyol used in the polyol polyacrylate.
  • polyisocyanate examples include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc.
  • hydroxyl group-containing acrylate examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- Hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethylacrylamide and the like can be mentioned. These may be used alone or in combination of two or more.
  • isocyanato group-containing acrylate examples include 2-isocyanatoethyl acrylate. These may be used alone or in combination of two or more.
  • the acrylic monomer is a compound obtained by removing the polyol polyacrylate, the epoxy acrylate, and the urethane acrylate from the acryloyl group-containing compound.
  • acrylic monomers include acryloyl-containing compounds having a cyclic ether group such as glycidyl acrylate and tetrahydrofurfuryl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and dicyclopentanyl acrylate.
  • a cyclic ether group such as glycidyl acrylate and tetrahydrofurfuryl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and dicyclopentanyl acrylate.
  • a monofunctional acryloyl group-containing compound having a cyclic aliphatic group such as dicyclopentanylethyl acrylate, 4-tert-butylcyclohexyl acrylate, lauryl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, Monofunctional acryloyl having a chain aliphatic group such as isooctyl acrylate and isoamyl acrylate Group-containing compounds, monofunctional acryloyl group-containing compounds having aromatic rings such as benzyl acrylate, phenoxyethyl acrylate, polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate And polyfunctional acryloyl group-containing compounds such as trimethylolprop
  • an acrylate compound monomer or a methacrylate compound monomer it is also possible to obtain as a commercial product, for example, a photocurable monomer (trade name: NK ester) sold by Shin-Nakamura Chemical Co., Ltd.
  • a photocurable monomer (trade name: NK ester) sold by Shin-Nakamura Chemical Co., Ltd.
  • Monofunctional acrylates eg, A-LEN-10, AM-90G, AM-130G, AMP-20GY, A-SA, S-1800A, etc.
  • bifunctional acrylates eg, 701A, A-200, A-400
  • polyfunctional acrylates for example, A-9300, A-GLY-9E, A-TMM-3, A-TMPT, AD-TMP, A-TMMT, A-DPH, etc.
  • methacrylate compound monomer monofunctional methacrylate (for example, CB-1, M-90G, PHE-1G, S, SA, etc.), bifunctional methacrylate (for example, 1G to 4G, BPE-80N, DCP, HD-N, HOD-N, NPG, 9PG, etc.).
  • monofunctional methacrylate for example, CB-1, M-90G, PHE-1G, S, SA, etc.
  • bifunctional methacrylate for example, 1G to 4G, BPE-80N, DCP, HD-N, HOD-N, NPG, 9PG, etc.
  • the acrylic silane coupling agent containing an acryloyl group in the present invention is a compound containing an acryloyl group and a silicon atom in the same structure, and may be a monomer tarp or a polymer type.
  • silane coupling agents containing acryloyl groups examples include 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3- Examples include acryloyloxypropylmethyldiethoxysilane.
  • acryloyl group-containing silane coupling agents include, as monomer types, KBM-5103 (3-acryloxypropyltrimethoxysilane) and KMB-502 (3-methacryloxypropylmethyldimethoxy) manufactured by Shin-Etsu Silicone.
  • KBM-503 (3-methacryloxypropyltrimethoxysilane), KBE-502 (3-methacryloxypropylmethyldiethoxysilane), KBE-503 (3-methacryloxypropyltriethoxysilane), manufactured by Dow Corning Z-6030 (3-methacryloxypropyltrimethoxysilane), Z-6033 (3-methacryloxypropylmethyldimethoxysilane), A1597 (3- (trimethoxysilyl) propyl acrylate) manufactured by Tokyo Chemical Industry Co., Ltd.
  • D4679 (3- [dimethoxy (methyl) silyl] propyl methacrylate), M0725 (3- (trimethoxysilyl) propyl methacrylate), M1324 (3- [tris (trimethylsilyloxy) silyl] propyl methacrylate, M1530 (3- [dimethoxy (Methyl) silyl] propyl methacrylate, M2525 (3-methoxydimethylsilyl) propyl acrylate, T2676 (3- (triethoxysilyl) methacrylate, etc. can be mentioned, and the polymer type is X-12-1048 (Shin-Etsu).
  • acryloyl group-containing silane coupling agents may be used alone or in combination of two or more, and acryloyl group-containing silane cups may also be used.
  • ring Examples of “compounds containing an acryloyl group and an alkoxysilyl group in one molecule” include, for example, polyorganosilsesquioxane introduced with a (meth) acryloyl group and polysiloxane-modified acrylic containing an unsaturated double bond Examples thereof include organic-inorganic hybrid materials such as resins, etc. These materials may be independently prepared with reference to conventionally known knowledge, or commercially available products may be used.
  • silane coupling agent (Compounds containing silicon atoms) ⁇ Silane coupling agent>
  • the silane coupling agent applicable to the present invention is not particularly limited, and examples thereof include the silane coupling agents listed below.
  • a silane coupling agent having a functional group such as an epoxy group (glycidoxy group), an amino group, a mercapto group, or a (meth) acryloyl group, and a functional group having reactivity with these functional groups.
  • a compound having a hydrolyzable silyl group obtained by reacting an agent, another coupling agent, polyisocyanate and the like with each functional group in an arbitrary ratio can also be used.
  • the silane coupling agent can be obtained as a commercial product.
  • KBM-1003 and KBE-1003 having a vinyl group as a functional group KBM-303, KBM-402, KMB-403, KBE-402 and KBE-403 having an epoxy group as a functional group, and a styryl group as a functional group.
  • KBM-1403 having an amino group as a functional group, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575 as a functional group, KBM- having an isocyanurate group as a functional group 9659, KBE-585 having a ureido group as a functional group, KBM-802, KBM-803 having a mercapto group as a functional group, and the like (manufactured by Shin-Etsu Silicone).
  • Z-6610, Z-6011, Z-6020, Z-6094, Z-6883, Z-6032 having an amino group as a functional group and Z having an epoxy group as a functional group are commercially available from Dow Corning. -6040, Z-6044, Z-6043, Z-6075, Z-6300, Z-6519, etc. having a vinyl group as a functional group.
  • olefinyl silanes glycidyloxyalkyl silanes, alkyl silanes, aryl silanes, aryl alkyl silanes, fluoroalkyl, which are described as “silane coupling agents” on the website of Tokyo Chemical Industry Co., Ltd. Silanes etc. can be mentioned.
  • silicon dioxide particles can be used as the compound containing silicon atoms.
  • silica particles produced by a gas phase method, a melting method, a sol-gel method or the like can be used.
  • a silica particle a well-known thing can be used.
  • the shape may be spherical or indeterminate, and is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core / shell type particles, or the like.
  • silica particles include Aerosil 200, 200V, 300, R972, R972V, R974, R976, R976S, R202, R812, R805, OX50, TT600, RY50, RX50, manufactured by Nippon Aerosil Co., Ltd. NY50, NAX50, NA50H, NA50Y, NX90, RY200S, RY200, RX200, R8200, RA200H, RA200HS, NA200Y, R816, R104, RY300, RX300, R106, and the like.
  • colloidal silica can be mentioned. Colloidal silica is obtained by heat-aging a silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer.
  • an organosilica sol that can stably disperse nano-level colloidal silica in an organic solvent.
  • Organosilica sol an organic solvent-dispersed silica sol, is commercially available from Nissan Chemical Industries, Ltd.
  • the general grades are methanol silica sol (dispersion medium: methanol, average particle size: 10 to 15 nm), MA-ST-M ( Dispersion medium: methanol, average particle diameter: 20 to 25 nm), MA-ST-L (dispersion medium: methanol, average particle diameter: 40 to 50 nm), IPA-ST (dispersion medium: isopropyl alcohol, average particle diameter: 10 to 15 nm), IPA-ST-L (dispersion medium: isopropyl alcohol, average particle diameter: 40 to 50 nm), EG-ST (dispersion medium: ethylene glycol, average particle diameter: 10 to 15 nm), PMA-ST (dispersion medium: Propylene glycol monomethyl ether acetate, average particle size: 10-15 nm), MEK-ST-40 (min Medium: methyl ethyl ketone, average particle size:
  • the particle size of the silica particles is not particularly limited, but the average particle size is preferably 3 to 200 nm.
  • the average particle size of primary particles of silicon dioxide dispersed in a primary particle state is more preferably 3 to 200 nm, and further preferably 3 to 100 nm. Particularly preferred is 3 to 50 nm.
  • the adhesive layer contains organic fine particles having an average particle diameter in the range of 300 to 1000 nm from the viewpoint of further improving the heat resistance.
  • organic fine particles applicable to the present invention include organic fine particles composed of resin components below, but the present invention is not limited to these.
  • Acrylic resin Polymethyl methacrylate, polyethyl methacrylate, propyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, methoxyethyl acrylate
  • Copolymer acrylic resin 1) Resin monomers and vinyl chloride, chloride Vinylidene, vinylpyridine, styrene, acrylonitrile, acrylic acid, methacrylic acid copolymer resin 3) Vinyl chloride resin: polyvinyl chloride, vinyl chloride and vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid, maleic acid ester Copolymer resin with acrylonitrile 4) Polyvinyl acetate and its partially saponified resin 5) Styrene resin: Copolymer resin of polystyrene, styrene and acrylonitrile 6) Vinylidene chloride resin: Poly salt Vinylidene, vinylidene chloride and
  • the average particle size of the organic fine particles is preferably 300 to 1000 nm, more preferably 400 to 900 nm.
  • the average particle diameter of the organic fine particles is obtained by calculating the equivalent circle diameter from the projected area using an electron microscope.
  • Method for forming adhesive layer 1 As a method for forming an adhesive layer according to the present invention, a solution (adhesive layer forming coating solution) in which each constituent material of the adhesive layer described above is dissolved in an appropriate solvent is applied to the surface of the gas barrier layer and dried. A method is illustrated.
  • the method for forming the adhesive layer is not particularly limited, and a coating solution for forming the adhesive layer containing the adhesive layer forming material is prepared by dipping, spraying, slide coating, bar coating, roll coater, die coater, gravure coater. It can be formed by coating on the gas barrier layer by a known method such as screen printing and removing the organic solvent by a drying treatment in an atmosphere such as air or nitrogen.
  • An appropriate photopolymerization initiator is added to the coating solution for forming the adhesive layer, the coating solution obtained by applying the coating solution and drying is subjected to a light irradiation treatment to obtain an acryloyl group-containing compound. Part may be polymerized. However, if it is completely polymerized, the unreacted acryloyl group contained in the adhesive layer disappears, so the polymerization should not be performed completely.
  • Solvents include, for example, toluene, xylene and other high boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, isopropyl alcohol And alcohol solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether.
  • the photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
  • photopolymerization initiator examples include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, -Isopropylthiox
  • the gas barrier film (101) of the second configuration according to the present invention has a gas barrier layer (103) on the resin base material (102), and further has an average on it.
  • Adhesive layer 2 containing inorganic fine particles (106) having a primary particle size in the range of 30 to 100 nm, organic fine particles (107) having an average primary particle size in the range of 300 to 1000 nm, and a binder component (105). 104).
  • the inorganic fine particles contained in the adhesive layer 2 are silica particles.
  • the binder component is preferably a silane coupling agent, and more preferably a polymer type silane coupling agent.
  • the binder component is an acryloyl group-containing compound, and further an acrylic polymer.
  • One feature of the adhesive layer according to the present invention is that it contains inorganic fine particles having an average primary particle size in the range of 30 to 100 nm.
  • inorganic fine particles applicable to the present invention include titanium oxide, zinc oxide, alumina (aluminum oxide), silica (silicon oxide), tin oxide, antimony oxide, indium oxide, bismuth oxide, magnesium oxide, lead oxide, and oxidation.
  • the fine particles include tantalum, yttrium oxide, cobalt oxide, copper oxide, manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, niobium oxide, molybdenum oxide, and vanadium oxide.
  • Particles (TiO 2 ) or silica particles (silicon dioxide, SiO 2 ) are preferable, and silica particles are more preferable.
  • silica particles are preferably used as the inorganic fine particles.
  • the refractive index of silica particles is in the range of 1.44 to 1.50.
  • silicon dioxide As silicon dioxide, the same thing as the silicon dioxide particle (silica particle) used for formation of the above-mentioned adhesion layer 1 can be mentioned.
  • the titanium oxide preferably contains anatase type (tetragonal) titanium dioxide or brookite type (orthorhombic) titanium oxide. Further, the BET specific surface area of titanium oxide is preferably 10 to 300 m 2 / g, and more preferably 20 to 100 m 2 / g. The particle size distribution of titanium oxide is preferably sharp. The refractive index of titanium oxide is in the range of 2.50 to 2.72.
  • an aqueous titanium oxide sol preferably has a solid content of 40% or less, more preferably 30% or less.
  • aqueous titanium oxide sol a commercially available product may be used, or it may be prepared and used.
  • preparation method any conventionally known method can be used.
  • Titanium oxide particles are also available as commercial products, for example, commercial products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercial products MT-100S, MT-100B, and MT-500BS manufactured by Teica. , MT-600, MT-600SS, JA-1, commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium, commercial products IT-S manufactured by Idemitsu Kosan , IT-OA, IT-OB, IT-OC, etc., titanium oxide particles having an average primary particle size in the range of 30 to 100 nm can be selected and used.
  • a commercial product manufactured by Ishihara Sangyo Co., Ltd. can also be applied, and is a TOO-55 series manufactured by a firing method of ultrafine titanium oxide, TTO-55 (A) (rutile crystal, surface treatment: Al ( OH) 3 , average particle size: 30-50 nm), TTO-55 (B) (rutile crystal, surface treatment: Al (OH) 3 , average particle size: 30-50 nm), TTO-55 (C) (rutile crystal) Surface treatment: Al (OH) 3 / stearic acid, average particle size: 30 to 50 nm).
  • the particle size of the inorganic fine particles such as silica particles is characterized in that the average primary particle size is in the range of 30 to 100 nm, preferably in the range of 30 to 80 nm, and more preferably It is within the range of 40 to 70 nm.
  • the average primary particle size of the inorganic fine particles according to the present invention including the silica particles was photographed by magnifying the inorganic fine particles 10,000 times with a transmission electron microscope, and 300 particles were randomly observed as the primary particles, and image analysis was performed. Is a value obtained by calculating the measured value as the number average diameter of the ferret diameter.
  • the cross section was cut out, the cross section was photographed with a transmission electron microscope, the diameter of 300 inorganic fine particles present was randomly measured, and the arithmetic average value was averaged.
  • the primary particle size can also be determined. At this time, when the inorganic fine particles were not circular, a diameter corresponding to a circle having the same area was obtained and used as the diameter of the inorganic fine particles.
  • the amount of the inorganic fine particles according to the present invention added to the adhesive layer is not particularly limited, and is in the range of 0.5 to 50% by mass with respect to the total solid content of the adhesive layer, preferably 1.0 to It is within the range of 40% by mass, and more preferably within the range of 5.0 to 30% by mass.
  • Organic fine particles One feature of the adhesive layer according to the present invention is that it contains organic fine particles having an average primary particle size in the range of 300 to 1000 nm.
  • organic fine particles applicable to the present invention include organic fine particles having an average primary particle size comprised of the following resin components in the range of 300 to 1000 nm, but the present invention is not limited to these. is not.
  • Acrylic resin polymethyl methacrylate, polyethyl methacrylate, propyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, etc.
  • Copolymer acrylic resin 1) Resin monomer and vinyl chloride, Vinylidene chloride, vinyl pyridine, styrene, acrylonitrile, acrylic acid, methacrylic acid copolymer resin, etc.
  • Vinyl chloride resin polyvinyl chloride, vinyl chloride and vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid, maleic Acidic ester, copolymer resin with acrylonitrile, etc.
  • Polyvinyl acetate and its partially saponified resin 5) Styrol resin: Copolymer resin of polystyrene, styrene and acrylonitrile, etc. 6) Vinylidene chloride resin Polyvinylidene chloride, vinylidene chloride and acrylonitrile copolymer resin, etc. 7) Acetal resin: Polyvinyl formal, polybutyl butyral, etc.
  • Fiber tree Cellulose acetate, cellulose propionate, cellulose butyrate, cellulose nitrate, etc.
  • Melamine resin Melamine-formaldehyde Condensation resin, benzoguanamine-melamine-formaldehyde condensation resin, etc.
  • organic fine particle dispersions are prepared by dissolving the polymer in an organic solvent and mixing and dispersing with water or an aqueous gelatin solution with vigorous stirring, or emulsion polymerization, precipitation polymerization, Alternatively, a method of depositing particles while polymerizing monomers by pearl polymerization, or a fine particle powder of a matting agent, using a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, etc. Obtained by dispersing in a liquid.
  • the average primary particle size of the organic fine particles was measured by magnifying the organic fine particles at a magnification of 10000 times with a transmission electron microscope, randomly observing 300 particles as primary particles, and measuring the number average diameter of the ferret diameter by image analysis. The value can be calculated and obtained.
  • the cross-sectional part was image
  • the average particle diameter of the organic fine particles is characterized by 300 to 1000 nm, but preferably 400 to 900 nm.
  • the amount of the organic fine particles according to the present invention added to the adhesive layer is not particularly limited, and is within the range of 0.5 to 50% by mass, preferably 1.0 to It is within the range of 40% by mass, and more preferably within the range of 5.0 to 30% by mass.
  • the mass ratio of the inorganic fine particles to the organic fine particles in the adhesive layer according to the present invention is not particularly limited, and can be appropriately selected from the range of 1:99 to 99: 1 as inorganic fine particles: organic fine particles, Preferably, it is in the range of 10:90 to 90:10, more preferably in the range of 20:80 to 80:20.
  • the adhesive layer according to the present invention contains a binder component together with the inorganic fine particles and the organic fine particles described above.
  • a silane coupling agent, a polymer type silane coupling agent, an acryloyl group containing compound, an acrylic polymer, etc. are preferable aspects, More specifically, as an acryloyl group containing compound, silane coupling Examples thereof include an acryloyl group-containing acrylic silane coupling agent and a polymer type acrylic silane coupling agent containing an agent in the structure.
  • silane coupling agent ⁇ Monomer type silane coupling agent>
  • Specific examples of the silane coupling agent applicable to the present invention include the same compounds as the silane coupling agent applicable to the formation of the adhesive layer 1.
  • the acrylic silane coupling agent containing an acryloyl group in the present invention is a compound containing an unreacted acryloyl group and a silicon atom in the same structure, and may be a monomer type or a polymer type.
  • Specific examples of the acrylsilane coupling agent containing an acryloyl group include the same compounds as the acrylsilane coupling agent containing an acryloyl group applicable to the formation of the adhesive layer 1 described above.
  • acryloyl group-containing compound examples include polymer tarps and monomer types, and examples include polyol polyacrylates, epoxy acrylates, urethane acrylates, and acrylic monomers. Specific examples of the acryloyl group-containing compound include the same compounds as the acryloyl group-containing compound applicable to the formation of the adhesive layer 1 described above.
  • the layer thickness of the adhesive layer 2 according to the present invention is preferably an aspect in which the average primary particle size of the inorganic fine particles is equal to or greater than and less than the average primary particle size of the organic fine particles.
  • the actual layer thickness is 100 nm or more and less than 1000 nm, more preferably in the range of 100 to 800 nm, and particularly preferably in the range of 200 to 500 nm.
  • the method for forming the adhesive layer 2 is not particularly limited, and a coating solution for forming an adhesive layer containing an adhesive layer forming material is prepared by dipping, spraying, slide coating, bar coating, roll coater, die coater, gravure. It can be formed by coating on the gas barrier layer by a known method such as a coater method or a screen printing method, and removing the organic solvent by a drying treatment in an atmosphere such as air or nitrogen.
  • An appropriate photopolymerization initiator is added to the coating solution for forming the adhesive layer, the coating solution obtained by applying the coating solution and drying is subjected to a light irradiation treatment to obtain an acryloyl group-containing compound. Part may be polymerized.
  • Solvents include, for example, toluene, xylene and other high boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, isopropyl alcohol And alcohol solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether.
  • the photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
  • photopolymerization initiator examples include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, -Isopropylthiox
  • the gas barrier layer and the adhesive layer 1 or the adhesive layer 2 are formed on the resin base material, but other functions are provided within the range not impairing the object effects of the present invention.
  • An adhesive layer may be provided.
  • Specific other functional layers include an underlayer (also referred to as a smooth layer or a primer layer), an anchor coat layer (also referred to as an anchor layer), a bleed-out prevention layer, a protective layer, a moisture absorption layer, or an antistatic layer. Examples include functionalized layers.
  • the gas barrier film of the present invention may have, for example, a smooth layer or a primer layer as a base layer between the resin substrate and the gas barrier layer.
  • the underlayer is for flattening the rough surface of the resin base material with protrusions or the like, or for flattening by filling the unevenness and pinholes generated in the gas barrier layer with the protrusions present on the resin base material.
  • Such an underlayer may be formed of any material, but is preferably composed of a carbon-containing polymer.
  • the underlayer is preferably configured to include a carbon-containing polymer, for example, a curable resin.
  • a curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated.
  • the thermosetting resin etc. which are obtained by curing by the above method.
  • UV curable organic / inorganic hybrid hard coating material manufactured by JSR Corporation OPSTAR (registered trademark) series (polymerizable unsaturated group on silica fine particles) And a compound obtained by bonding an organic compound having a compound (a).
  • thermosetting materials specifically, TutProm series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid silicone manufactured by Adeka, manufactured by DIC Corporation Unidic (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistance epoxy resin), silicone resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd.
  • thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohi Phosphorus resins.
  • the smoothness of the underlayer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably in the range of 10 to 30 nm.
  • the surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of ⁇ m many times.
  • AFM Anamic Force Microscope
  • the thickness of the underlayer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • an anchor coat layer On the surface of the resin substrate according to the present invention, an anchor coat layer (anchor layer) may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion).
  • the anchor coat agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, and alkyl titanate. One type or two or more types can be used in combination.
  • a commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” 3% isopropyl alcohol solution) can be used.
  • the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 ⁇ m.
  • the gas barrier film of the present invention can further have a bleed-out preventing layer.
  • the bleed-out prevention layer is used for the purpose of suppressing the bleed-out phenomenon in which unreacted oligomers are transferred from the film base material to the surface when the film having the base layer is heated to contaminate the contact surface. It is provided on the opposite surface of the resin substrate having a (smooth) layer.
  • the bleed-out prevention layer may basically have the same configuration as the base (smooth) layer as long as it has this function.
  • Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule.
  • Hard coat agents such as unitary unsaturated organic compounds can be mentioned.
  • the thickness of the bleed-out prevention layer is in the range of 1 to 10 ⁇ m, preferably in the range of 2 to 7 ⁇ m.
  • the gas barrier film of the present invention can be used for various applications.
  • the ultraviolet curable resin layer is disposed adjacent to the exposed surface of the adhesive layer having an acryloyl group (unreacted acryloyl group is exposed). It is suitably used for the intended use.
  • the ultraviolet curable resin layer is not particularly limited as long as it is a layer made of a cured product of an ultraviolet curable resin, but as a function thereof, in addition to a protective layer for protecting the gas barrier layer, a quantum dot (phosphor) The function as a resin layer containing particle
  • the ultraviolet curable resin layer is a quantum dot layer
  • at least one gas barrier as shown in FIG. 3A described above is used.
  • the adhesive layer constituting the gas barrier film and the phosphor particle-containing layer are disposed adjacent to each other, or two gas barrier properties as shown in FIG. 3B
  • the film is used to constitute an optical film that is arranged so that the adhesive layer containing the compound containing each acryloyl group is adjacently adhered to both surfaces of the phosphor particle-containing layer.
  • optical film the structure of the optical film in which the gas barrier film of the present invention is used and the adhesive layer of the gas barrier film and the phosphor particle-containing layer are disposed adjacent to each other will be described.
  • phosphor particles according to the present invention various phosphor particles conventionally used in various modes of light-emitting devices can be used, but it is preferable to use particles that function as quantum dots. In particular, it is preferable to use semiconductor nanoparticles described later.
  • the main components such as quantum dots and resin will be described.
  • Quantum dot In general, phosphor particles that exhibit a quantum confinement effect with a semiconductor material of nanometer size are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.
  • quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.
  • the quantum dots contained in the quantum dot-containing layer according to the present invention may be known, and can be generated using any method known to those skilled in the art.
  • suitable quantum dots and methods for forming suitable quantum dots include US Pat. No. 6,225,198, US Patent Application Publication No. 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Pat. No. 2011/299299, US Pat. No. 6,861,155 Refer to the contents described in Japanese Patent Application Laid-Open No. 2012-133158, 2012-169460, 2014-078381, 2015-099636, 2015-103728, 2015-127362, etc. Can do.
  • the quantum dots according to the present invention are generated from an arbitrary material, preferably an inorganic material, more preferably an inorganic conductor or a semiconductor material.
  • Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.
  • Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4 , Ge 3 N 4 , Al 2 O 3 , (Al,
  • the following core / shell type quantum dots for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS, and the like can be preferably used.
  • Resin can be used for the quantum dot content layer concerning the present invention as a binder holding a quantum dot.
  • the following resins can be used.
  • Polycarbonate polyarylate, polysulfone (including polyethersulfone), polyethylene terephthalate, polyester such as polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate propionate , Cellulose esters such as cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether ketone imide, Examples thereof include polyamide resins, fluororesins, nylon resins, and acrylic resins such as polymethyl methacrylate.
  • the quantum dot-containing layer preferably has a thickness in the range of 50 to 200 ⁇ m.
  • the optimum amount of quantum dots in the quantum dot-containing layer varies depending on the compound used, but is generally preferably in the range of 15 to 60% by volume.
  • the gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, in this invention, the electronic device containing the gas barrier film of this invention and an electronic device main body can be provided.
  • Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and the sun. Examples thereof include a battery (PV), a QD film having quantum dots which are phosphor particles, and the like. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • Example 1 Production of gas barrier film >> [Preparation of gas barrier film 1] A gas barrier film 1 was produced according to the following method.
  • a polyethylene terephthalate (PET) film with a double-sided easy-adhesion layer having a thickness of 50 ⁇ m was used as the resin substrate (2).
  • the film forming conditions are: conveyance speed: 7 m / min, supply amount of source gas (hexamethyldisiloxane, abbreviation: HMDSO): 150 mL / min, supply amount of oxygen gas: 150 mL / min, degree of vacuum: 1.5 Pa, application A gas barrier layer (3, composition SiOx) having a film thickness of 150 nm was formed at an electric power of 4.5 kw.
  • source gas hexamethyldisiloxane, abbreviation: HMDSO
  • HMDSO hexamethyldisiloxane
  • oxygen gas 150 mL / min
  • degree of vacuum 1.5 Pa
  • application A gas barrier layer (3, composition SiOx) having a film thickness of 150 nm was formed at an electric power of 4.5 kw.
  • ⁇ Corona treatment> Using a corona treatment device (manufactured by Kasuga Denki Co., Ltd.), surface modification of the exposed surface of the gas barrier layer under the conditions of output: 300 W, electrode length: 240 mm, work electrode distance: 3.0 mm, transport speed: 4 m / min Treatment (corona treatment) was performed.
  • DPEHA dipentaerythritol hexaacrylate
  • Silica sol PGM-AC-2140Y disersion medium: propylene glycol monomethyl ether, average particle size: 10 to 15 nm, silica content: 42% by mass, manufactured by Nissan Chemical Industries, Ltd.
  • this adhesive layer forming coating solution 1 was applied onto the gas barrier layer with a bar coater so that the layer thickness after drying was 800 nm, and then dried at 80 ° C. for 1 minute as drying conditions. .
  • an ultraviolet irradiation treatment is performed with a high-pressure mercury lamp under an air atmosphere under the conditions of an illuminance of 500 mW / cm 2 and an irradiation energy amount of 200 mJ / cm 2 , thereby forming the adhesive layer 1 (4) of the first embodiment.
  • a gas barrier film 1 (1) was produced.
  • a gas barrier film 2 was produced in the same manner as in the production of the gas barrier film 1 except that the layer thickness of the adhesive layer 1 (4) was changed to 100 nm.
  • a gas barrier film 3 was produced in the same manner as in the production of the gas barrier film 1 except that the layer thickness of the adhesive layer 1 (4) was changed to 500 nm.
  • gas barrier film 4 In the production of the gas barrier film 1, the gas barrier film 4 was produced in the same manner except that the adhesive layer 4 (4) was formed according to the following method.
  • the adhesive layer 4 (4) was formed by a method in which the polymerization layer was removed from the adhesive layer 1 except for the polymerization initiator.
  • Formation of adhesive layer 4 As a compound containing acryloyl group, dipentaerythritol hexaacrylate, which is a polyfunctional acrylate compound, is diluted with butyl acetate to a solid content concentration of 5% by mass, and as a silicon atom-containing compound, PGM-AC-, which is an organosilica sol, is used. 2140Y (dispersion medium: propylene glycol monomethyl ether, average particle size: 10 to 15 nm, silica content: 42% by mass, manufactured by Nissan Chemical Industries, Ltd.) with respect to 100% by mass of the solid content of the compound containing the acryloyl group A coating solution 4 for forming an adhesive layer was prepared by adding 50% by mass.
  • gas barrier film 5 In the production of the gas barrier film 1, the gas barrier film 5 was produced in the same manner except that the adhesive layer 5 (4) was formed using the adhesive layer forming coating solution 5 prepared by the following method.
  • the equivalent of 50% by mass is added to 100% by mass of the solid content of the group-containing compound, and Irgacure 184 manufactured by BASF Japan Ltd. is further added as a polymerization initiator to 100% by mass of the compound solid content containing the acryloyl group.
  • an amount corresponding to 3.0% by mass is added, and the adhesive layer forming coating solution 5 is added. It was manufactured.
  • this adhesive layer forming coating solution 5 was used to coat the gas barrier layer with a bar coater so that the layer thickness after drying was 300 nm, and then dried at 80 ° C. for 1 minute as a drying condition.
  • an ultraviolet irradiation treatment was performed with a high-pressure mercury lamp under an air atmosphere under the conditions of an illuminance of 500 mW / cm 2 and an irradiation energy amount of 200 mJ / cm 2 to form an adhesive layer 5 (4).
  • gas barrier film 6 In production of the gas barrier film 1, a gas barrier film 6 was produced in the same manner except that the adhesive layer 6 (4) was formed using the adhesive layer forming coating solution 6 prepared by the following method.
  • the equivalent of 50% by mass to 100% by mass of Irgacure 184 manufactured by BASF Japan Ltd. as a polymerization initiator is equivalent to 3.0% by mass with respect to 100% by mass of the compound solid content containing the acryloyl group.
  • a coating solution 6 for forming an adhesive layer was prepared.
  • this adhesive layer forming coating solution 6 was used to apply a bar coater on the gas barrier layer so that the layer thickness after drying was 300 nm, followed by drying at 80 ° C. for 1 minute as drying conditions.
  • an ultraviolet irradiation process is performed with a high-pressure mercury lamp in an air atmosphere under the conditions of an illuminance of 500 mW / cm 2 and an irradiation energy amount of 200 mJ / cm 2 , thereby forming the adhesive layer 6 (4) of the first embodiment. did.
  • the coating liquid 6 for forming the adhesive layer used in the production of the gas barrier film 6 is further mixed with PGM-AC-2140Y (dispersion medium: propylene glycol monomethyl ether, average particle diameter: organosilica sol) as a silicon atom-containing compound. 10 to 15 nm, silica content: 42% by mass, manufactured by Nissan Chemical Industries, Ltd.) is added in an amount corresponding to 30% by mass with respect to 100% by mass of the solid content of the acryloyl group-containing compound. Liquid 7 was prepared.
  • the gas barrier film 6 In the production of the gas barrier film 6, a gas was formed in the same manner except that the adhesive layer 7 (4) was formed using the prepared adhesive layer forming coating solution 7 instead of the adhesive layer forming coating solution 6. A barrier film 7 was produced.
  • the coating liquid 7 for forming the adhesive layer was further mixed with HIL-2070 (manufactured by Seiko PMC) as an acrylic group-containing polymer (abbreviation: AP), and a solid compound containing an acryloyl group.
  • HIL-2070 manufactured by Seiko PMC
  • AP acrylic group-containing polymer
  • AP solid compound containing an acryloyl group.
  • the gas barrier property is the same except that the coating solution 8 for forming the adhesive layer is prepared by adding an amount corresponding to 100% by mass with respect to 100% by mass, and the adhesive layer 8 (4) is formed using the coating solution 8.
  • Film 8 was produced.
  • gas barrier film 9 In the production of the gas barrier film 8, the gas barrier film 9 was produced in the same manner except that the ultraviolet irradiation treatment was not performed with a high-pressure mercury lamp.
  • gas barrier film 11 In the production of the gas barrier film 6, X-12-1048 (abbreviated name: manufactured by Shin-Etsu Silicone Co., Ltd.) which is a terminal acrylic silane coupling agent polymer containing an acryloyl group and a silicon atom simultaneously from the coating liquid 6 for forming an adhesive layer. A gas barrier film 11 was prepared in the same manner except that ASCP) was changed and the thickness of the adhesive layer was changed to 10 nm.
  • a gas barrier film 12 was produced in the same manner as in the production of the gas barrier film 7 except that the layer thickness of the adhesive layer (4) was changed to 80 nm.
  • a gas barrier film 13 was produced in the same manner as in the production of the gas barrier film 7, except that the layer thickness of the adhesive layer (4) was changed to 1200 nm.
  • Table 1 shows the structure of each gas barrier film produced above.
  • the CdO solution was cooled to room temperature.
  • 8.0 g of trioctylphosphine oxide (TOPO) and 12.0 g of 1-heptadecyl-octadecylamine (HDA) were added, and the mixture was heated again to 150 ° C., and then TOP-Se stock was added thereto. The solution was added quickly.
  • TOPO trioctylphosphine oxide
  • HDA 1-heptadecyl-octadecylamine
  • the temperature of the chamber was heated to 220 ° C., and further increased to 250 ° C. over 120 minutes at a constant rate (0.25 ° C./min). Thereafter, the temperature was lowered to 100 ° C., zinc acetate dihydrate was added and dissolved by stirring, and then a trioctylphosphine solution of hexamethyldisilylthiane was dropped, and stirring was continued for several hours to complete the reaction. Phosphor particles (7) made of CdSe / ZnS were obtained.
  • the particle size of the phosphor particle component contained in the phosphor particles is adjusted so as to emit light in red and green, and further, the red and green components of the phosphor particles contained therein are 0.75 mg and 4.12 mg.
  • Irgacure 184 manufactured by BASF Japan
  • a UV curable resin adjusted to 95/5 was added to prepare phosphor particle-containing layer forming coating solution 1 with a phosphor particle content of 1.0 mass%.
  • the prepared phosphor particle-containing layer forming coating solution 1 is applied on the adhesive layer 1 (4A) constituting the gas barrier film 1 (1A) so that the dry layer thickness is 100 ⁇ m, and the coating solution is formed at 75 ° C. for 3 minutes.
  • the phosphor particle-containing layer (6) was formed by heating. However, the curing process by ultraviolet irradiation is not performed at this stage.
  • the number in a parenthesis is the code
  • optical films 102 to 113 In the production of the optical film 101, the produced gas barrier films 2 to 13 are used in place of the gas barrier film 1 used as the gas barrier film 1 (1A) and the gas barrier film 1 (1B). Optical films 102 to 113 were produced in the same manner except that
  • the water vapor permeability 2 is measured in the same manner, and the rate of decrease (percentage) of the water vapor permeability 2 with respect to the water vapor permeability 1 is measured.
  • the heat resistance was evaluated according to the following criteria.
  • Reduction rate of water vapor transmission rate is less than 5.0% 4: Reduction rate of water vapor transmission rate is 5.0% or more and less than 10% 3: Reduction rate of water vapor transmission rate is 10% Above, less than 20% 2: Reduction rate of water vapor transmission rate is 20% or more and less than 30% 1: Reduction rate of water vapor transmission rate is 30% or more ⁇ Evaluation of Optical Film >> [Durability: Evaluation of adhesion] Each optical film produced above was allowed to stand for 500 hours under high temperature and high humidity conditions (60 ° C., 90% RH), and then the adhesion between the adhesive layer and the phosphor particle layer in each optical film was evaluated.
  • Each optical film was cut into a width of 50 mm and a length of 200 mm, and then the peel force was measured using a tensile tester specified in JIS B 7721. About the edge part of each optical film, after peeling the adhesive layer and the phosphor particle layer, each is sandwiched in a tensile tester, and it is required to peel off from the edge part peeled off at a pulling speed of 300 m / min in the 180 ° direction. The force was measured, and the adhesion was evaluated in five stages based on the following criteria.
  • each optical film subjected to forced deterioration treatment under the above-described high-temperature and high-humidity conditions 60 ° C., 90% RH is placed on a blue LED that emits light at 450 nm, respectively.
  • MS-804 manufactured by MS-804, lens MP-ZE25-200
  • the width of the region that does not emit light in the end region of the optical film was randomly measured at six points, and the average value was calculated.
  • the growth rate of the non-light-emitting region of the sample by forced degradation treatment was measured for the sample immediately after fabrication, and side leak resistance was evaluated according to the following criteria.
  • the gas barrier film of the present invention having an adhesive layer containing a compound containing an acryloyl group and a compound containing a silicon atom and having a layer thickness in the range of 100 to 1000 nm.
  • the optical film having a gas barrier layer excellent in heat resistance and having a phosphor particle-containing layer using the same has an adhesive property after being stored in a high-temperature and high-humidity environment with respect to the comparative example. It can also be seen that it has excellent side leak resistance.
  • Example 2 Production of optical film >> Optical films 201 to 216 were produced according to the following method.
  • the numerical values described in parentheses after each component are the reference numbers described in FIGS. 5A and 5B, respectively.
  • Optical film 201 was produced according to the following method [Production of gas barrier film 51] (Preparation of resin base material (102A)) A polyethylene terephthalate (PET) film with a double-sided easy-adhesion layer having a thickness of 50 ⁇ m (manufactured by Teijin DuPont Films Ltd., KEL86W) was used as the resin substrate (102A).
  • PET polyethylene terephthalate
  • Formation of gas barrier layer (103A) vacuum plasma CVD method
  • the film forming conditions are as follows: transfer speed 7 m / min, source gas (hexamethyldisiloxane, HMDSO) supply amount 150 mL / min, oxygen gas supply amount 150 mL / min, vacuum degree 1.5 Pa, applied power 4.5 kW, A gas barrier layer (composition SiO x ) having a thickness of 150 nm was formed.
  • source gas hexamethyldisiloxane, HMDSO
  • ⁇ Corona treatment> Using a corona treatment device (manufactured by Kasuga Denki Co., Ltd.), surface modification treatment of the exposed surface of the gas barrier layer 51 (corona) under the conditions of an output of 300 W, an electrode length of 240 mm, a work electrode distance of 3.0 mm, and a conveying speed of 4 m / min. Treatment).
  • DPEHA dipentaerythritol hexaacrylate
  • 106A inorganic fine particles
  • TTO-55 (A) titanium oxide, sintering method, rutile crystal, surface treatment: Al (OH) 3 , average primary particle size: 45 nm
  • the phosphor particle-containing layer (108) is formed on the gas barrier film 51 (101A), and the surface thereof is sealed with the gas barrier film 51 (101B), which is shown in FIG. 5B.
  • An optical film 201 (F) having the following structure was produced.
  • TOPO trioctylphosphine oxide
  • HDA 1-heptadecyl-octadecylamine
  • the temperature of the chamber was heated to 220 ° C., and further increased to 250 ° C. over 120 minutes at a constant rate (0.25 ° C./min). Thereafter, the temperature was lowered to 100 ° C., zinc acetate dihydrate was added and dissolved by stirring, and then a trioctylphosphine solution of hexamethyldisilylthiane was dropped, and stirring was continued for several hours to complete the reaction.
  • Phosphor particles (109) made of CdSe / ZnS were obtained.
  • ⁇ Preparation of phosphor particle layer forming coating solution 51> The particle size of the phosphor particle component contained in the phosphor particles is adjusted so as to emit light in red and green, and further, the red and green components of the phosphor particles contained therein are 0.75 mg and 4.12 mg. Dispersed in a toluene solvent, and further, a photopolymerization initiator Irgacure 184 (manufactured by BASF Japan) was added as a resin component (110) to UV curable resin Unidic V-5500 manufactured by Epoxy Acrylate DIC Co., Ltd. %)) was added to the resin / initiator: 95/5 to prepare a phosphor particle layer forming coating solution 51 having a phosphor particle content of 1.0 mass%.
  • ⁇ Coating of phosphor particle layer forming coating solution 51 The prepared phosphor particle layer forming coating solution 51 is applied on the adhesive layer 51 (104A) constituting the gas barrier film 51 (101A described in FIG. 5B) so that the dry layer thickness is 1000 ⁇ m, The phosphor particle layer (108) was formed by heating at 75 ° C. for 3 minutes. However, the curing process by ultraviolet irradiation is not performed at this stage.
  • optical film 202 In the production of the optical film 201, an optical film 202 was produced in the same manner except that the gas barrier film 52 produced by the following method was used instead of the gas barrier film 51.
  • gas barrier film 52 In the production of the gas barrier film 51, a gas barrier film 52 was produced in the same manner except that the adhesive layer 52 having the following constitution was used instead of the adhesive layer 51.
  • DPEHA dipentaerythritol hexaacrylate
  • PGM-AC-4130Y sica particles, dispersion medium: propylene glycol monomethyl ether, average primary particle size: 45 nm, silica content: 30% by mass
  • 1% polymethyl methacrylate fine particles (average primary particle size: 800 nm) are added as organic fine particles (107A) to 100% of the solid content of the acryloyl group-containing compound, and BASF Japan Ltd. is further used as a polymerization initiator.
  • Irgacure 184 made from acryloyl group 3% was added relative to 100% solids containing compound, to prepare a bonding layer-forming coating liquid 52.
  • this adhesive layer forming coating solution 52 was applied onto the gas barrier layer with a bar coater so that the layer thickness after drying was 800 nm, and then dried at 80 ° C. for 1 minute as drying conditions.
  • an ultraviolet irradiation treatment is performed with a high-pressure mercury lamp under an air atmosphere under the conditions of an illuminance of 500 mW / cm 2 and an irradiation energy amount of 200 mJ / cm 2 , thereby forming an adhesive layer 52 (104A) and gas barrier properties.
  • Film 52 (101A) was produced.
  • optical film 203 In the production of the optical film 202, an optical film 203 was produced in the same manner except that the gas barrier film 53 produced by the following method was used instead of the gas barrier film 52.
  • a gas barrier film 53 was produced in the same manner as in the production of the gas barrier film 52 except that the thickness of the adhesive layer 52 was changed to 500 nm.
  • optical film 204 In the production of the optical film 203, an optical film 204 was produced in the same manner except that the gas barrier film 54 produced by the following method was used instead of the gas barrier film 53.
  • gas barrier film 54 In the production of the gas barrier film 53, a gas barrier film 54 was produced in the same manner except that the adhesive layer 54 having the following constitution was used instead of the adhesive layer 53.
  • a binder component (105A) As a binder component (105A), inorganic fine particles were added to a solution obtained by diluting X-12-1048 (abbreviation: ASCP) manufactured by Shin-Etsu Silicone Co., Ltd., which is a polymer type silane coupling agent, with butyl acetate to a solid content concentration of 5% by mass.
  • ASCP diluting X-12-1048
  • PGM-AC-4130Y (dispersion medium: propylene glycol monomethyl ether, average primary particle size: 45 nm, silica content: 30 mass%) is used as a solid content of the above polymer type silane coupling agent (ASCP) 100
  • ASCP polymer type silane coupling agent
  • An amount equivalent to 80% by mass is added to mass%, and polymethyl methacrylate fine particles (average primary particle size: 800 nm) are added as organic fine particles (107A) to a solid content of a polymer type silane coupling agent (ASCP) 100.
  • the solid content 100 wt% of the polymer type of the silane coupling agent (ASCP) was added 3.0 wt% equivalent amount to prepare an adhesive layer coating solution 54.
  • the adhesive layer forming coating solution 54 prepared above was applied on the gas barrier layer (103A) with a bar coater so that the layer thickness after drying was 500 nm, and then dried at 80 ° C. for 1 minute. Drying was performed.
  • an ultraviolet ray irradiation treatment is performed with a high-pressure mercury lamp under an air atmosphere under the conditions of an illuminance of 500 mW / cm 2 and an irradiation energy amount of 200 mJ / cm 2 , thereby forming an adhesive layer 54 (104A), and gas barrier properties Film 54 (101A) was produced.
  • optical film 205 In the production of the optical film 204, an optical film 205 was produced in the same manner except that the gas barrier film 55 (101A) produced by the following method was used in place of the gas barrier film 54.
  • a gas barrier film 55 was produced in the same manner as in the production of the gas barrier film 54 except that an adhesive layer 55 having the following configuration was used instead of the adhesive layer 54.
  • a binder component (105A) As a binder component (105A), a polymer type silane coupling agent X-12-1048 (abbreviation: ASCP) manufactured by Shin-Etsu Silicone Co., Ltd. was diluted with butyl acetate to a solid content concentration of 5.0% by mass, Furthermore, as the second binder component, a silane coupling agent monomer (abbreviation: SCM), an acryloyl group-containing silane coupling agent KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone) is used as a polymer type.
  • SCM silane coupling agent monomer
  • KBM-5103 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone
  • An amount equivalent to 10.0% by mass is added to 100% by mass of the solid content of the silane coupling agent (ASCP), and then PGM-AC-4130Y (dispersion medium: propylene glycol monomethyl ether, as inorganic fine particles (106A), Average primary particle size: 45 nm, silica content: 30% by mass)
  • the polymer type silane coupling agent (ASCP) is added in an amount equivalent to 80% by mass with respect to 100% by mass of the solid content, and polymethyl methacrylate fine particles (average primary particle size: 800 nm) are polymerized as organic fine particles (107A).
  • a coating solution 55 for forming an adhesive layer was prepared by adding an amount equivalent to 3.0% by mass with respect to 100% by mass of ASCP).
  • optical film 206 In the production of the optical film 205, an optical film 206 was produced in the same manner except that the gas barrier film 56 produced by the following method was used in place of the gas barrier film 55.
  • gas barrier film 56 In the production of the gas barrier film 55, HIL-2070 manufactured by Seiko PMC Co., Ltd. was used as a polymer type silane coupling agent as an acryloyl group-containing polymer (abbreviation: AP) for the coating solution 55 for forming an adhesive layer.
  • AP acryloyl group-containing polymer
  • a gas barrier was prepared in the same manner except that an adhesive layer-forming coating solution 56 was prepared by adding an equivalent amount of 10% by mass to (ASCP) solid content of 100% by mass, and the adhesive layer 56 was formed using the same. Film 56 was produced.
  • optical film 207 In the production of the optical film 206, an optical film 107 was produced in the same manner except that the gas barrier film 57 produced by the following method was used instead of the gas barrier film 56.
  • gas barrier film 57 In the production of the gas barrier film 56, the inorganic fine particles (SiO 2 , average primary particle size: 45 nm) used for the preparation of the coating liquid 56 for forming the adhesive layer were changed to silica particles having an average primary particle size of 30 nm. A gas barrier film 57 was prepared in the same manner except that the adhesive layer 57 was formed using the adhesive layer forming coating solution 57 prepared in the same manner.
  • optical film 208 In the production of the optical film 206, an optical film 208 was produced in the same manner except that the gas barrier film 58 produced by the following method was used instead of the gas barrier film 56.
  • gas barrier film 58 Preparation of gas barrier film 58
  • the inorganic fine particles (SiO 2 , average primary particle size: 45 nm) used for the preparation of the coating liquid 56 for forming the adhesive layer were changed to silica particles having an average primary particle size of 90 nm.
  • a gas barrier film 58 was produced in the same manner except that the adhesive layer 58 was formed using the prepared adhesive layer forming coating solution 58.
  • optical film 209 In the production of the optical film 206, an optical film 209 was produced in the same manner except that the gas barrier film 59 produced by the following method was used instead of the gas barrier film 56.
  • the organic fine particles (PMMA, average primary particle size: 800 nm) used for the preparation of the coating liquid 56 for forming the adhesive layer are changed to PMMA particles having an average primary particle size of 300 nm.
  • a gas barrier film 59 was produced in the same manner except that the adhesive layer forming coating solution 59 was used and the layer thickness was further changed to 200 nm to form the adhesive layer 59.
  • optical film 210 In the production of the optical film 206, an optical film 210 was produced in the same manner except that the gas barrier film 60 produced by the following method was used instead of the gas barrier film 56.
  • the organic fine particles (PMMA, average primary particle size: 800 nm) used for the preparation of the coating liquid 56 for forming the adhesive layer are changed to PMMA particles having an average primary particle size of 1000 nm.
  • the gas barrier film 60 was produced in the same manner except that the adhesive layer forming coating solution 60 was used and the adhesive layer 60 was formed by changing the layer thickness to 600 nm.
  • optical film 211 In the production of the optical film 206, an optical film 211 was produced in the same manner except that the gas barrier film 61 produced by the following method was used instead of the gas barrier film 56.
  • the adhesive layer 61 was formed using the adhesive layer forming coating solution 61 prepared by removing the organic fine particles (PMMA) used for the preparation of the adhesive layer forming coating solution 56. Similarly, a gas barrier film 61 was produced.
  • optical film 212 In the production of the optical film 206, an optical film 212 was produced in the same manner except that the gas barrier film 62 produced by the following method was used instead of the gas barrier film 56.
  • the adhesive layer 62 was formed using the adhesive layer forming coating liquid 62 prepared by removing the inorganic fine particles (silica particles) used for the preparation of the adhesive layer forming coating liquid 56. In the same manner, a gas barrier film 62 was produced.
  • optical film 213 In the production of the optical film 211, an optical film 213 was produced in the same manner except that the gas barrier film 63 produced by the following method was used instead of the gas barrier film 61.
  • the adhesive layer 63 was formed using the adhesive layer forming coating solution 63 prepared by further removing the inorganic fine particles (silica particles) used in the preparation of the adhesive layer forming coating solution 61. Except for this, a gas barrier film 63 was produced in the same manner.
  • optical film 214 In the production of the optical film 206, an optical film 214 was produced in the same manner except that the gas barrier film 64 produced by the following method was used instead of the gas barrier film 56.
  • the inorganic fine particles (average primary particle size: 45 nm) used for the preparation of the coating solution 56 for forming the adhesive layer were converted to silica particles (organosilica sol, PGM-AC) having an average primary particle size of 15 nm.
  • -2140Y disersion medium: propylene glycol monomethyl ether, average particle size: 15 nm, manufactured by Nissan Chemical Industries, Ltd.
  • a gas barrier film 64 was produced.
  • optical film 215 In the production of the optical film 214, an optical film 215 was produced in the same manner except that the gas barrier film 65 produced by the following method was used instead of the gas barrier film 64.
  • gas barrier film 65 In the production of the gas barrier film 64, the organic fine particles (PMMA, average primary particle size: 800 nm) used for the preparation of the coating liquid 64 for forming the adhesive layer are changed to PMMA particles having an average primary particle size of 200 nm.
  • a gas barrier film 65 was produced in the same manner except that the adhesive layer forming coating liquid 65 was used and the adhesive layer 65 having a layer thickness of 300 nm was formed.
  • optical film 216 In the production of the optical film 206, an optical film 216 was produced in the same manner except that the gas barrier film 66 produced by the following method was used instead of the gas barrier film 56.
  • gas barrier film 66 In the production of the gas barrier film 56, the organic fine particles (PMMA, average primary particle size: 800 nm) used for the preparation of the coating liquid 56 for forming the adhesive layer are changed to PMMA particles having an average primary particle size of 100 nm.
  • a gas barrier film 66 was produced in the same manner except that the adhesive layer forming coating solution 66 was used and the adhesive layer 66 having a layer thickness of 300 nm was formed.
  • Table 3 shows the configuration of each optical film produced above.
  • Relative luminous efficiency is 115 or more 4: Relative luminous efficiency is 105 or more and less than 115 3: Relative luminous efficiency is 95 or more and less than 105 2: Relative luminous efficiency is 85 or more, 95 Less than 1: The relative luminous efficiency is less than 85 Table 4 shows the evaluation results obtained as described above.
  • the optical film provided with the gas barrier film having the structure defined in the present invention has an adhesive property after being stored in a high-temperature and high-humidity environment with respect to the comparative example, and It turns out that it is excellent in luminous efficiency.
  • a gas barrier film having high gas barrier properties and heat resistance, and the gas barrier film, adhesion with a phosphor particle-containing layer in a high temperature and high humidity environment, and side leak resistance The phosphor film-containing optical film having excellent luminous efficiency and light emission efficiency can be provided, and the optical film provided with the gas barrier film of the present invention includes an organic electroluminescence element (organic EL element) and a liquid crystal display element. (LCD), thin film transistor, touch panel, electronic paper, solar cell (PV), QD film having quantum dots that are phosphor particles, and the like.

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Abstract

La présente invention a pour but de fournir : un film barrière contre les gaz ayant des propriétés élevées de barrière contre les gaz et une résistance à la chaleur élevée ; un film optique, contenant des particules de phosphore, qui utilise ce film barrière contre les gaz et qui présente d'excellentes caractéristiques en termes de résistance aux fuites latérales et d'adhérence à une couche contenant des particules de phosphore dans un environnement à humidité élevée à haute température. Un film barrière contre les gaz selon la présente invention est caractérisé en ce qu'il comprend, sur une base de résine, une couche barrière contre les gaz et une couche de liaison dans cet ordre, et en ce que : la couche barrière contre les gaz contient un oxyde inorganique contenant au moins un atome de silicium ; la couche de liaison contient un composé contenant au moins un groupe acryloyle et un composé contenant un atome de silicium ; l'épaisseur de la couche de liaison se situe dans la plage allant de 100 à 1 000 nm.
PCT/JP2016/072272 2015-08-21 2016-07-29 Film barrière contre les gaz, son procédé de fabrication et film optique Ceased WO2017033665A1 (fr)

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JP2018013724A (ja) * 2016-07-22 2018-01-25 大日本印刷株式会社 波長変換シート及びそれに用いられるバリアフィルム
CN108594356A (zh) * 2018-05-08 2018-09-28 厦门佰亨源量子光电科技有限公司 一种水性量子点微晶导光板及其制备方法
JP2020071481A (ja) * 2018-10-29 2020-05-07 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 光学部材及びそれを包含するディスプレイ装置
CN111423611A (zh) * 2019-01-08 2020-07-17 颖华科技股份有限公司 高分子塑料前面板及其制法
JP2021165852A (ja) * 2020-06-29 2021-10-14 大日本印刷株式会社 波長変換シート及びそれに用いられるバリアフィルム
WO2024135958A1 (fr) * 2022-12-21 2024-06-27 이근수 Film stratifié pour module solaire ayant d'excellentes propriétés de refroidissement par rayonnement, et module solaire le comprenant

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JP2015008266A (ja) * 2013-05-31 2015-01-15 三菱樹脂株式会社 蛍光体含有シリコーンシートの製造方法
WO2015037733A1 (fr) * 2013-09-13 2015-03-19 凸版印刷株式会社 Feuille de conversion de longueur d'onde et unité de rétroéclairage
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JP2018013724A (ja) * 2016-07-22 2018-01-25 大日本印刷株式会社 波長変換シート及びそれに用いられるバリアフィルム
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JP2020071481A (ja) * 2018-10-29 2020-05-07 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 光学部材及びそれを包含するディスプレイ装置
JP7423252B2 (ja) 2018-10-29 2024-01-29 三星ディスプレイ株式會社 光学部材及びそれを包含するディスプレイ装置
CN111423611A (zh) * 2019-01-08 2020-07-17 颖华科技股份有限公司 高分子塑料前面板及其制法
JP2020113237A (ja) * 2019-01-08 2020-07-27 穎華科技股▲ふん▼有限公司 ポリマープラスチックフロントパネルとその製法
JP2021165852A (ja) * 2020-06-29 2021-10-14 大日本印刷株式会社 波長変換シート及びそれに用いられるバリアフィルム
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WO2024135958A1 (fr) * 2022-12-21 2024-06-27 이근수 Film stratifié pour module solaire ayant d'excellentes propriétés de refroidissement par rayonnement, et module solaire le comprenant
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