WO2017104332A1 - Film barrière de gaz - Google Patents

Film barrière de gaz Download PDF

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Publication number
WO2017104332A1
WO2017104332A1 PCT/JP2016/083809 JP2016083809W WO2017104332A1 WO 2017104332 A1 WO2017104332 A1 WO 2017104332A1 JP 2016083809 W JP2016083809 W JP 2016083809W WO 2017104332 A1 WO2017104332 A1 WO 2017104332A1
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Prior art keywords
layer
gas barrier
formation
barrier film
organic layer
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English (en)
Japanese (ja)
Inventor
俊平 一色
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2017556428A priority Critical patent/JP6720985B2/ja
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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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers

Definitions

  • the present invention relates to a gas barrier film.
  • the present invention relates to a gas barrier film excellent in interlayer adhesion between an organic layer and a gas barrier layer.
  • a gas barrier film in which a gas barrier layer made of an inorganic layer and an organic layer are laminated on a base material.
  • the gas barrier film is manufactured, for example, by forming an organic layer on a support by coating, and forming a gas barrier layer on the support by vapor phase film formation, thereby maintaining the smoothness of the base as it is.
  • a gas barrier film having a uniform gas barrier layer can be produced.
  • it can be set as a higher performance gas barrier film by repeatedly laminating
  • the gas barrier film having the above configuration has a problem that the interface between the gas barrier layer and the organic layer formed on the gas barrier layer is likely to be peeled off due to mechanical stress.
  • a method of adding an acrylate monomer or a methacrylate monomer having a phosphate ester as the polymerizable composition to the organic layer can be considered, but sufficient adhesion can be obtained.
  • the organic layer formed on the gas barrier layer of the gas barrier film contains a silane coupling agent having a specific structure so that the interlayer adhesion between the organic layer and the gas barrier layer can be improved.
  • a silane coupling agent having a specific structure so that the interlayer adhesion between the organic layer and the gas barrier layer can be improved.
  • the technique which improves both gas barrier property is proposed (for example, refer patent document 1).
  • the interlayer adhesion is not sufficient depending on the use of the gas barrier film, and a higher interlayer adhesion is required.
  • the present invention has been made in view of the above-mentioned problems and situations, and the solution is to provide a gas barrier film excellent in interlayer adhesion between a gas barrier layer and an organic layer formed on the gas barrier layer. Is to provide.
  • a gas barrier film in which at least three organic layers and gas barrier layers are alternately laminated on a substrate,
  • the organic layer formed on the surface of the gas barrier layer opposite to the base contains a polymerizable compound and a polymer of at least one of an organosilicon compound and an organophosphorus compound, and the gas barrier layer , Containing a group 12-14 metal (M1) and a transition metal (M2) and having a region satisfying a predetermined composition in the layer thickness direction, it has excellent interlayer adhesion between the organic layer and the gas barrier layer.
  • a gas barrier film in which at least three layers of organic layers and gas barrier layers are alternately laminated on a substrate,
  • the organic layer formed on the surface of the gas barrier layer opposite to the base contains a polymerizable compound and a polymer of at least one of an organosilicon compound and an organophosphorus compound,
  • the gas barrier layer contains a group 12-14 metal (M1) and a transition metal (M2), and in the layer thickness direction, (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, A gas barrier film having a region satisfying 0 ⁇ y and 0 ⁇ z).
  • the (M1) (M2) x O y N z further satisfies 0.1 ⁇ x in the layer thickness direction on the surface of the organic layer formed on the surface of the gas barrier layer opposite to the base. 3.
  • the metal (M1) is silicon (Si),
  • the transition metal (M2) is a metal selected from the group consisting of niobium (Nb), tantalum (Ta), and vanadium (V), any one of items 1 to 4
  • Item 6 The gas according to any one of Items 1 to 5, wherein the organosilicon compound contains a compound having an NR group (R represents a hydrogen atom or an alkyl group). Barrier film.
  • the said organic phosphorus compound contains phosphoric acid (meth) acrylate,
  • the gas barrier film as described in any one of Claim 1-6 characterized by the above-mentioned.
  • a represents the maximum valence of the metal (M1)
  • b represents the maximum valence of the transition metal (M2).
  • the gas barrier film excellent in the interlayer adhesiveness of a gas barrier layer and the organic layer formed on the said gas barrier layer can be provided.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the organic layer formed on the surface of the gas barrier layer opposite to the base material contains an organosilicon compound or an organophosphorus compound
  • the organosilicon compound or organophosphorus compound silicon (Si) And phosphorus (P) form a bonding state with the group 12-14 metal (M1) and transition metal (M2) contained in the gas barrier layer, so that the interlayer adhesion between the organic layer and the gas barrier layer I think that improved.
  • the gas barrier layer to have a region that satisfies (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49,0 ⁇ y, 0 ⁇ z), the interlayer adhesion between the organic layer We think that we can show superior gas barrier property while raising.
  • Sectional drawing which shows an example of schematic structure of the gas barrier film of this invention
  • Sectional drawing which shows an example of schematic structure of the gas barrier film of this invention
  • the gas barrier film of the present invention is a gas barrier film in which at least three organic layers and gas barrier layers are alternately laminated on a base material, and the surface of the gas barrier layer opposite to the base material.
  • the organic layer formed on the surface contains a polymer of a polymerizable compound and at least one of an organosilicon compound and an organophosphorus compound, and the gas barrier layer comprises a group 12-14 metal (M1) and a transition metal. (M2) containing a, and having a region satisfying the thickness direction (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49,0 ⁇ y, 0 ⁇ z) .
  • This feature is a technical feature common to or corresponding to the claims 1 to 8.
  • the transition metal (M2) is contained on the surface of the gas barrier layer on the side of the organic layer formed on the surface opposite to the base material.
  • the (M1) (M2) x O y N z is further 0 in the layer thickness direction on the surface of the organic layer side formed on the surface of the gas barrier layer opposite to the base material. More preferably, it has a region satisfying 1 ⁇ x.
  • the metal (M1) is preferably silicon (Si), and the gas barrier layer preferably contains at least one of silicon oxide and silicon nitride. Thereby, gas barrier property can further be improved.
  • the transition metal (M2) is preferably a metal selected from the group consisting of niobium (Nb), tantalum (Ta), and vanadium (V).
  • the organosilicon compound preferably contains a compound having an NR group (R represents a hydrogen atom or an alkyl group).
  • R represents a hydrogen atom or an alkyl group.
  • the said organic phosphorus compound contains phosphoric acid (meth) acrylate.
  • the gas barrier layer preferably has a region satisfying the (M1) (M2) x O y N z is further the formula (A) in the layer thickness direction. Thereby, the interlayer adhesion between the organic layer and the gas barrier layer and the gas barrier property can be further improved.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • ⁇ Gas barrier film ⁇ In the gas barrier film of the present invention, at least three organic layers and gas barrier layers are alternately laminated on a base material, and the organic layer formed on the surface of the gas barrier layer opposite to the base material is polymerized.
  • M1 (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 ⁇ y, 0 ⁇ z).
  • the gas barrier film 1 of the present invention is formed by alternately laminating two organic layers 3 and two gas barrier layers 4 on a base material 2. Further, the gas barrier layer 4 is configured by laminating a metal (M1) -containing layer 5 and a transition metal (M2) -containing layer 6 in this order from the base material 2 side.
  • M1 metal
  • M2 transition metal
  • the gas barrier layer 4 of the gas barrier film 1 is constituted by a single layer, and the single-layer gas barrier layer 4 contains a metal (M1) and a transition metal (M2).
  • the organic layer 3 and the gas barrier layer 4 provided on the substrate 2 are laminated in this order, but the total of the organic layer 3 and the gas barrier layer 4 is the same.
  • the number of layers may be three or more.
  • two organic layers 3 and one gas barrier layer 4 may be alternately laminated on the substrate 2, or three organic layers 3 and two gas barrier layers 4. And may be alternately stacked.
  • the organic layer 3 shall be arrange
  • the gas barrier layer 4 shall be arrange
  • the base material according to the present invention is not particularly limited as long as it can hold an organic layer, a gas barrier layer, and the like.
  • a resin substrate plastic film or sheet
  • a film or sheet made of a colorless and transparent resin is preferably used as the substrate.
  • the resin substrate used is not particularly limited in material, thickness, and the like, and can be appropriately selected according to the purpose of use.
  • the resin base material examples include poly (meth) acrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene ( PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyethersulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resins Film, heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) with silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a tree formed by laminating two or more layers of the above resin Mention may be made of the film, and the like.
  • PVC polyvinyl chloride
  • PE PE
  • PP polypropy
  • the thickness of the substrate is not particularly limited, but is preferably in the range of 5 to 300 ⁇ m, and more preferably in the range of 10 to 100 ⁇ m.
  • the substrate may have a functional layer such as a transparent conductive layer, a primer layer, or a clear hard coat layer.
  • a functional layer such as a transparent conductive layer, a primer layer, or a clear hard coat layer.
  • the functional layer those described in paragraphs 0036 to 0038 of JP-A-2006-289627 can be preferably used.
  • the base material according to the present invention is preferably transparent. Since the base material is transparent and the layer formed on the base material is also transparent, a transparent gas barrier film can be obtained.
  • a transparent substrate such as an organic EL element can be used. Become.
  • the substrate preferably has a 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 substrate, at least the side on which the organic layer and the gas barrier layer are provided, may be polished to improve smoothness.
  • various known treatments for improving adhesion for example, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, and lamination of a smooth layer to be described later Etc. may be performed, and it is preferable to combine the above-described processes as necessary.
  • the organic layer formed on the surface opposite to the base of the gas barrier layer contains a polymer of a polymerizable compound and at least one of an organosilicon compound and an organophosphorus compound.
  • the organosilicon compound preferably contains a compound having an N—R group (R represents a hydrogen atom or an alkyl group), and the organophosphorus compound preferably contains phosphoric acid (meth) acrylate.
  • the base of the gas barrier layer (the gas barrier layer when only one gas barrier layer is provided) disposed at the position closest to the substrate.
  • the organic layer formed on the surface on the material side only needs to be configured to contain a known organic material, and may contain a polymer composed only of the polymerizable compound, and the polymerizable compound and In addition, a polymer with at least one of the organosilicon compound and the organophosphorus compound may be contained.
  • Examples of the method for forming the organic layer include a method in which a polymerizable composition containing the above materials and a polymerization initiator is layered and then cured.
  • the layered polymerizable composition can be usually formed by applying the polymerizable composition on a substrate or a gas barrier layer.
  • a coating method a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294 is used.
  • Extrusion coating method and the like are exemplified, and among these, the extrusion coating method can be preferably employed.
  • a polymerizable composition containing at least one of a polymerizable compound, an organosilicon compound, and an organophosphorus compound, a polymerization initiator, and the like is cured with light (for example, ultraviolet rays), an electron beam, or a heat ray. However, it is preferably cured by light. In particular, it is preferable to cure the polymerizable composition after heating it at a temperature of 25 ° C. or higher (eg, 30 to 130 ° C.).
  • a silane coupling agent when used as the organosilicon compound, the hydrolysis reaction of the silane coupling agent proceeds to effectively cure the polymerizable composition, and the substrate It is possible to form a film without damaging or the like.
  • a polymer of a polymerizable compound and at least one of an organosilicon compound and an organophosphorus compound can be formed in the organic layer by such a curing treatment.
  • ultraviolet rays from a high pressure mercury lamp or a low pressure mercury lamp can be usually used.
  • the radiation energy is preferably 0.1 J / cm 2 or more, 0.5 J / cm 2 or more is more preferable.
  • a (meth) acrylate compound is employed as the polymerizable compound, it is preferably inhibited by oxygen concentration or oxygen partial pressure during the polymerization because it is inhibited by oxygen in the air.
  • the oxygen concentration at the time of polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% by volume or less, and more preferably 0.5% by volume or less.
  • the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm 2 or more under a reduced pressure condition of 100 Pa or less.
  • the organic layer in the present invention is preferably smooth and high in hardness.
  • the smoothness of the organic layer is preferably less than 1 nm as average roughness (Ra value) of 1 ⁇ m square, and more preferably less than 0.5 nm.
  • the polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more.
  • the polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture.
  • the polymerization rate can be quantified by an infrared absorption method.
  • the layer thickness of the organic layer is not particularly limited, but if it is too thin, it will be difficult to obtain uniformity of the layer thickness, and if it is too thick, cracks will be generated due to external force and gas barrier properties will be reduced. From this viewpoint, the thickness of the organic layer is preferably 50 to 2000 nm, more preferably 200 to 1500 nm.
  • the surface of the organic layer is required to be free from foreign matters such as particles and protrusions. For this reason, it is preferable that the organic layer is formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less. It is preferable that the organic layer has a high hardness.
  • the hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method.
  • the microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.
  • the polymerizable compound used in the present invention is preferably at least one of a compound having an ethylenically unsaturated bond at the terminal or side chain and a compound having an epoxy or oxetane at the terminal or side chain.
  • a compound having an ethylenically unsaturated bond at the terminal or side chain are preferred.
  • the compound having an ethylenically unsaturated bond at the terminal or side chain include a (meth) acrylate compound, an acrylamide compound, a styrene compound, maleic anhydride and the like, and a (meth) acrylate compound is preferable.
  • (meth) acrylate compound As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
  • styrene compound styrene, ⁇ -methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.
  • a methacrylate compound represented by the following general formula (1) can also be preferably employed.
  • R represents a substituent, and may be the same or different.
  • N represents an integer of 0 to 5, and may be the same or different. However, at least one of R contains a polymerizable group.
  • R examples include —CR 2 2 — (R 2 represents a hydrogen atom or a substituent), —CO—, —O—, a phenylene group, —S—, —C ⁇ C—, One or more of —NR 3 — (R 3 represents a hydrogen atom or a substituent), —CR 4 ⁇ CR 5 — (R 4 and R 5 each represent a hydrogen atom or a substituent), and polymerizable A group consisting of a combination with a group, one or more of —CR 2 2 — (R 2 represents a hydrogen atom or a substituent), —CO—, —O— and a phenylene group, a polymerizable group, A group consisting of a combination of R 2 represents a hydrogen atom or a substituent, and is preferably a hydrogen atom or a hydroxy group.
  • At least one of R includes a hydroxy group. Inclusion of a hydroxy group improves the curing rate of the organic layer.
  • the molecular weight of at least one R is preferably 10 to 250, more preferably 70 to 150.
  • the position where R is bonded is preferably bonded to the para position of the benzene ring of the general formula (1).
  • n represents an integer of 0 to 5, but is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.
  • the compound represented by the general formula (1) it is preferable that at least two of R have the same structure. Further, it is more preferable that all of n are 1 and at least two of the four Rs have the same structure, and it is further preferable that all of n are 1 and all of the four R have the same structure. .
  • a polymeric group which the compound represented by General formula (1) has it is preferable that it is a (meth) acryloyl group or an epoxy group, and it is more preferable that it is a (meth) acryloyl group.
  • the number of polymerizable groups contained in the compound represented by the general formula (1) is preferably 2 or more, and more preferably 3 or more.
  • the upper limit is not particularly defined, but is preferably 8 or less, and more preferably 6 or less.
  • the molecular weight of the compound represented by the general formula (1) is preferably 600 to 1400, and more preferably 800 to 1200.
  • the organic layer may contain only one type of compound represented by the general formula (1), or may contain two or more types. When two or more types are included, for example, compounds containing R having the same structure and different numbers of R and isomers thereof are exemplified.
  • the compound represented by the general formula (1) can be obtained as a commercial product.
  • the said compound is also compoundable by a well-known method.
  • epoxy acrylate can be obtained by reaction of an epoxy compound and acrylic acid. These compounds usually generate bifunctional, trifunctional, pentafunctional and isomers thereof during the reaction. When it is desired to separate these isomers, they can be separated by column chromatography, but in the present invention, they can also be used as a mixture.
  • Organic silicon compound contained in the organic layer preferably contains a compound having an NR group (R represents a hydrogen atom or an alkyl group).
  • R represents a hydrogen atom or an alkyl group.
  • the interlayer adhesion between the organic layer and the gas barrier layer can be improved, and the gas barrier property of the gas barrier film can be improved.
  • a silane coupling agent represented by the following general formula (2) can be used as the organosilicon compound.
  • R 1 to R 6 each independently represents a substituted or unsubstituted alkyl group or aryl group, provided that at least one of R 1 to R 6 is a radically polymerizable group. This is a substituent containing a carbon-carbon double bond.
  • R 1 to R 6 each represents a substituted or unsubstituted alkyl group or aryl group.
  • R 1 to R 6 are preferably an unsubstituted alkyl group or an unsubstituted aryl group except for a substituent containing a radically polymerizable carbon-carbon double bond.
  • the alkyl group an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
  • aryl group a phenyl group is preferable.
  • R 1 to R 6 a methyl group is particularly preferable.
  • At least one of R 1 ⁇ R 6 is a carbon radical polymerizable - having a substituent containing a carbon double bond, a carbon two of radical polymerizable R 1 ⁇ R 6 - carbon double bonds A substituent is preferred. Further, among R 1 to R 3 , the number of those having a substituent containing a radical polymerizable carbon-carbon double bond is 1, and among R 4 to R 6 , the number of radical polymerizable carbon-carbon two carbon atoms is one. The number of those having a substituent containing a heavy bond is particularly preferably 1.
  • the substituents in which the silane coupling agent represented by the general formula (2) includes two or more radically polymerizable carbon-carbon double bonds may be the same as or different from each other. Are preferably the same as each other.
  • the substituent containing a radically polymerizable carbon-carbon double bond is preferably represented by —XY.
  • X represents a single bond, an alkylene group having 1 to 6 carbon atoms or an arylene group, preferably a single bond, a methylene group, an ethylene group, a propylene group or a phenylene group.
  • Y represents a radically polymerizable carbon-carbon double bond group, and is preferably an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a propenyl group, a vinyloxy group or a vinylsulfonyl group. ) An acryloyloxy group is more preferred.
  • R 1 to R 6 may have a substituent other than a substituent containing a radically polymerizable carbon-carbon double bond.
  • substituents include alkyl groups (eg, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group).
  • aryl group eg, phenyl group, naphthyl group, etc.
  • halogen atom eg, fluorine atom, chlorine atom, bromine atom, iodine atom
  • acyl group eg, acetyl group, benzoyl group, formyl group, pivaloyl group
  • acyloxy groups eg acetoxy group, acryloyloxy group, methacryloyloxy group etc.
  • alkoxycarbonyl groups eg methoxycarbonyl group, ethoxycarbonyl group etc.
  • aryloxycarbonyl groups eg phenyloxycarbonyl group etc.
  • Sulfonyl groups eg methanesulfonate Group, and a benzenesulfonyl group, etc.
  • urea (multi)-(meth) acrylate (multi) -silane precursor compounds described in JP-A-2015-525823, (Co) polymer reaction of urethane (s)-(meth) acrylates (s) -silane composition and at least one urethane (s)-(meth) acrylates (s) -silane precursor compound described in Japanese Patent No. 527454 Products, diurethane (meth) acrylate-silane precursor compounds described in JP-A-2015-530427, and the like can be preferably used.
  • the silane coupling agent used in the present invention is preferably contained in the polymerizable composition in the range of 1 to 30% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 25%. % By mass. By setting it as such a range, it exists in the tendency for the effect of this invention to express more notably. Moreover, when the said organosilicon compound and the organophosphorus compound mentioned later are mixed and contained in an organic layer, it is preferable that the total amount of an organosilicon compound and an organophosphorus compound exists in the said range. In this case, the mixing ratio of the organosilicon compound and the organophosphorus compound is not particularly limited and may be any.
  • Organic phosphorus compounds As the organic phosphorus compound contained in the organic layer, the following phosphoric acid compounds can be used.
  • the phosphoric acid compound preferably contains a polymerizable group, and particularly preferably contains a (meth) acrylate group.
  • phosphoric acid (meth) acrylate When phosphoric acid (meth) acrylate is contained, the interlayer adhesion between the organic layer and the gas barrier layer can be improved, and the gas barrier property of the gas barrier film can be improved.
  • a preferable phosphoric acid compound includes a phosphoric acid compound represented by the following general formula (3).
  • R1 and R2 each independently represents a hydrogen atom or Ac—O—Y—, wherein R1 and R2 are not simultaneously a hydrogen atom.
  • Ac represents an acryloyl group or a methacryloyl group.
  • Y represents an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyl group, or a combination thereof, and n represents 0 or 1.
  • the alkylene group, the alkyleneoxy group, the alkyleneoxycarbonyl group and the alkylene moiety of the alkylenecarbonyl group may be linear or branched, but are preferably linear.
  • the alkylene group and the alkylene moiety may have 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms.
  • Specific examples of the alkylene group and the alkylene moiety include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
  • the phosphoric acid compound commercially available compounds such as KAYAMER series manufactured by Nippon Kayaku Co., Ltd. and the Phosmer series manufactured by Unichemical Co., Ltd. may be used as they are. It may be used.
  • the phosphoric acid compound is preferably contained in the polymerizable composition in the range of 1 to 30% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 25% by mass. By setting it as such a range, it exists in the tendency for the effect of this invention to express more notably.
  • the total amount of the organosilicon compound and the organophosphorus compound is preferably within the above range.
  • the mixing ratio of the organosilicon compound and the organophosphorus compound is not particularly limited and may be any.
  • two or more types of phosphoric acid compounds may be included, and it is preferable to make those total amounts into the said range in this case.
  • the polymerizable composition in the present invention usually contains a polymerization initiator.
  • a polymerization initiator When a polymerization initiator is used, its content is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of compounds involved in the polymerization.
  • generation reaction can be controlled appropriately.
  • photopolymerization initiator examples include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.) commercially available from BASF Japan. Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, Ezacure KTO 46 available from Lamberti) Etc.).
  • Irgacure series for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819,
  • the gas barrier layer according to the present invention contains a group 12-14 metal (M1) and a transition metal (M2), and in the layer thickness direction, (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 ⁇ y, 0 ⁇ z).
  • the gas barrier layer As a configuration of the gas barrier layer, as long as it has a region satisfying (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 ⁇ y, 0 ⁇ z) in the layer thickness direction, As shown in FIGS. 1 and 2, two or more layers may be stacked, or a single layer. Therefore, as shown in FIG. 1, the gas barrier layer does not necessarily have to be composed of two layers of a metal (M1) -containing layer and a transition metal (M2) -containing layer. A layer containing both the metal (M1) and the transition metal (M2) may exist between the metal (M2) -containing layer. In addition, as shown in FIG.
  • the gas barrier layer when the gas barrier layer is composed of a single layer, even if the content of the metal (M1) and the transition metal (M2) varies in the layer thickness direction. good.
  • the gas barrier layer When the gas barrier layer is formed by laminating two or more layers, the gas barrier layer has a layer containing a metal (M1) and a layer containing a transition metal (M2), and an interface between the two layers. it is preferable that the region satisfying the (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49,0 ⁇ y, 0 ⁇ z) in the vicinity is formed.
  • the metal (M1) and the transition metal (M2) are contained in the same layer, and at any position in the layer thickness direction (M1) (M2 ) x O y N z (0.02 ⁇ x ⁇ 49,0 ⁇ y, it is preferable that 0 ⁇ z) region satisfying a is formed.
  • the transition metal (M2) is contained in the surface of the organic layer side formed in the surface on the opposite side to the base material of a gas barrier layer.
  • the interlayer adhesiveness of an organic layer and a gas barrier layer can be improved.
  • the organic layer side surface formed on the surface opposite to the base material of the gas barrier layer is the base material of both surfaces of the gas barrier film by XPS composition analysis described later.
  • the composition distribution in the layer thickness direction is measured from the surface on the opposite side, and within the range of 10 nm in the layer thickness direction from the region where the organic layer-derived C is detected (organic layer) to the region where the C is not detected (gas barrier layer)
  • the gas barrier layer is composed of two or more layers
  • a metal (M1) -containing layer and a transition metal (M2) -containing layer It is preferable that the metal (M1) -containing layer and the transition metal (M2) -containing layer are arranged adjacent to each other. Further, as described above, the transition metal (M2) -containing layer is preferably disposed adjacent to the organic layer.
  • the gas barrier layer may be configured by laminating at least one of a metal (M1) -containing layer and a transition metal (M2) -containing layer in two or more layers.
  • the stacking order of the plurality of metal (M1) -containing layers and the transition metal (M2) -containing layer may be any, but the metal (M1) -containing layer, the transition metal (M2) -containing layer, Are preferably laminated alternately.
  • the metal (M1) containing layer according to the present invention contains a metal (M1) selected from the group consisting of elements of group 12-14.
  • the metal (M1) according to the present invention is not particularly limited as long as it is a metal selected from the group consisting of elements of Groups 12 to 14, and can be used alone or in combination.
  • Specific examples of the metal (M1) include Al, Si, Zn, Ga, Ge, Cd, In, Sn, Hg, Tl, Pb, and Cn. Among these, Si is preferable.
  • the metal (M1) -containing layer preferably contains the metal (M1) in the form of an oxide, nitride, oxynitride, oxycarbide, or the like, and an oxide of Si (composition: SiO x ), Nitride (composition: SiN x ), oxynitride (composition: SiO x N y ) or oxycarbide (composition: SiO x C y ) is most preferred.
  • the metal (M1) -containing layer contains at least one of silicon oxide and silicon nitride, the gas barrier property of the gas barrier film can be improved.
  • the chemical composition in the metal (M1) -containing layer can be measured by measuring the atomic composition ratio using an XPS (X-ray Photoelectron Spectroscopy) surface analyzer. It can also be measured by cutting the metal (M1) containing layer and measuring the atomic composition ratio of the cut surface with an XPS surface analyzer.
  • the chemical composition of the metal (M1) -containing layer is controlled by the type and amount of raw materials used when forming the metal (M1) -containing layer, conditions for forming or modifying the coating layer, and the like. be able to.
  • content of metal compounds such as a metal oxide contained in a metal (M1) content layer
  • content of metal compounds is not specifically limited, It is preferable that it is 50 mass% or more with respect to the total mass of a metal (M1) content layer, and 80 masses. % Or more, more preferably 95% by weight or more, particularly preferably 98% by weight or more, and 100% by weight (that is, the metal (M1) -containing layer is made of a metal compound. Most preferred).
  • the metal (M1) -containing layer contains a metal compound and thus has high density and further has gas barrier properties.
  • the gas barrier property of the metal (M1) -containing layer was calculated as a laminate in which the metal (M1) -containing layer was formed on the substrate, the water vapor was measured by a method in accordance with JIS K 7129-1992.
  • the transmittance (WVTR) (38 ° C., 100% RH) is preferably 0.1 g / (m 2 ⁇ 24 h) or less, and more preferably 0.01 g / (m 2 ⁇ 24 h) or less.
  • the metal (M1) -containing layer may be a single layer or a laminated structure of two or more layers.
  • the metals (or metal compounds) contained in the metal (M1) -containing layer may be the same or different.
  • the layer thickness of the metal (M1) -containing layer (the total thickness in the case of a laminated structure of two or more layers) is preferably in the range of 10 to 500 nm from the viewpoint of in-plane uniformity of gas barrier properties. More preferably, it is in the range of 30 to 300 nm.
  • a conventionally known film formation method can be applied, but a vapor phase film formation method such as a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method, Alternatively, a method of modifying a coating layer formed by coating a coating solution containing a metal compound, preferably a coating solution containing a silicon compound (hereinafter also simply referred to as a coating method), and the like can be mentioned. .
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the physical vapor deposition (PVD) method deposits a target substance, for example, a thin film such as a carbon film, on the surface of the substance in the gas phase by a physical technique.
  • a target substance for example, a thin film such as a carbon film
  • Examples of the method include sputtering (DC sputtering, RF sputtering, ion beam sputtering, magnetron sputtering, etc.), vacuum deposition, ion plating, and the like.
  • Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate.
  • a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .
  • the chemical vapor deposition (CVD) method is a method in which a raw material gas containing a target thin film component is supplied onto a substrate, and the film is deposited by a chemical reaction on the surface of the substrate or in the gas phase.
  • CVD chemical vapor deposition
  • the method etc. are mentioned.
  • the vacuum plasma CVD method and the plasma CVD method under atmospheric pressure or near atmospheric pressure are performed by selecting conditions such as a raw material (also referred to as a raw material) metal compound, decomposition gas, decomposition temperature, input power, etc. This is preferable because a metal (M1) -containing layer containing the above compound can be produced.
  • a raw material also referred to as a raw material
  • decomposition gas decomposition temperature
  • input power etc.
  • a metal (M1) -containing layer containing the above compound can be produced.
  • the metal (M1) -containing layer formed by such a method is preferably a layer containing an oxide, nitride, oxynitride or oxycarbide.
  • the metal (M1) -containing layer according to the present invention is, for example, a coating layer formed by coating a coating solution containing a metal compound, preferably a coating solution containing a silicon compound. You may form by the method (coating method) formed by a modification process.
  • a silicon compound will be described as an example of the metal compound.
  • the silicon compound is not particularly limited as long as a coating solution containing the silicon compound can be prepared.
  • a polysilazane compound, a silazane compound, an aminosilane compound, a silylacetamide compound, a silylimidazole compound, or other silicon compounds containing nitrogen are used.
  • the polysilazane compound (also simply referred to as polysilazane) is a polymer having a silicon-nitrogen bond.
  • ceramic precursor inorganic such as SiO 2 , Si 3 N 4 , or both intermediate solid solution SiO x N y has a bond such as Si—N, Si—H, or N—H in the structure. It is a polymer.
  • polysilazane compound examples are not particularly limited, and for example, those disclosed in paragraphs 0043 to 0058 of JP2013-022799A, paragraphs 0038 to 0056 of JP2013-226758A, and the like are appropriately employed.
  • the polysilazane compound is commercially available in the form of a solution dissolved in an organic solvent.
  • examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, manufactured by AZ Electronic Materials Co., Ltd. NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 etc. are mentioned.
  • polysilazane compound that can be used in the present invention
  • a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide Japanese Patent Laid-Open No.
  • silazane compounds include dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and the like. However, it is not limited to these.
  • aminosilane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-arylaminopropyltrimethoxysilane, propylethylenediaminesilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, 3 -Butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, and the like, but are not limited thereto.
  • silylacetamide compounds include N-methyl-N-trimethylsilylacetamide, N, O-bis (tert-butyldimethylsilyl) acetamide, N, O-bis (diethylhydrogensilyl) trifluoroacetamide, N, O-bis Examples include (trimethylsilyl) acetamide, N-trimethylsilylacetamide, and the like, but are not limited thereto.
  • silylimidazole compounds include, but are not limited to, 1- (tert-butyldimethylsilyl) imidazole, 1- (dimethylethylsilyl) imidazole, 1- (dimethylisopropylsilyl) imidazole, N-trimethylsilylimidazole, and the like. .
  • 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, silicon tetra
  • isothiocyanate is used, it is not limited to these.
  • polysilazane such as perhydropolysilazane and organopolysilazane
  • polysiloxane such as silsesquioxane are preferable because of their low film-forming properties, few defects such as cracks, and low residual organic matter, and high gas barrier performance.
  • Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because gas barrier performance is maintained even when bent and under high temperature and high humidity conditions.
  • an amine or a metal catalyst may be added to the coating liquid containing polysilazane in order to promote modification into silicon oxide, silicon nitride, and / or silicon oxynitride.
  • the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable.
  • the coating liquid containing polysilazane can contain an inorganic precursor compound in addition to polysilazane.
  • the inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared.
  • compounds other than polysilazane described in paragraphs 0110 to 0114 of JP2011-143577A can be appropriately employed.
  • polysiloxane and the like can be preferably contained.
  • the compound A siloxane compound or silsesquioxane compound having an organic group
  • This compound A has a reactive group such as a Si—H group or a Si—OH group, so that the polysilazane is combined with a matrix formed by modification with VUV light irradiation and is integrated while locally introducing an organic group. obtain.
  • the region where the organic group is introduced in the underlayer is formed in a uniformly dispersed state in the nano-size, contributing to the good gas barrier performance. can do.
  • the polysiloxane compound represented by the following general formula (4) described in International Publication No. 2015/041207 can also be preferably used.
  • each of R 11 is independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and an alkylsilyl group. is there. These groups may be substituted with one or more groups selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, amino groups, silyl groups, and alkylsilyl groups. These R 11 form a side chain of polysiloxane, but preferably do not contain a highly reactive substituent in order to prevent unnecessary reaction.
  • an alkyl group is preferable, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is most preferable.
  • R 11 may be a different group, but it is preferred that all are alkyl groups, particularly methyl groups.
  • R 11 may contain a trace amount of a reactive group as long as the effects of the present invention are not impaired. Specifically, the effects of the present invention can be exhibited if the total number of amino groups and alkoxy groups contained in all R 11 is 5% or less, preferably 3% or less of the total number of R 11 .
  • R 11 when R 11 contains a hydroxy group, a carboxy group or the like, a highly hydratable hydroxy group remains in the film, and thus it is difficult to improve the gas barrier performance. Therefore, it is preferred that R 11 does not contain a hydroxy group or a carboxy group.
  • R 12 is a terminal group bonded to a silicon atom at the terminal of the polysiloxane main chain. This end group portion is bonded to polysilazane, stabilizes the nitrogen atom in the polysilazane, and can contribute to the realization of high gas barrier performance. Then, in order to proceed properly the reaction of the polysiloxane and polysilazane, R 12 is required to be certain things.
  • R 12 is a hydrocarbon group having 1 to 8 carbon atoms. Moreover, a part of carbon contained in such a hydrocarbon group may be substituted with nitrogen. Examples of the nitrogen-substituted hydrocarbon group include —R 13 —N—R 14 2 .
  • R 13 is a hydrocarbon group having 1 to 5 carbon atoms
  • R 14 is independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
  • R 12 is selected to have an appropriate reactivity. Specifically, methyl group, ethyl group, propyl group, aminomethyl group, aminoethyl group, aminopropyl group, and N-ethylamino group are selected. A group selected from the group consisting of -2-methylpropyl groups is preferred.
  • a plurality of R 12 are contained in the polysiloxane represented by the general formula (4), but they may be the same or different.
  • the molecular weight of the polysiloxane compound is not particularly limited. For example, those having a polystyrene-reduced average molecular weight in the range of 500 to 100,000 are preferable, and those having a molecular weight in the range of 1,000 to 50,000 are more preferable.
  • An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane.
  • an organometallic compound of a metal element other than Si By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the coating composition can be changed to a stable composition close to SiO 2 after drying. it can.
  • metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like. In particular, Al, B, Ti and Zr are preferable, and Al is particularly preferable.
  • Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
  • Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate).
  • the temperature is preferably raised to 30 to 100 ° C. and maintained for 1 minute to 24 hours with stirring.
  • the content of the additive metal element in the polysilazane-containing layer constituting the gas barrier film of the present invention is preferably 0.05 to 10 mol%, more preferably 0 to 100 mol% of silicon (Si). .5-5 mol%.
  • the content of polysilazane in the metal (M1) -containing layer before the modification treatment may be 100% by mass when the total mass of the metal (M1) -containing layer is 100% by mass.
  • the content of polysilazane 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 in the range of 70 to 95% by mass.
  • the formation method by the application method of the metal (M1) -containing layer as described above is not particularly limited, and a known method can be applied. However, a metal (M1) containing a silicon compound and, if necessary, a catalyst in an organic solvent is contained. It is preferable to apply a layer forming coating solution by a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.
  • Modification treatment of the coating layer formed by the coating method refers to a conversion reaction of a silicon compound to silicon oxide or silicon oxynitride. Specifically, it refers to a treatment in which the gas barrier film forms an inorganic thin film at a level that can contribute to the development of gas barrier properties as a whole (water vapor permeability is 0.1 g / (m 2 ⁇ 24 h) or less).
  • water vapor permeability of the gas barrier film is a value measured by a method according to JIS K 7129-1992 under the conditions of 38 ° C. and 100% RH.
  • the conversion reaction of the silicon compound 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, and heat treatment.
  • the heat treatment is preferably performed in combination with other reforming treatments.
  • a conversion treatment by a plasma treatment or an ultraviolet irradiation treatment capable of a conversion reaction at a lower temperature is preferable.
  • the atmospheric pressure plasma CVD method which performs plasma CVD processing in the vicinity of atmospheric pressure, does not need to be reduced in pressure compared to the plasma CVD method under vacuum, and is not only high in productivity but also because the plasma density is high.
  • the film formation rate is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.
  • nitrogen gas or a gas containing a group 18 element is used as the discharge gas.
  • nitrogen, helium or argon is preferably used, and nitrogen is particularly preferable because of low cost.
  • Heat treatment By subjecting the coating layer containing the silicon compound to heat treatment in combination with another modification treatment, preferably an excimer irradiation treatment described later, the modification treatment can be performed efficiently.
  • a heat treatment In the case of forming a layer using a sol-gel method, it is preferable to use a heat treatment.
  • the heating conditions are preferably in the range of 50 to 300 ° C., more preferably in the range of 70 to 200 ° C., preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes.
  • condensation is performed and a metal (M1) -containing layer can be formed.
  • Examples of the heat treatment include a method of heating a coating layer by heat conduction by bringing a substrate into contact with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, and an infrared region such as an IR heater.
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater.
  • the temperature of the coating layer during the heat treatment is preferably adjusted as appropriate within the range of 50 to 250 ° C, and more preferably within the range of 50 to 120 ° C.
  • the heating time is preferably within a range of 1 second to 10 hours, and more preferably within a range of 10 seconds to 1 hour.
  • UV irradiation treatment As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperature. Is possible.
  • This UV irradiation heats the base material and excites and activates O 2 and H 2 O that contribute to ceramics conversion (silica conversion), UV absorbers, and polysilazanes themselves, thus promoting the conversion of polysilazanes into ceramics.
  • the metal (M1) -containing layer obtained becomes denser. Irradiation with ultraviolet rays is effective at any point after the coating layer is formed.
  • any commonly used ultraviolet ray generator can be used.
  • the ultraviolet ray referred to in the present invention generally means an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) irradiation treatment described later, it is preferably 210 to 375 nm. UV light is used.
  • the irradiation intensity and the irradiation time are set within a range in which the substrate carrying the coating layer to be irradiated is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm.
  • the distance between the base material and the ultraviolet irradiation lamp is set so as to be 2, and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the temperature of the base material during the ultraviolet irradiation treatment is 150 ° C. or higher
  • the base material is a plastic film or the like
  • the base material is deformed or its strength is deteriorated. It will be damaged.
  • the base material is 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 substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set depending on the type of the substrate.
  • 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, but are not particularly limited.
  • 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, but are not particularly limited.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • a laminate having a coating 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, and for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd. can be used.
  • the laminate having the coating layer on the surface is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. can do.
  • the time required for the ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the base material used and the composition and concentration of the coating layer.
  • the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (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. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action.
  • the radiation source in the present invention may be any source that generates light having a wavelength of 100 to 180 nm, but preferably an excimer radiator (for example, Xe excimer lamp) having a maximum emission at about 172 nm and a bright line at about 185 nm.
  • an excimer radiator for example, Xe excimer lamp
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. 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 of the active oxygen, ozone and ultraviolet radiation, the polysilazane coating layer 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 increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, at a short wavelength, so that the increase in the surface temperature of the irradiation object is suppressed.
  • it is suitable for flexible film materials such as PET, which are likely to be affected by heat.
  • Oxygen is necessary 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 is likely 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.
  • the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably 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 changing the flow rate ratio.
  • the illuminance of the vacuum ultraviolet light received by the polysilazane coating layer is preferably in the range of 1 mW / cm 2 to 10 W / cm 2 , more preferably in the range of 30 to 200 mW / cm 2 , More preferably, it is within the range of 50 to 160 mW / cm 2 . If 1 mW / cm 2 or more, sufficient reforming efficiency can be obtained, if 10 W / cm 2 or less, hardly occurs ablate coating layer, hardly damage the substrate.
  • the irradiation energy amount (integrated light amount) of vacuum ultraviolet rays on the coating layer surface is preferably in the range of 10 to 10000 mJ / cm 2 , more preferably in the range of 100 to 8000 mJ / cm 2 , and 200 to 6000 mJ / cm 2. More preferably, it is within the range of cm 2 . If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
  • 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 a carbon-containing gas) may be used alone, but a carbon-containing gas containing a rare gas or H 2 as a main gas is used. It is preferable to add a small amount.
  • the plasma generation method include capacitively coupled plasma.
  • the film density of the metal (M1) -containing layer is appropriately set depending on the purpose, but is preferably in the range of 1.5 to 2.6 g / cm 3 . Within this range, the density of the film becomes higher, and the gas barrier property deterioration and the oxidation deterioration of the film due to humidity hardly occur.
  • the metal (M1) -containing layer may consist of only a layer formed by a vapor deposition method or a layer formed by a coating method. Or a combination of a layer formed by a vapor deposition method and a layer formed by a coating method.
  • the metal (M1) -containing layer preferably contains a nitrogen atom or a carbon atom from the viewpoint of stress relaxation and absorption of ultraviolet rays.
  • Transition metal (M2) -containing layer contains a transition metal (M2).
  • the transition metal (M2) refers to an element belonging to groups 3 to 11 of the long-period periodic table.
  • Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W Examples thereof include Re, Os, Ir, Pt, and Au.
  • a transition metal (M2) is a metal from which the group which consists of Nb, Ta, and V is selected.
  • the transition metal (M2) is a metal selected from the group consisting of Nb, Ta and V, the interlayer adhesion between the organic layer and the gas barrier layer can be improved, and the gas barrier property of the gas barrier film can be improved. Can be improved.
  • the transition metal (M2) -containing layer according to the present invention contains a transition metal (M2) selected from the group consisting of Group 5 to 11 elements.
  • the transition metal (M2) is not particularly limited as long as it is a transition metal selected from the group consisting of Group 3 to 11 elements, and can be used alone or in combination.
  • transition metal (M2) from which favorable gas barrier property is obtained it is preferable that it is a transition metal selected from the group which consists of a group 5 element. This is because the transition metal (M2) (particularly Nb) is contained in the organic silicon compound Si contained in the organic layer, the organophosphorus compound P, the metal (M1) in the metal (M1) containing layer, etc. This is because bonding is considered to occur easily. Furthermore, if the metal (M1) is Si, a significant gas barrier property improvement effect can be obtained. Further, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb from which a compound with good transparency can be obtained.
  • the transition metal (M2) -containing layer preferably contains the transition metal (M2) in the form of an oxide, nitride, oxynitride, oxycarbide or the like.
  • the content of the transition metal compound such as a transition metal oxide is not particularly limited as long as the effects of the present invention are not impaired, but may be 50% by mass or more based on the total mass of the transition metal (M2) -containing layer. Preferably, it is 80% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, a transition metal (M2) -containing layer) Is most preferably a transition metal compound.
  • a conventionally known film formation method can be applied.
  • a vapor deposition method is used.
  • the vapor deposition method is not particularly limited.
  • a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, or an ion assist vapor deposition method, or a plasma CVD (Chemical Vapor).
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • ALD Atomic Layer Deposition
  • Film formation by the sputtering method is bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR (Electron Cyclotron Resonance) sputtering, or the like. Two or more types can be used in combination.
  • the target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.
  • a reactive sputtering method using a transition mode that is intermediate between a metal mode and an oxide mode can be used.
  • a metal oxide film can be formed at a high film formation speed, which is preferable.
  • a transition metal oxide thin film can be formed by using transition metal (M2) for the target and further introducing oxygen into the process gas.
  • M2 transition metal
  • a transition metal oxide target can be used.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a transition metal compound thin film such as a transition metal oxide, nitride, oxynitride, or oxycarbide can be formed.
  • Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, the material of the film, the film thickness, and the like.
  • a sputtering method using a transition metal oxide as a target is preferable because it has a higher film formation rate and higher productivity.
  • the transition metal (M2) -containing layer may be a single layer or a laminated structure of two or more layers.
  • the transition metal (or transition metal compound) contained in the transition metal (M2) -containing layer may be the same or different. May be.
  • the layer thickness of the transition metal (M2) -containing layer (the total thickness in the case of a laminated structure of two or more layers) may be in the range of 1 to 200 nm from the viewpoint of in-plane uniformity of gas barrier properties. Preferably, it is in the range of 2 to 100 nm, more preferably in the range of 3 to 50 nm. In particular, when the layer thickness of the transition metal (M2) -containing layer is 50 nm or less, the productivity of film formation of the transition metal (M2) -containing layer is further improved.
  • the gas barrier layer according to the present invention has (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 ⁇ y, 0 ⁇ z) in the layer thickness direction. It has the area
  • the element concentration distribution (hereinafter referred to as depth profile) in the layer thickness direction of the gas barrier film according to the present invention specifically includes a metal (M1) distribution curve, a transition metal (M2) distribution curve, an oxygen distribution curve, and nitrogen.
  • M1 metal
  • M2 transition metal
  • oxygen distribution curve oxygen distribution curve
  • nitrogen nitrogen
  • XPS X-ray photoelectron spectroscopy
  • a distribution curve and a carbon distribution curve are sequentially exposed while exposing the inside from the surface of the gas barrier film. It can be created by so-called XPS depth profile measurement in which surface composition analysis is performed.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time).
  • the etching time generally correlates with the distance from the surface of the gas barrier film in the layer thickness direction. The distance from the surface of the gas barrier film calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement can be employed.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • the background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • Data processing uses MultiPak manufactured by ULVAC-PHI.
  • the analyzed elements are metal (M1), transition metal (M2), oxygen (O), nitrogen (N), and carbon (C).
  • the composition ratio is calculated from the obtained data, and the metal (M1) and the transition metal (M2) coexist, and (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 It was determined whether or not there is a region satisfying ⁇ y, 0 ⁇ z).
  • the thickness of the region can be obtained by expressing the sputter depth in XPS analysis in terms of SiO 2 .
  • the thickness of the region satisfying (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 ⁇ y, 0 ⁇ z) is preferably in the range of 5 to 30 nm, more preferably It is in the range of 8 to 20 nm.
  • the gas barrier layer When the gas barrier layer is composed of a single layer, the gas barrier layer contains a metal (M1) and a transition metal (M2), and is in the layer thickness direction. having in any position of the region that satisfies (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49,0 ⁇ y, 0 ⁇ z) of.
  • M1 metal
  • M2 transition metal
  • the metal (M1) and transition metal (M2) contained in the gas barrier layer, and the formation method of the gas barrier layer are the same materials and formation methods as the metal (M1) containing layer and the transition metal (M2) containing layer. Is mentioned. Also, the presence or absence of a region that satisfies (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49,0 ⁇ y, 0 ⁇ z) can be confirmed by composition analysis by XPS as described above.
  • the layer thickness of the gas barrier layer in the case of a single layer is preferably in the range of 10 to 500 nm, more preferably in the range of 30 to 300 nm.
  • the gas barrier layer according to the present invention preferably has a region satisfying the following formula (A) in the layer thickness direction.
  • the gas barrier layer is composed of the metal (M1) -containing layer and the transition metal (M2) -containing layer
  • the region satisfying the formula (A) includes a metal (M1) -containing layer and a transition metal (M2) -containing layer.
  • the gas barrier layer exists in any of the layer thickness directions of the gas barrier layer.
  • the region satisfying the formula (A) is provided in the region satisfying the above-described (M1) (M2) x O y N z (0.02 ⁇ x ⁇ 49, 0 ⁇ y, 0 ⁇ z). Alternatively, they may be provided separately.
  • the composition of the composite oxide of the metal (M1) and the transition metal (M2) is represented by (M1) (M2) x O y N z .
  • the composite oxide may partially include a nitride structure.
  • the maximum valence of the metal (M1) is a
  • the maximum valence of the transition metal (M2) is b
  • the valence of O is 2
  • the valence of N is 3.
  • This formula means that the total number of bonds of metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N, and in this case, metal (M1) and transition metal ( Both M2) are bonded to either O or N.
  • metal (M1) and transition metal ( Both M2) are bonded to either O or N.
  • the abundance ratio of each element is set to the maximum valence of each element.
  • the composite valence calculated by performing the weighted average according to is adopted as the values of a and b of the “maximum valence”.
  • the minimum value in the oxygen deficient region is preferably (2y + 3z) / (a + bx) ⁇ 0.2, and (2y + 3z) / (A + bx) ⁇ 0.3 is more preferable, and (2y + 3z) / (a + bx) ⁇ 0.4 is further preferable.
  • the thickness of the oxygen deficient region that provides good gas barrier properties is preferably 5 nm or more, more preferably 8 nm or more, and more preferably 10 nm or more as the sputtering thickness in terms of SiO 2. More preferably, it is more preferably 20 nm or more.
  • the gas barrier film having the above-described configuration exhibits a very high gas barrier property that can be used as a substrate for an electronic device such as an organic EL device.
  • a gas barrier film is formed by using an oxygen-deficient composition film of a compound (oxide) of a metal (M1) alone, or a compound of a transition metal (M2)
  • an oxygen-deficient composition film of an oxide alone When a gas barrier film is formed using an oxygen-deficient composition film of an oxide alone, the tendency of the gas barrier property to improve as the degree of oxygen vacancy increases is observed, but the gas barrier property is significantly improved. It was not connected.
  • a metal (M1) -containing layer containing a compound (oxide) containing a metal (M1) as a main component and a transition metal (M2) containing a compound (oxide) containing a transition metal (M2) as a main component.
  • the inclusion layer is stacked to form a region where the metal (M1) and the transition metal (M2) are present at the same time, and the region has an oxygen deficiency composition
  • the gas barrier property increases as the degree of oxygen deficiency increases. I found it to be even better. As described above, this is because the bond between the metal (M1) and the transition metal (M2) is more likely to occur than the bond between the metals (M1) and the transition metal (M2). This is probably because a dense and high-density structure is formed by using an oxygen-deficient composition in a region where (M1) and the transition metal (M2) are present simultaneously.
  • the present inventors changed the thickness of the oxygen deficient composition of the composite oxide of the metal (M1) and the transition metal (M2), and the criticality that the effect of improving the gas barrier property is observed.
  • a co-evaporation method can be preferably used as a method for producing the above-described oxygen deficient region.
  • the co-evaporation method is preferably a co-sputtering method.
  • the co-sputtering method employed in the present invention includes, for example, a composite target made of an alloy containing both metal (M1) and transition metal (M2), or a composite oxide of metal (M1) and transition metal (M2). It can be a single sputtering using a composite target as a sputtering target.
  • the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single metal (M1) or its oxide and a single transition metal (M2) or its oxide.
  • the film forming conditions for performing the co-evaporation method include the ratio of transition metal (M2) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, Examples include one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation, and these film formation conditions (preferably oxygen partial pressure) ) Can be adjusted to form a thin film made of a complex oxide having an oxygen-deficient composition. That is, by forming the gas barrier layer using the co-evaporation method as described above, most of the region in the layer thickness direction can be made an oxygen deficient region. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the layer thickness. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method in order to control the layer thickness of a gas barrier layer, for example.
  • the gas barrier film of the present invention includes a base material, an organic layer, and a gas barrier layer as essential components, but may further include other members.
  • another member is provided between the substrate and the organic layer or the gas barrier layer, or on the surface of the substrate on which the organic layer and the gas barrier layer are not formed. You may have.
  • Other members are not particularly limited, and members used for conventional gas barrier films can be used in the same manner or appropriately modified. Specific examples include a base layer (smooth layer, primer layer), an anchor coat layer (anchor layer), a bleed-out prevention layer, a protective layer, a moisture absorption layer, and an antistatic layer functional layer. Said other member may be used independently and may be used in combination of 2 or more type.
  • the other member may exist as a single layer or may have a laminated structure of two or more layers.
  • the gas barrier film of the present invention may include, for example, a base layer (smooth layer, primer layer) between the base material and the organic layer or gas barrier layer.
  • the underlayer is for flattening the rough surface of the substrate where protrusions and the like are present, or for filling the unevenness and pinholes generated in the organic layer or gas barrier layer by the protrusions existing on the substrate to flatten the surface.
  • Such an underlayer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, the gas barrier film of the present invention preferably further comprises an underlayer containing a carbon-containing polymer between the base material and the organic layer or the gas barrier layer.
  • the underlayer also contains a carbon-containing polymer, preferably a curable resin.
  • the 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.
  • the curable resins may be used alone or in combination of two or more.
  • UV curable organic / inorganic hybrid hard coating material manufactured by JSR Co., Ltd.
  • OPSTAR (registered trademark) series polymerizable unsaturated to silica fine particles And a compound obtained by bonding an organic compound having a group).
  • 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, DIC Corporation Unidic (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant 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, polyamide Amine-epichlorohydrin tree Etc. The.
  • the smoothness of the underlayer is a value expressed by the surface roughness specified by 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 atomic force microscope (AFM) with a detector having a stylus with a minimum tip radius, and measured with a stylus with a minimum tip radius. This is the roughness related to the amplitude of fine irregularities, measured many times in a section whose direction is several tens of ⁇ m.
  • AFM atomic force microscope
  • the layer 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 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).
  • an anchor coat agent used for this anchor coat layer polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc.
  • One type or two or more types can be used in combination.
  • a commercially available product may be used as the anchor coating agent.
  • a siloxane-based UV curable polymer solution manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400” 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 may further include a bleed-out prevention layer.
  • the bleed-out prevention layer is used for the purpose of suppressing a phenomenon in which unreacted oligomers or the like migrate from the base material to the surface when the base material having the base layer is heated and contaminate the contact surface. It is provided on the opposite surface of the substrate.
  • the bleed-out prevention layer may basically have the same configuration as the underlayer as long as it has this function.
  • the compound that can be contained in the bleed-out prevention layer includes a polyunsaturated organic compound 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 layer thickness of the bleed-out preventing layer is in the range of 1 to 10 ⁇ m, preferably in the range of 2 to 7 ⁇ m.
  • Preparation of gas barrier film 101 (Preparation of base material)
  • PET polyethylene terephthalate
  • UH13 manufactured by Toray Industries, Inc.
  • a high refractive index easy-adhesion layer is provided on one side of the substrate, and the organic layer and the gas barrier layer are formed on the high refractive index easy-adhesion layer side.
  • first organic layer 100 parts by mass of a polymerizable compound (manufactured by Daicel Cytec Co., Ltd., trimethylolpropane triacrylate (TMPTA)), a photopolymerization initiator (manufactured by Ciba Chemical Co., Ltd., Irgacure 184), and 3 parts by mass of an organosilicon compound a1 represented by the following formula And a polymerizable composition comprising methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • the content of MEK was adjusted so that the dry layer thickness was 1 ⁇ m, and the content of the photopolymerization initiator was 3% by mass in the polymerizable composition.
  • the prepared polymerizable composition was applied onto a substrate with a bar coater, dried, and cured by ultraviolet irradiation to form a first organic layer.
  • R represents CH 2 ⁇ CHCOOCH 2 —.
  • the organosilicon compound a1 was synthesized in consideration of the method described in JP2009-67778A.
  • Formation of first gas barrier layer ⁇ Formation of the lower layer> It was formed using a magnetron sputtering apparatus (manufactured by Canon Anelva: Model EB1100 (hereinafter, the same apparatus was used for the sputtering method)).
  • a polycrystalline (Al) target was used as a target, and a metal (M1) -containing layer as a lower layer was formed on the first organic layer by a DC sputtering method using Ar and O 2 as process gases.
  • the layer thickness was 100 nm.
  • the oxygen partial pressure was adjusted so that the composition of the metal (M1) -containing layer was Al 2 O 3 .
  • a transition metal (M2) having a layer thickness of 10 nm as an upper layer on a metal (M1) -containing layer by a DC sputtering method using an oxygen-deficient Nb 2 O 5 target as a target and Ar and O 2 as process gases A containing layer was formed.
  • the oxygen partial pressure was adjusted so that the composition measured by XPS was Nb 2 O 3 .
  • the adjustment of the layer thickness was performed by setting the film formation time so that the layer thickness would be 10 nm using the relational expression between the film formation time and the layer thickness created in advance.
  • the layer thickness was adjusted in the same manner.
  • the 1st gas barrier layer which consists of a lower layer and an upper layer was formed.
  • a second organic layer was formed in the same manner as the formation of the first organic layer.
  • the gas barrier film 101 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • Formation of first gas barrier layer ⁇ Formation of the lower layer>
  • a polycrystalline Si target was used as a target, and a metal (M1) -containing layer as a lower layer was formed on the first organic layer by DC sputtering using Ar and O 2 as process gases.
  • the layer thickness was 100 nm.
  • the oxygen partial pressure was adjusted so that the composition of the metal (M1) -containing layer was SiO 2 or SiO 1.7 .
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 102 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 103 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the subsequent layer thickness In order to adjust the subsequent layer thickness, it was appropriately diluted with dibutyl ether to prepare a coating solution. Using this coating solution, it was applied on the first organic layer by spin coating so that the layer thickness after drying was 100 nm, and dried at 80 ° C. for 2 minutes. Thereafter, the Xe excimer lamp having a wavelength of 172 nm is used for the dried coating layer set on a stage whose temperature is adjusted to 80 ° C. in an excimer irradiation apparatus, the irradiation atmosphere is replaced with nitrogen, and the oxygen concentration is 0.1 vol%. , And irradiation energy of 3.0 J / cm 2 , vacuum ultraviolet irradiation treatment was performed to form a metal (M1) -containing layer as a lower layer.
  • M1 metal
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 104 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • first organic layer In the formation of the first organic layer in the gas barrier film 101, the first organic layer was formed in the same manner except that the polymerizable compound did not contain the organosilicon compound a1.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 105 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • Second organic layer Polymeric compound (the following acrylate 1) 50 parts by mass, polymerization initiator (Lamberti, Esacure KTO46) 1 part, phosphoric acid methacrylate represented by the following formula as organic phosphorus compound b1 (Nippon Kayaku Co., Ltd., KAYAMER) PM-21) 3 parts by weight and 400 parts by weight of methyl ethyl ketone (MEK) are applied onto the first gas barrier layer with a bar coater so that the dry layer thickness is 1 ⁇ m, and then dried and irradiated with ultraviolet rays. To form a second organic layer.
  • polymerization initiator Liberti, Esacure KTO46
  • phosphoric acid methacrylate represented by the following formula as organic phosphorus compound b1 (Nippon Kayaku Co., Ltd., KAYAMER) PM-21
  • MEK methyl ethyl ketone
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 105.
  • the gas barrier film 107 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 108 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 109 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a transition metal (M2) -containing layer as an upper layer was formed in the same manner except that the layer thickness of the formed layer was changed to 3 nm.
  • the 1st gas barrier layer which consists of a lower layer and an upper layer was formed.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 110 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a transition metal (M2) -containing layer having a layer thickness of 10 nm as an upper layer is formed on the metal (M1) -containing layer by a DC sputtering method using an Nb 2 O 5 target as a target and Ar and O 2 as process gases. Formed. In the sputtering method, the oxygen partial pressure was adjusted so that the composition measured by XPS was Nb 2 O 5 . Thus, the 1st gas barrier layer which consists of a lower layer and an upper layer was formed.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 111 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 112 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 113 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the second organic layer in the gas barrier film 106.
  • the gas barrier film 114 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • Aluminum ethyl acetoacetate diisopropylate was diluted with dibutyl ether to a solid content concentration of 5% by mass to prepare an aluminum compound solution. Further, a dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS: inorganic polysilazane) (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-) Mix with a 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing 1,6-diaminohexane (TMDAH) at a ratio of 4: 1 (mass ratio) and further dry.
  • PHPS perhydropolysilazane
  • a polysilazane solution In order to adjust the later thickness, it was diluted appropriately with dibutyl ether to prepare a polysilazane solution.
  • the prepared polysilazane solution and aluminum compound solution were mixed so that the Al / Si atomic ratio was 0.01, heated to 80 ° C. with stirring, held at 80 ° C. for 2 hours, and then gradually cooled to room temperature. did.
  • a coating solution was prepared.
  • the irradiation atmosphere is replaced with nitrogen, and the oxygen concentration is 0.1 vol%.
  • irradiation energy of 0.5 J / cm 2 vacuum ultraviolet irradiation treatment was performed to form a metal (M1) containing layer as an upper layer.
  • M1 metal
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 115 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a polycrystalline Si target and an Nb target are used as targets, and a first gas barrier layer is formed on the first organic layer by performing a dual simultaneous sputtering by a DC sputtering method using Ar and O 2 as process gases. did.
  • the layer thickness was 100 nm.
  • the sputtering conditions for the polycrystalline Si target, the sputtering conditions for the metal Nb target, and the oxygen partial pressure during DC sputtering are adjusted so that the composition ratio of the metal (M1) and the transition metal (M2) is 1: 1. did.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 116 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first gas barrier layer was formed in the same manner as the formation of the lower layer of the first gas barrier layer in the gas barrier film 102.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second gas barrier layer was formed in the same manner as the formation of the lower layer of the first gas barrier layer in the gas barrier film 102.
  • the gas barrier film 117 provided with the 1st organic layer, the 1st gas barrier layer, the 2nd organic layer, and the 2nd gas barrier layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a transition metal (M2) -containing layer having a thickness of 10 nm as an upper layer was formed on the metal (M1) -containing layer by a DC sputtering method using a ZrO 2 target as a target and Ar and O 2 as process gases. .
  • the oxygen partial pressure was adjusted so that the composition measured by XPS was ZrO 2 .
  • the 1st gas barrier layer which consists of a lower layer and an upper layer was formed.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 118 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the second organic layer was formed in the same manner except that the organic phosphorus compound b1 was changed to the organic phosphorus compound b2 (tributyl phosphate).
  • the gas barrier film 120 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • Second organic layer 100 parts by mass of a polymerizable compound (manufactured by Daicel Cytec Co., Ltd., trimethylolpropane triacrylate (TMPTA)), a photopolymerization initiator (manufactured by Ciba Chemical Co., Ltd., Irgacure 184), 3 parts by mass of the organosilicon compound a1, and methyl ethyl ketone (MEK) )
  • TMPTA trimethylolpropane triacrylate
  • MEK methyl ethyl ketone
  • Polymerizable compound (above acrylate 1) 50 parts by mass, polymerization initiator (Lamberti, Esacure KTO46) 1 part by mass, organophosphorus compound b1 (Nippon Kayaku Co., Ltd., KAYAMER PM-21) 3 parts by mass, methyl ethyl ketone (MEK)
  • S2 polymerizable composition
  • S1 and S2 were mixed so that the mass ratio of the organosilicon compound a1 and the organophosphorus compound b1 was 1: 1.
  • the mixed solution of S1 and S2 was applied onto the substrate with a bar coater so that the dry layer thickness was 1 ⁇ m, dried, and cured by ultraviolet irradiation to form a second organic layer.
  • the gas barrier film 121 provided with the 1st organic layer, the 1st gas barrier layer, and the 2nd organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first gas barrier layer was formed in the same manner as the formation of the first gas barrier layer in the gas barrier film 116.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second gas barrier layer was formed in the same manner as the formation of the first gas barrier layer in the gas barrier film 116.
  • the gas barrier film 124 provided with the 1st organic layer, the 1st gas barrier layer, the 2nd organic layer, and the 2nd gas barrier layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a second organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • a gas barrier film 129 including the first organic layer, the first gas barrier layer, and the second organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • the gas barrier film 130 including the first organic layer, the first gas barrier layer, and the second organic layer was produced.
  • the first organic layer was formed in the same manner as the formation of the first organic layer in the gas barrier film 101.
  • composition analysis of gas barrier layer The composition distribution profile of the thickness direction was measured from the surface side of the gas barrier film by XPS analysis.
  • the XPS analysis conditions are as follows.
  • the sample used for the analysis is a sample stored in an environment of 20 ° C. and 50% RH after sample preparation.
  • the background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • MultiPak manufactured by ULVAC-PHI was used for data processing.
  • the analyzed elements are metal (M1), transition metal (M2), O, N, and C.
  • This acrylic resin-containing light emitting layer forming coating solution was applied on each second organic layer or second gas barrier layer of each of the produced gas barrier films to form a quantum dot (QD) -containing coating film.
  • the second organic layer or the second gas barrier layer side of the same gas barrier film is disposed so as to be in contact with the quantum dot (QD) -containing coating film (the quantum dot (QD) -containing coating film with two gas barrier films) across the.), curing the quantum dot-containing coating by applying ultraviolet irradiation treatment by 800mW / cm 2, 300mJ / cm 2 conditions a high pressure mercury lamp, corresponding to the respective gas barrier films 101 to 131
  • a QD sheet for evaluation having an acrylic resin-containing light emitting layer (QD-containing resin layer) was prepared.
  • the thickness of the cured layer (QD-containing resin layer) of the quantum dot-containing coating film was 100 ⁇ m.
  • both surfaces of the quantum dot-containing coating film were cured by sandwiching them between two gas barrier films, and after one gas barrier film was peeled off as a release film, the following adhesion evaluation was performed.
  • the gas barrier film of the present invention is superior in gas barrier properties to the gas barrier film of the comparative example, and has a gas barrier layer and an organic layer formed on the gas barrier layer. It can be seen that the interlaminar adhesion is excellent.
  • the present invention is suitable for providing a gas barrier film excellent in interlayer adhesion between a gas barrier layer and an organic layer formed on the gas barrier layer.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention vise à fournir un film barrière de gaz au moyen duquel l'adhérence inter-couche entre une couche barrière de gaz et une couche organique formée sur la couche barrière de gaz est excellente. Un film barrière de gaz (1) représente un film barrière de gaz dans lequel une couche organique (3) et une couche barrière de gaz (4) sont stratifiées de manière alternée pour fournir au moins trois couches sur un substrat (2), caractérisé en ce que : la couche organique (3) qui est formée sur la surface de la couche barrière de gaz (4) sur le côté opposé au matériau de base (2) comprend un polymère d'un composé polymérisable et au moins un parmi un composé d'organosilicium et un composé d'organophosphore ; et la couche barrière de gaz (4) contient un métal (M1) du groupe 12 à 14 et un métal de transition (M2), et a une région dans la direction d'épaisseur de couche qui satisfait (M1)(M2)xOyNz (0,02 < x < 49, 0 < y, 0 ≤ z).
PCT/JP2016/083809 2015-12-17 2016-11-15 Film barrière de gaz Ceased WO2017104332A1 (fr)

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JP2015-245753 2015-12-17

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CN112724444A (zh) * 2020-12-14 2021-04-30 兰州空间技术物理研究所 一种工业封装用超高阻隔薄膜及其制备方法
TWI876082B (zh) * 2020-08-19 2025-03-11 日商大日本印刷股份有限公司 障壁膜、以及使用其之波長轉換片材、背光及液晶顯示裝置

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