WO2015115314A1 - Film barrière contre les gaz - Google Patents

Film barrière contre les gaz Download PDF

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Publication number
WO2015115314A1
WO2015115314A1 PCT/JP2015/051772 JP2015051772W WO2015115314A1 WO 2015115314 A1 WO2015115314 A1 WO 2015115314A1 JP 2015051772 W JP2015051772 W JP 2015051772W WO 2015115314 A1 WO2015115314 A1 WO 2015115314A1
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layer
gas barrier
inorganic layer
silicon
barrier film
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PCT/JP2015/051772
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English (en)
Japanese (ja)
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森健太郎
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東レ株式会社
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Priority to KR1020167010494A priority Critical patent/KR102355268B1/ko
Priority to JP2015510220A priority patent/JP6578943B2/ja
Priority to CN201580003271.5A priority patent/CN105829093B/zh
Publication of WO2015115314A1 publication Critical patent/WO2015115314A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a gas barrier film used for food and pharmaceutical packaging applications that require high gas barrier properties and electronic device applications such as solar cells, electronic paper, and organic electroluminescence (EL) displays.
  • gas barrier film used for food and pharmaceutical packaging applications that require high gas barrier properties
  • electronic device applications such as solar cells, electronic paper, and organic electroluminescence (EL) displays.
  • a film of an inorganic substance (including inorganic oxides) such as aluminum oxide, silicon oxide, magnesium oxide, etc. on the surface of the polymer substrate is deposited by physical vapor deposition (PVD) such as vacuum deposition, sputtering, or ion plating.
  • PVD physical vapor deposition
  • a gas barrier film formed using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like.
  • CVD method chemical vapor deposition method
  • This film is used as a packaging material for foods, pharmaceuticals, and the like that require blocking of various gases such as water vapor and oxygen, and as an electronic device member such as a flat-screen TV and a solar battery.
  • a gas containing an organic silicon compound vapor and oxygen is used to form a silicon oxide as a main component on a substrate by a plasma CVD method, and at least one kind of carbon, hydrogen, silicon and oxygen.
  • a method for improving gas barrier properties while maintaining transparency by using a contained compound has been disclosed (Patent Document 1).
  • a gas barrier property improving technique other than a film forming method such as a plasma CVD method
  • a method using a smooth base material in which protrusions and unevenness causing generation of pinholes and cracks that reduce the gas barrier property are reduced or surface smoothing is used.
  • Some have used a base material provided with an undercoat layer for the purpose of conversion Patent Documents 2, 3 and 4).
  • Also known is a method of converting a polysilazane film formed by a wet coating method into a silicon oxide film or a silicon oxynitride film (Patent Documents 5 and 6).
  • JP-A-8-142252 JP 2002-113826 A International Publication No. 2012/137762 International Publication No. 2013/061726 International Publication No. 2011/007543 International Publication No. 2011/004698
  • Patent Document 1 in the method of forming a gas barrier layer mainly composed of silicon oxide by the plasma CVD method, the film quality of the formed gas barrier layer differs depending on the type of substrate, and stable gas barrier properties are obtained. It was not obtained. In order to stabilize the gas barrier property, it is necessary to increase the film thickness, and as a result, there is a problem that the bending resistance is lowered and the manufacturing cost is increased.
  • Patent Document 2 a method using a smooth substrate for forming a gas barrier layer or a method using a substrate provided with an undercoat layer for the purpose of smoothing the surface includes pinholes and cracks. Although the gas barrier property is improved by preventing the occurrence of the above, the performance improvement is insufficient.
  • Patent Documents 3 and 4 have a problem that although the film quality of the formed gas barrier layer is improved, the performance is improved, but it is difficult to stably exhibit a high gas barrier property.
  • the gas barrier film is easily affected by conditions at the time of forming the layer, and a gas barrier film having sufficient gas barrier properties can be stably obtained. Needed to laminate a plurality of polysilazane layers. As a result, there has been a problem that the bending resistance is lowered and the manufacturing cost is increased.
  • the present invention has been made in view of the background of the prior art, and it is an object of the present invention to provide a gas barrier film having a high gas barrier property and excellent in bending resistance and adhesion without being thickened or multilayered. .
  • the gas barrier film according to (1) wherein the inorganic layer [A] contains a zinc compound and a silicon oxide.
  • inorganic layer [A] is any one selected from the following inorganic layers [A1] to [A3].
  • Inorganic layer [A1] Inorganic layer consisting of coexisting phases of (i) to (iii) (i) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide
  • Inorganic layer [A2] From the coexisting phase of zinc sulfide and silicon dioxide
  • Inorganic layer [A3] An inorganic layer mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0.
  • the inorganic layer [A] is the inorganic layer.
  • Layer [A1], and the inorganic layer [A1] has a zinc atom concentration of 20 to 40 atom%, a silicon atom concentration of 5 to 20 atom%, and an aluminum atom concentration of 0.5 to 0.5 as measured by ICP emission spectroscopy.
  • the gas barrier film according to (4) which is constituted by a composition having 5 atom% and an oxygen atom concentration of 35 to 70 atom%.
  • the inorganic layer [A] is the inorganic layer [A2], and the inorganic layer [A2] has a molar fraction of zinc sulfide to the total of zinc sulfide and silicon dioxide of 0.7 to 0.9.
  • the gas barrier film according to (4) which is constituted by a certain composition.
  • the present invention also provides the following electronic device using a gas barrier film.
  • a gas barrier film having a high gas barrier property against water vapor and excellent in bending resistance and adhesion is provided.
  • SiN x H y Nitrogen and hydrogen are bonded to a silicon atom present in the compound, and the number of bonds from silicon to each element is x and y.
  • SiO p N q Oxygen and nitrogen are bonded to a silicon atom present in the compound, and the number of bonds from silicon to each element is p and q.
  • SiO a (OH) 4-2a The structure of the compound when the silicon atom is 1.
  • FIG. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention.
  • the gas barrier film of the present invention has an inorganic layer [A] (reference numeral 2), SiN x H y , SiO on one side of the polymer base material (reference numeral 1) from the polymer base material side.
  • a silicon compound layer [B] (reference numeral 3) containing three silicon compounds having a structure represented by p N q and SiO a (OH) 4-2a (x + y 4, a ⁇ 2) is laminated in this order. It is what you are doing.
  • the gas barrier film of the present invention shows the minimum structure of the gas barrier film of the present invention, and only the inorganic layer [A] and the silicon compound layer [B] are arranged on one side of the polymer substrate.
  • another layer may be disposed between the polymer base material and the inorganic layer [A], and the other side of the polymer base material 1 opposite to the side on which the inorganic layer [A] is laminated. These layers may be arranged.
  • the reason why a remarkable effect is obtained in the present invention is estimated as follows. That is, by contacting the inorganic layer [A] and the silicon compound layer [B], defects such as pinholes and cracks existing near the surface of the inorganic layer [A] on the side on which the silicon compound layer [B] is formed are treated. The components constituting the silicon compound layer [B] are filled, and high barrier properties can be expressed.
  • the above three types of silicon compounds can easily form chemical bonds with the components constituting the inorganic layer [A]
  • the adhesion between the inorganic layer [A] and the silicon compound layer [B] is improved. Needless to say, excellent adhesion can be obtained also when another layer is laminated on the silicon compound layer [B].
  • the silicon compound layer [B] including the above structure is excellent in flexibility, excellent bending resistance can be obtained.
  • the polymer substrate used in the present invention preferably has a film form from the viewpoint of ensuring flexibility.
  • the structure of the film may be a single-layer film or a film having two or more layers, for example, a film formed by a coextrusion method.
  • a film stretched in a uniaxial direction or a biaxial direction may be used.
  • the material of the polymer substrate used in the present invention is not particularly limited, but is preferably an organic polymer as a main constituent.
  • organic polymer that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, Examples include polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymer, various polymers such as polyacrylonitrile and polyacetal.
  • the organic polymer may be either a homopolymer or a copolymer, and only one type may be used as the organic polymer, or a plurality of types may be mixed and used.
  • the surface of the polymer base on which the inorganic layer [A] is formed has a corona treatment, a plasma treatment, an ultraviolet treatment, an ion bombard treatment, a solvent treatment, an organic substance or an inorganic substance to improve adhesion and smoothness.
  • a pretreatment such as an undercoat layer forming treatment composed of the above mixture may be applied.
  • a coating layer of an organic material, an inorganic material, or a mixture thereof may be laminated for the purpose of improving the slipping property at the time of winding the film.
  • the thickness of the polymer substrate used in the present invention is not particularly limited, but is preferably 500 ⁇ m or less from the viewpoint of ensuring flexibility, and preferably 5 ⁇ m or more from the viewpoint of securing strength against tension or impact. Furthermore, the thickness of the polymer substrate is more preferably 10 ⁇ m or more and 200 ⁇ m or less because of the ease of film processing and handling.
  • the inorganic layer [A] in the present invention includes zinc (Zn), silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), tin (Sn), indium (In), niobium (Nb), Examples include oxides, nitrides, sulfides, or mixtures of elements such as molybdenum (Mo) and tantalum (Ta). Although it will not specifically limit if such an inorganic substance is included, It is preferable that inorganic layer [A] contains a silicon oxide, and it is more preferable that a zinc compound and a silicon oxide are further included.
  • any one selected from the following inorganic layers [A1] to [A3] is preferably used.
  • the thickness of the inorganic layer [A] in the present invention is preferably 10 nm or more and 1,000 nm or less as the thickness of the layer exhibiting gas barrier properties. If the thickness of the layer is small, there may be places where sufficient gas barrier properties cannot be secured, and the gas barrier properties may vary within the polymer substrate surface. In addition, if the thickness of the layer is too large, the stress remaining in the layer becomes large, so that the inorganic layer [A] is liable to be cracked by bending or external impact, and the gas barrier properties are lowered with use. There is a case. Therefore, the thickness of the inorganic layer [A] is 10 nm or more, more preferably 100 nm or more, while 1,000 nm or less and 500 nm or less. The thickness of the inorganic layer [A] can usually be measured by cross-sectional observation with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the center plane average roughness SRa of the inorganic layer [A] used in the present invention is preferably 10 nm or less.
  • SRa is larger than 10 nm, the irregular shape on the surface of the inorganic layer [A] becomes large, and a gap is formed between the sputtered particles to be laminated. The improvement effect may be difficult to obtain.
  • SRa is larger than 10 nm, the film quality of the silicon compound layer [B] laminated on the inorganic layer [A] is not uniform, and the gas barrier property may be lowered. Therefore, SRa of the inorganic layer [A] is preferably 10 nm or less, and more preferably 7 nm or less.
  • SRa of the inorganic layer [A] in the present invention can be measured using a three-dimensional surface roughness measuring machine.
  • the method for forming the inorganic layer [A] is not particularly limited, and can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or the like.
  • a vacuum deposition method for example, a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or the like.
  • the sputtering method or the CVD method is preferable because the inorganic layer [A] can be easily and precisely formed.
  • the reason why the gas barrier property is improved by applying the inorganic layer [A1] in the gas barrier film of the present invention is that the crystalline component contained in zinc oxide and the amorphous component of silicon dioxide coexist. It is presumed that the crystal growth of zinc oxide, which tends to generate crystals, is suppressed and the particle diameter is reduced, so that the layer is densified and the permeation of water vapor is suppressed.
  • the coexistence of aluminum oxide can suppress the crystal growth more than the case of coexistence of zinc oxide and silicon dioxide, so that the layer can be further densified, and accordingly, cracks during use can be reduced. It is considered that the gas barrier property deterioration due to the generation could be suppressed.
  • the composition of the inorganic layer [A1] can be measured by ICP emission spectroscopy as described later.
  • the zinc atom concentration measured by ICP emission spectroscopy is 20 to 40 atom%
  • the silicon atom concentration is 5 to 20 atom%
  • the aluminum atom concentration is 0.5 to 5 atom%
  • the O atom concentration is 35 to 70 atom%.
  • the zinc atom concentration is higher than 40 atom% or the silicon atom concentration is lower than 5 atom%, the silicon dioxide and / or aluminum oxide that suppresses the crystal growth of zinc oxide is insufficient, so that void portions and defect portions increase. High gas barrier properties may not be obtained.
  • the amorphous component of silicon dioxide inside the layer may increase and the flexibility of the layer may be lowered.
  • the aluminum atom concentration is higher than 5 atom%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that the film becomes hard, and cracks are likely to occur due to heat and external stress.
  • the aluminum atom concentration is smaller than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved, so that the flexibility may be lowered.
  • the oxygen atom concentration is higher than 70 atom%, the amount of defects in the inorganic layer [A1] increases, so that a desired gas barrier property may not be obtained.
  • the oxygen atom concentration is lower than 35 atom%, the oxidation state of zinc, silicon, and aluminum becomes insufficient, the crystal growth cannot be suppressed, and the particle diameter increases, so that the gas barrier property may be lowered.
  • the zinc atom concentration is 25 to 35 atom%
  • the silicon atom concentration is 10 to 15 atom%
  • the aluminum atom concentration is 1 to 3 atom%
  • the oxygen atom concentration is 50 to 64 atom%. It is more preferable.
  • the composition of the inorganic layer [A1] is formed with the same composition as the mixed sintered material used at the time of forming the layer. Therefore, by using a mixed sintered material having a composition that matches the composition of the target layer, the inorganic layer [A1] It is possible to adjust the composition of the layer [A1].
  • the composition of the inorganic layer [A1] is calculated as a composition ratio of zinc oxide, silicon dioxide, aluminum oxide, and the inorganic oxide contained by quantifying each element of zinc, silicon, and aluminum by ICP emission spectroscopy.
  • the oxygen atoms are calculated on the assumption that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO 2 ), and aluminum oxide (Al 2 O 3 ), respectively.
  • the ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis.
  • ICP emission spectroscopic analysis can be performed after removing the layer by ion etching or chemical treatment as necessary.
  • a coexisting phase of zinc sulfide and silicon dioxide (hereinafter referred to as a coexisting phase of zinc sulfide and silicon dioxide) is preferably used as the inorganic layer [A] in the present invention.
  • the details of the inorganic layer [A2], which is a layer formed from the above, will be described.
  • silicon dioxide (SiO 2 ) may be generated (SiO to SiO 2 ) slightly deviating from the composition ratio of silicon and oxygen in the composition formula on the left depending on the conditions at the time of production. Alternatively, it will be expressed as SiO 2 .
  • the deviation of the composition ratio from the chemical formula the same applies to zinc sulfide, and it is expressed as zinc sulfide or ZnS regardless of the deviation of the composition ratio depending on the conditions at the time of production.
  • the reason why the gas barrier property is improved by applying the inorganic layer [A2] in the gas barrier film of the present invention is that the crystalline component contained in zinc sulfide and the amorphous component of silicon dioxide coexist. It is presumed that the crystal growth of zinc sulfide, which tends to generate crystals, is suppressed and the particle diameter is reduced, so that the layer is densified and the permeation of water vapor is suppressed.
  • the zinc sulfide-silicon dioxide coexisting phase containing zinc sulfide with suppressed crystal growth is more flexible than a layer formed only of inorganic oxides or metal oxides, and is resistant to heat and external stress.
  • produce a crack it is thought by applying this inorganic layer [A2] that the gas barrier property fall resulting from the production
  • the composition of the inorganic layer [A2] is preferably such that the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. If the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is greater than 0.9, there will be insufficient silicon dioxide to suppress zinc sulfide crystal growth, resulting in an increase in voids and defects, resulting in the prescribed gas barrier properties. May not be obtained.
  • the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is less than 0.7, the amorphous component of silicon dioxide inside the inorganic layer [A2] increases and the flexibility of the layer decreases. The flexibility of the gas barrier film against mechanical bending may be reduced.
  • a more preferable range of the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is 0.75 to 0.85 from the tendency due to the content of each compound shown above.
  • the composition of the inorganic layer [A2] is formed with the same composition as the mixed sintered material used at the time of forming the layer, by using the mixed sintered material having a composition suitable for the purpose, the inorganic layer [A2] It is possible to adjust the composition.
  • the composition ratio of zinc and silicon is first obtained by ICP emission spectroscopic analysis. Based on this value, each element is quantitatively analyzed by using Rutherford backscattering method, and zinc sulfide and silicon dioxide are analyzed. And the composition ratio of other inorganic oxides contained.
  • the ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis.
  • the inorganic layer [A2] is a composite layer of sulfide and oxide, analysis by Rutherford backscattering method capable of analyzing the composition ratio of sulfur and oxygen is performed.
  • the layer is removed by ion etching or chemical treatment as necessary, and then analyzed by ICP emission spectroscopic analysis and Rutherford backscattering method. be able to.
  • the inorganic layer [A3] mainly composed of a silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0, which is preferably used as the inorganic layer [A] in the present invention. Details will be described.
  • the main component means 60% by mass or more of the entire inorganic layer [A3], and preferably 80% by mass or more.
  • the main component silicon dioxide (SiO 2 ) may be slightly shifted from the composition ratio of silicon and oxygen in the composition formula (SiO to SiO 2 ) depending on the conditions at the time of generation. It will be expressed as silicon dioxide or SiO 2 .
  • the formation method of the inorganic layer [A3] is preferably a CVD method capable of forming a dense film.
  • a gas of silane or an organosilicon compound which will be described later, is used as a monomer, activated by high-intensity plasma, and a dense film can be formed by a polymerization reaction.
  • organic silicon compound examples include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethylsilane, propoxysilane, dipropoxysilane, tripropoxysilane, tetrapropoxysilane, tetra Methoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethyldisiloxane, tetramethyldisiloxane, hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, undecamethylcyclohexasiloxane, Dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, t
  • the composition of the inorganic layer [A3] can be measured by X-ray photoelectron spectroscopy (XPS method) as described later.
  • the number ratio of oxygen atoms to silicon atoms measured by XPS method is preferably in the range of 1.5 to 2.0, more preferably in the range of 1.4 to 1.8.
  • the ratio of the number of silicon atoms to oxygen atoms is larger than 2.0, the amount of oxygen atoms contained is increased, so that void portions and defect portions increase, and a predetermined gas barrier property may not be obtained.
  • the atomic ratio of silicon atoms to oxygen atoms is smaller than 1.5, oxygen atoms are reduced to form a dense film, but flexibility may be lowered.
  • other silicon compounds such as alkoxysilane and organopolysiloxane may be included.
  • the composition of each compound in the silicon compound layer [B] can be measured by 29 Si CP / MAS NMR method.
  • the layer contains silicon oxynitride represented by SiO p N q , so that the layer becomes denser than the layer formed only of SiO 2 , and oxygen and water vapor are transmitted. Since it is suppressed, it becomes a layer with a high gas barrier property, and in addition, since it is more flexible than a layer formed only of Si 3 N 4 , cracks are hardly generated against heat and external stress during use. It is presumed that the layer can suppress a decrease in gas barrier properties due to crack generation.
  • the thickness of the silicon compound layer [B] used in the present invention is preferably from 50 nm to 2,000 nm, more preferably from 50 nm to 1,000 nm. If the thickness of the silicon compound layer [B] is small, stable water vapor barrier performance may not be obtained. When the thickness of the silicon compound layer [B] becomes too large, the residual stress in the silicon compound layer [B] increases, causing the polymer substrate to warp, and the silicon compound layer [B] and / or the inorganic layer [A] ] May be cracked to lower the gas barrier properties.
  • the thickness of the silicon compound layer [B] can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the center surface average roughness SRa of the silicon compound layer [B] used in the present invention is preferably 10 nm or less. It is preferable to set SRa to 10 nm or less because the repeatability of gas barrier properties is improved.
  • the SRa on the surface of the silicon compound layer [B] is larger than 10 nm, cracks due to stress concentration are likely to occur in a portion with many irregularities, which may cause a decrease in reproducibility of gas barrier properties. Therefore, in the present invention, the SRa of the silicon compound layer [B] is preferably 10 nm or less, more preferably 7 nm or less.
  • SRa of the silicon compound layer [B] in the present invention can be measured using a three-dimensional surface roughness measuring machine.
  • FIG. 4 shows the 29 Si CP / MAS NMR spectrum of the silicon compound layer [B] of the present invention.
  • the absorption of silicon is observed in the chemical shift region of ⁇ 30 to ⁇ 50 ppm, ⁇ 50 to ⁇ 90 ppm region, and ⁇ 90 to ⁇ 120 ppm.
  • the total peak area of ⁇ 30 to ⁇ 120 ppm is 100
  • the total peak area of ⁇ 30 to ⁇ 50 ppm is 10 to 40
  • the total peak area of ⁇ 50 to ⁇ 90 ppm is 10 to 40
  • the silicon compound layer [B] preferably contains 0.1 to 100% by mass of the total of the three silicon compounds of the present invention.
  • a silicon compound having a polysilazane skeleton is preferably used as a raw material of the silicon compound layer [B] used in the present invention.
  • the silicon compound having a polysilazane skeleton for example, a compound having a partial structure represented by the following chemical formula (1) can be preferably used.
  • at least one selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof can be used.
  • perhydropolysilazane in which all of R 1 , R 2 , and R 3 represented by the following chemical formula (1) are hydrogen from the viewpoint of improving gas barrier properties, but part or all of hydrogen is used.
  • an organopolysilazane substituted with an organic group such as an alkyl group may be used.
  • n represents an integer of 1 or more.
  • the solid content concentration of the paint containing the compound (1) on the inorganic layer [A] is adjusted so that the thickness after drying becomes a desired thickness, and reverse coating, gravure coating, rod coating, bar coating It is preferably applied by a method, a die coating method, a spray coating method, a spin coating method or the like. Moreover, in this invention, it is also preferable to dilute the coating material containing the said Chemical formula (1) using an organic solvent from a viewpoint of coating suitability.
  • hydrocarbon solvents such as xylene, toluene, terpene, and solvesso
  • ether solvents such as dibutyl ether, ethyl butyl ether, and tetrahydrofuran can be used. And it is preferable to use it, diluting solid content concentration to 10 mass% or less. These solvents may be used alone or in combination of two or more.
  • Various additives can be blended in the coating material containing the raw material of the silicon compound layer [B] as necessary within a range that does not impair the effect of the silicon compound layer [B].
  • a catalyst an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent, or the like can be used.
  • the heating temperature is preferably 50 to 150 ° C.
  • the heat treatment time is preferably several seconds to 1 hour.
  • the temperature may be constant during the heat treatment, or the temperature may be gradually changed.
  • the heat treatment may be performed while adjusting the humidity within the range of 20 to 90% RH in terms of relative humidity. You may perform the said heat processing in the state enclosed with air
  • the composition of the coating film is modified by subjecting the dried coating film to active energy ray irradiation treatment such as plasma treatment, ultraviolet irradiation treatment, and flash pulse treatment, and contains the three types of silicon compounds of the present invention.
  • a silicon compound layer [B] can be obtained.
  • the active energy ray irradiation treatment it is preferable to use an ultraviolet treatment since it is simple and excellent in productivity and it is easy to obtain a uniform composition of the silicon compound layer [B].
  • the ultraviolet treatment may be performed under atmospheric pressure or reduced pressure, but it is preferable to perform ultraviolet treatment under atmospheric pressure from the viewpoint of versatility and production efficiency.
  • the oxygen gas partial pressure is preferably 1.0% or less, and more preferably 0.5% or less.
  • the relative humidity can be set to a desired composition ratio. In the ultraviolet treatment, it is more preferable to reduce the oxygen concentration using nitrogen gas.
  • an ultraviolet ray generation source a known source such as a high pressure mercury lamp, a metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp, or the like can be used, but a xenon lamp is used in the present invention from the viewpoint of production efficiency. It is preferable.
  • the accumulated amount of ultraviolet irradiation is preferably 0.5 to 10 J / cm 2 , more preferably 0.8 to 7 J / cm 2 . If the integrated light quantity is 0.5 J / cm 2 or more, a desired silicon compound layer [B] composition can be obtained, which is preferable. Moreover, it is preferable if the integrated light quantity is 10 J / cm 2 or less because damage to the polymer substrate and the inorganic layer [B] can be reduced.
  • the heating temperature is preferably 50 to 150 ° C, more preferably 80 to 130 ° C.
  • a heating temperature of 50 ° C. or higher is preferable because high production efficiency can be obtained, and a heating temperature of 150 ° C. or lower is preferable because deformation and alteration of other materials such as a polymer base material hardly occur.
  • the gas barrier film of the present invention is preferably provided with an undercoat layer [C] between the polymer substrate and the inorganic layer [A] in order to improve gas barrier properties and flex resistance.
  • an undercoat layer [C] between the polymer substrate and the inorganic layer [A] in order to improve gas barrier properties and flex resistance.
  • the undercoat layer [C] used in the present invention preferably includes a structure obtained by crosslinking the polyurethane compound [C1] having an aromatic ring structure from the viewpoint of thermal dimensional stability and flex resistance. Furthermore, it is more preferable to contain one or more silicon compounds selected from ethylenically unsaturated compounds [C2], photopolymerization initiators [C3], organic silicon compounds [C4] and inorganic silicon compounds [C5].
  • the polyurethane compound [C1] having an aromatic ring structure that can be used in the present invention has an aromatic ring and a urethane bond in the main chain or side chain.
  • a hydroxyl group and an aromatic ring are present in the molecule. It can be obtained by polymerizing the epoxy (meth) acrylate (c1), the diol compound (c2), and the diisocyanate compound (c3).
  • Examples of the epoxy (meth) acrylate (c1) having a hydroxyl group and an aromatic ring in the molecule include aromatic glycols such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, and hydroquinone. This can be obtained by reacting the diepoxy compound with a (meth) acrylic acid derivative.
  • diol compound (c2) examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol Neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2 , 4,4-Tetramethyl-1,3-cyclobutanediol,
  • diisocyanate compound (c3) examples include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4.
  • -Aromatic diisocyanates such as diphenylmethane diisocyanate, aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate
  • Diisocyanate compounds isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate
  • Alicyclic isocyanate compounds such as xylylene diisocyanate, aromatic aliphatic isocyanate compounds such as tetramethyl xylylene diisocyanate. These can be used alone or in combination of two or more.
  • the component ratios of (c1), (c2), and (c3) are not particularly limited as long as they are within a desired weight average molecular weight.
  • the polyurethane compound [C1] having an aromatic ring structure of the present invention preferably has a weight average molecular weight (Mw) of 5,000 to 100,000.
  • a weight average molecular weight (Mw) of 5,000 to 100,000 is preferable because the resulting cured film has excellent thermal dimensional stability and flex resistance.
  • the weight average molecular weight (Mw) in this invention is the value measured using the gel permeation chromatography method and converted with standard polystyrene.
  • Ethylenically unsaturated compound [C2] examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like.
  • Di (meth) acrylate pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.
  • Epoxy acrylates such as polyfunctional (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol S type epoxy di (meth) acrylate, etc. It is. Among these, polyfunctional (meth) acrylates excellent in thermal dimensional stability and surface protection performance are preferable. Moreover, these may be used by a single composition, and may mix and use two or more components.
  • the content of the ethylenically unsaturated compound [C2] is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, the total amount with the polyurethane compound [C1] having an aromatic ring structure is 100% by mass. It is preferably in the range of -90% by mass, more preferably in the range of 10-80% by mass.
  • the photopolymerization initiator [C3] that can be used as a raw material for the undercoat layer [C] is particularly limited as long as the gas barrier property and the bending resistance of the gas barrier film of the present invention can be maintained and the photopolymerization can be started. Not. The following are illustrated as a photoinitiator which can be used suitably for this invention.
  • Acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • a titanocene photopolymerization initiator such as bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
  • Photopolymerization initiators having an oxime ester structure such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (0-benzoyloxime)].
  • a photopolymerization initiator selected from -trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferred.
  • these may be used by a single composition, and may mix and use two or more components.
  • the content of the photopolymerization initiator [C3] is not particularly limited, but is in the range of 0.01 to 10% by mass with respect to 100% by mass of the total amount of polymerizable components from the viewpoint of curability and surface protection performance.
  • the range is preferably 0.1 to 5% by mass.
  • organosilicon compound [C4] examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropi Me
  • the content of the organosilicon compound [C4] is not particularly limited, but is preferably in the range of 0.01 to 10% by mass in 100% by mass of the total amount of polymerizable components from the viewpoint of curability and surface protection performance.
  • the range of 0.1 to 5% by mass is more preferable.
  • the inorganic silicon compound [C5] that can be used as the raw material for the undercoat layer [C] is preferably silica particles from the viewpoint of surface protection performance and transparency, and the primary particle diameter of the silica particles is in the range of 1 to 300 nm. Preferably, it is in the range of 5 to 80 nm.
  • the primary particle diameter here refers to the particle diameter d calculated
  • required by the gas adsorption method to following formula (2). d 6 / ⁇ s (2) where ⁇ is the density of the particles.
  • the thickness of the undercoat layer [C] is preferably from 200 nm to 4,000 nm, more preferably from 300 nm to 3,000 nm, and further preferably from 500 nm to 2,000 nm. If the thickness of the undercoat layer [C] is too small, the adverse effects of defects due to protrusions or small scratches present on the polymer substrate may not be suppressed. If the thickness of the undercoat layer [C] is too large, the smoothness of the undercoat layer [C] is reduced, and the uneven shape on the surface of the inorganic layer [A] laminated on the undercoat layer [C] is also increased. Since gaps are formed between the sputtered particles to be stacked, the film quality is difficult to be dense, and the effect of improving the gas barrier property may be difficult to obtain.
  • the thickness of the silicon compound layer [B] can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the center surface average roughness SRa of the undercoat layer [C] is preferably 10 nm or less. SRa of 10 nm or less is preferable because a homogeneous inorganic layer [A] can be easily obtained on the undercoat layer [C], and the reproducibility of gas barrier properties is improved. If the SRa on the surface of the undercoat layer [C] is too large, the uneven shape on the surface of the inorganic layer [A] on the undercoat layer [C] also increases and gaps are formed between the laminated sputtered particles, so that the film quality is improved. In some cases, the gas barrier property is hardly obtained and the effect of improving the gas barrier property is hardly obtained.
  • the SRa of the undercoat layer [C] is preferably 10 nm or less, more preferably 7 nm or less.
  • SRa of the undercoat layer [C] in the present invention can be measured using a three-dimensional surface roughness measuring machine.
  • a hard coat layer may be formed for the purpose of improving scratch resistance as long as the gas barrier property does not deteriorate, or a film made of an organic polymer compound is laminated. It is good also as a laminated structure.
  • the outermost surface as used herein refers to the side that is not in contact with the inorganic layer [A] after being laminated in this order so that the inorganic layer [A] and the silicon compound layer [B] are in contact with each other on the polymer substrate. The surface of the silicon compound layer [B].
  • the gas barrier film of the present invention Since the gas barrier film of the present invention has a high gas barrier property, it can be used in various electronic devices. For example, it can be suitably used for an electronic device such as a back sheet of a solar cell or a flexible circuit board. Since the electronic device using the gas barrier film of the present invention has an excellent gas barrier property, it is possible to suppress degradation of the device performance due to water vapor or the like.
  • the gas barrier film of the present invention has a high gas barrier property, it can be suitably used as a packaging film for foods and electronic parts in addition to electronic devices.
  • Layer thickness A sample for cross-sectional observation was prepared by a focused ion beam (FIB) method using a micro sampling system (FB-2000A manufactured by Hitachi, Ltd.). Using a transmission electron microscope (H-9000UHRII, manufactured by Hitachi, Ltd.), the cross section of the observation sample was observed at an acceleration voltage of 300 kV, and the inorganic layer [A], silicon compound layer [B], and undercoat layer [C] The thickness of was measured.
  • FIB focused ion beam
  • the number of samples of water vapor permeability was 2 samples per level, the number of measurements was 5 times for each sample, and the average value of 10 points obtained was the water vapor permeability (g / (m 2 ⁇ d)).
  • composition analysis of [A1] was performed by ICP emission spectroscopic analysis (manufactured by SII Nanotechnology, SPS4000). Samples sampled at the stage of forming the inorganic layer [A1] on the polymer substrate or undercoat layer (before the silicon compound layer [B] is laminated) are thermally decomposed with nitric acid and sulfuric acid, and heated and dissolved with dilute nitric acid And then filtered. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate.
  • composition of inorganic layer [A2] was performed by ICP emission spectroscopic analysis (SPS4000, manufactured by SII Nanotechnology). Samples sampled at the stage of forming the inorganic layer [A2] on the polymer substrate or undercoat layer (before the silicon compound layer [B] is laminated) are thermally decomposed with nitric acid and sulfuric acid and heated with dilute nitric acid Dissolved and filtered. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate. About this solution, content of a zinc atom and a silicon atom was measured.
  • SPS4000 ICP emission spectroscopic analysis
  • the Rutherford backscattering method (AN-2500 manufactured by Nissin High Voltage Co., Ltd.) was used to quantitatively analyze zinc atoms, silicon atoms, sulfur atoms, and oxygen atoms. And the composition ratio of silicon dioxide.
  • composition analysis of inorganic layer [A3] was performed by calculating the atomic ratio of oxygen atoms to silicon atoms by using X-ray photoelectron spectroscopy (XPS method). The measurement conditions were as follows. Apparatus: Quantera SXM (manufactured by PHI) Excitation X-ray: monochromatic AlK ⁇ 1,2 X-ray diameter: 100 ⁇ m Photoelectron escape angle: 10 °.
  • composition of silicon compound layer [B] A powder sample obtained by scraping the silicon compound layer [B] with a single blade is filled in a 7.5 mm ⁇ sample tube, and a composition analysis is performed using 29 Si CP / MAS NMR, and a spectrum as shown in FIG. 4 is obtained. Asked. The sum of peak areas of ⁇ 30 to ⁇ 50 ppm, the sum of peak areas of ⁇ 50 to ⁇ 90 ppm, and the sum of peak areas of ⁇ 90 to ⁇ 120 ppm when the sum of peak areas of ⁇ 30 to ⁇ 120 ppm in the spectrum is defined as 100 was calculated. .
  • the measurement conditions were as follows.
  • the gas barrier film is formed of a metal cylinder having a diameter of 5 mm at the center on the side opposite to the surface (reference numeral 21) on which the inorganic layer [A] and silicon compound layer [B] of (reference numeral 19) are formed.
  • the holding angle of the cylinder is 0 ° (the sample is in a flat state) and the holding angle to the cylinder is 180 ° (a state where the sample is folded back) along the cylinder.
  • the water vapor permeability was evaluated by the method shown in (3). The number of measurements was 5 for each specimen, and the average value of the 10 points obtained was the water vapor permeability after the flex resistance test.
  • the polymer substrate is set on the unwinding roll (symbol 8) so that the surface on which the inorganic layer [A1] is provided faces the sputter electrode, unwinding, unwinding side guide roll (symbol 9, 10 and 11) and passed through a cooling drum (reference numeral 12).
  • Argon gas and oxygen gas were introduced at an oxygen gas partial pressure of 10% so that the degree of decompression was 2 ⁇ 10 ⁇ 1 Pa, and an argon / oxygen gas plasma was generated by applying an input power of 4,000 W from a DC power source.
  • the inorganic layer [A1] was formed on the surface of the polymer substrate by sputtering. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll (code
  • a sputter target which is a mixed sintered material formed of zinc sulfide and silicon dioxide, is formed on one surface of a polymer substrate (reference numeral 5) using a winding type sputtering apparatus (reference numeral 6a) having the structure shown in FIG. Sputtering was used to provide an inorganic layer [A2].
  • the specific operation is as follows. First, unwinding in a winding chamber (symbol 7) of a winding type sputtering apparatus in which a sputtering target sintered with a zinc sulfide / silicon dioxide molar ratio of 80/20 is installed on the sputtering electrode (symbol 13).
  • the polymer base material was set on the roll (symbol 8), unwound, and passed through the cooling drum (symbol 12) through the unwinding side guide rolls (symbol 9, 10, 11).
  • Argon gas was introduced so that the degree of decompression was 2 ⁇ 10 ⁇ 1 Pa, and an applied power of 500 W was applied from a high-frequency power source to generate argon gas plasma, and an inorganic layer [on the surface of the polymer substrate by sputtering [ A2] was formed. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll (code
  • the specific operation is as follows. First, in the winding chamber (symbol 7) of the winding type CVD apparatus, the polymer base material is set on the unwinding roll (symbol 8), unwinding, and unwinding side guide rolls (symbols 9, 10, 11). ) was passed through a cooling drum (reference numeral 12). Oxygen gas 0.5 L / min and hexamethyldisiloxane 70 cc / min are introduced so that the degree of decompression is 2 ⁇ 10 ⁇ 1 Pa, and plasma is generated by applying an input power of 3,000 W from a high-frequency power source to the CVD electrode. Then, an inorganic layer [A3] was formed on the surface of the polymer substrate by CVD. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll via the winding side guide roll (code
  • Example 1 A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m was used as the polymer substrate, and the inorganic layer [A1] was provided on one side of the polymer substrate so as to have a thickness of 180 nm. .
  • the Zn atom concentration was 27.5 atom%
  • the Si atom concentration was 13.1 atom%
  • the Al atom concentration was 2.3 atom%
  • the O atom concentration was 57.1 atom%.
  • a test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the inorganic layer [A1] was formed, and the center plane average roughness SRa of the inorganic layer [A1] was evaluated.
  • the results are shown in Table 1.
  • a coating liquid for forming the silicon compound layer [B] 100 parts by mass of a coating agent mainly composed of perhydropolysilazane (“NN120-20” manufactured by AZ Electronic Materials, solid content concentration: 20% by mass)
  • a coating liquid 1 diluted with 300 parts by mass of butyl ether was prepared.
  • the coating liquid 1 is applied onto the inorganic layer [A1] with a micro gravure coater (gravure wire number 200UR, gravure rotation ratio 100%), dried at 120 ° C. for 1 minute, dried, and then subjected to UV treatment under the following conditions.
  • a silicon compound layer [B] having a thickness of 120 nm was provided to obtain a gas barrier film.
  • Ultraviolet treatment device MEIRH-M-1-152-H (manufactured by M. D. Excimer) Introduced gas: N 2 Oxygen concentration: 300-800ppm Integrated light quantity: 3,000 mJ / cm 2 Sample temperature control: 100 ° C.
  • the obtained gas barrier film was subjected to composition analysis using 29 Si CP / MAS NMR method, and the total peak area of ⁇ 30 to ⁇ 50 ppm when the total peak area of ⁇ 30 to ⁇ 120 ppm in the obtained spectrum was taken as 100.
  • the sum of peak areas from -50 to -90 ppm and the sum of peak areas from -90 to -120 ppm were calculated. The results are shown in Table 1.
  • Example 2 A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m was used as the polymer substrate.
  • a coating liquid for forming the undercoat layer [C] 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), and 1-hydroxy- 5 parts by mass of cyclohexyl phenyl-ketone (trade name: “IRGACURE” (registered trademark) 184) manufactured by BASF Japan Ltd.) and 3-methacryloxypropylmethyldiethoxysilane (trade name: KBM-503) manufactured by Shin-Etsu Silicone Co., Ltd.
  • a coating liquid 2 was prepared by blending part by mass, 170 parts by mass of ethyl acetate, 350 parts by mass of toluene, and 170 parts by mass of cyclohexanone. Next, the coating liquid 2 is applied onto the polymer substrate with a micro gravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, dried, and then subjected to UV treatment under the following conditions. An undercoat layer [C] having a thickness of 1,000 nm was provided.
  • a micro gravure coater gravure wire number 150UR, gravure rotation ratio 100%
  • Ultraviolet treatment device LH10-10Q-G (manufactured by Fusion UV Systems Japan) Introduced gas: N 2 (nitrogen inert BOX) Ultraviolet light source: Microwave type electrodeless lamp Integrated light quantity: 400 mJ / cm 2 Sample temperature control: room temperature.
  • Example 1 an inorganic layer [A1] and a silicon compound layer [B] were provided on the undercoat layer [C] in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.
  • the results are shown in Table 1.
  • Example 3 A gas barrier film was prepared in the same manner as in Example 1 except that an amorphous cyclic polyolefin film having a thickness of 100 ⁇ m (“ZEONOR FILM” ZF14 manufactured by ZEON Corporation) (“ZEONOR” is a registered trademark) was used as the polymer substrate. Obtained.
  • an amorphous cyclic polyolefin film having a thickness of 100 ⁇ m (“ZEONOR FILM” ZF14 manufactured by ZEON Corporation) (“ZEONOR” is a registered trademark) was used as the polymer substrate. Obtained.
  • Example 4 A gas barrier film was obtained in the same manner as in Example 2 except that an amorphous cyclic polyolefin film having a thickness of 100 ⁇ m (“ZEONOR FILM” ZF14 manufactured by Nippon Zeon Co., Ltd.) was used as the polymer substrate.
  • an amorphous cyclic polyolefin film having a thickness of 100 ⁇ m (“ZEONOR FILM” ZF14 manufactured by Nippon Zeon Co., Ltd.) was used as the polymer substrate.
  • Example 5 A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A1] was provided to have a thickness of 950 nm.
  • Example 6 A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A2] was provided to a thickness of 150 nm in place of the inorganic layer [A1].
  • Example 7 A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A3] was provided to a thickness of 150 nm in place of the inorganic layer [A1].
  • Example 8 A gas barrier film was obtained in the same manner as in Example 2 except that the silicon compound layer [B] was provided to have a thickness of 50 nm.
  • Example 9 A gas barrier film was obtained in the same manner as in Example 2 except that the silicon compound layer [B] was provided to have a thickness of 1,000 nm.
  • Example 10 A gas barrier film was obtained in the same manner as in Example 2 except that when the silicon compound layer [B] was formed, the amount of UV irradiation integrated light was changed to 1,500 mJ / cm 2 .
  • Example 11 A gas barrier film was obtained in the same manner as in Example 2 except that when the silicon compound layer [B] was formed, the UV irradiation integrated light amount was changed to 1,000 mJ / cm 2 .
  • Example 1 Comparative Example 1 Except that the inorganic layer [A] was not formed on the polymer substrate, and the silicon compound layer [B] was provided directly on the surface of the polymer substrate so as to have a thickness of 120 nm, the same as in Example 1. A gas barrier film was obtained.
  • Example 2 A gas barrier film was obtained in the same manner as in Example 1 except that the silicon compound layer [B] was not provided on the inorganic layer [A].
  • Example 3 (Comparative Example 3) In Example 1, the order of forming the inorganic layer [A] and the silicon compound layer [B] was changed to obtain a gas barrier film having a layer configuration different from that of Example 1.
  • Example 4 A gas barrier film was obtained in the same manner as in Example 7 except that the silicon compound layer [B] was not provided on the inorganic layer [A].
  • Example 5 A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A3] was provided on the inorganic layer [A] by the CVD method.
  • Example 2 is the same as Example 2 except that instead of the silicon compound layer [B], a layer made of only SiO p N q without SiN x H y and SiO a (OH) 4-2a is formed. Thus, a gas barrier film was obtained.
  • the method of forming the layer consisting only of SiO p N q uses a winding type sputtering apparatus having the structure shown in FIG. 2, on one side of the polymer substrate, using a sputtering target formed of silicon nitride Sputtering was performed to provide a layer made of only SiO p N q .
  • a polymer substrate is placed on the winding roll with a SiO p N q layer.
  • the surface to be provided was set so as to face the sputter electrode, and the polymer substrate was unwound and passed through a cooling drum through a guide roll.
  • Argon gas and oxygen gas were introduced into the sputtering chamber at an oxygen gas partial pressure of 10% so that the degree of vacuum was 2 ⁇ 10 ⁇ 1 Pa.
  • the gas barrier film of the present invention is excellent in gas barrier properties against oxygen gas, water vapor, etc., it can be usefully used, for example, as a packaging material for foods, pharmaceuticals, etc., and as a member for electronic devices such as thin televisions and solar cells. .

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Abstract

L'objet de la présente invention est de proposer un film barrière contre les gaz qui présente une performance de barrière contre les gaz élevée tout en présentant une excellente résistance à la flexion. Un film barrière contre les gaz selon la présente invention comprend de manière séquentielle, sur au moins une surface d'une base polymère, une couche inorganique (A) et une couche de composé de silicium (B) dans cet ordre à partir du côté base polymère. La couche de composé de silicium (B) contient au moins des composés de silicium présentant des structures représentées par SiNxHy, SiOpNq et SiOa(OH)4-2a (où x + y = 4, p + q =4, a < 2 et x, y, p, q > 0) ; et la couche inorganique (A) et la couche de composé de silicium (B) sont en contact l'une avec l'autre.
PCT/JP2015/051772 2014-01-29 2015-01-23 Film barrière contre les gaz WO2015115314A1 (fr)

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