WO2015115314A1 - Gas barrier film - Google Patents
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- 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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- 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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
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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
- 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
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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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
- 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
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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
- 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
Description
(1)高分子基材の少なくとも片側に、無機層[A]とケイ素化合物層[B]とを前記高分子基材側からこの順に有するガスバリア性フィルムであって、ケイ素化合物層[B]が、少なくともSiNxHy、SiOpNqおよびSiOa(OH)4-2a(x+y=4、p+q=4、a≦2 x,y,p,q>0)で表される構造を有するケイ素化合物を含み、かつ無機層[A]とケイ素化合物層[B]が接しているガスバリア性フィルム。 The present invention employs the following means in order to solve such problems. That is,
(1) A gas barrier film having an inorganic layer [A] and a silicon compound layer [B] in this order from the polymer substrate side on at least one side of the polymer substrate, wherein the silicon compound layer [B] , Silicon having a structure represented by at least SiN x H y , SiO p N q and SiO a (OH) 4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) A gas barrier film containing a compound and in contact with an inorganic layer [A] and a silicon compound layer [B].
(2)前記無機層[A]が、亜鉛化合物とケイ素酸化物とを含む(1)に記載のガスバリア性フィルム。
(3)前記ケイ素化合物層[B]の29Si CP/MAS NMRスペクトルにおいて、-30~-120ppmのピーク面積総和を100としたとき、-30~-50ppmのピーク面積総和が10以上、-50~-90ppmのピーク面積総和が10以上、かつ-90~-120ppmのピーク面積総和が80以下である(1)または(2)に記載のガスバリア性フィルム。
(4)前記無機層[A]が、以下の無機層[A1]~[A3]から選ばれるいずれかである(1)~(3)のいずれかに記載のガスバリア性フィルム。
無機層[A1]:(i)~(iii)の共存相からなる無機層
(i)酸化亜鉛
(ii)二酸化ケイ素
(iii)酸化アルミニウム
無機層[A2]:硫化亜鉛と二酸化ケイ素の共存相からなる無機層
無機層[A3]:ケイ素原子に対する酸素原子の原子数比が1.5~2.0であるケイ素
酸化物を主成分とする無機層
(5)前記無機層[A]が前記無機層[A1]であり、該無機層[A1]が、ICP発光分光分析法により測定される亜鉛原子濃度が20~40atom%、ケイ素原子濃度が5~20atom%、アルミニウム原子濃度が0.5~5atom%、酸素原子濃度が35~70atom%である組成により構成されたものである(4)に記載のガスバリア性フィルム。
(6)前記無機層[A]が前記無機層[A2]であり、該無機層[A2]が、硫化亜鉛と二酸化ケイ素の合計に対する硫化亜鉛のモル分率が0.7~0.9である組成により構成されたものである(4)に記載のガスバリア性フィルム。
(7)前記高分子基材と前記無機層[A]との間に、芳香族環構造を有するポリウレタン化合物[C1]を架橋して得られる構造を含むアンダーコート層[C]を有する(1)~(6)のいずれかに記載のガスバリア性フィルム。
(8)前記アンダーコート層[C]が有機ケイ素化合物および/または無機ケイ素化合物を含む(7)に記載のガスバリア性フィルム。 Further, as a preferred embodiment of the present invention, there are the following means.
(2) The gas barrier film according to (1), wherein the inorganic layer [A] contains a zinc compound and a silicon oxide.
(3) In the 29 Si CP / MAS NMR spectrum of the silicon compound layer [B], when the total peak area of −30 to −120 ppm is defined as 100, the total peak area of −30 to −50 ppm is 10 or more, −50 The gas barrier film according to (1) or (2), wherein the total peak area at ˜−90 ppm is 10 or more and the total peak area at −90 to −120 ppm is 80 or less.
(4) The gas barrier film according to any one of (1) to (3), wherein the 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. (5) 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%.
(6) 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.
(7) Between the polymer substrate and the inorganic layer [A], there is an undercoat layer [C] including a structure obtained by crosslinking a polyurethane compound [C1] having an aromatic ring structure (1) ) To (6).
(8) The gas barrier film according to (7), wherein the undercoat layer [C] contains an organosilicon compound and / or an inorganic silicon compound.
(9)(1)~(8)のいずれかに記載のガスバリア性フィルムを用いた電子デバイス。 The present invention also provides the following electronic device using a gas barrier film.
(9) An electronic device using the gas barrier film according to any one of (1) to (8).
なお、上記3つの構造の意味はそれぞれ以下のとおりである。
SiNxHy:化合物中に存在するケイ素原子へ窒素および水素が結合し、ケイ素からそれぞれの元素への結合数がxおよびyである。
SiOpNq:化合物中に存在するケイ素原子へ酸素および窒素が結合し、ケイ素からそれぞれの元素への結合数がpおよびqである。
SiOa(OH)4-2a:ケイ素原子を1としたときの化合物の構造。 The inventors have made extensive studies for the purpose of obtaining a gas barrier film having a high gas barrier property against water vapor and the like, and having excellent bending resistance and adhesion, and at least one side of the polymer base material is inorganic. Layer [A] and represented by SiN x H y , SiO p N q and SiO a (OH) 4-2 a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) When the silicon compound layer [B] containing three silicon compounds having a structure is laminated so as to be in this order, it has been found that the above-mentioned problems are solved.
The meanings of the three structures are as follows.
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.
本発明に用いられる高分子基材は、柔軟性を確保する観点からフィルム形態を有することが好ましい。フィルムの構成としては、単層フィルム、または2層以上の、例えば、共押し出し法で製膜したフィルムであってもよい。フィルムの種類としては、一軸方向あるいは二軸方向に延伸されたフィルム等を使用してもよい。 [Polymer substrate]
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. As the type of film, a film stretched in a uniaxial direction or a biaxial direction may be used.
本発明における無機層[A]は、亜鉛(Zn)、ケイ素(Si)、アルミニウム(Al)、チタン(Ti)、ジルコニウム(Zr)、スズ(Sn)、インジウム(In)、ニオブ(Nb)、モリブデン(Mo)、タンタル(Ta)等の元素の酸化物、窒化物、硫化物、または、それらの混合物が例示される。このような無機物を含んでいれば特に限定されるものではないが、無機層[A]がケイ素酸化物を含むことが好ましく、さらに亜鉛化合物とケイ素酸化物とを含むことがより好ましい。また、高いガスバリア性が得られる無機層[A]として、以下の無機層[A1]~[A3]から選ばれるいずれかが好適に用いられる。
無機層[A1]:(i)~(iii)の共存相からなる無機層
(i)酸化亜鉛
(ii)二酸化ケイ素
(iii)酸化アルミニウム
無機層[A2]:硫化亜鉛と二酸化ケイ素の共存相からなる無機層
無機層[A3]:ケイ素原子に対する酸素原子の原子数比が1.5~2.0であるケイ素酸化物を主成分とする無機層
無機層[A1]から[A3]のそれぞれの詳細は後述する。 [Inorganic layer [A]]
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. In addition, as the inorganic layer [A] from which high gas barrier properties can be obtained, any one selected from the following inorganic layers [A1] to [A3] is preferably used.
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 Each of the inorganic layers [A3]: [A3]: the inorganic layers [A1] to [A3] each of which is mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0 Details will be described later.
本発明において無機層[A]として好適に用いられる、(i)酸化亜鉛、(ii)二酸化ケイ素、および(iii)酸化アルミニウムの共存相(以下、(i)酸化亜鉛、(ii)二酸化ケイ素、および(iii)酸化アルミニウムの共存相を「酸化亜鉛-二酸化ケイ素-酸化アルミニウム共存相」と表記することもある)からなる層である無機層[A1]について詳細を説明する。なお、二酸化ケイ素(SiO2)は、生成時の条件によって、左記組成式のケイ素と酸素の組成比率から若干ずれたもの(SiO~SiO2)が生成することがあるが、ここでは二酸化ケイ素あるいはSiO2と表記することとする。かかる組成比の化学式からのずれに関しては、酸化亜鉛、酸化アルミニウムについても同様の扱いとし、それぞれ、生成時の条件に依存する組成比のずれに関わらず、それぞれ酸化亜鉛またはZnO、酸化アルミニウムまたはAl2O3と表記することとする。 [Inorganic layer [A1]]
In the present invention, (i) zinc oxide, (ii) silicon dioxide, and (iii) a coexisting phase of aluminum oxide (hereinafter referred to as (i) zinc oxide, (ii) silicon dioxide, And (iii) the inorganic layer [A1], which is a layer composed of the coexisting phase of aluminum oxide (sometimes referred to as “zinc oxide-silicon dioxide-aluminum oxide coexisting phase”) will be described in detail. Note that silicon dioxide (SiO 2 ) may be generated (SiO to SiO 2 ) that slightly deviates from the composition ratio of silicon and oxygen in the composition formula on the left, depending on the conditions at the time of production. It shall be described as SiO 2 . Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc oxide and aluminum oxide. Regardless of the deviation of the composition ratio depending on the conditions at the time of production, zinc oxide or ZnO, aluminum oxide or Al, respectively. It shall be expressed as 2 O 3 .
次に、本発明において無機層[A]として好適に用いられる、硫化亜鉛と二酸化ケイ素の共存相(以下、硫化亜鉛と二酸化ケイ素の共存相を「硫化亜鉛-二酸化ケイ素共存相」と表記することもある)からなる層である無機層[A2]について詳細を説明する。なお、ここでも二酸化ケイ素(SiO2)は、その生成時の条件によって、左記組成式のケイ素と酸素の組成比率から若干ずれたもの(SiO~SiO2)が生成することがあるが、二酸化ケイ素あるいはSiO2と表記することとする。かかる組成比の化学式からのずれに関しては、硫化亜鉛についても同様の扱いとし、生成時の条件に依存する組成比のずれに関わらず、硫化亜鉛またはZnSと表記することとする。 [Inorganic layer [A2]]
Next, 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. In this case as well, 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 . Regarding 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.
次に、本発明において無機層[A]として好適に用いられる、ケイ素原子に対する酸素原子の原子数比が1.5~2.0であるケイ素酸化物を主成分とする無機層[A3]について詳細を説明する。ここで、主成分とは無機層[A3]全体の60質量%以上であることを意味し、80質量%以上であれば好ましい。なお、前記の主成分二酸化ケイ素(SiO2)は、その生成時の条件によって、前記組成式のケイ素と酸素の組成比率から若干ずれたもの(SiO~SiO2)が生成することがあるが、二酸化ケイ素あるいはSiO2と表記することとする。 [Inorganic layer [A3]]
Next, 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. Here, 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 .
次に、ケイ素化合物層[B]について詳細を説明する。本発明におけるケイ素化合物層[B]は、SiNxHy、SiOpNqおよびSiOa(OH)4-2a(x+y=4、p+q=4、a≦2 x,y,p,q>0)で表される構造を有するケイ素化合物を含む層である。屈折率、硬さ、密着性などの制御を目的として、アルコキシシランやオルガノポリシロキサンなど他のケイ素化合物を含んでいてもよい。なお、ケイ素化合物層[B]の各化合物の組成は、29Si CP/MAS NMR法により測定することができる。 [Silicon compound layer [B]]
Next, the silicon compound layer [B] will be described in detail. In the present invention, the silicon compound layer [B] includes SiN x H y , SiO p N q and SiO a (OH) 4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0 ) Is a layer containing a silicon compound having a structure represented by: For the purpose of controlling the refractive index, hardness, adhesion, etc., 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.
無機層[A]が有するピンホールやクラック等の欠陥にケイ素化合物層[B]を構成する成分が充填され高いバリア性を発現することが可能となること。
ケイ素化合物層[B]が無機層[A]と接することで、前記無機層[A]に含まれる亜鉛等の成分が触媒として作用してケイ素化合物層[B]の膜質が改質し易くなり、ガスバリア性がさらに向上する。 (Ii) Next, the following are estimated as contributions by laminating the inorganic layer [A] and the silicon compound layer [B] in contact with each other.
The defect that the inorganic layer [A] has, such as pinholes and cracks, is filled with the components constituting the silicon compound layer [B], and high barrier properties can be expressed.
When the silicon compound layer [B] is in contact with the inorganic layer [A], components such as zinc contained in the inorganic layer [A] act as a catalyst to easily improve the film quality of the silicon compound layer [B]. Further, the gas barrier property is further improved.
本発明のガスバリア性フィルムには、ガスバリア性向上、耐屈曲性向上のため、前記高分子基材と前記無機層[A]との間にアンダーコート層[C]を設けることが好ましい。高分子基材上に突起や小擦り傷などの欠点が存在する場合、前記欠点を起点に高分子基材上に積層する無機層[A]にもピンホールやクラックが発生してガスバリア性や耐屈曲性が損なわれる場合があるため、本発明のアンダーコート層[C]を設けるのが好ましい。また、高分子基材と無機層[A]との熱寸法安定性の差が大きい場合も、ガスバリア性や耐屈曲性が低下する場合があるため、アンダーコート層[C]を設けるのが好ましい。また、本発明に用いられるアンダーコート層[C]は、熱寸法安定性、耐屈曲性の観点から芳香族環構造を有するポリウレタン化合物[C1]を架橋して得られる構造を含むことが好ましく、さらに、エチレン性不飽和化合物[C2]、光重合開始剤[C3]ならびに有機ケイ素化合物[C4]および無機ケイ素化合物[C5]から選ばれる1種以上のケイ素化合物を含有することがより好ましい。 [Undercoat layer [C]]
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. When defects such as protrusions and small scratches are present on the polymer substrate, pinholes and cracks also occur in the inorganic layer [A] laminated on the polymer substrate starting from the defects, resulting in gas barrier properties and resistance. Since the flexibility may be impaired, it is preferable to provide the undercoat layer [C] of the present invention. In addition, even when the difference in thermal dimensional stability between the polymer substrate and the inorganic layer [A] is large, it is preferable to provide the undercoat layer [C] because the gas barrier property and the bending resistance may be lowered. . 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].
本発明に用いることができる芳香族環構造を有するポリウレタン化合物[C1]は、主鎖あるいは側鎖に芳香族環およびウレタン結合を有するものであり、例えば、分子内に水酸基と芳香族環とを有するエポキシ(メタ)アクリレート(c1)、ジオール化合物(c2)、ジイソシアネート化合物(c3)とを重合させて得ることができる。 [Polyurethane compound having an aromatic ring structure [C1]]
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. For example, 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).
アンダーコート層[C]の原料とすることができるエチレン性不飽和化合物[C2]としては、例えば、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート等のジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の多官能(メタ)アクリレート、ビスフェノールA型エポキシジ(メタ)アクリレート、ビスフェノールF型エポキシジ(メタ)アクリレート、ビスフェノールS型エポキシジ(メタ)アクリレート等のエポキシアクリレート等を挙げられる。これらの中でも、熱寸法安定性、表面保護性能に優れた多官能(メタ)アクリレートが好ましい。また、これらは単一の組成で用いてもよいし、二成分以上を混合して使用してもよい。 [Ethylenically unsaturated compound [C2]]
Examples of the ethylenically unsaturated compound [C2] that can be used as a raw material for the undercoat layer [C] 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.
アンダーコート層[C]の原料とすることができる光重合開始剤[C3]としては、本発明のガスバリア性フィルムのガスバリア性および耐屈曲性を保持することができ、光重合を開始できれば特に限定されない。本発明に好適に用いることができる光重合開始剤としては、以下のものが例示される。
2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシルフェニルーケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン、フェニルグリオキシリックアシッドメチルエステル、2-メチル-1-(4-メチルチオフェニル)-2-モルホリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン等のアルキルフェノン系光重合開始剤。
2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキシド、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキシド等のアシルホスフィンオキシド系光重合開始剤。
ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム等のチタノセン系光重合開始剤。
1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(0-ベンゾイルオキシム)]等オキシムエステル構造を持つ光重合開始剤等。 [Photoinitiator [C3]]
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.
2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] Phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] 1- [4- (4-morpholinyl) phenyl] -1-alkyl phenone photopolymerization initiator such as butanone.
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 (η5-2,4-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)].
アンダーコート層[C]の原料とすることができる有機ケイ素化合物[C4]としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-イソシアネートプロピルトリエトキシシラン等が挙げられる。 [Organic silicon compound [C4]]
Examples of the organosilicon compound [C4] that can be used as the raw material for the undercoat layer [C] 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 Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanate propyl triethoxysilane, and the like.
アンダーコート層[C]の原料とすることができる無機ケイ素化合物[C5]としては、表面保護性能、透明性の観点からシリカ粒子が好ましく、さらにシリカ粒子の一次粒子径が1~300nmの範囲であることが好ましく、5~80nmの範囲であることがより好ましい。なお、ここでいう一次粒子径とは、ガス吸着法により求めた比表面積sを下記の式(2)に適用することで求められる粒子直径dを指す。
d=6/ρs(2)ここでρは粒子の密度である。 [Inorganic silicon compound [C5]]
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. In addition, the primary particle diameter here refers to the particle diameter d calculated | required by applying the specific surface area s calculated | required by the gas adsorption method to following formula (2).
d = 6 / ρs (2) where ρ is the density of the particles.
アンダーコート層[C]の厚みは、200nm以上、4,000nm以下が好ましく、300nm以上3,000nm以下がより好ましく、500nm以上、2,000nm以下がさらに好ましい。アンダーコート層[C]の厚みが小さすぎると、高分子基材上に存在する突起や、小擦り傷などによる欠点の悪影響を抑制できない場合がある。アンダーコート層[C]の厚みが大きすぎると、アンダーコート層[C]の平滑性が低下して前記アンダーコート層[C]上に積層する無機層[A]表面の凹凸形状も大きくなり、積層されるスパッタ粒子間に隙間ができるため、膜質が緻密になりにくく、ガスバリア性の向上効果が得られにくくなる場合がある。 [Thickness of undercoat layer [C]]
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.
本発明のガスバリア性フィルムの最表面の上には、ガスバリア性が低下しない範囲で耐擦傷性の向上を目的としたハードコート層を形成してもよいし、有機高分子化合物からなるフィルムをラミネートした積層構成としてもよい。なお、ここでいう最表面とは、高分子基材上に無機層[A]およびケイ素化合物層[B]が接するようにこの順に積層された後の、無機層[A]と接していない側のケイ素化合物層[B]の表面をいう。 [Other layers]
On the outermost surface of the gas barrier film of the present invention, 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].
本発明のガスバリア性フィルムは高いガスバリア性を有するため、様々な電子デバイスに用いることができる。例えば、太陽電池のバックシートやフレキシブル回路基板のような電子デバイスに好適に用いることができる。本発明のガスバリア性フィルムを用いた電子デバイスは、優れたガスバリア性を有するため、水蒸気等によるデバイスの性能低下を抑制することができる。 [Electronic device]
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.
本発明のガスバリア性フィルムは高いガスバリア性を有するため、電子デバイス以外にも、食品や電子部品の包装用フィルム等として好適に用いることができる。 [Other uses]
Since 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.
まず、各実施例および比較例における評価方法を説明する。特に記載のない限り評価n数は水準当たり5検体とし、得られた5検体の測定値の平均値を測定結果とした。 [Evaluation methods]
First, an evaluation method in each example and comparative example will be described. Unless otherwise stated, the number of evaluation n was 5 samples per level, and the average value of the measured values of the 5 samples obtained was used as the measurement result.
断面観察用サンプルをマイクロサンプリングシステム((株)日立製作所製 FB-2000A)を使用して集束イオンビーム(Focused Ion Beam:FIB)法により作製した。透過型電子顕微鏡((株)日立製作所製 H-9000UHRII)により、加速電圧300kVとして、観察用サンプルの断面を観察し、無機層[A]、ケイ素化合物層[B]、アンダーコート層[C]の厚みを測定した。 (1) 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.
三次元表面粗さ測定機(小坂研究所社製)を用いて、以下の条件で各層表面について測定した。
システム:三次元表面粗さ解析システム「i-Face model TDA31」
X軸測定長さ/ピッチ:500μm/1.0μm
Y軸測定長さ/ピッチ:400μm/5.0μm
測定速度:0.1mm/s
測定環境:温度23℃、相対湿度65%RH、大気中。 (2) Center plane average roughness SRa
Using a three-dimensional surface roughness measuring machine (manufactured by Kosaka Laboratory), the surface of each layer was measured under the following conditions.
System: Three-dimensional surface roughness analysis system “i-Face model TDA31”
X-axis measurement length / pitch: 500 μm / 1.0 μm
Y-axis measurement length / pitch: 400 μm / 5.0 μm
Measurement speed: 0.1 mm / s
Measurement environment: temperature 23 ° C., relative humidity 65% RH, in air.
真空蒸着により、ガスバリア性フィルムのケイ素化合物層[B]面に厚さ100nmのカルシウム層を形成し、次いで、同じく真空蒸着により前記カルシウム層上に、カルシウム層全域を覆うように厚さ3000nmのアルミニウム層を形成した。さらに、アルミニウム層形成後、前記アルミニウム層面に熱硬化性エポキシ樹脂を介して厚さ1mmのガラスを貼り合わせ、100℃で1時間処理し、評価サンプルを得た。得られたサンプルを、温度40℃、相対湿度90%RH、800時間処理し、前記処理後、水蒸気により腐食したカルシウムの量を算出することにより水蒸気の透過量を測定した。水蒸気透過度サンプル数は水準当たり2検体とし、測定回数は各検体について5回とし、得られた10点の平均値を水蒸気透過度(g/(m2・d))とした。 (3) Water vapor permeability (g / (m 2 · d))
A calcium layer having a thickness of 100 nm is formed on the silicon compound layer [B] side of the gas barrier film by vacuum deposition, and then aluminum having a thickness of 3000 nm so as to cover the entire calcium layer on the calcium layer by vacuum deposition. A layer was formed. Furthermore, after the aluminum layer was formed, glass having a thickness of 1 mm was bonded to the surface of the aluminum layer via a thermosetting epoxy resin and treated at 100 ° C. for 1 hour to obtain an evaluation sample. The obtained sample was treated at a temperature of 40 ° C. and a relative humidity of 90% RH for 800 hours, and after the treatment, the amount of calcium corroded by water vapor was calculated to measure the amount of water vapor permeated. 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)).
[A1]の組成分析はICP発光分光分析(エスアイアイ・ナノテクノロジー社製、SPS4000)により行った。高分子基材またはアンダーコート層上に無機層[A1]を形成した段階(ケイ素化合物層[B]を積層する前)でサンプリングした試料を硝酸および硫酸で加熱分解し、希硝酸で加温溶解してろ別した。不溶解分は加熱灰化したのち、炭酸ナトリウムで融解し、希硝酸で溶解して、先のろ液とあわせて定容とした。この溶液について、亜鉛原子、ケイ素原子、アルミニウム原子の含有量を測定し、原子数比に換算した。なお、酸素原子は亜鉛原子、ケイ素原子、アルミニウム原子が、それぞれ酸化亜鉛(ZnO)、二酸化ケイ素(SiO2)、酸化アルミニウム(Al2O3)として存在すると仮定して求めた計算値とした。 (4) Composition of inorganic layer [A1] The 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. About this solution, content of a zinc atom, a silicon atom, and an aluminum atom was measured, and it converted into atomic ratio. The oxygen atoms were calculated values assuming 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.
無機層[A2]の組成分析はICP発光分光分析(エスアイアイ・ナノテクノロジー社製、SPS4000)により行った。高分子基材またはアンダーコート層上に無機層[A2]を形成した段階(ケイ素化合物層[B]を積層する前)でサンプリングした試料を、硝酸および硫酸で加熱分解し、希硝酸で加温溶解してろ別した。不溶解分は加熱灰化したのち、炭酸ナトリウムで融解し、希硝酸で溶解して、先のろ液とあわせて定容とした。この溶液について、亜鉛原子、ケイ素原子の含有量を測定した。次に、この値をもとにさらにラザフォード後方散乱法(日新ハイボルテージ(株)製 AN-2500)を使用して、亜鉛原子、ケイ素原子、硫黄原子、酸素原子を定量分析し、硫化亜鉛と二酸化ケイ素の組成比を求めた。 (5) Composition of inorganic layer [A2] The composition analysis of the 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. Next, based on this value, 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.
無機層[A3]の組成分析はX線光電子分光法(XPS法)を用いることにより、ケイ素原子に対する酸素原子の原子数比を算出した。測定条件は下記の通りとした。
装置:Quantera SXM(PHI社製)
励起X線:monochromatic AlKα1,2
X線径:100μm
光電子脱出角度:10° 。 (6) Composition of inorganic layer [A3] The 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 AlKα1,2
X-ray diameter: 100 μm
Photoelectron escape angle: 10 °.
ケイ素化合物層[B]を片刃で削り取った粉末試料を7.5mmφの試料管に充填し、29Si CP/MAS NMR法を用いて組成分析を行い、図4に例を示したようなスペクトルを求めた。前記スペクトルにおける-30~-120ppmのピーク面積総和を100としたときの-30~-50ppmのピーク面積総和、-50~-90ppmのピーク面積総和、-90~-120ppmのピーク面積総和を算出した。測定条件は下記のとおりとした。
装置:Chemagnetics社製 CMX-300
測定核周波数:59.636511MHz(29Si核)
スペクトル幅:30.03kHz
パルス幅:4.5sec(90°パルス)、2.2sec(45°パルス)
パルス繰り返し時間:ACQTM;0.0682sec,PD;5.0sec
コンタクトタイム:2.0sec
観測ポイント:2048 データポイント;8192
基準物質:ヘキサメチルシクロトリシロキサン(外部基準;-9.66ppm)
温度:室温(約22℃)
試料回転数:5.0kHz
ピーク面積の算出:積分法。 (7) 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 mmφ 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.
Equipment: CMX-300 manufactured by Chemanetics
Measurement nuclear frequency: 59.636511 MHz ( 29 Si nucleus)
Spectrum width: 30.03 kHz
Pulse width: 4.5 sec (90 ° pulse), 2.2 sec (45 ° pulse)
Pulse repetition time: ACQTM; 0.0682 sec, PD; 5.0 sec
Contact time: 2.0 sec
Observation point: 2048 data points; 8192
Reference material: Hexamethylcyclotrisiloxane (external standard; -9.66 ppm)
Temperature: Room temperature (about 22 ° C)
Sample rotation speed: 5.0 kHz
Peak area calculation: integration method.
ガスバリア性フィルムを100mm×140mmに水準当たり2検体サンプリングした。図5に示すとおり、ガスバリア性フィルムを(符号19)の無機層[A]およびケイ素化合物層[B]が形成された面と反対面(符号21)の側の中央部に直径5mmの金属円柱(符号20)を固定し、この円柱に沿って、円柱の抱き角0°(サンプルが平面の状態)から、円柱への抱き角が180°(円柱で折り返した状態)となる範囲で、100回折り曲げ動作を行った後、(3)に示す方法で水蒸気透過度評価を行った。測定回数は各検体について5回とし、得られた10点の平均値を耐屈曲性試験後の水蒸気透過度とした。 (8) Flexibility Two samples of gas barrier film were sampled per 100 mm × 140 mm per level. As shown in FIG. 5, 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. In the range where 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. After performing the folding operation, 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.
JIS K5600-5-6:1999に準拠し、ケイ素化合物層[B]に1×1mmの直角の格子パターン25マスの切り込みを入れ、密着性を評価した。評価結果を密着性良好なものから順に分類0から分類5までの6段階に分類した。 (9) Adhesiveness In accordance with JIS K5600-5-6: 1999, the silicon compound layer [B] was cut into a 1 × 1 mm square lattice pattern of 25 squares to evaluate the adhesiveness. The evaluation results were classified into 6 levels from
(無機層[A1]の形成)
図2に示す構造の巻き取り式のスパッタリング装置(符号6a)を使用し、高分子基材(符号5)の片面に酸化亜鉛と二酸化ケイ素と酸化アルミニウムで形成された混合焼結材であるスパッタターゲットを用いてスパッタリングを実施し、無機層[A1]を設けた。 [Method for Forming Inorganic Layer [A] in Examples 1 to 11]
(Formation of inorganic layer [A1])
Sputtering, which is a mixed sintered material formed of zinc oxide, silicon dioxide and aluminum oxide on one side of a polymer substrate (reference numeral 5) using a winding type sputtering apparatus (reference numeral 6a) having the structure shown in FIG. Sputtering was performed using a target to provide an inorganic layer [A1].
図2に示す構造の巻き取り式のスパッタリング装置(符号6a)を使用し、高分子基材(符号5)の片面に、硫化亜鉛および二酸化ケイ素で形成された混合焼結材であるスパッタターゲットを用いてスパッタリングを実施し無機層[A2]を設けた。 (Formation of inorganic layer [A2])
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].
図3に示す構造の巻き取り式のCVD装置(符号6b)を使用し、高分子基材(5)の片面に、ヘキサメチルジシロキサンを原料とした化学気相蒸着を実施し無機層[A3]を設けた。 (Formation of inorganic layer [A3])
Using a roll-up type CVD apparatus (
5リットルの4つ口フラスコに、ビスフェノールAジグリシジルエーテルアクリル酸付加物(共栄社化学社製、商品名:エポキシエステル3000A)300質量部と、酢酸エチル710質量部とを入れ、内温60℃になるよう加温した。合成触媒としてジラウリン酸ジ-n-ブチル錫0.2質量部を添加し、攪拌しながらジシクロヘキシルメタン4,4’-ジイソシアネート(東京化成工業社製)200質量部を1時間かけて滴下した。滴下終了後2時間反応を続行し、続いてジエチレングリコール(和光純薬工業社製)25質量部を1時間かけて滴下した。滴下後5時間反応を続行し、重量平均分子量20,000の芳香族環構造を有するポリウレタン化合物を得た。 [Synthesis example of polyurethane compound [C1] having an aromatic ring structure]
In a 5 liter four-necked flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (trade name: Epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.) and 710 parts by mass of ethyl acetate were placed, and the internal temperature was 60 ° C It was heated so that it might become. As a synthesis catalyst, 0.2 part by mass of di-n-butyltin dilaurate was added, and 200 parts by mass of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. Reaction was continued for 2 hours after completion | finish of dripping, and 25 mass parts of diethylene glycol (made by Wako Pure Chemical Industries Ltd.) was dripped over 1 hour continuously. The reaction was continued for 5 hours after the dropwise addition to obtain a polyurethane compound having an aromatic ring structure with a weight average molecular weight of 20,000.
高分子基材として厚み50μmのポリエチレンテレフタレートフィルム(東レ株式会社製 “ルミラー”(登録商標)U48)を使用し、この高分子基材の片面に無機層[A1]を厚み180nmとなるよう設けた。無機層[A1]の組成は、Zn原子濃度が27.5atom%、Si原子濃度が13.1atom%、Al原子濃度が2.3atom%、O原子濃度が57.1atom%であった。無機層[A1]を形成したフィルムから縦100mm、横100mmの試験片を切り出し、無機層[A1]の中心面平均粗さSRaの評価を実施した。結果を表1に示す。 Example 1
A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm 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. . As for the composition of the inorganic layer [A1], the Zn atom concentration was 27.5 atom%, the Si atom concentration was 13.1 atom%, the Al atom concentration was 2.3 atom%, and 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.
紫外線処理装置:MEIRH-M-1-152-H(エム・ディ・エキシマ社製)
導入ガス:N2
酸素濃度:300~800ppm
積算光量:3,000mJ/cm2
試料温調:100℃。 Next, as 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
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.
高分子基材として厚み50μmのポリエチレンテレフタレートフィルム(東レ株式会社製 “ルミラー”(登録商標)U48)を使用した。
アンダーコート層[C]形成用の塗液として、前記ポリウレタン化合物150質量部と、ジペンタエリスリトールヘキサアクリレート(共栄社化学社製、商品名:ライトアクリレートDPE-6A)20質量部と、1-ヒドロキシ-シクロヘキシルフェニルーケトン(BASFジャパン社製、商品名:“IRGACURE”(登録商標)184)5質量部と、3-メタクリロキシプロピルメチルジエトキシシラン(信越シリコーン社製、商品名:KBM-503)3質量部と、酢酸エチル170質量部と、トルエン350質量部と、シクロヘキサノン170質量部とを配合して塗液2を調整した。次いで、塗液2を高分子基材上にマイクログラビアコーター(グラビア線番150UR、グラビア回転比100%)で塗布、100℃で1分間乾燥し、乾燥後、下記条件にて紫外線処理を施して厚み1,000nmのアンダーコート層[C]を設けた。 (Example 2)
A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the polymer substrate.
As 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. 3 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,
導入ガス:N2(窒素イナートBOX)
紫外線発生源:マイクロ波方式無電極ランプ
積算光量:400mJ/cm2
試料温調:室温。 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.
高分子基材として厚み100μmの非晶性環状ポリオレフィンフィルム(日本ゼオン社製 “ゼオノアフィルム”ZF14)(“ゼオノア”は登録商標)を使用した以外は、実施例1と同様にしてガスバリア性フィルムを得た。 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 μm (“ZEONOR FILM” ZF14 manufactured by ZEON Corporation) (“ZEONOR” is a registered trademark) was used as the polymer substrate. Obtained.
高分子基材として厚み100μmの非晶性環状ポリオレフィンフィルム(日本ゼオン社製 “ゼオノアフィルム”ZF14)を使用した以外は、実施例2と同様にしてガスバリア性フィルムを得た。 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 μm (“ZEONOR FILM” ZF14 manufactured by Nippon Zeon Co., Ltd.) was used as the polymer substrate.
無機層[A1]を厚み950nmとなるよう設けた以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (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.
無機層[A1]に代えて無機層[A2]を厚み150nmとなるよう設けた以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (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].
無機層[A1]に代えて無機層[A3]を厚み150nmとなるよう設けた以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (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].
ケイ素化合物層[B]を厚み50nmとなるよう設けた以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (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.
ケイ素化合物層[B]を厚み1,000nmとなるよう設けた以外は、実施例2と同様にしてガスバリア性フィルムを得た。 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.
ケイ素化合物層[B]形成時、紫外線照射積算光量を1,500mJ/cm2に変更した以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (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 .
ケイ素化合物層[B]形成時、紫外線照射積算光量を1,000mJ/cm2に変更した以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (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 .
高分子基材上に無機層[A]を形成しないで、高分子基材の表面に直接、ケイ素化合物層[B]を厚み120nmとなるように設けた以外は、実施例1と同様にしてガスバリア性フィルムを得た。 (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.
無機層[A]上にケイ素化合物層[B]設けない以外は、実施例1と同様にしてガスバリア性フィルムを得た。 (Comparative 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].
実施例1において、無機層[A]とケイ素化合物層[B]とを形成する順序を入れ替え、実施例1と層構成が異なるガスバリア性フィルムを得た。 (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.
無機層[A]上にケイ素化合物層[B]を設けない以外は、実施例7と同様にしてガスバリア性フィルムを得た。 (Comparative 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].
CVD法により無機層[A]上に無機層[A3]を設ける以外は、実施例2と同様にしてガスバリア性フィルムを得た。 (Comparative 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.
実施例2において、ケイ素化合物層[B]に代えてSiNxHy並びにSiOa(OH)4-2aを含まずSiOpNqのみからなる層を形成すること以外は、実施例2と同様にしてガスバリア性フィルムを得た。
なお、SiOpNqのみからなる層の形成方法は、図2に示す構造の巻き取り式のスパッタリング装置を使用し、高分子基材の片面に、窒化珪素で形成されたスパッタターゲットを用いてスパッタリングを実施しSiOpNqのみからなる層を設けた。具体的な操作は、まず、スパッタ電極に窒化珪素で形成されたスパッタターゲットを設置した巻き取り式スパッタ装置の巻き取り室の中で、巻き出しロールに高分子基材をSiOpNq層を設ける側の面がスパッタ電極に対向するようにセットし、高分子基材を巻き出し、ガイドロールを介して、クーリングドラムに通した。減圧度2×10-1Paとなるように酸素ガス分圧10%としてアルゴンガスおよび酸素ガスをスパッタリング室へ導入した。さらに高周波電源により投入電力1,000Wを印加することにより、アルゴン・酸素ガスプラズマを発生させ、スパッタリングにより高分子基材の表面上にSiOpNq層を形成した。厚みは、フィルム搬送速度により調整した。その後、ガイドロールを介して巻き取りロールに巻き取った。 (Comparative Example 6)
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.
In addition, 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 . Specifically, first, in the winding chamber of a winding-type sputtering apparatus in which a sputtering target formed of silicon nitride is installed on the sputtering electrode, 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. Further, by applying an input power of 1,000 W from a high frequency power source, argon / oxygen gas plasma was generated, and a SiO p N q layer 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 via the guide roll.
2 無機層[A]
3 ケイ素化合物層[B]
4 アンダーコート層[C]
5 高分子基材
6a 巻き取り式スパッタリング装置
6b 巻き取り式CVD装置
7 巻き取り室
8 巻き出しロール
9、10、11 巻き出し側ガイドロール
12 クーリングドラム
13 スパッタ電極
14 CVD電極
15、16、17 巻き取り側ガイドロール
18 巻き取りロール
19 ガスバリア性フィルム
20 金属円柱
21 無機層[A]およびケイ素化合物層[B]が形成された面と反対面 1 Polymer substrate 2 Inorganic layer [A]
3 Silicon compound layer [B]
4 Undercoat layer [C]
5
Claims (9)
- 高分子基材の少なくとも片側に、無機層[A]とケイ素化合物層[B]とを前記高分子基材側からこの順に有するガスバリア性フィルムであって、ケイ素化合物層[B]が、少なくともSiNxHy、SiOpNqおよびSiOa(OH)4-2a(x+y=4、p+q=4、a≦2 x,y,p,q>0)で表される構造を有するケイ素化合物を含み、かつ無機層[A]とケイ素化合物層[B]が接しているガスバリア性フィルム。 A gas barrier film having an inorganic layer [A] and a silicon compound layer [B] in this order from the polymer substrate side on at least one side of the polymer substrate, in which the silicon compound layer [B] is at least SiN a silicon compound having a structure represented by x H y , SiO p N q and SiO a (OH) 4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) And a gas barrier film in which the inorganic layer [A] and the silicon compound layer [B] are in contact.
- 前記無機層[A]が、亜鉛化合物とケイ素酸化物とを含む請求項1に記載のガスバリア性フィルム。 The gas barrier film according to claim 1, wherein the inorganic layer [A] contains a zinc compound and a silicon oxide.
- 前記ケイ素化合物層[B]の29Si CP/MAS NMRスペクトルにおいて、-30~-120ppmのピーク面積総和を100としたとき、-30~-50ppmのピーク面積総和が10以上、-50~-90ppmのピーク面積総和が10以上、かつ-90~-120ppmのピーク面積総和が80以下である請求項1または2に記載のガスバリア性フィルム。 In the 29 Si CP / MAS NMR spectrum of the silicon compound layer [B], when the total peak area of −30 to −120 ppm is defined as 100, the total peak area of −30 to −50 ppm is 10 or more, −50 to −90 ppm The gas barrier film according to claim 1 or 2, wherein the total peak area is 10 or more and the total peak area of -90 to -120 ppm is 80 or less.
- 前記無機層[A]が、以下の無機層[A1]~[A3]から選ばれるいずれかである請求項1~3のいずれかに記載のガスバリア性フィルム。
無機層[A1]:(i)~(iii)の共存相からなる無機層
(i)酸化亜鉛
(ii)二酸化ケイ素
(iii)酸化アルミニウム
無機層[A2]:硫化亜鉛と二酸化ケイ素の共存相からなる無機層
無機層[A3]:ケイ素原子に対する酸素原子の原子数比が1.5~2.0であるケイ素酸化物を主成分とする無機層 The gas barrier film according to any one of claims 1 to 3, wherein the 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]: inorganic layer mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0 - 前記無機層[A]が前記無機層[A1]であり、該無機層[A1]が、ICP発光分光分析法により測定される亜鉛原子濃度が20~40atom%、ケイ素原子濃度が5~20atom%、アルミニウム原子濃度が0.5~5atom%、酸素原子濃度が35~70atom%である組成により構成されたものである請求項4に記載のガスバリア性フィルム。 The inorganic layer [A] is the inorganic layer [A1], and the inorganic layer [A1] has a zinc atom concentration of 20 to 40 atom% and a silicon atom concentration of 5 to 20 atom% as measured by ICP emission spectroscopy. The gas barrier film according to claim 4, wherein the gas barrier film is composed of a composition having an aluminum atom concentration of 0.5 to 5 atom% and an oxygen atom concentration of 35 to 70 atom%.
- 前記無機層[A]が前記無機層[A2]であり、該無機層[A2]が、硫化亜鉛と二酸化ケイ素の合計に対する硫化亜鉛のモル分率が0.7~0.9である組成により構成されたものである請求項4に記載のガスバリア性フィルム。 The inorganic layer [A] is the inorganic layer [A2], and the inorganic layer [A2] has a composition in which the molar fraction of zinc sulfide to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier film according to claim 4, which is constituted.
- 前記高分子基材と前記無機層[A]との間に、芳香族環構造を有するポリウレタン化合物[C1]を架橋して得られる構造を含むアンダーコート層[C]を有する請求項1~6のいずれかに記載のガスバリア性フィルム。 An undercoat layer [C] including a structure obtained by crosslinking a polyurethane compound [C1] having an aromatic ring structure is provided between the polymer substrate and the inorganic layer [A]. The gas barrier film according to any one of the above.
- 前記アンダーコート層[C]が有機ケイ素化合物および/または無機ケイ素化合物を含む請求項7に記載のガスバリア性フィルム。 The gas barrier film according to claim 7, wherein the undercoat layer [C] contains an organosilicon compound and / or an inorganic silicon compound.
- 請求項1~8のいずれかに記載のガスバリア性フィルムを用いた電子デバイス。 An electronic device using the gas barrier film according to any one of claims 1 to 8.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012240222A (en) * | 2011-05-16 | 2012-12-10 | Toppan Printing Co Ltd | Gas barrier film, and back protection sheet for solar cell using the same |
JP2013188871A (en) * | 2012-03-12 | 2013-09-26 | Toppan Printing Co Ltd | Gas barrier laminated film |
JP2013198983A (en) * | 2012-03-23 | 2013-10-03 | Toray Advanced Film Co Ltd | Gas barrier film |
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