JP6750285B2 - Gas barrier laminate - Google Patents

Description

The present invention relates to a gas barrier laminate.

The gas barrier layered product is a layered product having a property (gas barrier property) of not permeating gas such as oxygen and water vapor. Therefore, the member held at the site shielded by the gas barrier laminate can suppress deterioration/deterioration and the like due to external gas. In recent years, such a gas barrier laminate has been utilized in various fields.

Such a gas barrier laminate is utilized, for example, as a packaging material used for packaging foods and the like. In packaging applications such as foods, it is required to prevent alteration of the contents. Specifically, it is required to suppress oxidation and deterioration of proteins, fats and oils, and to maintain flavor and freshness. Therefore, the gas barrier laminate is preferably used.

Further, such a gas barrier laminate is utilized as a packaging material used for packaging pharmaceuticals, for example. In packaging applications such as pharmaceuticals, it is required to prevent alteration of the contents. Specifically, it is required to maintain the aseptic condition, suppress the alteration of the active ingredient of the contents, and maintain its efficacy. Therefore, the gas barrier laminate is preferably used.

In addition, such a gas barrier laminate is utilized as a packaging material used for packaging electronic components such as semiconductor wafers and precision components. When exposed to an external gas, the precision component may become a defective product because the external gas may act as a foreign substance, and thus it is required to shield the external gas. Therefore, the gas barrier laminate is preferably used.

Further, such a gas barrier laminate is utilized as a member for flat panel displays such as liquid crystal displays and organic EL displays. In applications of flat panel displays, it is required to prevent deterioration of internal members such as pixel elements. Therefore, the gas barrier laminate is preferably used.

In addition, such a gas barrier laminate is utilized as, for example, a back sheet or a front sheet in a solar cell. In solar cell applications, it is required to prevent deterioration of the internal mechanism due to ultraviolet rays and moisture. Therefore, the gas barrier laminate is preferably used.

Here, when such a gas barrier laminate is used as a packaging member, it is preferable that it also has transparency. Since the packaging material is transparent, it is possible to visually check the shape and color of the contents from the outside of the package, thereby preventing the contents from being mixed up, the presence or absence of damage, and the contents. It is possible to grasp the presence or absence of alteration before opening the package.

As described above, the gas barrier laminate is required to have not only gas barrier properties but also properties such as transparency, moisture resistance, weather resistance, and durability at a high level so that it can be applied to a wide variety of applications. To be

Conventionally, as a gas barrier laminate, a gas barrier laminate in which a gas barrier substance is vapor-deposited on a film substrate is known. The vapor-deposited film of the gas barrier substance has a gas barrier property and is also extremely transparent because it is extremely thin.

Examples of such a gas barrier laminate include a silica-based vapor deposition film and an alumina reaction vapor deposition film. The silica-based vapor deposition film is a laminated body in which silicon monoxide or a Si/SiO ₂ mixed material is vapor deposited on a film base material. Further, the alumina reactive vapor deposition film is a laminate in which metallic aluminum is vaporized and reacted with oxygen to vapor-deposit it on a film base material.

Here, since the gas barrier properties of silica-based vapor deposition films and alumina reaction vapor deposition films are easily affected by temperature and moisture, gas barrier laminates having improved heat resistance, water resistance, and moisture resistance have been proposed (Patent Reference 1 and Patent Reference 2).

The laminated body disclosed in Patent Document 1 and Patent Document 2 further comprises a water-soluble polymer such as polyvinyl alcohol and an alkoxysilane such as tetraethoxysilane or its hydrolysis on a vapor deposition film provided on a substrate. A coating liquid containing a substance is applied and dried by heating to form a gas barrier film. With such a structure, gas barrier properties, heat resistance, water resistance, moisture resistance, etc. are improved.

JP-A-7-164591 International Publication No. 2004/048081

However, as the applications are expanded, the gas barrier laminate is required to be used in a more severe environment. Therefore, further improvements in durability such as moisture resistance, heat resistance, water resistance, weather resistance, bending resistance, and stretch resistance are required. Here, examples of the harsh environment include plastic deformation due to pulling, load due to exposure to high temperature and high humidity, and the like.

Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a gas barrier laminate that exhibits excellent gas barrier properties even in a harsh environment.

As a result of intensive studies, the present inventors have found a compound suitable for an overcoat layer laminated on a vapor deposition layer in a gas barrier laminate, and have completed the present invention.

The present invention has the following aspects.

[1] A resin base material, a vapor deposition layer laminated on at least one surface of the resin base material, and an overcoat layer laminated on the vapor deposition layer, wherein the overcoat layer has the following general formula (a): ) at least one member selected from the materials and the group consisting of the hydrolyzate represented by Ri name contains a water-soluble polymer having a hydroxyl group, a vinyl group or methacryloxy group in the overcoat layer gas barrier laminate, characterized that you have remaining.
_{X- (CH 2) n -Si (} OR) 3 ...... (a)
[However, X is a vinyl group or a methacryloxy group, R is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 6 or more. ]

[2] The gas barrier laminate according to the above [1], wherein the gas barrier laminate has an oxygen permeability after a 3% tensile test of 10 times or less than the initial value.

[3] The gas barrier laminate according to the above [1] or [2], wherein the gas barrier laminate has an oxygen permeability within 10 times the initial value after a storage test at 40° C. and 90% RH for 500 hours. body.

[4] A gas barrier laminate comprising an anchor coat layer between the resin base material and the vapor deposition layer, wherein the anchor coat layer comprises an acrylic polyol having two or more hydroxyl groups and an NCO group in the molecule. An isocyanate compound having at least two or more is contained, and the hydroxyl value of the acrylic polyol is 50 mgKOH/g or more and 250 mgKOH/g or less, and the equivalent ratio of the NCO group of the isocyanate compound to the hydroxyl group of the acrylic polyol (NCO/OH ) Is 0.3 or more and 2.5 or less, The gas barrier laminate according to any one of the above [1] to [3].

The gas barrier laminate of the present invention has an overcoat layer formed from a coating material containing a specific organic silicon compound or its hydrolyzate and a water-soluble polymer having a hydroxyl group on the vapor deposition layer. As a result, even in a harsh environment, deterioration of the overcoat layer and the vapor deposition layer is suppressed, and excellent gas barrier properties are exhibited. Therefore, even in applications where deformation is added by processing, harsh treatment such as boil sterilization, retort sterilization, and harsh environments such as outdoor placement, excellent gas barrier properties are provided over a long period of time. It is possible to provide a gas-barrier laminate that exhibits performance.

It is a schematic sectional drawing which shows a certain aspect of a gas barrier laminated body. It is a schematic sectional drawing which shows a certain aspect of a gas barrier laminated body.

Hereinafter, embodiments of the gas barrier laminate according to the present invention will be specifically described with reference to the drawings. However, the specific configuration of the present invention is not limited to the contents of the following embodiments, and even if there are design changes and the like within the scope of the present invention, they are included in the present invention.

(Gas barrier laminate)
FIG. 1 shows a schematic sectional view of an embodiment of the gas barrier laminate of the present invention. The gas barrier laminate 10 is a laminate having a structure in which a vapor deposition layer 12 and an overcoat layer 13 are sequentially laminated on one surface of a resin base material 11. Hereinafter, the direction in which the vapor deposition layer 12 and the overcoat layer 13 are laminated will be described as the upper side (layer) based on the resin base material 11.

<Resin base material>
The resin base material is a layer serving as a base body of the gas barrier laminate.

The resin base material may be appropriately selected and used from among various commonly used sheet-like base materials (including film-like base materials). For example, (1) polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), (2) polyolefin films such as polyethylene and polypropylene, (3) polyethersulfone (PES), polystyrene film, polyamide film, poly Examples thereof include vinyl chloride film, polycarbonate film, polyacrylonitrile film, polyimide film, and biodegradable plastic film such as polylactic acid.

Further, the resin base material may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant and a colorant.

Further, the thickness of the resin base material is not particularly limited and may be appropriately determined according to specifications and the like. Practically, the thickness of the resin substrate is preferably 6 μm or more and 200 μm or less, preferably 12 μm or more and 125 μm or less, more preferably 12 μm or more and 50 μm or less. However, in the gas barrier laminate of the present embodiment, the thickness of the resin base material is not limited to the above range.

Further, the surface of the resin substrate may be surface-treated. By performing the surface treatment, the adhesion with other layers can be increased when laminating other layers (evaporation layer, anchor coat layer, etc.). Here, as the surface treatment, for example, (1) physical treatment such as corona treatment, plasma treatment, and flame treatment, and (2) chemical treatment such as chemical treatment with acid or alkali may be used.

<Deposition layer>
The vapor deposition layer is a layer formed on the resin base material by vapor deposition of a vapor deposition material in order to impart gas barrier properties.

The vapor deposition material used for the vapor deposition layer may be appropriately selected and used from known inorganic materials for forming a vapor barrier vapor deposition film. Examples thereof include metals such as Si, Al, Zn, Sn, Fe, and Mn, and inorganic compounds containing one or more of these metals. Examples of the inorganic compound include oxides, nitrides, carbides and fluorides. Among these, at least one selected from metals and metal oxides is preferable. Specifically, for example, silicon monoxide, silicon oxide such as silicon dioxide (SiO _x ), aluminum oxide, magnesium oxide, tin oxide and the like can be mentioned.

The method for forming the vapor deposition layer may be appropriately selected from known vapor deposition methods and used. For example, a chemical vapor deposition (CVD) method such as a physical vapor deposition (PVD: Physical Vapor Deposition) method such as a vacuum vapor deposition method and a sputtering method, an ion plating method, a plasma vapor deposition method, and an ALD: Atomic Layer Deposition method or the like may be used. In particular, the EB: Electron Beam heating vacuum vapor deposition method can obtain a high film formation rate, and is preferable as a method for forming a vapor deposition layer of the gas barrier laminate of the present embodiment.

Moreover, you may use the reactive vapor deposition method in performing vapor deposition. The reactive vapor deposition method is a method in which, when a vapor deposition material is vapor-deposited, the vaporized particles are caused to react with a gas introduced into an atmosphere to perform vapor deposition. Examples of the gas to be introduced include oxygen gas and argon gas. By performing reactive vapor deposition with oxygen gas or the like, the metal component in the vapor deposition material is oxidized and the transparency of the vapor deposition layer can be improved. Further, when the reactive vapor deposition method is used, it is desirable that the pressure in the film forming chamber be 2×10 ⁻¹ Pa or less when introducing the gas. If the pressure in the film forming chamber is higher than 2×10 ⁻¹ Pa, the vapor deposition layer may not be laminated neatly and the water vapor barrier property may deteriorate.

The thickness of the vapor deposition layer is preferably 5 nm or more and 300 nm or less, more preferably 10 nm or more and 150 nm or less. When the thickness is 5 nm or more, sufficient barrier properties are exhibited, and when the thickness is 300 nm or less, cracking and deterioration of the barrier properties due to cracks are less likely to occur in a later step. However, in the gas barrier laminate of the present embodiment, the film thickness of the vapor deposition layer is not limited to the above range.

<Overcoat layer>
The overcoat layer is a layer formed on the vapor deposition layer. By stacking the overcoat layer on the vapor deposition layer, it is possible to obtain excellent gas barrier properties that cannot be exhibited by a gas barrier laminate having a single vapor deposition layer. The overcoat layer also has a function of protecting the dense and fragile vapor deposition layer, and can suppress the generation of cracks due to rubbing and bending.

The overcoat layer is formed by adjusting the coating liquid, applying the coating liquid on the vapor deposition layer, and heating and drying the coating liquid.

In the gas barrier laminate of the present embodiment, the coating liquid for forming the overcoat layer contains at least one selected from the group consisting of a substance represented by the following general formula (a) and a hydrolyzate thereof and a hydroxyl group. And a water-soluble polymer having.
_{X- (CH 2) n-Si} (OR) 3 ...... (a)
[However, X is a vinyl group or a methacrylic group, R is an alkyl group, and n is an integer of 6 or more. ]

In the organosilicon compound having a Si-OR bond, the OR group bonded to the silicon atom becomes a hydroxyl group by a hydrolysis reaction, and a siloxane bond is formed by dehydration condensation of the hydroxyl group. By using the organosilicon compound represented by the formula (a), a dense and strong network polymerized film can be formed. Further, by having a vinyl group or a methacrylic group in the molecule, an organic-inorganic composite film having both toughness and flexibility is formed. Further, since there are 6 or more carbon atoms between the organosilicon compound and the vinyl group or methacrylic group, the molecules at both ends are easily moved, and a film having high flexibility is formed. Therefore, it is possible to obtain an overcoat layer having excellent heat resistance, water resistance, moisture resistance, bending resistance, stretch resistance, and the like.

The water-soluble polymer having a hydroxyl group is preferably polyvinyl alcohol, polycarboxylic acid, starch, or celluloses. Especially when polyvinyl alcohol (hereinafter PVA) is used for the coating agent of the present invention, the gas barrier property is excellent. Since PVA is a polymer having the largest number of hydroxyl groups in the monomer unit, it has a very strong hydrogen bond with the hydroxyl groups of the organosilicon compound after hydrolysis. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and is a complete saponification in which only a few percent of acetic acid groups remain from a so-called partially saponified PVA in which several tens percent of acetic acid groups remain. Including up to PVA. Although the molecular weight of PVA varies from 300 to several thousand, there is no problem in the effect regardless of the molecular weight. However, in general, a high molecular weight PVA having a high degree of saponification and a high degree of polymerization has high water resistance and is therefore preferable.

In formula (a), the alkyl group of R is preferably an alkyl group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group, or a propyl group. Examples of the substance represented by the formula (a) include 7-octenyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane.

Examples of the hydrolyzate of the organosilicon compound represented by the formula (a) include those in which at least one of ORs in the formula is OH. The hydrolyzate can be prepared by a known method. For example, it can be prepared by dissolving an organosilicon compound in an alcohol such as methanol or isopropyl alcohol, and adding an aqueous solution of an acid such as hydrochloric acid to the solution to cause a hydrolysis reaction.

The substance represented by the formula (a) and its hydrolyzate may be used alone or in combination of two or more. The compounding amount of the substance represented by the formula (a) and its hydrolyzate in the coating liquid can be appropriately set in consideration of gas barrier properties, durability, suitability for post-processing, etc., but is not particularly limited, but is based on the total solid content. 1 mass% or more and 100 mass% or less is preferable, and 3 mass% or more and 90 mass% or less is more preferable. When it is 1 mass% or more, the gas barrier property and the wet heat durability are good. When it is 90% by mass or less, the durability is better.

Further, the gas barrier laminate preferably has an oxygen permeability of 10 times or less, more preferably 5 times or less of the initial value after the 3% tensile test. When it exceeds 10 times, the stability of the barrier property is lowered.

Further, it is preferable that the gas barrier laminate has an oxygen permeability within 10 times the initial value after a storage test at 40° C. and 90% RH for 500 hours.

The oxygen permeability after the treatment at 40° C. and 90% RH for 500 hours is preferably within 10 times the initial value, more preferably within 5 times the initial value. When it exceeds 10 times, the stability of the barrier property is lowered.

The coating liquid for forming the overcoat layer is prepared by mixing the substance represented by the formula (a) and its hydrolyzate, a water-soluble polymer having a hydroxyl group, and a solvent. Any solvent can be used as long as it can dissolve the components, and examples thereof include water, alcohol, toluene, ethyl acetate, acetone, and methyl ethyl ketone. These solvents may be used alone or in combination of two or more.

As a coating method of the coating liquid, a usual coating method can be used. For example, well-known methods such as a dipping method, a low coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method and a gravure offset method can be used. As the drying method, hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation and the like can be used alone or in combination of two or more. The heating temperature at the time of drying is preferably in the range of 60° C. or higher and 200° C. or lower, and more preferably in the range of 100° C. or higher and 150° C. or lower. When the temperature is 60° C. or higher, the desired barrier property is exhibited, which is favorable. When the temperature is 150° C. or lower, the substrate is not deformed and the vapor deposition film is not cracked for a short time, which is preferable.

The thickness of the overcoat layer is preferably about 0.1 μm or more and 2 μm or less, more preferably about 0.2 μm or more and 1.0 μm or less. When the thickness is 0.1 μm or more, the barrier property is stably exhibited, and when the thickness is 1 μm or less, the post-processability such as printing, laminating of other films and bending is excellent. However, in the gas barrier laminate of the present embodiment, the film thickness of the overcoat layer is not limited to the above range.

Further, the gas barrier laminate of the present embodiment may have a plate shape or a film shape. For example, it may be formed into a film by winding with a roll.

(Anchor coat layer)
The gas barrier laminate of the present embodiment may further include an anchor coat layer between the resin base material and the vapor deposition layer. By providing the anchor coat layer, it is possible to enhance the adhesion between the resin base material and the vapor deposition layer and suppress the occurrence of peeling between the layers.

FIG. 2 shows a schematic sectional view of an embodiment of the gas barrier laminate of the present invention in which an anchor coat layer is laminated. The gas barrier laminate 20 is a laminate in which the anchor coat layer 24, the vapor deposition layer 12, and the overcoat layer 13 are sequentially laminated on one surface of the resin substrate 11.

The anchor coat layer is formed by adjusting the anchor coat agent, applying the anchor coat agent on the resin substrate, and heating and drying the applied anchor coat agent.

The anchor coating agent preferably contains an acrylic polyol having two or more hydroxyl groups and an isocyanate compound having at least two NCO groups in the molecule.

As the acrylic polyol, a polymer compound obtained by polymerizing a (meth)acrylic acid derivative monomer having a hydroxyl group, and a polymer compound obtained by copolymerizing a (meth)acrylic acid derivative monomer having a hydroxyl group with another monomer And so on. Examples of the (meth)acrylic acid derivative monomer having a hydroxyl group include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate. As the other monomer copolymerizable with the (meth)acrylic acid derivative monomer having a hydroxyl group, a (meth)acrylic acid derivative monomer having no hydroxyl group is preferable. Examples of the (meth)acrylic acid derivative monomer having no hydroxyl group include (meth)acrylic acid derivative monomers having an alkyl group, (meth)acrylic acid derivative monomers having a carboxyl group, and (meth)acrylic acid having a ring structure. Examples thereof include derivative monomers. Examples of the (meth)acrylic acid derivative monomer having an alkyl group include alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate and t-butyl(meth)acrylate. Is mentioned. Examples of the (meth)acrylic acid derivative monomer having a carboxyl group include (meth)acrylic acid. Examples of the (meth)acrylic acid derivative monomer having a ring structure include benzyl (meth)acrylate and cyclohexyl (meth)acrylate. As the other monomer, a monomer other than the (meth)acrylic acid derivative monomer may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer. Monomers other than the (meth)acrylic acid derivative monomer may have a hydroxyl group.

The hydroxyl value of the acrylic polyol is preferably 50 [mgKOH/g] or more and 250 [mgKOH/g] or less. The hydroxyl value [mgKOH/g] is an index of the amount of hydroxyl groups in the acrylic polyol, and indicates the mg number of potassium hydroxide required to acetylate the hydroxyl groups in 1 g of the acrylic polyol. When the hydroxyl value is less than [50 mgKOH/g], the reaction amount with the isocyanate compound is small, and the effect of improving the adhesion between the resin base material and the vapor deposition layer by the anchor coat layer may not be sufficiently exhibited. On the other hand, when the hydroxyl value is larger than [250 mgKOH/g], the reaction amount with the isocyanate compound becomes too large, and the film shrinkage of the anchor coat layer may become large. If the film shrinkage is large, the vapor-deposited layer may not be laminated neatly on it, and sufficient gas barrier properties may not be exhibited.

The weight average molecular weight of the acrylic polyol is not particularly limited, but is preferably 3000 or more and 200,000 or less, more preferably 5000 or more and 100000 or less, and further preferably 5000 or more and 40,000 or less. In the present specification, the weight average molecular weight is a weight average molecular weight measured by GPC (gel permeation chromatography) with polystyrene as a reference. The acrylic polyol may be used alone or in combination of two or more.

The isocyanate compound may be one having at least two NCO groups in the molecule. For example, as a monomeric isocyanate, an aromatic isocyanate such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate Aliphatic isocyanate such as (H12MDI), xylene diisocyanate (XDI), araliphatic isocyanate such as tetramethylxylylene diisocyanate (TMXDI) may be used. Further, polymers or derivatives of these monomeric isocyanates may also be used. Examples of the polymer or derivative include trimeric nurate type, adduct type reacted with 1,1,1-trimethylolpropane, and biuret type reacted with biuret. The isocyanate compound may be arbitrarily selected from the above-mentioned monomeric isocyanates, polymers and derivatives thereof, and one kind may be used alone or two or more kinds may be used in combination.

In the anchor coating agent, the equivalent ratio (NCO/OH) of the NCO group of the isocyanate compound to the hydroxyl group of acrylic polyol is preferably 0.3 or more and 2.5 or less, and 0.5 or more and 2.0 or less. Is more preferable. When NCO/OH is 0.3 or more, the adhesion to the substrate is improved, and when NCO/OH is 2.0 or less, the adhesion after the wet heat resistance test is improved. The amount of the acrylic polyol and the isocyanate compound in the anchor coating agent is preferably blended based on an equivalent ratio, and the isocyanate compound is approximately 10 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the acrylic polyol. Is preferred, and more preferably about 20 parts by mass or more and 80 parts by mass or less.

Further, the anchor coating agent may further contain a silane coupling agent in order to further improve the adhesion between the resin base material and the vapor deposition layer. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and those such as 3-mercaptopropyltrimethoxysilane. Examples thereof include those having a mercapto group and those having an isocyanate group such as 3-isocyanatepropyltriethoxysilane. The silane coupling agent may be used alone or in combination of two or more.

The anchor coating agent can be prepared by mixing an acrylic polyol, an isocyanate compound, an optional component (such as a silane coupling agent), and a solvent. The solvent may be any solvent that can dissolve the acrylic polyol and the isocyanate compound, and examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, and acetone. These solvents may be used alone or in combination of two or more.

As a method of applying the anchor coating agent, a usual coating method can be used. For example, a known method such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, a gravure offset method can be used. As the drying method, hot air drying, hot roll drying, high-frequency irradiation, infrared irradiation, UV irradiation, or the like can be used alone or in combination of two or more. The heating temperature at the time of drying is not particularly limited, but is preferably in the range of 60° C. or higher and 140° C. or lower, there is no residual solvent, and there is a so-called blocking phenomenon in which the coated surface sticks to the back surface even after winding. Conditions that do not occur can be appropriately selected. If necessary, the aging treatment may be performed within the range of 40° C. or higher and 60° C. or lower.

The thickness of the anchor coat layer is preferably 0.02 μm or more and 1.0 μm or less, and more preferably 0.04 μm or more and 0.5 μm or less. When it is 0.02 μm or more, the adhesion between the resin base material and the vapor deposition layer becomes sufficiently good. If it is thicker than 0.5 μm, the influence of internal stress becomes large, the vapor deposition layer 12 may not be laminated neatly, and the gas barrier property may be insufficiently expressed.

Hereinafter, examples of the gas barrier laminate of the present invention will be described in detail. However, the gas barrier laminate of the present invention is not limited to the mode shown in the examples. The "solid content" indicating the content of the organosilicon compound or its hydrolyzate in the coating solution for forming the overcoat layer and the anchor coating agent is a coating film formed by polymerization of the hydrolyzed organosilicon compound. The amount converted to weight.

(Example 1)
First, a vapor deposition layer was formed on a resin base material. As the resin base material, a biaxially stretched polyethylene terephthalate (PET) film (PET) having a thickness of 12 μm, one surface of which was corona-treated, was used. Further, using a vacuum vapor deposition machine, a vapor deposition material in which metallic silicon powder and silicon dioxide powder were mixed was vapor deposited directly on the corona-treated surface of the resin base material so that the element ratio O/Si was 1.5. A vapor deposition layer was formed on the resin substrate. At this time, the formed vapor deposition layer (SiO _X vapor deposition film) had a thickness of 50 nm.

Next, a coating liquid for forming the overcoat layer was prepared. The coating solution was prepared by mixing a hydrolysis solution of 7-octenyltrimethoxysilane and an aqueous solution of polyvinyl alcohol (PVA) so that the solid content weight ratio after drying was 50:50, and the solid content was 5% by mass. Solution.

Next, the coating liquid was applied onto the vapor deposition layer and dried by heating to form an overcoat layer. Bar coating was used for coating the coating liquid. The conditions for heat drying were 120° C. and 2 minutes. At this time, the dry film thickness of the formed overcoat layer was 0.5 μm.

From the above, the gas barrier laminate of Example 1 in which the resin substrate/vapor deposition layer/overcoat layer was laminated in this order was manufactured. In the gas barrier laminate of Example 1, the film thickness of each layer was resin substrate: 12 μm/vapor deposition layer: 50 nm/overcoat layer: 0.5 μm.

[Inspection measurement]
The oxygen permeability (OTR) of the gas barrier laminate of Example 1 was measured. Here, the OTR was measured by (1) before laminating the overcoat layer, (2) immediately after production (initial), (3) after tensile test (3% tensile test at 100 μm/sec), and (4) ) After the storage test (storage test at 40° C. and 90% RH for 500 hours), the test was performed four times. In addition, in the measurement of the oxygen permeability, an oxygen permeability meter (MOCON OX-TRAN 2/21) manufactured by Modern Control Co. was used, and the oxygen permeability [cc/m ² · day·atm] was measured. The magnification of oxygen permeability was defined as the magnification of the value of oxygen permeability after (3) the tensile test or (4) the storage test, where (2) the initial value of oxygen permeability was 1. The measurement results are shown in Table 1.

(Example 2)
First, an anchor coating agent was prepared. The anchor coating agent is a monomer such that hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) are copolymerized to prepare an acrylic polyol (weight average molecular weight of about 10,000) so that the hydroxyl value is 178 mgKOH/g. Hexamethylene diisocyanate (HDI) was used as a curing agent containing the acrylic polyol as a main component so as to be 0.5 equivalent with respect to the OH group amount of the main component to obtain a methyl ethyl ketone solution having a solid content of 5% by mass.

Next, an anchor coating agent was applied on the resin substrate to form an anchor coating layer. As the resin base material, a biaxially stretched polyethylene terephthalate (PET) film (PET) having a thickness of 12 μm, one side of which was corona-treated, was used. An anchor coating agent was applied to the corona-treated surface of the resin base material using a gravure coater and stored in a thermostatic chamber at 50°C for 48 hours (aging treatment) to form an anchor coat layer. At this time, the dry film thickness of the anchor coat layer was 0.1 μm.

Next, a vapor deposition layer was formed on the anchor coat layer. Using a vacuum vapor deposition machine, a vapor deposition material in which metallic silicon powder and silicon dioxide powder were mixed was vapor-deposited so that the element ratio O/Si was 1.5, and a vapor deposition layer was formed on the resin substrate. At this time, the formed vapor deposition layer (SiOx vapor deposition film) had a thickness of 50 nm.

Next, a coating liquid for forming the overcoat layer was prepared. The coating liquid was the same as in Example 1.

Next, the coating liquid was applied onto the vapor deposition layer and dried by heating to form an overcoat layer. Bar coating was used for coating the coating liquid. The conditions for heat drying were 120° C. and 2 minutes. At this time, the dry film thickness of the formed overcoat layer was 0.5 μm.

From the above, a gas barrier laminate of this example was manufactured in which the resin substrate/anchor coat layer/vapor deposition layer/overcoat layer were laminated in this order. In the gas barrier laminate of this example, the film thickness of each layer was: resin substrate: 12 μm/anchor coat layer: 0.15 μm/vapor deposition layer: 50 nm/overcoat layer: 0.5 μm.

[Inspection measurement]
The oxygen permeability (OTR) of the gas barrier laminate obtained in Example 2 was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 3)
The vapor barrier of this example was the same as that of Example 2 except that aluminum was vapor-deposited on the vapor-deposited layer by heating with an electron beam heating method, oxygen gas was introduced, and an aluminum oxide vapor-deposited layer having a film thickness of 15 nm was formed. A transparent laminate was produced.

[Inspection measurement]
Regarding the gas barrier laminate obtained in Example 3, the oxygen transmission rate (OTR) was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 4)
The coating liquid for forming the overcoat layer is a solid solution after drying a hydrolysis solution of 8-methacryloxyoctyltrimethoxysilane, a hydrolysis solution of tetraethoxysilane (TEOS), and an aqueous solution of polyvinyl alcohol (PVA). A gas barrier laminate of this example was produced in the same manner as in Example 3 except that a solution having a solid content of 5% by mass was mixed so that the weight ratio was 35:35:30.

[Inspection measurement]
With respect to the gas barrier laminate obtained in Example 4, the oxygen transmission rate (OTR) was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative example 1)
The coating liquid for forming the overcoat layer is a solid obtained by mixing a hydrolysis solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) so that the solid content weight ratio after drying is 50:50. A gas barrier laminate of this example was produced in the same manner as in Example 3 except that a solution containing 5% by mass was used.

[Inspection measurement]
With respect to the gas barrier laminate obtained in Comparative Example 1, the oxygen transmission rate (OTR) was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative example 2)
The coating liquid for forming the overcoat layer was prepared by mixing a hydrolyzing solution of vinylmethoxysilane and an aqueous solution of polyvinyl alcohol (PVA) so that the solid content weight ratio after drying was 50:50, and the solid content was 5 mass. %, a gas barrier laminate of this example was manufactured in the same manner as in Example 2 except that the solution was made into a solution.

[Inspection measurement]
With respect to the gas barrier laminate obtained in Comparative Example 2, the oxygen transmission rate (OTR) was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative example 3)
The coating liquid for forming the overcoat layer is a solid solution after drying a hydrolysis solution of 3-methacryloxypropyltrimethoxysilane, a hydrolysis solution of tetraethoxysilane (TEOS), and an aqueous solution of polyvinyl alcohol (PVA). This example was the same as Example 4 except that a solution having a solid content of 5% by mass was mixed by mixing so that the weight ratio was 35:35:30 (the content of the organic component was 25% by mass). The gas-barrier laminate was manufactured.

[Inspection measurement]
With respect to the gas barrier laminate obtained in Comparative Example 3, the oxygen transmission rate (OTR) was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Table 1 shows the layered structures (materials used) of the laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 3 and the measurement results of the oxygen transmission rate (OTR). In addition, "AC layer" in Table 1 indicates "anchor coat layer", and "OC layer" in Table 1 indicates "overcoat layer". Further, "AOH/NCO" in Table 1 indicates "anchor coating agent prepared in Example 2". In addition, “a-1” in Table 1 represents “hydrolyzate of 7-octenyltrimethoxysilane”, and “a-2” represents “hydrolyzate of 8-methacryloxyoctyltrimethoxysilane”. , "B-1" means "hydrolyzate of TEOS", "c-1" means "hydrolyzate of vinylmethoxysilane", and "d-1" means "3-methacryloxypropyltrimethoxysilane". And "PVA" means "polyvinyl alcohol".

<Evaluation>
Regarding the gas barrier properties of the gas barrier laminates of Examples 1 to 4, the initial value of OTR was low and the gas barrier properties were excellent. In addition, the OTR value did not increase much from the initial value after the tensile test and the storage test. On the other hand, the gas barrier properties of the gas barrier laminate of Comparative Example 1 were 10 times or more the initial OTR after the tensile test and the storage test. In addition, the gas barrier properties of the gas barrier laminates of Comparative Examples 2 and 3 were 10 times or more the initial OTR after the tensile test.

From the above, the gas barrier laminate of the present invention exhibits gas barrier properties even after a tensile test (3% tensile test at 100 μm/sec) and a storage test (storage test at 40° C. 90% RH for 500 hours). It was confirmed that the gas barrier property can be maintained (specifically, the OTR is about 3.0 [cc/m ² ·day·atm] or less), and the gas barrier property is maintained even in a severe environment.

INDUSTRIAL APPLICABILITY The gas barrier laminate of the present invention has gas barrier properties, transparency, and durability at a high level, and thus can be widely used in fields requiring a gas barrier laminate. For example, (1) packaging film for medicines and foods, (2) packaging film for electronic parts and precision parts such as semiconductor wafers, (3) liquid crystal display, flat panel display member such as organic EL display, (4) It is expected to be suitably used in fields such as back sheet application and front sheet application in solar cells, but the present invention is not limited to this.

10 Gas Barrier Laminate 11 Resin Substrate 12 Deposition Layer 13 Overcoat Layer 20 Gas Barrier Laminate 24 Anchor Coat Layer

Claims (4)

A resin substrate, a vapor deposition layer laminated on at least one surface of the resin substrate, and an overcoat layer laminated on the vapor deposition layer,
The overcoat layer, Ri greens contain at least one member selected from the group consisting of substances and their hydrolysates represented by the following general formula (a), and a water-soluble polymer having a hydroxyl group,
Gas barrier laminate vinyl group or methacryloxy group in the overcoat layer is characterized that you have remained.
_{X- (CH 2) n-Si} (OR) 3 ...... (a)
[However, X is a vinyl group or a methacryloxy group, R is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 6 or more. ] The gas barrier laminate according to claim 1, wherein the gas barrier laminate has an oxygen permeability after a 3% tensile test within 10 times the initial value. The gas barrier laminate according to claim 1 or 2, wherein the gas barrier laminate has an oxygen permeability within 10 times the initial value after a storage test at 40°C and 90% RH for 500 hours. A gas barrier laminate comprising an anchor coat layer between the resin substrate and the vapor deposition layer,
The anchor coat layer is an acrylic polyol having two or more hydroxyl groups,
An isocyanate compound having at least two NCO groups in the molecule,
The hydroxyl value of the acrylic polyol is 50 mgKOH/g or more and 250 mgKOH/g or less,
4. The gas barrier according to claim 1, wherein an equivalent ratio (NCO/OH) of the NCO group of the isocyanate compound to the hydroxyl group of the acrylic polyol is 0.3 or more and 2.5 or less. Laminate.