JP2018058294A - Gas barrier laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate capable of realizing improving tolerance to drawing and securing transparency.SOLUTION: A gas barrier laminate includes a resin substrate 11, and an anchor coat layer 24, a vapor-deposited layer 12 and an overcoat layer 13 laminated in this order on one side of the resin substrate 11. As the vapor-deposited layer 12, a vapor-deposited layer including SiOsatisfying 1.50≤X≤1.80 is used. As the overcoat layer 13, an overcoat layer including at least one selected from a group consisting of a water-soluble polymer having a hydroxyl group, alkoxysilane and a hydrolyzate thereof is used.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier laminate.

  It is necessary to protect the contents of packaging materials for foods and pharmaceuticals, and packaging materials used for hard disks and semiconductor modules. In particular, in food packaging, it is necessary to suppress the oxidation and alteration of proteins, fats and oils, and maintain the taste and freshness. In addition, pharmaceuticals that require handling in a sterile state are required to suppress the alteration of the active ingredient and maintain its efficacy. In order to protect the quality of these contents, there is a need for a package having a gas barrier property that blocks oxygen, water vapor, and other gases that alter the contents.

Suitable for export products such as medical drugs and inkjet tank members, and plastics, etc., for accelerated tests under high temperatures and high humidity, prevention of solvent evaporation under high temperatures, and transportation by sea (especially directly under the equator) There is a need for a package that stably exhibits high oxygen barrier properties and water vapor barrier properties.
In addition, the solar cell protective sheet is arranged on the back side of the solar cell to prevent deterioration due to humidity of the patterned silicon thin film that is the electromotive part of the solar cell module, and blocks gas such as oxygen and water vapor. At the same time, there is a demand for durability that does not deteriorate the gas barrier performance even when used under severe conditions such as outdoors.

These packaging bodies and sheets have processing steps in which the film undergoes stretching and bending. Even after processing steps such as stretching and bending, durability such that gas such as oxygen and water vapor is shut off and gas barrier properties are not deteriorated even under severe conditions such as long-term storage is required.
In order to solve these problems, many gas barrier films in which a metal film made of aluminum or the like, or a metal oxide film made of aluminum oxide, silicon oxide or the like is formed on a plastic film are generally put into practical use.

  Here, as one of the gas barrier films having excellent durability, an aluminum film formed by a vapor deposition method can be given. However, when an aluminum film is used, it has excellent resistance to physical stress such as stretching, but it has a problem of poor transparency, and when used for food packaging materials, it cannot be inspected by a metal detector. There are also problems such as the fact that the aluminum film is boehmite due to hot water treatment such as steam treatment and retort treatment, resulting in deterioration of gas barrier performance.

  In order to solve the problems of the aluminum film described above, there is a means for obtaining a gas barrier film made of aluminum oxide by using an aluminum material as a film forming material and introducing and reacting a reactive gas such as oxygen in the space. . If this method is used, the problem that the aluminum film has poor transparency and cannot be inspected by a metal detector can be solved. However, the problem that the gas barrier performance is deteriorated due to the aluminum oxide film becoming boehmite by hot water treatment such as steam treatment or retort treatment cannot be solved. In addition, the metal oxide film is excellent in transparency, but the resistance to physical stress such as stretching is inferior to that of the metal film. For example, the gas barrier performance before and after the stretching test of the gas barrier film using the metal oxide film is compared. Then, there exists a problem that it will deteriorate greatly after an extending | stretching test. For this reason, aluminum oxide has very poor resistance to physical stress such as stretching.

  Therefore, in order to solve the problems of the aluminum film and the aluminum oxide film, there is a means for obtaining a gas barrier film made of a silicon oxide film by using silicon oxide as a film forming material. Using a silicon oxide film with excellent durability solves the problem of deterioration of gas barrier performance due to the aluminum film and aluminum oxide film becoming boehmite by hot water treatment such as steam treatment and retort treatment. can do. In addition, in terms of resistance to physical stress such as stretching, the silicon oxide film is superior to the aluminum oxide film, but greatly inferior to the aluminum film.

The silicon oxide film has improved gas barrier performance as the element ratio O / Si is lowered, but has a problem that transparency is lowered. Moreover, it will fall also about the tolerance with respect to physical stress, such as extending | stretching. Even when a silicon oxide film is used, it is difficult to improve resistance to physical stress such as stretching, and further diligent solutions are required for its solution.
For example, the laminates disclosed in Patent Document 1 and Patent Document 2 are further provided with a water-soluble polymer such as polyvinyl alcohol and an alkoxysilane such as tetraethoxysilane or the like on the vapor deposition layer provided on the substrate. A coating liquid containing a hydrolyzate is applied and dried by heating to provide a gas barrier film. By providing such an overcoat layer, gas barrier properties, durability, and the like are improved by protecting the deposited film.

Japanese Patent Laid-Open No. 7-164591 International Publication No. 2004/048081

However, with the expansion of applications, gas barrier laminates are required to be used in more severe environments. Even when a silicon oxide film and an overcoat layer are used, it is difficult to improve resistance to physical stress such as stretching, and further improvement in durability and the like is desired.
This invention is made | formed in view of the said situation, Comprising: It aims at providing the gas-barrier laminated body which can implement | achieve the improvement of the tolerance with respect to extending | stretching, and ensuring of transparency.

As a result of intensive studies, the present inventors have found a suitable combination of a vapor deposition layer and an overcoat layer laminated thereon in a gas barrier laminate, and have completed the present invention.
According to one aspect of the present invention, 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, the vapor deposition layer is SiO _X X is 1.50 ≦ X ≦ 1.80, and the overcoat layer includes at least one selected from the group consisting of a water-soluble polymer having a hydroxyl group, alkoxysilane and a hydrolyzate thereof, A gas barrier laminate is provided.

  According to one embodiment of the present invention, even after applying physical stress such as stretching, deterioration of the vapor deposition layer and the overcoat layer is suppressed, and is excellent in resistance to physical stress such as stretching, and has a gas barrier property. It is possible to realize a gas barrier laminate excellent in the above.

It is a schematic sectional drawing which shows an example of the gas-barrier laminated body which concerns on one Embodiment of this invention. It is the graph which showed the water vapor transmission rate after extending | stretching the gas-barrier laminated body in this invention, and the relationship with time.

Hereinafter, a gas barrier laminate according to an embodiment of the present invention will be described with reference to the drawings. However, the same reference numerals are given to portions corresponding to each other in the drawings to be described below, and description of the overlapping portions will be omitted as appropriate. Each drawing is exaggerated as appropriate for easy explanation.
Furthermore, the embodiment of the present invention exemplifies a configuration for embodying the technical idea of the present invention, and specifies the material, shape, structure, arrangement, dimensions, etc. of each part as follows. Not. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

(Gas barrier laminate)
In FIG. 1, the schematic sectional drawing of the gas-barrier laminated body which concerns on one Embodiment of this invention is shown.
The gas barrier laminate 10 is a laminate in which an anchor coat layer 24, a vapor deposition layer 12, and an overcoat layer 13 are laminated in this order on one surface of a resin base material 11.
Hereinafter, the direction in which the anchor coat layer 24, the vapor deposition layer 12, and the overcoat layer 13 are laminated will be described with reference to the resin base material 11.

<Resin substrate>
The resin base material 11 is a layer that becomes a base of the gas barrier laminate.
The resin base material may be appropriately selected from various sheet-like base materials (including film-like materials) that are generally used. For example, (1) Polyester film such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), (2) Polyolefin film such as polyethylene and polypropylene, (3) Polyether sulfone (PES), polystyrene film, polyamide film, poly Examples thereof include a biodegradable plastic film such as a vinyl chloride film, a polycarbonate film, a polyacrylonitrile film, a polyimide film, and polylactic acid.

The resin substrate 11 may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant.
In addition, the thickness of the resin base material 11 is not particularly limited, and may be appropriately determined according to specifications and the like. In practice, the thickness of the resin base material 11 is preferably about 6 μm to 200 μm, preferably about 12 μm to 125 μm, and more preferably about 12 μm to 50 μm. However, in the gas barrier laminate 10 of the present embodiment, the thickness of the resin base material 11 is not limited to the above range.
Moreover, the resin base material 11 may be surface-treated on the resin base material surface. By performing the surface treatment, adhesion of other layers (anchor coat layer 24, vapor deposition layer 12, etc.) can be enhanced. Here, as the surface treatment, for example, (1) physical treatment such as corona treatment, plasma treatment, flame treatment, or (2) chemical treatment such as chemical treatment with acid or alkali may be used.

<Deposition layer>
Examples of the composition of the vapor deposition layer 12 include SiO _X composed of silicon and oxygen. Carbon, hydrogen, and nitrogen may be added to SiO _X. The vapor deposition layer 12 is formed on the resin base material 11 via the anchor coat layer 24 by vapor deposition of a vapor deposition material in order to impart gas barrier properties.
The vapor deposition material used when vapor-depositing a silicon film or a silicon oxide film is not particularly limited, and a known material can be used. However, when the element ratio O / Si of the film forming material is compared with the element ratio O / Si of the formed film, there is a relationship of O / Si of the formed film> O / Si of the film forming material. If O / Si of the film forming material is increased, sufficient gas barrier properties may not be exhibited in the formed film, and splash may easily occur when the O / Si of the film forming material is low. Therefore, the O / Si of the film forming material is 1.00 <O / Si <2.00, and more preferably 1.50 ≦ O / Si ≦ 1.70.

As the composition of the vapor deposition layer 12, in the case of a gas barrier layer represented by SiO 2 _X , the physical properties such as stretching are satisfied when X (element ratio O / Si of the vapor deposition layer 12) satisfies 1.50 ≦ X ≦ 1.80. It is possible to form the vapor deposition layer 12 that realizes improvement of resistance to mechanical stress and ensuring transparency. Transparency is impaired when X <1.50, and when 1.80 <X, the water vapor permeability after 5% tensile test is greater than 1.3 times the value before tensile test. Become.
The formation method of the vapor deposition layer 12 may be appropriately selected from known vapor deposition methods. For example, a physical vapor deposition (PVD) method such as a vacuum deposition method or a sputtering method, a chemical vapor deposition (CVD) method such as an ion plating method or a plasma vapor deposition method, or ALD: An atomic layer deposition method or the like may be used. In particular, the vacuum deposition method using EB (electron beam heating) can obtain a high film formation rate, and is preferable as a method for forming the vapor deposition layer 12 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 vapor deposition is performed by reacting vaporized particles with a gas introduced into the atmosphere when vapor deposition is performed. Examples of the gas to be introduced include organosilane monomers. As the organic silane monomer, tetraethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, or the like can be used, but is not particularly limited as long as silicon Si and carbon C are contained. In view of safety and handling, it is preferable to use hexamethyldisiloxane. By performing reactive vapor deposition with an organosilane monomer, the vapor deposition layer 12 can be given flexibility.

In addition, when the reactive vapor deposition method is used, it is desirable that the pressure in the film formation chamber be 2 × 10 ⁻¹ Pa or less when the gas is introduced. If the pressure in the film forming chamber is higher than 2 × 10 ⁻¹ Pa, the vapor deposition layer 12 may not be neatly laminated, and the water vapor barrier property may be deteriorated. As a method for controlling the amount of the organosilane monomer introduced, for example, it is effective to perform film formation while controlling the flow rate using a mass flow controller or the like.
The film thickness of the vapor deposition layer 12 is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm. When the thickness is 5 nm or more, sufficient barrier properties are exhibited, and when the thickness is 300 nm or less, cracks are hardly generated in the post-process and the like, and the barrier properties are not easily lowered. However, in the gas barrier laminate of the present embodiment, the thickness of the vapor deposition layer is not limited to the above range.

  In order to further improve the barrier property, a means for supplementing and supplementing the lost kinetic energy by applying a new kinetic energy to the evaporated particles is effective. Among them, a method using plasma is conceivable. When the film is formed at a high film formation speed, the number of vapor deposition particles is very large. It is difficult to develop changes to improve. For this reason, it is optimal to use any of ICP plasma method, helicon wave plasma method, microwave plasma method, and holo cathode discharge method as means for developing a high plasma density. In addition, when these methods are used, the film quality can be improved, so that it is possible to obtain gas barrier performance superior to the conventional one. Furthermore, the influence on the deterioration of the gas barrier performance against the film thickness fluctuation can be reduced. Moreover, the effect of accelerating the reaction between the vapor deposition particles and the reactive gas can be expected by using high-density plasma.

<Overcoat layer>
The overcoat layer 13 is a layer formed on the vapor deposition layer 12. By laminating the overcoat layer 13 on the vapor deposition layer 12, it is possible to obtain an excellent gas barrier property that cannot be manifested in the gas barrier laminate 10 in which the vapor deposition layer 12 is composed of a single layer. The overcoat layer 13 also has a function of protecting the dense and fragile deposited layer 12 and can suppress the generation of cracks due to rubbing and bending.
The overcoat layer 13 is formed by adjusting the coating solution, coating the coating solution on the vapor deposition layer, and heating and drying the coating solution.
In the gas barrier laminate 10 according to one embodiment of the present invention, the coating liquid for forming the overcoat layer 13 is selected from the group consisting of a water-soluble polymer having a hydroxyl group, alkoxysilane, and a hydrolyzate thereof. And at least one kind.

  The water-soluble polymer is preferably polyvinyl alcohol, polycarboxylic acid, starch, or cellulose. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used for the coating agent of the present invention (that is, the overcoat layer 13), gas barrier properties are excellent. The PVA mentioned here is generally obtained by saponifying polyvinyl acetate, and saponified PVA in which only several percent of acetic acid remains from a so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. Including up to. The molecular weight of PVA has various degrees of polymerization ranging from 300 to several thousand, but there is no problem in the effect even if any molecular weight is used.

  Further, in alkoxysilane, an alkoxy group bonded to a 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 alkoxysilane, a dense and strong network polymerization film can be formed. As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, or the like can be used.

  The coating liquid for forming the overcoat layer 13 is prepared by mixing a water-soluble polymer having a hydroxyl group, at least one selected from the group consisting of alkoxysilanes and hydrolysates thereof, and a solvent. Any solvent may be used as long as it can dissolve the compounding components, and examples thereof include water, alcohol, toluene, ethyl acetate, acetone, and methyl ethyl ketone. These solvents can be used alone or in combination of two or more.

  As a coating method of the coating solution, a normal coating method can be used. For example, a known method 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, or a gravure offset method can be used. As the drying method, a method of applying heat, such as 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. In the drying method, the heating temperature is preferably in the range of about 60 ° C. to 200 ° C., more preferably in the range of about 120 ° C. to 180 ° C. When the temperature is 120 ° C. or higher, desired barrier properties are exhibited, which is favorable. If it is 180 ° C. or lower, the resistance to physical stress such as stretching is suitable without deformation of the base material and cracks in the vapor deposition layer 12 for a short time of vapor deposition. When it exceeds 200 ° C., the shrinkage of the resin base material 11 becomes large, so that the processability is impaired.

The film thickness of the overcoat layer 13 is preferably about 0.1 μm to 2 μm, and more preferably about 0.2 μm to 1.0 μm. When it is 0.1 μm or more, the barrier property is stably expressed, and when it is 1 μm or less, it is excellent in post-processing suitability such as printing or lamination of other films or bending. However, in the gas barrier laminate 10 according to one embodiment of the present invention, the film thickness of the overcoat layer 13 is not limited to the above range.
Moreover, the gas barrier laminate 10 according to one embodiment of the present invention may be plate-shaped or film-shaped. For example, it may be formed into a film shape by winding with a roll or the like.

(Anchor coat layer)
As shown in FIG. 1, by providing an anchor coat layer 24 between the resin base material 11 and the vapor deposition layer 12, the adhesion between the resin base material 11 and the vapor deposition layer 12 is improved, and the peeling between each layer is improved. Occurrence can be suppressed.
The anchor coat layer 24 is formed by adjusting the anchor coat agent, applying the anchor coat agent on the resin substrate 11, 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 an acrylic polyol, a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having a hydroxyl group, a polymer compound obtained by copolymerizing a (meth) acrylic acid derivative monomer having a hydroxyl group and other monomers Etc. 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 (meth) acrylic acid derivative monomers 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 include derivative monomers. Examples of (meth) acrylic acid derivative monomers 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 other monomers, monomers other than (meth) acrylic acid derivative monomers may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer. Monomers other than the above (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 group in the acrylic polyol, and indicates the number of mg of potassium hydroxide necessary for acetylating the hydroxyl group 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 11 and the vapor deposition layer 12 by the anchor coat layer 24 may not be sufficiently exhibited. . On the other hand, if the hydroxyl value is larger than [250 mgKOH / g], the amount of reaction with the isocyanate compound increases so that the film shrinkage of the anchor coat layer 24 may increase. If the film shrinkage is large, the deposited layer 12 is not neatly laminated thereon, and there is a possibility that sufficient gas barrier properties are not exhibited.

  The weight average molecular weight of the acrylic polyol is not particularly defined, but is preferably 3000 or more and 200000 or less, more preferably 5000 or more and 100000 or less, and further preferably 5000 or more and 40000 or less. In this specification, the weight average molecular weight is a weight average molecular weight measured by GPC (gel permeation chromatography) based on polystyrene. Moreover, acrylic polyol may be used individually by 1 type, or may use 2 or more types together.

  Any isocyanate compound may be used as long as it has at least two NCO groups in the molecule. For example, monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate. Aliphatic isocyanates such as (H12MDI), aromatic aliphatic isocyanates such as xylene diisocyanate (XDI), and 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 a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret, and the like. As an isocyanate compound, you may select arbitrarily from said monomeric isocyanate, its polymer, a derivative, etc., 1 type can be used individually or in combination of 2 or more types.

  In the anchor coating agent, the equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound to the hydroxyl group of the acrylic polyol is preferably 0.3 or more and 2.5 or less, and is 0.5 or more and 2.0 or less. It is more preferable. When NCO / OH is 0.3 or more, the adhesion with the resin substrate 11 is improved, and when it is 2.0 or less, the adhesion with the resin substrate 11 after the wet heat resistance test is improved. The blending amount of the acrylic polyol and the isocyanate compound in the anchor coating agent is preferably blended based on the equivalent ratio, and the isocyanate compound is generally about 10 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the acrylic polyol. It is more preferable that it is about 20 to 80 parts by mass.

  In addition, the anchor coating agent may further contain a silane coupling agent in order to further improve the adhesion between the resin substrate 11 and the vapor deposition layer 12. 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 3-mercaptopropyltrimethoxysilane. Examples thereof include those having a mercapto group and those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. Moreover, as a silane coupling agent, 1 type may be used independently or 2 or more types may be used together.

  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 is not particularly limited as long as it can dissolve the acrylic polyol and the isocyanate compound. Examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, and acetone. These solvents can be used alone or in combination of two or more.

  As a method for applying the anchor coating agent, a normal coating method can be used. For example, known methods 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, and a gravure offset method can be used. As the drying method, a method of applying heat, such as 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. In the drying method, the heating temperature is not particularly limited, but is preferably in the range of about 60 ° C. or more and 140 ° C. or less, so that there is no residual solvent, and the coated surface sticks to the back surface even after winding. Conditions under which the phenomenon does not occur can be appropriately selected, and the aging treatment may be performed within a range of about 40 ° C. to 60 ° C. as necessary.

  The film thickness of the anchor coat layer 24 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. Adhesiveness of the resin base material 11 and the vapor deposition layer 12 becomes fully favorable as it is 0.02 micrometer or more. If the thickness of the anchor coat layer 24 is thicker than 0.5 μm, the influence of internal stress becomes large, and the vapor deposition layer 12 is not neatly laminated, and there is a possibility that the expression of gas barrier properties may be insufficient.

The water vapor permeability of the gas barrier laminate 10 was measured twice: (1) immediately after production (initial stage) and (2) after 5% tensile test. The water vapor permeability after the tensile test was measured immediately after 5% tensile test at 100 μm / sec, after maintaining the tensile state for 1 minute, and returning to the original state at the same speed. If left after the stretching test, recovery of water vapor permeability cannot be observed.
Further, the gas barrier laminate 10 has a water vapor permeability immediately after the 5% tensile test, preferably within 20 times that before the tensile test, and more preferably within 10 times. When it exceeds 20 times, the barrier property does not recover until before the tensile test. When the barrier property recovers before the tensile test, the water vapor permeability after recovery falls within 1.3 times the value before the tensile test. When the barrier property is not sufficiently recovered, the water vapor permeability after the recovery is 3 times or more of the value before the tensile test.
Further, the transmittance of the gas barrier laminate 10 is preferably 80% or more, and particularly preferably 85% or more in consideration of visibility when used for a packaging material and appearance improvement. When the transmittance is less than 80%, the transparency cannot be ensured and the appearance is impaired.

  Hereinafter, examples of the gas barrier laminate 10 according to an embodiment of the present invention will be described in detail. However, the gas barrier laminate 10 according to one embodiment 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 the hydrolyzate thereof in the coating liquid for forming the overcoat layer and the anchor coat agent is a coating film formed by polymerizing the hydrolyzed organosilicon compound. The amount converted to weight.

Example 1
First, an anchor coating agent was prepared. The anchor coating agent is prepared by copolymerizing hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as monomers so that the hydroxyl value is 178 mgKOH / g, and adjusting acrylic polyol (weight average molecular weight of about 10,000), A methyl ethyl ketone solution having a solid content of 5% by mass was prepared by using this acrylic polyol as a main agent and hexamethylene diisocyanate (HDI) as a curing agent in an amount of 0.5 equivalent to the amount of OH groups in the main agent.
As the resin base material 11, a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60) having a corona treatment on one surface was used. An anchor coat agent was applied to the corona-treated surface of the resin substrate 11 to form an anchor coat layer 24. At this time, the formed anchor coat layer 24 had a thickness of 0.15 μm.

Next, the vapor deposition layer 12 was formed on the anchor coat layer 24. Specifically, the metal silicon powder and the silicon dioxide are directly applied to the surface of the resin substrate 11 on which the anchor coat layer 24 is formed using a vacuum vapor deposition machine so that the element ratio O / Si is 1.6. The vapor deposition material mixed with the powder was vapor-deposited, and the vapor deposition layer 12 was formed on the resin substrate 11 via the anchor coat layer 24. At this time, the thickness of the formed vapor deposition layer (SiO _X vapor deposition film) 12 was 50 nm.

Next, a coating solution for forming an overcoat layer was prepared. This coating solution was prepared by mixing a hydrolyzed solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) containing a carbonyl group so that the weight ratio after drying was 55:45. A 5% by weight solution was obtained.
Next, a coating solution was applied onto the vapor deposition layer 12 and dried by heating to form an overcoat layer 13. The bar coating method was used for coating the coating solution. The heating and drying conditions were 160 ° C. and 2 minutes. At this time, the dry film thickness of the formed overcoat layer 13 was 0.5 μm.

From the above, the gas barrier laminate 10 of Example 1 in which the resin base material 11 / anchor coat layer 24 / vapor deposition layer 12 / overcoat layer 13 were laminated in this order was produced. In the gas barrier laminate 10 of Example 1, the film thickness of each layer was resin base material 11: 12 μm / anchor coat layer 24: 0.15 μm / deposition layer 12: 50 nm / overcoat layer 13: 0.5 μm. It was.
The gas barrier laminate 10 was laminated with LLDPE (linear low density polyethylene, manufactured by Mitsui Chemicals, Inc., TUX-TCS) by a dry laminating method. In addition, Takelac A525 (made by Mitsui Chemicals) and Takenate A52 (made by Mitsui Chemicals) were mixed in the ratio of 9: 1, and the thing mixed with ethyl acetate was used for the adhesive agent.

[Evaluation 1]
About the gas-barrier laminated body 10 of Example 1, the water vapor transmission rate (WVTR) was measured. Here, the WVTR was measured twice: (1) immediately after production (initial stage) and (2) within 15 minutes after the tensile test (5% tensile test at 100 μm / sec). In the measurement of water vapor transmission rate, the water vapor transmission rate [g / m 2 under an atmosphere of 40 ° C. and 90% RH using a water vapor transmission measuring device (trade name: MOCON PERMATRAN 3/21) manufactured by Modern Control Co., Ltd. [Day] was measured. The magnification of the water vapor transmission rate was defined as (2) the magnification of the value after the tensile test, assuming that the initial value of the water vapor transmission rate was 1. The measurement results are shown in Table 1.

[Evaluation 2]
For the gas barrier laminate 10 of Example 1, the transmittance was measured with a spectrophotometer (UV-2450 manufactured by SHIMADZU) with the baseline as the atmosphere. In addition, the transmittance | permeability was measured by the structure of the resin base material 11 / anchor coat layer 24 / deposition layer 12. Table 1 shows the measurement results of transmittance at a wavelength of 366 nm. The transmittance of a polyethylene terephthalate film having a thickness of 12 μm (P60 manufactured by Toray Industries, Inc.) was 86%.

(Example 2)
First, an anchor coating agent was prepared in the same manner as in Example 1, and the anchor coating agent was applied on the resin substrate 11 to form the anchor coating layer 24. As the resin base material 11, a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60) having a corona treatment on one surface was used. The film thickness of the anchor coat layer 24 formed at this time was 0.15 μm.

Next, the vapor deposition layer 12 was formed on the anchor coat layer 24 in the same procedure as in Example 1. Using a vacuum deposition machine, metal silicon powder and silicon dioxide powder were mixed directly on the surface of the resin substrate 11 on which the anchor coat layer 24 was formed so that the element ratio O / Si was 1.5. The vapor deposition material was vapor-deposited and the vapor deposition layer 12 was formed on the resin base material 11. FIG. At that time, 50 sccm of hexamethyldisiloxane was introduced as an organosilane monomer using a mass flow controller (MC-3102E manufactured by Lintec Corporation). At this time, the formed vapor deposition layer (SiO _X vapor deposition film) 12 had a thickness of 50 nm.

Next, a coating solution for forming an overcoat layer was prepared. The coating solution was prepared by mixing a hydrolyzed solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) containing a carbonyl group so that the weight ratio after drying was 55:45. A 5% by mass solution was obtained.
Next, a coating solution was applied onto the vapor deposition layer 12 and dried by heating to form an overcoat layer 13. The bar coating method was used for coating the coating solution. The heating and drying conditions were 160 ° C. and 2 minutes. At this time, the dry film thickness of the formed overcoat layer 13 was 0.5 μm.

From the above, the gas barrier laminate 10 of Example 2 in which the resin base material 11 / anchor coat layer 24 / deposition layer 12 / overcoat layer 13 were laminated in this order was produced. In the gas barrier laminate 10 of Example 2, the film thickness of each layer was: resin base material 11: 12 μm / anchor coat layer 24: 0.15 μm / deposition layer 12: 50 nm / overcoat layer 13: 0.5 μm. It was.
In the same manner as in Example 1, the gas barrier laminate 10 was laminated with LLDPE (linear low density polyethylene, manufactured by Mitsui Chemicals, Inc., TUX-TCS) by a dry laminating method.

[Evaluation]
For the gas barrier laminate 10 obtained in Example 2, the water vapor transmission rate (WVTR) and the light transmittance were measured in the same procedure as in Example 1. The measurement results are shown in Table 1.

(Example 3)
First, an anchor coat agent was prepared in the same procedure as in Example 1, and the anchor coat agent was applied on the resin substrate 11 to form the anchor coat layer 24. As the resin base material 11, a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60) having a corona treatment on one surface was used. The film thickness of the anchor coat layer 24 formed at this time was 0.15 μm.
Next, the vapor deposition layer 12 was formed on the anchor coat layer 24 in the same procedure as in Example 1. Specifically, the metal silicon powder and the silicon dioxide are directly applied to the surface of the resin substrate 11 on which the anchor coat layer 24 is formed using a vacuum vapor deposition machine so that the element ratio O / Si is 1.6. The vapor deposition material mixed with the powder was vapor-deposited, and the vapor deposition layer 12 was formed on the resin substrate 11 via the anchor coat layer 24. At this time, the formed vapor deposition layer (SiOx vapor deposition film) 12 had a thickness of 50 nm.

Next, a coating solution for forming an overcoat layer was prepared. The coating liquid was prepared by mixing a hydrolyzed solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) containing a carbonyl group so that the solid weight ratio after drying was 70:30. A 5% by mass solution was obtained.
Next, a coating solution was applied onto the vapor deposition layer 12 and dried by heating to form an overcoat layer 13. The bar coating method was used for coating the coating solution. Moreover, the conditions of heat drying were 120 degreeC and 2 minutes. At this time, the dry film thickness of the formed overcoat layer 13 was 0.5 μm.

From the above, the gas barrier laminate 10 of Example 3 in which the resin base material 11 / anchor coat layer 24 / vapor deposition layer 12 / overcoat layer 13 were laminated in this order was produced. In the gas barrier laminate 10 of Example 3, the film thickness of each layer was resin base material 11: 12 μm / anchor coat layer 24: 0.15 μm / deposition layer 12: 50 nm / overcoat layer 13: 0.5 μm. It was.
The gas barrier laminate 10 obtained in Example 3 was laminated with LLDPE (linear low density polyethylene, manufactured by Mitsui Chemicals, Inc., TUX-TCS) by the same procedure as in Example 1 by a dry laminating method.
[Evaluation]
For the gas barrier laminate 10 obtained in Example 3, the water vapor transmission rate (WVTR) and the light transmittance were measured in the same procedure as in Example 1. The measurement results are shown in Table 1.

(Comparative Example 1)
A gas barrier laminate is produced in the same procedure as in Example 1 except that a vapor deposition material in which metal silicon powder and silicon dioxide powder are mixed so that the element ratio O / Si is 1.3 is used for the vapor deposition layer. did.
[Evaluation]
The gas barrier laminate obtained in Comparative Example 1 was measured for water vapor transmission rate (WVTR) and light transmittance in the same procedure as in Example 1. The measurement results are shown in Table 1.

(Comparative Example 2)
A gas barrier laminate is produced in the same procedure as in Example 2 except that a vapor deposition material in which metal silicon powder and silicon dioxide powder are mixed so that the element ratio O / Si is 1.8 is used for the vapor deposition layer. did.
[Evaluation]
The gas barrier laminate obtained in Comparative Example 2 was measured for water vapor transmission rate (WVTR) and light transmittance in the same procedure as in Example 1. The measurement results are shown in Table 1.

(Comparative Example 3)
A gas barrier laminate was produced in the same procedure as in Example 3 except that the conditions for heating and drying the coating solution were 100 ° C. and 2 minutes in the formation of the overcoat layer.
[Evaluation]
With respect to the gas barrier laminate obtained in Comparative Example 3, the water vapor transmission rate (WVTR) and the light transmittance were measured in the same procedure as in Example 1. The measurement results are shown in Table 1.
Table 1 summarizes the measurement results of O / Si, water vapor transmission rate (WVTR), and light transmittance of the deposited layers of the laminates obtained in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3. In addition, FIG. 2 shows the change over time in the water vapor transmission rate (WVTR) after a 5% tensile test for the gas barrier laminates of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3.

  As the gas barrier properties of the gas barrier laminates of Examples 1, 2, and 3, the WVTR after the 5% tensile test almost recovered until 24 hours after the tensile test. As for the gas barrier properties of the gas barrier laminates of Examples 1, 2, and 3, the recovered WVTR value was within 1.3 times the value before the tensile test. On the other hand, the gas barrier property of the gas barrier laminate of Comparative Example 1 was that the WVTR immediately after the 5% tensile test was within 20 times before the tensile test, but recovered to within 1.3 times the value before the tensile test. I did not. Further, the gas barrier laminate of Comparative Example 1 had low transparency. Further, the gas barrier property of the gas barrier laminate of Comparative Example 2 is also within 20 times that of the WVTR immediately after the 5% tensile test, and is 1 for the value before the tensile test although the WVTR after the tensile test recovers. It did not recover up to 3 times. Furthermore, the gas barrier property of the gas barrier laminate of Comparative Example 3 was also within 20 times that of the WVTR immediately after the 5% tensile test, but the WVTR after the 5% tensile test hardly recovered.

As described above, the gas barrier laminate 10 according to an embodiment of the present invention maintains gas barrier properties even after a tensile test (5% tensile test at 100 μm / sec) (specifically, after 24 hours). It was confirmed that it was almost recovered to the value before the tensile test) and was excellent in resistance to physical stress such as stretching.
In the above embodiment, as shown in FIG. 1, the case where the gas barrier laminate 10 in which the anchor coat layer 24 is provided between the resin base material 11 and the vapor deposition layer 12 is described. The present invention can also be applied to a gas barrier laminate that does not have 24. In the gas barrier laminate having no anchor coat layer 24, as shown in the above-described embodiment, the vapor deposition layer and the overcoat layer include SiO _x and X is 1.50 ≦ X ≦ 1.80. By using an overcoat layer including a layer, a water-soluble polymer having a hydroxyl group, and at least one selected from the group consisting of alkoxysilane and a hydrolyzate thereof, stretching is performed in the same manner as in the above embodiment. A gas barrier laminate excellent in resistance to physical stress such as the above can be realized.
As mentioned above, although embodiment of this invention was explained in full detail, actually, it is not restricted to said embodiment, Even if there is a change of the range which does not deviate from the summary of this invention, it is included in this invention.

  Since the gas barrier laminate according to an embodiment of the present invention has high levels of gas barrier properties, transparency, and durability, it can be widely used in fields that require gas barrier laminates. For example, (1) packaging films for pharmaceuticals and foods, (2) packaging films for electronic parts and precision parts such as semiconductor wafers, (3) flat panel display members such as liquid crystal displays and organic EL displays, (4) Although it is expected to be suitably used in fields such as a back sheet use and a front sheet use in a solar cell, it is not limited to this.

DESCRIPTION OF SYMBOLS 10 Gas barrier laminated body 11 Resin base material 12 Deposition layer 13 Overcoat layer 24 Anchor coat layer

Claims (4)

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,
The vapor deposition layer includes SiO _X , where X is 1.50 ≦ X ≦ 1.80,
The gas barrier laminate, wherein the overcoat layer includes a water-soluble polymer having a hydroxyl group and at least one selected from the group consisting of alkoxysilane and a hydrolyzate thereof.   The gas barrier laminate according to claim 1, wherein the water vapor permeability immediately after the 5% tensile test is within 20 times that before the tensile test.   The gas barrier laminate according to claim 1 or 2, wherein the water vapor permeability after 24 hours from the 5% tensile test is within 1.3 times that before the tensile test. An anchor coat layer is provided between the resin base material and the vapor deposition layer,
The anchor coat layer contains an acrylic polyol having two or more hydroxyl groups and an isocyanate compound having at least two NCO groups in the molecule, and the hydroxyl value of the acrylic polyol is 50 mgKOH / g or more and 250 mgKOH / g or less. The 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, and any one of claims 1 to 3 The gas barrier laminate according to Item.

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