JP6578765B2 - Gas barrier laminate and method for producing the same - Google Patents

Description

  The present invention relates to a gas barrier laminate and a method for producing the same.

The gas barrier laminate is a laminate having a property (gas barrier property) that prevents gas such as oxygen and water vapor from permeating. For this reason, the member hold | maintained at the site | part shielded with the gas-barrier laminated body can suppress degradation / deterioration etc. resulting from external gas. In recent years, such gas barrier laminates have been used in various fields.
Such a gas barrier laminate is used as a packaging material used for packaging foods, for example. In packaging applications such as food, it is required to prevent the contents from being altered. Specifically, it is required to suppress oxidation and alteration of proteins, oils and fats, and to maintain flavor and freshness. For this reason, a gas barrier laminate is preferably used.

  Moreover, such a gas barrier laminate is used as a packaging material used for packaging pharmaceutical products, for example. In packaging applications such as pharmaceuticals, it is required to prevent the contents from being altered. Specifically, it is required to maintain the sterility, suppress the alteration of the active ingredient in the contents, and maintain its efficacy. For this reason, a gas barrier laminate is preferably used.

Moreover, such a gas barrier laminate is utilized as a packaging material used for packaging electronic parts such as semiconductor wafers and precision parts, for example. When precision parts are exposed to an external gas, the external gas may act as a foreign substance and become a defective product. Therefore, it is required to shield the external gas. For this reason, a gas barrier laminate is preferably used.
Such a gas barrier laminate is also used as a member of a flat panel display such as a liquid crystal display or an organic EL display, a light source such as an illumination or a backlight, and a member for extracting light. In light-related applications, it is required to prevent deterioration of internal members such as pixel elements. For this reason, a gas barrier laminate is preferably used.

Such a gas barrier laminate is used 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 from ultraviolet rays and moisture. For this reason, a gas barrier laminate is preferably used.
Here, when such a gas barrier laminate is used as a packaging member, it is preferable to have transparency. Because the packaging material has transparency, the shape of the contents and the color of the contents can be visually confirmed from the outside of the package, which prevents the contents from being mixed, the presence or absence of damage, the contents The presence or absence of alteration can be ascertained before opening.

As described above, the gas barrier laminate has not only gas barrier properties but also transparency, moisture resistance, weather resistance, durability, and other characteristics at a high level so that it can be used in a wide variety of applications. Is required.
Conventionally, a gas barrier laminate in which a gas barrier substance is vapor-deposited on a film substrate is known as a gas barrier laminate. The vapor deposited film of the gas barrier material has a gas barrier property and is also very thin because it is extremely thin.

Examples of such gas barrier laminates include silica-based vapor deposition films and alumina reaction vapor deposition films. Silica-vapor deposited film, the film substrate is a laminate formed by depositing silicon monoxide or Si / SiO ₂ mixed material. The alumina reactive vapor deposition film is a laminate in which metal aluminum is evaporated and reacted with oxygen on a film substrate.

Here, since the silica-based vapor deposition film and the alumina reaction vapor deposition film have gas barrier properties that are easily affected by temperature and moisture, gas barrier laminates with improved heat resistance, water resistance, and moisture resistance have been proposed. (See Patent Document 1 and Patent Document 2).
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 its hydrolysis on a vapor deposition film provided on a substrate. A coating solution containing the product is applied and dried by heating to provide a gas barrier film. With such a configuration, gas barrier properties, heat resistance, water resistance, moisture resistance, and the like are improved.

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

  However, with the expansion of applications, gas barrier laminates are required to have long-term durability and use in more severe environments. For this reason, further improvements in durability such as moisture resistance, heat resistance, water resistance, and weather resistance are required. Here, as a harsh environment, for example, (1) For packaging materials, processing such as boil and retort sterilization is performed while being surrounded by packaging materials, and (2) display devices and light-related members (lighting) And solar cell) applications include long-term indoor and outdoor use and accelerated tests under high temperature and high humidity to ensure long-term reliability.

  Therefore, the present invention has been made in view of the above circumstances, and provides a gas barrier laminate that exhibits excellent optical properties and gas barrier properties over a long period of time even in a harsh environment, and a method for manufacturing the same. With the goal.

  As a result of intensive studies, the present inventors have found a means capable of controlling the gas barrier property of the gas barrier laminate, and have completed the present invention. The present invention is as follows.

1. A gas barrier laminate which is obtained by laminating a vapor deposition layer and an overcoat layer on at least one surface of a resin base material and satisfies the following conditions (a) and (b).
(A) Water vapor permeability under measurement conditions of 40 ° C. and relative humidity 90% is 0.1 g / (m ² · day) or less.
(B) A high humidity test was performed in which the gas barrier laminate was stored for 500 hours under conditions of 60 ° C. and 90% relative humidity, and the gas barrier laminate before and after the high humidity test defined by the following formula (1) A gas barrier laminate having a maximum change rate (ΔT%) of light transmittance at a visible wavelength of 400 to 700 nm of less than 3%.
ΔT% = | transmittance before high humidity test−transmittance after high humidity test | / transmittance before high humidity test × 100 (1)
2. 2. The vapor deposition layer is formed by vapor deposition of a vapor deposition material containing metallic silicon and silicon dioxide, and the refractive index at a wavelength of 500 nm is in the range of 1.5 to 1.8. Gas barrier laminate.
3. There is an anchor coat between the resin base material and the vapor deposition layer, the anchor coat layer has two or more OH (hydric acid) groups, and an OH group value of 50 mgKOH / g or more and 250 mgKOH / g or less. And an isocyanate compound having two or more NCO (isocyanate) groups in the molecule, and the equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound to the OH group of the acrylic polyol is The gas barrier laminate according to 1 or 2 above, which is 0.3 or more and 2.5 or less.
4). 4. The gas barrier laminate according to any one of 1 to 3, wherein one or more sets of the vapor deposition layer and the overcoat layer are laminated on the overcoat layer.
5). A method for producing the gas barrier laminate according to any one of 1 to 4,
A gas barrier laminate including at least the resin base material, the vapor deposition layer, and the overcoat layer is formed at a temperature not lower than a glass transition point and not higher than a melting point of the resin base material, a relative humidity of 40% or higher and 100% or lower, and 0 The manufacturing method of the gas-barrier laminated body characterized by having the process of performing the wet heat processing on the conditions under pressure of 12 MPa or more and 0.50 MPa or less.
6). A method for producing the gas barrier laminate according to any one of 1 to 4,
A gas barrier laminate including at least the resin substrate, the vapor deposition layer, and the overcoat layer is formed at a temperature not lower than a glass transition point and not higher than a melting point of the resin substrate, a relative humidity is not lower than 2% and not higher than 90%, and 0 A method for producing a gas barrier laminate, comprising a step of performing a wet heat treatment under atmospheric pressure at a pressure of 0.09 MPa or more and 0.11 MPa or less.

  According to the present invention, a gas barrier laminate having specific optical characteristics and gas barrier characteristics can be provided. Thereby, even under a harsh environment, deterioration of the overcoat layer and the vapor deposition layer is suppressed, and excellent gas barrier properties are exhibited over a long period of time. Therefore, according to the present invention, a gas barrier that exhibits excellent gas barrier properties over a long period of time even in harsh environments such as boil sterilization and retort sterilization, and in harsh environments such as outdoor placement. A functional laminate can be provided.

It is a schematic sectional drawing which shows one Embodiment of a gas-barrier laminated body. It is a schematic sectional drawing which shows another embodiment of a gas-barrier laminated body. It is a schematic sectional drawing which shows another embodiment of a gas-barrier laminated body.

  Hereinafter, embodiments of a 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 embodiment, and even if there is a design change or the like within a range not departing from the gist of the present specification, they are included in the present invention.

The gas barrier laminate of the present embodiment has (a) a water vapor permeability of 0.1 g / (m ² · day) or less under measurement conditions of 40 ° C. and a relative humidity of 90%, and (b) the gas barrier. The high-humidity test is performed in which the porous laminate is stored for 500 hours under the conditions of 60 ° C. and 90% relative humidity, and the visible wavelength range 400 to 400 of the gas-barrier laminate before and after the high-humidity test defined by the formula (1) The maximum change rate (ΔT%) of the light transmittance at each wavelength at 700 nm is less than 3%. According to this characteristic, a change in the optical characteristics of the laminate is suppressed, and a laminate having excellent durability and the like can be obtained while having a high water vapor barrier property.

In a thin film structure in which materials with different refractive indexes such as a base material, a vapor deposition layer, and an overcoat layer are laminated, thin film interference occurs according to the wavelength of light due to the relationship between the refractive index difference and the optical film thickness. It is known. Although this optical interference can be reduced by reducing the refractive index difference or adjusting the film thickness of each layer by the optical thin film design, it is difficult to completely eliminate the optical interference.
These optical interferences may result in a waveform in which a plurality of peaks and valleys are seen in the transmittance curve, which is referred to as spectral ripple in the spectral transmittance waveform in the visible range.
In general, an inorganic vapor deposition film is a material with a large change in refractive index in a high-temperature, humid-heat environment, and the refractive index of the film changes during long-term use or reliability tests as an accelerated test for long-term use. The interference waveform may change, causing a deviation from the original optical design, resulting in a decrease in transmittance and problems such as color reproducibility.
In particular, silica-based vapor-deposited films are widely used in applications that require barrier properties and adhesion strength over a long period of time because of their high chemical durability, but optical properties such as refraction change greatly. The laminate of the present invention can stabilize optical properties such as visibility and color reproducibility by suppressing changes in optical properties while maintaining excellent barrier properties.

  Further, the production method of the present invention comprises a gas barrier laminate including a resin base material, a vapor deposition layer, and an overcoat layer, at a specific temperature, a specific relative humidity, and a specific pressure or atmospheric pressure. It has a step of performing a wet heat treatment, which can provide high barrier properties and stabilization of optical properties over a long period of time.

(Gas barrier laminate)
FIG. 1 is a schematic cross-sectional view showing an embodiment of a gas barrier laminate.
The gas barrier laminate 10 is a laminate having a configuration 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, on the basis of the resin base material 11, the direction in which the vapor deposition layer 12 and the overcoat layer 13 are laminated will be described as the top (layer).

<Resin substrate>
The resin base material is a layer that becomes a base of the gas barrier laminate. The resin base material may be appropriately selected and used from various commonly used sheet-like base materials (including film-like materials). 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 vinyl chloride film, a polycarbonate film, a polyacrylonitrile film, a polyimide film, and a biodegradable plastic film such as polylactic acid.

The resin base material 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 is not particularly limited, and may be appropriately determined according to specifications. Practically, the thickness of the resin substrate is desirably 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 of the present embodiment, the thickness of the resin base material is not limited to the above range.

  The resin base material may be subjected to a surface treatment on the resin base material surface. By performing the surface treatment, adhesion with other layers can be improved in stacking other layers (evaporated layer, anchor coat layer, etc.). 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>
A vapor deposition layer is a layer formed in the upper layer from a resin base material by vapor-depositing vapor deposition material in order to provide gas-barrier property.
The vapor deposition material used for the vapor deposition layer may be appropriately selected from inorganic materials constituting a known gas 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, fluorides, and the like. Among these, at least one selected from metals and metal oxides is preferable. Specifically, silicon oxide (SiOx), such as silicon monoxide and silicon dioxide, aluminum oxide, magnesium oxide, tin oxide, etc. are mentioned, for example.

  The vapor deposition layer is particularly preferably formed by vacuum vapor deposition using a vapor deposition material containing metal silicon and silicon dioxide. The vapor deposition layer formed as described above is particularly excellent in transparency and barrier properties against oxygen gas and water vapor. In the vapor deposition material, the content ratio of metal silicon to silicon dioxide is preferably such that the element ratio O / Si between silicon and oxygen is 1.0 or more and 1.8 or less, and O / Si is 1 More preferably, it is contained at a ratio of 2 or more and 1.7 or less. When O / Si is 1.0 or more, transparency is good, and when O / Si is 1.8 or less, barrier properties are good. However, in the gas barrier laminate of the present embodiment, the content ratio in the case of using a vapor deposition material containing metal silicon and silicon dioxide is not limited to the above range. In the gas barrier laminate of this embodiment, the refractive index of the vapor deposition layer at a wavelength of 500 nm is preferably in the range of 1.5 to 1.8 from the viewpoint of transparency.

  In addition, the vapor deposition material containing metal silicon and silicon dioxide further includes at least one metal selected from the group consisting of Al, Zn, Sn, Fe, and Mn (hereinafter referred to as a specific metal) or Those oxides may be contained. Thereby, a vapor deposition layer having a higher film density can be formed than in the case where a mixture of metal silicon and silicon dioxide is used as a vapor deposition material, and high gas barrier properties are exhibited.

  Moreover, when using the vapor deposition material which contained metal silicon, silicon dioxide, and the specific metal or those oxides, content of the specific metal or its oxide in vapor deposition material is a total of 100 mass of metal silicon and silicon dioxide. % To 50% by mass, preferably 1% to 40% by mass, more preferably 5% to 30% by mass. If it is 1 mass% or more, the effect of improving the film density is sufficiently obtained. If it exceeds 50% by mass, the contents of metal silicon and silicon dioxide are relatively reduced, so that the transparency of the vapor-deposited layer, the barrier property in a moist heat resistant environment, and the like may be lowered. Moreover, it is preferable that remainder other than a specific metal or its oxide consists of silicon metal and silicon dioxide. That is, the total of the specific metal or its oxide, metal silicon, and silicon dioxide is preferably 100% by mass.

  As described above, when a vapor deposition material containing metal silicon and silicon dioxide is vacuum deposited, a vapor deposition layer made of an inorganic material containing silicon oxide (SiOx) is formed. Further, when a vapor deposition material containing metal silicon, silicon dioxide, and a specific metal or oxide thereof is vacuum-deposited, a vapor deposition layer composed of silicon oxide and an inorganic material containing the specific metal or oxide thereof is formed. . The kind and abundance ratio of the elements constituting the formed vapor deposition layer can be measured by an X-ray photoelectron spectrometer (ESCA).

  When a vapor deposition material containing metal silicon and silicon dioxide is used as the vapor deposition material, the content of silicon oxide in the vapor deposition layer is 15 atm% or more as an abundance ratio of Si elements in all elements constituting the vapor deposition layer. Is preferable, and 25 atm% or more is more preferable. If it is 25 atm% or more, it is excellent in transparency, barrier properties, and the like.

  When a vapor deposition material containing metal silicon, silicon dioxide, and a specific metal or oxide thereof is used as the vapor deposition material, the content of the specific metal or oxide thereof in the vapor deposition layer is based on the total elements constituting the vapor deposition layer. The abundance ratio of the specific metal element is preferably 1 atm% or more and 20 atm% or less, more preferably 3 atm% or more and 15 atm% or less, and further preferably 3 atm% or more and 10 atm% or less. If it is 1 atm% or more, a high gas barrier property will express. If it exceeds 20 atm%, the content of the silicon oxide is relatively reduced, so that the transparency of the deposited layer, the barrier property in a moist heat resistant environment, and the like may be deteriorated. The vapor deposition layer in which the abundance ratio of the specific metal element is 1 atm% or more and 20 atm% or less is, for example, a ratio of 1% by mass or more and 50% by mass or less of the specific metal or its oxide with respect to 100% by mass of metal silicon and silicon dioxide It can form by using the vapor deposition material mix | blended with.

  As a method for forming the vapor deposition layer, a known vapor deposition method may be appropriately selected and used. 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 evaporation method of EB: electron beam heating method can obtain a high film forming speed, and is preferable as a method for forming the 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 vapor deposition is performed by reacting evaporated particles with a gas introduced into the atmosphere when vapor deposition is performed. 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. 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 may not be neatly stacked, and the water vapor barrier property may be deteriorated.

  The thickness of the vapor deposition layer is preferably 5 nm or more and 300 nm or less, and 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, generation of cracks in the post-process and the like, and deterioration of the barrier properties are less likely to occur. However, in the gas barrier laminate of the present embodiment, the thickness of the vapor deposition layer is not limited to the above range.

<Overcoat layer>
An overcoat layer is a layer formed on a vapor deposition layer. By laminating the overcoat layer on the vapor deposition layer, it is possible to obtain an excellent gas barrier property that cannot be expressed in a gas barrier laminate in which the vapor deposition layer is composed of a single layer. The overcoat layer also has a function of protecting the dense and fragile deposited layer, and can suppress generation of cracks due to rubbing or bending.
The overcoat layer is formed by adjusting the coating solution, coating the coating solution on the vapor deposition layer, and heating and drying the coating solution.

  The overcoat layer 13 is made of a component containing any one of a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group. A coating solution containing any one of a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group is applied onto the vapor deposition layer 12. It is formed by drying.

  Water-soluble polymers that form the overcoat layer include polyvinyl alcohol resin (PVA), polyacrylic acid resin (PAA), ethylene-vinyl alcohol copolymer resin (EV hydroxyl), polyvinyl pyrrolidone resin (PVP), or hydroxyl. An acrylic polyol having a group and a carboxyl group can be used, and these may be used alone or in combination.

  Moreover, in order to improve the adhesiveness with the vapor deposition layer 12, you may add an alkoxysilane. As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, or the like can be used. Examples of the hydrolysis product of alkoxysilane include those prepared by dissolving alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and causing a hydrolysis reaction.

  Moreover, in order to improve adhesiveness with the vapor deposition layer 12, you may add a silane coupling agent. 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 mercapto groups such as 3-mercaptopropyltrimethoxysilane. And those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

  In order to improve the adhesion to the vapor deposition layer 12, an isocyanate compound having at least two isocyanate groups in the molecule may be added.

  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 a drying method, one or a combination of two or more methods of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, can be used. 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 100 ° C. to 150 ° C. When it is 60 ° C. or higher, desired barrier properties are exhibited, which is good. If it is 150 degreeC or less, if it is a vapor deposition short time, it will be suitable, without a deformation | transformation of a base material and a crack generating in a vapor deposition film.

The thickness of the overcoat layer is preferably about 0.1 μm to 2 μm, and more preferably about 0.2 μm to 1.0 μm. When it is 0.2 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 of this 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 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)
Moreover, the gas barrier laminate of this embodiment may further include an anchor coat layer between the resin base material and the vapor deposition layer. By providing the anchor coat layer, the adhesion between the resin base material and the vapor deposition layer can be improved, and the occurrence of peeling between the layers can be suppressed.
The anchor coat layer is a layer serving as a base for the vapor deposition layer, and has a great influence on the number of defects in the vapor deposition layer, has high thermal stability, has few foreign matters, and is preferably in a smooth and homogeneous state.
FIG. 2 shows a schematic cross-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 having a structure 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 base material 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 (1) having two or more OH groups and an isocyanate compound (2) having at least two NCO groups in the molecule.

  As the acrylic polyol (1), a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having an OH group and another monomer are copolymerized. Examples thereof include a polymer compound obtained. Examples of the (meth) acrylic acid derivative monomer having an OH 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 an OH group, a (meth) acrylic acid derivative monomer having no OH group is preferable. Examples of (meth) acrylic acid derivative monomers having no OH group include (meth) acrylic acid derivative monomers having an alkyl group, (meth) acrylic acid derivative monomers having a carboxyl group, and (meth) acrylic having a ring structure. Examples include acid 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 (meth) acrylic acid derivative monomer may have an OH group.

  Moreover, it is preferable that OH group value of acrylic polyol (1) is 50 [mgKOH / g] or more and 250 [mgKOH / g] or less. The OH group value [mgKOH / g] is an index of the amount of OH groups 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. If the OH group value is less than 50 [mgKOH / g], the reaction amount with the isocyanate compound (2) is small, and the effect of improving the adhesion between the resin substrate and the vapor deposition layer by the anchor coat layer may not be sufficiently exhibited. There is. On the other hand, if the OH group value is larger than [250 mgKOH / g], the amount of reaction with the isocyanate compound (2) increases so that the shrinkage of the anchor coat layer may be increased. When the film shrinkage is large, the vapor deposition layer 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 (1) 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 (1) may be used individually by 1 type, or may use 2 or more types together.

  The isocyanate compound (2) may be any compound having 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 (2), you may select arbitrarily from said monomeric isocyanate, its polymer, a derivative, etc., and can be used individually by 1 type 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 (2) to the OH group of the acrylic polyol (1) is preferably 0.3 or more and 2.5 or less, More preferably, it is 2.0 or less. When NCO / OH is 0.3 or more, the adhesion to the substrate is improved, and when it is 2.0 or less, the adhesion after the wet heat resistance test is improved. The blending amount of the acrylic polyol (1) and the isocyanate compound (2) in the anchor coating agent is preferably blended based on the equivalent ratio, and the isocyanate compound (2) is generally based on 100 parts by mass of the acrylic polyol (1). The amount is preferably about 10 parts by mass or more and 90 parts by mass or less, and more preferably about 20 parts by mass or more and 80 parts by mass or less.

  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 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 (1), an isocyanate compound (2), an optional component (such as a silane coupling agent), and a solvent. Any solvent may be used as long as it can dissolve the acrylic polyol (1) and the isocyanate compound (2). 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 a drying method, one or a combination of two or more methods of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, can be used. 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-called blocking phenomenon in which the coated surface sticks to the back surface even if winding processing is performed so that there is no residual solvent. The aging treatment may be performed within a range of about 40 ° C. to 60 ° C. as necessary.

  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 substrate and the vapor deposition layer is sufficiently good. If it 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 risk that the expression of gas barrier properties will be insufficient.

<Multilayer laminate>
In addition, the gas barrier laminate may have a multilayer structure in which at least one or more vapor deposition layers and an overcoat layer are further laminated on the overcoat layer. By having one or more sets of multilayer structures, the barrier property is further improved and the effect of greatly reducing the transmittance of neon and carbon dioxide is high, and the overcoat layer is suitable for maintaining long-term durability.

<Laminated resin layer>
Further, the gas barrier laminate may further include a laminate resin layer laminated via an adhesive layer, and the outermost surface may be a laminate resin layer. By providing a laminate resin layer on the outermost surface, it is possible to impart functions and properties according to the application and to enhance practicality. Here, the laminate resin layer may be formed only on one side or on both sides.

  FIG. 3 is a schematic cross-sectional view showing an aspect of a gas barrier laminate having a laminate resin layer on both sides. The gas barrier laminate 30 has an anchor coat layer 24, a vapor deposition layer 12, an overcoat layer 13, an adhesive layer 31, and a laminate resin layer 32 sequentially laminated on one surface of the resin base material 11. This is a laminate in which an adhesive layer 33 and a laminate resin layer 34 are sequentially laminated on the surface.

  The material of the laminate resin layer may be appropriately selected from known materials according to desired functions and characteristics. For example, by using a sealant film made of a heat-sealable resin for the laminate resin layer, the gas barrier laminate can be used as an adhesive part when forming a bag-like package or the like. Examples of the resin constituting the sealant film include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene- Examples thereof include acrylic acid ester copolymers and their metal cross-linked products. The thickness of the sealant film is determined according to the purpose, but is generally in the range of 15 μm to 200 μm. In addition, when laminating the laminate resin layers on both surfaces, a structure using a sealant film on one side and a resin film other than the sealant film on the other side may be used.

For example, by using a polyethylene terephthalate film or polyethylene naphthalate film for the laminate resin layer, the gas barrier laminate can be used as a sealing material for liquid crystal display elements, solar cells, electromagnetic wave shields, transparent conductive sheets used in touch panels, etc. It can also be used.
The formation of the laminate resin layer may be appropriately performed using a known bonding method depending on the material of the selected laminate resin layer. For example, a laminating method such as dry lamination using an adhesive or extrusion molding using a heat-adhesive resin may be used. In the case of dry lamination using an adhesive, the adhesive forms an adhesive layer. Further, in the case of extrusion molding using a heat-adhesive resin, the heat-adhesive resin forms a bonding layer.

  A method for producing a gas barrier laminate according to an embodiment of the present invention includes a gas barrier laminate including a resin base material, a vapor deposition layer, and an overcoat layer, a specific temperature, a specific relative humidity, and a specific It includes a step of performing a wet heat treatment under pressure or atmospheric pressure.

<Humid heat treatment>
The wet heat treatment method is divided into “wet heat treatment performed under conditions under pressure” and “wet heat treatment performed under conditions under atmospheric pressure”.
In the method for producing a gas barrier laminate, the wet heat treatment temperature is not less than the glass transition point of the resin substrate and not more than the melting point. When the temperature of the wet heat treatment is lower than the glass transition point of the resin base material, the effect of the wet heat treatment hardly appears. If it is higher than the melting point of the resin substrate, the resin substrate is melted and the entire film is collapsed, so that the water vapor barrier property is lowered.

(Humid heat treatment carried out under pressure)
First, the conditions of the wet heat treatment performed under conditions under pressure will be described. The temperature of the wet heat treatment is desirably not less than the glass transition point of the resin substrate 11 and not more than the melting point. When the temperature of the wet heat treatment is lower than the glass transition point of the resin base material 11, the effect of the wet heat treatment hardly appears. If it is higher than the melting point of the resin base material 11, the resin base material 11 is melted and the whole film is collapsed, so that the water vapor barrier property is lowered. As described above, the temperature of the wet heat treatment varies depending on the material of the resin base material 11. Specifically, the wet heat treatment is performed in the range of about 70 ° C to 200 ° C. Further, the wet heat treatment time varies depending on the material of the resin base material 11 like the temperature, but specifically, the wet heat treatment is performed for a short time of about 5 minutes and for a long time of about 100 hours. The humidity of the wet heat treatment is preferably 40% RH or more and 100% RH or less (relative humidity 40% or more and 100% or less). When the humidity of the wet heat treatment is lower than 40% RH, the effect of the wet heat treatment hardly appears. The humidity does not theoretically exceed 100% RH. The relative humidity is calculated as (specific weight of water vapor in humid air g / m ³ ) / (specific weight of water vapor in saturated humid air g / m ³ )) × 100 (%) at the temperature at that time. Is done. The pressure for the wet heat treatment is preferably 0.12 MPa or more and 0.50 MPa or less. If it is lower than 0.12 MPa, the effect of wet heat treatment in a pressurized atmosphere is difficult to appear. When it is higher than 0.50 MPa, the film is deformed by pressurization, and the water vapor barrier property is lowered.

(Humid heat treatment carried out under atmospheric pressure)
Next, conditions for the wet heat treatment performed under conditions under atmospheric pressure will be described. The temperature of the wet heat treatment is desirably not less than the glass transition point of the resin substrate 11 and not more than the melting point. When the temperature of the wet heat treatment is lower than the glass transition point of the resin base material 11, the effect of the wet heat treatment hardly appears. If it is higher than the melting point of the resin base material 11, the resin base material 11 is melted and the whole film is collapsed, so that the water vapor barrier property is lowered. As described above, the temperature of the wet heat treatment varies depending on the material of the resin base material 11. Specifically, the wet heat treatment is performed in the range of about 70 ° C to 200 ° C. Moreover, about the time of wet heat processing, it changes with the materials of the resin base material 11, like temperature. Specifically, wet heat treatment is performed for a short time of about 5 seconds and a long time of about 1 hour. The humidity of the wet heat treatment is desirably 2% RH or more and 90% RH or less (relative humidity 2% or more and 90% or less). When the humidity of the wet heat treatment is lower than 2% RH, the effect of the wet heat treatment is difficult to appear. If the humidity is higher than 90% RH, the water resistance of the film decreases due to condensation. The pressure for the wet heat treatment is preferably 0.09 MPa or more and 0.11 MPa or less. When it is lower than 0.09 MPa or higher than 0.11 MPa, it deviates from the atmospheric pressure atmosphere.

  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.

  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 liquid for forming the overcoat layer and the anchor coat agent is a coating film formed by polymerization of the hydrolyzed organosilicon compound. The amount converted to weight.

Example 1
First, the vapor deposition layer was formed on the resin base material. As the resin base material, a biaxially stretched polyethylene naphthalate (PEN) film (Teijin DuPont Films, Teonex Q65, glass transition temperature = 120 ° C., melting point = 269 ° C.) having a corona treatment on one side is used. It was. Further, a vapor deposition material (A) in which a metal silicon powder and a silicon dioxide powder are mixed directly on the corona-treated surface of the resin base material so that the element ratio O / Si is 1.5 using a vacuum vapor deposition machine. Was vapor-deposited to form a vapor-deposited layer on the resin substrate. At this time, the formed vapor deposition layer (SiOx vapor deposition film) was 80 nm in thickness.

  Next, a coating solution for forming an overcoat layer was prepared. Overcoat coating solution: Tetraethoxysilane (TEOS) hydrolyzed solution (water added with 5-fold molar equivalent of tetraethoxysilane as water using 0.01N hydrochloric acid) and an aqueous solution of polyvinyl alcohol, SiO2 of TEOS A solution having a solid content of 5% by mass was prepared by mixing so that the mass ratio of the converted amount to PVA was 50:50.

Next, a coating solution was applied onto the vapor deposition layer and dried by heating to form an overcoat layer.
A bar coat 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 was 0.5 μm.

  Subsequently, using the advanced accelerated life test apparatus (manufactured by Espec Co., Ltd.), the produced gas barrier laminate was wet heat-treated in an environment of a temperature of 120 ° C., a relative humidity of 85%, a treatment time of 10 minutes, and a pressure of 0.17 MPa. did.

  From the above, the gas barrier laminate of Example 1 in which the resin base material / vapor deposition layer / overcoat layer was laminated in this order was produced. In the gas barrier laminate of Example 1, the thickness of each layer was resin substrate: 12 μm / deposition layer: 80 nm / overcoat layer: 0.5 μm.

[Inspection measurement]
About the gas-barrier laminated body of Example 1, the spectral transmittance measurement of wavelength 400-800nm was performed with the water vapor transmission rate (WVTR) measurement and the spectral-light transmittance measuring apparatus. Here, the measurement was performed twice: (1) immediately after production (initial stage) and (2) after accelerated deterioration test (high humidity test) (temperature 60 ° C., relative humidity 90%, 500 hours storage test). .
In addition, in the measurement of water vapor transmission rate, the water vapor transmission rate [g / m ² ··· in a 40 ° C.-90% RH atmosphere using a water vapor transmission meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control Co., Ltd. day].
In the spectral transmittance measurement, a visible transmittance (wavelength 400-800 nm) spectral transmittance curve is measured using a spectral transmittance measuring device manufactured by Shimadzu, and the transmittance that has changed most before and after the accelerated deterioration test is obtained. The rate of change was determined by (Equation 1) (ΔT (%)).
ΔT (%) = | transmittance before test−transmittance after test | / transmittance before test × 100 (Equation 1)
The refractive index of the vapor deposition film was obtained from the above spectral transmittance curve by an optical simulation method.
As a result, the initial WVTR was 0.03 g / (m ² · day), the light transmittance at a wavelength of 500 nm was 87.2%, the WVTR after the accelerated deterioration test was 0.06 g / (m ² · day), and the transmittance 87 0.6% and ΔT 0.5%. The measurement results are shown in Table 1. In addition, since the difference of the light transmittance became maximum in the vicinity of 500 nm, a value of 500 nm is shown.

(Example 2)
First, an anchor coating agent was prepared.
The anchor coat agent is prepared by copolymerizing hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as monomers so that the OH group 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 mixing the 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 of the main agent.

Next, an anchor coat agent was applied on the resin base material to form an anchor coat layer.
A biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, T60, glass transition temperature = 80 ° C., melting point = 260 ° C.) having a thickness of 50 μm and one side corona-treated on the resin base was used. Further, using a gravure coater, the anchor coat agent was applied to the corona-treated surface of the resin substrate, and stored in an oven 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 0.15 μm.

Next, a vapor deposition layer was formed on the anchor coat layer.
Using a vacuum deposition apparatus, a deposition material (A) in which metal silicon powder and silicon dioxide powder were mixed so as to have an element ratio O / Si of 1.5 was deposited, and a deposition layer was formed on the resin substrate. . At this time, the formed vapor deposition layer (SiOx vapor deposition film) was 50 nm in thickness.

Next, a coating solution for forming an overcoat layer was prepared.
The coating solution was a 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate hydrolysis solution (0.001N hydrochloric acid was added as a water and a 6-fold molar equivalent of silylisocyanurate), Tetraethoxysilane was mixed so that silyl isocyanurate: tetraethoxysilane = 20: 80 (molar ratio) and diluted with IPA to obtain a solution having a solid content of 5% by mass.

Next, a coating solution was applied onto the vapor deposition layer and dried by heating to form an overcoat layer. A bar coat was used for coating the coating solution. The heating and drying conditions were 120 ° C. and 2 minutes. At this time, the dry film thickness of the formed overcoat layer was 0.5 μm.
Using the advanced accelerated life test apparatus (manufactured by Espec Co., Ltd.), the produced gas barrier laminate was subjected to wet heat treatment in an environment of a temperature of 120 ° C., a relative humidity of 85%, a treatment time of 10 minutes, and a pressure of 0.17 MPa.
From the above, the gas barrier laminate of this example in which the resin base material / anchor coat layer / deposition layer / overcoat layer were laminated in this order was produced. In the gas barrier laminate of this example, the film thickness of each layer was: resin substrate: 50 μm / anchor coat layer: 0.15 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm.

[Inspection measurement]
About the gas-barrier laminated body obtained in Example 2, it carried out similarly to Example 1, and measured the water-vapor permeability and the light transmittance of wavelength 500nm. As a result, the initial WVTR is 0.03 g / (m ² · day), the light transmittance is 89.3%, the WVTR after the accelerated deterioration test is 0.03 g / (m ² · day), and the light transmittance is 90.1. %, And ΔT was 0.9%. The measurement results are shown in Table 1.

(Example 3)
The coating liquid for overcoat layer formation has the following coating liquid composition, and is further added to a material in which metal silicon powder and silicon dioxide powder are mixed so that the element ratio (O / Si) in the vapor deposition material is 1.5. The gas barrier property of the present example was the same as that of Example 2 except that the vapor deposition material (B) mixed with 20% by mass of metal tin powder was deposited to form a 50 nm thick vapor deposition layer (SiOx-Sn composite vapor deposition film). A laminate was produced.

<Coating solution>
The coating solution for overcoat layer formation was a hydrolyzed solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate (6 times molar equivalent of silylisocyanurate as water using 0.001N hydrochloric acid) And glycidoxypropyltrimethoxy sealant tetraethoxysilane are mixed so that silyl isocyanurate: glycidoxypropyltrimethoxysilane: tetraethoxysilane = 20: 10: 70 (molar ratio), A solution having a solid content of 5% by mass (Example 3 solution A) was prepared by dilution with IPA.

Next, the solution A and a methyl ethyl ketone solution (mixed solution of acrylic polyol and isocyanate compound) having a solid content of 5% by mass prepared as an anchor coating agent in Example 2 were mixed at a solid content ratio of 90: The resulting mixture was mixed to prepare a coating solution. Using the advanced accelerated life test apparatus (manufactured by Espec Co., Ltd.), the produced gas barrier laminate was subjected to wet heat treatment in an environment of a temperature of 120 ° C., a relative humidity of 85%, a treatment time of 10 minutes, and a pressure of 0.17 MPa.
From the above, the gas barrier laminate of this example in which the resin base material / anchor coat layer / deposition layer / overcoat layer were laminated in this order was produced. In the gas barrier laminate of Example 3, the thickness of each layer was: resin substrate: 50 μm / anchor coat layer: 0.15 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm. Further, when the element ratio in the deposited film was measured with an X-ray photoelectron spectroscopic analyzer (manufactured by JEOL Ltd., model JPS-90MXV), Si, Sn, and O elements were detected. 4 atm%, Sn: 5.2 atm%, O: 63.4 atm%.

[Inspection measurement]
About the gas-barrier laminated body obtained in Example 3, it carried out similarly to Example 1, and measured the water-vapor permeability and the light transmittance of wavelength 500nm.
As a result, the initial WVTR is 0.02 g / (m ² · day), the light transmittance is 86.1%, the WVTR after the accelerated deterioration test is 0.02 g / (m ² · day), and the light transmittance is 87.5. %, ΔT 1.6%. The measurement results are shown in Table 1.

(Comparative Example 1)
Using a biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, S10, glass transition temperature = 80 ° C., melting point = 260 ° C.) having a thickness of 50 μm and one side corona-treated on the resin substrate, Example 2 Similarly, a gas barrier laminate was produced. However, the application of the coating solution for forming the overcoat layer and the wet heat treatment step were not performed.

  From the above, a gas barrier laminate of Comparative Example 1 in which the resin base material / anchor coat layer / deposition layer was laminated in this order was produced.

[Inspection measurement]
The gas barrier laminate obtained in Comparative Example 1 was subjected to various gas permeability measurements in the same manner as in Example 1.
As a result, the initial WVTR was 0.3 g / (m ² · day), the light transmittance was 85.8%, and the WVTR in the accelerated deterioration test was 3.2 g / (m ² · day). The light transmittance was 89.3. %, And ΔT was 4.1%. The measurement results are shown in Table 1.

(Comparative Example 2)
The composition of the coating liquid for overcoat layer formation was the same as that of the anchor coating agent used in Example 2, and the drying conditions after coating the coating liquid for overcoat layer formation were 120 ° C. for 1 minute. A gas barrier laminate was produced in the same manner as in No. 3. However, no wet heat treatment was performed.
From the above, a gas barrier laminate of Comparative Example 2 in which the resin base material / anchor coat layer / deposition layer / overcoat layer was laminated in this order was produced. In Comparative Example 2, the anchor coat layer and the overcoat layer are made of materials having the same composition.

[Inspection measurement]
About the gas-barrier laminated body obtained by the comparative example 2, it carried out similarly to Example 1, and measured the water-vapor permeability and the light transmittance measurement with a wavelength of 500 nm.
As a result, the initial WVTR is 0.4 g / (m ² · day), the light transmittance is 83.2%, the WVTR after the accelerated deterioration test is 2.8 g / (m ² · day), and the light transmittance. They were 88.4% and ΔT 6.3%. The measurement results are shown in Table 1.

  Table 1 summarizes the measurement results of the layer structures (used materials), water vapor transmission rate (WVTR), light transmittance, etc. of the laminates obtained in Examples 1 to 3 and Comparative Examples 1 and 2. “AC layer” in Table 1 indicates “anchor coat layer”, and “OC layer” in Table 1 indicates “overcoat layer”.

<Evaluation>
As for the gas barrier properties of the gas barrier laminates of Examples 1 to 3, the initial value of WVTR was low, and the gas barrier properties were excellent. In addition, even after the accelerated deterioration test, the value of WVTR did not increase so much from the initial value, and the change in optical characteristics was as small as 3% change. On the other hand, the gas barrier properties of the gas barrier laminates of Comparative Examples 1 and 2 showed that after the accelerated deterioration test, the value of WVTR increased by 7 times or more compared to the initial value, and the WVTR was 1.0 g / (m ² · day). ) Larger value, and the rate of change of optical characteristics also increased.

As described above, the gas barrier laminate of the present invention maintains optical properties and gas barrier properties even after a high humidity test (storage test at 60 ° C. and 90% RH for 500 hours) (specifically, WVTR). Was about 0.1 g / (m ² · day) or less, and the light transmission change rate was less than 5%), and it was confirmed that the optical characteristics and gas barrier properties were maintained even in a harsh environment. For this reason, it has been confirmed that it can be suitably used even in harsh environments such as packaging material applications that perform treatments such as boil and retort sterilization, and solar cell applications that are expected to be used for a long time outdoors. It was.

  Since the gas barrier laminate of the present invention has a high level of gas barrier properties, transparency, and durability, it can be widely used in fields requiring a gas barrier laminate. 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 application and a front sheet application in a solar cell, it is not limited to this.

10, 20, 30 Gas barrier laminate 11 Resin substrate 12 Vapor deposition layer 13 Overcoat layer 24 Anchor coat layer 31, 33 Adhesive layer 32, 34 Laminate resin layer

Claims (6)

A vapor deposition layer and an overcoat layer containing tetraethoxysilane or a hydrolyzate thereof are laminated on at least one surface of the resin base material, and the temperature of the resin base material is higher than the glass transition point and lower than the melting point, and the relative humidity is 40% or higher and 100%. Hereinafter, after performing a wet heat treatment under a time of 5 minutes to 100 hours and under a pressure of 0.12 MPa to 0.50 MPa, or a temperature above the glass transition point of the resin base material and below the melting point, relative humidity After performing wet heat treatment under atmospheric pressure conditions of 2% to 90%, 5 seconds to 1 hour, and pressure of 0.09 MPa to 0.11 MPa, the following conditions (a) and (b) Gas barrier laminate satisfying the requirements.
(A) Water vapor permeability under measurement conditions of 40 ° C. and relative humidity 90% is 0.1 g / (m ² · day) or less.
(B) A high humidity test was performed in which the gas barrier laminate was stored for 500 hours under conditions of 60 ° C. and 90% relative humidity, and the gas barrier laminate before and after the high humidity test defined by the following formula (1) A gas barrier laminate having a light transmittance change rate (ΔT%) of less than 3% at a visible wavelength of 400 to 700 nm.
ΔT% = | transmittance before high humidity test−transmittance after high humidity test | / transmittance before high humidity test × 100 (1)   The vapor deposition layer is formed of a vapor deposition material containing metal silicon and silicon dioxide by a vacuum vapor deposition method, and has a refractive index in a range of 1.5 to 1.8 at a wavelength of 500 nm. The gas barrier laminate as described. There is an anchor coat layer between the resin base material and the vapor deposition layer, the anchor coat layer has two or more OH (hydric acid) groups, and the OH group value is 50 mgKOH / g or more, 250 mgKOH / g. The following is an acrylic polyol and an isocyanate compound having two or more NCO (isocyanate) groups in the molecule, and the equivalent ratio of the NCO group of the isocyanate compound to the OH group of the acrylic polyol (NCO / OH) The gas barrier laminate according to claim 1 or 2, wherein is 0.3 or more and 2.5 or less.   The gas barrier laminate according to any one of claims 1 to 3, wherein one or more layers each including the vapor deposition layer and the overcoat layer are laminated on the overcoat layer. A method for producing the gas barrier laminate according to any one of claims 1 to 4,
A gas barrier laminate including at least the resin base material, the vapor deposition layer, and the overcoat layer is formed at a temperature not lower than a glass transition point and not higher than a melting point of the resin base material, and a relative humidity is not lower than 40% and not higher than 100% for 5 minutes. A method for producing a gas barrier laminate, comprising a step of performing a wet heat treatment under a pressure of 0.12 MPa to 0.50 MPa under a time of 100 hours to 100 hours . A method for producing the gas barrier laminate according to any one of claims 1 to 4,
A gas barrier laminate including at least the resin base material, the vapor deposition layer, and the overcoat layer is formed at a temperature not lower than the glass transition point and not higher than the melting point of the resin base material, relative humidity of 2% to 90%, and 5 seconds. 1 to 1 hour, and the process of performing the wet heat processing on the conditions under atmospheric pressure of the pressure of 0.09 MPa or more and 0.11 MPa or less, The manufacturing method of the gas-barrier laminated body characterized by the above-mentioned.

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