JP2016203465A - Gas barrier laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate that can be used under a severer environment along with increase of purposes, capable of improving endurance such as moisture resistance, heat resistance, water resistance, weather resistance, flex resistance and extension resistance.SOLUTION: A gas barrier laminate includes: a resin substrate 11; a vapor-deposited layer 12 laminated at least on one side of the resin substrate 11; and an overcoat layer 13 laminated on the vapor-deposited layer 12. In the overcoat layer 13, a coating liquid is applied onto the vapor-deposited layer 12, then heated and dried, so that the content of organic substances is formed to be 30-90 mass%. The coating liquid includes: silyl isocyanurate expressed by X-((CH)-Si(OR))m or hydrolyzate (A) thereof; and a water-soluble polymer having a hydroxy group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier laminate.

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 used as a member for flat panel displays such as liquid crystal displays and organic EL displays. In flat panel display 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 properties such as transparency, moisture resistance, weather resistance, durability, etc. at a high level so that it can be used for various wide applications. Desired.
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 WO2004 / 048081 Pamphlet

However, with the expansion of applications, gas barrier laminates are required to be used in more severe environments. For this reason, further improvement in durability such as moisture resistance, heat resistance, water resistance, weather resistance, flex resistance, and stretch resistance is required. Here, examples of the harsh environment include plastic deformation caused by pulling and a load caused by exposure to high temperature and high humidity.
Then, this invention is made | formed in view of the said situation, Comprising: It aims at providing the gas-barrier laminated body which exhibits the outstanding gas-barrier property also in a severe environment.

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

[1] A resin base material, a vapor deposition layer laminated on at least one surface of the resin base material, and an overcoat layer laminated on the vapor deposition layer,
The overcoat layer is an overcoat layer formed by applying a coating solution on the vapor deposition layer and heating and drying the coating solution so that the organic content is 30% by mass or more and 90% by mass or less.
The coating solution contains at least one (A) selected from the group consisting of silyl isocyanurate represented by the following general formula (a) and a hydrolyzate thereof, and a water-soluble polymer having a hydroxyl group. A gas barrier laminate, which is a liquid.
_{X - ((CH 2) n} -Si (OR) 3) m ...... (a)
[However, X is an isocyanurate ring, R is an alkyl group, and m and n are each independently an integer of 1 to 5. ]

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

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

[4] An anchor coat layer is further provided between the resin base material and the vapor deposition layer, and the anchor coat layer is formed by applying an anchor coat agent on the resin base material. An anchor coat layer formed by heating and drying, wherein the anchor coat agent includes an acrylic polyol (1) having two or more hydroxyl groups, and an isocyanate compound (2) having at least two NCO groups in the molecule. The acrylic polyol (1) has a hydroxyl value of 50 mgKOH / g or more and 250 mgKOH / g or less, and the equivalent ratio of the NCO group of the isocyanate compound (2) to the hydroxyl group of the acrylic polyol (1) (NCO / The gas barrier laminate according to any one of [1] to [3], wherein OH) is 0.3 or more and 2.5 or less.

  The gas barrier laminate of the present invention has an overcoat layer formed on a vapor deposition layer by a coating solution containing a specific organosilicon compound or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group. Thereby, even in a harsh environment, deterioration of the overcoat layer and the vapor deposition layer is suppressed, and excellent gas barrier properties are exhibited. Therefore, excellent gas barrier properties can be obtained for a long time even in applications where deformation is applied by processing, harsh treatments such as boil sterilization, retort sterilization, and harsh environments such as outdoor placement. A gas barrier 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.

  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 without departing from the spirit of the present invention, they are included in the present invention.

(Gas barrier laminate)
FIG. 1 shows a schematic cross-sectional view of one embodiment of the gas barrier laminate of the present invention. 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 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. Specific examples include silicon oxide (SiO _x ) such as silicon monoxide and silicon dioxide, aluminum oxide, magnesium oxide, and tin oxide.

  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 introducing the gas. If the pressure in the film forming chamber is higher than 2 × 10 ⁻¹ Pa, the vapor deposition layer may not be 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.

In the gas barrier laminate of the present embodiment, the coating liquid for forming the overcoat layer is at least one selected from the group consisting of silyl isocyanurate represented by the following general formula (a) and a hydrolyzate thereof (hereinafter referred to as the following). And (A) component) and a water-soluble polymer having a hydroxyl group.
_{X - ((CH 2) n} -Si (OR) 3) m ...... (a)
[However, X is an isocyanurate ring, R is an alkyl group, and m and n are each independently an integer of 1 to 5. ]

  In an organosilicon compound having a Si-OR structure, an OR 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 the organic silicon compound represented by the formula (a), a dense and strong network polymerization film can be formed. Moreover, by having an isocyanurate ring in the molecule, an organic-inorganic composite film having both toughness and flexibility is formed. For this reason, an overcoat layer excellent in heat resistance, water resistance, moisture resistance, flex resistance, stretch resistance and the like can be obtained.

  The water-soluble polymer having a hydroxyl group 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, gas barrier properties are excellent. Since PVA is a polymer containing the most hydroxyl groups in the monomer unit, it has a very strong hydrogen bond with the hydroxyl groups of the organosilicon compound after hydrolysis. PVA as used herein is generally obtained by saponifying polyvinyl acetate, and saponification is complete saponification in which only several percent of acetic acid groups remain from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. Includes up to PVA. 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. However, a high molecular weight PVA having a high degree of saponification and a high degree of polymerization is preferred because of its high water resistance.

  In formula (a), the alkyl group represented by R is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. Examples of the silyl isocyanurate represented by the formula (a) include 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate and 1,3,5-tris (3-triethoxysilylpropyl). Examples include isocyanurate.

  Examples of the hydrolyzate of the organosilicon compound represented by formula (a) include those in which at least one of 9 or more ORs in the formula is OH. The hydrolyzate can be prepared by a known method. For example, it can be prepared by dissolving an organosilicon compound in an alcohol such as methanol or isopropyl alcohol, and adding an aqueous solution of an acid such as hydrochloric acid to the solution to cause a hydrolysis reaction.

(A) A component may be used individually by 1 type, or may use 2 or more types together. The blending amount of the component (A) in the coating liquid can be appropriately set in consideration of gas barrier properties, durability, suitability for post-processing, and the like, and is not particularly limited, but about 1% by mass to 100% by mass with respect to the total solid content. Is preferable, and about 3 mass% or more and 90 mass% or less is more preferable. When it is 1% by mass or more, gas barrier properties and wet heat durability are good. When it is 90% by mass or less, durability is better.
In the coating solution, the ratio of the component (A) and the water-soluble polymer having a hydroxyl group is such that the weight ratio of the solid content after drying is, for example, 10:90 to 90:10, preferably 20:80 to 80:20. It is good to set.
In addition, you may add alkoxysilane, such as tetraethoxysilane, or its hydrolyzate to the coating liquid in the ratio of 50 mass% or less as needed.

  Moreover, it is preferable that the organic substance of the overcoat layer formed by heat-drying the said gas-barrier laminated body is 30 to 90 mass%.

  Since the organic component is highly flexible, the flexibility and the stretch resistance are improved by containing the organic component. The content of the organic component is preferably about 30% by mass to 90% by mass and more preferably about 40% by mass to 85% by mass with respect to the total solid content. When it is less than 30% by mass, gas barrier properties, flex resistance, and stretch resistance are lowered. When it is higher than 90% by mass, wet heat durability is lowered.

Further, the gas barrier laminate preferably has an oxygen permeability after a 3% tensile test within 10 times the initial value. The 3% tensile test can be performed according to the method described in JIS K7127.
<Extension test>
A sample cut out to 26 cm × 26 cm (MD × TD) was attached to a stretching apparatus so that the length of the stretched portion (MD direction) was 20.0 cm, and an initial tension of 1.2 kgf was applied using a spring balance. After pulling in the MD direction to a predetermined stretching rate at a moving speed of 0.1 mm / sec, holding in the tensioned state for 1 minute, the stage was moved to the initial position at the same speed.

  When pulled by 3% in a tensile test, the oxygen permeability is preferably within 10 times of the initial value, and more preferably within 5 times. When it exceeds 10 times, the stability of the barrier property is lowered.

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

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

  The coating liquid for forming the overcoat layer is prepared by mixing the component (A), a water-soluble polymer having a hydroxyl group, 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 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 0.1 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 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)
The gas barrier laminate of the present embodiment may further include an anchor coat layer between the resin base material and the vapor deposition layer. By providing the anchor coat layer, 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.
FIG. 2 shows a schematic cross-sectional view of another 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 hydroxyl groups and an isocyanate compound (2) having at least two NCO groups in the molecule.

  The acrylic polyol (1) is obtained by polymerizing a (meth) acrylic acid derivative monomer having a hydroxyl group, and a copolymer of a (meth) acrylic acid derivative monomer having a hydroxyl group and another monomer. Examples thereof include polymer compounds. 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.

  Moreover, it is preferable that the hydroxyl value of acrylic polyol (1) is 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 (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. . On the other hand, if the hydroxyl value is larger than [250 mgKOH / g], the amount of reaction with the isocyanate compound (2) becomes too large, and the film 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 hydroxyl group of the acrylic polyol (1) is preferably 0.3 or more and 2.5 or less, more preferably 0.5 or more. 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.

  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 substrate, a biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60) having a thickness of 12 μm and one side corona-treated was used. In addition, using a vacuum deposition machine, a deposition material in which metal silicon powder and silicon dioxide powder are mixed is directly deposited on the corona-treated surface of the resin base material so that the element ratio O / Si is 1.5. A vapor deposition layer was formed on the resin substrate. At this time, the formed vapor deposition layer (SiO _x vapor deposition film) had a thickness of 50 nm.

Next, a coating solution for forming an overcoat layer was prepared.
The coating solution was a 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate hydrolyzed solution and an aqueous solution of polyvinyl alcohol (PVA) having a solids weight ratio of 50:50 after heat drying. (The content of the organic component after heat drying is 80% by mass) 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.
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 film thickness of each layer was resin substrate: 12 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm.

[Inspection measurement]
The gas permeability laminate of Example 1 was measured for oxygen permeability (OTR).
Here, the OTR is measured by (1) before laminating an overcoat layer, (2) immediately after production (initial stage), (3) after a tensile test (3% tensile test at 100 μm / sec), and (4 ) After a storage test (a storage test for 500 hours at 40 ° C. and 90% RH), the test was performed four times. The oxygen permeability was measured using an oxygen permeability meter (MOCON OX-TRAN 2/21) manufactured by Modern Control Co., Ltd. in an atmosphere of 30 ° C.-70% RH [cc / m ² · day.atm] was measured. The magnification of oxygen permeability was defined as (2) the value of the oxygen permeability value after the tensile test or (4) the oxygen permeability value after the storage test, when the initial value of oxygen permeability was 1. The measurement results are shown in Table 1.

(Example 2)
First, an anchor coating agent was prepared.
The anchor coating agent is 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 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.
As the resin substrate, a biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60) having a thickness of 12 μm and one side corona-treated 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 0.1 μm.

Next, a vapor deposition layer was formed on the anchor coat layer.
Using a vacuum deposition machine, a deposition material 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 to form a deposition layer on the resin substrate. At this time, the formed vapor deposition layer (SiO _x vapor deposition film) had a thickness of 50 nm.
Next, a coating solution for forming an overcoat layer was prepared.

  The coating solution was the same as in Example 1.

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.
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: 12 μm / anchor coat layer: 0.15 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm.

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

Example 3
The gas barrier of the present example was the same as that of Example 2 except that aluminum was used as the deposition source, heat-deposited by an electron beam heating method, oxygen gas was introduced, and an aluminum oxide deposition layer having a film thickness of 15 nm was formed. A conductive laminate was produced.

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

Example 4
The coating solution for forming the overcoat layer comprises a hydrolysis solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, a hydrolysis solution of tetraethoxysilane (TEOS), and polyvinyl alcohol (PVA). A solution having a solid content of 5% by mass was mixed with an aqueous solution so that the solid content weight ratio after drying was 43:43:14 (content of the organic component after heat drying was 40% by mass) A gas barrier laminate of this example was produced in the same manner as in Example 3 except that.

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

(Comparative Example 1)
The coating solution for forming the overcoat layer is prepared by adding a tetraethoxysilane (TEOS) hydrolysis solution and a polyvinyl alcohol (PVA) aqueous solution so that the solid weight ratio after drying is 50:50 (after heat drying). The gas barrier laminate of this example was produced in the same manner as in Example 1 except that the content of the organic component was 50% by mass) and mixed to obtain a solution having a solid content of 5% by mass.

[Inspection measurement]
About the gas-barrier laminated body obtained by the comparative example 1, it carried out similarly to Example 1, and measured oxygen permeability (OTR). The measurement results are shown in Table 1.

(Comparative Example 2)
The coating solution for forming the overcoat layer has a solid weight ratio after drying of a hydrolysis solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate and an aqueous solution of polyvinyl alcohol (PVA). The gas barrier laminate of the present example was the same as Example 2 except that the solution was mixed to obtain a solution having a solid content of 5% by mass so that the ratio was 13:87 (content of the organic component was 95% by mass). Manufactured.

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

(Comparative Example 3)
The coating solution for forming the overcoat layer comprises a hydrolysis solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, a hydrolysis solution of tetraethoxysilane (TEOS), and polyvinyl alcohol (PVA). The aqueous solution was mixed so that the solid weight ratio after drying was 22:66:12 (content of the organic component was 25% by mass) to obtain a solution having a solid content of 5% by mass, A gas barrier laminate of this example was produced in the same manner as in Example 4.

[Inspection measurement]
About the gas-barrier laminated body obtained by the comparative example 3, it carried out similarly to Example 1, and measured oxygen permeability (OTR). The measurement results are shown in Table 1.

  Table 1 summarizes the measurement results of the layer structure (materials used) and oxygen permeability (OTR) of the laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 3. “AC layer” in Table 1 indicates “anchor coat layer”, and “OC layer” in Table 1 indicates “overcoat layer”. Further, “AOH / NCO” in Table 1 indicates “anchor coating agent prepared in Example 2”. In Table 1, “a-1” represents “1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate hydrolyzate”, and “b-1” represents “TEOS hydrolyzate”. "PVA" means "polyvinyl alcohol".

<Evaluation>
As for the gas barrier properties of the gas barrier laminates of Examples 1 to 4, the initial value of OTR was low, and the gas barrier properties were excellent. Moreover, the value of OTR did not increase so much from the initial value even after the tensile test and after the storage test. On the other hand, the gas barrier properties of the gas barrier laminates of Comparative Examples 1 and 2 showed that after the storage test, OTR was 50 times or more of the initial value, and OTR was larger than 50 [cc / m ² · day · atm]. . Moreover, the gas barrier property of the gas barrier laminate of Comparative Example 3 was 50 times or more of the initial value after the tensile test, and the OTR value was larger than 50 [cc / m ² · day · atm].

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

  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 Gas barrier laminate 11 Resin substrate 12 Vapor deposition layer 13 Overcoat layer 24 Anchor coat layer

Claims (4)

A resin base material, a vapor deposition layer laminated on at least one side of the resin base material, and an overcoat layer laminated on the vapor deposition layer,
The overcoat layer is an overcoat layer formed by applying a coating solution on the vapor deposition layer and heating and drying the coating solution so that the organic content is 30% by mass or more and 90% by mass or less.
The coating solution contains at least one (A) selected from the group consisting of silyl isocyanurate represented by the following general formula (a) and a hydrolyzate thereof, and a water-soluble polymer having a hydroxyl group. A gas barrier laminate, which is a liquid.
_{X - ((CH 2) n} -Si (OR) 3) m ...... (a)
[However, X is an isocyanurate ring, R is an alkyl group, and m and n are each independently an integer of 1 to 5. ]   The gas barrier laminate according to claim 1, wherein the gas barrier laminate has an oxygen permeability after a 3% tensile test within 10 times the initial value.   3. The gas barrier laminate according to claim 1, wherein the gas barrier laminate has an oxygen permeability within 10 times the initial value after a storage test at 40 ° C. and 90% RH for 500 hours. An anchor coat layer is further provided between the resin base material and the vapor deposition layer,
The anchor coat layer is an anchor coat layer formed by applying an anchor coat agent on the resin base material,
The anchor coating agent is
An acrylic polyol (1) having two or more hydroxyl groups;
An isocyanate compound (2) having at least two NCO groups in the molecule,
The acrylic polyol (1) has a hydroxyl value of 50 mgKOH / g or more and 250 mgKOH / g or less,
The equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound (2) to the hydroxyl group of the acrylic polyol (1) is 0.3 or more and 2.5 or less. The gas barrier laminate according to one item.

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