JP6550886B2 - Gas barrier laminate - Google Patents

Description

  The present invention relates to a gas barrier laminate.

The gas barrier laminate is a laminate having a property (gas barrier property) that does not allow gas such as oxygen and water vapor to permeate. 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 are utilized in various fields.
Such a gas barrier laminate is used, for example, as a packaging material used for packaging food and the like. In packaging applications such as food, it is required to prevent the deterioration of contents. Specifically, it is required to be able to suppress oxidation and deterioration of proteins, fats and oils, etc., and to maintain flavor and freshness. For this reason, a gas barrier laminate is suitably 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 that the aseptic condition is maintained, the deterioration of the active ingredient of the contents is suppressed, and the efficacy can be maintained. For this reason, a gas barrier laminate is suitably 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. The precision parts are required to shield the external gas because the external gas may act as foreign matter and become a defective product when exposed to the external gas. For this reason, a gas barrier laminate is preferably used.
Moreover, such a gas barrier laminate is used as a member of flat panel displays such as liquid crystal displays and organic EL displays, for example. 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.

Moreover, such a gas barrier laminate is used, for example, as a back sheet or a front sheet in a solar cell. In solar cell applications, it is required to prevent deterioration of internal mechanisms from ultraviolet light 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 that it also has transparency. The transparency of the packaging material makes it possible to visually check the shape of the contents and the color of the contents from the outside of the package, thereby preventing the contents from being mistaken, whether there is any damage, and the contents The presence or absence of deterioration can be grasped 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, as a gas barrier laminate, a gas barrier laminate in which a gas barrier substance is vapor-deposited on a film substrate is known. The vapor deposition film of the gas barrier substance has gas barrier properties, and also has excellent transparency since it is extremely thin.

Examples of such a gas barrier laminate include a silica-based vapor deposition film and an alumina reaction vapor deposition film. The silica-based vapor deposition film is a laminate in which silicon monoxide and a Si / SiO ₂ mixed material are vapor-deposited on a film substrate. In addition, the alumina reaction vapor deposition film is a laminate obtained by evaporating metal aluminum and reacting it 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 further include a water-soluble polymer such as polyvinyl alcohol, an alkoxysilane such as tetraethoxysilane, or a hydrolysis thereof on a vapor deposition film provided on a substrate. A coating solution containing a substance 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, etc. are improved.

Japanese Patent Application Laid-Open No. 7-164591 International Publication WO 2004/048081 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 in view of the said situation, Comprising: It aims at providing the gas-barrier laminated body which exhibits the gas-barrier property excellent also under a severe environment.

As a result of intensive studies, the present inventors have found a compound suitable for a component used in an overcoat layer laminated on a vapor deposition layer in a gas barrier laminate, and came to complete 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 to have an organic content of 30% by mass to 90% by mass.
The coating solution contains at least one member (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 characterized by being a liquid.
X-((CH ₂ ) _n- Si (OR) ₃ ) m (a)
[Wherein 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 the above [1], wherein the gas barrier laminate has an oxygen permeability after a 3% tensile test of at most 10 times the initial permeability.

[3] The gas barrier laminate according to the above [1] or [2], wherein the gas barrier laminate has an oxygen permeability after storage test at 40 ° C. and 90% RH for 500 hours within 10 times of the initial one. 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 obtained by applying an anchor coat agent on the resin base material, and the anchor coat agent It is an anchor coat layer formed by heat-drying, and the above-mentioned anchor coat agent is an acrylic polyol (1) which has two or more hydroxyl groups, and an isocyanate compound (2) which has at least two or more NCO groups in a molecule. And the hydroxyl value of the acrylic polyol (1) is from 50 mg KOH / g to 250 mg KOH / g, and the equivalent ratio of NCO groups of the isocyanate compound (2) to the hydroxyl groups 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 of a coating solution containing a specific organosilicon compound or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group on a vapor deposition layer. Thereby, even under a severe environment, deterioration of the overcoat layer and the vapor deposition layer is suppressed, and excellent gas barrier properties are exhibited. Therefore, long-term excellent gas barrier properties can be achieved even in applications where deformation is applied by processing, and applications that are subjected to severe processing such as boiling sterilization and retort sterilization, and harsh environments such as outdoor placement. The gas barrier laminate can be provided.

It is a schematic sectional drawing which shows one embodiment of a gas barrier laminate. 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 embodiments, and even if there are design changes within the scope 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 the vapor deposition layer 12 and the overcoat layer 13 are sequentially laminated on one surface of the resin substrate 11. Hereinafter, the direction in which the vapor deposition layer 12 and the overcoat layer 13 are stacked will be described as the upper (layer) with reference to the resin substrate 11.

<Resin base material>
The resin base is a layer to be 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 vinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films, biodegradable plastic films such as polylactic acid, and the like.

The resin base material may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant.
The thickness of the resin substrate is not particularly limited, and may be appropriately determined according to the specification and the like. 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 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, the adhesion to another layer can be enhanced in laminating the other layer (vapor deposition layer, anchor coat layer, etc.). Here, as the surface treatment, for example, (1) physical treatment such as corona treatment, plasma treatment, or flame treatment, or (2) chemical treatment such as chemical treatment with an 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 known gas barrier vapor deposition films. Examples thereof include metals such as Si, Al, Zn, Sn, Fe, and Mn, and inorganic compounds containing one or more of these metals. Examples of the inorganic compound include oxides, nitrides, carbides, and fluorides. Among these, at least one selected from metals and metal oxides is preferable. Specifically, for example, silicon oxide (SiO _x ) such as silicon monoxide and silicon dioxide, aluminum oxide, magnesium oxide, tin oxide and the like can be mentioned.

  As a method for forming the vapor deposition layer, a known vapor deposition method may be appropriately selected and used. For example, physical vapor deposition (PVD: Physical Vapor Deposition) method such as vacuum evaporation method, sputtering method, chemical vapor deposition (CVD: Chemical Vapor Deposition) method such as ion plating method, plasma vapor deposition method, ALD: An atomic layer deposition method or the like may be used. In particular, the vacuum deposition method of the EB: electron beam heating method can obtain a high deposition rate, and is preferable as a method of forming a deposition layer of the gas barrier laminate of the present embodiment.

In addition, reactive evaporation may be used in 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. As a gas to introduce | transduce, oxygen gas, argon gas, etc. are mentioned, for example. By performing reactive vapor deposition with oxygen gas or the like, the metal component in the vapor deposition material is oxidized, and the transparency of the vapor deposition layer can be improved. Further, in the case of using a reactive vapor deposition method, when introducing a gas, it is preferable to set the pressure in the film formation chamber to 2 × 10 ⁻¹ Pa or less. If the pressure in the film formation chamber is higher than 2 × 10 ⁻¹ Pa, the vapor deposition layer may not be laminated well, and the water vapor barrier property may be lowered.

  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, a sufficient barrier property is expressed, and when the thickness is 300 nm or less, generation of a crack in a post process or the like and a decrease in the barrier property due to the generation hardly 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>
The overcoat layer is a layer formed on the vapor deposition layer. By laminating the overcoat layer on the vapor deposition layer, it is possible to obtain excellent gas barrier properties which can not be exhibited by the gas barrier laminate in which the vapor deposition layer is constituted 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, applying the coating solution on the 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: And (A) component and a water-soluble polymer having a hydroxyl group.
X-((CH ₂ ) _n- Si (OR) ₃ ) m (a)
[Wherein X is an isocyanurate ring, R is an alkyl group, and m and n are each independently an integer of 1 to 5]. ]

  In the organosilicon compound having a Si-OR structure, the OR group bonded to the silicon atom becomes a hydroxyl group by a hydrolysis reaction, and forms a siloxane bond by dehydration condensation of the hydroxyl group. By using the compound represented by the formula (a) as the organosilicon compound, 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. Therefore, 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 largest number of hydroxyl groups in the monomer unit, it has a very strong hydrogen bond with the hydroxyl group of the organosilicon compound after hydrolysis. PVA referred to here is generally obtained by saponifying polyvinyl acetate, and so-called partially saponified PVA in which several tens of acetic acid groups remain, completely saponified in which only a few acetic groups remain. Including 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), as an alkyl group of R, a C1-C3 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group etc. are mentioned. Examples of silyl isocyanurate represented by the formula (a) include 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate and 1,3,5-tris (3-triethoxysilylpropyl). An isocyanurate etc. are mentioned.

  As a hydrolyzate of the organosilicon compound represented by Formula (a), that by which at least 1 became OH among 9 or more OR in Formula is mentioned. The hydrolyzate can be prepared by known methods. 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.

As the component (A), one type may be used alone, or two or more types may be used in combination. Although the compounding quantity of (A) component in a coating liquid can be suitably set up in consideration of gas barrier property, durability, post-process aptitude etc., it is not limited in particular, but it is about 1 mass% or more and 100 mass% or less. Is preferable, and about 3 to 90 mass% is more preferable. Gas barrier property and wet heat durability are favorable in it being 1 mass% or more. Durability is more favorable in it being 90 mass% or less.
In the coating solution, the ratio of the component (A) and the water-soluble polymer having a hydroxyl group is such that the solid content weight ratio after drying is, for example, 10:90 to 90:10, preferably 20:80 to 80:20. It is good to set.
If necessary, an alkoxysilane such as tetraethoxysilane or a hydrolyzate thereof may be added to the coating solution in a proportion of 50% by mass or less.

  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. If it is higher than 90% by mass, the wet heat durability is reduced.

Moreover, it is preferable that the said gas-barrier laminate has an oxygen permeability after a 3% tensile test within 10 times of the initial level. The 3% tensile test can be conducted 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.

  The oxygen permeability is preferably within 10 times the initial level, more preferably within 5 times, when pulled 3% in a tensile test. If it exceeds 10 times, the stability of the barrier property is reduced.

  Moreover, it is preferable that the said gas-barrier laminated body is 10 times or less of the oxygen permeability after an initial stage storage test after 40 degreeC90% RH 500 hours storage test.

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

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

  The coating method of a coating liquid can use the normal coating method. For example, known methods such as dipping, low coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, and gravure offset can be used. As a drying method, it is possible to use 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, UV irradiation, and the like. In the drying method, the heating temperature is preferably in the range of about 60 ° C. to 200 ° C., and more preferably in the range of about 100 ° C. to 150 ° C. A desired barrier property is expressed as it is 60 degreeC or more, and it is favorable. If it is vapor deposition for a short time as it is 150 degrees C or less, it is suitable, without a deformation | transformation of a base material or a crack generate | occur | producing 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 the present embodiment, the film thickness of the overcoat layer is not limited to the above range.
Further, the gas barrier laminate of the present embodiment may be plate-like or film-like. For example, it may be formed into a film by winding on a roll.

(Anchor coat layer)
The gas barrier laminate of the present embodiment may further include an anchor coat layer between the resin base material and the vapor deposition layer. By providing the anchor coat layer, 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 is a schematic cross-sectional view of another embodiment of the gas barrier laminate of the present invention in which the 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 heat-drying the applied anchor coat agent.
The anchor coating agent preferably contains an acrylic polyol (1) having 2 or more hydroxyl groups, and an isocyanate compound (2) having at least 2 or more NCO groups in the molecule.

  The acrylic polyol (1) is obtained by copolymerizing a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having a hydroxyl group, a (meth) acrylic acid derivative monomer having a hydroxyl group, and another monomer A high molecular compound etc. are mentioned. 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 another monomer copolymerizable with the (meth) acrylic acid derivative monomer which has a hydroxyl group, the (meth) acrylic acid derivative monomer which does not have a hydroxyl group is preferable. As the (meth) acrylic acid derivative monomer having no hydroxyl group, for example, (meth) acrylic acid derivative monomer having an alkyl group, (meth) acrylic acid derivative monomer having a carboxyl group, (meth) acrylic acid having a ring structure Derivative monomers and the like can be mentioned. 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, t-butyl (meth) acrylate, etc. Can be 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, cyclohexyl (meth) acrylate and the like. 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 mg KOH / g], the reaction amount with the isocyanate compound (2) is small, and there is a possibility that the adhesion improvement effect between the resin substrate and the vapor deposition layer by the anchor coat layer may not be sufficiently expressed. . On the other hand, when the hydroxyl value is larger than [250 mg KOH / g], the amount of reaction with the isocyanate compound (2) is too large, and the membrane shrinkage of the anchor coat layer may be increased. If the film shrinkage is large, the vapor deposition layer may not be laminated well on top of that, and there is a possibility that sufficient gas barrier properties may not be exhibited.

  The weight average molecular weight of the acrylic polyol (1) is not particularly limited, but is preferably 3,000 or more and 200,000 or less, more preferably 5,000 or more and 100,000 or less, and still more preferably 5,000 or more and 40000 or less. In the present 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, as monomeric isocyanates, aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanatomethylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate Aliphatic isocyanates such as (H12 MDI), and aromatic aliphatic isocyanates such as xylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI) may be used. Also, polymers or derivatives of these monomeric isocyanates may 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 NCO group of isocyanate compound (2) to hydroxyl group of acrylic polyol (1) is preferably 0.3 or more and 2.5 or less. More preferably, it is 2.0 or less. When the NCO / OH is 0.3 or more, the adhesion to the substrate is improved, and when the NCO / OH is 2.0 or less, the adhesion after the wet heat resistance test is improved. The compounding amount of the acrylic polyol (1) and the isocyanate compound (2) in the anchor coating agent is preferably compounded 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 substrate and the vapor deposition layer. As a silane coupling agent, for example, those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, such as 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 (silane coupling agent etc.) and a solvent. As the solvent, any solvent capable of dissolving the acrylic polyol (1) and the isocyanate compound (2) may be used, and examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, acetone and the like. 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 dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, and gravure offset can be used. As a drying method, it is possible to use 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, UV irradiation, and the like. 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, and the so-called blocking phenomenon in which the coated surface sticks to the back surface even with no residual solvent Conditions that do not occur can be appropriately selected, and the aging treatment may be performed within a range of about 40 ° C. or more and 60 ° C. or less 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. When the thickness is more than 0.5 μm, the influence of internal stress becomes large, the deposition layer 12 is not laminated well, and the gas barrier properties may be insufficiently developed.

  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 the hydrolyzate thereof in the coating solution for forming the overcoat layer and the anchor coating agent is a coating film formed by polymerization of the hydrolyzed organosilicon compound. It is the amount converted to weight.

Example 1
First, the vapor deposition layer was formed on the resin base material.
As a resin substrate, a 12 μm-thick biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60), one side of which was corona-treated, was used. Also, using a vacuum deposition machine, deposit a deposition material in which metal silicon powder and silicon dioxide powder are mixed directly on the corona-treated surface of the resin base 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 deposition layer (SiO _x deposition film) had a thickness of 50 nm.

Next, a coating solution for forming an overcoat layer was prepared.
The coating solution was prepared by heating a hydrolysis solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate and an aqueous solution of polyvinyl alcohol (PVA) at a solid content weight ratio of 50:50 after drying by heating. (The content of the organic component after heating and drying is 80% by mass) to obtain a solution with a solid content of 5% by mass.

Next, the coating solution was applied onto the 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 made into 120 degreeC and 2 minutes. At this time, the dry film thickness of the formed overcoat layer was a film thickness of 0.5 μm.
From the above, the gas barrier laminate of Example 1 in which the resin base material / the vapor deposition layer / the overcoat layer were laminated in this order was manufactured. In the gas barrier laminate of Example 1, the film thickness of each layer was resin substrate: 12 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm.

[Inspection measurement]
The oxygen permeability (OTR) of the gas barrier laminate of Example 1 was measured.
Here, the measurement of OTR is (1) before laminating an overcoat layer, (2) immediately after production (initial stage), (3) after a tensile test (3% tensile test at 100 μm / sec), (4 4.) After storage test (storage test at 40 ° C. and 90% RH for 500 hours) In the measurement of oxygen permeability, oxygen permeability in an atmosphere of 30 ° C. and 70% RH [cc / m ² ··· using an oxygen permeability meter (MOCON OX-TRAN 2/21) manufactured by Modern Control, Inc. day.atm] was measured. The ratio of oxygen permeability was defined as the ratio of the value of oxygen permeability after (3) tensile test to (4) storage test when the initial value of oxygen permeability was 1 time. 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 substrate to form an anchor coat layer.
As a resin substrate, a 12 μm-thick biaxially stretched polyethylene terephthalate (PET) film (Toray Film Processing, P60), one side of which was corona-treated, was used. Further, an anchor coating agent was applied to the corona-treated surface of the above-mentioned resin base using a gravure coating machine, and stored (aging treatment) in a temperature-controlled room at 50 ° C. for 48 hours to form an anchor coating 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.
A vapor deposition material in which metallic silicon powder and silicon dioxide powder were mixed so as to have an element ratio O / Si of 1.5 was vapor deposited using a vacuum vapor deposition machine, and a vapor deposition layer was formed on the resin substrate. At this time, the formed deposition layer (SiO _x deposition film) had a thickness of 50 nm.
Next, the coating liquid for overcoat layer formation was adjusted.

  The coating solution was the same as in Example 1.

Next, the coating solution was applied onto the 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 made into 120 degreeC and 2 minutes. At this time, the dry film thickness of the formed overcoat layer was a film thickness of 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 base material: 12 μm / anchor coat layer: 0.15 μm / vapor deposited layer: 50 nm / overcoat layer: 0.5 μm.

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

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

[Inspection measurement]
The oxygen permeability (OTR) of the gas barrier laminate obtained in Example 3 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). An aqueous solution is mixed to give a solid content of 5% by mass so that the solid content weight ratio after drying is 43:43:14 (the content of the organic component after heating and drying is 40% by mass) The gas barrier laminate of this example was produced in the same manner as in Example 3 except for the above.

[Inspection measurement]
The oxygen permeability (OTR) of the gas barrier laminate obtained in Example 4 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 was prepared by heating a hydrolysis solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) so that the weight ratio of solids after drying is 50: 50 (after heating and 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 in the mixture was 50% by mass) to obtain a solution with a solid content of 5% by mass.

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

(Comparative example 2)
The coating solution for forming the overcoat layer had a solid content 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 as in Example 2 except that the solution was mixed to give a solution with a solid content of 5% by mass so as to be 13: 87 (the content of the organic component is 95% by mass). Manufactured.

[Inspection measurement]
Regarding the gas barrier laminate obtained in Comparative Example 2, the oxygen permeability (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 content weight ratio after drying was 22:66:12 (the content of the organic component is 25% by mass) to obtain a solution with a solid content of 5% by mass, The gas barrier laminate of this example was produced in the same manner as in Example 4.

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

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

<Evaluation>
The gas barrier properties of the gas barrier laminates of Examples 1 to 4 were low in the initial value of OTR, and had excellent gas barrier properties. Also, after the tensile test and after the storage test, the value of OTR did not increase so much from the initial value. On the other hand, after the storage test, the gas barrier properties of the gas barrier laminates of Comparative Examples 1 and 2 show that the OTR is at least 50 times the initial level and the OTR is greater than 50 [cc / m ² · day atm]. . Further, the gas barrier properties of the gas barrier laminate of Comparative Example 3 were such that after the tensile test, the OTR was 50 times or more the initial level and the OTR was a value 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 tensile test (3% tensile test at 100 μm / sec) and storage test (storage test at 40 ° C. 90% RH for 500 hours) It can be maintained (specifically, the OTR is about 3.0 [cc / m ² · day · atm] or less), and it has been confirmed that the gas barrier property is maintained even under a severe environment.

  The gas barrier laminate of the present invention has gas barrier properties, transparency, and durability at a high level, and can be widely used in fields requiring the gas barrier laminate. For example, (1) films for packaging pharmaceuticals and foods, (2) films for packaging electronic parts such as semiconductor wafers and precision parts, (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 base 12 Vapor deposited 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, a coating solution was coated on the deposited layer, an overcoat layer was made form by heating and drying the coating solution,
The coating liquid is
The hydrolysis solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate and an aqueous solution of polyvinyl alcohol (PVA) are mixed so that the weight ratio of solids after heating and drying becomes 50: 50. Solution, or
Solid content after drying a hydrolysis solution of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, a hydrolysis solution of tetraethoxysilane (TEOS), and an aqueous solution of polyvinyl alcohol (PVA) It is a solution mixed so that a weight ratio may be 43:43:14 . The gas barrier laminate characterized by the above-mentioned.   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 permeability.   The gas barrier laminate according to claim 1 or 2, wherein the gas barrier laminate has an oxygen permeability after a 3% tensile test within 10 times the initial permeability. 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,
And an isocyanate compound (2) having at least two or more NCO groups in the molecule,
The hydroxyl value of the acrylic polyol (1) is 50 mg KOH / g or more and 250 mg KOH / 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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