JP2015058631A - Gas barrier laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate capable of exerting excellent gas barrier properties for a long period of time even under a harsh environment.SOLUTION: A gas barrier laminate includes an overcoat layer formed by a coating agent including a specific organosilicon compound or a hydrolyzate thereof on a vapor deposition layer. Accordingly, even under a harsh environment, the degradation of the overcoat layer and the vapor deposition layer is suppressed, and excellent gas barrier properties are exerted for a long period of time. As a result, the gas barrier laminate exerts excellent gas barrier properties for a long period of time under an extremely severe treatment such as boil sterilization and retort sterilization and in a use put under a harsh environment such as outdoor arrangement.

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 held in the portion shielded by the gas barrier laminate can suppress deterioration / degeneration caused by the external gas. In recent years, such gas barrier laminates have been used in various fields.

  For example, it is used as a packaging material used for packaging foods. 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.

  For example, it is used as a packaging material used for packaging pharmaceutical products. 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.

  For example, it is used as a packaging material used for packaging electronic parts such as semiconductor wafers and precision parts. 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.

  For example, it is used as a member of 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.

  For example, it is used as 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.

  Moreover, when using as a packaging member, it is preferable to also 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 is required to have properties such as gas barrier properties, transparency, moisture resistance, weather resistance, durability, and the like at a high level so as to be compatible with various wide applications.

  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.

For example, a silica-based vapor deposition film has been proposed in which silicon monoxide or a Si / SiO ₂ mixed material is vapor-deposited on a film substrate.

  For example, an alumina reactive vapor deposition film has been proposed in which metal aluminum is evaporated and reacted with oxygen on a film substrate.

  In addition, since the silica-based vapor deposition film and the alumina reactive vapor deposition film are easily affected by temperature and moisture, gas barrier laminates having improved heat resistance, water resistance, and moisture resistance have been proposed.

  For example, in order to improve gas barrier properties, heat resistance, water resistance, moisture resistance, etc., a water-soluble polymer such as polyvinyl alcohol and an alkoxy such as tetraethoxysilane are further formed on the deposited film provided on the substrate. It has been proposed that a coating liquid containing silane or a hydrolyzate thereof is applied and dried by heating to provide a gas barrier film (see Patent Document 1 and Patent Document 2).

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

  With the expansion of applications, gas barrier laminates are required to be used in more severe environments. For this reason, further improvements in durability such as moisture resistance, heat resistance, water resistance, and weather resistance are required. Here, as a harsh environment, for example, (1) In packaging material use, processing such as boil and retort sterilization is performed while being surrounded by packaging material. (2) In solar cell use, outdoor For example, use for a long time.

  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 gas-barrier property excellent over the long term also in the severe environment.

  As a result of intensive studies, the present inventors have found an organosilicon compound suitable for a structural 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 above the resin base material, and an overcoat layer laminated on the vapor deposition layer, wherein the overcoat layer is coated on the vapor deposition layer An overcoat layer formed by applying a solution and heating and drying the coating solution, wherein the coating solution is selected from the group consisting of an organosilicon compound represented by the following general formula (a) and a hydrolyzate thereof. A gas barrier laminate comprising a coating solution containing at least one selected (A).
^{_{R 1 O- (CH 2 CH 2}} O) m - (CH 2) n -Si (OR) 3 ...... (a)
[However, R ¹ is H, CH ₃ , or — (CH ₂ ) _n —Si (OR) ₃ , R is an alkyl group, and m and n are integers of 1 to 3. ]
[2] The coating solution further comprises an organosilicon compound represented by the following general formula (b ¹ ), an organosilicon compound represented by the following general formula (b ² ), and a hydrolyzate thereof. The gas barrier laminate according to claim 1, comprising at least one (B) selected from the group.
Si (OR ² ) ₄ (b ¹ )
R ³ —Si (OR ² ) ₃ (b ² )
[However, R ² is an alkyl group, and R ³ is an organic group having one of an epoxy group and an NCO group. ]
[3] The gas barrier laminate according to [1] or [2], wherein the coating liquid further contains an acrylic polyol (C) having two or more OH groups.
[4] The gas barrier according to any one of [1] to [3], wherein the coating liquid further contains an isocyanate compound (D) having at least two NCO groups in the molecule. Laminate.
[5] An anchor coat layer is further provided between the resin substrate and the vapor deposition layer, and the anchor coat layer is formed by applying an anchor coat agent on the resin substrate, An anchor coat layer formed by heating and drying, wherein the anchor coat agent includes an acrylic polyol (1) having two or more OH groups and an isocyanate compound (2) having at least two NCO groups in the molecule. The OH group value of the acrylic polyol (1) is from 50 mgKOH / g to 250 mgKOH / g, and the equivalent ratio of the NCO group of the isocyanate compound (2) to the OH group of the acrylic polyol (1) (NCO / OH) is not less than 0.3 and not more than 2.5, and the gas barrier according to any one of [1] to [4] Sex laminate.
[6] The gas barrier according to any one of [1] to [5], wherein the vapor deposition layer is formed by vacuum vapor deposition using a vapor deposition material containing metal silicon and silicon dioxide. Laminate.
[7] The vapor deposition material further contains at least one metal selected from the group consisting of Al, Zn, Sn, Fe, Mn, or an oxide thereof, and the vapor deposition layer includes Al, Zn The gas barrier laminate according to [6], containing at least one metal selected from the group consisting of Sn, Fe, and Mn at a ratio of 1 atm% to 20 atm%.
[8] The gas barrier laminate according to [1], wherein a laminate resin layer is further laminated on the overcoat layer via an adhesive layer.

  The gas barrier laminate of the present invention has an overcoat layer formed from a coating agent containing a specific organosilicon compound or a hydrolyzate thereof on the vapor deposition layer. 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 over a long period of time. Therefore, it is possible to provide a gas barrier laminate that exhibits excellent gas barrier properties over a long period of time even in severe applications such as boil sterilization and retort sterilization, and in harsh environments such as outdoor placement. .

It is a schematic sectional drawing which shows an example of the gas-barrier laminated body of this invention. It is a schematic sectional drawing which shows an example of the gas-barrier laminated body of this invention. It is a schematic sectional drawing which shows an example of the gas-barrier laminated body of this invention.

  Hereinafter, the gas barrier laminate of the present invention will be specifically described. 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.

  FIG. 1 shows a schematic cross-sectional view of an example 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.

(Resin base material)
A resin base material is a site | part used as the base | substrate of a gas-barrier laminated body.

  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.

  Further, 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 invention, 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 enhanced 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)
In order to impart gas barrier properties, the vapor deposition layer is formed in an upper layer than the resin base material by vapor deposition of a vapor deposition material.

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.

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

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

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

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

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

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

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

Moreover, you may use the reactive vapor deposition method in performing vapor deposition. The reactive vapor deposition method is a method in which vapor deposition is performed by reacting evaporated particles with a gas introduced into the atmosphere when vapor deposition is performed. Examples of the gas to be introduced include oxygen gas and argon gas. By performing reactive vapor deposition with oxygen gas or the like, the metal component in the vapor deposition material is oxidized, and the transparency of the vapor deposition layer can be improved. In addition, when the reactive vapor deposition method is used, it is desirable that the pressure in the film formation chamber be 2 × 10 ⁻¹ Pa or less when the gas is introduced. If the pressure in the film forming chamber is higher than 2 × 10 ⁻¹ Pa, the vapor deposition layer may not be neatly stacked, and the water vapor barrier property may be deteriorated.

  The thickness of the vapor deposition layer is preferably 5 nm or more and 300 nm or less, and more preferably 10 nm or more and 150 nm or less. When the thickness is 5 nm or more, sufficient barrier properties are exhibited, and when the thickness is 300 nm or less, generation of cracks in the post-process and the like, and deterioration of the barrier properties are less likely to occur. However, in the gas barrier laminate of the present invention, the thickness of the vapor deposition layer is not limited to the above range.

(Overcoat layer)
The overcoat layer is 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 that cannot be achieved by a single vapor deposition 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 invention, the coating liquid for forming the overcoat layer is at least one selected from the group consisting of an organosilicon compound represented by the following general formula (a) and a hydrolyzate thereof (A). Containing.
^{_{R 1 O- (CH 2 CH 2}} O) m - (CH 2) n -Si (OR) 3 ...... (a)
[However, R ¹ is H, CH ₃ , or — (CH ₂ ) _n —Si (OR) ₃ , R is an alkyl group, and m and n are integers of 1 to 3. ]

In an organosilicon compound having a Si-OR structure, an OR group bonded to a silicon atom becomes an OH group (hydroxyl group) by a hydrolysis reaction, and a siloxane bond is formed by dehydration condensation of the OH 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 (CH ₂ ) _n in the molecule, an organic-inorganic composite film having both toughness and flexibility is formed. For this reason, the overcoat layer excellent in heat resistance, water resistance, moisture resistance, etc. can be obtained.

  Further, according to the coating liquid for forming an overcoat layer of the present invention, unlike a conventional gas barrier laminate, the content of the water-soluble polymer is reduced without using a water-soluble polymer or by using a water-soluble polymer. An organic-inorganic composite film can be formed with a small amount of composition. For this reason, it is thought that the obtained organic-inorganic composite film can suppress the influence of a decrease in water resistance and moisture resistance due to the water-soluble polymer.

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 organosilicon compound represented by the formula (a) include CH ₃ O— (CH ₂ CH ₂ O) ₃ — (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ : ethylene oxide-containing propylene trimethoxylane. , (CH ₃ 0) ₃ —Si—CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ —0—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ : bistrimethoxysilylpropyleneoxyethylene, etc. It is done. Examples of the hydrolyzate of the organosilicon compound represented by the formula (a) include those in which at least one of three or six 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.

Further, the coating solution is further selected from the group consisting of an organosilicon compound represented by the following general formula (b ¹ ), an organosilicon compound represented by the following general formula (b ² ), and a hydrolyzate thereof. It is preferable to contain at least one selected (B).
Si (OR ² ) ₄ (b ¹ )
R ³ —Si (OR ² ) ₃ (b ² )
[However, R ² is an alkyl group, and R ³ is an organic group having one of an epoxy group and an NCO group. ]

The component (B) functions as an auxiliary component for the component (A). By further containing the component (B), barrier properties, particularly wet heat resistance, are improved. Among the above, the organosilicon compound represented by the formula (b ¹ ) and the hydrolyzate thereof are particularly preferable in terms of barrier properties. The organosilicon compound represented by the formula (b ² ) and the hydrolyzate thereof are particularly preferable in terms of resistance to wet heat. Component (B), among the above, preferably contains at least one compound selected from organosilicon compounds represented by the formula (b ²⁾ and a hydrolyzate thereof.

In the formula (b ¹ ), the alkyl group represented by R ² 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 organosilicon compound represented by the formula (b ¹ ) include tetraethoxysilane, tetramethoxysilane, and tetrapropoxysilane. These may be used alone or in combination of two or more. The hydrolyzate of the organic silicon compound represented by the formula (b ^1), of the four OR ¹ in the formula, at least one include those became OH.

In the formula (b ² ), the alkyl group represented by R ² 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 alkyl group for R ³ include a group represented by the following general formula (α).
X- (CH ₂ ) _m − (α)
[However, X is a glycidoxy group or an NCO group, and m is an integer of 1-8. ]

Examples of the organosilicon compound represented by the formula (b ² ) include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, and NCO groups (isocyanate groups) such as 3-isocyanatopropyltriethoxysilane. And the like. The hydrolyzate of the organic silicon compound represented by the formula (b ^2), of the three OR ² in the formula, at least one include those became OH.

The hydrolyzate of the organosilicon compound represented by the formula (b ¹ ) or the formula (b ² ) 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.

  (B) A component may be used individually by 1 type, or may use 2 or more types together. The amount of the component (B) in the coating solution is preferably such that the sum of the component (A) is 1% by mass or more and 100% by mass or less with respect to the total solid content. The ratio (B) / (A) of the component (B) to the component (A) in the coating solution is preferably 1/100 or more and 100/1 or less, and more preferably 1/10 or more and 10/1 or less. preferable. The effect which mix | blends (B) component is fully acquired as it is 1/100 or more. If it exceeds 10/1, the proportion of the component (A) is relatively low, so that flexibility, barrier properties and the like may be lowered.

Moreover, it is preferable that a coating liquid contains the acrylic polyol (C) which has 2 or more of OH groups further. The component (C) is compatible with a polymer formed by polymerization of a hydrolyzate of an organosilicon compound represented by the formula (a), (b ¹ ) or (b ² ). By adding the component (C) in addition to the organosilicon compound (component (A), component (B)), a homogeneous organic-inorganic composite is formed when the coating solution is applied and heat-dried. Since a homogeneous organic-inorganic composite film can be obtained, (1) a vapor deposition layer can be suitably formed, and the effect of improving gas barrier properties by interaction with the vapor deposition layer is further enhanced. (2) In a high temperature and high humidity atmosphere And the effect of suppressing the swelling deterioration of the overcoat layer in a hot water atmosphere. Therefore, a gas barrier laminate that exhibits excellent gas barrier properties over a long period of time can be provided even for uses in harsh environments.

  As component (C), a polymer compound obtained by polymerizing an (OH) group-containing (meth) acrylic acid derivative monomer, an OH group-containing (meth) acrylic acid derivative monomer and other monomers are copolymerized. And high molecular compounds that can be used. In the present specification, “(meth) acrylic acid derivative” includes (meth) acrylic acid in addition to those obtained by changing a part of the structure of (meth) acrylic acid (for example, (meth) acrylic acid ester). It is intended to include itself. Examples of the (meth) acrylic acid derivative monomer having an OH group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.

  As the other monomer copolymerizable with the (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having no OH group is preferable. Examples of (meth) acrylic acid derivative monomers having no OH group include (meth) acrylic acid derivative monomers having an alkyl group, (meth) acrylic acid derivative monomers having a carboxyl group, and (meth) acrylic having a ring structure. Examples include acid derivative monomers. Examples of (meth) acrylic acid derivative monomers having an alkyl group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. Is mentioned. Examples of the (meth) acrylic acid derivative monomer having a carboxyl group include (meth) acrylic acid. Examples of the (meth) acrylic acid derivative monomer having a ring structure include benzyl (meth) acrylate and cyclohexyl (meth) acrylate. As other monomers, monomers other than (meth) acrylic acid derivative monomers may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer. Monomers other than the (meth) acrylic acid derivative monomer may have an OH group.

The component (C) preferably has an OH group value of 50 [mgKOH / g] to 250 [mgKOH / g]. The hydrolyzate of the organosilicon compound represented by the general formula (a) and the hydrolyzate of the organosilicon compound represented by the general formula (b ¹ ) or the general formula (b ² ) have an OH group content. Many polymers are formed. When the OH group value of the component (C) is within the above range, the compatibility with the polymer is excellent. Here, the OH group value [mgKOH / g] is an index of the amount of OH groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide required to acetylate the hydroxyl group in 1 g of the acrylic polyol.

  Although the weight average molecular weight of (C) component is not prescribed | regulated, 3000 or more and 200,000 or less are preferable, 5000 or more and 100,000 or less are more preferable, and 5000 or more and 40000 or less are more preferable. In the present specification, the weight average molecular weight is a weight average molecular weight measured by GPC (gel permeation chromatography) based on polystyrene.

  (C) A component may be used individually by 1 type, or may use 2 or more types together. The blending amount of the component (C) in the coating solution is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 25% by mass or less with respect to the total solid content. The effect which mix | blends (C) component is fully acquired as it is 5 mass% or more. If it exceeds 50% by mass, the barrier property may be lowered.

Further, the coating solution preferably further contains an isocyanate compound (D) having at least two NCO groups in the molecule. The component (D) reacts with an Si—OH group formed by hydrolysis of the organosilicon compound represented by the formula (a), (b ¹ ) or (b ² ) to form a urethane bond. Thereby, the tolerance in long-term storage under high temperature and high humidity further improves. By adding the component (D) in addition to the organosilicon compound (component (A), component (B)), a homogeneous organic-inorganic composite is formed when the coating solution is applied and dried by heating. Since a homogeneous organic-inorganic composite film can be obtained, (1) a vapor deposition layer can be suitably formed, and the effect of improving gas barrier properties by interaction with the vapor deposition layer is further enhanced. (2) In a high temperature and high humidity atmosphere And the effect of suppressing the swelling deterioration of the overcoat layer in a hot water atmosphere. Therefore, a gas barrier laminate that exhibits excellent gas barrier properties over a long period of time can be provided even for uses in harsh environments.

  The component (D) may be any component having at least two NCO groups in the molecule. For example, as the monomer isocyanate, aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexa Fragrances such as aliphatic isocyanates such as methylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) Aliphatic isocyanates and the like can be mentioned. Also, polymers or derivatives of these monomeric isocyanates can 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.

  The component (D) may be arbitrarily selected from the above-mentioned monomeric isocyanates, polymers thereof, derivatives, and the like, and may be used alone or in combination of two or more. The blending amount of the component (D) in the coating liquid is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less with respect to the total solid content. The effect which mix | blends (D) component is fully acquired as it is 5 mass% or more. If it exceeds 50 mass%, the barrier property may be lowered.

  Moreover, it is preferable that a coating liquid contains both (C) component and (D) component. When both (C) component and (D) component are used together, the OH group of (C) component reacts with the NCO group of (D) component to form a urethane bond. Therefore, a composite cross-linked structure is formed by a urethane bond in addition to the siloxane bond, and an excellent gas barrier property improving effect is obtained.

  The coating liquid for forming the overcoat layer is prepared by mixing the component (A), optional components (components (B), (C), (D)), 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. About (A) component and (B) component, when mix | blending a hydrolyzate, you may use the hydrolysis liquid obtained by hydrolyzing beforehand. In addition, as optional components (B), (C), and (D), one kind may be added, a plurality of kinds may be added in combination, or all kinds may be added. .

  As a coating method of the coating solution, 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 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 the present invention, the thickness of the overcoat layer is not limited to the above range.

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

(Anchor coat layer)
The gas barrier laminate of the present invention 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 enhanced, and the occurrence of peeling between the layers can be suppressed.

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

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

  The anchor coating agent preferably contains an acrylic polyol (1) having two or more OH groups and an isocyanate compound (2) having at least two NCO groups in the molecule.

  As the acrylic polyol (1), a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having an OH group and another monomer are copolymerized. Examples thereof include a polymer compound obtained. Examples of the (meth) acrylic acid derivative monomer having an OH group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate. As the other monomer copolymerizable with the (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having no OH group is preferable. Examples of (meth) acrylic acid derivative monomers having no OH group include (meth) acrylic acid derivative monomers having an alkyl group, (meth) acrylic acid derivative monomers having a carboxyl group, and (meth) acrylic having a ring structure. Examples include acid derivative monomers. Examples of (meth) acrylic acid derivative monomers having an alkyl group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. Is mentioned. Examples of the (meth) acrylic acid derivative monomer having a carboxyl group include (meth) acrylic acid. Examples of the (meth) acrylic acid derivative monomer having a ring structure include benzyl (meth) acrylate and cyclohexyl (meth) acrylate. As other monomers, monomers other than (meth) acrylic acid derivative monomers may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer. Monomers other than the (meth) acrylic acid derivative monomer may have an OH group.

  Moreover, it is preferable that OH group value of acrylic polyol (1) is 50 [mgKOH / g] or more and 250 [mgKOH / g] or less. The OH group value [mgKOH / g] is an index of the amount of OH groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide necessary for acetylating the hydroxyl group in 1 g of the acrylic polyol. If the OH group value is less than [50 mgKOH / g], the reaction amount with the isocyanate compound (2) is small, and the effect of improving the adhesion between the resin base material and the vapor deposition layer by the anchor coat layer may not be sufficiently exhibited. is there. On the other hand, if the OH group value is larger than [250 mgKOH / g], the amount of reaction with the isocyanate compound (2) increases so that the shrinkage of the anchor coat layer may be increased. When the film shrinkage is large, the vapor deposition layer is not neatly laminated thereon, and there is a possibility that sufficient gas barrier properties are not exhibited.

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

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

  In the anchor coating agent, the equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound (2) to the OH group of the acrylic polyol (1) is preferably 0.3 or more and 2.5 or less, More preferably, it is 2.0 or less. When NCO / OH is 0.3 or more, the adhesion to the substrate is improved, and when it is 2.0 or less, the adhesion after the wet heat resistance test is improved. The blending amount of the acrylic polyol (1) and the isocyanate compound (2) in the anchor coating agent is preferably blended based on the equivalent ratio, and the isocyanate compound (2) is generally based on 100 parts by mass of the acrylic polyol (1). The amount is preferably about 10 parts by mass or more and 90 parts by mass or less, and more preferably about 20 parts by mass or more and 80 parts by mass or less.

  The anchor coating agent may further contain a silane coupling agent in order to further improve the adhesion between the resin base material and the vapor deposition layer. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Examples thereof include those having a mercapto group and those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. Moreover, as a silane coupling agent, 1 type may be used independently or 2 or more types may be used together.

  The anchor coating agent can be prepared by mixing an acrylic polyol (1), an isocyanate compound (2), an optional component (such as a silane coupling agent), and a solvent. Any solvent may be used as long as it can dissolve the acrylic polyol (1) and the isocyanate compound (2). Examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, and acetone. These solvents can be used alone or in combination of two or more.

  As a method for applying the anchor coating agent, a normal coating method can be used. For example, known methods such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, and a gravure offset method can be used. As a drying method, one or a combination of two or more methods of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, can be used. In the drying method, the heating temperature is not particularly limited, but is preferably in the range of about 60 ° C. or more and 140 ° C. or less. 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.

(Laminate resin layer)
Moreover, the gas barrier laminate of the present invention may further include a laminate resin layer laminated via an adhesive layer, and the outermost surface may be a laminate resin layer. By providing a laminate resin layer on the outermost surface, it is possible to impart functions and properties according to the application and to enhance practicality. Here, the laminate resin layer may be formed only on one side or on both sides.

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

  The material of the laminate resin layer may be appropriately selected from known materials according to desired functions and characteristics.

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

  For example, by using a polyethylene terephthalate film or a polyethylene naphthalate film for the laminate resin layer, the gas barrier laminate of the present invention is sealed in a liquid crystal display element, a transparent conductive sheet used in a solar cell, an electromagnetic wave shield, a touch panel, or the like. It can also be used as a stop material.

  The formation of the laminate resin layer may be appropriately performed using a known bonding method depending on the material of the selected laminate resin layer. For example, a laminating method such as dry lamination using an adhesive or extrusion molding using a heat-adhesive resin may be used. In the case of dry lamination using an adhesive, the adhesive forms an adhesive layer. Further, in the case of extrusion molding using a heat-adhesive resin, the heat-adhesive resin forms a bonding layer.

  Hereinafter, the present invention will be described in detail using examples and comparative examples. However, the present invention is not limited to the modes 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. Moreover, the vapor deposition material (A) which mixed the metal silicon powder and the silicon dioxide powder so that element ratio O / Si might be set to 1.5 directly on the corona treatment surface of the said resin base material using a vacuum vapor deposition machine. Was vapor-deposited to form a vapor-deposited layer on the resin substrate. At this time, the formed vapor deposition layer (SiO _x vapor deposition film) had a thickness of 50 nm.

Next, a coating solution for forming an overcoat layer was prepared.
Coating solution, ethylene oxide-containing trimethoxysilane _{(CH 3 O- (CH 2 CH} 2 O) 3 - (CH 2) 3 -Si (OCH 3) 3)) with hydrochloric acid hydrolysis solution (0.001 N in In addition, 4 times molar equivalent of ethylene oxide-containing trimethoxysilane as water was diluted with isopropyl alcohol (IPA) to obtain a solution having a solid content of 5% by mass.

Next, a coating solution was applied onto the vapor deposition layer and dried by heating to form an overcoat layer.
A bar coat was used for coating the coating solution. Moreover, the conditions of heat drying were 120 degreeC-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 the present invention 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.

<Example 2>
First, an anchor coat agent was prepared.
The anchor coat agent is prepared by copolymerizing hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as monomers so that the OH group value is 178 mgKOH / g, and adjusting acrylic polyol (weight average molecular weight of about 10,000). Then, a methyl ethyl ketone solution having a solid content of 5% by mass was prepared by blending hexamethylene diisocyanate (HDI) as the curing agent with the acrylic polyol as the main component and 0.5 equivalent to the amount of OH groups in the main component.

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 base material and stored (aging treatment) in a thermostatic chamber at 50 ° C. for 48 hours to form an anchor coat layer. At this time, the dry film thickness of the anchor coat layer was 0.15 μm.

Next, a vapor deposition layer was formed on the anchor coat layer.
Vapor deposition material (B), in which 20% by mass of metal tin powder is further mixed with a material in which metal silicon powder and silicon dioxide powder are mixed so that the element ratio O / Si is 1.5, is deposited using a vacuum deposition machine. Then, a 50 nm thick vapor deposition layer (SiOx-Sn composite vapor deposition film) was formed.

Next, a coating solution for forming an overcoat layer was prepared.
Coating solution, ethylene oxide-containing trimethoxysilane _{(CH 3 O- (CH 2 CH} 2 O) 3 - (CH 2) 3 -Si (OCH 3) 3)) with hydrochloric acid hydrolysis solution (0.001 N in Water, ethylene oxide-containing trimethoxysilane added 4 times molar equivalent) and glycidoxypropyltrimethoxysilane, bistrimethoxysilylethane: glycidoxypropyltrimethoxysilane = 80: 20 (molar ratio) The solution was mixed so that the solution was diluted with IPA to obtain a solution having a solid content of 5% by mass.

Next, a coating solution was applied onto the vapor deposition layer and dried by heating to form an overcoat layer.
A bar coat was used for coating the coating solution. Moreover, the conditions of heat drying were 120 degreeC-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 the present invention in which the resin base material / anchor coat layer / deposition layer / overcoat layer was laminated in this order was produced. In the gas barrier laminate of Example 2, the thickness of each layer was: resin substrate: 12 μm / anchor coat layer: 0.15 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm. Further, when the element ratio in the deposited film was measured with an X-ray photoelectron spectroscopic analyzer (manufactured by JEOL, model JPS-90MXV), elements of Si, Sn, and O were detected. 4 atm%, Sn: 5.2 atm%, O: 63.4 atm%.

<Example 3>
A gas barrier laminate of the present invention was produced in the same manner as in Example 2. However, the coating solution for forming the overcoat layer was the composition of the coating solution of Example 3 shown below.

(Example 3 coating solution)
First, bistrimethoxysilylpropyleneoxyethylene ((CH ₃ 0) ₃ —Si—CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ 0 —CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ) A decomposition solution (a 4-fold molar equivalent added as water using 0.001N hydrochloric acid) and glycidoxypropyltrimethoxysilane were mixed with bistrimethoxysilylhexane: glycidoxypropyltrimethoxysilane = 80: 20. (Molar ratio) was mixed and diluted with IPA to prepare a 5% by mass solid solution (Example 3 solution A).

  Next, the solution A in Example 3 and the methyl ethyl ketone solution (mixed solution of acrylic polyol and isocyanate compound) having a solid content of 5% by mass prepared as the anchor coating agent in Example 2 were mixed with the solid content in the overcoat layer. The mixture was mixed so that the ratio was 90:10 to prepare the coating solution of Example 3.

  From the above, the gas barrier laminate of the present invention in which the resin base material / anchor coat layer / deposition layer / overcoat layer was laminated in this order was produced. In the gas barrier laminate of Example 3, the thickness of each layer was: resin substrate: 12 μm / anchor coat layer: 0.15 μm / deposition layer: 50 nm / overcoat layer: 0.5 μm.

<Comparative Example 1>
A gas barrier laminate was produced in the same manner as in Example 1. However, the composition of the overcoat layer forming coating solution is the composition of Comparative Example 1 coating solution shown below containing polyvinyl alcohol, which is a water-soluble polymer, and the drying conditions after coating the overcoat layer forming coating solution are 120 ° C. -1 minute.

(Comparative Example 1 coating solution)
A hydrolyzed solution of tetraethoxysilane (TEOS) (5N molar equivalent of tetraethoxysilane as water using 0.01N hydrochloric acid) and an aqueous solution of polyvinyl alcohol (PVA) were mixed with SiO _{2 of} TEOS. A solution having a solid content of 5% by mass was prepared by mixing so that the mass ratio of the converted amount to PVA was 50:50.

  From the above, a gas barrier laminate in which the resin base material / vapor deposition layer / overcoat layer was laminated in this order was produced.

<Comparative Example 2>
A gas barrier laminate was produced in the same manner as in Example 2. However, the composition of the overcoat layer forming coating solution was the same as that of the anchor coating agent used in Example 2, and the drying condition after coating the overcoat layer forming coating solution was 120 ° C. for 1 minute.

  From the above, the gas barrier laminate of the present invention in which the resin base material / anchor coat layer / deposition layer / overcoat layer was laminated in this order was produced. In Comparative Example 2, the anchor coat layer and the overcoat layer are made of materials having the same composition.

<Inspection measurement>
About the gas-barrier laminated body obtained in Examples 1-3 and Comparative Examples 1-2, the water vapor transmission rate (WVTR) was measured. Here, the water vapor transmission rate (WVTR) is measured by (1) before laminating the overcoat layer, (2) immediately after production (initial), and (3) accelerated deterioration test (85 hours at 85 ° C. and 85% RH for 500 hours) The storage test was carried out three times. In addition, in the measurement of water vapor transmission rate, the water vapor transmission rate [g / m ² ··· in a 40 ° C.-90% RH atmosphere using a water vapor transmission meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control Co., Ltd. day]. The measurement results are shown below.

Example 1: Before the overcoat layer is laminated (resin substrate / deposition layer), the WVTR is 1.2 [g / m ² · day], the initial WVTR is 0.3 [g / m ² · day], WVTR after accelerated degradation test is 0.5 [g / m ² · day]
Example 2: The WVTR before laminating the overcoat layer (resin substrate / anchor coat layer / deposition layer) is 0.5 [g / m ² · day], and the initial WVTR is 0.1 [g / m ² · Day], WVTR after accelerated degradation test is 0.2 [g / m ² · day]
Example 3: The WVTR before laminating the overcoat layer (resin substrate / anchor coat layer / deposition layer) was 0.5 [g / m ² · day], and the initial WVTR was 0.1 [g / m ² · Day], WVTR after accelerated degradation test is 0.2 [g / m ² · day]
Comparative Example 1: WVTR 1.5 [g / m ² · day] before laminating the overcoat layer (resin base material / deposition layer), initial WVTR 0.3 [g / m ² · day], accelerated deterioration The test WVTR is 1.8 [g / m ² · day].
Comparative Example 2: Before laminating the overcoat layer (resin substrate / anchor coat layer / deposition layer), the WVTR is 0.7 [g / m ² · day], and the initial WVTR is 0.6 [g / m ² · Day], and the WVTR after the accelerated deterioration test is 7.8 [g / m ² · day].

Table 1 summarizes the measurement results of the layer structure (used materials) and water vapor permeability (WVTR) of the laminates obtained in Examples 1 to 3 and Comparative Examples 1 and 2. In addition, the symbol in Table 1 shows the following, respectively.
AC layer: Anchor coat layer.
OC layer: Overcoat layer.
AOH / NCO: Anchor coating agent prepared in Example 2.
a-1: Hydrolyzate of ethylene oxide-containing trimethoxysilane.
a-2: Hydrolyzate of bistrimethoxysilylpropyleneoxyethylene.
b1-1: TEOS hydrolyzate.
b2-1: Glycidoxypropyltrimethoxysilane.
PVA: polyvinyl alcohol.

<Evaluation>
As for the gas barrier properties of the gas barrier laminates of the present invention shown in Examples 1 to 3, the initial value of WVTR was low and the gas barrier properties were excellent. Further, even after the accelerated deterioration test, the value of WVTR did not increase so much from the initial value. On the other hand, in the gas barrier properties of the gas barrier laminates shown in Comparative Examples 1 and 2, after the accelerated deterioration test, the value of WVTR increased by 6 times or more compared to the initial value, and the WVTR was 1.0 [g / m ^2. -Day] A larger value was shown.

As described above, the gas barrier laminate of the present invention maintains gas barrier properties even after an accelerated deterioration test (storage test at 85 ° C. and 85% RH for 500 hours) (specifically, WVTR is 1.0). [G / m ² · day] or less) and the gas barrier property was confirmed to be maintained even under a harsh environment. For this reason, it is confirmed that it can be suitably used even in harsh environments such as packaging material applications that perform treatments such as boil and retort sterilization, and solar cell applications that are expected to be used for a long time outdoors. It was done.

  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.

DESCRIPTION OF SYMBOLS 10 ... Gas barrier laminate 11 ... Resin base material 12 ... Deposition layer 13 ... Overcoat layer 20 ... Gas barrier laminate 24 ... Anchor coat layer 30 ... Gas barrier laminate 31 ... Adhesive layer 32 ... Laminate resin layer 33 ... Adhesive layer 34 ... Laminate resin layer

Claims (8)

A resin substrate;
A vapor deposition layer laminated above the resin base material;
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.
The coating liquid is a coating liquid containing at least one kind (A) selected from the group consisting of an organosilicon compound represented by the following general formula (a) and a hydrolyzate thereof. Laminated body.
^{_{R 1 O- (CH 2 CH 2}} O) m - (CH 2) n -Si (OR) 3 ...... (a)
[However, R ¹ is H, CH ₃ , or — (CH ₂ ) _n —Si (OR) ₃ , R is an alkyl group, and m and n are integers of 1 to 3. ] The coating liquid further includes
At least one selected from the group consisting of an organosilicon compound represented by the following general formula (b ¹ ), an organosilicon compound represented by the following general formula (b ² ), and a hydrolyzate thereof (B The gas barrier laminate according to claim 1, comprising:
Si (OR ² ) ₄ (b1)
R ³ —Si (OR ² ) ₃ (b2)
[However, R ² is an alkyl group, and R ³ is an organic group having one of an epoxy group and an NCO group. ] The coating liquid further includes
The gas barrier laminate according to claim 1 or 2, comprising an acrylic polyol (C) having two or more OH groups. The coating liquid further includes
The gas barrier laminate according to any one of claims 1 to 3, comprising an isocyanate compound (D) having at least two NCO groups in the molecule. 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 OH groups;
An isocyanate compound (2) having at least two NCO groups in the molecule,
The acrylic polyol (1) has an OH group 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 OH group of the acrylic polyol (1) is 0.3 or more and 2.5 or less, any one of claims 1 to 4 2. The gas barrier laminate according to claim 1. The gas barrier laminate according to any one of claims 1 to 5, wherein the vapor deposition layer is formed by vacuum vapor deposition using a vapor deposition material containing metal silicon and silicon dioxide. The vapor deposition material further contains at least one metal selected from the group consisting of Al, Zn, Sn, Fe, Mn, or an oxide thereof.
The said vapor deposition layer contains at least 1 or more types of metal chosen from the group which consists of Al, Zn, Sn, Fe, and Mn in the ratio of 1 atm% or more and 20 atm% or less. The gas barrier laminate as described. The gas barrier laminate according to claim 1, wherein a laminate resin layer is further laminated on the overcoat layer via an adhesive layer.

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