JP2006007565A - Gas barrier transparent laminate - Google Patents

Abstract

[PROBLEMS] To perform post-processing under a wide range of post-processing conditions, and because the transparency is excellent, the contents can be seen through, a metal detector can be used, excellent bending resistance, and high gas barrier properties under high temperature and high humidity. And a pinhole-free gas barrier transparent laminate.
A transparent laminate A having a gas barrier layer formed of a vapor-deposited thin film layer made of an inorganic oxide and a polymer layer formed on at least one surface of a transparent plastic substrate having a thickness of at least 1 μm is at least 1 μm thick. A gas-barrier transparent laminate C in which at least one stack structure 10 obtained by sandwiching and laminating and laminating the transparent plastic substrate B having the above moisture absorption holding ability is laminated.
[Selection] Figure 1

Description

  The present invention relates to a laminate such as a sheet or film for packaging used in the packaging field of foods, non-foods and pharmaceuticals, or a laminate such as a sheet or film used for electronic equipment-related members. In particular, the present invention relates to a gas barrier transparent laminate that is developed in the packaging field where electronic materials having no pinholes are required or in the field of electronic device members / packaging.

  Packaging materials used for packaging foods, non-foods, and pharmaceuticals contain oxygen, water vapor, and other contents that permeate the packaging material in order to suppress the alteration of the contents and maintain the functions and properties of the contents. It is necessary to prevent the influence of the gas to be altered, and it is required to have a gas barrier property that blocks these gases.

  Conventionally, a vinylidene chloride resin film having a relatively excellent gas barrier property among polymers or a film coated with them has been often used. However, they have problems such as a large influence of gas barrier properties due to temperature, humidity, etc., and inability to meet demands for high gas barrier properties. Therefore, for materials that require high gas barrier properties, a packaging material using a metal foil made of a metal such as aluminum as a gas barrier layer must be used.

  However, packaging materials using metal foils made of metal such as aluminum are not affected by temperature and humidity and have high gas barrier properties, but the contents cannot be confirmed through the packaging materials. There are many drawbacks, such as the fact that it must be treated as an incombustible material at the time of subsequent disposal, and a metal detector cannot be used for inspection.

  Accordingly, as a packaging material that overcomes these drawbacks, an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like described in, for example, US Pat. No. 3,442,686 and Japanese Patent Publication No. 63-28017 is used as a polymer film. A film having a deposited film formed thereon by a forming means such as a vacuum deposition method or a sputtering method has been developed.

  These vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foil or the like. Yes.

  However, even if it is a film suitable for the packaging material described above, it is rarely used as a vapor deposition film alone as a packaging container or packaging material, and characters, designs, etc. are printed on the surface of the vapor deposition film as post-processing after vapor deposition. Or the packaging body is completed through various processes, such as bonding with a film etc. and shape processing to packaging bodies, such as a container.

  Therefore, when the gas barrier properties such as oxygen permeability and water vapor permeability were measured after the bag was made by laminating with the sealant film using the above-mentioned vapor deposition film or the like, A single gas barrier film could not achieve a gas barrier property equivalent to that of a metal foil due to the influence of barrier layer defects caused by microdefects (microcracks) in the deposited layer, pinholes on the lubricant, foreign matter, and the like.

That is, as a condition to be used as a packaging material that requires a high level of gas barrier properties, the metal foil that blocks the transparency that can directly see through the contents and the gas that affects the contents The same high gas barrier properties are required.

  As a technique for solving such a problem, a vapor deposition layer made of an inorganic compound is used as the first layer, and includes at least one of a water-soluble polymer and one or more types of metal alkoxides, metal alkoxide hydrolysates, or tin chloride. There has been proposed a gas barrier packaging material in which a gas barrier coating formed by applying a coating agent mainly composed of an aqueous solution or a hydroalcoholic solution and drying by heating is used as a second layer. No. 192454, JP-A-7-233463, and JP-A-11-262969.

  This gas barrier packaging material is obtained by laminating a first layer of a vapor deposition layer made of an inorganic compound and a second layer of a gas barrier coating on a transparent substrate such as a transparent film, exhibiting high gas barrier properties, and water resistance. It has moisture resistance and can withstand some deformation. However, since the gas barrier coating of the gas barrier packaging material comprises a vapor-deposited layer made of an inorganic compound, the barrier property may be slightly lowered depending on the post-processing conditions when the packaging container or packaging material is used.

The known patent documents are described below.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017 JP-A-6-192454 JP-A-7-233463 JP-A-11-262969

  The present invention is intended to solve the above-described problems of the prior art, can be post-processed under a wide range of post-processing conditions, and has excellent transparency so that the contents can be seen through, and a metal detector is used. An object of the present invention is to provide a gas barrier transparent laminate that is excellent in bending resistance, has a high gas barrier property under high temperature and high humidity, and is free of pinholes.

  The present invention is for achieving the above object, and the invention according to claim 1 of the present invention is a deposition made of an inorganic oxide on at least one surface of a transparent plastic substrate (1) having a thickness of at least 1 μm. A transparent plastic substrate (B) having a water absorption retention capacity of at least 1 μm or more is sandwiched and bonded by a transparent laminate (A) having a gas barrier layer (2) by a thin film layer and a polymer layer (3) thus formed. The gas barrier transparent laminate is characterized in that at least one set of stacked stack structures is laminated.

  The invention according to claim 2 of the present invention is the gas barrier transparent laminate according to claim 1, wherein the gas barrier layer (2) of the transparent laminate (A) is aluminum oxide, silicon oxide, magnesium oxide or the like. It is a vapor-deposited thin film layer made of an inorganic oxide of a mixture of the above, and has a layer thickness of 5 to 300 nm.

The invention according to claim 3 of the present invention is the gas barrier transparent laminate according to claim 1 or 2, wherein the polymer layer (3) of the transparent laminate (A) is a vacuum-deposited polymerizable monomer or oligomer. Or a coating layer of a mixture thereof, wherein the thickness of the coating layer is 0.02 to
Gas barrier transparent, characterized by being successively laminated by vacuum deposition and polymerization curing on the gas barrier layer (2) of the transparent plastic substrate (1) so as to be 20 μm, more preferably 0.2 to 10 μm It is a laminate.

  The invention according to claim 4 of the present invention is the gas barrier transparent laminate according to claim 3, wherein the polymerizable monomer or oligomer of the coating layer to be the polymer layer (3) or a mixture thereof is an acrylate group, A gas barrier transparent laminate having a polymerizable portion such as a methacrylate group or a vinyl group.

  The invention according to claim 5 of the present invention is the gas barrier transparent laminate according to claim 3 or 4, wherein the coating layer to be the polymer layer (3) is cured by electron beam irradiation and / or ultraviolet irradiation. It is a gas-barrier transparent laminated body characterized by having.

  The invention according to claim 6 of the present invention is the gas barrier transparent laminate according to any one of claims 1 to 5, wherein the gas barrier layer (2) comprises the transparent plastic substrate (1) and an inorganic oxide. A plasma treatment layer (4), and / or a gas barrier layer comprising a plasma treatment layer (5) between the polymer barrier layer (2) and the gas barrier layer (2) made of the inorganic oxide. Transparent laminate.

  The invention according to claim 7 of the present invention is the gas barrier transparent laminate according to any one of claims 1 to 6, wherein the plasma treatment of the plasma treatment layer (5) is performed by using nitrogen, argon or the like as a plasma gas. It is a reactive gas composed of one kind of inert gas, oxygen, carbon dioxide, etc., or a reactive gas obtained by mixing any two or more of these gases.

  The invention according to claim 8 of the present invention is the gas barrier transparent laminate according to any one of claims 1 to 7, wherein the transparent plastic substrate (B) is a hygroscopic resin or an inorganic hygroscopic material, Alternatively, it is a gas barrier transparent laminate comprising a resin in which a mixture thereof is dispersed and held in a substrate.

  As described above, according to the gas barrier transparent laminate of the present invention, the laminated structure in which the vapor-deposited thin film layer and the gas barrier coating are sequentially laminated on the transparent plastic base material sandwiches the moisture-absorbing transparent plastic base material. Since it has at least one set of stack structures bonded together, it has excellent bending resistance, and when used as a gas barrier packaging material having a gas barrier layer, it exhibits a gas barrier property similar to that of a metal foil, With regard to post-processing suitability, it can be post-processed under a wide range of post-processing conditions, and since it has excellent transparency, the contents can be seen through, a metal detector can be used, it has excellent bending resistance, and it can be used at high temperatures and high humidity It has a high gas barrier property and can provide a pinhole-free gas barrier transparent laminate and has various resistances similar to gas barrier films made of ordinary metal foil. Runode, in the same manner as the gas barrier packaging material according to the conventional metal foil, it is possible to use by conventional processing. In addition, the gas barrier transparent laminate of the present invention is excellent in transparency, enables the contents to be confirmed through the packaging material, and obtains a versatile packaging material having a high level of gas barrier properties comparable to metal foil, Wide use is possible in the packaging technology field and the electronic equipment field.

  The gas barrier transparent laminate of the present invention will be described in more detail with reference to the drawings. FIG. 1 is a side sectional view for explaining an example of a laminated structure of the gas barrier transparent laminated body of the present invention.

The present invention is to achieve the above object, and the invention according to claim 1 of the present invention is shown in FIG.
As shown in FIG. 1, a gas barrier layer (2) by a vapor-deposited thin film layer made of an inorganic oxide and a polymer layer (3) are formed on at least one surface of a transparent plastic substrate (1) having a thickness of at least 1 μm. With the transparent laminate (A), as shown in FIG. 1, a transparent plastic substrate (B) having a water absorption retention capacity of at least 1 μm or more is sandwiched and bonded, and the stacked stack structure (10) is laminated. The gas barrier transparent laminate (C) is characterized in that at least one set or one or more sets are laminated.

  First, based on FIG. 1, the gas barrier transparent laminate of the present invention will be described. A transparent laminate (A) has a water absorption retention capacity of at least 1 μm or more via a bonding layer (6). The plastic substrate (B) is laminated and laminated in a sandwiched manner.

  FIG. 2 is a side sectional view for explaining an example of the laminated structure of the transparent laminate (A), and is a vapor-deposited thin film made of an inorganic oxide on at least one surface of a transparent plastic substrate (1) made of a transparent plastic film. The gas barrier layer (2) and the formed polymer layer (3) are sequentially laminated.

  More preferably, the plasma treatment layer (4), between the transparent plastic substrate (1) and the gas barrier layer (2), and / or between the gas barrier layer (2) and the polymer layer (3), respectively. (5) may be provided.

  Further, the transparent laminate (A) used for laminating the gas barrier transparent laminate C of the present invention shown in FIG. 1 may be laminated in any combination using either the front or back side of the laminate (A). Absent. Further, the gas barrier transparent laminate C according to the present invention may be a laminate in which the stacked stack structures (10) as shown in FIG. It is better to stack more than one set. FIG. 3 shows, for example, two sets of stack structures (10) laminated as necessary through a bonding layer (6) as the barrier transparent laminate C of the present invention.

  The transparent plastic substrate (1) described above is a transparent plastic material, and a transparent film is preferable in order to make use of the transparency of the deposited thin film layer. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films, polylactic acid films A biodegradable plastic film or the like such as is used, which may be either stretched or unstretched, and preferably has mechanical strength and dimensional stability. These are processed into a film and used. In particular, polyethylene terephthalate arbitrarily stretched biaxially from the viewpoint of heat resistance or the like is preferably used. In addition, various known additives and stabilizers such as antistatic agents, ultraviolet inhibitors, plasticizers, lubricants, and the like may be used on the surface of the substrate 1 to improve the adhesion to the thin film. In addition, corona treatment, low temperature plasma treatment, ion bombardment treatment may be performed as pretreatment, and chemical treatment, solvent treatment, etc. may be performed.

  The thickness of the transparent plastic substrate 1 is 1 μm or more, and it is not only suitable as a packaging material, but may be laminated with other layers, a gas barrier layer (2) using a vapor-deposited thin film made of an inorganic oxide, and gas barrier properties Considering the processability when forming the polymer layer (3) as the coating layer, it is practically in the range of 3 to 200 μm, and preferably 6 to 30 μm depending on the application.

  In consideration of mass productivity, the transparent plastic substrate 1 is preferably a long film so that each layer can be formed continuously.

Although the gas barrier layer (2) by the vapor deposition thin film which consists of inorganic oxides does not specifically limit the kind of the inorganic oxide, For example, aluminum oxide, silicon oxide, tin oxide, magnesium oxide, titanium oxide, iron oxide, Or what consists of vapor deposition film | membrane of inorganic oxides, such as those mixtures, and has transparency and gas barrier properties, such as oxygen and water vapor | steam, should just be used. Among these, aluminum oxide, silicon oxide, and magnesium oxide are particularly preferable because they are excellent in oxygen transmission rate and water vapor transmission rate. However, the above-mentioned inorganic oxide of the gas barrier layer (2) is SiO _x , AlO _x, etc., and does not need to be a fully saturated oxide, and is transparent enough to allow the contents to be directly seen through. In addition, any material can be used as long as it is suitable for conditions such as high gas barrier properties such as a metal foil that blocks a gas that affects the contents.

  The optimum condition of the thickness of the gas barrier layer (2) varies depending on the type and configuration of the inorganic compound to be used, but generally it is preferably in the range of 5 to 300 nm, and the value is appropriately selected. However, if the film thickness of the gas barrier layer (2) is less than 5 nm, a uniform film may not be obtained, or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. is there. On the other hand, when the film thickness exceeds 300 nm, the thin film cannot maintain flexibility, and there is a possibility that the thin film may be cracked due to external factors such as bending and pulling after the film formation. Therefore, the range of 5 to 100 nm is preferable.

  There are various methods for forming the gas barrier layer (2) with a vapor-deposited thin film made of an inorganic oxide on the transparent plastic substrate 1, and it can be formed by a normal vacuum vapor deposition method, but sputtering is another thin-film formation method. A method, an ion plating method, a plasma vapor deposition method (CVD), or the like can also be used. However, considering productivity, the vacuum deposition method is the best at present. As a heating means of the vacuum deposition apparatus by the vacuum deposition method, an electron beam heating method, a resistance heating method, an induction heating method, or the like is preferable. In order to improve the adhesion between the thin film and the substrate and the denseness of the thin film, the plasma assist method is used. Alternatively, an ion beam assist method can be used. In addition, in order to increase the transparency of the deposited film, it is possible to perform reactive deposition by blowing oxygen gas or the like at the time of deposition.

  The polymer layer (3) is provided on the gas barrier layer (2) made of a vapor-deposited thin film made of an inorganic oxide in order to impart a high level of gas barrier properties similar to a metal foil.

  In order to achieve this, the polymer layer (3) is a vacuum-deposited polymerizable monomer and oligomer, and the thickness of the polymer layer (3) is 0.02 to 20 μm, more preferably 0.2 to 10 μm. A coating layer formed by polymerization and curing is sequentially laminated on the gas barrier layer (2).

  Each component contained in the above-described vacuum-deposited polymerizable monomer, oligomer, or mixture thereof and the method thereof will be described in more detail.

  The coating layer to be the polymer layer (3) heats a resin component made of a polymerizable monomer such as an acrylic, an oligomer, or a mixture thereof to the gas barrier layer (2) by an inorganic oxide vapor-deposited thin film under vacuum. Vaporized and spray-coated, and polymerized and cured by electron beam and / or ultraviolet irradiation. In the case of curing by ultraviolet irradiation, an acrylic resin coating agent in which a photopolymerization initiator is mixed as a second component is used in addition to a resin component consisting of an acrylic monomer or oligomer or a mixture thereof.

The film thickness of the film layer to be the polymer layer (3) is preferably 0.02 to 20 μm, more preferably 0.2 to 10 μm in order to obtain a film characteristic of the present invention. This is a film thickness of 0.
If the thickness is less than 02 μm, it is difficult to form a uniform film. If the thickness is more than 20 μm, the curing rate is lowered and it is difficult to sufficiently cure.

  In particular, in the case of electron beam curing of the coating layer that becomes the polymer layer (3), the balance between the film thickness of the polymer layer (3), the electron beam energy condition, the processing speed, and the charge removal is important. Care must be taken because excessive energy supply causes charging and the resulting discharge may impair the barrier properties.

  Examples of polymerizable monomers and oligomers include acrylics having a polymerizable double bond such as alkyd, polyester acrylate, polyether acrylate, acrylic acrylate, urethane acrylate, epoxy acrylate, silicone acrylate, polyacetal acrylate, polybutadiene acrylate, and melamine acrylate. Mention may be made of system monomers or oligomers. As the monomer or oligomer, monofunctional, bifunctional, trifunctional, or higher polyfunctional monomers can be appropriately selected and used depending on the number of reactive functional groups. These monomers or oligomers can be used as a mixture of two or more.

  The molecular weight of the monomer or oligomer is 10,000 or less, preferably 2,000 or less, more preferably 100 to 600. The viscosity is 500 cps or less at room temperature, preferably 100 cps or less.

  Examples of the photopolymerization initiator to be added in the case of performing ultraviolet curing include, for example, benzoin ethers, benzophenones, xanthones, acetophenone derivatives, etc., with respect to the above-mentioned monomers, oligomers or their total amount of 100% by weight. % To 10% by weight, preferably 0.1 to 2% by weight is used.

  In addition, as the photopolymerization initiator, in order to prevent elution from the cured film, it is preferable to use a molecularly immobilized monomer or oligomer that can be polymerized as described above.

  As shown in FIG. 1, a transparent laminate (A) having a polymer layer (3) formed in the gas barrier transparent laminate according to claim 1 is applied to a transparent plastic substrate (B) having a water absorption retention capability. As a method of bonding, it can be laminated by a known method such as a dry laminating method, a non-solvent laminating method, an extrusion laminating method in which an adhesive such as a two-component curable urethane resin is used as the bonding layer (6). .

  Furthermore, as shown in FIG. 2, it is also possible to laminate | stack another layer on the polymer layer (3) of a transparent laminated body (A). For example, a printing layer, an outer substrate layer, an intermediate layer, a heat seal layer, and the like.

  The printing layer provided on the polymer layer (3) is formed for practical use as a packaging bag or the like, and has been conventionally used such as urethane-based, acrylic-based, nitrocellulose-based, rubber-based, and vinyl chloride-based. It is a layer that is printed and printed using inks made by adding various pigments, extender pigments, and additives such as plasticizers, desiccants, stabilizers, etc. Etc. are formed.

  As a method for forming the printing layer, for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating may be used. The thickness of the printing layer is not particularly limited, but for example, about 0.1 to 2.0 μm is appropriate.

  In addition, the outer base material layer provided on the polymer layer (3) is a printing base material to be printed when the gas barrier layer is used as an intermediate layer. On the other hand, either front printing or back printing may be used.

  In general, from the viewpoint of mechanical strength, the outer substrate layer (printing substrate) is made of a polyester film such as polyethylene terephthalate (PET) and polyethylene naphthalate, a polyolefin film such as polyethylene or polypropylene, a polyamide film, a polycarbonate film, A polyacrylonitrile film, a polyimide film, or the like is preferably used, and a polyethylene terephthalate film, a polypropylene film, or the like arbitrarily stretched in a biaxial direction is particularly preferable.

  Although the thickness of an outer side base material layer is decided according to a material and required quality, generally it is in the range of 5-50 micrometers, alternatively 5-180 micrometers, or 5-188 micrometers. In addition, as the formation method, the polymer layer (3) may be formed on the polymer layer (3) by a known method such as a dry lamination method, a non-solvent lamination method, or an extrusion lamination method, which are bonded using an adhesive such as a two-component curable urethane resin. Can be laminated.

  The intermediate layer provided on the polymer layer (3) is provided to increase the bag breaking strength and the piercing strength in the case of a bag-like package, and is generally biaxial in terms of mechanical strength and thermal stability. It needs to be a kind selected from a stretched nylon film, a biaxially stretched polyethylene terephthalate film, and a biaxially stretched polypropylene film.

  The thickness of the intermediate layer is determined according to the material and required quality, but is generally in the range of 5 to 50 μm. In addition, as the formation method, the polymer layer (3) may be formed on the polymer layer (3) by a known method such as a dry lamination method, a non-solvent lamination method, or an extrusion lamination method, which are bonded using an adhesive such as a two-component curable urethane resin. Can be laminated.

  The heat seal layer provided on the polymer layer (3) is provided as an adhesive layer when forming a bag-shaped package or the like. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and their metals A resin such as a cross-linked product is used. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm. As a forming method, it is common to use a dry laminating method in which a film-like material made of the above resin is bonded using an adhesive such as a two-component curable urethane resin. (3) It can be laminated on.

  As the transparent plastic substrate (B) having a moisture absorption and holding ability, a general purpose material such as a hygroscopic polyvinyl alcohol film, an eval film, or a nylon film may be used. In addition, an inorganic hygroscopic material may be dispersed and held in the transparent plastic substrate. As the inorganic hygroscopic material, an inorganic salt such as anhydrous calcium chloride, an adsorbent such as synthetic zeolite, or the like can be used.

  The gas barrier transparent laminate of the present invention will be further described with reference to specific examples.

<Example 1>
As shown in FIG. 2, as a transparent plastic substrate (1), metal aluminum is evaporated on one side of a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film by a vacuum vapor deposition apparatus using an electron beam heating method. Oxygen gas was introduced into the film, aluminum oxide having a film thickness of 15 nm was vapor-deposited, and a gas barrier layer (2) formed of a vapor-deposited thin film layer made of an inorganic oxide was laminated. A coating agent having a composition (for example, propoxylated neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.)) is deposited by a vacuum deposition method to form a coating layer having a thickness of 0.5 μm. Polymerized and cured by electron beam irradiation, and polymerized and cured polymer layer (3) was laminated to obtain a transparent laminate (A) having gas barrier properties shown in FIG.

  As the coating agent, propoxylated neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) was used.

  Subsequently, as shown in FIG. 1, the transparent laminate (B) composed of a 12 μm polyvinyl alcohol film is sandwiched between the two transparent laminates (A) having a gas barrier property. A pair of (A) and the moisture-absorbing plastic substrate (B) are laminated and formed as a bonding layer (6) through a two-component curable urethane adhesive by a dry laminating method, as shown in FIG. The gas barrier transparent laminate (C) of the present invention was obtained from the stack structure (10).

<Example 2>
In the gas barrier transparent laminate (C) of the present invention by the set of stack structures (10) obtained in Example 1, as shown in FIG. 3, on the set of stack structures (10), as shown in FIG. Further, by bonding one set of the stack structures (10) as a bonding layer (6) in the same manner as in Example 1 through a two-component curable urethane adhesive by a dry laminating method. A gas barrier transparent laminate C according to the present invention was obtained from two sets of stack structures (10) shown in FIG.

<Example 3>
In the gas barrier transparent laminate (C) of the present invention by the two sets of stack structures (10) obtained in Example 2, the two sets of the stack structures (10) are further provided with one set of the above-described stack structures (10). By stacking the stack structure (10) in the same manner as in Example 1 above as a bonding layer (6) through a two-component curable urethane adhesive by a dry laminating method, three sets of stack structures A gas barrier transparent laminate C according to (10) of the present invention was obtained.

<Comparative Example 1>
A gas barrier transparent laminate was obtained in the same manner as in Example 1 except that the film thickness of the gas barrier layer (2) by the vapor-deposited thin film layer made of aluminum oxide was 4 nm.

<Comparative example 2>
In Example 1 above, gas barrier properties were obtained in the same manner as in Example 1 except that the film thickness of the coating layer to be the polymer layer (3) deposited by the vacuum evaporation method was 0.01 μm. A transparent laminate was obtained.

<Comparative Example 3>
In Example 1, except that the moisture-absorbing plastic base material (B) is not laminated, two transparent laminates (A) having gas barrier properties are bonded together in the same manner as in Example 1, and the gas barrier transparent laminate is laminated. Got.

<Test 1>
Each of the gas barrier transparent laminates of the present invention obtained in Examples 1 to 3 and each of the gas barrier transparent laminates obtained in Comparative Examples 1 to 3 was used as a single sample, and water vapor barrier properties (water vapor permeability ( g / m 2 · day)) and gas barrier performance was evaluated. The measurement and evaluation results are shown in Table 1.

<Test 2>
On the polymer layer (3) of each of the gas barrier transparent laminates of the present invention obtained by Examples 1 to 3 above and on the polymer layer (3) of each of the gas barrier transparent laminates obtained by Comparative Examples 1 to 3 In addition, as a sample after printing a laminate obtained by laminating and laminating outer substrate layers each having a printed layer, water vapor barrier properties (water vapor transmission rate (g / m 2 · day)) were measured, and gas barrier performance was evaluated. . The measurement and evaluation results are shown in Table 1.

Good …… ◎
Slightly good ... ○
Somewhat bad ... △
Defect ...
<Test 3>
The polymer layer (3) side of each of the gas barrier transparent laminates of the present invention obtained by the above Examples 1 to 3, and the polymer layer (3) side of each of the gas barrier transparent laminates obtained by Comparative Examples 1 to 3 In addition, as a heat-seal layer for bag-making, a packaging material for bag-making in which a 70 μm-thick unstretched polypropylene film is laminated by a dry laminating method through a two-component curable urethane adhesive into a bag shape Using a bag-processed sample as a sample, the pinhole part through which water vapor permeated became a dark spot (dark spot), and a calcium test was conducted to visually visualize the state of water vapor transmission. Counted and evaluated. The counts and evaluation results are shown in Table 1.

<Test 4>
The polymer layer (3) side of each of the gas barrier transparent laminates of the present invention obtained by the above Examples 1 to 3, and the polymer layer (3) side of each of the gas barrier transparent laminates obtained by Comparative Examples 1 to 3 In addition, as a heat-seal layer for bag making, a packaging material for bag making in which a 70 μm-thick unstretched polypropylene film is laminated by a dry laminating method through a two-component curable urethane adhesive in a bag shape Using a bag-processed sample as a sample, the pinhole part through which oxygen has permeated turns blue and an agar gel evaluation that allows the oxygen permeation state to be visually visualized is performed, and the number of pinholes is counted, evaluated. The counts and evaluation results are shown in Table 1.

<Summary of evaluation>
The gas barrier transparent laminates obtained in Comparative Examples 1 to 3 were used as the packaging materials described above for the gas barrier transparent laminates of the present invention obtained in Examples 1 to 3, respectively. The gas barrier transparent laminates of the present invention obtained by Examples 1 to 3 above do not satisfy all of the high gas barrier properties for blocking gas etc., pinhole free properties, and resistance to post-processing. It can be said that all are satisfied.

Total evaluation
Good …… ◎
Slightly good ... ○
Somewhat bad ... △
Defect ...

The lamination | stacking sectional drawing explaining 1 set of stack structures of the gas-barrier transparent laminated body of this invention. The lamination | stacking sectional drawing of the gas-barrier transparent laminated body which comprises the stack structure of the gas-barrier transparent laminated body of this invention. The lamination | stacking sectional drawing explaining 2 sets of stack structures of the gas-barrier transparent laminated body of this invention.

Explanation of symbols

A ... gas barrier transparent laminate B ... moisture-absorbing plastic substrate 1 ... transparent plastic substrate 2 ... vapor deposited thin film layer 3 made of inorganic oxide ... gas barrier coating layer 4, 5 ... plasma treatment layer 6 ... bonded layer ( Adhesive etc.)
10 ... Stack structure

Claims (8)

  A transparent laminate (A) having a gas barrier layer (2) by a vapor-deposited thin film layer made of an inorganic oxide and a polymer layer (3) formed on at least one surface of a transparent plastic substrate (1) having a thickness of at least 1 μm or more ), A gas barrier transparent laminate characterized in that at least one or more sets of stack structures in which a transparent plastic substrate (B) having a moisture absorption retention capacity of at least 1 μm is sandwiched and laminated are laminated. body.   The gas barrier layer (2) of the transparent laminate (A) is a vapor-deposited thin film layer made of an inorganic oxide of aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof, and the layer thickness is 5 to 300 nm. The gas barrier transparent laminate according to claim 1.   The polymer layer (3) of the transparent laminate (A) is a coating layer formed of a vacuum-deposited polymerizable monomer or oligomer or a mixture thereof, and the thickness of the coating layer is 0.02 to 20 μm, more preferably The gas barrier according to claim 1 or 2, wherein the gas barrier layer (2) of the transparent plastic substrate (1) is sequentially deposited by vacuum deposition and polymerization curing so as to have a thickness of 0.2 to 10 µm. Transparent laminate.   The polymerizable monomer or oligomer of the coating layer to be the polymer layer (3) or a mixture thereof has a polymerizable portion such as an acrylate group, a methacrylate group, or a vinyl group. Gas barrier transparent laminate.   The gas barrier transparent laminate according to claim 3 or 4, wherein the coating layer to be the polymer layer (3) is cured by electron beam irradiation and / or ultraviolet irradiation.   A plasma treatment layer (4) between the transparent plastic substrate (1) and a gas barrier layer (2) made of an inorganic oxide, or / and a gas barrier layer (2) and a polymer layer (3) made of the inorganic oxide. A gas barrier transparent laminate according to any one of claims 1 to 5, wherein a plasma treatment layer (5) is provided therebetween.   The plasma treatment of the plasma treatment layer (5) is performed by mixing a reactive gas composed of one of inert gases such as nitrogen and argon, oxygen and carbon dioxide as a plasma gas, or any two or more of these. The gas barrier transparent laminate according to any one of claims 1 to 6, wherein the gas barrier transparent laminate is a reactive gas.   8. The transparent plastic substrate (B) is made of a hygroscopic resin, an inorganic hygroscopic material, or a resin in which a mixture thereof is dispersed and held in the substrate. Gas barrier transparent laminate.

Images