JP2007261018A - Transparent laminate being suitable to hold contents and method for producing the laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent and high practical laminate which has high gas-barrier properties equivalent to those of a metal foil and is suitable for holding contents high in practicality and a method for producing the laminate. <P>SOLUTION: In the transparent laminate suitable for holding contents, at least a gas-barrier coat layer is formed on a transparent plastic substrate. A coating agent containing at least one of a macromolecular compound having hydroxyl groups, a metal alkoxide and/or its hydrolyzate and/or its polymer as a component is applied, and the paint film is heated, dried, and subjected to water treatment, to form the gas-barrier coating layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate for packaging used in the packaging field of foods, non-foods, pharmaceuticals, etc., or a laminate used for electronic equipment-related members, and the packaging field where particularly high gas barrier properties are required. Or, it relates to the field of electronic equipment and packaging.

  Packaging materials used for packaging foods, non-foods, pharmaceuticals, etc. are oxygen, water vapor, and other gases that alter the contents that permeate the packaging material in order to prevent the contents from being altered and to maintain their functions and properties. It is necessary to prevent the influence of the above, 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 have high gas barrier properties without the influence of temperature and humidity, but the contents cannot be confirmed through the packaging materials. There are many disadvantages such as having to treat it as an incombustible material at the time of disposal, and being unable to use a metal detector at the time of inspection.

Therefore, as a packaging material that has overcome these drawbacks, for example, an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like, as described in Patent Documents 1 and 2, is deposited on a polymer film by vacuum deposition or A film in which a deposited film is formed by a forming means such as 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.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017

  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 the packaging bodies, such as a container.

  Therefore, after the bag was bonded to the sealant film using the above-described vapor-deposited film, etc., the gas barrier properties such as oxygen permeability and water vapor permeability were measured. An average gas barrier property could not be achieved.

  In other words, as a condition to be used as a packaging material that requires a high level of gas barrier properties, it is transparent enough to allow the contents to be directly seen through, and is equivalent to a metal foil that blocks gases that affect the contents. A high gas barrier property is required.

The present invention has been made in consideration of the above technical background, and provides a transparent laminate having a high level of gas barrier properties comparable to that of a metal foil and a highly practical content storage suitability, and a method for producing the same. For the purpose.

As a means for achieving the above object, the invention according to claim 1 is a transparent laminate having a content storage suitability formed by forming at least a gas barrier coating layer on a transparent plastic substrate,
As the gas barrier coating layer, a coating agent having at least one of a hydroxyl group-containing polymer compound, a metal alkoxide and / or a hydrolyzate thereof and / or a polymer thereof as a component is applied, dried by heating, and treated with water. It is a transparent laminate having a content storage suitability characterized by being subjected to the above.

  The invention according to claim 2 is the transparent laminate having the content storage suitability according to claim 1, wherein the water treatment sprays water on the gas barrier coating layer.

  According to a third aspect of the present invention, at least one surface of the transparent plastic substrate is subjected to a pretreatment by reactive ion etching (RIE) using plasma, and a transparent vapor-deposited thin film layer made of an inorganic oxide is formed thereon, 3. The transparent laminate having contents storage suitability according to claim 1, wherein the gas barrier coating layer is sequentially laminated and the gas barrier coating layer is subjected to water treatment.

  The invention according to claim 4 is characterized in that the hydroxyl group-containing polymer compound has at least one of polyvinyl alcohol or poly (vinyl alcohol-co-ethylene), cellulose, and starch as a component. 3. A transparent laminate having the content storage suitability described in any one of 3 above.

  The invention according to claim 5 is characterized in that the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof, and the content storage suitability according to any one of claims 1 to 4 It is a transparent laminated body which has.

  The invention according to claim 6 is characterized in that the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof, and the content storage suitability according to any one of claims 1 to 4 It is a transparent laminated body which has.

  The invention according to claim 7 is characterized in that the content storage suitability according to any one of claims 1 to 6, wherein nitrogen gas is introduced into the apparatus when the transparent vapor-deposited thin film layer is laminated. It is a transparent laminate having.

Invention of Claim 8 is a manufacturing method of the transparent laminated body which has the content preservation | save property of any one of Claim 1 thru | or 7, Comprising:
After applying a coating agent containing at least one of hydroxyl group-containing polymer compound, metal alkoxide and / or hydrolyzate thereof and / or polymer thereof as a component to at least a gas barrier coating layer on a transparent plastic substrate, and then heating It is a method for producing a transparent laminate having contents storage suitability, characterized in that the gas barrier coating layer is dried and subjected to water treatment in which water is sprayed onto the gas barrier coating layer.

According to the ninth aspect of the present invention, at least one surface of the transparent plastic substrate is subjected to pretreatment by reactive ion etching (RIE) using plasma, and nitrogen gas is introduced into the vapor deposition apparatus thereon. 9. A transparent vapor-deposited thin film layer made of an inorganic oxide is laminated, the gas barrier coating layer is sequentially laminated on the transparent vapor-deposited thin film layer, and the gas barrier coating layer is subjected to water treatment. It is a manufacturing method of the transparent laminated body which has the content storage suitability of description.

  ADVANTAGE OF THE INVENTION According to this invention, the transparent laminated body which has the content preservation aptitude, and its manufacturing method can be provided. The transparent laminate having the content storage suitability of the present invention provides a versatile packaging material that is excellent in transparency and allows the contents to be confirmed through the laminate packaging material and has a high gas barrier property similar to that of a metal foil. Therefore, it can be widely used as a packaging material in the packaging field and the electronic equipment field.

  An example of an embodiment of the present invention will be described in more detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of a transparent laminate having contents storage suitability of the present invention.

  First, the transparent laminated body of this invention of FIG. 1 is demonstrated. The substrate (1) in FIG. 1 is a film made of a transparent plastic material, and at least one surface thereof is subjected to pretreatment (2) by RIE using plasma. And the vapor deposition thin film layer (3) and gas barrier film layer (4) which consist of inorganic oxides are laminated | stacked in order on the processing surface or both surfaces.

  The 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, etc. The biodegradable plastic film or the like is used, and 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 base material (1) has a thickness of 1 μm or more, suitability as a packaging material, may be laminated with other layers, a vapor-deposited thin film layer (3) made of an inorganic oxide, a gas barrier coating layer (4) In consideration of the workability when forming the film, 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, it is desirable to use a long film so that each layer can be formed continuously.

In general, as a packaging material, the substrate (1) is often a polyester film. As a polyester film usable in the present invention, the storage elastic modulus at a temperature of −20 ° C. to + 40 ° C. is in the range of 9 × 10 ⁸ to 1 × 10 ¹⁰ Pa, and the β transition tan δ peak temperature is + 10 ° C. or less. There is no particular limitation as long as it is a polyester film having a recognized dynamic viscoelasticity. When the storage elastic modulus is less than 9 × 10 ⁸ Pa, the flexibility of the polyester film is insufficient, and impact resistance and pinhole resistance equivalent to those of the polyamide film cannot be obtained. On the other hand, when the storage elastic modulus exceeds 1 × 10 ¹⁰ Pa, the flexibility is sufficient, but the handling property as a stretched film is inferior. Furthermore, when the peak temperature due to the β transition of the polyester film 1 is not observed at + 10 ° C. or lower, the molecular chain cannot respond to an external load in the low temperature region, so that deformation in the low temperature region becomes difficult, and in the low temperature region Insufficient bending pinhole resistance. Moreover, it is preferable that it is a transparent film base material if possible in order to make use of transparency of a vapor deposition thin film layer.

  Examples of the polyester film under the above conditions include, for example, terephthalic acid, naphthalenecarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfone as dicarboxylic acid components constituting the polyester. Aromatic dicarboxylic acids such as isophthalic acid and phthalic acid, alicyclic dicarboxylic acids such as cyclohexyne dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid and fumaric acid And oxycarboxylic acids such as p-oxybenzoic acid. As alcohol components, aliphatic glycols such as ethylene glycol, propanediol, 1,4 butanediol, 1,6 hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,4 cyclohexanedimethanol And polyoxyalkylene glycols, aromatic glycols such as bisphenol A and bisphenol S, and derivatives thereof. Among these polyesters, those mainly composed of polyethylene terephthalate are preferred from the viewpoints of film forming properties such as biaxial stretching properties, humidity properties, heat resistance, chemical resistance, and low cost, and various excellent properties of polyethylene terephthalate. Within the range where physical properties can be maintained, other alcohol components are controlled to be incorporated into the main chain in the polymerization stage, and by copolymerization, a segment with a little rotational hindrance (soft segment) is formed in the molecular chain, and impact from the outside The bending force is absorbed by the soft segment in the molecular chain, resulting in excellent impact resistance and flexibility. A copolymerized polyester in which 50 mol% or more of each of the carboxylic acid component and the alcohol component of the polyester of the present invention is terephthalic acid, ethylene glycol, and derivatives thereof is preferably used.

  Regarding the stretching ratio of the polyester film, there are a sequential biaxial stretching process and a simultaneous biaxial stretching process, and the stretching ratio (vertical stretching ratio × horizontal stretching ratio) is preferably 5 to 20 times. Moreover, it is preferable that the hot-water heat shrinkage rate on 120 degreeC 30 minute conditions at the time of forming into a film on the said conditions shall be 4% or less in MD / TD direction. If it exceeds 4%, the shrinkage is large, and the deterioration of the gas barrier property after post-processing becomes large.

  In order to improve the adhesion between the substrate (1) and the transparent vapor-deposited thin film layer (3) made of an inorganic oxide, the surface is subjected to a pretreatment (2) by reactive ion etching (RIE) using plasma. By performing this RIE treatment, the generated radicals and ions are used to cause chemical effects such as imparting functional groups to the surface of the substrate (1), and the surface is ion etched to scatter impurities and the like. It is possible to simultaneously obtain two physical effects such as smoothing. By performing such surface treatment, a dense thin film of inorganic oxide can be formed in the next vapor deposition step. As a result, the adhesion between the base material (1) and the vapor-deposited thin film layer (3) made of an inorganic oxide can be strengthened, leading to improvements in gas barrier properties and moisture resistance and prevention of cracks in the vapor-deposited thin film layer. It is.

  There is no limitation on the method of performing the RIE processing with a winding-type in-line apparatus, but a method of performing processing using a plasma processor is common.

  Argon, oxygen, nitrogen, hydrogen, nitrous oxide, and helium can be used as gas species for performing the pretreatment by RIE. These gases may be used alone, or two or more kinds of gases may be mixed and used. Moreover, you may process continuously using several processor. At this time, it is not necessary to use the same plurality of processors.

The type of gas to be used is determined by the energy given, effects, and ease of handling.

  The processing conditions for the pretreatment by RIE can be indicated by processing speed, energy level, and the like, and are set as appropriate according to the composition of the substrate (1), application, discharge device characteristics, and the like. However, it is preferable that the self-bias value of the plasma is 200 V or more and 2000 V or less, and even if the value is slightly lower than 200 V, it is possible to develop a certain degree of adhesion, but it has an advantage over the untreated one. Low. Moreover, when it is a high value exceeding 2000V, a strong process will be applied too much, the surface of a base material (1) will deteriorate, and it will become a cause by which adhesiveness falls. Regarding the gas used for plasma and its mixing ratio, etc., the flow rate differs depending on the pump performance, the mounting position, and the like, so that the flow rate differs depending on the film composition, application, and apparatus characteristics.

  The vapor-deposited thin film layer (3) made of an inorganic oxide is made of a vapor-deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof, and has transparency and oxygen, water vapor, etc. Any gas barrier property may 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 vapor-deposited thin film layer (3) made of the inorganic oxide of the present invention is not limited to the inorganic oxide described above, and any material that meets the above conditions can be used.

  The optimum thickness of the vapor-deposited thin film layer (3) made of an inorganic oxide varies depending on the type and configuration of the inorganic compound used, but is generally preferably in the range of 5 to 300 nm, and the value is appropriately selected. The However, if the film thickness 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. On the other hand, when the film thickness exceeds 300 nm, flexibility cannot be maintained in the thin film, and the thin film may be cracked due to external factors such as bending and pulling after the film formation. Preferably, it exists in the range of 5-100 nm.

  There are various methods for forming the deposited thin film layer (3) made of an inorganic oxide on the pretreatment (2) layer by reactive ion etching (RIE) using plasma, and it is formed by a normal vacuum deposition method. However, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition (CVD) 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, and in order to improve the adhesion between the thin film and the substrate and the denseness of the thin film, An ion beam assist method can also be used. In addition, in order to increase the transparency of the deposited film, it is possible to carry out reactive deposition by blowing oxygen gas or the like during deposition.

  One feature of the present invention is that nitrogen gas is introduced into the apparatus during the vapor deposition. By introducing nitrogen gas, physical and chemical effects such as repair of an incomplete portion of the vapor deposition layer and efficient reaction between aluminum and oxygen gas can be expected.

  Various methods can be considered for introduction to the equipment, but it is also introduced as a mixed gas with the introduced oxygen gas, the introduction is pure nitrogen gas, but the piping uses the same pipe as oxygen gas, completely new nitrogen gas Although introduction with a pipe for introduction is conceivable, it is not particularly limited.

  The amount introduced is related to the degree of vacuum (exhaust capacity of the apparatus). Nitrogen gas was introduced so as not to impair the degree of vacuum in the apparatus exhibiting gas barrier properties, and O2 / N2 was selected as a reaction gas for vapor deposition.

  The gas barrier coating layer (4) is provided on the vapor-deposited thin film layer (3) made of an inorganic oxide in order to impart a high level of gas barrier properties similar to metal foils and to physically protect the vapor-deposited thin film layer. It is what

  In order to achieve this, the gas barrier coating layer (4) is formed using a gas barrier coating agent mainly composed of a hydroxyl group-containing polymer or one or more metal alkoxides and hydrolysates. Each component contained in the gas barrier coating agent will be described in more detail.

  The hydroxyl group-containing polymer used for the gas barrier coating agent in the present invention refers to polyvinyl alcohol (hereinafter abbreviated as PVA) or poly (vinyl alcohol-co-ethylene), cellulose, and starch. In particular, PVA is excellent in handling property and gas barrier property improvement in this application, but is not limited thereto. PVA here is generally obtained by saponifying polyvinyl acetate. Examples of the PVA include, but are not limited to, complete PVA in which only a few percent of acetic acid groups remain from a so-called partially saponified PVA in which several tens of percent of acetate groups remain.

  Further, although there are various metal alkoxides, silicon alkoxides are preferable in view of handling properties and cost. In addition, if there is a demand for improving the flexibility and adhesion of the coating, it is preferable to appropriately add a so-called silane coupling agent without being limited to tetraalkoxide.

  For the coating method of the coating agent, conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method, a gravure printing method and the like that are usually used can be used. The thickness of the coating varies depending on the type of coating agent, processing machine, and processing conditions. When the thickness after drying is 0.01 μm or less, a uniform coating film may not be obtained and sufficient gas barrier properties may not be obtained. Further, when the thickness exceeds 50 μm, there is a problem because cracks are likely to be generated in the film. It is preferably in the range of 0.01 to 50 μm, more preferably in the range of 0.1 to 10 μm. In particular, in the case of electron beam curing, the balance between the film thickness of the gas barrier coating layer (4), the electron beam energy conditions, the processing speed, and the charge removal is important. Excessive energy supply causes charging, and care must be taken because the resulting discharge may impair the barrier properties.

  The layer which is the most characteristic in the present invention is a layer which sprays water vapor after applying and drying the gas barrier coating layer (4) (water treatment surface (5)). Various possible methods are conceivable on the apparatus, and the method is not particularly limited. However, since a thickness sufficient to form a layer is not required, a spray method is considered appropriate.

  Based on this, it is considered that 0.01 to 0.1 g / m 2 is appropriate for the application amount by spraying. If it is 0.01 g or less, there is a depletion effect and an effect cannot be expected. When it is 0.1 g or more, there is a high possibility of affecting the gas barrier coating layer (4).

  The temperature of the water vapor sprayed is not particularly limited. Although it is a vapor | steam, it does not need to be around 100 degreeC, and if a water molecule exists, there is no problem.

  As a phenomenon that may occur, it is conceivable that water molecules make the surface of the gas barrier coating layer (4) uniform and dense.

  Expected effects are water vapor barrier property UP and content suitability UP for liquid content.

  The heat seal layer (6) is provided as an adhesive layer when forming a bag-like 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 or the like in which a film-like material made of the above resin is bonded using an adhesive such as a two-component curable urethane resin. be able to.

  The transparent laminate having a high water vapor barrier property of the present invention will be further described with reference to specific examples.

<Example 1>
Storage modulus at −20 ° C. and + 40 ° C. when dynamic viscoelasticity measurement was performed under the measurement conditions of a frequency of 1 Hz, a heating rate of 2 ° C./min, and a measurement temperature range of −150 to + 150 ° C. Are 3.5 × 10 ⁹ Pa and 3.2 × 10 ⁹ Pa, respectively, and are observed at a peak temperature of 0.6 ° C. of β transition tan δ, warp stretching 3.5 times, horizontal stretching 3.5 times, heat treatment A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm formed at a temperature of 220 ° C. was used. The hot water shrinkage of the PET film at 120 ° C. for 30 minutes was MD 3.0% and TD 2.1%. One side of this PET film was pretreated by RIE using a plasma processor. At this time, a high frequency power source having a frequency of 13.56 MHz was used for the electrodes, and an argon / oxygen mixed gas was used for the processing gas. The plasma self-bias value at this time was 680V. Subsequently, a transparent vapor deposition thin film layer made of aluminum oxide having a thickness of 15 nm was laminated on the pretreatment layer by RIE on an in-line by a vacuum vapor deposition apparatus by an electron beam heating method. During vapor deposition, nitrogen gas was introduced simultaneously with oxygen gas.

  Next, a coating agent having the following composition was applied by a gravure coating method and then dried at 120 ° C. for 1 minute to form a gas barrier coating layer (4) having a thickness of 0.5 μm. After drying at this time, the transparent laminate A of the present invention was obtained by uniformizing in the width direction and applying water at room temperature using a spray.

[Composition of gas barrier coating agent]
(A) Liquid and (b) liquid mixed at 60/40 by weight% (a) Liquid: 89.6 g of 0.1N hydrochloric acid was added to 10.4 g of tetraethoxysilane, and the mixture was stirred for 30 minutes for hydrolysis. Hydrolysis solution having a solid content of 3% by weight (in terms of SiO2) (b) Solution: water / isopropyl alcohol solution (water: isopropyl alcohol = 90: 10, weight ratio)

<Comparative Example 1>
A transparent laminate B was obtained in the same manner as in the transparent laminate of Example 1, except that water was not applied after drying the gas barrier coating layer (4).

<Comparative example 2>
A transparent laminate C was obtained in the same manner as in the transparent laminate of Example 1, except that nitrogen gas was not introduced during aluminum oxide vapor deposition.

<Comparative Example 3>
In the transparent laminate of Example 1, a transparent laminate D was obtained in the same manner except that the pretreatment by RIE was not performed and water was not applied after the gas barrier coating layer (4) was dried. .

<Comparative example 4>
In the transparent laminate of Example 1, the transparent laminate was similarly used except that no processing gas was used in the pretreatment by RIE and that no water was applied after drying the gas barrier coating layer (4). E was obtained.

<Comparative Example 5>
A transparent laminate F was obtained in the same manner as in the transparent laminate of Example 1, except that a 7 μm aluminum foil was used instead of the aluminum oxide deposited thin film layer (3).

<Evaluation 1>
For each of the laminates A to F of Examples 1 to 2 and Comparative Examples 1 to 4 using the high barrier transparent laminate of the present invention, the water vapor transmission rate (g / m ² · day) was measured as the moisture proof evaluation. did. The measurement results are shown in Table 1.

<Evaluation 2>
As an evaluation of the suitability of the contents of the examples and comparative examples, a 10 cm square pouch was made from a laminate obtained by dry laminating 30 μm CPP as a heat seal layer, and about 10 g of tap water was filled as the contents. The pouch was stored in an environment of 40 ° C.-20% RH, and the weight loss was measured. The quality was judged according to the situation. {(Low decrease amount) ◎>○>△> × (High decrease amount)}. The comparison results are also shown in Table 1.

<Evaluation 3>
As the workability evaluation of Examples and Comparative Examples, vapor deposition, coating, and post-processing (extrusion lamination) were targeted, and the quality was determined according to the situation. {(Good) ◎>○>△> × (Poor)}. The comparison results are also shown in Table 1.

<Evaluation 4>
As a waste evaluation of the examples and comparative examples, the quality was determined in the same manner as described above. {(Good) ◎>○>△> × (Poor)}. The comparison results are also shown in Table 1.

<Evaluation 5>
As the cost evaluation of the examples and comparative examples, the quality was determined in the same manner as described above from the viewpoint of materials, facilities, possible loss, and the like. {(Low) ◎>○>△> × (High)}. The comparison results are also shown in Table 1.

The transparent laminate having the shelf life of the present invention obtained in Example 1 has a high moisture-proof property (0.1 g / m ² / day or less), and has excellent transparency and content through the laminate packaging material. A versatile packaging material having a gas barrier property as high as that of a metal foil can be obtained, and can be widely used as a packaging material in the packaging field and the electronic equipment field.

It is a fragmentary sectional view of the transparent laminated body which shows an example of the transparent laminated body which has the content preservation | save ability of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Pretreatment surface 3 made of RIE Deposition thin film layer 4 made of inorganic oxide 4 Gas barrier coating layer 5 Water treatment surface 6 Heat seal layer 7 Transparent laminate

Claims (9)

A transparent laminate having a content storage suitability formed by forming at least a gas barrier coating layer on a transparent plastic substrate,
As the gas barrier coating layer, a coating agent having at least one of a hydroxyl group-containing polymer compound, a metal alkoxide and / or a hydrolyzate thereof and / or a polymer thereof as a component is applied, dried by heating, and treated with water. The transparent laminated body which has the preservability of the content characterized by being given.   The transparent laminate having contents storage suitability according to claim 1, wherein the water treatment sprays water on the gas barrier coating layer.   At least one surface of the transparent plastic substrate is pretreated by reactive ion etching (RIE) using plasma, and a transparent vapor-deposited thin film layer made of an inorganic oxide and the gas barrier coating layer are sequentially laminated thereon. And the transparent laminated body which has the water preservation | save property of Claim 1 or 2 formed by water-treating the gas-barrier film layer.   The hydroxyl group-containing polymer compound has at least one of polyvinyl alcohol or poly (vinyl alcohol-co-ethylene), cellulose, and starch as a component. A transparent laminate having the ability to preserve contents.   5. The transparent laminate having contents storage suitability according to claim 1, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.   6. The transparent vapor-deposited thin film layer made of an inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof, and has a thickness of 5 to 300 nm. The transparent laminated body which has the content preservation | save property as described in a term.   7. The transparent laminate having contents storage suitability according to any one of claims 1 to 6, wherein nitrogen gas is introduced into the apparatus when the transparent vapor-deposited thin film layer is laminated. A method for producing a transparent laminate having contents storage suitability according to any one of claims 1 to 7,
After applying a coating agent containing at least one of hydroxyl group-containing polymer compound, metal alkoxide and / or hydrolyzate thereof and / or polymer thereof as a component to at least a gas barrier coating layer on a transparent plastic substrate, and then heating A method for producing a transparent laminate having contents storage suitability, wherein the gas barrier coating layer is dried and subjected to water treatment for spraying water on the gas barrier coating layer. A transparent vapor deposition thin film made of an inorganic oxide while pretreating at least one surface of the transparent plastic substrate by reactive ion etching (RIE) using plasma and introducing nitrogen gas into the vapor deposition apparatus. 9. The contents storage suitability according to claim 8, wherein the gas barrier coating layer is sequentially laminated on the transparent vapor-deposited thin film layer, and the gas barrier coating layer is subjected to water treatment. A method for producing a transparent laminate.

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