JP2006168340A - Transparent gas barrier layered product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered product which is excellent in adhesion between a substrate film and a membrane comprising an inorganic oxide also after a processing such as printing working or the like, and excellent in a gas barrier nature which prevents permeation of oxygen gas or the like, in which there is little degradation of the gas barrier nature even if exposed to physical stress such as tension or the like, further which is excellent in transparency. <P>SOLUTION: The transparent gas barrier layered product comprises a layered product in which a plasma etching protection layer and a carbon content oxidation silicon layer are layered one by one to one surface of a substrate film, wherein the above plasma etching protection layer comprises a resin layer by a mixed resin composition including an acrylic based resin and a polyurethane based resin, further when the yellow degree of the above layered product obtained from a separate formula is (YI<SB>a</SB>) and the yellow degree of the above plasma etching protection layer coating substrate film obtained from the same separate formula is (YI<SB>b</SB>), the inequality of ΔYI(YI<SB>a</SB>-YI<SB>b</SB>)<0.6 is satisfied. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent gas barrier laminate, and more specifically, excellent adhesion between a base film and a carbon-containing silicon oxide layer even after processing such as printing, lamination, heat treatment, and the like. In addition, it has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., and even when exposed to physical stress such as tension, stagnation, and ironing, the gas barrier properties are less deteriorated, and the transparent gas barrier has excellent transparency. It relates to a conductive laminate.

Conventionally, as packaging materials for filling and packaging foods, beverages, chemicals, miscellaneous goods, etc., the permeation of oxygen gas, water vapor, etc. is blocked in order to prevent alteration, discoloration, etc. of the contents to be filled and packaged. A gas barrier substrate having various forms has been developed and proposed.
For example, an aluminum foil or a vapor-deposited film thereof has been proposed as the most typical one, but this one exhibits an extremely stable gas barrier property. There is a problem that it is inferior to incineration, and disposal processing after use is not easy, and there is also a problem that transparency is lacking.

In order to cope with this, for example, it is attempted to use a barrier resin film that blocks or prevents permeation of oxygen gas, water vapor, and the like made of polyvinylidene chloride resin, ethylene-vinyl alcohol copolymer, etc. It has been.
However, since the polyvinylidene chloride resin contains chlorine atoms in its structure, when it is incinerated as waste after use, harmful chlorine gas is generated, which is unfavorable for environmental hygiene.
On the other hand, the ethylene-vinyl alcohol copolymer has the advantages that the oxygen permeability is low and the adsorptivity of the flavor component is low, but there is a problem that the gas barrier property is remarkably lowered when it comes into contact with water vapor. .
For this reason, in order to block the ethylene-vinyl alcohol copolymer as a barrier base material from water vapor, it is necessary to make it a complicated laminated structure, and the fact is that the manufacturing cost is increasing.

Therefore, in recent years, a barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide has been provided as a gas barrier base material that stably exhibits high gas barrier properties and fragrance retention properties and has transparency. Barrier substrates have been developed and proposed.
Thus, as the gas barrier substrate, for example, plasma chemical vapor deposition is performed on one surface of a substrate film made of a resin film such as a polyester resin, a polyamide resin, or a polypropylene resin. An inorganic oxide such as silicon oxide is deposited by vapor deposition using a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. It is manufactured by providing a thin film of the inorganic oxide.
Specifically, on one surface of the substrate film, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen A vapor deposition layer made of an inorganic oxide such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using oxygen gas or the like as a supply gas and using a low temperature plasma generator or the like.
In addition, as the gas barrier substrate, for example, on one surface of a substrate film made of a resin film such as a polyester resin, a polyamide resin, or a polypropylene resin, for example, a vacuum deposition method, a sputtering method, An inorganic oxide such as silicon oxide and aluminum oxide is deposited by vacuum deposition using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as an ion plating method or an ion cluster beam method. It is manufactured by providing a thin film of the inorganic oxide.
Specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one surface of a base film, or a metal or metal oxide as a raw material Using an oxidation reaction deposition method in which oxygen is introduced to oxidize and vapor deposition is performed on one surface of the base film, and further, a plasma assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma, and the like. Can be formed.

However, in the above chemical vapor deposition method (CVD method), an inorganic oxide thin film is formed into an extremely thin film and has an advantage that excellent gas barrier performance can be obtained. There is a problem that the productivity is inferior to that of the PVD method (PVD method).
In the above chemical vapor deposition method (CVD method), it is necessary to increase the applied power in order to improve the film formation rate and increase the productivity. However, if excessive power is applied, the productivity is increased. Although the gas barrier performance can be improved, the surface of the base film is exposed to plasma at the same time as the deposition for the convenience of the film formation method. Therefore, yellowing due to excessive plasma etching on the base film and the weak interface layer There arises a problem that (WBL) is easily formed.
For this reason, in the gas-barrier base material manufactured above, the problem of appearance due to yellowing and the peel strength after lamination with other base materials due to the formation of the weak interface layer (WBL) Therefore, these problems are fatal drawbacks for the gas barrier base material as a packaging material and cannot be used.
Thus, for the purpose of improving the gas barrier performance and improving the adhesion strength between the base film and the thin film of the inorganic oxide, for example, a method of previously performing plasma pretreatment on the surface of the base film has been proposed. However, when aiming to alleviate excessive plasma etching as described above, the plasma pre-treatment has already added some damage to the surface of the base film, although this is a slight process. This is not preferable as a pretreatment for performing (CVD method).
Further, as an improvement of the gas barrier performance and the adhesion strength between the base film and the inorganic oxide thin film, for example, an anchor coating agent or a primer is previously applied to the surface of the base film. Many methods for coating agents and the like have been proposed.

For example, on at least one side of a stretched polyester film, 5 to 95% by weight of polyester is dispersed or dissolved in water or a solvent and mixed with 95 to 5% by weight of a compound having a carbon-carbon unsaturated bond and reacted. The product is applied and dried to form a product layer having a thickness of 0.01 to 5 μm, and a transparent thin film layer of silicon oxide having a thickness of 5 to 500 nm is formed on at least one side of the product layer. A transparent plastic film excellent in gas barrier properties, which is characterized in that it has been proposed, is proposed (for example, see Patent Document 1).
Further, it is a coated polyester film in which a resin coating layer is formed on at least one side of a base film made of a polyester resin, and the resin coating layer contains at least one segment having an ester bond in the molecule, and is insoluble in water. The thermoplastic resin is a polyester polyurethane, and the film made of the resin composition has a tensile progress ε (%) at 60 ° C. of 100 ≦ A coated polyester film in which ε ≦ 500 and the microdeformation recovery rate R shown in the following formula of the resin composition is 90% or more has been proposed (formula is omitted) (for example, patent document). 2).
Further, on at least one surface of the polyester film, a surface modification layer mainly composed of an aqueous self-emulsifying type thermoreactive urethane having a solvent swelling ratio of 50% or less and a water swelling ratio of 80% or less is further provided. A metal vapor-deposited polyester film characterized by providing a metal vapor-deposited layer on the surface modification layer has also been proposed (see, for example, Patent Document 3).
Next, in a configuration in which a transparent primer layer, a thin film layer made of an inorganic oxide having a thickness of 5 to 300 nm, and a gas barrier film layer are sequentially laminated on at least one surface of a base material made of a transparent plastic material, the gas barrier film layer is An aqueous solution or a water / alcohol mixed solution containing at least one of an aqueous polymer and (a) one or more metal alkoxides and hydrolysates thereof or (b) tin chloride. A highly adhesive high barrier transparent laminate characterized in that it is a layer formed by applying and drying by heating (see, for example, Patent Document 4).
Japanese Patent Publication No. 8-25244 (Claims) Japanese Patent No. 2570462 (Claims etc.) Japanese Patent No. 2964568 (claims, etc.) JP-A-9-327882 (Claims etc.)

However, in the inventions according to the above Patent Documents 1 to 4, the chemical vapor deposition method (CVD method) is mainly used, focusing on plasma etching of the base film, not only improving its gas barrier performance, Improvement of yellowing by plasma etching of base film, improvement of adhesion strength between base film and thin film layer made of inorganic oxide accompanying formation of weak interface layer (WBL), and other improvements are disclosed. There is nothing.
For example, in the above Patent Documents 1 to 4, as a method of forming a thin film made of an inorganic oxide, specifically, a thin film layer made of an inorganic oxide is formed by physical vapor deposition (PVD method). It is illustrated and the formation of a thin film layer made of an inorganic oxide by a chemical vapor deposition method (CVD method) is not intended at all.
Therefore, the present invention improves the influence of plasma etching on the base film when forming a thin film made of an inorganic oxide by chemical vapor deposition (CVD), yellowing, formation of a weak interface layer, The adhesion strength between the base film and the thin film layer made of inorganic oxide is improved. For example, even after processing such as printing, lamination, heat treatment, etc., the base film and the inorganic oxide It has excellent adhesion to the thin film, and has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., and even when exposed to physical stress such as tension, stagnation, and ironing, its gas barrier properties are less deteriorated. An object of the present invention is to provide a transparent gas barrier laminate having excellent transparency.

As a result of various studies to improve the influence of plasma etching on the base film when the inventor forms a thin film made of an inorganic oxide by the chemical vapor deposition method (CVD method) described above, In particular, an acrylic resin and a polyurethane resin are selected from the resin composition for forming a treatment layer, and both are included in combination, and the former is 50 to 80% by weight in terms of solid content, the latter However, paying attention to the mixed resin composition contained at a blending ratio of 20 to 50% by weight, first, on one surface of the base film, the acrylic resin and the polyurethane resin are included, and the solid content is In the former, a plasma etching protective layer comprising a resin layer made of a mixed resin composition containing 50 to 80% by weight of the latter and 20 to 50% by weight of the latter is provided, and then the plasma etching protective layer is provided. Using a base film, using at least two film forming chambers on the plasma etching protective layer, and forming at least one organic silicon compound in each chamber Using two or more film-forming mixed gas compositions prepared by changing the mixing ratio of each gas component of the film-forming mixed gas composition containing monomer gas, oxygen gas, and inert gas, It comprises two or more layers of carbon-containing silicon oxide layers formed by plasma chemical vapor deposition using a mixed gas composition for film formation, and each of the carbon-containing silicon oxide layers contains carbon atoms in the film. And a carbon-containing silicon oxide layer having a different carbon content for each carbon-containing silicon oxide layer, and further, the above-described base film, plasma etching protective layer and carbon-containing oxidation obtained from the formula described later Laminate silicon layers sequentially If yellowness of the laminate and (YI _a), was also yellowness below to above that obtained from the formula plasma etching protective layer covering the substrate film and _{(YI b), ΔYI (YI} a -YI b) <0 Produced a transparent gas barrier laminate satisfying .6, the effect of plasma etching on the base film was improved, the yellowing, the formation of a weak interface layer, and the thin film layer composed of the base film and an inorganic oxide. The adhesion strength is improved, the adhesion between the base film and the carbon-containing silicon oxide layer is excellent, and the carbon-containing silicon oxide layer is excellent in spreadability, flexibility, flexibility, etc. From the above, it is possible to form a film having an extremely excellent high barrier property and to continuously form a carbon-containing silicon oxide layer using a plasma chemical vapor deposition apparatus comprising at least two film forming chambers. Laminate two or more layers in In addition, since each layer can form a film having a high barrier property, it is possible to obtain a gas barrier property higher than that of a single layer, and further, a continuous production that opens to the atmosphere. By forming a film, it is possible to prevent foreign matter, dust, and the like that cause cracks from entering between the film-forming layers, and no deterioration of the gas barrier property is observed. Further, each carbon-containing silicon oxide Since the layer is a discontinuous layer containing carbon atoms in the film and having a different carbon content for each carbon-containing silicon oxide layer, it can completely prevent transmission of oxygen gas, water vapor, and the like. For example, as a barrier base material used for packaging materials, etc., it is excellent in gas barrier property that prevents permeation of oxygen gas, water vapor, etc., and further, a very useful barrier that does not show a decrease in performance of the gas barrier property And it completed the present invention have found that it is possible to produce a sex film.

That is, the present invention comprises a laminate in which a plasma etching protective layer and a carbon-containing silicon oxide layer are sequentially laminated on one surface of a base film, and the plasma etching protective layer comprises an acrylic resin and polyurethane. A resin layer comprising a mixed resin composition containing a resin and a solid content, the former being 50 to 80% by weight and the latter being 20 to 50% by weight. the above laminate yellowness more obtained (YI _a), similarly yellowness of the plasma etching protection layer coated substrate film obtained from the following equation when the _{(YI b), ΔYI (YI} a -YI _b) <transparent gas barrier laminate and satisfying 0.6, further, the transparent gas barrier laminate of the above, the carbon-containing silicon oxide layer described above, at least two or more rooms Made in Each of the mixed gas composition for film formation containing a monomer gas for film formation, oxygen gas, and an inert gas composed of at least one organic silicon compound is used for each chamber. Two or more plasma chemical vapor deposition methods using two or more film-forming mixed gas compositions prepared by changing the mixing ratio of gas components, and using each of the film-forming mixed gas compositions to form a film And each carbon-containing silicon oxide layer contains carbon atoms in the film, and each carbon-containing silicon oxide layer has a different carbon content. The present invention relates to a transparent gas barrier laminate.
Yellowness (YI): YI = 100 (1.28X-1.06Z) / Y
(However, in the formula, X, Y, and Z represent the three-color stimulus values X, Y, and Z of the CIS-XYZ color system.)

The present invention improves the influence of plasma etching on the base film by providing a plasma etching protective layer on one side of the base film, and its yellowing, formation of weak interface layer, base film and inorganic oxidation The adhesion strength with a thin film layer made of a material is improved, and the adhesion between the base film and the carbon-containing silicon oxide layer is extremely excellent.
Further, the present invention can form a carbon-containing silicon oxide layer excellent in high barrier properties from the first layer, and can be formed into a plasma chemical vapor phase comprising at least two film forming chambers. Two or more carbon-containing silicon oxide layers are continuously laminated using a growth apparatus, and each layer can form a film having a high barrier property. Furthermore, a higher gas barrier property can be obtained.
Furthermore, the present invention can prevent foreign matter, dust, and the like causing cracks from entering between the film forming layers by continuously forming the film that is open to the atmosphere, and its gas barrier properties. A decrease in the temperature is not recognized.
Further, according to the present invention, each carbon-containing silicon oxide layer is a discontinuous layer containing carbon atoms in the film and having different carbon contents for each silicon oxide layer. And the like can be completely prevented.
Thus, the present invention has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., for example, as a barrier substrate used for packaging materials, etc. Furthermore, it is extremely useful in that no deterioration in gas barrier performance is observed.

The transparent gas barrier laminate according to the present invention will be described below in more detail with reference to the drawings.
1 and 2 are schematic cross-sectional views showing two examples of the layer structure of the transparent gas barrier laminate according to the present invention, and FIGS. 3 and 4 show the transparent gas barrier laminate according to the present invention. It is a schematic block diagram which shows the schematic structure of one example of the film forming apparatus of the carbon containing silicon oxide layer.

First, as the transparent gas barrier laminate A according to the present invention, as shown in FIG. 1, a laminate in which a plasma etching protective layer 2 and a carbon-containing silicon oxide layer 3 are sequentially laminated on one surface of a base film 1. Further, the plasma etching protective layer 2 includes an acrylic resin and a polyurethane resin, and the solid content is 50 to 80% by weight, and the latter is 20 to 50%. The plasma etching comprising the resin layer 2a of the mixed resin composition contained in a percentage by weight, and the yellowness (YI _a ) of the laminate 4 obtained from the following formula, which is also obtained from the following formula When the yellowness (YI _b ) of the protective layer 2-coated base film 1 is used, the basic structure is a structure characterized by satisfying ΔYI (YI _a −YI _b ) <0.6. .
Yellowness (YI): YI = 100 (1.28X-1.06Z) / Y
(However, in the formula, X, Y, and Z represent the three-color stimulus values X, Y, and Z of the CIS-XYZ color system.)

Thus, specific examples of the transparent gas barrier laminate according to the present invention include a plasma etching protective layer 2 and a carbon-containing silicon oxide layer 3 on one surface of the base film 1 as shown in FIG. The plasma etching protective layer 2 comprises an acrylic resin and a polyurethane resin, and the former is 50 to 80% by weight and the latter is the latter. Is formed of a resin layer 2a of a mixed resin composition containing 20 to 50% by weight, and the carbon-containing silicon oxide layer 3 uses at least two film forming chambers, and each chamber Prepared by changing the mixing ratio of each gas component of the mixed gas composition for film formation containing at least one kind of organosilicon compound, oxygen gas, and inert gas for each film For film formation of 2 or more A carbon-containing silicon oxide layer 3a, 3b, 3c formed by plasma chemical vapor deposition using two or more layers formed using a mixed gas composition and a mixed gas composition for film formation thereof; and Each of the carbon-containing silicon oxide layers 3a, 3b, 3c contains carbon atoms in the film, and the carbon-containing silicon oxide layer 3a has a different carbon content for each of the carbon-containing silicon oxide layers 3a, 3b, 3c. 3b and 3c, and the yellowness (YI _a ) of the laminate 4 obtained from the following formula, and the yellow color of the plasma etching protective layer 2 coated base film 1 obtained from the following formula. A transparent gas barrier laminate A ₁ characterized by satisfying ΔYI (YI _a −YI _b ) <0.6 in the case of the degree (YI _b ) can be exemplified.
Yellowness (YI): YI = 100 (1.28X-1.06Z) / Y
(However, in the formula, X, Y, and Z represent the three-color stimulus values X, Y, and Z of the CIS-XYZ color system.)

Next, in the present invention, the method for producing the transparent gas barrier laminate according to the present invention, materials used, and the like will be described. First, in the present invention, the transparent gas barrier laminate according to the present invention is described. Explaining the constituent base film, the base film is excellent in chemical or physical strength, withstands the conditions for forming a plasma etching protective layer or a carbon-containing silicon oxide layer, and the like. A resin film or sheet that can be satisfactorily maintained without impairing film properties such as a plasma etching protective layer and a carbon-containing silicon oxide layer can be used.
Thus, in the present invention, as the resin film or sheet, specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene Copolymer (AS resin), acrylonitrile loop tagene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, various nylons, etc. Various resin films or sheets such as polyamide resins, polyurethane resins, acetal resins, cellulose resins, and the like can be used.
In the present invention, among the above-described resin films or sheets, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, extrusion method, cast molding method, T-die method, cutting method, inflation method, Using other film-forming methods, a method for forming the above-mentioned various resins alone, or a method for forming a multi-layer co-extrusion film using two or more types of resins, Using two or more kinds of resins, by mixing and forming a film before forming a film, various resin films or sheets are produced, and if necessary, for example, a tenter method, or Various resin films or sheets that are stretched uniaxially or biaxially using a tubular method or the like can be used.
In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

In addition, when using one or more of the above-mentioned various resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can be used.

Next, in the present invention, the plasma etching protective layer constituting the transparent gas barrier laminate according to the present invention will be described. As the plasma etching protective layer, a carbon-containing silicon oxide layer is formed by plasma chemical vapor deposition. To improve the influence of plasma etching on the base film and prevent the base film from turning yellow, forming a weak interface layer on the base film surface, etc. It is provided to improve the adhesion strength with the silicon layer.
Thus, in the present invention, the plasma etching protective layer includes an acrylic resin, specifically, one or more water-soluble or water-dispersible acrylic resins, a polyurethane resin, specifically Includes one or more water-soluble or water-dispersible polyurethane-based resins and has a solid content of 50 to 80% by weight of the former and 20 to 50% by weight of the latter. It consists of the resin layer by the mixed resin composition containing.

  In the above, as the water-soluble or water-dispersible acrylic resin, for example, an acrylic or methacrylic resin composed mainly of an alkyl acrylate and / or an alkyl methacrylate and a copolymer of this with another monomer. Resin can be used. Specifically, the blending ratio of the alkyl acrylate and / or alkyl methacrylate component is 40 to 80 mol%, and the copolymerizable vinyl monomer component content is 20 to 60 mol%. It is preferable to use a water-soluble or water-dispersible acrylic or methacrylic resin having a proportion.

As a vinyl monomer copolymerizable with the above alkyl acrylate and / or alkyl methacrylate and having a functional group, hydrophilicity is imparted to the resin to improve the water dispersibility of the resin, and further, a base film, carbon What has a functional group which makes adhesiveness with a containing silicon oxide layer etc. favorable, and makes affinity with the water-soluble or water-dispersible polyurethane resin mixed is preferable.
Thus, examples of the functional group include a carboxyl group, an acid anhydride group, a sulfonic acid group or a salt thereof, an amide group or an alkylmethylolated amide group, an amino group (including a substituted amino group), an alkyl group. Examples thereof include a methylolated amino group or a salt thereof, a hydroxyl group, and an epoxy group, and a carboxyl group, an acid anhydride group, an epoxy group, and the like are particularly preferable.
Two or more kinds of these groups may be contained in the resin.

  In the present invention, when the alkyl acrylate and / or the alkyl methacrylate is 40 mol% or more, the coating property, the strength of the coating film, and the blocking resistance are particularly favorable, and the alkyl acrylate and / or Or, by making alkyl methacrylate 80 mol% or less and introducing 20 mol% or more of a compound having a specific functional group into the acrylic resin as a copolymerization component, it becomes easy to make water-soluble or water-dispersible and stabilize its state over a long period of time. Improvement of adhesion between the resin layer and the base film, improvement of the strength, water resistance, and chemical resistance of the resin layer by reaction in the resin layer, and further, the base film in the present invention and others It is possible to improve the adhesiveness with other materials.

  In the above, examples of the alkyl group of alkyl acrylate and alkyl methacrylate include, for example, methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 2-ethylhexyl group, lauryl group, stearyl group, and cyclohexyl group. Etc.

Next, in the above vinyl monomer, examples of the compound having a carboxyl group or an acid anhydride include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and alkali metals thereof. Examples thereof include salts, alkaline earth metal salts, ammonium salts, and maleic anhydride.
Examples of the compound having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, metal salts such as sodium of these sulfonic acids, ammonium salts, and the like.
Next, as a compound having an amide group or an alkylmethylolated amide group, acrylamide, methacrylamide, N-methylmethacrylamide, methylolated acrylamide, methylolated methacrylamide, ureido vinyl ether, β-ureido isobutyl vinyl ether, ureidoethyl An acrylate etc. are mentioned.
Further, compounds having an amino group or an alkylmethylolated amino group or a salt thereof include diethylaminoethyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, dimethylaminoethyl methacrylate, dimethyl Examples include aminoethyl vinyl ether, those obtained by methylolation of those amino groups, quaternization with alkyl halide, dimethyl sulfate, sultone, and the like.
Examples of the compound having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, β-hydroxyvinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, Examples include polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate.
Furthermore, examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

  Furthermore, in the present invention, examples of vinyl monomers that can be used in combination include acrylonitrile, methacrylonitrile, styrenes, butyl vinyl ether, maleic acid mono- or dialkyl esters, fumaric acid mono- or dialkyl esters, itaconic acid mono- or dialkyls. Examples thereof include esters, methyl vinyl ketone, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl pyridine, vinyl pyrrolidone, and vinyl trimethoxysilane.

Thus, in the present invention, the acrylic resin can be produced using a conventionally known polymerization method.
Specifically, for example, radical polymerization is initiated by polymerization initiators such as peroxides and azo compounds, heat, ultraviolet rays, radiation, etc. to produce a high molecular weight polymer. , Bulk polymerization, solution polymerization, suspension polymerization, etc.

Next, in the above, the water-soluble or water-dispersible polyurethane resin is produced, for example, by reacting a polyhydroxy compound and a polyisocyanate compound according to a conventional method.
As the water-soluble or water-dispersible polyurethane-based resin, for example, a resin containing a carboxyl group or a salt thereof is preferable in order to increase the affinity with an aqueous medium or increase the reactivity with the acrylic resin. .

  Examples of the polyhydroxy compound include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaprolactone, Examples include polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, and glycerin.

  Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, an adduct of tolylene diisocyanate and trimethylol propane, an adduct of hexamethylene diisocyanate and trimethylol ethane, and the like. It is done.

  In the present invention, the introduction of a carboxyl group into the side chain of the polyurethane constituting the water-soluble or water-dispersible polyurethane resin is, for example, a carboxyl group-containing polyhydroxy compound as one of the raw material polyhydroxy compounds during polyurethane synthesis. Or by reacting a hydroxyl group-containing carboxylic acid or amino group-containing carboxylic acid with an isocyanate group of a polyurethane having an unreacted isocyanate group, and then adding the reaction product to an alkaline aqueous solution under high-speed stirring. It can be easily performed by a method such as summing.

Examples of the carboxyl group-containing polyhydroxy compound include dimethylolpropionic acid, dimethylolacetic acid, dimethylolvaleric acid, trimellitic acid bis (ethylene glycol) ester, and the like.
Examples of the hydroxyl group-containing carboxylic acid include 3-hydroxypropionic acid, γ-hydroxybutyric acid, p- (2-hydroxyethyl) benzoic acid, malic acid, and the like, and amino group-containing carboxylic acid. Examples thereof include β-aminopropionic acid, γ-aminobutyric acid, P-aminobenzoic acid, and the like.

Next, in the present invention, an acrylic resin as described above, specifically, one or more water-soluble or water-dispersible acrylic resins, and a polyurethane resin, specifically water-soluble or One or more water-dispersible polyurethane resins are used, and these are mixed at a solid content, the former being 50 to 80% by weight, and the latter being mixed in a proportion of 20 to 50% by weight, Furthermore, if necessary, a required additive is arbitrarily added, and further, water or a solution containing water is added and sufficiently stirred and mixed to prepare a mixed resin composition.
In the above mixed resin composition, when the acrylic resin and the polyurethane resin are mixed in a solid content, the former is blended at 50 to 80% by weight and the latter is blended at a blending ratio of 20 to 50% by weight. If the resin is less than 50% by weight, the reason is not clear, but it is not preferable because the tendency of the gas barrier performance to decrease is seen, and if it exceeds 80% by weight, the slipperiness of the film is too good, Problems such as meandering occur at the time of winding the film, and there is also a problem that adhesion to the carbon-containing silicon oxide layer is lower than that of the urethane-based resin, which is not preferable.
On the other hand, if the polyurethane resin is less than 20% by weight, it is not preferable because there is a problem that the color of the film surface after plasma etching becomes deep, and if it exceeds 50% by weight, the slipping property of the film is unfavorable. It is bad, and there is a problem that wrinkles easily enter during the winding process, and the heat resistance of the carbon-containing silicon oxide layer is insufficient, and there is a problem that gas barrier properties and the like are lowered, which is not preferable. .

In the above mixed resin composition, the required additives include, for example, inorganic fine particles, for example, silica, silica sol, alumina, alumina sol, zirconium sol, kaolin, talc, for the purpose of improving adhesion and slipperiness. Calcium carbonate, titanium oxide, barium salt, carbon black, molybdenum sulfide, antimony oxide sol, and the like can be used.
Furthermore, in the present invention, an antifoaming agent, a coating property improver, a thickener, an antistatic agent, an organic lubricant, an organic polymer particle, an antioxidant, an ultraviolet absorber, and a foaming agent, as necessary. , Dyes and pigments can also be used.
In the present invention, in order to modify the film quality of the plasma etching protective layer according to the present invention, for example, a saturated or unsaturated polyester resin, polyamide resin, various vinyl resins, and other An acrylic resin or a polyurethane resin can also be added.
Furthermore, in the present invention, if necessary, the reactivity between the acrylic resin and the polyurethane resin is increased, and the adhesion (blocking property), water resistance, solvent resistance of the plasma etching protective layer made of the resin layer is increased. In order to improve the properties and mechanical strength, epoxy-based crosslinking agents, methylolated or alkylmethylolated urea-based, melamine-based, guanamine-based, acrylamide-based, polyamide-based amino compounds, aziridine compounds, block polyisocyanate compounds, Silane coupling agents, titanium coupling agents, zirco aluminate coupling agents, peroxides, photoreactive vinyl compounds, photosensitive resins, and the like can also be used.

Next, in the present invention, the above mixed resin composition is used, and this is applied to one side of the above-mentioned base film, for example, reverse roll coat, gravure roll coat, kiss roll coat, squeeze roll. -Using known coating methods such as coat, rod coat, air doctor coat, dip coat, etc., or known printing methods such as gravure printing, offset printing, transfer printing, etc. Then, it is coated or printed, then subjected to heat treatment, etc., and dried, and further, if necessary, subjected to aging treatment, etc., according to the present invention comprising the resin layer of the above mixed resin composition A plasma etching protective layer can be formed.
In the present invention, when the plasma etching protective layer is formed on the base film as described above, for example, the mixed resin composition is coated or printed on a base film uniaxially stretched in the longitudinal direction. The plasma etching protective layer according to the present invention can be formed on one surface of the base film by further stretching in the transverse direction in a dry or undried state and then applying a heat treatment.

The film thickness of the plasma etching protective layer is desirably in the range of about 0.01 to 5 μm, and preferably in the range of 0.02 to 1 μm in a dry state.
In the above, when the film thickness is less than 0.01 μm, it is difficult to form a plasma etching protective layer composed of a uniform resin layer. This is not preferable because the film tends to be difficult to handle. In the above, the surface of the base film can be optionally subjected to pretreatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., if necessary.

Next, in the present invention, the carbon-containing silicon oxide layer constituting the transparent gas barrier laminate according to the present invention will be described. The carbon-containing silicon oxide layer has a gas barrier performance that blocks and blocks permeation of oxygen gas, water vapor, and the like. And can be manufactured by a method of forming a silicon oxide layer using, for example, chemical vapor deposition or the like. Specifically, for example, plasma chemical vapor deposition, thermochemistry It can be produced by forming a silicon oxide layer by using a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor deposition method or a photochemical vapor deposition method. Of these, it is particularly desirable to produce a film by using a low temperature plasma chemical vapor deposition method.
In the present invention, specifically, on the plasma etching protective layer provided on one surface of the base film, a film-forming monomer gas composed of one or more organic silicon compounds is used as a raw material, and a carrier gas. As a low temperature plasma chemical vapor deposition method using an inert gas such as argon gas or helium gas, further using an oxygen gas as an oxygen supply gas, and using a low temperature plasma generator or the like The carbon-containing silicon oxide layer according to the present invention can be manufactured by forming a silicon oxide layer made of silicon oxide or the like into a film.
In the above, for example, high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, highly active and stable plasma is obtained. Therefore, it is desirable to use a high-frequency plasma generator.

Specifically, a method for forming a carbon-containing silicon oxide layer according to the present invention will be described. FIG. 3 shows a low-temperature plasma chemical vapor deposition apparatus for forming a carbon-containing silicon oxide layer by plasma chemical vapor deposition. It is a schematic block diagram which shows the outline | summary.
In the present invention, as shown in FIG. 3, the plasma chemical vapor deposition apparatus 11 includes a base film supply chamber 12, a first film formation chamber 13, a second film formation chamber 14, and a third film formation. And a winding chamber 16 for winding the transparent gas barrier laminate according to the present invention in which a carbon-containing silicon oxide layer is formed and overlaid on the plasma etching protective layer provided on the base film. The basic structure is what is done.
Thus, in the present invention, first, the base film 1 wound on the unwinding roll 17 and provided with the plasma etching protection layer on one surface thereof is unwound to the first film forming chamber 13. Further, the base film 1 is conveyed on the circumferential surface of the cooling / electrode drum 19 through the auxiliary roll 18 at a predetermined speed.
Next, in the present invention, a film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organic silicon compounds are supplied from the raw material volatilization supply device 20 and the gas supply device 21 or the like. The film-forming mixed gas composition is introduced into the first film-forming chamber 13 through the raw material supply nozzle 22 while adjusting the film-forming mixed gas composition, and the cooling / electrode A plasma is generated by the glow discharge plasma 23 on the plasma etching protection layer provided on the base film 1 transported on the peripheral surface of the drum 19, and this is irradiated to irradiate the plasma. One carbon-containing silicon oxide layer is formed.

Next, the base film 1 obtained by forming the first carbon-containing silicon oxide layer in the first film forming chamber 13 is transferred to the second film forming chamber 14 through the auxiliary rolls 24 and 25. Next, in the same manner as described above, the base film 1 formed with the first carbon-containing silicon oxide layer is transported onto the cooling / electrode drum 26 circumferential surface at a predetermined speed.
Thereafter, similarly to the above, in the present invention, the raw material volatilization supply device 27, the gas supply device 28, and the like are used to form a film-forming monomer gas, oxygen gas, inert gas, and the like. While supplying the other, adjusting the film-forming mixed gas composition comprising them, introducing the film-forming mixed gas composition into the second film-forming chamber 14 through the raw material supply nozzle 29, and The glow discharge plasma is formed on the first carbon-containing silicon oxide layer of the base film 1 obtained by forming the first carbon-containing silicon oxide layer transported on the circumferential surface of the cooling / electrode drum 26. Plasma is generated by 30 and irradiated to form a second carbon-containing silicon oxide layer made of silicon oxide or the like.

Further, in the present invention, in the same manner as described above, the base film 1 in which the first layer and the second carbon-containing silicon oxide layer are formed in the second film forming chamber 14 is used as an auxiliary roll. The base film 1 formed by forming the carbon-containing silicon oxide layers of the first layer and the second layer into the third film-forming chamber 15 through the first and second layers 31, 32, etc. Then, it is transported onto the cooling / electrode drum 33 circumferential surface.
Thereafter, similarly to the above, in the present invention, the raw material volatilization supply device 34, the gas supply device 35 and the like are used to form a film-forming monomer gas, oxygen gas, inert gas, and the like. The above-mentioned mixed gas composition for film formation is introduced into the third film forming chamber 15 through the raw material supply nozzle 36 while supplying the other and the like, and adjusting the mixed gas composition for film formation made of them, and On the second carbon-containing silicon oxide layer of the base film 1 formed by forming the first and second carbon-containing silicon oxide layers conveyed on the peripheral surface of the cooling / electrode drum 33. Then, plasma is generated by the glow discharge plasma 37 and irradiated to form a third carbon-containing silicon oxide layer made of silicon oxide or the like.
Next, in the present invention, the first layer, the second layer, and the third layer of the carbon-containing silicon oxide layer are formed as described above, and the base film 1 in which the carbon-containing silicon oxide layers are stacked is provided via the auxiliary roll 38. The transparent gas barrier according to the present invention in which the carbon-containing silicon oxide layers of the first layer, the second layer, and the third layer are overlaid by winding into the winding chamber 16 and then winding up on the winding roll 39. It is possible to produce a conductive laminate.
Of course, the carbon-containing silicon oxide layers of the first layer, the second layer, and the third layer are layered on the plasma etching protective layer provided on the base film.

In the present invention, each of the cooling / electrode drums 19, 26, 33 disposed in each of the first, second, and third film forming chambers 13, 14, 15 is provided in each of the first, second, 2 and 3 and a predetermined power is applied from a power source 40 arranged outside the third film forming chambers 13, 14, 15, and in the vicinity of each cooling / electrode drum 19, 26, 33. The generation of plasma is promoted by arranging magnets 41, 42 and 43.
Although not shown, the plasma chemical vapor deposition apparatus is provided with a vacuum pump or the like, and it is needless to say that each film forming chamber can be prepared to be kept in vacuum.
The above exemplification is an example, and it goes without saying that the present invention is not limited thereby.
For example, in the above example, the transparent gas barrier laminate according to the present invention in which the carbon-containing silicon oxide layers of the first layer, the second layer, and the third layer are overlaid is manufactured. The layer can be formed into a structure in which a film-forming chamber is arbitrarily prepared, carbon-containing silicon oxide layers such as two layers or four layers or more are arbitrarily formed, and these are stacked. And the present invention is not limited to the example of producing the transparent gas barrier laminate according to the present invention in which the carbon-containing silicon oxide layers of the first layer, the second layer, and the third layer are overlaid. There is nothing.

  Next, in the present invention, as another example of the plasma chemical vapor deposition apparatus for producing the carbon-containing silicon oxide layer according to the present invention, as shown in FIG. 4, the plasma chemical vapor phase shown in FIG. In the growth apparatus 11, from the raw material volatilization supply apparatus 20, 27, 34 and the gas supply apparatuses 21, 28, 35, etc., a film-forming monomer gas, oxygen gas, and inert gas composed of one or more of organic silicon compounds. , And the like, and the mixed gas composition for film formation comprising them is adjusted, and the first, second, and third film forming chambers 13, 14, 15 are fed through the raw material supply nozzles 22, 29, 36. Instead of introducing the mixed gas composition for film formation, two raw material supply nozzles are provided in one film forming chamber, that is, two raw material supply nozzles are provided in the first film forming chamber 13. 22 and 22a are provided. A vapor deposition monomer gas, oxygen gas, inert gas, etc. made of one or more organic silicon compounds are supplied from the supply devices 20, 20, the gas supply devices 21, 21, etc., and a film is formed of these. While adjusting the mixed gas composition, the film forming mixed gas composition is introduced into the first film forming chamber 13 from the two raw material supply nozzles 22 and 22a, and the cooling and The plasma is generated by the glow discharge plasma 23 on the plasma etching protective layer provided on the base film 1 conveyed on the peripheral surface of the electrode drum 19 and is irradiated with the plasma to form silicon oxide or the like. The first carbon-containing silicon oxide layer is formed into a film, and thereafter, in the same manner as described above, two raw material supply nozzles 29 and 29a are provided in the second film forming chamber 14, and the raw material volatilization supply devices 27 and 27, And gas supply device 2 28, etc., while supplying a film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organic silicon compounds, and adjusting the film-forming mixed gas composition comprising the above, The film-forming mixed gas composition is introduced into the second film-forming chamber 14 through the two raw material supply nozzles 29 and 29a, and is conveyed onto the cooling / electrode drum 26 peripheral surface. Plasma is generated by the glow discharge plasma 30 on the first carbon-containing silicon oxide layer of the base film 1 obtained by forming one carbon-containing silicon oxide layer, and this is irradiated to oxidize silicon. A second carbon-containing silicon oxide layer made of a material or the like is formed into a film, and in the same manner as described above, two raw material supply nozzles 36 and 36a are provided in the third film forming chamber 15 to supply the raw material by volatilization. Devices 34, 34 and gas supply devices 35, 35 etc. While supplying a film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organosilicon compounds, and adjusting the film-forming mixed gas composition composed of them, the above two The above-mentioned mixed gas composition for film formation is introduced into the third film forming chamber 15 through the raw material supply nozzles 36 and 36a, and the first layer conveyed on the peripheral surface of the cooling / electrode drum 33; Plasma is generated by glow discharge plasma 37 on the second carbon-containing silicon oxide layer of the base film 1 obtained by forming the second carbon-containing silicon oxide layer, and this is irradiated with silicon. A third carbon-containing silicon oxide layer made of an oxide or the like is formed, and then in the present invention, the first, second, and third carbon-containing silicon oxide layers are formed as described above. And the base film 1 on which they are layered are passed through the auxiliary roll The transparent gas barrier according to the present invention in which the carbon-containing silicon oxide layers of the first layer, the second layer, and the third layer are overlaid by winding into the winding chamber 16 and then winding up on the winding roll 39. It is possible to produce a conductive laminate.

In the above, each film forming chamber is depressurized by a vacuum pump or the like, and the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to prepare it.
On the other hand, since a predetermined voltage is applied to each cooling / electrode drum from a power source, glow discharge plasma is generated in the vicinity of the opening of the material supply nozzle in each film forming chamber and the cooling / electrode drum, This glow discharge plasma is derived from one or more gas components in the mixed gas composition for film formation, and in this state, the base film is conveyed at a constant speed, A carbon-containing silicon oxide layer made of silicon oxide or the like can be formed on the plasma etching protective layer provided on the substrate film on the cooling / electrode drum peripheral surface.
At this time, the degree of vacuum in each film forming chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable that the conveying speed of the base film is adjusted to about 10 to 300 m / min, preferably about 50 to 150 m / min.
In the present invention, the degree of vacuum in each film forming chamber may be the same or different in each chamber.

Further, in the raw material volatilization supply device, a film forming monomer gas composed of one or more organic silicon compounds as raw materials is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, The film-forming mixed gas composition is introduced into each film-forming chamber through a raw material supply nozzle while adjusting the film-forming mixed gas composition.
In this case, as the gas mixing ratio of each gas component of the mixed gas composition for film formation, the content of the monomer gas for film formation composed of one kind of organic silicon compound is about 1 to 40%, and the content of oxygen gas It is preferable that the amount is adjusted in the range of about 0 to 70% and the content of the inert gas is in the range of about 1 to 60%.
Thus, in the present invention, for each film forming chamber, a film forming mixed gas composition prepared by changing the gas mixing ratio of each gas component of the film forming mixed gas composition introduced into each film forming chamber. The transparent gas barrier laminate according to the present invention is manufactured by forming a film for each film forming chamber and overlaying a carbon-containing silicon oxide layer made of silicon oxide or the like.
That is, in the present invention, the mixing ratio of each gas component of a film-forming mixed gas composition containing at least one monomer gas for forming a film, oxygen gas, and inert gas, which is composed of at least one organic silicon compound. And at least two or more film-forming mixed gas compositions are prepared, and the film-forming mixed gas compositions are used by changing each film-forming chamber, and each of these film-forming mixed gas compositions is used. Thus, a carbon-containing silicon oxide layer formed by two or more plasma chemical vapor deposition methods can be formed.

By the way, in this invention, as mixing ratio of each gas component of said film-forming mixed gas composition, as a 1st film-forming mixed gas composition, monomer gas for film forming: oxygen gas: A mixed gas composition for film formation having a gas composition ratio of inert gas = 1.2: 0.1 to 3: 1 (unit: slm, an abbreviation for stand-driter-minit), The film-forming mixed gas composition 2 is a film-forming monomer gas: oxygen gas: inert gas = 1.2: 3 to 6: 1 (unit: slm, abbreviation of stand-driter-minit. ) Gas composition ratio, and another third mixed gas composition for film formation includes: monomer gas for film formation: oxygen gas: inert gas = 1.2: 6-15: 1 (unit: slm, abbreviation of standard-driter-minit) It can be used for film formation gas mixture composition and the like having the composition ratio.
Thus, in the present invention, the mixed gas composition for film formation as described above is arbitrarily combined, and the mixed gas composition for film formation is placed in the first, second, or third film forming chamber. The film can be formed using a mixed gas composition for film formation in which the mixing ratio of each gas component is changed.

In addition, when forming into a film using the mixed gas composition for film forming which changed the mixing ratio of each gas component of said mixed gas composition for film forming, the 1st mixed gas composition for film forming is used. Then, the carbon amount in the silicon oxide layer formed into a film increases, and there is a tendency that the C—C bond and the Si—CH ₃ bond increase, thereby being highly flexible and high with respect to water vapor. A water-repellent carbon-containing silicon oxide layer having barrier properties can be formed.
In the present invention, when the second mixed gas composition for film formation is used, an appropriate amount of carbon can be contained in the formed carbon-containing silicon oxide layer, and Si—CH ₃ bonds are also present. The carbon-containing silicon oxide layer which can be contained appropriately and thereby has high flexibility and high barrier property against oxygen can be formed into a film.
Furthermore, in the present invention, when the third mixed gas composition for film formation is used, the carbon content in the formed carbon-containing silicon oxide layer tends to decrease, and Si—CH _{The number of three} bonds can also be reduced, whereby the flexibility is inferior, but a carbon-containing silicon oxide layer having a high gas barrier property against oxygen or the like can be formed.
Thus, in the present invention, when the film-forming mixed gas composition as described above is used to form a film, the order in which the film-forming mixed gas composition is used is arbitrary. First, second and third film-forming mixed gas compositions, first, second and first film-forming mixed gas compositions, third, first and second film-forming compositions Each product is manufactured in the order of the mixed gas composition, the order of the third, first, and first mixed gas composition for film formation, or the order of the third, third, and first mixed gas composition for film formation. The film mixed gas composition can be introduced into each film forming chamber to form a film. In the present invention, the film formation is performed in the order of the third, first, and second film forming mixed gas compositions. Is preferable.
In the above, by using the first mixed gas composition for film formation in two chambers, it is possible to form a carbon-containing silicon oxide layer having high flexibility and high barrier property against water vapor. It is what has.

  Furthermore, in the present invention, when the film is formed by the method shown in FIG. 4, the third mixed gas composition for film formation, the first mixed gas composition for film formation, It is preferable to form a film by introducing each mixed gas composition for film formation into each film forming chamber in the order of the mixed gas composition for film. Thus, in the present invention, by forming the film in the order as described above, the carbon content in the carbon-containing silicon oxide layer becomes a discontinuous layer different for each carbon-containing silicon oxide layer, and The carbon-containing silicon oxide layer made of a water-repellent film having high flexibility and high barrier properties against water vapor can be formed.

In the plasma chemical vapor deposition apparatus described above, the carbon-containing silicon oxide layer made of silicon oxide or the like is formed on the plasma etching layer provided on the base film in each film forming chamber. Since the plasma source gas is oxidized with oxygen gas, it is formed into a thin film in the form of SiO _x , so the carbon-containing silicon oxide layer made of silicon oxide or the like to be formed is stacked in multiple layers. Each layer is a thin film that is dense, has few gaps, is rich in spreadability, flexibility, flexibility, etc. Therefore, the barrier property of the carbon-containing silicon oxide layer made of silicon oxide or the like is In addition, it is much higher than a silicon oxide layer made of silicon oxide or the like formed by a conventional vacuum vapor deposition method and the like, and since it is made of a multilayered structure, it has an extremely high and sufficient barrier property. Can get It is kill things.
Further, in the present invention, the surface of the plasma etching protective layer provided on the base film is cleaned by SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface. The carbon-containing silicon oxide layer made of silicon oxide or the like to be formed and the base film have the advantage of high close adhesion.
Further, the degree of vacuum at the time of forming the carbon-containing silicon oxide layer made of silicon oxide or the like as described above is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to Since it is adjusted to 1 × 10 ⁻² Torr, the degree of vacuum when forming a carbon-containing silicon oxide layer made of silicon oxide or the like by a conventional vacuum deposition method is 1 × 10 ⁻⁴ to 1 × 10 ^{−. 5 Since the} vacuum level is lower than that of the Torr position, it is possible to shorten the time for setting the vacuum state of the base film when replacing the original fabric, making it easy to stabilize the vacuum level and stabilizing the film forming process. is there.

Further, in the present invention, a carbon-containing silicon oxide layer made of silicon oxide or the like formed using a vapor deposition monomer gas made of one or more kinds of organic silicon compounds formed in each film forming chamber, A vapor-deposited monomer gas composed of one or more organic silicon compounds chemically reacts with oxygen gas, and the reaction product closely adheres to the surface of the plasma etching protective layer provided on one surface of the base film. It forms a dense thin film rich in flexibility, and is usually a continuous state mainly composed of silicon oxide represented by the general formula SiO _x (where X represents a number from 0 to 2). It consists of a thin film of a carbon-containing silicon oxide layer.
Thus, the carbon-containing silicon oxide layer formed in each film forming chamber has a general formula SiO _X (where X is 1.3 to 1.. It is preferably a thin film of a carbon-containing silicon oxide layer mainly composed of silicon oxide represented by the number of 9. In the above, the value of X varies depending on the molar ratio of vapor-deposited monomer gas and oxygen gas composed of one or more organic silicon compounds, the energy of the plasma, etc. Although the transmittance is small, the film itself is yellowish and the transparency is poor.

In the present invention, the carbon-containing silicon oxide layer made of silicon oxide or the like formed in each film-forming chamber is mainly composed of silicon oxide, and further, carbon, hydrogen, silicon, or oxygen. It is characterized in that it contains at least one kind of compound composed of two or more kinds of elements by chemical bonding or the like, and in particular, the carbon atom component consists of a deposited film containing it as an essential component.
For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc. A derivative may be contained by a chemical bond or the like.
Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.
Other than the above, the type, amount, etc. of the compound contained in the carbon-containing silicon oxide layer formed in each film forming chamber can be changed by changing the conditions of the film forming process. It is.

Thus, the content of the compound contained in the carbon-containing silicon oxide layer formed in each film forming chamber is about 0.1 to 50%, preferably about 5 to 20%. Is desirable.
In the above, if the content rate is less than 0.1%, the impact resistance, spreadability, flexibility, flexibility, flexibility, etc. of the carbon-containing silicon oxide layer formed in each film forming chamber are improved. It becomes inadequate, and scratches, cracks, etc. are likely to occur due to bending, etc., and it becomes difficult to stably maintain a high barrier property. is there.
Furthermore, in the present invention, in the carbon-containing silicon oxide layer formed in each film-forming chamber, the content of the above compound is increased from the surface of each carbon-containing silicon oxide layer in the depth direction. In this way, on the surface of each carbon-containing silicon oxide layer, the impact resistance and the like can be enhanced by the above-described compound, and on the other hand, at the interface with the plasma etching protective layer provided on the base film, Since the content of the above compound is large, the adhesion between the plasma etching protective layer provided on the base film and the carbon-containing silicon oxide layer or the adhesion between each carbon-containing silicon oxide layer is strong. It has the advantage of becoming.
Thus, in the present invention, for the carbon-containing silicon oxide layer formed in each film forming chamber, for example, an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary) Using a surface analysis device such as Ion Mass Spectroscopy (SIMS), etc., and performing an elemental analysis of each carbon-containing silicon oxide layer using a method of analyzing by ion etching or the like in the depth direction, the above physical properties can be obtained. Can be confirmed.

Further, in the present invention, the carbon-containing silicon oxide layer formed by using the first mixed gas composition for film formation has 80 to 120 O atoms and 100 C atoms to 100 Si atoms. consist component ratio of 100 to 150, further, there is IR absorption based on Si-O-Si stretching vibration between 1030cm ^-1 ~1060cm ^-1, and the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 It is characterized by IR absorption based on it.
Thus, the above is because the carbon-containing silicon oxide layer contains a carbon component and contains many C—C bonds and Si—CH ₃ bonds. This shows that the peak position of IR absorption based on vibration is shifted toward a decreasing direction.
That is, it can be confirmed that the film is highly water-repellent and has a high barrier property against water vapor.
Furthermore, in the present invention, the carbon-containing silicon oxide layer formed by using the second mixed gas composition for film formation has 100 to 150 O atoms and 100 C atoms to 100 Si atoms. 100 consists of the following component ratio, further, there is IR absorption based on Si-O-Si stretching vibration between 1045cm ^-1 ~1075cm ^-1, and, based on the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 It is characterized by IR absorption.
Thus, the above-described phenomenon has a low carbon component in the carbon-containing silicon oxide layer and contains only Si—CH ₃ bonds. Therefore, the IR absorption peak based on the Si—O—Si stretching vibration is present. This indicates that the shift position does not shift.
That is, it can be confirmed that the film is highly flexible and has a high barrier property against oxygen.
In the present invention, the carbon-containing silicon oxide layer formed by using the third mixed gas composition for film formation has an oxygen atom number of 150 to 190 and a C atom number with respect to the Si atom number of 100. 80 consists of the following component ratio, further, there is IR absorption based on Si-O-Si stretching vibration between 1045cm ^-1 ~1075cm ^-1, and, based on the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 It is characterized by IR absorption.
Thus, the above-described phenomenon has a low carbon component in the carbon-containing silicon oxide layer and contains only Si—CH ₃ bonds. Therefore, the IR absorption peak based on the Si—O—Si stretching vibration is present. This indicates that the position does not shift, the degree of oxidation is higher, the film is denser, and the flexibility is reduced, but it has a high barrier property against oxygen, and the base film It can be confirmed that the film has excellent adhesion.

Next, in the present invention, the total film thickness of the carbon-containing silicon oxide layer formed in each film forming chamber constituting the barrier layer is preferably about 60 mm to 4000 mm. The film thickness is preferably about 100 to 1000 mm, and in the above, it is not preferable that the film thickness is more than 1000 mm, more preferably 4000 mm, because cracks and the like are easily generated in the film. Furthermore, if it is less than 60 mm, it is not preferable because it becomes difficult to achieve a barrier effect.
In the present invention, as the film thickness of each carbon-containing silicon oxide layer formed in each film-forming chamber constituting the barrier layer, first, the film of the carbon-containing silicon oxide layer constituting the first layer The thickness is 20 to 200 mm, preferably 30 to 100 mm, and the carbon-containing silicon oxide layer constituting the second layer has a thickness of 20 to 200 mm, preferably 30 to 100 mm. Further, the film thickness of the carbon-containing silicon oxide layer constituting the third layer is preferably about 20 to 200 mm, more preferably about 30 to 100 mm.
In the above, if it is 20 mm or less, its own barrier property is not exhibited, and it is not preferable. If it exceeds 200 mm, cracks and the like are likely to occur in the film. It is not preferable because cracks tend to occur during the process.
In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. In the above, as a means for changing the film thickness of the carbon-containing silicon oxide layer, a method of increasing the volume velocity of the layer, that is, a method of increasing the amount of the monomer gas for film formation and the oxygen gas, It can be performed by a method of slowing the film forming speed.

Next, in the present invention, examples of the organosilicon compound constituting the monomer gas for film formation include 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, Hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octa Methylcyclotetrasiloxane, etc. can be used.
In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material.
Moreover, in this invention, argon gas, helium gas etc. can be used as inert gas, for example.

As apparent from the above description, in the present invention, the carbon-containing silicon oxide layers having different compositions can be obtained by changing the mixing ratio of each gas component of each mixed gas composition for film formation in each film forming chamber. To form.
For example, in the present invention, by increasing the carbon atom content in the carbon-containing silicon oxide layer, it is possible to form a carbon-containing silicon oxide layer in which the water vapor permeability decreases while the oxygen permeability increases. It is.
In addition, for example, when a carbon-containing silicon oxide layer having an extremely low carbon atom content is formed, a high oxygen gas barrier performance can be obtained, but carbon having a large deterioration in barrier performance when physical stress such as pulling or stagnation is applied. A silicon oxide layer is formed.
As described above, each mixed gas composition for film formation having a different mixing ratio of these gas components has advantages and disadvantages, and conventionally, an appropriate composition ratio is prepared in accordance with required performance. For this reason, the carbon-containing silicon oxide layer has to have a moderate performance.
In the present invention, a carbon-containing silicon oxide layer having a different carbon atom content can be formed by changing the mixing ratio of each gas component in each film-forming mixed gas composition in each film-forming chamber, and the gas barrier performance. It is possible to form a carbon-containing silicon oxide layer having excellent physical stress resistance and the like.
In the present invention, a carbon-containing silicon oxide layer having good adhesion to the base film side and excellent in oxygen gas barrier performance and having a low carbon content is provided, and is continuously rich in flexibility and water vapor barrier performance. An excellent carbon-containing silicon oxide layer having a high carbon content is provided, and further, an intermediate carbon-containing silicon oxide layer having a carbon content that is moderate in adhesion, oxygen gas barrier performance and water vapor barrier performance is provided. The transparent gas barrier laminate according to the present invention, which is excellent in gas barrier performance, adhesion, physical stress resistance, etc., can be produced by combining and stacking silicon oxide layers.

Next, in the present invention, when the yellowing of the base film by plasma etching is observed for the base film, in the present invention, the plasma etching protective layer and the carbon-containing silicon oxide layer are sequentially laminated on the base film. The above-mentioned laminate obtained by the following formula is compared with the yellowness of the laminated body, and the yellowness of the plasma etching protective layer-coated base film provided with the plasma etching layer on the base film. In the case of yellowness (YI _a ), and the yellowness (YI _b ) of the above-mentioned plasma etching protective layer-coated substrate film obtained from the following formula, ΔYI (YI _a −YI _b ) <0.6 is satisfied. Thus, the transparent gas barrier laminate according to the present invention was found to be sufficiently practical for use as a barrier substrate as a packaging material. Those were.
Yellowness (YI): YI = 100 (1.28X-1.06Z) / Y
(However, in the formula, X, Y, and Z represent the three-color stimulus values X, Y, and Z of the CIS-XYZ color system.)
In the above, when ΔYI (YI _a −YI _b ) exceeds 0.6, the yellowness of the film is high and appearance problems occur. For example, white powder appears yellowish, and packaging It becomes difficult to use it sufficiently as a barrier substrate as a material for use.
The yellowness was measured by measuring YI using a spectrocolorimeter (ASTM E313, ASTM D1925).

Further, in the present invention, when the etching rate of the base film by plasma etching is seen with respect to the base film, the plasma etching protective layer coating in which the plasma etching protective layer is laminated on one surface of the base film in the present invention. When the substrate film is etched for a predetermined time with oxygen plasma, the etching rate of the plasma etching protective layer-coated base film is 95% or less of the etching rate of the base film without the plasma etching protective layer. It is preferable that it consists of.
In the above, if the etching rate exceeds 95%, it is not preferable for reasons such as a decrease in peel strength after lamination due to the formation of a weak interface layer, a yellowing of the film, and a decrease in barrier properties.
In addition, said etching rate installs a base material in a flat plate type PE-CVD apparatus, irradiates oxygen plasma in a decompression environment, measures the thickness of the base material before and after irradiation for a predetermined time with a thickness meter, Obtained from the formula.
Etching rate: R = (base material thickness before irradiation (μm) −base material thickness after irradiation (μm) / irradiation time (min))
Applied output: 300W
Oxygen flow rate: 60sccm
Degree of vacuum: 30mT
Irradiation time: 5 min

As is clear from the above description, the transparent gas barrier laminate according to the present invention produced by film formation as described above is formed on one surface of the base film 1 as shown in FIG. The plasma etching protective layer 2 and the carbon-containing silicon oxide layer 3 are sequentially laminated, and the plasma etching protective layer 2 includes an acrylic resin and a polyurethane resin, and has a solid content. The former is composed of a resin layer 2a made of a mixed resin composition containing 50 to 80% by weight of the former and 20 to 50% by weight of the latter, and the carbon-containing silicon oxide layer 3 is at least 2%. A film-forming mixture containing a film-forming monomer gas, an oxygen gas, and an inert gas composed of at least one organic silicon compound is used in each room. Each gas component of the gas composition Carbon content by plasma chemical vapor deposition of two or more layers formed using two or more film-forming mixed gas compositions prepared by changing the mixing ratio and using each film-forming mixed gas composition Each of the carbon-containing silicon oxide layers 3a, 3b, and 3c is composed of silicon oxide layers 3a, 3b, and 3c, and the carbon-containing silicon oxide layers 3a, 3b, and 3c contain carbon atoms in the film. The transparent gas barrier laminate A ₁ is composed of carbon-containing silicon oxide layers 3a, 3b, and 3c each having a different carbon content.

Thus, the transparent gas barrier laminate according to the present invention has a carbon-containing silicon oxide layer composed of a silicon oxide layer or the like formed by a plasma chemical vapor deposition method on a base film through a plasma etching protective layer. By stacking multiple layers, the adhesion between the base film and the carbon-containing silicon oxide layer is excellent and the carbon-containing silicon oxide layer is excellent in spreadability, flexibility, flexibility, etc. From the above, it is possible to form a film having an extremely high barrier property and to continuously form a carbon-containing silicon oxide layer using a plasma chemical vapor deposition apparatus comprising at least two film forming chambers. Since two or more layers can be laminated on each other and a film having a high barrier property can be formed for each layer, a gas barrier property higher than that of a single layer can be obtained. Open to continuous By forming a film, it is possible to prevent foreign matter, dust and the like that cause cracks from entering between the film forming layers, and no deterioration of the barrier property is observed. The silicon layer is mainly composed of silicon oxide, contains at least one compound composed of one or more elements of carbon, hydrogen, silicon, and oxygen, and is provided for each silicon oxide layer. It is a discontinuous layer with different contents of the above compounds, and further, since it contains carbon atoms as essential components, it has various advantages that it can completely block the transmission of oxygen gas, water vapor, etc. It is what you have.
For this reason, the transparent gas barrier laminate according to the present invention is excellent in gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like as a barrier substrate used for packaging materials, for example. This is a very useful barrier film in which no decrease in performance is observed.

That is, in the present invention, the transparent gas barrier laminate according to the present invention produced as described above uses this as a barrier substrate, and other plastic film, paper substrate, metal foil or metal plate, One or two or more kinds of various base materials such as cellophane, woven or non-woven fabric, glass plate, and the like are arbitrarily laminated to produce a laminated material having various forms. Various materials such as packaging materials, optical members, protective sheets for solar cell modules, protective films for organic EL displays, protective films for film liquid crystal displays, packaging materials for polymer batteries, aluminum packaging materials, etc. It can be applied to other uses.
As an example of the method for producing the laminated material, for example, if necessary, plasma is first formed on the surface of the carbon-containing silicon oxide layer forming the barrier layer constituting the transparent gas barrier laminate according to the present invention. After performing a pretreatment such as treatment, a primer layer is formed, and then a laminating adhesive layer is formed on the surface of the primer layer, and then the primer layer and the laminating layer are formed. -Laminates having various forms can be produced by laminating a base material such as a plastic film using a dry laminate lamination method via an adhesive layer for a tote.
Alternatively, in the present invention, for example, the carbon-containing silicon oxide layer forming the barrier layer constituting the transparent gas barrier laminate according to the present invention is first subjected to pretreatment such as plasma treatment if necessary. After that, a primer agent layer is formed, and then an anchor coat agent layer is formed on the surface of the primer agent layer, and then the primer agent layer, the anchor coat agent layer, etc. Then, by laminating using an extrusion laminating method in which various resins and the like are melt-extruded to laminate a desired base material, laminated materials having various forms can be produced.
In the present invention, in the same manner as described above, another base material can be arbitrarily inserted between the above layers and laminated, and the base material constituting the transparent gas barrier laminate according to the present invention. Similarly to the above, other desired base materials can be arbitrarily laminated on the surface of the film to produce laminated materials having various forms. In the present invention, the purpose of use and the form of use Depending on the application, etc., other substrates can be arbitrarily laminated, and various forms of laminated materials can be designed and manufactured.

Next, in the present invention, a packaging container will be described as an example of use of the above laminated material. In the present invention, for example, two sheets of the above laminated material are prepared as packaging containers. Then, the surfaces of the heat-sealable resin layer located in the innermost layer are made to face each other, and thereafter, the seal part is formed by heat-sealing the three ends of the outer periphery. At the same time, a three-sided seal type flexible packaging container can be manufactured by providing an opening on the upper side.
Thus, in the present invention, although not shown, from the opening of the three-sided seal type soft packaging container manufactured above, for example, the contents such as food and drink, etc. are filled, and then the upper Heat-seal the opening to form an upper seal, etc., and further, for example, boil treatment, retort treatment, etc., to produce packaged products of various forms Is something that can be done.
In the present invention, it is needless to say that the present invention is not limited to the illustrated packaging containers shown above. Depending on the purpose, use, etc., flexible packaging bags, liquid paper containers, paper cans, It goes without saying that various types of packaging containers such as others can be manufactured.

Next, in the present invention, the primer agent layer constituting the laminate material will be described. First, as the primer agent layer, a polyurethane resin or a polyester resin is used as a main component of the vehicle, and the polyurethane agent layer The silane coupling agent is about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, and the filler is 0.1 to 20% by weight with respect to 1 to 30% by weight of the resin or polyester resin. , Preferably in a proportion of about 1 to 10% by weight, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. are optionally added to the solvent. Then, a diluent or the like is added and mixed well to prepare a polyurethane-based or polyester-based resin composition, and thus the polyurethane-based or polyester-based resin composition is used. For example, the barrier property of the transparent gas barrier laminate according to the present invention described above by roll coating, gravure coating, knife coating, dip coating, spray coating, other coating methods, etc. After coating on the surface of the carbon-containing silicon oxide layer forming the layer, the coating film is dried to remove the solvent, diluent, etc., and if necessary, an aging treatment is performed. Thus, the primer layer according to the present invention can be formed.
In the present invention, the film thickness of the primer layer is preferably, for example, about 0.1 g / m ^{2 to} 1.0 g / m ² (dry state).
Thus, in the present invention, a carbon-containing silicon oxide layer that forms a barrier layer constituting the transparent gas barrier laminate according to the present invention by the primer layer as described above, and heat sealability The present invention at the time of post-processing improves the post-processing suitability such as laminating or bag making, for example, by improving the tight adhesion with the resin layer and improving the degree of elongation of the primer layer. This prevents the occurrence of cracks and the like in the carbon-containing silicon oxide layer constituting the transparent gas barrier laminate.

In the above, as a polyurethane-type resin which comprises a polyurethane-type resin composition, the polyurethane-type resin obtained by reaction of a polyfunctional isocyanate and a hydroxyl-group containing compound can be used, for example.
Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate One obtained by reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as a salt with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol, a polyacrylate polyol, or the like. A liquid or two-component curable polyurethane resin can be used.

In the above, the polyester resin constituting the polyester resin composition includes, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton, A thermoplastic polyester resin produced by polycondensation with one or more valent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like.
In the above, saturated divalent alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, 2.2- Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalene diol, other aromatic geo- and the like can be used.

In the present invention, specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene glycol. Polybutylene terephthalate resin produced by polycondensation with styrene, thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, terephthalic acid Polyethylene terephthalate resin produced by copolycondensation of styrene, isophthalic acid and ethylene glycol, produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin, terephthalic acid and isophthalic acid And ethylene glycol - le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - can be used Le resin, other like.
In the present invention, in addition to the saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, One or more aliphatic saturated dicarboxylic acids such as sebacic acid and dodecanoic acid can be added and copolycondensed, and the amount used is an aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, It is preferable to add 1 to 10% by weight.

  Next, in the above, as the silane coupling agent constituting the polyurethane-based or polyester-based resin composition, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, γ One or more of ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, an aqueous solution of γ-aminopropylsilicone, and the like can be used.

In the silane coupling agent as described above, a functional group at one end of the molecule, usually chloro, alkoxy, or acetoxy group is hydrolyzed to form a silanol group (SiOH), which contains carbon. The carbon-containing silicon oxide layer or the active group on the film surface of the carbon-containing silicon oxide layer, for example, a functional group such as a hydroxyl group causes a reaction such as a dehydration condensation reaction to cause carbon-containing A silane coupling agent is modified with a covalent bond or the like on the film surface of the silicon oxide layer, and further, a strong bond is formed on the film surface of the carbon-containing silicon oxide layer of the silanol group itself by adsorption or hydrogen bond.
On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. -Reacts with substances constituting the adhesive layer, anchor coating layer, other layers, etc. to form a strong bond, and further, the above-mentioned printed pattern layer, laminating adhesive layer, The heat-sealable resin layer is firmly and tightly bonded through the anchor coating agent layer and the like to increase the laminating strength. Thus, in the present invention, the laminating strength is increased. It is possible to form a strong and highly laminated structure.
In the present invention, the inorganic property and organic property of the silane coupling agent are utilized, and the heat treatment is performed through the carbon-containing silicon oxide layer and the printed pattern layer, the adhesive layer, or the anchor coating agent layer. -Improving the tight adhesion with the rusty resin layer, thereby increasing the laminating strength and the like.

Next, in the present invention, examples of the filler constituting the polyurethane-based or polyester-based resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used.
Thus, the above-mentioned filler adjusts the viscosity of the polyurethane-based or polyester-based resin composition liquid, improves its coating suitability, and is a silane coupling with a polyurethane-based or polyester-based resin as a binder resin. It binds via an agent to improve the cohesive strength of the coating film.

Next, in the present invention, the laminating adhesive layer constituting the laminated material will be described. Examples of the laminating adhesive layer constituting the laminating adhesive layer include a polyvinyl acetate adhesive and acrylic acid. Homopolymers such as ethyl, butyl, 2-ethylhexyl ester, etc., or polyacrylate adhesives comprising these and copolymers of methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene Ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimides, and the like, and copolymers of monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc. -Based adhesives, amino resin-based adhesives made of urea resin or melamine resin, and phenolic resin-based adhesives Epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate Inorganic adhesives made of low-melting glass or the like, and other adhesives can be used.
The composition system of the above adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof are film / sheet type, powder type, solid type, etc. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
Thus, the above adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method, etc., or a printing method. The coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, the anchor coat agent layer constituting the laminated material will be described. As the anchor coat agent constituting the anchor coat agent layer, for example, alkyl titanate or the like is used. Various aqueous or oil-based anchor coating agents such as organic titanium, isocyanate, polyethyleneimine, polyptadiene, etc. can be used.
The above-mentioned anchor coating agent can be coated using a coating method such as a roll coat, a gravure roll coat, a kiss coat, and the like. The amount is preferably 0.1 to 5 g / m ² (dry state).

Examples of the melt-extruded resin layer in the melt-extrusion laminating method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, saps. 1 of thermoplastic resins such as phosphorus resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. Species or two or more can be used.
In the melt extrusion lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed through an anchor coating agent layer such as the above-described anchor coating agent.

Next, in the present invention, as a base material such as a plastic film for forming the innermost layer of the laminated material, for example, a heat-seal resin film or sheet that can be melted by heat and fused to each other is used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α-olefin polymerized using a metallocene catalyst Copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer Polymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene Polyolefin resins such as pyrene modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meta ) A film or sheet of a resin such as an acrylic resin, a polyvinyl chloride resin, or the like can be used.
Thus, the above film or sheet can be used in the state of a coating film made of a composition containing the resin.
The thickness of the film or film or sheet is preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

Furthermore, in the present invention, as a base material such as a plastic film constituting the above laminated material, for example, as a basic material of the laminated material, excellent properties in mechanical, physical, chemical, etc. In particular, a resin film or sheet having strength, toughness, and heat resistance can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid Films, sheets, etc. of tough resins such as resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. can be used. .
Thus, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm.
In the present invention, the above-mentioned base film is subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as characters, figures, symbols, patterns, patterns, etc., for example. May be.

Next, in the present invention, as the base material constituting the laminated material, for example, various paper base materials constituting the paper layer can be used. Specifically, in the present invention, Materials include formability, bending resistance, rigidity, etc., for example, strong sized bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used.
In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² .
Of course, in the present invention, the paper base material constituting the paper layer and various resin films or sheets as the base film mentioned above can be used in combination.

Furthermore, in the present invention, examples of the material constituting the laminated material include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, and ethylene having barrier properties such as water vapor and water. -Resin film or sheet such as propylene copolymer, or polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, nylon MXD6 resin having barrier properties against oxygen, water vapor, etc. Films or sheets of the above-mentioned resins, colorants such as pigments to the resin, and other various colored resin films or sheets having light-shielding properties obtained by kneading into a film by adding desired additives. Can be used.
These materials can be used alone or in combination.
The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

In the present invention, usually, when the above laminated material is applied to various applications, it is subjected to severe conditions both physically and chemically. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required. Can be used by arbitrarily selecting a material that satisfies the above-mentioned conditions. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene , Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methyl Pentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene Resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. You can select and use.
In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used.
In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

  Thus, in the present invention, when performing the above-mentioned lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film, and for example, isocyanate (urethane) Type), polyethyleneimine type, polybutadiene type, organic titanium type anchor coating agent, or polyurethane type, polyacrylic type, polyester type, epoxy type, polyvinyl acetate type, cellulose type, etc. -Known pretreatments such as adhesives for coating, anchor coating agents, adhesives, and the like can be used.

In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminated material.
Thus, the printed pattern layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet ray, and the like. One or more additives such as an absorbent, a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like are arbitrarily added, and a colorant such as a dye / pigment is added, and a solvent is added. The ink composition is prepared by sufficiently kneading with a diluent, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. The printing pattern layer according to the present invention can be formed by printing a desired printing pattern composed of characters, figures, symbols, patterns, etc. on the above-described coating thin film using a printing method such as .

In the present invention, the primer layer provided on the surface of the silicon oxide such as silicon oxide or aluminum oxide, in addition to the primer layer made of the polyurethane-based or polyester-based resin composition, For example, a polyamide resin, an epoxy resin, a phenol resin, a (meth) acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene aly polypropylene, or a copolymer or modified resin thereof, cellulose A primer agent layer can be formed by using a resin composition containing a glass-based resin or the like as a main component of the vehicle.
In the present invention, for example, a primer coating layer is formed by coating using a coating method such as a roll coat, a gravure roll coat, a kiss coat, or the like. Therefore, the coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, a description will be given of a bag making or box making method for manufacturing a packaging container using the above laminated material. For example, when the packaging container is a flexible packaging bag made of a plastic film or the like Using the laminated material manufactured by the method as described above, facing the heat-sealable film of the inner layer facing each other, folding the two sheets or overlapping the two sheets, The bag body can be configured by heat sealing the portion to provide a seal portion.
Thus, as the bag-making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or two of them are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type The various types of packaging containers according to the present invention can be manufactured by heat sealing in the form of heat sealing such as flat bottom sealing, square bottom sealing, and the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-described laminated material.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container including a paper base material as a packaging container, for example, as a laminated material, a laminated material in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is prepared from this. After that, the body, bottom, head, etc. can be boxed by using the blank plate, and for example, a brick type, flat type or gable top type liquid paper container can be manufactured. .
Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

In the present invention, the packaging container produced as described above can be used for filling and packaging various foods, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other items. It is what is used.
Thus, in the present invention, in particular, for example, a liquid sachet for filling and packaging soy sauce, sauce, soup, etc., a sachet for filling and packaging rice cake, a soft packaging bag for filling and packaging fresh confectionery, etc. It is useful as a packaging container for filling and packaging foods and beverages such as soft packaging bags for filling and packaging boiled or retort foods.
Hereinafter, the present invention will be described in more detail with reference to examples.

(1). A biaxially stretched polyethylene terephthalate film (trade name, P60, manufactured by Toray Industries, Inc.) having a thickness of 12 μm was prepared as a base film.
On the other hand, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating solution. (Coating solution composition)
Water-soluble acrylic resin (Nippon Pure Chemicals Co., Ltd., trade name)
"Julima FC-60") 75 (wt%)
Water-soluble polyurethane resin (trade name, manufactured by Enomoto Kasei Co., Ltd.)
“NeoRez R-9737” 25
Water-soluble epoxy curing agent 5
Total 105 (wt%)
Next, on the surface of the corona-treated surface of the above biaxially stretched polyethylene terephthalate film, the coating liquid produced above is used, and this is coated by the gravure roll coating method, and then the winding speed is 100 m / A plasma etching protective layer having a thickness of 0.1 μm (in a dry operation state) was formed by processing at a drying temperature of 100 ° C. for min.
(2). Next, the biaxially stretched polyethylene terephthalate film in which the plasma etching protective layer was formed in the above (1) was used, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO) which is an organic silicon compound which is a raw material is volatilized in a raw material volatilization supply device, and oxygen gas and inert gas helium and argon which are supplied from the gas supply device; The raw material gas was obtained by mixing.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 6.0: 0.5: 0.5 (unit: slm, stander) -Dritter-Minute), and as a raw material gas used in the second film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 0.5: 0.5: 0.5 (unit: slm), and furthermore, as a raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 3.0: 0. .5: 0.5 (unit: slm).
The source gas as described above is used, and the source gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively, and then the plasma etching protective layer described above is used. While the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is conveyed at a line speed of 200 m / min, electric power is applied and one of the corona-treated surfaces of the 12 μm thick biaxially stretched polyethylene terephthalate film is applied. On top of the plasma etching protection layer provided above, a three-layer carbon-containing silicon oxide comprising a first layer thickness of 30 mm, a second layer thickness of 30 mm, a third layer thickness of 30 mm, and a total thickness of 90 mm The layer was formed into a film to produce a transparent gas barrier laminate according to the present invention.

In Example 1 above, instead of the coating liquid shown in Example 1 above, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating liquid. A transparent gas barrier laminate according to the present invention was produced in the same manner as in Example 1 above, exactly as in Example 1 above.
(Coating solution composition)
Water-soluble acrylic resin (same as Example 1) 80 (wt%)
Water-soluble polyurethane resin (same as Example 1) 20
Water-soluble epoxy curing agent 5
Total 105 (wt%)

In Example 1 above, instead of the coating liquid shown in Example 1 above, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating liquid. A transparent gas barrier laminate according to the present invention was produced in the same manner as in Example 1 above, exactly as in Example 1 above.
(Coating solution composition)
Water-soluble acrylic resin (same as Example 1) 50 (wt%)
Water-soluble polyurethane resin (same as Example 1) 50
Water-soluble epoxy curing agent 5
Total 105 (wt%)

(1). A biaxially stretched polyethylene terephthalate film (same as in Example 1) having a thickness of 12 μm was prepared as a base film.
On the other hand, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating solution. (Coating solution composition)
Water-soluble acrylic resin (same as Example 1) 75 (wt%)
Water-soluble polyurethane resin (same as Example 1) 25
Total 100 (wt%)
Next, on the surface of the corona-treated surface of the above biaxially stretched polyethylene terephthalate film, the coating liquid produced above is used, and this is coated by the gravure roll coating method, and then the winding speed is 100 m / A plasma etching protective layer having a thickness of 0.1 μm (in a dry operation state) was formed by processing at a drying temperature of 100 ° C. for min.
(2). Next, two supply pipes using the biaxially stretched polyethylene terephthalate film on which the plasma etching protective layer is formed in the above (1) can be independently controlled as shown in FIG. Was installed in a plasma chemical vapor deposition apparatus.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, HMDSO (hexamethyldisiloxane), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas supplied from the gas supply device and helium and argon as inert gases. Gas was used.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 6.0: 0.5: 0.5 (unit: slm, stander) -Dritter-Minute), and as a raw material gas used in the second film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 0.5: 0.5: 0.5 (unit: slm), and furthermore, as a raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 3.0: 0. .5: 0.5 (unit: slm).
Next, using the source gas having the above gas mixture ratio, the source gas is supplied to the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. Then, while the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm provided with the plasma etching protective layer was conveyed at a line speed of 200 m / min, electric power was applied to the biaxial film having a thickness of 12 μm. On the plasma etching protective layer provided on one corona-treated surface of the stretched polyethylene terephthalate film, the thickness of the first layer is 30 mm, the thickness of the second layer is 30 mm, the thickness of the third layer is 30 mm, A transparent carbon barrier laminate according to the present invention was produced by forming a three-layer carbon-containing silicon oxide layer having a thickness of 90 mm.

In Example 4 above, instead of the coating liquid shown in Example 4 above, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating liquid. The transparent gas barrier laminate according to the present invention was produced in the same manner as in Example 4 above, exactly as in Example 4 above.
(Coating solution composition)
Water-soluble acrylic resin (same as Example 1) 80 (wt%)
Water-soluble polyurethane resin (same as Example 1) 20
Total 100 (wt%)

In Example 4 above, instead of the coating liquid shown in Example 4 above, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating liquid. The transparent gas barrier laminate according to the present invention was produced in the same manner as in Example 4 above, exactly as in Example 4 above.
(Coating solution composition)
Water-soluble acrylic resin (same as Example 1) 50 (wt%)
Water-soluble polyurethane resin (same as Example 1) 50
Total 100 (wt%)

[Comparative Example 1]
A biaxially stretched polyethylene terephthalate film (same as Example 1) having a thickness of 12 μm was prepared as a base film, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO) which is an organic silicon compound which is a raw material is volatilized in a raw material volatilization supply device, and oxygen gas and inert gas helium and argon which are supplied from the gas supply device; The raw material gas was obtained by mixing.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 6.0: 0.5: 0.5 (unit: slm, stander) -Dritter-Minute), and as a raw material gas used in the second film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 0.5: 0.5: 0.5 (unit: slm), and furthermore, as a raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 3.0: 0. .5: 0.5 (unit: slm).
Using the source gas as described above, the source gas is introduced into the first film-forming chamber, the second film-forming chamber, and the third film-forming chamber, respectively. While feeding the biaxially stretched polyethylene terephthalate film at a line speed of 200 m / min, electric power was applied, and on the one corona-treated surface of the 12 μm thick biaxially stretched polyethylene terephthalate film, A three-layer carbon-containing silicon oxide layer having a thickness of 30 mm, a second layer thickness of 30 mm, a third layer thickness of 30 mm, and a total thickness of 90 mm was formed into a transparent gas barrier laminate.

[Comparative Example 2]
(1). A biaxially stretched polyethylene terephthalate film (same as in Example 1) having a thickness of 12 μm was prepared as a base film.
On the other hand, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating solution. (Coating solution composition)
Water-soluble acrylic resin (same as Example 1) 100 (wt%)
Water-soluble epoxy curing agent 5
Total 105 (wt%)
Next, on the surface of the corona-treated surface of the above biaxially stretched polyethylene terephthalate film, the coating liquid produced above is used, and this is coated by the gravure roll coating method, and then the winding speed is 100 m / A plasma etching protective layer having a thickness of 0.1 μm (in a dry operation state) was formed by processing at a drying temperature of 100 ° C. for min.
(2). Next, the biaxially stretched polyethylene terephthalate film in which the plasma etching protective layer was formed in the above (1) was used, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO) which is an organic silicon compound which is a raw material is volatilized in a raw material volatilization supply device, and oxygen gas and inert gas helium and argon which are supplied from the gas supply device; The raw material gas was obtained by mixing.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 6.0: 0.5: 0.5 (unit: slm, stander) -Dritter-Minute), and as a raw material gas used in the second film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 0.5: 0.5: 0.5 (unit: slm), and furthermore, as a raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 3.0: 0. .5: 0.5 (unit: slm).
The source gas as described above is used, and the source gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively, and then the plasma etching protective layer described above is used. While the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is conveyed at a line speed of 200 m / min, electric power is applied and one of the corona-treated surfaces of the 12 μm thick biaxially stretched polyethylene terephthalate film is applied. On top of the plasma etching protection layer provided above, a three-layer carbon-containing silicon oxide layer comprising a first layer thickness of 30 mm, a second layer thickness of 30 mm, a third layer thickness of 30 mm, and a total thickness of 90 mm The layer was formed into a film to produce a transparent gas barrier laminate.

[Comparative Example 3]
(1). A biaxially stretched polyethylene terephthalate film (same as in Example 1) having a thickness of 12 μm was prepared as a base film.
On the other hand, according to the composition shown below, each composition component was sufficiently stirred and mixed to obtain a coating solution. (Coating solution composition)
Water-soluble polyurethane resin (same as Example 1) 100 (wt%)
Water-soluble epoxy curing agent 5
Total 105 (wt%)
Next, on the surface of the corona-treated surface of the above biaxially stretched polyethylene terephthalate film, the coating liquid produced above is used, and this is coated by the gravure roll coating method, and then the winding speed is 100 m / A plasma etching protective layer having a thickness of 0.1 μm (in a dry operation state) was formed by processing at a drying temperature of 100 ° C. for min.
(2). Next, the biaxially stretched polyethylene terephthalate film in which the plasma etching protective layer was formed in the above (1) was used, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO) which is an organic silicon compound which is a raw material is volatilized in a raw material volatilization supply device, and oxygen gas and inert gas helium and argon which are supplied from the gas supply device; The raw material gas was obtained by mixing.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 6.0: 0.5: 0.5 (unit: slm, stander) -Dritter-Minute), and as a raw material gas used in the second film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 0.5: 0.5: 0.5 (unit: slm), and furthermore, as a raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He: Ar = 1.2: 3.0: 0. .5: 0.5 (unit: slm).
The source gas as described above is used, and the source gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively, and then the plasma etching protective layer described above is used. While the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is conveyed at a line speed of 200 m / min, electric power is applied and one of the corona-treated surfaces of the 12 μm thick biaxially stretched polyethylene terephthalate film is applied. On top of the plasma etching protection layer provided above, a three-layer carbon-containing silicon oxide layer comprising a first layer thickness of 30 mm, a second layer thickness of 30 mm, a third layer thickness of 30 mm, and a total thickness of 90 mm The layer was formed into a film to produce a transparent gas barrier laminate.

[Experimental Example 1]
About the transparent gas-barrier laminated body manufactured in said Examples 1-6 and Comparative Examples 1-3, oxygen permeability and water vapor permeability were measured.
(1). Measurement of Oxygen Permeability This was measured with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 90% RH.
(2). Measurement of Water Vapor Permeability This was measured with a measuring instrument (model name, Permatran 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH.
The measurement results are shown in Table 1 below.

(Table 1)
┌─────┬────────────────┐ │ │ Transparent gas barrier laminate │ │ ├ ───────┬──────── │ │ │ Oxygen permeability │ Water vapor permeability │ ├─────┼───────┼────────┤ │Example 1 │ 1.2 │ 1.5 │ ├─ ────┼───────┼────────┤ │Example 2 │ 1.2 │ 1.6 │ ├─────┼───────┼ ────────┤ │Example 3 │ 1.4 │ 1.8 │ ├─────┼───────┼────────┤ │Example 4 │ 1.3 │ 1.5 │ ├─────┼───────┼────────┤ Example 5 │ 1.3 │ 1.6 │ ├─── ──┼───────┼────────┤ │Example 6 │ 1.5 │ 1.8 │ ├─────┼───────┼ ────────┤ │Comparative Example 1 │ 3.4 │ 6.0 │ ├────┼┼───────┼────────┤ │Comparative Example 2 │ 1.2 │ 1.5 │ ├─────┼───────┼────────┤ │Comparative Example 3 │ 4.7 │ 4.0 │ └─── ──┴───────┴────────┘ In Table 1 above, the unit of oxygen permeability is [cc / m ² / day · 23 ℃ ・ 90% RH] The unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90% RH].

  As is clear from the results shown in Table 1 above, the transparent gas barrier laminate according to the present invention was excellent in oxygen permeability and water vapor permeability.

[Experimental example 2]
About the transparent gas barrier laminated body manufactured in said Examples 1-6 and Comparative Examples 1-3, yellowness was measured.
The spectrocolorimeter was used to determine the value of YI _a -YI _b as the measured value YI _b of the film before vapor deposition and the measured value YI _a of the film after vapor deposition.
The measurement results are shown in Table 2 below.

(Table 2)
┌─────┬────────────────┐ │ │ Transparent gas barrier laminate │ │ ├ ──────────────── │ │ │ Yellowness │ ├─────┼────────────────┤ │Example 1 │ 0.5 │ ├─────┼──── ────────────┤ │Example 2 │ 0.4 │ ├─────┼────────────────┤ │Example 3 │ 0.3 │ ├─────┼────────────────┤ │Example 4 │ 0.5 │ ├─────┼───── ───────────┤ │Example 5 │ 0.4 │ ├─────┼────────────────┤ │Example 6 │ 0.3 │ ├─────┼────────────────┤ │Comparative Example 1 │ 3.9 │ ├─────┼────── ──── ──────┤ │Comparative Example 2 │ 1.7 │ ├─────┼────────────────┤ │Comparative Example 3 │ 0.3 │ └ ─────┴────────────────┘

  As is clear from the results shown in Table 2 above, the transparent gas barrier laminate according to the present invention has a small yellowness and can be sufficiently put into practical use as a barrier substrate as a packaging material. There was found.

[Experimental Example 3]
For the transparent gas barrier laminates produced in Examples 1 to 6 and Comparative Examples 1 to 3, first, a glow discharge plasma generator was used on the surface of the carbon-containing silicon oxide layer, and the power was 9 kW. , Oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm) is used, and the mixed gas pressure is 6 × 10 ⁻⁵ Torr and the processing speed is 420 m / min. Oxygen / argon mixed gas plasma treatment was performed to form a plasma treated surface in which the surface tension of the film surface of the carbon-containing silicon oxide layer was improved by 54 dyne / cm or more.
Next, an epoxy-based silane coupling agent (8.0 wt%) and an anti-blocking agent (1.0 wt%) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. Then, a primer composition obtained by sufficiently kneading is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.4 g / m ² (dry state). An agent layer was formed.
Further, a two-component curing type polyurethane laminating adhesive is used on the surface of the primer layer formed as described above, and this is applied to a film thickness of 4.0 g / m ² (by a gravure roll coating method. The adhesive layer for laminating was formed by coating so as to be in a dry state.
Next, on the surface of the laminating adhesive layer formed as described above, a linear low density polyethylene film having a thickness of 50 μm is overlapped with its corona-treated surface facing each other, and then both are laminated with dry laminating. The laminated material was manufactured by laminating.
Next, the peel strength (laminate strength) of the laminated material produced above was measured.
This was measured using a Tensilon measuring instrument under the conditions of a test piece width of 15 mm, T-shaped peeling, and peeling speed of 50 mm / min.
The measurement results are shown in Table 3 below.

(Table 3)
┌─────┬────────────────┐ │ │ Peel strength [gf] │ ├─────┼──────────── ─────┤ │Example 1 │ 380 │ ├─────┼────────────────┤ │Example 2 │ 580 │ ├───── ┼────────────────┤ │Example 3 │ 600 │ ├─────┼────────────────┤ │ Example 4 │ 490 │ ├─────┼────────────────┤ │Example 5 │ 640 │ ├────┼────── ──────────┤ │Example 6 │ 720 │ ├─────┼────────────────┤ │Comparative Example 1 │ 30 (interlayer Peeling) │ ├─────┼────────────────┤ │Comparative Example 2 │ 30 (Delamination) │ ├ ────┼────────────────┤ │Comparative Example 3 │ 600 │ └─────┴─────────────── --┘

  As is clear from the results shown in Table 3 above, the laminate using the transparent gas barrier laminate according to the present invention has excellent peel strength (laminate strength) and can be sufficiently put into practical use. There was found.

[Experimental Example 4]
In the transparent gas barrier laminates produced in Examples 1 to 3 and Comparative Examples 1 to 3, a plasma etching protective layer-coated substrate film before forming a carbon-containing silicon oxide layer by plasma chemical vapor deposition About (Examples 1-3, Comparative Examples 2-3) and a base film (Comparative Example 1), the etching rate by oxygen plasma was measured.
The substrate was placed in a flat plate type plasma chemical vapor deposition apparatus, irradiated with oxygen plasma in a reduced pressure environment, the thickness of the substrate before and after irradiation for a predetermined time was measured with a thickness meter, and the following formula was obtained.
Etching rate: R = [base material thickness before irradiation (μm) −base material thickness after irradiation (μm)] / irradiation time (min)
The applied output was 300 W, the oxygen flow rate was 60 sccm, the degree of vacuum was 30 mT, and the irradiation time was 5 min.
The measurement results are shown in Table 4 below.

(Table 4)
┌─────┬────────────────┐ │ │ R [μm / min] │ ├─────┼────────── ──────┤ │Example 1 │ 0.17 │ ├────┼────────────────┤ │Example 2 │ 0.14 │ ├ ─────┼────────────────┤ │Example 3 │ 0.12 │ ├─────┼─────────── ─────┤ │Comparative Example 1 │ 0.22 │ ├─────┼────────────────┤ │Comparative Example 2 │ 0.20 │ ├─ ────┼────────────────┤ │Comparative Example 3 │ 0.08 │ └─────┴──────────── ────┘

  As is clear from the results shown in Table 4 above, those according to the present invention can form a plasma etching protective layer that is excellent in adhesion and has a high effect of suppressing the generation of weak interface layer (WBL) and yellowing. It was a thing.

[Reference Example 1]
(1). Next, on the surface of the carbon-containing silicon oxide layer of the transparent gas barrier laminate produced in Example 1 above, first, a glow discharge plasma generator is used, and the power is 9 kw, oxygen gas (O ₂ ): argon. Using a mixed gas consisting of gas (Ar) = 7.0: 2.5 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min. Thus, a plasma-treated surface was formed in which the surface tension of the film surface of the carbon-containing silicon oxide layer was improved by 54 dyne / cm or more.
Next, an epoxy-based silane coupling agent (8.0 wt%) and an anti-blocking agent (1.0 wt%) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. Then, a primer composition obtained by sufficiently kneading is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.4 g / m ² (dry state). An agent layer was formed.
Furthermore, after a desired printed pattern is formed on the surface of the primer layer formed as described above, a two-component curable polyurethane laminating adhesive is applied to the entire surface including the printed pattern by the gravure roll coating method. To form a laminating adhesive layer by coating to a thickness of 4.0 g / m ² (in a dry state), and then, on the surface of the laminating adhesive layer, a thickness of 60 μm A low density polyethylene film was laminated by dry lamination to produce a laminate according to the present invention.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product was then boiled under the boil treatment conditions consisting of 60 minutes at a temperature of 95 ° C. to produce the boiled packaged food according to the present invention.
The boiled packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Furthermore, it has excellent barrier properties against oxygen gas, water vapor, etc., no bag breakage or leakage of contents, etc., and functions as a food container, for example, filling and packaging suitability, distribution suitability, storage suitability, etc. It was. (2). Next, after the plasma-treated surface, the primer layer, and the desired printing pattern are formed on the surface of the carbon-containing silicon oxide layer of the transparent gas barrier laminate produced in Example 1 as described above. Then, on the entire surface including the printed pattern, a two-component curable polyurethane laminating adhesive was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method. A laminating adhesive layer is formed, and then a biaxially stretched nylon 6 film having a thickness of 15 μm is laminated on the surface of the laminating adhesive layer with its corona-treated surfaces facing each other. Both were laminated by dry lamination.
Next, after applying the corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above, and thereafter The laminate material according to the present invention was manufactured by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. The retort packaged food according to the present invention was manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

[Reference Example 2]
Using the transparent gas barrier laminate according to the present invention produced in Example 2 above, the boiled packaged food and the retort packaged food were treated in the same manner as in Reference Example 1 in the same manner as in Reference Example 1 above. Manufactured.

[Reference Example 3]
Using the transparent gas barrier laminate according to the present invention produced in Example 3 above, exactly the same as in Reference Example 1 above, the boiled packaged food and retort packaged food in the same manner as in Reference Example 1 above. Manufactured.

[Reference Example 4]
(1). Next, on the surface of the carbon-containing silicon oxide layer of the transparent gas barrier laminate produced in Example 4 above, first, a glow discharge plasma generator is used, and the power is 9 kw, oxygen gas (O ₂ ): argon. Using a mixed gas consisting of gas (Ar) = 7.0: 2.5 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min. Thus, a plasma-treated surface was formed in which the surface tension of the film surface of the carbon-containing silicon oxide layer was improved by 54 dyne / cm or more.
Next, an epoxy-based silane coupling agent (8.0 wt%) and an anti-blocking agent (1.0 wt%) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. Then, a primer composition obtained by sufficiently kneading is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.4 g / m ² (dry state). An agent layer was formed.
Furthermore, after a desired printed pattern is formed on the surface of the primer layer formed as described above, a two-component curable polyurethane laminating adhesive is applied to the entire surface including the printed pattern by the gravure roll coating method. To form a laminating adhesive layer by coating to a thickness of 4.0 g / m ² (in a dry state), and then, on the surface of the laminating adhesive layer, a thickness of 60 μm A low density polyethylene film was laminated by dry lamination to produce a laminate according to the present invention.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product was then boiled under the boil treatment conditions consisting of 60 minutes at a temperature of 95 ° C. to produce the boiled packaged food according to the present invention.
The boiled packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Furthermore, it has excellent barrier properties against oxygen gas, water vapor, etc., no bag breakage or leakage of contents, etc., and functions as a food container, for example, filling and packaging suitability, distribution suitability, storage suitability, etc. It was. (2). Next, after forming the plasma-treated surface, the primer layer, and the desired printing pattern on the surface of the carbon-containing silicon oxide layer of the transparent gas barrier laminate produced in Example 4 as described above. Then, on the entire surface including the printed pattern, a two-component curable polyurethane laminating adhesive was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method. A laminating adhesive layer is formed, and then a biaxially stretched nylon 6 film having a thickness of 15 μm is laminated on the surface of the laminating adhesive layer with its corona-treated surfaces facing each other. Both were laminated by dry lamination.
Next, after applying the corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above, and thereafter The laminate material according to the present invention was manufactured by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. The retort packaged food according to the present invention was manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

[Reference Example 5]
Using the transparent gas barrier laminate according to the present invention produced in the above Example 5, exactly the same as the above Reference Example 4, the boiled packaged food and the retort packaged food as in the above Reference Example 4. Manufactured.

[Reference Example 6]
Using the transparent gas barrier laminate according to the present invention produced in the above Example 6, exactly the same as the above Reference Example 4, the boiled packaged food and the retort packaged food as in the above Reference Example 4. Manufactured.

  The transparent gas barrier laminate according to the present invention is excellent in adhesion between the base film and the carbon-containing silicon oxide layer, and the carbon-containing silicon oxide layer is excellent in stretchability, flexibility, flexibility, In addition, there is no generation of cracks, and there is a high barrier property that can completely block the transmission of oxygen gas, water vapor, etc., for example, oxygen gas as a barrier material used for packaging materials, etc. In addition, it is possible to produce an extremely useful barrier film that is excellent in gas barrier properties that prevent permeation of water vapor and the like, and further, the performance of the gas barrier properties is not deteriorated.

It is a schematic sectional drawing which shows an example of the layer structure about the transparent gas-barrier laminated body which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the transparent gas-barrier laminated body which concerns on this invention. It is a schematic block diagram which shows the general | schematic structure of an example of the film forming apparatus which film-forms the carbon containing oxidation meter layer about the transparent gas barrier laminated body which concerns on this invention. It is a schematic block diagram which shows the general | schematic structure of an example of the film forming apparatus which film-forms the carbon containing oxidation meter layer about the transparent gas barrier laminated body which concerns on this invention.

Explanation of symbols

A, A ₁ Transparent gas barrier laminate 1 Base film 2, 2a Plasma etching protective layer 3, 3a, 3b, 3c Carbon-containing silicon oxide layer

Claims (6)

It consists of a laminate in which a plasma etching protective layer and a carbon-containing silicon oxide layer are sequentially laminated on one surface of the base film, and further, the plasma etching protective layer includes an acrylic resin and a polyurethane resin, And the said lamination | stacking which consists of a resin layer by the mixed resin composition which the former is 50-80 weight% and the latter is 20-50 weight% in a solid content rate, and also obtains from the following formula If the body of yellowness and (YI _a), and also the yellow degree of the plasma etching protective layer coated substrate film obtained from the following formula and _{(YI b), ΔYI (YI} a -YI b) <0.6 A transparent gas barrier laminate characterized in that:
Yellowness (YI): YI = 100 (1.28X-1.06Z) / Y
(However, in the formula, X, Y, and Z represent the three-color stimulus values X, Y, and Z of the CIE-XYZ color system.) 2. The transparent gas barrier laminate according to claim 1, wherein the base film comprises a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. . The plasma etching protective layer is composed of a resin layer made of a mixed resin composition of a water-soluble or water-dispersible acrylic resin and a water-soluble or water-dispersible polyurethane resin. 2. The transparent gas barrier laminate according to item 1. The transparent gas barrier laminate according to any one of claims 1 to 3, wherein the plasma etching protective layer has a thickness of 0.01 to 5.0 µm. When a plasma etching protective layer-coated base film having a plasma etching protective layer laminated on one surface of the base film is etched with oxygen plasma for a predetermined time, the etching rate of the plasma etching protective layer-coated base film is The transparent gas barrier laminate according to any one of claims 1 to 4, which comprises 95% or less of the etching rate of the base film without the plasma etching protective layer. The carbon-containing silicon oxide layer uses at least two film forming chambers, and for each chamber, a film forming monomer gas composed of at least one organic silicon compound, an oxygen gas, and a non-forming film. Two or more film forming mixed gas compositions prepared by changing the mixing ratio of each gas component of the film forming mixed gas composition containing an active gas are used, and each film forming mixed gas composition is used. Each of the carbon-containing silicon oxide layers formed by plasma chemical vapor deposition using two or more layers, and each carbon-containing silicon oxide layer contains carbon atoms in the film and each carbon-containing oxide layer. The transparent gas barrier laminate according to any one of claims 1 to 5, wherein the carbon content is different for each silicon layer.

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