JP5034258B2 - Transparent deposited film and method for producing the same - Google Patents

Description

  The present invention relates to a transparent vapor deposition film and a method for producing the same. More specifically, in the present invention, when an inorganic oxide is deposited on a biaxially stretched polyethylene terephthalate film by physical vapor deposition (PVD), the surface of the biaxially stretched polyethylene terephthalate film is micronized before the deposition step. The present invention relates to a method for producing a transparent vapor-deposited film comprising treating with a nitriding plasma formed by waves and further depositing an inorganic oxide, and a transparent vapor-deposited film produced by the method.

  Conventionally, various packaging materials have been developed and proposed for filling and packaging foods, beverages, pharmaceuticals, cosmetics, and other various articles. Among them, in recent years, inorganic oxides such as silicon oxide, aluminum oxide and magnesium oxide have been used on the surface of plastic substrates as a barrier material against oxygen gas or water vapor, and vacuum deposition, sputtering, ion Uses physical vapor deposition (PVD) such as plating, or chemical vapor deposition (CVD) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition Thus, a transparent vapor deposition film formed by forming a vapor deposition film of the inorganic oxide has attracted attention. Furthermore, various means for improving the barrier property of such a transparent vapor deposition film against oxygen gas or water vapor and the adhesion between the plastic substrate and the inorganic oxide have been proposed.

For example, in Patent Document 1 and Patent Document 2, “on the surface of a plastic substrate, a biaxially stretched polyethylene terephthalate film, or the like, a plasma processing surface by oxygen gas, a mixed gas of oxygen gas and argon gas or helium gas, or the like is provided. Furthermore, there is shown a “transparent barrier film characterized in that an inorganic oxide vapor deposition film is provided on the plasma treated surface”.
Patent Document 1 and Patent Document 2 disclose that an inorganic gas is converted into plasma by a general plasma forming means to treat the surface of a polyethylene terephthalate film, but by irradiating nitrogen gas or ammonia gas with microwaves. Nothing is disclosed about the surface treatment by the generated nitriding plasma, that is, the plasma treatment of the surface of the polyethylene terephthalate film by a specific combination of nitrogen gas or the like and microwaves. Therefore, the transparent barrier films described in Patent Document 1 and Patent Document 2 are inferior in water resistance, and the inorganic oxide is peeled off from the polyethylene terephthalate film by retort and boil treatment, and cannot be put to practical use. In addition, oxygen barrier properties and water vapor barrier properties are insufficient.

  Patent Document 3 discloses that “a plasma treatment surface such as oxygen gas or a mixed gas of oxygen gas and nitrogen gas is provided on the surface of a plastic substrate, a biaxially stretched polyethylene terephthalate film, etc .; In addition, a transparent barrier film characterized by providing a vapor-deposited film of an inorganic oxide is shown. Since the surface modification of the polyethylene terephthalate film in the transparent barrier film described in Patent Document 3 is performed by a plasma gas generated by ionizing the gas by arc discharge, that is, a plasma gas having a low processing energy, sufficient processing is performed. The water resistance strength is inferior, and the inorganic oxide is peeled off from the polyethylene terephthalate film by retort and boil treatment. Further, the oxygen barrier property and the water vapor barrier property are insufficient.

  Patent Document 4 states that “a vapor deposition layer made of an inorganic compound is a first layer on a base material made of a polymer resin composition, a water-soluble polymer, and (a) one or more alkoxides and / or their A gas barrier film formed by applying an aqueous solution containing at least one of hydrolyzate or (b) tin chloride, or a water / alcohol mixed solution as a main ingredient and heating and drying is laminated as a second layer. A gas barrier laminate film characterized in that The gas barrier laminate film described in Patent Document 4 has a high barrier property by forming a gas barrier coating layer comprising an inorganic compound, a water-soluble polymer, a metal alkoxide or / and a hydrolyzate thereof, and tin chloride on a transparent base film. Although it aims at obtaining, since the adhesiveness of an inorganic compound and a base material is bad, there exists a problem that water resistance strength is bad and an inorganic compound peels from a base material by a retort and a boil process.

Further, in Patent Document 5, “a transparent gas barrier laminated film having a metal oxide layer on at least one surface of a transparent polymer film, in contact with the metal oxide layer and outside thereof, an alkoxysilane having a certain chemical structure. A transparent gas barrier laminated film characterized in that a cured film containing a polyvinyl alcohol crosslinked by a (partial) hydrolyzate, a (partial) condensate thereof, or a mixture thereof is laminated. The transparent gas barrier laminated film described in Patent Document 5 is formed by forming a metal oxide vapor-deposited layer on one side by chemical vapor deposition (CVD), and forming a polyvinyl alcohol crosslinked with a mixture of a metal alkoxide hydrolyzate and a condensate thereof. The purpose is to form a hardened coating film on the vapor deposition surface and to obtain a high gas barrier property. However, since the adhesion between the metal oxide vapor deposition layer and the substrate is poor, the water resistance is poor and the metal oxide is oxidized by retort and boil treatment. There is a problem that an object peels off from a base material.
JP-A-11-262970 Japanese Patent Laid-Open No. 11-322979 JP-A-10-193502 Japanese Patent No. 2790054 Japanese Patent No. 3403880

  As described above, various means for improving the barrier property of the transparent vapor deposition film against oxygen gas or water vapor and the adhesion between the plastic substrate and the inorganic oxide have been proposed. In addition, sufficient adhesion between the plastic substrate and the inorganic oxide is not obtained.

  On the other hand, the present invention has a high barrier property against oxygen gas or water vapor and the like, and has high adhesion between the biaxially stretched polyethylene terephthalate and the inorganic oxide. For example, food and drink, pharmaceuticals, cosmetics, The present invention provides a method for producing a transparent vapor deposition film useful for filling and packaging chemicals, electronic parts, and other various articles.

  As a result of diligent research to solve the above-mentioned problems, the present inventor, when depositing an inorganic oxide on a biaxially stretched polyethylene terephthalate film by physical vapor deposition (PVD), before the vapor deposition step, the biaxial The surface of the stretched polyethylene terephthalate film is treated with a nitriding plasma formed by microwaves, and then an inorganic oxide is deposited, thereby barrier properties such as oxygen permeability and water vapor permeability, and biaxially stretched polyethylene terephthalate and inorganic oxidation. The present inventors have found that the adhesion between the product and the object is remarkably improved and have completed the present invention.

That is, this invention includes the invention shown to the following (a)-(e).
(A) A method for producing a transparent vapor-deposited film, wherein the surface of a biaxially stretched polyethylene terephthalate film is treated with a nitriding plasma formed by microwaves, and further an inorganic oxide is laminated.
(B) a transparent vapor-deposited film in which an inorganic oxide is laminated on the surface of a biaxially stretched polyethylene terephthalate film,
The transparent evaporated film, wherein the biaxially stretched polyethylene terephthalate film contains a nitrogen atom bonded to at least one carbon atom.
(C) In the element ratio of carbon, nitrogen, and oxygen of the biaxially stretched polyethylene terephthalate film, the ratio of nitrogen element is 1% to 7% (Atomic%), the ratio of carbon element is 75% or more, and the ratio of oxygen element is The transparent vapor-deposited film as described in (b) above, which is 25% or less.
(D) The surface roughness of the biaxially stretched polyethylene terephthalate film is 1.0 nm or less in arithmetic average roughness (Ra), 2.0 nm or less in root mean square roughness (Rms), and 8.8 in maximum roughness (Rmax). The transparent vapor-deposited film according to (b) or (c), which satisfies all the conditions of 0 nm or less.
(E) A transparent vapor deposition film obtained by coating a gas barrier coating film on a vapor deposition film of an inorganic oxide provided on the biaxially stretched polyethylene terephthalate film surface of the transparent vapor deposition film,
The gas barrier coating film has a general formula R ¹ _n M (OR ₂ ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M.), a polyvinyl alcohol-based resin and / or A gas barrier comprising an ethylene-vinyl alcohol copolymer, and further comprising a gas barrier composition that undergoes polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, water, and an organic solvent. The transparent vapor deposition film in any one of said (b)-(d) which provided the adhesive coating film.

  In the present invention, the plasma treatment of the surface of the biaxially stretched polyethylene terephthalate film is performed using nitriding plasma formed by microwaves, and the smoothness of the surface of the biaxially stretched polyethylene terephthalate film is improved and nitrogen is doped into the film. Therefore, adhesion between the inorganic oxide and the biaxially stretched polyethylene terephthalate film, and gas barrier properties such as oxygen barrier properties and water vapor barrier properties are improved.

  Further, by providing the gas barrier coating film on the transparent vapor deposition film produced by the production method of the present invention, cracks and the like are generated in the vapor deposition film of inorganic oxide such as silicon oxide and aluminum oxide constituting the barrier layer. In addition, it is possible to provide a transparent vapor deposition film having excellent barrier properties that prevents permeation of oxygen gas, water vapor, and the like.

Hereinafter, the present invention will be described in more detail with reference to the drawings.
1. Manufacturing method of transparent vapor deposition film The manufacturing method of the transparent vapor deposition film of this invention is demonstrated. FIG. 1 is a schematic configuration diagram of a winding-type vacuum vapor deposition apparatus showing an example of a method for producing a transparent vapor deposition film according to the present invention.
Specifically, as shown in FIG. 1, the method for producing a transparent vapor-deposited film according to the present invention is as follows. First, in a vacuum chamber 2 of a take-up vacuum vapor deposition apparatus 1, a biaxially stretched polyethylene is formed from an unwinding portion 4. The terephthalate film 6 is fed out, and the biaxially stretched polyethylene terephthalate film 6 is guided to the cooling drum 11 through the guide roll 5. In the present invention, the microwave plasma device 9 is disposed between the guide roll 5 and the cooling drum 11, and the microwave plasma device 9 is used on the surface of the biaxially stretched polyethylene terephthalate film 6. A plasma treatment is performed by generating a nitriding plasma 10 from the microwave plasma apparatus 9 to form a plasma treatment surface on the surface of the biaxially stretched polyethylene terephthalate film 6. Next, after the biaxially stretched polyethylene terephthalate film 6 provided with the plasma treated surface is guided onto the cooling drum 11, a metal or an inorganic oxide is used as a deposition source 15 on the plasma treated surface of the biaxially stretched polyethylene terephthalate film 6. Then, these are put into a crucible 16 and the metal or inorganic oxide heated in the crucible 16 is evaporated. At that time, oxygen gas or the like is ejected from the oxygen pipe 14 and the inorganic material is passed through the shutter 13. An oxide deposition film is formed. Next, the biaxially stretched polyethylene terephthalate film 6 on which the metal or inorganic oxide vapor-deposited film is formed is wound around the take-up portion 12 through the guide roll 5 'to produce the transparent vapor-deposited film according to the present invention. .

In the above vapor deposition machine, the degree of vacuum in the vacuum chamber is preferably 10 ⁰ to 10 ⁻⁵ mbar, preferably 10 ⁻¹ to 10 ⁻⁴ mbar. The degree of vacuum of the coding chamber is preferably 10 ⁻² to 10 ⁻⁸ mbar, preferably 10 ⁻³ to 10 ⁻⁷ mbar before introducing oxygen, and 10 ⁻¹ after introducing oxygen. 10 ⁻⁶ mbar, preferably 10 ⁻² to 10 ⁻⁵ mbar. The above illustration is an example of the production method, and the present invention is not limited thereby.

Next, the biaxially stretched polyethylene terephthalate film, plasma type, plasma treatment conditions, and inorganic oxide used in the production method of the present invention will be described.
(1) Biaxially stretched polyethylene terephthalate film The biaxially stretched polyethylene terephthalate film used in the production method of the present invention is, for example, a polyester resin film or sheet obtained by a condensation reaction of terephthalic acid or a derivative thereof and ethylene glycol. And what is extended | stretched to 2 directions by a tenter system or a tubular system etc. is used, for example. The thickness of the biaxially stretched polyethylene terephthalate film can be set as appropriate from the standpoint of stability during production, but is preferably about 6 μm to 100 μm, more preferably 12 μm to 50 μm. In addition, the biaxially stretched polyethylene terephthalate film may be added with a desired additive such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, or a filler within a range that does not affect the transparency. It can be added arbitrarily.

(2) Plasma species In the present invention, the plasma treatment of the biaxially stretched polyethylene terephthalate film surface is performed by nitriding plasma formed by irradiating a nitrogen gas (N ₂ ) or ammonia gas (NH ₃ ) with microwaves. As a result, the surface of the biaxially stretched polyethylene terephthalate film is smoothed and nitrogen is doped into the biaxially stretched polyethylene terephthalate film to form a covalent bond between the nitrogen atom and the carbon atom on the biaxially stretched polyethylene terephthalate film. To do. As a result, the adhesion between the inorganic oxide and the biaxially stretched polyethylene terephthalate film is improved.

  In addition, the ratio of the nitrogen element doped in the biaxially stretched polyethylene terephthalate film is the atomic ratio of carbon, nitrogen, and oxygen in the biaxially stretched polyethylene terephthalate film. 1% to 7% (preferably 1.0% to 6.5%), carbon element 75% or more (preferably 75% to 99%), oxygen element 25% or less (preferably 1. 0% to 25%) is preferable. When the ratio of the nitrogen atom is less than 1%, the adhesion between the biaxially stretched polyethylene terephthalate film and the inorganic oxide is lowered, and when it exceeds 7%, the barrier property is lowered, which is not preferable.

  The surface roughness of the biaxially stretched polyethylene terephthalate film after plasma treatment is 1.0 nm or less (preferably 0.1 to 0.9 nm) in terms of arithmetic average roughness (Ra), and the mean square roughness (Rms). It is preferable to satisfy all conditions of 2.0 nm or less (preferably 0.2 to 1.8 nm) and maximum roughness (Rmax) of 8.0 nm or less (preferably 1.6 to 7.8 nm). If any of the arithmetic average roughness, the root mean square roughness, and the maximum roughness exceeds the above numerical values, the adhesion between the biaxially stretched polyethylene terephthalate film and the inorganic oxide deposited film is deteriorated, which is not preferable.

(3) Plasma treatment conditions As described above, in the present invention, the adhesion between the inorganic oxide and the biaxially stretched polyethylene terephthalate film is the ratio of the nitrogen element contained in the biaxially stretched polyethylene terephthalate film. Since it greatly depends on the surface roughness of the stretched polyethylene terephthalate film, the processing conditions of the plasma treatment are extremely important. In the present invention, factors that affect the plasma treatment and chemical reaction include plasma output, gas type, gas pressure, treatment time, and the like. Nitrogen gas or ammonia gas is used for the plasma treatment, and the gas pressure is 1.33 × 10 ^{−5 to} 1.33 × 10 ⁻¹ mbar, more preferably 1.07 × 10 ^{−2 to} 6. .67 × 10 ^-2 mbar is desirable. The plasma output is preferably 0.2 to 15 kW, more preferably 0.5 to 10 kW. Further, the processing speed is 100 to 1000 m / min, more preferably 200 to 800 m / min. desirable. In the above gas pressure, if the gas pressure is too low, the number of nitrogen molecules activated by the plasma is reduced, and the introduction of nitrogen into the biaxially stretched polyethylene terephthalate film surface is inhibited. Further, when the plasma output is less than 0.2 kW, or even less than 0.5 kW, the activation of the gas is lowered and it becomes difficult to generate highly active nitrogen atoms. On the other hand, if it exceeds 15 kW, and further if it exceeds 10 kW, the plasma output is too high, and the physical properties of the transparent vapor-deposited film itself deteriorate due to deterioration of the biaxially stretched polyethylene terephthalate film. Further, when the treatment speed is less than 100 m / min, and further less than 200 m / min, the biaxially stretched polyethylene terephthalate film becomes porous, the barrier property is lowered, and exceeds 1000 m / min. Further, if it exceeds 800 m / min, the amount of nitrogen plasma with respect to the biaxially stretched polyethylene terephthalate film is reduced, and the adhesion between the biaxially stretched polyethylene terephthalate film and the inorganic oxide is lowered.

(4) Inorganic oxide As the vacuum-deposited inorganic oxide in the production method of the present invention, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin ( Examples thereof include oxides such as Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y).
Preferable examples include vapor deposited films of metal oxides such as silicon (Si) and aluminum (Al).

The metal oxide vapor deposition film can also be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of x are each range differs by the metal element) as _X, etc. represented by.

  In addition, as a range of the value of x described above, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, titanium (Ti) is 0 to 2, Lead (Pb) can take values in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.

  In the above, when x = 0, it is a perfect metal and cannot be used because it is not transparent. Further, the upper limit of the range of x is a value when completely oxidized.

  Desirably, silicon (Si) having a value in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5 can be used.

  The film thickness of the vapor-deposited film of the inorganic oxide varies depending on the metal to be used or the kind of the metal oxide, but can be arbitrarily selected within the range of, for example, 50 to 2000 mm, preferably 100 to 1000 mm. .

  Moreover, as the inorganic oxide vapor deposition film, the metal or metal oxide to be used may be used in one kind or a mixture of two or more kinds to constitute a vapor deposition film of an inorganic oxide mixed with different materials. it can.

2. A method for producing a transparent vapor deposition film, further comprising a gas barrier coating film on the inorganic oxide vapor deposition film of the transparent vapor deposition film of the present invention. A gas barrier coating film is further formed on the inorganic oxide vapor deposition film of the transparent vapor deposition film. By providing, the barrier property of a transparent vapor deposition film can be improved further. Below, the manufacturing method of the transparent vapor deposition film which provided the gas-barrier coating film of this invention is demonstrated.
The transparent vapor deposition film provided with the gas barrier coating film is formed by a process including the following (i) to (iii).
(I) As a gas barrier composition, for example, general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M), and a polyvinyl alcohol resin. And / or a process of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, water, and an organic solvent, and / or an ethylene / vinyl alcohol copolymer,
(Ii) A gas barrier that is polycondensed by the above-described sol-gel method on an inorganic oxide vapor-deposited film provided on one surface of a biaxially stretched polyethylene terephthalate film, if necessary, via a plasma-treated surface with oxygen gas, etc. A step of applying a functional composition to provide a coating film,
(Iii) The transparent vapor-deposited film provided with the above-described coating film is subjected to heat treatment at a temperature of 20 ° C. to 180 ° C. and a temperature not higher than the melting point of the above biaxially stretched polyethylene terephthalate film for 10 seconds to 10 minutes, A gas barrier coating film made of the above gas barrier composition, if necessary, over a vapor-deposited film of an inorganic oxide provided on one surface of the biaxially stretched polyethylene terephthalate film. Forming.

In the present invention, the gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, A metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol system A gas barrier composition containing a resin and / or an ethylene / vinyl alcohol copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, water, and an organic solvent is prepared. Two or more layers were laminated on the inorganic oxide vapor-deposited film provided on one surface of the biaxially stretched polyethylene terephthalate film, and two or more gas barrier coating films of the above gas barrier composition were laminated. Composite port It can also be produced by forming a remmer layer.

Next, an alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a gas barrier composition, which can be used in the production method of the present invention. The manufacturing method of a thing is demonstrated.
(1) In the general formula R ¹ _n M (OR ²⁾ alkoxide general formula R ¹ _n M (OR ²⁾ represented by _m alkoxide represented by _m, the metal atom represented by M is silicon, zirconium , Titanium, aluminum, etc. can be used. In the present invention, alkoxysilane in which M is Si is particularly preferable. Moreover, the alkoxide of 2 or more types of different metal atoms can also be mixed and used in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group and n-octyl group.

Specific examples of the alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) ₄ etc. can be used. These alkoxysilanes may be used alone or in admixture of two or more.

(2) Polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer forming the gas barrier coating film, polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer is used. A vinyl alcohol copolymer can be used alone, respectively, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used in combination. When a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is, as a weight ratio, polyvinyl alcohol-based resin: ethylene / vinyl alcohol copolymer = 10: 0.05. -10: 6, more preferably about 10: 1.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by weight, preferably about 20 to 100 parts by weight based on 100 parts by weight of the total amount of the alkoxide. It is preferable to prepare the gas barrier composition at a blending ratio of 200 parts by weight.

  Specific examples of the polyvinyl alcohol resin include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1,400), and the like can be used.

  As a specific example of the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer may be used. it can.

(3) Preparation method of gas barrier composition The gas barrier composition for forming the gas barrier coating film has the above general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are carbon atoms) An organic group having a number of 1 to 8, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M). In the presence of a sol-gel catalyst, water, and an organic solvent, and at least one alkoxide to be mixed with the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer. It can be prepared by polycondensation by a sol-gel method.

  In preparing the gas barrier composition, the flexibility and workability of the gas barrier coating film can be further improved by adding a silane coupling agent or the like. As such silane coupling agents, known organic reactive group-containing organoalkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such a silane coupling agent can be used within a range of 1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. In the above, the use of 20 parts by weight or more is not preferable because the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulating property and workability of the gas barrier coating film tend to be lowered.

  Further, as the sol-gel method catalyst used in the above gas barrier composition, mainly as a polycondensation catalyst, a tertiary amine or acid that is substantially insoluble in water and soluble in an organic solvent is used. Can be used.

  As the tertiary amine, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. These tertiary amines are preferably used in an amount of 0.01 to 1.0 parts by weight, preferably about 0.03 parts by weight, per 100 parts by weight of the total amount of alkoxide and silane coupling agent.

  Moreover, as an acid used in said gas-barrier composition, mineral acids, such as a sulfuric acid, hydrochloric acid, and nitric acid, organic acids, such as an acetic acid and tartaric acid, etc. can be used, for example. These acids are preferably used in an amount of 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, can be used with respect to 1 mol of the total molar amount of the alkoxide.

  Furthermore, as the organic solvent used in the gas barrier composition, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

The gas barrier coating film according to the present invention is manufactured, for example, as follows.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier composition (coating liquid). In the gas barrier composition (coating liquid), the polycondensation reaction gradually proceeds.

Next, the above gas barrier composition (coating liquid) is applied by an ordinary method on an inorganic oxide vapor-deposited film provided on one surface of the substrate, and dried.
Furthermore, the above coating operation is repeated to laminate a plurality of coating films composed of two or more layers.
The barrier layer according to the present invention thus obtained is excellent in gas barrier properties.

  The inorganic oxide vapor-deposited film and the gas barrier coating film form, for example, a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation reaction. The two-layer synergistic effect can provide a better gas barrier effect.

  As a method of applying the gas barrier composition, for example, a roll coating such as a gravure roll coater, spray coating, spin coating, dipping, brush, barcode, applicator or the like, one or more times. By coating, a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed. Furthermore, in a normal environment, 50 to 300 ° C., preferably 70 to Condensation is performed by heating and drying at a temperature of 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, to form the first or second gas barrier coating film. Can do.

  If necessary, when applying the gas barrier composition, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance, and corona discharge treatment or plasma treatment, etc. The pre-treatment can be arbitrarily performed.

3. Use of the transparent vapor-deposited film of the present invention The packaging container produced using the transparent vapor-deposited film according to the present invention is excellent in transparency, gas barrier properties against oxygen gas, water vapor, etc., impact resistance, etc., and further laminated and printed. It has suitability for post-processing such as processing, bag-making or box-making, and prevents peeling of the vapor-deposited thin film as a barrier film, and also prevents the occurrence of thermal cracks and prevents its deterioration. It exhibits excellent resistance as a barrier film, for example, filling and packaging suitability and storage suitability for various articles such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other chemicals and cosmetics. Etc. are excellent.

Next, the present invention will be specifically described with reference to examples.
[Example 1]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film, and the above-described biaxially stretched polyethylene terephthalate film is the same as that of the winding-type vacuum deposition apparatus (physical vapor deposition apparatus) in FIG. Mounted on the delivery roll.
Next, this was conveyed at a line speed of 600 m / min, nitrogen gas 500 sccm was introduced into the microwave plasma processing apparatus at a pressure of 1.0 × 10 ⁻³ mbar, and plasma processing was performed at an output of 1.5 kW. Under the vapor deposition conditions, aluminum oxide was laminated and wound up by a vacuum vapor deposition method using an electron beam (EB) heating method to produce a transparent vapor deposition film of the present invention. The film thickness of the aluminum oxide at this time was 20 nm.
Vacuum chamber vacuum degree: 2 × 10 ^-2 mbar
Coating chamber vacuum (before introducing oxygen gas): 1 × 10 ⁻⁵ mbar
Coating chamber vacuum degree (after introducing oxygen gas): 5 × 10 ⁻⁴ mbar
Deposition source: Aluminum

(2) After forming the transparent vapor deposition film, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: Using a mixed gas of 2.5 (unit: slm), performing oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 8.0 × 10 ⁻⁵ mbar and a treatment speed of 100 m / min, and depositing an aluminum oxide film A plasma-treated surface in which the surface tension of the surface was improved by 54 dyne / cm or more was formed.

On the other hand, according to the composition shown in Table 1 below, the prepared composition a. A pre-prepared composition b. In a mixed solution comprising an aqueous polyvinyl alcohol solution, isopropyl alcohol and ion-exchanged water. A hydrolyzed solution consisting of ethyl silicate, silane coupling agent, isopropyl alcohol, 0.5N hydrochloric acid aqueous solution and ion-exchanged water was added and stirred sufficiently to obtain a colorless and transparent barrier coating solution.
(Table 1)
a Polyvinyl alcohol 2.33 (wt%)
(RS-110: manufactured by Kuraray Co., Ltd., degree of saponification = 99%, degree of polymerization = 1,000)
Isopropyl alcohol 2.70
H ₂ O 51.75
b Ethyl silicate 16.60
Silane coupling agent 1.66
(Γ-glycidoxypropyltrimethoxysilane)
Isopropyl alcohol 3.90
0.5N hydrochloric acid aqueous solution 0.53
H ₂ O 20.53
Total 100.00 (wt%)

  Next, the gas barrier composition produced above is used for the plasma treatment surface of the aluminum oxide vapor deposition film formed in (1) above, and this is coated by the gravure roll coating method, and then at 100 ° C. A transparent vapor deposition film having a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) formed by heat treatment for 30 seconds and further provided with a gas barrier coating film on the inorganic oxide vapor deposition film of the present invention. Manufactured.

[Example 2]
(1) By transporting a biaxially stretched polyethylene terephthalate film at 300 m / min, introducing nitrogen gas 800 sccm into a microwave plasma generator, and performing plasma treatment at an output of 3 kW, the same method as in Example 1, The transparent vapor deposition film of this invention was manufactured. In addition, the film thickness of the aluminum oxide at this time was 20 nm.
(2) A gas barrier coating film is further formed on the inorganic oxide vapor deposition film of the present invention by the same method as described in Example 1 (2) except that the transparent vapor deposition film produced in (1) above is used. The transparent vapor deposition film which provided this was manufactured.

[Example 3]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film, and the above-described biaxially stretched polyethylene terephthalate film is the same as that of the winding-type vacuum deposition apparatus (physical vapor deposition apparatus) in FIG. Mounted on the delivery roll.
Next, this was conveyed at a line speed of 400 m / min, nitrogen gas 500 sccm was introduced into the microwave plasma processing apparatus at a pressure of 1.0 × 10 ⁻³ mbar, and plasma processing was performed at an output of 1.5 kW. Under the vapor deposition conditions, silicon oxide was laminated and wound up by a vacuum vapor deposition method using an electron beam (EB) heating method to produce the transparent vapor deposition film of the present invention. The silicon oxide film thickness at this time was 25 nm.
Vacuum chamber vacuum degree: 2 × 10 ^-2 mbar
Coating chamber vacuum (before introducing oxygen gas): 1 × 10 ⁻⁵ mbar
Coating chamber vacuum degree (after introducing oxygen gas): 5 × 10 ⁻⁴ mbar
Vapor deposition source: silicon oxide (2) On the inorganic oxide vapor deposition film of the transparent vapor deposition film by the same method as shown in Example 1 (2) except that the transparent vapor deposition film produced in (1) above is used. Then, a gas barrier coating film was formed, and the transparent vapor deposition film of the present invention provided with the gas barrier coating film was produced.

[Example 4]
(1) A biaxially stretched polyethylene terephthalate film is conveyed at 300 m / min, nitrogen gas 800 sccm is introduced into a microwave plasma generator, and plasma treatment is performed at an output of 3 kW. The transparent vapor deposition film of the invention was produced. In addition, the film thickness of the silicon oxide at this time was 30 nm.
(2) Gas barrier coating on the inorganic oxide vapor-deposited film of the transparent vapor-deposited film by the same method as shown in Example 1 (2) except that the transparent vapor-deposited film produced in (1) above is used. A transparent vapor deposition film of the present invention in which a film was formed and a gas barrier coating film was provided was produced.

[Comparative Example 1]
(1) The transparent vapor deposition film of this invention was manufactured by the method similar to Example 1 except not using a microwave plasma apparatus. The film thickness of the aluminum oxide at this time was 20 nm.
(2) Gas barrier coating on the inorganic oxide vapor-deposited film of the transparent vapor-deposited film by the same method as shown in Example 1 (2) except that the transparent vapor-deposited film produced in (1) above is used. A transparent vapor deposition film provided with a film was produced.

[Comparative Example 2]
(1) The transparent vapor deposition film of this invention was manufactured by the method similar to Example 1 except introduce | transducing argon gas 1000sccm into a direct current glow discharge plasma processing apparatus, and performing plasma processing with an output of 20 kW. The film thickness of the aluminum oxide at this time was 20 nm.
(2) A gas barrier property is further formed on the inorganic oxide vapor-deposited film of the transparent vapor-deposited film by the same method as shown in Example 1 (2) except that the transparent vapor-deposited film produced in (1) above is used. A transparent vapor deposition film provided with a coating film was produced.

[Comparative Example 3]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film, and the above-described biaxially stretched polyethylene terephthalate film is the same as that of the winding-type vacuum deposition apparatus (physical vapor deposition apparatus) in FIG. Mounted on the delivery roll.
Next, this was transported at a line speed of 300 m / min, nitrogen gas 800 sccm was introduced into a direct current glow discharge plasma processing apparatus at a pressure of 1.0 × 10 ⁻³ mbar, and plasma processing was performed at an output of 20 kW. Under the same vapor deposition conditions, aluminum oxide was laminated and wound up by a vacuum vapor deposition method using an electron beam (EB) heating method to produce a transparent vapor deposition film. At this time, the film thickness of the aluminum oxide was 20 nm.
(2) A gas barrier property is formed on the inorganic oxide vapor-deposited film of the transparent vapor-deposited film by the same method as shown in (2) of Example 1 except that the transparent vapor-deposited film produced in (1) above is used. A transparent film having a coating film formed thereon and a gas barrier coating film was produced.

[Experimental example]
1. Elemental analysis Examples 1-4 in which X-ray photoelectron spectroscopy analyzer (model name, XPS) manufactured by VG Scientific, UK, was used, and aluminum oxide was not deposited and only plasma treatment was performed, and Comparative Example 1 The biaxially stretched polyethylene terephthalate film of ~ 3 was used, and the treated surface was analyzed under the following conditions. The chart of Examples 1 to 4 obtained by X-ray photoelectron spectroscopy analysis is shown in FIG. 2, the chart of Comparative Examples 1 to 3 is shown in FIG. 3, and the biaxially stretched polyethylene terephthalate of each Example and each Comparative Example derived from the chart. The results of elemental analysis of the film are shown in (Table 2).
X-ray output: 100 W, irradiation area: 400 μmφ

  As described above (Table 2), the biaxially stretched polyethylene terephthalate film surface of Examples 1 to 4 in which the surface of the biaxially stretched polyethylene terephthalate film was treated with a nitriding plasma formed by microwaves had a peak derived from N1s, that is, from 387 eV. A peak was observed at 394 eV, and it was confirmed that organic nitrogen, that is, a nitrogen atom bonded to at least one carbon atom was present on the surface of the biaxially stretched polyethylene terephthalate film. On the other hand, Comparative Example 1 in which the microwave plasma apparatus was not used, Comparative Example 2 in which surface treatment was performed with argon gas plasma, and Comparative Example 3 in which a direct current glow discharge plasma processing apparatus was used instead of the microwave plasma apparatus. In the stretched polyethylene terephthalate film, no peak derived from N1s was observed, and it was confirmed that organic nitrogen was not present on the surface of the biaxially stretched polyethylene terephthalate film.

2. Measurement of surface shape Examples 1 to 4 in which Digital Scope NanoScope IIIa manufactured by Digital Instrument was used as an atomic force microscope (AFM), and only plasma treatment was performed without depositing aluminum oxide in the production of a transparent vapor deposition film in a tapping mode. The biaxially stretched polyethylene terephthalate films of Comparative Examples 1 to 3 were used, and their treated surfaces were measured under the following conditions. Surface roughness (arithmetic average roughness: Ra, root mean square roughness: Rms, maximum roughness: Rmax ) Was measured. The results are shown in Table 3 below.
Scan Mode: Tapping AFM
Scan Size: 1μm
Scan Rate: 1Hz

As described above (Table 3), the biaxially stretched polyethylene terephthalate film of Examples 1 to 4 in which the surface of the biaxially stretched polyethylene terephthalate film was treated with a nitriding plasma formed by microwaves had an arithmetic average roughness (Ra), a square. It was confirmed that both the average roughness (Rms) and the maximum roughness (Rmax) were small, and the surface smoothness of the biaxially stretched polyethylene terephthalate film was improved. On the other hand, the biaxially stretched polyethylene terephthalate film of Comparative Example 1 that did not use the microwave plasma apparatus had a large maximum roughness (Rmax) and was further surface treated with argon gas plasma. It was confirmed that the terephthalate film had large arithmetic average roughness (Ra) and maximum roughness (Rmax), and the surface smoothness was inferior.
That is, it was confirmed that the surface smoothness was greatly improved by treating the biaxially stretched polyethylene terephthalate film surface with nitriding plasma.

3. Measurement of barrier property Oxygen permeability is OX-TRAN 2/20 manufactured by MOCON, measuring conditions 23 ° C, 90
It was measured according to the measurement method of JIS K7126 at% RH. The water vapor permeability was measured according to the measurement method of JIS 7129 using PERMATRANT 3/31 manufactured by MOCON under measurement conditions of 40 ° C. and 100% RH.
As a measurement sample, the transparent vapor-deposited film provided with the gas barrier coating films of Examples 1 to 4 and Comparative Examples 1 to 3, and the transparent vapor-deposited film were biaxially stretched nylon film (ONy) 15 μm via an adhesive layer. A laminate of 70 μm of unstretched polypropylene film (CPP) (laminated body of transparent deposited film 12 μm / adhesive layer / ONy 15 μ / adhesive layer / CPP 70 μ) was used. The results are shown in (Table 4).

  The transparent vapor deposition film which provided the gas barrier coating film of Examples 1-4 as mentioned above (Table 4), and the laminated body using the same were the transparent vapor deposition film which provided the gas barrier coating film of Comparative Examples 1-3 In addition, oxygen permeability and water vapor permeability are both low compared to a laminate using the same, and the surface of the biaxially stretched polyethylene terephthalate film is treated with nitrogen gas plasma formed by microwaves, thereby producing oxygen. It was confirmed that the barrier property against both gas and water vapor was improved.

4). Retort evaluation Using the transparent vapor deposition film provided with the gas barrier coating film produced in Examples 1 to 4 and Comparative Examples 1 to 3, transparent vapor deposition film 12μ / adhesive layer / ONy15μ / adhesive through the adhesive layer A layer / CPP 70μ laminate was produced. Furthermore, a three-sided bag was made using this, and sealed after filling with tap water. The retort conditions were 120 ° C., 30 minutes, 2 atm. The barrier property after retorting, the peel strength between the biaxially stretched polyethylene terephthalate film and the inorganic oxide (aluminum oxide, silicon oxide) and the appearance were examined. The peel strength was measured using a sample obtained by cutting the laminate in a 15 mm width strip with a low-speed tensile tester under the conditions of a tensile speed of 50 mm / min and a T-shape peel. Moreover, the peeling interface was specified by XPS.

  As described above (Table 5), the peel strength of the three-sided bag using the transparent vapor deposition film provided with the gas barrier coating films of Examples 1 to 4 hardly changed before and after the retort. In contrast, the peel strength after retorting of the three-sided bags of Comparative Examples 1 to 3 was greatly reduced. In particular, in the three-sided bag of Comparative Example 1, peeling was observed between the biaxially stretched polyethylene terephthalate film and the inorganic oxide deposited film after retorting.

  That is, the surface of the biaxially stretched polyethylene terephthalate film is treated with nitriding plasma formed by microwaves, the surface of the biaxially stretched polyethylene terephthalate film is smoothed, and nitrogen is doped into the film. It was confirmed that the adhesion with the inorganic oxide, that is, the water resistance strength was greatly improved.

It is a schematic block diagram which shows an example of the winding-type vacuum evaporation apparatus which forms the thin film film | membrane of the inorganic oxide by the physical vapor deposition method used for the manufacturing method of the transparent vapor deposition film of this invention. It is a figure which shows the X-ray photoelectron spectroscopy analysis result of the biaxial stretching polyethylene terephthalate film after the plasma processing of Examples 1-4. It is a figure which shows the X-ray photoelectron-spectral-analysis result of the biaxially-stretched polyethylene terephthalate film of the untreated or the plasma processing of Comparative Examples 1-3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Rewind-type vacuum apparatus 2 Vacuum chamber 3 Coating chamber 4 Unwinding part 5, 5 'Guide roll 6 Biaxially stretched polyethylene terephthalate film 7 Microwave generator 8 Nitrogen gas 9 Microwave plasma apparatus 10 Nitride plasma 11 Cooling drum 12 rolls Take-up part 13 Shutter 14 Oxygen pipe 15 Deposition source 16 Crucible 17 Electron gun 18 Electron beam

Claims (6)

The surface of the biaxially stretched polyethylene terephthalate film is treated with a nitriding plasma formed by microwaves , and the ratio of nitrogen on the film surface is 1 Atomic% or more, 7 Atomic% with respect to 100 Atomic% of the total of carbon, nitrogen and oxygen. %, And further, an inorganic oxide is laminated.   The manufacturing method according to claim 1, wherein the inorganic oxide is aluminum oxide. A transparent vapor-deposited film in which an inorganic oxide is laminated on the surface of a biaxially stretched polyethylene terephthalate film,
The biaxially oriented polyethylene terephthalate film contains nitrogen atoms bonded to at least one carbon atom ;
Transparent vapor deposited film in the film surface, the proportion of nitrogen, the carbon, nitrogen, relative to the total sum 100 atomic% of oxygen, 1 atomic% or more, wherein the this or less 7Atomic%. The surface roughness of the biaxially stretched polyethylene terephthalate film is 1.0 nm or less in arithmetic mean roughness (Ra), 2.0 nm or less in root mean square roughness (Rms), and 8.0 nm or less in maximum roughness (Rmax). All the conditions are satisfy | filled, The transparent vapor deposition film of Claim 3 characterized by the above-mentioned. The transparent vapor-deposited film according to claim 3 or 4 , wherein the inorganic oxide is aluminum oxide. A transparent vapor deposition film obtained by coating a gas barrier coating film on a vapor deposition film of an inorganic oxide provided on the surface of a biaxially stretched polyethylene terephthalate film of a transparent vapor deposition film,
The gas barrier coating film has a general formula R ¹ _n M (OR ₂ ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), a polyvinyl alcohol-based resin and / or ethylene. A gas barrier property, characterized in that it contains a vinyl alcohol copolymer and is a gas barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, water, and an organic solvent. The transparent vapor deposition film as described in any one of Claims 3-5 which provided the coating film.

Images