JP5098603B2 - Gas barrier vapor deposition film, method for producing the same, and laminate material using the same - Google Patents

Description

  The present invention relates to a vapor-deposited film having gas barrier properties, a method for producing the same, and a laminate using the same. More specifically, the present invention has high barrier properties against oxygen gas or water vapor, etc., and suitable physical properties for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, chemicals, electronic products, and sundries. It is related with the vapor deposition film which has a color tone, its manufacturing method, and the laminated material using the same.

  Various packaging materials have been developed and proposed for filling and packaging articles such as food and drink, pharmaceuticals, and cosmetics. Among them, in recent years, as a barrier material against oxygen gas or water vapor, etc., oxides such as silicon oxide, aluminum oxide, magnesium oxide are used on the surface of the plastic film, and the oxide deposited film is formed by various deposition methods. A gas barrier vapor-deposited film formed by forming a film has been attracting attention.

  For example, Patent Document 1 is a film having excellent transparency and gas barrier properties, in which an oxide vapor deposition film is provided on a plastic film as a base material, and a coating film made of a silicon oxide film is provided thereon. A transparent gas barrier film is disclosed.

  In such a gas barrier vapor-deposited film, a polyester film such as a polyethylene terephthalate (PET) film, which is excellent in mechanical strength and chemical stability, and is lightweight and inexpensive, is widely used as a base plastic film. ing.

  Polyester requires some catalyst in the polycondensation reaction during its production, and examples of the polycondensation catalyst include antimony catalysts and germanium catalysts. However, the germanium-based catalyst is very expensive and has a large cost burden, so that it is limited in use on an industrial scale. On the other hand, the antimony-based catalyst is inexpensive, and the polyester obtained thereby has high transparency, and can exhibit excellent gas barrier properties when an oxide is deposited. Therefore, at present, antimony-based catalysts such as antimony trioxide are most commonly used in the production of polyester films used as substrates for gas barrier vapor-deposited films.

However, in recent years, with respect to polyester products, lack of safety and hygiene based on the toxicity of antimony catalysts and the burden on the environment are regarded as problems. Specifically, in the polyester produced using an antimony catalyst, antimony of several hundred ppm is mixed, which is not preferable for the environment, and in drinking water placed in a packaging container made of the polyester. Has been shown to increase the concentration of antimony, and there are concerns about adverse effects on the human body.
Japanese Patent Laid-Open No. 11-151774

  The present invention is a vapor-deposited film manufactured without using an antimony-based catalyst, exhibits excellent gas barrier properties, and has color tone, moisture resistance, impact resistance, etc. suitable for packaging applications and optical applications. The present invention provides a vapor-deposited film, a production method thereof, and a laminated material using the vapor-deposited film.

  The present inventors have intensively studied to solve the above-mentioned problems, and as a base film, polyester films made of polyesters produced using various polycondensation catalysts other than antimony-based catalysts, and having various physical properties are shown. Using this, an anchor coat, an oxide vapor deposition film, and a barrier coat were laminated in this order, and the compatibility was examined. As a result, the inventors have found conditions regarding the properties of the base film necessary for obtaining a vapor-deposited film that exhibits excellent gas barrier properties and has color tone, moisture resistance, impact resistance, etc. suitable for packaging and optical applications. .

Specifically, a film comprising a polyester produced using a titanium-based catalyst as a polycondensation catalyst, the color coordinate b value of which is −0.5 to 5, and a load of 0.05 to 0.15 N / When the temperature is raised to 25 to 200 ° C at a rate of temperature rise of 5 ° C / min while loading mm, the dimensional change rates in the vertical and horizontal directions are -5.0 to + 1.0% and -2.0 to +2.0, respectively. %, Using a polyester film as a base film, a vapor deposition film was prepared by sequentially laminating an anchor coat, an oxide vapor deposition film and a barrier coat on one side of the film. As a result, the above-mentioned vapor deposition film was obtained. .
Moreover, the laminated material suitable for a packaging use was obtained by laminating | stacking a heat-sealable resin layer on the surface by the side of the barrier coat of this gas-barrier vapor deposition film.

  That is, the present invention is a gas barrier vapor deposition film in which an anchor coat, an oxide vapor deposition film, and a barrier coat are sequentially laminated on one surface of a base film, and the base film is a titanium-based catalyst as a polycondensation catalyst. The base film has a color coordinate b value of −0.5 to 5 and a rate of temperature increase while a load of 0.05 to 0.15 N / mm is applied to the base film. When the temperature is raised to 25 to 200 ° C. at 5 ° C./min, the longitudinal and lateral dimensional change rates of the base film are −5.0 to + 1.0% and −2.0 to + 2.0%, respectively. The present invention relates to a gas barrier vapor deposition film and a laminated material using the same.

The gas barrier vapor-deposited film of the present invention and the laminate using the same do not contain antimony, and are therefore preferable in terms of environment, safety and hygiene.
Moreover, the polyester film used as a base film in the present invention has (i) a color coordinate b value of −0.5 to 5 and (ii) a load corresponding to a load applied to the base film during vapor deposition in an actual process. Dimensional change rate in the vertical direction -5.0 to + 1.0% when the temperature is raised to 25 to 200 ° C at a heating rate of 5 ° C / min while applying 0.05 to 0.15 N / mm, and (iii) horizontal direction The dimensional change rate of −2.0 to + 2.0% is satisfied. A polyester film that satisfies all these conditions has a color tone suitable for packaging applications and optical applications, and it is difficult to elute low molecular weight components. Can be deposited extremely densely, and the deterioration of the gas barrier property due to the deterioration of the film quality of the deposited film can be minimized. Therefore, according to the present invention, a high gas barrier property against oxygen gas, water vapor and the like can be stably maintained, and at the same time, a vapor deposition film having good color tone, moisture resistance, impact resistance and the like can be obtained.

The present invention will be described in more detail below with reference to the drawings.
<1> Layer Configuration of Gas Barrier Vapor Deposition Film of the Present Invention First, the layer configuration of the gas barrier vapor deposition film of the present invention will be described. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a gas barrier vapor deposition film according to the present invention.
As shown in FIG. 1, the gas barrier vapor deposition film A according to the present invention has a basic structure in which an anchor coat 2, an oxide vapor deposition film 3 and a barrier coat 4 are sequentially laminated on one surface of a base film 1. To do.
In the present invention, the oxide vapor deposition film may be a single layer or a multilayer composed of two or more layers.

<2> Base film In the present invention, a polyester film is used as the base film for supporting the oxide vapor deposition film. The polyester film should not be produced using an antimony catalyst, which is a harmful heavy metal, and is preferably produced using a titanium catalyst that is inexpensive and has no problems in health and safety.
(1) Color coordinate b value Among polyesters produced using a titanium-based catalyst, in the present invention, the color of Hunter's color difference formula in the Lab color system described in Reference 1 of JIS Z8730 is particularly used as the color tone. The coordinate b value is −0.5 to 5, more preferably 0 to 4. Polyesters produced using titanium-based catalysts generally have a unique yellowish color and change in color through the film, so many are not suitable for food packaging or optical applications. Those having a color coordinate b value of (2) exhibit a color tone suitable for the above-mentioned application when an anchor coat, an oxide deposited film and a barrier coat are laminated according to the present invention.
When the color coordinate b value is less than −0.5, the blueness becomes too strong when the anchor coat, the oxide deposited film and the barrier coat are laminated, and when the color coordinate b value is more than 5, the yellowness becomes too strong. It is not preferable.

(2) Catalyst The adjustment of the color coordinate b value in the above range is achieved by various titanium-based catalysts developed to obtain a polyester with suppressed yellowing, for example, a group consisting of a group 4A titanium group element in the periodic table. It can be carried out by using a titanium-based catalyst which is a mixture of at least one element compound selected from at least one element selected from magnesium compounds and phosphorus compounds.

(3) Dimensional change rate In the present invention, since the substrate film is a substrate that supports the anchor coat, oxide vapor deposition film and barrier coat, it is excellent in thermal dimensional change, anchor coat, oxide vapor deposition. It must be able to withstand conditions such as the formation and processing of a film and a barrier coat, and be able to support well without impairing the properties of the deposited film.
From this point of view, in accordance with the color coordinate b value and the conditions relating to the catalyst, in the present invention, the temperature is increased from 25 to 200 ° C. at a rate of temperature increase of 5 ° C./min while applying a load of 0.05 to 0.15 N / mm. When heated, the dimensional change rate in the vertical direction is −5.0 to + 1.0%, preferably −5.0 to −2.0%, and the dimensional change rate in the horizontal direction is −2.0 to + 2.0%, preferably − A polyester film that is 1.0 to + 1.0% is used.
When the dimensional change rate in the vertical direction and the horizontal direction is out of the above range, it is not preferable because micro cracks are formed in the oxide deposited film due to the dimensional change of the polyester film accompanying the temperature increase.

  In the present invention, such a numerical limitation of the polyester film is that the environment in which the polyester film is exposed in the vapor deposition step of laminating the oxide vapor deposition film, that is, the environment in which the belt runs in a high temperature region with tension (tension) applied. Focusing on the dimensional change of the polyester film below, the range is limited. The limitation of 0.05 to 0.15 N / mm means the tension actually applied to the polyester film, and the limitation of 25 to 200 ° C. at a heating rate of 5 ° C./min. Means the temperature range within.

(4) Material In the gas barrier vapor-deposited film of the present invention, as the polyester film constituting the base material layer that supports the oxide vapor-deposited film, a film made of polyethylene terephthalate (PET) is optimal, and polybutylene terephthalate ( A film made of a resin such as PBT), polyethylene naphthalate (PEN), or polycyclohexylenedimethylene terephthalate (PCT) can be used.

(5) Film thickness The thickness of the polyester film is about 6 to 100 μm, preferably 10 to 40 μm in consideration of stability during production.

(6) Production method In the present invention, the polyester film is, for example, one or more of the above-mentioned polyester-based resins, used individually or mixed, using an appropriate titanium-based catalyst, extrusion method, casting It can be manufactured using a film forming method such as a forming method, a T-die method, a cutting method, an inflation method, a multilayer coextrusion method, or the like. The polyester film may be an unstretched film, a stretched film stretched in one of the longitudinal direction or the transverse direction, or in a biaxial direction. As the stretching method, for example, a known method such as a flat method or an inflation method can be used, and a stretching ratio of 2 to 10 times can be used.

(7) Additives For the polyester film, any desired additive such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, or a filler can be arbitrarily selected within a range that does not affect the color tone. Can be added.

<3> Anchor coat In this invention, an anchor coat layer is provided between a base film and an oxide vapor deposition film. Thereby, the adhesive strength of a base film and an oxide vapor deposition film can be improved, and generation | occurrence | production of the delamination after a hot-water sterilization process can be prevented.
For such purposes, the anchor coat agent that can be used in the present invention includes an anchor coat made of any resin having a heat-resistant temperature of 135 ° C. or higher, for example, a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or the like. In particular, an anchor coating agent composed of a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure and an isocyanate compound as a curing agent can be preferably used.
Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.

  In the present invention, the polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure is a polymer compound obtained by polymerizing an acrylic acid derivative monomer alone or copolymerizing with other monomers. Means having a terminal hydroxyl group, for example, an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate, or other monomers such as styrene. Acrylic polyol and the like which are copolymerized by adding.

  In the present invention, an isocyanate compound is a compound that reacts with an acrylic polyol to form a urethane bond, and is any compound known as an isocyanate curing agent, such as aromatic tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI). ), Hydrogenated products of TDI, MDI, monomers such as aliphatic xylene diisocyanate (XDI), hexadiisocyanate (HMDI), isophorone diisocyanate (IPDI), and polymers and derivatives thereof. Are used alone or as a mixture.

  The anchor coat layer is coated with the above-mentioned anchor coat agent by a known coating method such as roll coat, gravure coat, knife coat, dip coat, spray coat, etc., and the solvent, diluent, etc. are removed by drying and cured. Can be formed. The thickness of the anchor coat layer is preferably about 0.2 to 0.3 μm.

<4> Oxide Deposition Film In the present invention, the oxide deposition film includes silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium ( Examples thereof include vapor deposition films made of oxides such as Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y).
Preferable examples include vapor deposition films made 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, etc., and its notation is, for example, SiO _x , AlO _x , MgO _x. Etc., where MO _x represents a metal element, and the value of x varies depending on the metal element.

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 0-0.5, tin (Sn) is 0-2, sodium (Na) is 0-0.5, boron (B) is 0-1.5, titanium (Ti) is 0-2, lead (Pb) is 0-1 Zirconium (Zr) can take values in the range of 0 to 2, and yttrium (Y) can take values 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 thickness of the oxide vapor deposition film varies depending on the metal used, the type of metal oxide, or the like, but can be arbitrarily selected within the range of, for example, 50 to 1000 mm, preferably 100 to 500 mm.
Moreover, the metal to be used or an oxide of a metal can be used by 1 type, or 2 or more types of mixtures as an oxide vapor deposition film, and the oxide vapor deposition film mixed with the dissimilar material can also be comprised.

  Further, when the oxide is silicon oxide, it may be a carbon-containing silicon oxide represented by SiOxCy [wherein x is in the range of 1.5 to 2.2 and y is in the range of 0.15 to 0.80. And preferably x is in the range of 1.7 to 2.1 and y is in the range of 0.39 to 0.47].

<5> Vapor Deposition Method In the present invention, in order to obtain a desired gas barrier property, the oxide vapor deposition film can be formed by a chemical vapor deposition method or a physical vapor deposition method, or a combination thereof.
(1) Chemical vapor deposition (Chemical Vapor Deposition method, CVD method)
Examples of chemical vapor deposition include plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.
In the present invention, specifically, on the anchor coat provided on one surface of the base film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, and argon gas, helium gas or the like is used as a carrier gas. Using an inert gas, further using an oxygen gas as an oxygen supply gas, and using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator, etc., to form a deposited film made of oxide. Can do.

  An example of the method for forming an oxide deposited film by low temperature plasma chemical vapor deposition in the present invention will be described. FIG. 2 is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus used in the above-described plasma chemical vapor deposition method.

  In the present invention, as shown in FIG. 2, the base film 1 previously laminated with the anchor coat is fed out from the unwinding roll 23 arranged in the vacuum chamber 22 of the low temperature plasma chemical vapor deposition apparatus 21, The base film 1 is conveyed onto the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed. Oxygen gas, inert gas, monomer gas for vapor deposition, and the like are supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and a vacuum chamber is formed through the raw material supply nozzle 29 while adjusting a mixed gas composition for vapor deposition. The mixed gas composition for vapor deposition is introduced into 22 and the glow discharge is carried out on the anchor coat provided on one surface of the base film 1 conveyed on the cooling / electrode drum 25 peripheral surface. Plasma is generated by the plasma 30 and irradiated to form an oxide vapor deposition film. At that time, the cooling / electrode drum 25 is applied with a predetermined power from a power source 31 disposed outside the vacuum chamber 22, and a magnet 32 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted. Next, the base film 1 is wound around the take-up roll 34 via the auxiliary roll 33 after forming an oxide vapor deposition film on the surface on which the anchor coat has been previously laminated. In the figure, 35 represents a vacuum pump.

  Although not shown, in the present invention, the layer of the oxide vapor deposition film may be a single layer or a multilayer composed of two or more layers, and the oxide to be used may be used alone, You may use it as a mixture of 2 or more types.

  Further, in the above low temperature plasma chemical vapor deposition apparatus, the oxide vapor deposition film is formed into a thin film on the base film using the plasma source gas, so that it is dense and flexible with few gaps. A continuous layer rich in properties. Accordingly, the barrier property is much higher than that of an oxide vapor deposition film formed by a conventional vacuum vapor deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness.

  In the present invention, the surface of the base film is cleaned by plasma, and polar groups and free radicals are generated on the surface of the base film. It has the advantage that it is highly wearable.

(2) Physical vapor deposition method (Physical Vapor Deposition method, PVD method)
Examples of the physical vapor deposition method include a vacuum deposition method, a sputtering method, an ion plating method, an ion cluster beam method, and the like.
The oxide vapor deposition method of the present invention will be described more specifically with an example. FIG. 3 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an example of an oxide deposition method in the present invention.

  As shown in FIG. 3, in a vacuum chamber 42 of a take-up vacuum deposition apparatus 41, a base film 1 on which an anchor coat has been previously laminated is fed out from an unwind roll 43, and the base film 1 is then transferred to a guide roll. Guide to the cooled coating drum 46 via 44, 45. Next, an evaporation source 48 heated by a crucible 47 is formed on an anchor coat provided on one surface of the base film 1 guided on the cooled coating drum 46, if necessary, from an oxygen gas outlet 49. Evaporation is performed while supplying oxygen gas or the like, and an oxide vapor deposition film is formed through the mask 50. Next, the base film 1 on which the oxide vapor deposition film is laminated is wound around the winding roll 53 via the guide rolls 51 and 52. Thereby, the gas barrier vapor deposition film which concerns on this invention can be manufactured.

<6> Barrier coat and method for forming the same (1) Barrier coat In the transparent gas barrier film of the present invention, a barrier coat is further provided on the oxide vapor-deposited film. Thereby, gas barrier property can be improved further. As such a barrier coat, a composition containing at least one alkoxide represented by the general formula: R ¹ _n M (OR ² ) _m , polyvinyl alcohol and / or ethylene / vinyl alcohol is overlapped by a sol-gel method. A gas barrier composition obtained by condensation can be preferably used.

The alkoxide that can be suitably used for the above barrier coat has the general formula: R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M is a metal atom, and n is An integer of 0 or more, m is an integer of 1 or more, and n + m represents a valence of M), and at least one kind of a partial hydrolyzate of this alkoxide or a hydrolysis condensate of alkoxide is used. can do. In addition, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which one or more was hydrolyzed, and its mixture may be sufficient. Moreover, the condensate of hydrolysis represents that the partially hydrolyzed alkoxide is a dimer or more, and a 2-6 mer is usually used.

As the metal atom represented by M in the general formula: R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum and the like can be used. In the present invention, alkoxysilane in which M is Si is particularly preferable. Moreover, the alkoxide of a single or 2 or more types of different metal atoms can also be mixed and used in the same solution.

In the alkoxide represented by the above 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, Examples thereof include alkyl groups such as i-propyl group.

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.

  In the present invention, it is preferable to use a silane coupling agent in combination with the alkoxide. Thereby, it becomes possible to prevent the gas barrier property from being lowered under high temperature and high humidity, or after the retort / boil treatment. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. Two or more kinds of such silane coupling agents may be mixed and used, and the amount used is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. When 20 parts by weight or more is used, the composite polymer formed is increased in rigidity and brittleness, and the insulation and workability of the composite polymer layer are lowered.

In the present invention, the composition for forming a barrier coat contains polyvinyl alcohol and / or an ethylene / vinyl alcohol copolymer. By combining polyvinyl alcohol and ethylene / vinyl alcohol copolymer, the gas barrier properties, water resistance, weather resistance and the like of the resulting barrier coat are remarkably improved. Furthermore, a laminated film in which polyvinyl alcohol and an ethylene / vinyl alcohol copolymer are combined is excellent in hot water resistance and gas barrier properties after hot water treatment in addition to gas barrier properties, water resistance, and weather resistance.
When the combination of polyvinyl alcohol and ethylene / vinyl alcohol copolymer is employed, the content weight ratio is preferably 10: 0.05 to 10: 6.

  The total content of the polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer is in the range of 5 to 600 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide. If it exceeds 600 parts by weight, the brittleness of the composite polymer will increase, and the water resistance and weather resistance of the resulting laminated film will also decrease. When the amount is less than 5 parts by weight, the gas barrier property is lowered.

  Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 ( Saponification degree = 98-99%, polymerization degree = 2400), PVA135H (saponification degree = 99.7% or more, polymerization degree = 3500), RS-110 (saponification degree = 99%, polymerization) manufactured by the same company Degree = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1400) and Gohsenol NH-18 (degree of saponification = 98 to 99%, degree of polymerization = 1700) and the like can be used.

  In the present invention, as 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 should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used. Specific examples of the above ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%). ) Etc. can be used.

  In the present invention, the above composition is applied onto a vapor deposition film, and the composition is polycondensed by a sol-gel method to form a barrier coat. As a sol-gel catalyst, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, there are N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like. The amount used is 0.01 to 1 part by weight per 100 parts by weight of the total amount of alkoxide and silane coupling agent.

  In the present invention, the above composition may further contain an acid instead of or in addition to the tertiary amine. The acid is used as a sol-gel catalyst, mainly as a catalyst for hydrolysis of alkoxides, silane coupling agents and the like. As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  In the present invention, it is desirable that the above-mentioned composition for forming a barrier coat contains water in a proportion of 0.1 to 100 mol with respect to 1 mol of the total molar amount of alkoxide. Moreover, it is preferable that the composition for barrier coat formation contains the organic solvent. As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like are used.

(2) Barrier coat forming method The barrier coat forming method of the present invention will be described below.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, water, an organic solvent, and, if necessary, a metal alkoxide, etc. Are mixed to prepare a gas barrier composition. In the gas barrier composition, a polycondensation reaction gradually proceeds.

  Next, the above gas barrier composition is applied by an ordinary method on an oxide vapor deposition film provided on one surface of the base film and dried. By the drying, the polycondensation of the alkoxide, metal alkoxide, silane coupling agent, and vinyl alcohol polymer further proceeds to form a composite polymer layer. Preferably, the above operation is repeated to laminate a plurality of composite polymer layers.

  Finally, the film coated with the above composition is preferably 70 ° C. to 200 ° C. from the viewpoint of barrier property deterioration under normal environment, 50 ° C. to 300 ° C., high temperature / high humidity, or after retort / boil treatment. Condensation is performed by heating and drying at a temperature of 0.005 minutes to 60 minutes, and a barrier coat can be formed.

  In the present invention, an ethylene / vinyl alcohol copolymer or a composition using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol may be used instead of the vinyl alcohol polymer. By using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol, gas barrier properties after hot water treatment such as boil treatment and retort treatment are further improved.

As a method for applying the composition for forming a barrier coat, for example, it is applied once or a plurality of times by a coating means such as a roll coat such as a gravure coater, spray coat, spin coat, dipping, brush, bar code, applicator and the like. Thus, a barrier coat having a dry film thickness of 0.01 μm to 30 μm, preferably 0.1 μm to 10 μm can be formed.
If necessary, when applying the barrier coat forming composition, a primer agent or the like can be applied on the oxide deposited film in advance.

  In the present invention, after a vapor deposition layer and a barrier coat are provided on the resin film, a vapor deposition layer may be further provided, and the barrier coat may be formed on the vapor deposition layer in the same manner as described above. Thus, by increasing the number of stacked layers, the gas barrier property can be further improved.

<7> Laminate using Gas Barrier Vapor Deposition Film of the Present Invention Next, the layer structure of the laminate using the gas barrier vapor deposition film A of the present invention as a front substrate will be described.
FIG. 4 is a schematic cross-sectional view showing a laminate B in which a heat-sealable resin layer 5 is laminated on the barrier coat side surface of the gas barrier vapor-deposited film A of the present invention shown in FIG.
FIG. 5 is a schematic cross-sectional view showing a laminated material B _{1 in} which an intermediate base material 6 is laminated between the barrier coat 4 and the heat-sealable resin layer 5.
Moreover, the plastic film, for example, the polyester film manufactured without using an antimony catalyst, can also be laminated | stacked on the surface at the side of the base film of the gas barrier vapor deposition film of this invention.

Hereinafter, a heat-sealable resin layer, an intermediate base material layer, and the like that can be used for the laminated material of the present invention will be described.
(1) Heat-sealable resin layer In the present invention, as the heat-sealable resin constituting the heat-sealable resin layer, resins that can be melted by heat and fused to each other can be used. , Low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene -Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, fumaric acid Unsaturated carboxylic acid such as maleic anhydride Acid-modified polyolefin resin modified with acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, acrylonitrile-styrene copolymer (AS resin) ), Acrylonitrile-butadiene-styrene copolymer (ABS resin), and the like. In the present invention, the heat-sealable resin layer can be composed of a resin film or sheet as described above, or a coating film made of a resin composition mainly composed of the resin as described above. The thickness is 1 to 200 μm, preferably 5 to 100 μm.

(2) Intermediate base material layer As described above, in the present invention, an intermediate base material layer may be provided between the barrier coat and the heat-sealable resin layer, and by providing such an intermediate base material layer, Strength and puncture resistance are improved.
As a resin film used as an intermediate substrate layer, it has excellent strength in mechanical, physical, chemical, etc., excellent in puncture resistance, etc., in addition, heat resistance, moisture resistance, pinhole resistance, A resin film or sheet excellent in transparency and the like can be used. Specifically, for example, polyester resins, polyamide resins, polyaramid resins, polypropylene resins, polystyrene resins, polyacrylic or methacrylic resins, polycarbonate resins, polyacetal resins, fluorine resins, polyacrylonitrile resins. Polyvinyl alcohol resins and other tough resin films or sheets can be used.

  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. Further, in the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, etc. If it is too thick, the cost increases and conversely On the other hand, if it is too thin, there arises a problem that strength, puncture resistance and the like deteriorate.

(3) Method for Producing Laminate of the Present Invention Next, a method for producing the laminate of the present invention will be described. The laminating step in this production method is a method of laminating a normal laminating material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a coextrusion lamination method, an inflation method. For example, a coextrusion inflation method or the like. In that case, pre-treatments such as corona treatment, ozone treatment, and frame treatment can be applied to the film to be bonded as necessary. Also, for example, polyester-based, isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based In addition, known anchor coating agents and adhesives such as other adhesives for laminating can be used.

<8> Use of Laminated Material of the Present Invention The gas-barrier vapor deposition film according to the present invention or the packaging container produced using the laminated material is produced without using an antimony-based catalyst, and therefore does not contain antimony. In addition, it has a color tone suitable for packaging applications and optical applications, has excellent gas barrier properties against oxygen gas, water vapor, etc., impact resistance, etc., and further post-processing such as laminating, printing, bag making or box making For example, it is excellent in filling and packaging suitability, storage suitability, etc. for various articles such as chemicals and cosmetics such as food and drink, medicine, detergent, shampoo, oil, toothpaste, adhesive, adhesive, etc. is there.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
(1) The dimensional change rate in the vertical direction is -3.0% when the temperature is raised from 25 to 200 ° C at a temperature increase rate of 5 ° C / min while applying a load of 0.07 N / mm, and the dimensional change in the horizontal direction. A biaxially stretched polyethylene terephthalate film (film thickness 12 μm) having a rate of 0.1% or less and a color coordinate b value of 2.4 was produced using a titanium-based catalyst. An anchor coat agent was applied to the film and dried to form a 0.3 μm anchor coat layer. The anchor coating agent is composed of a main agent obtained by mixing and stirring 1 part by weight of nitrified cotton and 5 parts by weight of acrylic polyol in a dilute solvent of methyl ethyl ketone (MEK) / ethyl acetate 1: 1, and isophorone diisocyanate (IPDI). Here, the NCO group was prepared in an equivalent amount with respect to the OH group of the main agent. Next, after aging at 40 ° C. for 48 hours, an aluminum oxide vapor deposition film having a thickness of 200 mm was laminated by a vacuum vapor deposition method using an electron beam (EB) heating method under the following vapor deposition conditions. The cooling drum temperature at this time was −15 ° C.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ^-4 mbar
Vacuum level in the winding chamber: 2 × 10 ^-2 mbar
Electron beam power: 25 kw
Film transport speed: 480 m / min
Deposition surface: Corona treatment

(2) On the formed deposited film, a composition for forming a barrier coat having the following composition was applied by a gravure roll coating method, and then heat-treated at 180 ° C. for 60 seconds to obtain a thickness of 0.3 μm (dry A gas barrier vapor deposition film according to the present invention was obtained.

(Preparation method)
To the prepared mixture of polyvinyl alcohol of composition a, isopropyl alcohol and ion-exchanged water, add a hydrolyzed solution of ethyl silicate, silane coupling agent, hydrochloric acid, isopropyl alcohol and ion-exchanged water of composition b prepared in advance. And stirred to obtain a colorless and transparent composition for forming a barrier coat.

[Example 2]
The dimensional change rate in the vertical direction is -3.5% when the temperature is raised to 25 to 200 ° C at a heating rate of 5 ° C / min while applying a load of 0.07 N / mm, and the dimensional change rate in the horizontal direction is 0.1%. %, And a biaxially stretched polyethylene terephthalate film (film thickness 12 μm) having a color coordinate b value of 3.2 was produced using a titanium-based catalyst. As in Example 1, an anchor coat layer and a vapor deposition film were laminated on this film. However, instead of the aluminum oxide vapor deposition film, a silicon oxide vapor deposition film (film thickness of 300 mm) was laminated, and the following vapor deposition conditions were used. The cooling drum temperature at this time was −15 ° C.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ^-4 mbar
Vacuum level in the winding chamber: 2 × 10 ^-2 mbar
Electron beam power: 40 kw
Film transport speed: 240 m / min
Deposition surface: Corona treatment A barrier coat layer was formed in the same manner as in Example 1 to obtain a gas barrier vapor deposition film according to the present invention.

[Example 3]
The dimensional change rate in the vertical direction is -2.5% when the temperature is raised to 25 to 200 ° C at a heating rate of 5 ° C / min while applying a load of 0.07 N / mm, and the dimensional change rate in the horizontal direction is 0.1. %, And a biaxially stretched polyethylene terephthalate film (film thickness 12 μm) having a color coordinate b value of 2.8 was produced using a titanium-based catalyst. An anchor coat was laminated on this film in the same manner as in Example 1. This was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then a silicon oxide vapor deposition film having a thickness of 120 mm was formed on the surface of the film on the side where the anchor coat was laminated under the following conditions.
(Deposition conditions)
Deposition surface: Corona treatment Gas introduction amount: Hexamethyldisiloxane: Oxygen gas: Helium =
1.0: 3.0: 3.0 (Unit: slm)
Degree of vacuum in the vacuum chamber: 2-6 × 10 ^-6 mbar
Degree of vacuum in the deposition chamber: 2-5 × 10 ^-3 mbar
Cooling and electrode drum power supply: 10 kw
Line speed: 100 m / min

Next, immediately after forming the silicon oxide vapor deposition film, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: Using a mixed gas consisting of 2.5 (unit: slm), performing oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 6 × 10 ^-5 Torr and a processing speed of 420 m / min, the surface tension of the deposited film surface of silicon oxide Was formed to a plasma-treated surface with an improvement of 54 dyn / cm or more.
Thereafter, a barrier coat layer was formed on the plasma treated surface in the same manner as in Example 1 to obtain a gas barrier vapor deposition film according to the present invention.

[Comparative Example 1]
While applying a load of 0.07 N / mm, the dimensional change rate in the vertical direction when the temperature was raised to 25 to 200 ° C. at a heating rate of 5 ° C./min was −6.0%, and the dimensional change rate in the horizontal direction was 0.1%. %, And a biaxially stretched polyethylene terephthalate film (film thickness 12 μm) having a color coordinate b value of 3.2 was produced using a titanium-based catalyst. As in Example 1, an anchor coat layer, a vapor deposition film, and a barrier coat layer were laminated on this film.

[Comparative Example 2]
The dimensional change rate in the vertical direction is -3.0% when the temperature is raised to 25 to 200 ° C at a heating rate of 5 ° C / min while applying a load of 0.07N / mm, and the dimensional change rate in the horizontal direction is 0.1%. %, And a biaxially stretched polyethylene terephthalate film (film thickness 12 μm) having a color coordinate b value of 5.5 was produced using a titanium-based catalyst. As in Example 1, an anchor coat layer, a vapor deposition film, and a barrier coat layer were laminated on this film.

[Comparative Example 3]
A vapor-deposited film was obtained in the same manner as in Example 1 except that no anchor coat layer was provided between the biaxially stretched polyethylene terephthalate film and the vapor-deposited film.

[result]
The following measurements were performed on the deposited films produced in Examples 1 to 3 and Comparative Examples 1 to 3.
(1) Measurement of oxygen permeability This was measured with a measuring instrument (OXTRAN: OX-TRAN2 / 21) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.

(2) Measurement of water vapor transmission rate This was measured with a measuring machine (Permatran 3/31) manufactured by Mocon, USA under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.

(3) Measurement of color tone This was a spectral color difference meter “SE-2000 type” manufactured by Nippon Denshoku Industries Co., Ltd., and the b value by the transmission method was measured according to the method of JIS Z-8722.
The rate of dimensional change due to temperature rise was measured with a TMA / SS6000 manufactured by Seiko Instruments Inc., which is a thermomechanical analyzer.

  As is clear from the measurement results shown in Table 1 above, it was confirmed that the vapor deposition films of Examples 1 to 3 had low oxygen permeability and water vapor permeability, and excellent gas barrier properties. It had transparency and was excellent in the visibility of the contents.

  On the other hand, the vapor deposition films of Comparative Examples 1 and 2 showed higher values of oxygen permeability and water vapor permeability. Therefore, when judged comprehensively, the gas barrier properties were extremely inferior.

Furthermore, using the vapor deposition films produced in Examples 1 to 3 and Comparative Examples 1 to 3, laminated material samples for boil and retort having the following structures were produced:
Laminated material sample for boil: vapor deposition film / adhesive layer / polyethylene film 60 μm
Laminated material sample for retort: vapor deposition film / adhesive layer / stretched nylon film 15 μm / adhesive layer / unstretched polypropylene film 60 μm

  Using the resulting laminated material sample, 200 cc of water is filled inside to create a four-sided pouch, and hot water sterilization is performed at a boiling condition of 95 ° C / 60 minutes and a retort condition of 135 ° C / 60 minutes. The oxygen permeability immediately before and after the treatment and the peel strength (gf / 15 mm, T-peel, measurement speed 50 mm / min) were measured. Oxygen permeability measurement conditions: 23 ° C, 90% RH.

  In the same manner, a four-sided pouch filled with 100 cc of water is prepared, a ruled line is formed on the pouch, bent at 180 ° and fixed with a clip, and boil and retort sterilization are performed in the same manner as described above. The presence or absence of lamination was confirmed.

  Moreover, it peeled, dipping water on the peeling interface of the laminated material sample for boil, and measured the water-resistant lamination strength (gf / 15mm, T-shaped peeling, measurement speed 50mm / min).

  As apparent from Table 2 above, the laminated materials using the vapor deposition films of Examples 1 to 3 had almost no change in oxygen permeability and peel strength before and after the boil treatment, and had low oxygen permeability and desired values. The peel strength was maintained. In all cases, delamination did not occur and a beautiful appearance was maintained.

  On the other hand, as for the laminated material using the vapor deposition film of Comparative Examples 1-3, oxygen permeability rose all after the boil process. In addition, the laminates using the vapor deposition films of Comparative Examples 1 and 3 showed a significant decrease in peel strength after the boil treatment, and the occurrence of delamination was confirmed.

  As is apparent from Table 3 above, the laminates using the vapor deposition films of Examples 1 to 3 had a low oxygen permeability, the oxygen permeability and peel strength did not change significantly before and after the retort treatment. And the adhesion between the layers remained strong. In all cases, delamination did not occur and a beautiful appearance was maintained.

  On the other hand, as for the laminated material using the vapor deposition film of Comparative Examples 1-3, oxygen permeability rose all significantly after the retort process. In addition, the laminates using the vapor deposition films of Comparative Examples 1 and 3 showed a significant decrease in peel strength after retorting, and the occurrence of delamination was confirmed.

  As apparent from Table 4 above, it was found that the laminates using the vapor deposition films of Examples 1 to 3 showed sufficient water-resistant laminate strength and were suitable for treatment in water.

  On the other hand, the laminate material using the vapor deposition films of Comparative Examples 1 and 3 had a significantly reduced laminate strength due to the presence of water at the peeling interface.

It is a schematic sectional drawing which shows the layer structure of the gas barrier vapor deposition film which concerns on this invention. It is a schematic block diagram which shows the outline | summary of the example about a plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the gas-barrier vapor deposition film which concerns on this invention shown in FIG. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the gas-barrier vapor deposition film which concerns on this invention shown in FIG.

Claims (7)

On one surface of a substrate film made of polyester produced using a titanium catalyst as a polycondensation catalyst, an anchor coat layer, an oxide deposited film, and the gas barrier vapor deposition fill beam formed by laminating a barrier coat layer in this order, the The base film has a color coordinate b value of −0.5 to 5, and 25 to 25 ° C./min at a temperature rising rate of 5 ° C./min while applying a load of 0.05 to 0.15 N / mm. When the temperature is raised to 200 ° C., the dimensional change rates of the base film in the vertical direction and the horizontal direction are −5.0 to + 1.0% and −2.0 to + 2.0%, respectively. A gas barrier vapor deposition film. The titanium-based catalyst is a mixture of a compound of at least one element selected from the group consisting of titanium group elements of Group 4A of the periodic table and at least one compound selected from magnesium compounds and phosphorus compounds. The gas barrier vapor deposition film according to claim 1 . The gas barrier vapor deposition film according to claim 1 or 2 , wherein the oxide vapor deposition film is laminated by a chemical vapor deposition method or a physical vapor deposition method. The gas barrier vapor deposition film according to any one of claims 1 to 3 , wherein the oxide is aluminum oxide or silicon oxide. The barrier coat layer has the 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, and n is an integer of 0 or more) Wherein m is an integer of 1 or more, and n + m represents a valence of M), and a composition comprising at least one alkoxide, polyvinyl alcohol, and / or ethylene vinyl alcohol. The gas barrier vapor deposition film according to any one of claims 1 to 4 , which is a layer comprising a hydrolyzate of alkoxide obtained by polycondensation by a sol-gel method or a hydrolyzate condensate of alkoxide. Anchor coat layer is a layer with polyacrylic or polymethacrylic resins having two or more hydroxyl groups in its structure, and an isocyanate compound as a curing agent obtained by reaction curing, claim 1-5 2. A gas barrier vapor deposition film according to item 1. The laminated material which uses the gas-barrier vapor deposition film of any one of Claims 1-6 as a surface base material.

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