JP2020078941A - Barrier film and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film made of a polyester resin film using biomass ethylene glycol. SOLUTION: The base material layer 11 has a base material layer 12 and a vapor deposition layer 12 formed on at least one surface of the base material layer, and the base material layer contains ethylene glycol derived from biomass as a diol unit and terephthal derived from fossil fuel. It contains a biomass polyester resin having an acid as a dicarboxylic acid unit and a polyester resin made from a fossil fuel-derived raw material having a fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived terephthalic acid as a dicarboxylic acid unit. It is composed of an axially stretched resin film, and the biaxially stretched resin film contains 90% by mass or less of biomass polyester resin, and the vapor deposition layer is silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium. , Ittrium, or a barrier film consisting of a vapor-deposited film of these oxides. [Selection diagram] Fig. 1

Description

  The present invention relates to a barrier film having a substrate layer made of a biomass polyester resin composition obtained from a plant-derived raw material and a laminate using the same, and more specifically, a biomass-derived ethylene glycol as a diol component. The present invention relates to a barrier film having a base material layer made of a resin composition containing a polyester used and a laminate using the same.

  Polyester is widely used in various industrial applications because it is excellent in mechanical properties, chemical stability, heat resistance, transparency and the like and is inexpensive. Polyester is obtained by polycondensing a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying ethylene glycol and terephthalic acid as raw materials. It is manufactured by subjecting it to polycondensation reaction. These raw materials are produced from petroleum, which is a fossil resource, for example, ethylene glycol is industrially produced from ethylene and terephthalic acid is industrially produced from xylene.

  In recent years, with the increasing demand for the establishment of a recycling-based society, there is a desire in the materials field to break away from fossil fuels as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by utilizing it, it is carbon-neutral renewable energy that becomes carbon dioxide and water again. In recent years, the practical use of biomass plastics using these biomasses as raw materials has been rapidly progressing, and attempts have been made to produce polyester, which is a general-purpose polymer material, from these biomass raw materials.

  For example, as a polyester using a biomass raw material, a polyester composed of isosorbide, which is one of the biomass raw materials, terephthalic acid, and ethylene glycol, has been proposed (Patent Document 1).

  In addition, biomass ethanol obtained by fermenting starch and sugars obtained from plants such as corn and sugar cane with microorganisms has been put to practical use, and ethylene glycol can be industrially produced from this biomass ethanol via ethylene. Is also successful.

Japanese Patent Publication No. 2002-512304

The present inventors have focused on ethylene glycol, which is a raw material for polyester, and instead of ethylene glycol obtained from conventional fossil fuels, polyesters made from plant-derived ethylene glycol as a raw material are obtained from conventional fossil fuels. It has been found that a polyester produced using ethylene glycol can be obtained in the same physical properties as mechanical properties.
Furthermore, a barrier film having a base material layer made of such a biomass-derived polyester and a laminate using the same are also used as a barrier film having a base material layer made of a raw material obtained from a conventional fossil fuel and the same. It has been found that a laminate having the same physical properties as the existing laminate can be obtained. The present invention is based on this finding.

  Therefore, an object of the present invention is to provide a barrier film having a base material layer made of a resin composition containing a carbon-neutral polyester using biomass ethylene glycol, which is obtained from a raw material obtained from a conventional fossil fuel. It is an object of the present invention to provide a barrier film having a substrate layer made of a polyester resin film having physical properties comparable to those of the produced barrier film having a substrate layer. Another object of the present invention is to provide a laminate using the barrier film.

According to the present invention, a barrier film having a substrate layer, and a vapor deposition layer formed on at least one surface of the substrate layer,
The base material layer is made of a biaxially stretched resin film,
The biaxially stretched resin film has a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived terephthalic acid as a dicarboxylic acid unit, and a biomass polyester resin and a fossil-fuel-derived ethylene glycol as a diol unit, and a fossil-fuel-derived resin film. A terephthalic acid as a dicarboxylic acid unit, and a polyester resin made of a fossil fuel-derived raw material,
90 mass% or less of the biomass polyester resin is contained in the biaxially stretched resin film,
A barrier film, wherein the vapor-deposited layer comprises silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, or a vapor deposited film of these oxides. To be done.
In the aspect of the present invention, a gas barrier coating film may be further provided on the vapor deposition layer.
In an aspect of 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, and 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.) and at least one alkoxide represented by the formula, It may contain a polyvinyl alcohol-based resin and/or an ethylene/vinyl alcohol copolymer.
In the aspect of the present invention, the resin film may further include a recycled polyester resin made of a fossil fuel-derived raw material having fossil fuel-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. ..
In the aspect of the present invention, the resin film may contain the recycled polyester in an amount of 5 to 45% by mass.
In the aspect of the present invention, the content of carbon derived from biomass by radiocarbon (C14) measurement may be 10 to 19% with respect to the total carbon in the polyester.
In the aspect of the present invention, the vapor deposition layer may be formed of a vapor deposition film of aluminum, aluminum oxide, or silicon oxide. In another aspect of the present invention, a laminated film using the barrier film is provided. ..
In another aspect of the present invention, there is provided a packaging bag, a sheet molded product, a label material, a lid material, a laminated tube, and a packaged product, which are provided with the above-mentioned laminated film.

  According to the present invention, in a barrier film having a base material layer and a vapor deposition layer formed on at least one surface of the base material layer, the base material layer comprises a biaxially stretched resin film. The film contains biomass-derived ethylene glycol as a diol unit and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit, and a biomass polyester resin and fossil fuel-derived ethylene glycol as a diol unit, and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit. The acid unit is a polyester resin made of a fossil fuel-derived raw material, and the biaxially stretched resin film contains 90% by mass or less of the biomass polyester resin, and the vapor deposition layer includes silicon, aluminum, magnesium, and calcium. A barrier film having a base material layer made of a carbon-neutral resin can be realized by using a vapor deposition film of platinum, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, or an oxide thereof. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional one, and the environmental load can be reduced. Further, the barrier film of the polyester resin composition of the present invention is not inferior to the barrier film of the polyester resin composition produced from a raw material obtained from conventional fossil fuels in terms of physical properties such as mechanical properties. Since the polyester resin composition is used, the barrier film of the conventional polyester resin composition can be substituted.

It is a schematic cross section which shows an example of the laminated body using the barrier film by this invention. It is a schematic cross section which shows an example of the laminated body using the barrier film by this invention.

<Barrier film>
In the barrier film according to the present invention, the base material layer is composed of a resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, and the resin composition is an ethylene glycol in which the diol unit is derived from biomass. The carbon-neutral polyester resin contains 50 to 95% by mass, preferably 50 to 90% by mass, of the polyester whose dicarboxylic acid unit is a dicarboxylic acid derived from fossil fuel, based on the entire resin composition. It is possible to realize a barrier film having a base material layer made of In addition, since biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, polyesters using biomass-derived ethylene glycol are similar to polyesters polymerized from conventional fossil fuel-derived raw materials. Therefore, the substrate layer of the barrier film of the present invention is comparable to the conventional polyester film in physical properties such as mechanical properties. Therefore, since the barrier film of the present invention and the laminate using the same have a layer made of a carbon neutral material, the barrier film produced from a raw material obtained from a conventional fossil fuel and a laminate using the same. Compared with, the amount of fossil fuel used can be significantly reduced and the environmental load can be reduced. Moreover, according to a preferable aspect, the laminate may further include a resin layer.

  According to one aspect of the present invention, there is provided a laminate using a barrier film, which has a base material layer, a vapor deposition layer, and a resin layer. Specifically, FIG. 1 shows a schematic cross-sectional view of an example of a laminate using the barrier film according to the present invention. The laminated body 10 shown in FIG. 1 includes a base material layer 11, a vapor deposition layer 12 formed on one surface of the base material layer 11, and a resin layer 13 having a printed layer 15 formed thereon. The vapor-deposited surface of the base material layer 11 and the printed surface of the resin layer 13 are bonded together via the adhesive layer 14. Further, the resin layer 16 is laminated on the other surface (the surface opposite to the vapor deposition layer) of the base material layer 11 via the adhesive layer 14.

  According to one aspect of the present invention, there is provided a laminate using a barrier film, which has a base material layer, a vapor deposition layer, and a resin layer. Specifically, FIG. 2 shows a schematic cross-sectional view of an example of a laminate using the barrier film according to the present invention. The laminated body 20 shown in FIG. 2 includes a base material layer 21, a vapor deposition layer 22 formed on one surface of the base material layer 21, and a resin layer 23, and the vapor deposition of the base material layer 11 is performed. The surface and the resin layer 23 are attached to each other with the adhesive layer 24 interposed therebetween. Further, a resin layer 25 is laminated on the resin layer 23 via an adhesive layer 24. Hereinafter, each layer structure of the present invention will be described.

<Base material layer>
In the present invention, the base material layer is made of a resin composition containing polyester as a main component, which will be described below.

<Polyester>
The polyester contained in the resin composition forming the base material layer is composed of a diol unit and a dicarboxylic acid unit, using ethylene glycol derived from biomass as the diol unit and dicarboxylic acid derived from fossil fuel as the dicarboxylic acid unit. It is obtained by a polycondensation reaction.

  The biomass-derived ethylene glycol uses ethanol produced from biomass as a raw material (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method and a method of producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.

  As the dicarboxylic acid unit of polyester, a dicarboxylic acid derived from fossil fuel is used. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl ester of aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl ester. Esters and the like can be mentioned. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.

  As the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc., usually having 2 to 40 carbon atoms. Chain-like or alicyclic dicarboxylic acids. Further, as the derivative of the aliphatic dicarboxylic acid, a lower alkyl ester such as methyl ester, ethyl ester, propyl ester and butyl ester of the above aliphatic dicarboxylic acid, or a cyclic acid anhydride of the above aliphatic dicarboxylic acid such as succinic anhydride may be used. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and one containing succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, the methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

  These dicarboxylic acids may be used alone or in admixture of two or more.

  The polyester contained in the resin composition forming the base material layer may be a copolymerized polyester obtained by adding a copolymerization component as a third component in addition to the above-mentioned diol component and dicarboxylic acid component. Specific examples of the copolymerization component include a bifunctional oxycarboxylic acid, a trifunctional or higher functional polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher functional polycarboxylic acid and/or an anhydride thereof, and a trifunctional polycarboxylic acid. At least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids can be mentioned. Among these copolymerization components, a bifunctional and/or trifunctional or higher functional oxycarboxylic acid is particularly preferably used because a copolyester having a high degree of polymerization tends to be easily produced. Among them, the use of a trifunctional or higher functional oxycarboxylic acid is most preferable because a polyester having a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

  The polyester may be a high molecular weight polyester obtained by chain extension (coupling) of these copolyesters. As the chain extender, it is possible to use a chain extender such as a carbonate compound or a diisocyanate compound, but the amount thereof is usually 100% by mole of all the monomer units constituting the polyester and the amount of the carbonate bond and the urethane bond is It is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less.

  Specific examples of the carbonate compound include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, dicyclohexyl. Carbonate etc. are illustrated. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can be used.

  Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene. Known diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate can be used.

  The polyester forming the base material layer can be obtained by a conventionally known method in which the above-mentioned diol unit and dicarboxylic acid unit are polycondensed. Specifically, a general method of melt polymerization in which a polycondensation reaction is performed under reduced pressure after an esterification reaction and/or a transesterification reaction between the above dicarboxylic acid component and a diol component, and an organic solvent Can be produced by a known solution heating dehydration condensation method using.

  The amount of the diol used for producing the polyester is substantially equimolar to 100 mol of the dicarboxylic acid or its derivative, but in general, during the esterification and/or transesterification reaction and/or polycondensation reaction. Therefore, it is used in an excess of 0.1 to 20 mol %.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and may be added at the time of charging the raw materials or at the start of depressurization.

  As the polymerization catalyst, a compound containing a Group 1 to Group 14 metal element other than hydrogen and carbon in the periodic table is generally used. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium. Examples thereof include compounds containing an organic group such as a carboxylate, an alkoxy salt, an organic sulfonate, or a β-diketonate salt, and an inorganic compound such as the above-mentioned metal oxide or halide, and a mixture thereof. Among these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferable, and titanium compounds, zirconium compounds and germanium compounds are particularly preferable. Further, the catalyst is preferably a liquid compound at the time of polymerization or a compound soluble in the ester low polymer or polyester because the polymerization rate becomes high if it is in a molten or dissolved state at the time of polymerization.

  As the titanium compound, tetraalkyl titanate is preferable, and specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Benzyl titanate and mixed titanates thereof may be mentioned. Further, titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide)acetylacetonate, titanium bis(ammonium lactate)dihydroxide, titanium bis(ethylacetoacetate)diisopropoxide, titanium (triethanolaminate). ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer and the like are also preferably used. Furthermore, titanium oxide or a composite oxide containing titanium and silicon is also preferably used. Among these, tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate, titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate. , Titanium lactate, butyl titanate dimer, titanium oxide, titania/silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) is preferable, and tetra-n-butyl titanate and polyhydroxytitanium stearate are particularly preferable. , Titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, and titania/silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) are preferable.

  Specific examples of the zirconium compound include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, and polyhydroxyzirconium. Stearates, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. Alternatively, zirconium oxide or a composite oxide containing zirconium and silicon may be used. Among these, zirconyl diacetate, zirconium tris(butoxy) stearate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium ammonium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxy. Preferred are zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide.

  Specific examples of the germanium compound include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. Germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferable in terms of price and availability, and germanium oxide is particularly preferable.

  When using a metal compound as the polymerization catalyst, the amount of the catalyst used is, as a metal amount relative to the polyester produced, a lower limit value of usually 5 ppm or more, preferably 10 ppm or more, and an upper limit value of usually 30,000 ppm or less, preferably 1000 ppm or less, It is more preferably 250 ppm or less, and particularly preferably 130 ppm or less. If the amount of the catalyst used is too large, not only is it economically disadvantageous, but the thermal stability of the polymer is low, while conversely, if it is too small, the polymerization activity is low, and the decomposition of the polymer during polymer production is accompanied. Is more likely to be triggered. As for the amount of catalyst used here, the amount of the terminal carboxyl groups of the polyester produced decreases as the amount of use decreases, so the method of reducing the amount of catalyst used is a preferred embodiment.

  The reaction temperature of the esterification reaction and/or transesterification reaction of the dicarboxylic acid component and the diol component is usually in the range of 150 to 260° C., and the reaction atmosphere is usually an atmosphere of an inert gas such as nitrogen or argon. .. The reaction pressure is usually atmospheric pressure to 10 kPa. The reaction time is usually about 1 hour to 10 hours.

In the above manufacturing process, a chain extender (coupling agent) may be added to the reaction system.
After completion of the polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state to react with the polyester obtained by the polycondensation.

  High molecular weight polyesters using these chain extenders (coupling agents) can be produced by known techniques. After completion of the polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state to react with the polyester obtained by the polycondensation. Specifically, a polyester obtained by catalytically reacting a diol and a dicarboxylic acid and having a terminal hydroxyl group substantially having a hydroxyl group and a mass average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more. By reacting the chain extender with the prepolymer, a polyester resin having a higher molecular weight can be obtained. If the prepolymer has a mass average molecular weight of 20,000 or more, a small amount of coupling agent is used, and even under severe conditions such as a molten state, it is not affected by the remaining catalyst, so that gelation does not occur during the reaction. A high molecular weight polyester can be produced.

  The obtained polyester may be solid-phase-polymerized, if necessary, after solidification, in order to further increase the degree of polymerization and to remove oligomers such as cyclic trimers. Specifically, after the polyester is made into chips and dried, the polyester is pre-crystallized by heating at a temperature of 100 to 180° C. for about 1 to 8 hours, and then inert at a temperature of 190 to 230° C. It is carried out by heating under gas flow or reduced pressure for 1 to several tens of hours.

  The intrinsic viscosity (measured with an orthochlorophenol solution at 35° C.) of the polyester obtained as described above is preferably 0.5 dl/g to 1.5 dl/g, more preferably 0.6 dl/g. g to 1.2 dl/g. When the intrinsic viscosity is less than 0.5 dl/g, the mechanical properties required for the polyester film as a semi-transmissive reflective film substrate, such as tear strength, may be insufficient. On the other hand, when the intrinsic viscosity exceeds 1.5 dl/g, the productivity in the raw material manufacturing process and the film forming process is impaired.

  Various additives may be added to the polyester in the production process or to the produced polyester within a range not impairing the properties thereof, for example, a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent. A deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a release agent, an antioxidant, an ion exchange agent, a coloring pigment and the like can be added. These additives are added in an amount of 5 to 50% by mass, preferably 5 to 20% by mass, based on the entire polyester resin composition.

  The polyester which may be contained in the resin composition forming the base material layer in an amount of 5 to 45% by mass (hereinafter, also referred to as recycled polyester) is composed of a diol unit and a dicarboxylic acid unit, and the diol unit is a diol unit. Is a polyester obtained by recycling a product made of a polyester resin obtained by a polycondensation reaction using a fossil fuel-derived diol or biomass-derived ethylene glycol and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

  The resin that is the source of recycled polyester (that is, the polyester resin before recycling) is a biomass polyester as described above, even if both diol units and dicarboxylic acid units are made of fossil fuel-derived raw materials. Good.

  Examples of the fossil fuel-derived diol used for the resin that forms the basis of recycled polyester include aliphatic diols, aromatic diols, and derivatives thereof, and those used as diol units of conventional polyesters are preferably used. be able to. The aliphatic diol is not particularly limited as long as it is an aliphatic or alicyclic compound having two OH groups, but the lower limit of the number of carbon atoms is 2 or more and the upper limit thereof is usually 10 or less, preferably 6 The following aliphatic diols may be mentioned. Specific examples include ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol. Be done. These may be used alone or as a mixture of two or more kinds. Among these, ethylene glycol, 1,4-butanediol, 1,3-propylene glycol and 1,4-cyclohexane dimethanol are preferable, and ethylene glycol is particularly preferable.

In the resin composition containing the polyester obtained as described above, it is preferable that the content of the biomass-derived carbon measured by radioactive carbon (C14) is 10 to 19% based on the total carbon in the polyester. Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the content of C14 in plants that grow by taking in carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in the polyester, the proportion of carbon derived from biomass can be calculated. In the present invention, when the content of C14 in polyester is P _C14 , the content P _bio of carbon derived from biomass is defined as follows.
P _bio (%)=P _C14 /105.5×100

Taking polyethylene terephthalate as an example, since polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1, only polyethylene glycol derived from biomass is available. when using the content P _{bio Bio} carbon from biomass in the polyester is 20%. In the present invention, the content of carbon derived from biomass by radiocarbon (C14) measurement is preferably 10 to 19% with respect to the total carbon in the resin composition. When the carbon content derived from biomass in the resin composition is less than 10%, the effect as a carbon offset material becomes poor. On the other hand, as described above, the carbon content derived from the biomass in the resin composition is preferably as close as possible to 20%. However, from the viewpoint of problems in the manufacturing process of the film and physical properties, the recycled polyester and the above-mentioned recycled polyester are contained in the resin. Since it is preferable to include the additive, the actual upper limit is 18%.

<Resin film>
The substrate layer of the barrier film is preferably a polyester resin film made of the above resin composition. In order to process the resin composition into a film, a conventional method of molding the film from a polyester resin can be adopted. Specifically, after drying the resin composition described above, the resin composition is melted by supplying the resin composition to a melt extruder heated to a temperature (Tm) to Tm+70° C. higher than the melting point of polyester to melt the resin composition. A film can be formed by extruding into a sheet form from a die such as a T die and rapidly quenching and solidifying the extruded sheet form with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

  The base material layer of the barrier film is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched film. This stretching is preferably performed by utilizing the peripheral speed difference between two or more rolls. The longitudinal stretching is usually performed in the temperature range of 50 to 100°C. The longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, though it depends on the required characteristics of the film application. When the draw ratio is less than 2.5 times, it is difficult to obtain a good film because the polyester film has large unevenness in thickness.

  The longitudinally stretched film is sequentially subjected to the treatment steps of transverse stretching, heat setting and heat relaxation to obtain a biaxially stretched film. The transverse stretching is usually performed in the temperature range of 50 to 100°C. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, though it depends on the properties required for this application. When it is less than 2.5 times, it is difficult to obtain a good film because the thickness unevenness of the film becomes large, and when it exceeds 5.0 times, breakage easily occurs during film formation.

  After the transverse stretching, a heat setting treatment is subsequently carried out, but a preferable heat setting temperature range is Tg+70 to Tm-10° C. of polyester. The heat setting time is preferably 1 to 60 seconds. Further, for applications requiring a low heat shrinkage, heat relaxation treatment may be carried out as necessary.

The thickness of the stretched film of the resin film obtained as described above is arbitrary depending on the application, but is usually about 5 to 500 μm. Breaking strength of such a resin film is 5 to 35 kg / mm ² at 5~40kg / ^mm 2, TD direction MD direction, elongation at break, 50 to 350% in MD direction, the TD direction It is 50 to 300%. Further, the shrinkage rate when left for 30 minutes in a temperature environment of 150° C. is 0.1 to 5%. As described above, the film made of the resin composition according to the present invention has the same physical properties as the polyester film produced only from the conventional fossil fuel-derived material.

<Deposition layer>
In the present invention, the vapor deposition layer is composed of a vapor deposition film of an inorganic substance or an inorganic oxide. The vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and forming method are not particularly limited. Since the barrier film has the vapor deposition layer, it is possible to impart or improve the gas barrier property of blocking the transmission of oxygen gas and water vapor and the light blocking property of blocking the transmission of visible light and ultraviolet ray. The barrier film may have two or more vapor deposition layers. When two or more vapor deposition layers are provided, they may have the same composition or different compositions.

  Examples of the vapor deposition film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti). ), lead (Pb), zirconium (Zr), yttrium (Y), and other inorganic substances or inorganic oxide vapor deposition films can be used. In particular, as a material suitable for a packaging material (bag) or the like, a vapor deposition film of aluminum metal or a vapor deposition film of silicon oxide or aluminum metal or aluminum oxide is preferably used.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As the range of the value of X, 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 and 5, titanium (Ti). Is 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is 0 to 1.5. In the above, when X=0, the substance is a complete inorganic substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used for the packaging material, and silicon (Si) is in the range of 1.0 to 2.0 and aluminum (Al) is in the range of 0.5 to 1.5. The value of can be used.

In the present invention, the thickness of the vapor deposition film of the inorganic material or the inorganic oxide as described above varies depending on the type of the inorganic material or the inorganic oxide to be used, but is, for example, 50 to 2000 Å, preferably 100 to 1000 Å. It is desirable to form it by arbitrarily selecting within the range.
More specifically, in the case of a vapor deposited film of aluminum, a film thickness of 50 to 600 Å, more preferably 100 to 450 Å, is desirable, and in the case of a vapor deposited film of aluminum oxide or silicon oxide, The film thickness is preferably about 50 to 500Å, more preferably 100 to 300Å.

  As a method for forming a vapor deposition film, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical method The chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) etc., such as a vapor phase epitaxy method and a photochemical vapor phase epitaxy method, can be mentioned.

  Hereinafter, the vapor deposition film will be described in more detail as one embodiment of the present invention.

  On one surface of the base material layer (base material film), a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is further supplied. Oxygen gas or the like is used as the gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed by a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like. In the above, as the low temperature plasma generator, for example, a generator of high frequency plasma, pulse wave plasma, microwave plasma or the like can be used. In order to obtain highly active and stable plasma, it is desirable to use a high frequency plasma generator.

A vapor-deposited film of silicon oxide formed by using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is a base film. It adheres closely to the surface to form a dense, flexible thin film, and is usually composed mainly of silicon oxide represented by the general formula SiO _x (where X represents a number of 0 to 2). Is a continuous thin film. The vapor deposition film of silicon oxide is made of silicon oxide represented by the general formula SiO _x (where X represents a number of 1.3 to 1.9) from the viewpoints of transparency and barrier properties. It is preferably a thin film mainly composed of a vapor deposition film. In the above, the value of X changes depending on the molar ratio of vapor deposition monomer gas and oxygen gas, the energy of plasma, etc. Generally, the smaller the value of X, the lower the gas permeability, but the film itself becomes yellow. It becomes more transparent and becomes less transparent.

In addition, the above-mentioned vapor-deposited film of silicon oxide is mainly composed of silicon oxide, and further, at least one kind of carbon, hydrogen, silicon or oxygen, or at least one kind of compound consisting of two or more kinds of elements is chemically added to the film. It is characterized in that it is composed of a vapor deposition film which is contained by bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit having a graphite shape, a diamond shape, a fullerene shape, or the like, a raw material organosilicon compound or those The derivative may be contained by a chemical bond or the like. Specific examples thereof include hydrocarbon having a CH ₃ moiety, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and a hydroxyl group derivative such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the vapor deposition film of silicon oxide can be changed by changing the conditions of the vapor deposition process and the like. The content of the above compound in the vapor-deposited film of silicon oxide is preferably about 0.1 to 50%, more preferably about 5 to 20%. In the above, if the content rate is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the vapor deposited film of silicon oxide become insufficient, and scratches, cracks, etc. easily occur due to bending, It becomes difficult to stably maintain a high barrier property, and when it exceeds 50%, the barrier property is deteriorated, which is not preferable.

  Further, in the present invention, in the silicon oxide vapor deposition film, it is preferable that the content of the above compound is decreased in the depth direction from the surface of the silicon oxide vapor deposition film, whereby the silicon oxide vapor deposition film is formed. On the surface of, the impact resistance and the like can be enhanced by the above compounds and the like. On the other hand, at the interface with the surface of the base film, the content of the above compounds is small, so that the base film and silicon oxide are vapor-deposited. This has the advantage that the tight adhesion with the film becomes strong.

  In the present invention, for the above-described deposited film of silicon oxide, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS) is used. The above-mentioned physical properties can be confirmed by carrying out elemental analysis of the vapor-deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction.

  Further, in the present invention, the film thickness of the vapor deposition film of silicon oxide is preferably about 50 Å to 4000 Å, and specifically, the film thickness is preferably about 100 to 1000 Å. If the film thickness is more than 1000Å, or more than 4000Å, cracks and the like are likely to occur in the film, which is not preferable, and if it is less than 100Å, or less than 50Å, it is difficult to exert the barrier effect. Therefore, it is not preferable. In the above, the film thickness can be measured by the fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Co., Ltd. Further, in the above, as means for changing the film thickness of the above-mentioned vapor-deposited film of silicon oxide, increasing the volumetric velocity of the vapor-deposited film, that is, a method of increasing the amount of monomer gas and oxygen gas or a vapor deposition rate It can be done by a method such as slowing down.

  Next, in the above, as the vapor deposition monomer gas such as an organic silicon compound that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane and hexamethyldisiloxane. , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used.

  In the present invention, among the above-mentioned organosilicon compounds, it is preferable to use 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and continuous film formed. It is a particularly preferable raw material in view of the characteristics and the like. Further, in the above, as the inert gas, for example, argon gas, helium gas or the like can be used.

  Next, in the present invention, the inorganic oxide vapor deposition film by the physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor deposition film by the physical vapor deposition method include a vacuum vapor deposition method and a sputtering method. A vapor-deposited film of an inorganic oxide can be formed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a method, an ion plating method, or an ion cluster beam method.

  In the present invention, specifically, a metal or an oxide of a metal is used as a raw material, which is heated and vaporized, and this is vapor-deposited on the surface of a base film, or a metal or a metal is oxidized as a raw material. To form a vapor-deposited film using an oxidation reaction deposition method that introduces oxygen to oxidize and deposits on the surface of the base film, and a plasma-assisted oxidation reaction deposition method that further assists the oxidation reaction with plasma. can do. In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB) or the like can be used.

As the inorganic oxide vapor deposition film by the above physical vapor deposition method, for example, specifically, it is preferable to use a non-crystalline thin film of aluminum oxide. More specifically, the formula AlO _X ( In the formula, X represents a number in the range of 0.5 to 1.5), which is a non-crystalline thin film of aluminum oxide, and the non-crystalline thin film of aluminum oxide is It is possible to use a non-crystalline thin film of aluminum oxide whose X value decreases in the depth direction from the surface of the thin film toward the inner surface. Alternatively, in the present invention, the non-crystalline thin film of aluminum oxide is a non-crystalline thin film of aluminum oxide represented by the formula AlO _x (where X represents a number in the range of 0.5 to 1.5). A non-crystalline thin film of aluminum oxide, which is a crystalline thin film, wherein the non-crystalline thin film of aluminum oxide has a value of X increasing in the depth direction from the surface of the thin film to the inner surface. Can be used. In the present invention, as the value of X in the above formula, it is possible to basically use X=0.5 or more, but in the present invention, X=less than 1.0. If so, it is desirable to use X=1.0 or more because the coloring is severe and the transparency is poor. For X=1.5, aluminum and oxygen are completely oxidized. Since it is in the state, the upper limit can be X=1.5.

  Next, in the present invention, it is desirable that the amorphous thin film of aluminum oxide is arbitrarily selected and formed within a range of, for example, about 10 to 3,000 Å, preferably about 60 to 1,000 Å.

Further, in the present invention, a non-crystalline thin film of aluminum oxide can be formed by using a roll-up type vacuum vapor deposition apparatus. In the above vapor deposition, the degree of vacuum in the vacuum chamber is preferably about 10 ⁰ to 10 ⁻⁵ mbar, preferably 10 ⁻¹ to 10 ⁻⁴ mbar. The degree of vacuum of the vapor deposition chamber is preferably 10 ⁻² to 10 ⁻⁸ mbar, preferably 10 ⁻³ to 10 ⁻⁷ mbar before introducing oxygen, and 10 ⁻ after introducing oxygen. ^{The position of 1} to 10 ^-6 mbar, preferably 10 ^-2 to 10 ^-5 mbar, is desirable. Next, the transport speed of the substrate film is preferably 10 to 800 m/minute, more preferably 50 to 600 m/minute. The amount of oxygen introduced varies depending on the size of the vapor deposition machine.

  In the present invention, in the thin film layer made of the inorganic oxide by the physical vapor deposition method, as the vapor deposition layer made of aluminum oxide, if the degree of oxidation is too high, the quality of the formed film becomes hard, and thus cracks easily occur. Further, if the degree of oxidation is too low, the transparency decreases, so that the ultraviolet (wavelength 366 nm) transmittance during vapor deposition or immediately after vapor deposition is in the range of 85 to 96%, and more preferably 87 to 94%. It is preferable to use a vapor-deposited film of aluminum oxide having a thickness within the range of 150 to 600 Å in consideration of post-processing suitability. The vapor-deposited layer made of a mixture of silicon monoxide and silicon is a vapor-deposited film of silicon oxide formed by physical vapor deposition, which has a film thickness within the range of 50 to 300 Å in consideration of post-processing suitability. It is preferred to use.

  In the present invention, in the case of forming a vapor deposition film of an inorganic oxide on the substrate film, it is possible to improve the close adhesion property between the surface of the substrate film and the surface of the vapor deposition film of the inorganic oxide, and the like. In order to firmly adhere them to each other and prevent the occurrence of delamination, etc., the surface of the above-mentioned base film is subjected to a plasma treatment with an inert gas in advance to form a plasma treated surface. It is preferable to provide them.

In the present invention, a plasma-treated surface with an inert gas will be described. As such a plasma-treated surface, one surface of the substrate film is a surface using plasma gas generated by ionizing gas by arc discharge. A plasma-treated surface can be formed by utilizing a plasma surface treatment method for performing modification. That is, in the present invention, the plasma treated surface can be formed by performing the plasma treatment by the plasma surface treatment method using an inert gas such as nitrogen gas, argon gas, helium gas or the like as the plasma gas.
In the present invention, as the plasma gas, a mixed gas obtained by further adding oxygen gas to the above-mentioned inert gas can be used.

  Further, in the present invention, when forming a plasma-treated surface with an inert gas, for example, plasma treatment is performed in-line immediately before forming a vapor deposition film of an inorganic oxide by physical vapor deposition or chemical vapor deposition. This is desirable because it removes water, dust and the like on the surface of the base film and enables surface treatment such as smoothing, activation and the like of the surface.

  Further, in the present invention, as the plasma treatment, it is preferable to perform plasma discharge treatment in consideration of conditions such as plasma output, type of plasma gas, supply amount of plasma gas, treatment time, and the like. Further, in the present invention, as a method for generating plasma, for example, a device such as DC glow discharge, high frequency discharge, microwave discharge, or the like can be used. Further, in the present invention, the plasma-treated surface can be formed by utilizing the atmospheric pressure plasma treatment method or the like.

As the gas barrier coating film, 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.), at least one kind of alkoxide represented by polyvinyl alcohol resin, and And/or an ethylene/vinyl alcohol copolymer, and a step of preparing a gas barrier composition that polycondenses by the sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent, On the barrier thin film layer made of an inorganic oxide provided on one surface of the material film, a gas barrier composition that is polycondensed by the sol-gel method described above is applied, if necessary, via the plasma-treated surface with oxygen gas. The step of coating to provide a coating film, the substrate film provided with the above coating film is heat-treated at 20° C. to 180° C. for 10 seconds to 10 minutes at a temperature not higher than the melting point of the substrate film. Then, on the barrier thin film layer made of an inorganic oxide provided on one surface of the substrate film, if necessary, through a plasma treated surface by oxygen gas, a gas barrier by the gas barrier composition It can be manufactured by a manufacturing process including a process of forming a functional coating film and the like.

In the present invention, the gas barrier coating film forming the barrier film according to the present invention has a general formula R ¹ _n M(OR ² ) _m (wherein R ¹ and R ² are carbon atoms of 1). ~ 8 represents an organic group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, n + m represents the valence of M). Containing at least one or more alkoxides and a polyvinyl alcohol resin and/or an ethylene/vinyl alcohol copolymer, and further in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent, A gas barrier composition for polycondensation is prepared by the sol-gel method, and using this, two or more layers are laminated on the barrier thin film layer made of an inorganic oxide provided on one surface of the base film, It can also be produced by forming a composite polymer layer in which two or more gas barrier coating films of the gas barrier composition are laminated.

In the above, as the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m that forms the gas barrier coating film constituting the gas barrier film according to the present invention, a partial hydrolyzate of the alkoxide and hydrolysis of the alkoxide can be used. At least one kind of condensate can be used, and as the partial hydrolyzate of the above alkoxide, it is not necessary that all of the alkoxy groups are hydrolyzed, and one or more of them are hydrolyzed. The hydrolyzed condensate may be a dimer or more of partially hydrolyzed alkoxide, specifically, a dimer or dimer of the partially hydrolyzed alkoxide.

In the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , the metal atom represented by M may be silicon, zirconium, titanium, aluminum, or the like. In the present invention, preferable metals include, for example, silicon and titanium. In the present invention, the alkoxide may be used alone or as a mixture of two or more different alkoxides of different metal atoms 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, methyl group, ethyl group, 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, n-octyl group and others. In the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, and i. Examples include -propyl group, n-butyl group, sec-butyl group, and the like. In the present invention, these alkyl groups may be the same or different in the same molecule.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si. The above-mentioned alkoxysilane is represented by the general formula Si(ORa) ₄ (wherein Ra represents a lower alkyl group). In the above, as Ra, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or the like is used. Specific examples of the above-mentioned alkoxysilane include, for example, 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.

Further, in the present invention, the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m is, for example, the general formula Rb _n Si(ORc) _4-m (where n is 0). Represents the above integer, m represents an integer of 1, 2, and 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like). Alkoxysilanes can be used. Specific examples of the alkyl alkoxysilane described above, for example, methyltrimethoxysilane _{CH 3 Si (OCH 3) 3} , methyltriethoxysilane _{CH 3 Si (OC 2 H 5} ) 3, dimethyldimethoxysilane _{(CH 3)} 2 Si (OCH ₃ ) ₂ , dimethyldiethoxysilane (CH ₃ ) ₂ Si(OC ₂ H ₅ ) ₂ , and the like can be used. The above-mentioned alkoxysilane, alkylalkoxysilane and the like can be used alone or in combination of two or more. Further, in the present invention, the polycondensation product of the above-mentioned alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

Next, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , for example, a zirconium alkoxide in which M is Zr can be used. Specific examples of the zirconium alkoxide include, for example, tetramethoxyzirconium Zr(OCH ₃ ) ₄ , tetraethoxyzirconium Zr(OC ₂ H ₅ ) ₄ , tetra i propoxyzirconium Zr(iso-OC ₃ H ₇ ) ₄ , tetra. n-Butoxyzirconium Zr(OC ₄ H ₉ ) ₄ and others can be used.

Further, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , for example, a titanium alkoxide in which M is Ti can be used. Specific examples of the titanium alkoxide, for example, tetramethoxy titanium Ti _{(OCH 3) 4,} tetraethoxy titanium _{Ti (OC 2 H 5) 4} , tetraisopropoxy titanium _{Ti (iso-OC 3 H 7} ) 4, tetra n-Butoxytitanium Ti(OC ₄ H ₉ ) ₄ and others can be used.

Further, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , for example, an aluminum alkoxide in which M is Al can be used. Specific examples of the above-mentioned aluminum alkoxide include, for example, tetramethoxyaluminum Al(OCH ₃ ) ₄ , tetraethoxyaluminum Al(OC ₂ H ₅ ) ₄ , tetraisopropoxyaluminum Al(iso-OC ₃ H ₇ ) ₄ , tetra. n-Butoxyaluminum Al(OC ₄ H ₉ ) ₄ and others can be used.

  In the present invention, the above alkoxides may be used as a mixture of two or more thereof. In the present invention, in particular, by using a mixture of an alkoxysilane and a zirconium alkoxide, it is possible to improve the toughness, heat resistance, etc. of the obtained barrier film, and reduce the retort resistance of the film during stretching. Is avoided. The amount of zirconium alkoxide used is in the range of not more than 10 parts by weight, preferably about 5 parts by weight, based on 100 parts by weight of the alkoxysilane. In the above, when the amount exceeds 10 parts by weight, the formed gas barrier coating film is apt to gel and the brittleness of the film becomes large, and the gas barrier coating film is easily peeled off when the substrate film is coated. It is not preferable because it tends to occur.

  Further, in the present invention, in particular, by mixing and using the alkoxysilane and the titanium alkoxide, there is an advantage that the thermal conductivity of the obtained gas barrier coating film is lowered and the heat resistance of the barrier film is remarkably improved. In the above, the amount of titanium alkoxide used is in the range of 5 parts by weight or less, preferably about 3 parts by weight, based on 100 parts by weight of the above-mentioned alkoxysilane. In the above, if it exceeds 5 parts by weight, the brittleness of the gas barrier coating film to be formed becomes large, and the gas barrier coating film tends to be easily peeled off when the substrate film is coated, which is not preferable. is there.

  Next, as the polyvinyl alcohol resin and/or the ethylene/vinyl alcohol copolymer forming the gas barrier coating film constituting the barrier film according to the present invention, a polyvinyl alcohol resin or ethylene is used. -Vinyl alcohol copolymers can be used each alone, or can be used in combination with a polyvinyl alcohol-based resin and an ethylene-vinyl alcohol copolymer, and in the present invention, By using a polyvinyl alcohol-based resin and/or an ethylene/vinyl alcohol copolymer, it is possible to remarkably improve the gas barrier properties, water resistance, weather resistance, and other physical properties of the gas barrier coating film. is there. In particular, in the present invention, by using a polyvinyl alcohol-based resin in combination with an ethylene/vinyl alcohol copolymer, in addition to the above-mentioned physical properties such as gas barrier property, water resistance, and weather resistance, hot water resistance and heat resistance It is possible to form a gas-barrier coating film that is remarkably excellent in gas barrier properties after water treatment.

  In the present invention, when a polyvinyl alcohol-based resin and an ethylene/vinyl alcohol copolymer are used in combination, the mixing ratio of each is a polyvinyl alcohol-based resin: ethylene/vinyl alcohol-based resin. It is preferable that the copolymer is 10:0.05 to 10:6, and it is even more preferable to use the compound at a mixing ratio of about 10:1.

  In the present invention, the content of the polyvinyl alcohol-based resin and/or the ethylene/vinyl alcohol copolymer is in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the above alkoxide. It is preferable to prepare the gas barrier composition at a blending ratio of about 20 to 200 parts by weight. In the above, if the amount exceeds 500 parts by weight, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the obtained gas barrier laminated film tend to be lowered, which is not preferable. If it is less than the above range, the gas barrier property is deteriorated, which is not preferable.

In the present invention, as the polyvinyl alcohol-based resin and/or ethylene/vinyl alcohol copolymer, first, as the polyvinyl alcohol-based resin, those obtained by saponifying polyvinyl acetate are generally used. be able to. As the polyvinyl alcohol-based resin, a partially saponified polyvinyl alcohol-based resin in which several tens% of acetic acid groups remain, or a completely saponified polyvinyl alcohol in which acetic acid groups do not remain, or an OH group is modified A modified polyvinyl alcohol-based resin may be used and is not particularly limited.
Specific examples of the polyvinyl alcohol-based resin include RS-110 (saponification degree=99%, polymerization degree=1,000), which is an RS polymer manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (saponified by the same company). Degree=40%, degree of polymerization=2,000), and Gohsenol NM-14 (saponification degree=99%, degree of polymerization=1400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

  Further, in the present invention, as the ethylene-vinyl alcohol copolymer, use a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer. You can Specifically, the partial saponified product in which the acetic acid group remains several tens mol% to the complete saponified product in which the acetic acid group remains only a few mol% or the acetic acid group does not remain is particularly limited. However, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more, from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the above ethylene/vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol %, preferably 20 to 45 mol %. Is preferred. Specific examples of the 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.

Next, in the present invention, the gas barrier composition for forming the gas barrier coating film constituting the barrier film according to the present invention will be described. As such a gas barrier composition, the above 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, and m represents At least one alkoxide represented by an integer of 1 or more, and n+m represents a valence of M), and the polyvinyl alcohol resin and/or ethylene/vinyl alcohol copolymer weight as described above. A gas-barrier composition containing the combined substance and further polycondensed by the sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent.

  When preparing the above gas barrier composition, for example, a silane coupling agent or the like can be added. As the silane coupling agent, known organic reactive group-containing organoalkoxysilane can be used. In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable, and for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β-( For example, 3,4-epoxycyclohexyl)ethyltrimethoxysilane can be used. The silane coupling agents as described above may be used alone or in combination of two or more. In the present invention, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the alkoxysilane. When 20 parts by weight or more is used in the above, the rigidity and brittleness of the formed gas barrier coating film tend to increase, and the insulating property and workability of the gas barrier coating film tend to deteriorate, which is not preferable. Is.

  Next, as a sol-gel method catalyst, mainly as a polycondensation catalyst, used in the above gas barrier composition, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and the like can be used. In the present invention, N,N-dimethylbenzylamine is particularly preferable. The amount used is 0.01 to 1.0 part by weight, preferably about 0.03 part by weight, per 100 parts by weight of the total amount of alkoxide and silane coupling agent. The acid used in the gas barrier composition is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide or a silane coupling agent. As the above-mentioned acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The above-mentioned acid is used in an amount of 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total mol of the alkoxide and the alkoxide component (eg, silicate portion) of the silane coupling agent. Is preferred.

  Further, in the above gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, per 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 moles, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked with each other to have low density and porosity. And the porous polymer is not preferable because the gas barrier property of the barrier film cannot be improved. On the other hand, if the amount of water is less than 0.8 mol, the hydrolysis reaction tends to be difficult to proceed, which is not preferable.

Furthermore, as the organic solvent used in the gas barrier composition, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, or the like can be used. Further, in the above gas barrier composition, the polyvinyl alcohol resin and/or the ethylene/vinyl alcohol copolymer should be in a state of being dissolved in a coating liquid containing the above alkoxide, silane coupling agent and the like. Therefore, the type of the above organic solvent is appropriately selected.
When a polyvinyl alcohol resin and an ethylene/vinyl alcohol copolymer are used in combination, n-butanol is preferably used. In the present invention, the ethylene-vinyl alcohol copolymer solubilized in the solvent may be, for example, one commercially available as Soarnol (trade name). The amount of the above organic solvent used is usually 30 per 100 parts by weight of the total amount of the above alkoxide, silane coupling agent, polyvinyl alcohol resin and/or ethylene/vinyl alcohol copolymer, acid and sol-gel method catalyst. ~500 parts by weight.

  Next, according to one aspect of the present invention, the barrier film according to the present invention can be specifically produced, for example, as follows. First, an alkoxide such as the above alkoxysilane, a silane coupling agent, a polyvinyl alcohol-based resin and/or an ethylene/vinyl alcohol copolymer, a sol-gel method catalyst, an acid, water, an organic solvent, and, if necessary, A gas barrier composition (coating liquid) is prepared by mixing metal alkoxide and the like. Next, the polycondensation reaction gradually progresses in the above gas barrier composition (coating liquid). Then, the above gas barrier composition (coating solution) is applied by a conventional method on the barrier thin film layer made of an inorganic oxide provided on one surface of the base film, and dried. .. Then, by the above drying, polycondensation of the above-mentioned alkoxides such as alkoxysilanes, metal alkoxides, silane coupling agents and polyvinyl alcohol resins and/or ethylene-vinyl alcohol copolymers proceeds, and a coating film is formed. To be done. Furthermore, preferably, the above-mentioned coating operation is repeated to laminate a plurality of coating films composed of two or more layers. Finally, the substrate film coated with the above-mentioned coating liquid is at a temperature of about 20°C to 180°C, and a temperature not higher than the melting point of the substrate film, preferably at a temperature in the range of about 50°C to 160°C. A gas barrier coating film of the above-mentioned gas barrier composition (coating liquid) is formed on the barrier thin film layer made of an inorganic oxide formed on one surface of the substrate film by heat treatment for 10 seconds to 10 minutes. The barrier film according to the present invention can be produced by forming one or more layers. The barrier film according to the present invention thus obtained has excellent gas barrier properties.

  In the present invention, instead of the polyvinyl alcohol-based resin, an ethylene/vinyl alcohol copolymer, or both a polyvinyl alcohol-based resin and an ethylene/vinyl alcohol copolymer are used, and coating is performed in the same manner as above. The barrier film according to the present invention produced by performing drying and heat treatment has an advantage that the gas barrier property after hot water treatment such as boil treatment and retort treatment is further improved.

  Further, in the present invention, when the ethylene/vinyl alcohol copolymer or the polyvinyl alcohol resin and the ethylene/vinyl alcohol copolymer are not used in combination as described above, that is, only the polyvinyl alcohol resin is used. Then, in the case of producing the barrier film according to the present invention, in order to improve the gas barrier property after hot water treatment, for example, a gas barrier composition using a polyvinyl alcohol-based resin is applied in advance. Forming a first coating layer, and then coating a gas barrier composition containing an ethylene/vinyl alcohol copolymer on the coating layer to form a second coating layer; By forming the composite layer of, it is possible to improve the gas barrier property of the barrier film according to the present invention.

  Furthermore, a coating layer formed of a gas barrier composition containing the above ethylene/vinyl alcohol copolymer, or a gas barrier composition containing a polyvinyl alcohol resin and an ethylene/vinyl alcohol copolymer in combination It is also an effective means to improve the gas barrier property of the barrier film according to the present invention by forming a plurality of coating layers formed of a material to form multiple layers.

Next, as one aspect of the present invention, the operation of the method for producing a barrier film according to the present invention will be described by taking the case of using alkoxysilane as the alkoxide as an example. First, the alkoxysilane and the metal alkoxide are hydrolyzed by the added water.
At that time, the acid serves as a catalyst for hydrolysis. Next, by the action of the sol-gel method catalyst, protons are taken from the generated hydroxyl groups, and the hydrolysis products are dehydrated and polycondensed. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group. In addition, the base catalyst works to cause ring opening of the epoxy group, thereby generating a hydroxyl group. The polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. Furthermore, since the reaction system contains a polyvinyl alcohol resin, an ethylene/vinyl alcohol copolymer, or a polyvinyl alcohol resin and an ethylene/vinyl alcohol copolymer, the polyvinyl alcohol resin and the ethylene/vinyl alcohol are present. A reaction with the hydroxyl group of the copolymer also occurs. The resulting polycondensate contains, for example, an inorganic portion composed of a bond such as Si-O-Si, Si-O-Zr, Si-O-Ti, and the like, and an organic portion derived from the silane coupling agent. In the above reaction which constitutes the composite polymer, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a moiety derived from the silane coupling agent is first produced. .. This polymer has an OR group (alkoxy group such as ethoxy group) in a branched form from a linear polymer. This OR group is hydrolyzed by the existing acid as a catalyst to become an OH group, and the OH group is first deprotonated by the action of the sol-gel method catalyst (base catalyst), and then polycondensation proceeds. That is, the OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene/vinyl alcohol copolymer represented by the following formula (II) to produce Si-O-Si. It is believed that, for example, a conjugated polymer having a bond and represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is produced.

  The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition (coating liquid) increases during preparation. This gas barrier composition (coating liquid) is applied onto the barrier thin film layer made of an inorganic oxide when it is provided on one surface of the substrate film, and heated to remove the solvent and alcohol produced by the polycondensation reaction. When removed, the polycondensation reaction is completed, and a transparent coating layer is formed on the barrier thin film layer made of an inorganic oxide provided on one surface of the base film. When a plurality of the above-mentioned coating layers are laminated, the composite polymers in the coating layers between the layers also condense, and the layers are firmly bonded. Further, an organic reactive group of the silane coupling agent or a hydroxyl group generated by hydrolysis is bonded to a hydroxyl group or the like on the surface of the barrier thin film layer made of an inorganic oxide provided on one surface of the base film, The adhesiveness and the adhesiveness between the surface of the barrier thin film layer made of an inorganic oxide provided on one surface of the material film and the coating layer are also improved.

  In the method of the present invention, the amount of water added is adjusted to 0.8 to 2 moles, preferably 1.5 moles, relative to 1 mole of alkoxides. Is formed. Such a linear polymer has crystallinity and has a structure in which many minute crystals are embedded in an amorphous portion. Such a crystal structure is similar to that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), a polar group (OH group) is partially present in the molecule, and the molecule has high cohesive energy and molecular chain. Since it has high rigidity, it exhibits good gas barrier properties.

INDUSTRIAL APPLICABILITY The barrier film according to the present invention is useful as a packaging material because it has the above-mentioned excellent properties, and in particular, it has gas barrier properties (O ₂ , N ₂ , H ₂ O, CO ₂ , etc.) which are permeated. Since it is excellent in blocking and blocking), it is preferably used as a barrier base material constituting a film for food packaging. In particular, when used in so-called gas-filled packaging filled with N ₂ or CO ₂ gas, the excellent gas barrier property is extremely effective for holding the filled gas. Furthermore, the barrier film according to the present invention is excellent in hot water treatment, particularly high pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier property.

  In the present invention, the barrier thin film layer made of an inorganic oxide and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis/cocondensation reaction to form an inorganic oxide. The adhesiveness between the barrier thin film layer and the coating film having gas barrier properties is improved, and the synergistic effect of the two layers can exert a better gas barrier property. As a method for applying the gas barrier composition of the present invention, for example, once by a coating means such as a roll coat such as a gravure roll coater, a spray coat, a spin coat, a dipping, a brush, a bar code and an applicator. Alternatively, a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed by coating a plurality of times, and further, in a normal environment, at 50 to 300° C. The condensation is preferably carried out by heating and drying at a temperature of 70 to 200° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. A gas barrier coating film can be formed. Further, if necessary, when applying the gas barrier composition of the present invention, it is also possible to previously apply a primer agent or the like on the barrier thin film layer made of an inorganic oxide. It is possible to optionally perform a pretreatment such as a discharge treatment, a plasma treatment, or the like.

  As described above, the barrier film according to the present invention is, on one surface of the substrate film, a plasma-treated surface with an inert gas provided if necessary, a barrier thin film layer made of an inorganic oxide, if necessary. The plasma-treated surface by the oxygen gas to be provided or the primer agent layer and the gas barrier coating film may be sequentially laminated.

<Resin layer>
The laminate using the barrier film according to the present invention may further have at least one resin layer. Examples of the resin layer include a layer made of a resin material containing a raw material derived from biomass and a layer made of a resin material containing a raw material derived from a conventional fossil fuel. When two or more resin layers are provided, they may have the same composition or different compositions. The resin layer can be formed on the base material layer or the vapor deposition layer directly or via an adhesive layer.

  According to one aspect of the present invention, the resin layer is preferably made of a resin material containing a biomass-derived raw material. A carbon-neutral resin layer can be formed by forming the resin layer from a resin material containing a biomass-derived raw material. Therefore, the amount of fossil fuel used can be significantly reduced, and the environmental load can be reduced.

  The resin layer made of a biomass-derived raw material is, for example, one or more resin materials selected from the group consisting of cellophane, starch, polylactic acid, polyethylene, polypropylene, nylon, polymethylene terephthalate, polyethylene terephthalate, and cellulose. Can be mentioned. It is preferable that the biomass material is used for at least a part of the resin material forming the resin layer. The resin layer can be formed by a conventionally known method and is not particularly limited. In the present invention, the base material layer and the resin layer may be formed of the same biomass-derived raw material (for example, biomass ethanol). Furthermore, you may synthesize|combine the resin material for forming a resin layer using commercially available biomass ethylene glycol similarly to a base material layer. The composition of the resin layer may be the same as the composition of the base material layer.

  In the laminate of the present invention, by laminating a resin layer made of a conventional biomass-derived resin on a barrier film, a laminate having two or more layers made of a carbon-neutral resin can be produced. .. As the resin layer, a commercially available polylactic acid film may be used, and for example, a polylactic acid film commercially available from Mitsui Chemicals Tohcello can be suitably used.

  Further, according to another aspect, the resin layer may be a resin layer made of a resin material containing a conventional fossil fuel-derived raw material. In the laminate of the present invention, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, and resistance are obtained by laminating a resin layer made of a conventional fossil fuel-derived resin on the barrier film. The piercing property and other physical properties can be imparted or improved.

  Examples of the resin layer made of a fossil fuel-derived raw material include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Resins such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer or ionomer can be used. These resins may be formed by an extrusion laminating method, or a film formed in advance by a T-die method or an inflation method may be laminated with a heat resistant substrate layer by a dry laminating or extrusion laminating method. ..

  Further, stretched polyethylene terephthalate film, silica vapor deposition stretched polyethylene terephthalate film, alumina vapor deposition stretched polyethylene terephthalate film, stretched nylon film, silica vapor deposition stretched nylon film, alumina vapor deposition stretched nylon film, stretched polypropylene film, polyvinyl alcohol coated stretched polypropylene film, nylon 6 /Metaxylylenediamine nylon 6 co-pushed co-stretched film or polypropylene/ethylene-vinyl alcohol copolymer co-pushed co-stretched film, or a composite film in which two or more of these films are laminated.

<Other layers>
According to one aspect of the present invention, the laminate according to the present invention may further include at least one other layer in addition to the base material layer, the vapor deposition layer, and the resin layer. Examples of the other layer include a layer made of a metal foil obtained by rolling a metal, an adhesive layer, and a printed layer. When two or more other layers are provided, they may have the same composition or different compositions. Other layers can be formed on the base material layer, the vapor deposition layer, or the like.

  A conventionally known metal foil can be used as the metal foil. Aluminum foil and the like are preferable from the viewpoint of gas barrier properties that prevent transmission of oxygen gas and water vapor and the like and light blocking properties that prevent transmission of visible light and ultraviolet light.

The printing layer can be formed using a conventionally known pigment or dye, and the forming method is not particularly limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed for laminating any two layers by laminating. As the adhesive for lamination, for example, one-component or two-component curing or non-curing type vinyl type, (meth)acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, Other solvent-based, water-based, emulsion-type, or other laminating adhesives can be used. As a method for coating the above-mentioned adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method, or another method can be applied. As the coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry state) position are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry state) position is more preferred.

  A resin layer made of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, as the material of the adhesive resin layer, low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, and ethylene/α-olefin polymerized using a metallocene catalyst are used. Copolymer resin, ethylene/polypropylene copolymer resin, ethylene/vinyl acetate copolymer resin, ethylene/acrylic acid copolymer resin, ethylene/ethyl acrylate copolymer resin, ethylene/methacrylic acid copolymer resin, Ethylene/methyl methacrylate copolymer resin, ethylene/maleic acid copolymer resin, ionomer resin, polyolefin resin, unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, graft polymerization of ester monomer, Alternatively, a copolymerized resin, a resin obtained by graft-modifying a maleic anhydride with a polyolefin resin, or the like can be used. These materials can be used alone or in combination of two or more.

<Layer composition>
The layer structure of the laminate of the present invention is not particularly limited as long as it has a base material layer and a vapor deposition layer, and may be the same layer structure as a conventional laminated film. For example, PET/deposition layer/PE (PEF), PET/deposition layer/CPP, PET/deposition layer/CNY, PET/deposition layer/PET/PE, PET/deposition layer/PET/CPP, PET/deposition layer/AL /PE, PET/deposition layer/AL/CPP, PET/deposition layer/ONY/PE, PET/deposition layer/ONY/CPP, ONY/deposition layer/PET/PE, ONY/deposition/PET/CPP, PET/deposition Layer/PVA/PE, PET/deposited layer/PVA/CPP, PET/deposited layer/PVC/PE, PET/deposited layer/PVC/CPP, PET/deposited layer/AL/ONY/PE, PET/deposited layer/AL /ONY/CPP, PET/deposition layer/ONY/AL/PE, PET/deposition layer/ONY/AL/CPP, PET/deposition layer/paper/PE, PET/deposition layer/paper/CPP, paper/AL/PET /Vapor-deposited layer/PE, paper/AL/PET/vapor-deposited layer/CPP, and OPP/PET/vapor-deposited layer/AL/OPP. The names of the abbreviations are as follows. PET: polyethylene terephthalate, PE: polyethylene, PEF: polyethylene film, CNY: unstretched nylon, ONY: stretched nylon, AL: aluminum foil, CPP: unstretched polypropylene, OPP: biaxially stretched polypropylene, PVA: polyvinyl alcohol, PVC: PVC.

<Processing>
The laminate according to the present invention is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. For the purpose, it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, bonding, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.) and the like. Further, the laminate according to the present invention may be subjected to laminating processing (dry laminating or extrusion laminating), bag-making processing, and other post-treatment processing to produce a molded product.

<Use>
The laminate using the barrier film according to the present invention can be suitably used for applications such as packaging products, various label materials, lid materials, sheet moldings, laminated tubes, and the like. In particular, laminated films or packaging bags ( For example, pillow bags, pouches such as standing pouches and four-way pouches) are preferable. The thickness of the laminate can be appropriately determined depending on its application. For example, it is used in the form of a film or sheet having a thickness of about 5 to 500 μm, preferably about 10 to 300 μm.

<Other aspects>
Another object of the present invention is to provide a barrier film having a substrate layer made of a resin composition containing a carbon-neutral polyester using biomass ethylene glycol, which is obtained from a raw material obtained from a conventional fossil fuel. It is an object of the present invention to provide a barrier film having a substrate layer made of a polyester resin film which is comparable to the manufactured barrier film having a substrate layer in physical properties such as mechanical properties. Another object of the present invention is to provide a laminate using the barrier film.
According to yet another aspect of the invention,
A barrier film having a substrate layer and a vapor deposition layer formed on at least one surface of the substrate layer,
The base layer is made of a resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, and the resin composition has a diol unit of ethylene glycol derived from biomass and a dicarboxylic acid unit of The polyester, which is a dicarboxylic acid derived from fossil fuel, is contained in an amount of 50 to 95 mass% with respect to the entire resin composition,
There is provided a barrier film, wherein the vapor deposition layer comprises a vapor deposition film of an inorganic material or an inorganic oxide.
In an aspect of the present invention, the resin composition is a resin product made of polyester whose diol unit is a diol derived from fossil fuel or ethylene glycol derived from biomass and whose dicarboxylic acid unit is a dicarboxylic acid derived from fossil fuel. The polyester obtained by the above may be further contained.
In the aspect of the present invention, the resin composition may contain the polyester obtained by recycling the resin composition in an amount of 5 to 45 mass% with respect to the entire resin composition.
In the aspect of the present invention, the fossil fuel-derived dicarboxylic acid may be terephthalic acid.
In the aspect of the present invention, the resin composition may further contain an additive.
In the aspect of the present invention, the additive may be contained in an amount of 5 to 50% by mass based on the entire resin composition.
In the aspect of the present invention, the additive is a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a release agent. , One or more selected from the group consisting of an antioxidant, an ion exchanger, and a coloring pigment.
In the aspect of the present invention, the content of carbon derived from biomass by radiocarbon (C14) measurement may be 10 to 19% with respect to the total carbon in the polyester.
In the aspect of the present invention, a resin film obtained by biaxially stretching the base material layer may be used.
In the aspect of the present invention, the vapor deposition layer may be a vapor deposition film formed by a physical vapor deposition method or a chemical vapor deposition method.
In the aspect of the present invention, the vapor deposition layer may be a vapor deposition film of aluminum, aluminum oxide, or silicon oxide.
In the aspect of the present invention, a laminate using the barrier film may be used.
In the aspect of the present invention, the laminate may be a laminated film or a packaging bag.
According to still another embodiment of the present invention, in a barrier film having a base material layer and a vapor deposition layer formed on at least one surface of the base material layer, the base material layer comprises a diol unit and a dicarboxylic acid unit. A resin composition comprising a polyester comprising as a main component, wherein the resin composition is a polyester in which the diol unit is a biomass-derived ethylene glycol and the dicarboxylic acid unit is a fossil fuel-derived dicarboxylic acid. A barrier film having a base material layer made of a carbon-neutral resin can be realized by containing 50 to 95 mass% of the entire composition and forming the vapor deposition layer from a vapor deposition film of an inorganic material or an inorganic oxide. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional one, and the environmental load can be reduced. Further, the barrier film of the polyester resin composition of the present invention is not inferior to the barrier film of the polyester resin composition produced from a raw material obtained from conventional fossil fuels in terms of physical properties such as mechanical properties. Since the polyester resin composition is used, the conventional barrier film of the polyester resin composition can be substituted.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

<Synthesis of biomass-derived polyester>
83 parts by mass of terephthalic acid and 62 parts by mass of biomass ethylene glycol (manufactured by India Glycol Co., Ltd.) were supplied to the reaction tank as a slurry, and the esterification reaction was carried out at 240° C. for 5 hours by an ordinary direct weight method. Then, 0.013 parts by mass of trimethyl phosphate (manufactured by Aldrich Co.) was added (15 mmol% with respect to the acid component), and then the polymerization reaction was performed under a high temperature vacuum condition. First, in 40 minutes, the degree of vacuum was raised to 4000 Pa and the polymerization temperature was raised to 280° C., and then the degree of vacuum was lowered to 200 Pa while the polymerization temperature was kept at 280° C. to carry out the melt polymerization reaction. The reaction time was 3 hours. The synthesized polymer was discharged in running water in the form of strands and pelletized by a pelletizer. The pellets were dried at 160° C. for 5 hours, and then solid-state polymerized at 205° C. under a vacuum of 50 Pa in a nitrogen atmosphere to obtain a polymer having an intrinsic viscosity of 0.8 dl/g. The intrinsic viscosity was calculated from the melt viscosity measured at 35° C. using a phenol/tetrachloroethane (component ratio: 3/2) solvent. The obtained polymer was subjected to a differential thermal analysis (apparatus: Shimadzu DSC-60, measurement condition: heated in helium gas at 6° C./min), and showed a glass transition temperature of 69° C., which was derived from fossil fuel. It was equivalent to the known polyethylene terephthalate obtained from the raw material. Further, when the radiation-produced carbon measurement of the obtained biomass-derived polyethylene terephthalate was carried out, the content of the biomass-derived carbon by the measurement of radioactive carbon (C14) was 16%.

<Film preparation 1>
90 parts by mass of the polyethylene terephthalate pellets obtained as described above and 10 parts by mass of a fossil fuel-derived polyethylene terephthalate masterbatch containing 200 ppm of porous silica having an average particle size of 0.9 μm as a lubricant were dried and then placed in an extruder. It was supplied, melted at 285° C., extruded in a sheet form from a T die, and cooled and solidified by a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched in the longitudinal direction at a magnification of 3.5 times with the speed of the low-speed side driving roll set at 6.5 m/min and the speed of the high-speed side driving roll set at 22 m/min. A biaxially stretched polyester film 1 having a thickness of 12.02 μm was obtained by stretching the film in the transverse direction at a magnification of 3.5 times.

<Production of film 2>
60 parts by mass of the polyethylene terephthalate pellets obtained as described above, 30 parts by mass of recycled PET (re-pelletized in the manufacturing process such as ear loss during film formation), and the polyethylene terephthalate master used above After drying 10 parts by mass of the batch, it was supplied to an extruder, melted at 285° C., extruded into a sheet form from a T die, and cooled and solidified by a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched in the longitudinal direction at a magnification of 3.5 times with the speed of the low-speed side driving roll set at 6.5 m/min and the speed of the high-speed side driving roll set at 22 m/min. A biaxially stretched polyester film 2 having a thickness of 12.13 μm was obtained by stretching the film in the transverse direction at a magnification of 3.5 times.

<Production of film 3>
60 parts by mass of polyethylene terephthalate (intrinsic viscosity 0.83 dl/g) manufactured from conventional fossil fuel-derived raw materials, and recycled PET (re-pelletized in the manufacturing process such as ear loss during film formation) 30 parts by mass and 10 parts by mass of the polyethylene terephthalate masterbatch used above were dried and then fed to an extruder, melted at 285° C., extruded in a sheet form from a T die, and cooled and solidified by a cooling roll to be unsolidified A stretched sheet was obtained.
Next, this unstretched sheet was stretched in the longitudinal direction at a magnification of 3.5 times with the speed of the low-speed side driving roll set at 6.5 m/min and the speed of the high-speed side driving roll set at 22 m/min. A biaxially stretched polyester film 3 having a thickness of 12.06 μm was obtained by stretching the film in the transverse direction at a magnification of 3.5 times.

<Radiation carbon measurement>
When the radiant carbon production of the obtained film 1 was measured, the content of carbon derived from biomass by radiocarbon (C14) measurement was 14%. Further, when the carbon production from radiation was similarly measured for the films 2 and 3, the carbon content derived from biomass was 10% and 0%, respectively.

<Evaluation of film>
Each of the obtained films was cut into a width of 15 mm and a length of 200 mm from each of the MD direction (winding direction) and the TD direction (direction formed by an angle of 90 degrees with the MD direction) to obtain a test piece, and a tensile tester (tensilon RTC-125A (manufactured by Orientec Co., Ltd.) was used to measure the strength and elongation of the test piece in an environment of a temperature of 23° C. and a humidity of 50 RH%. In addition, F5 values in the MD direction and the TD direction (tensile strength when the film stretched by 5%) were measured. The tensile strength (kg/mm ² ) and the elongation at break (%) in each of the MD direction and the TD direction, and the F5 value (kg/mm ² ) were as shown in Table 1.

  Moreover, the test piece cut out from each of MD direction and TD direction was put into a 150 degreeC heating oven, and the heat shrinkage rate when heat-processing for 30 minutes at 150 degreeC based on JIS/C-2318 was measured. The results were as shown in Table 1.

  Further, each of the films obtained above was cut into a test piece by cutting it into a width of 50 mm and a length of 50 mm, and using this test piece, a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.), 23° C. and a humidity of 50 RH% The haze of the film was measured under the following environment. The measurement was performed according to JIS K7136:2000. The measurement results were as shown in Table 1 below.

  In addition, a wettension test mixture (made by Wako Pure Chemical Industries, Ltd.) was used for the test pieces cut into a width of 50 mm and a length of 50 mm for each of the films with and without corona treatment on the surface of each film. Then, the wetting tension was measured under the environment of 23° C. and humidity of 50 RH%. The measurement was performed according to JIS K6768:1999. The measurement results were as shown in Table 1 below.

  In addition, the coefficient of friction between the test pieces whose surfaces were corona-treated and the coefficient of friction between the test pieces which were not corona-treated were measured by a friction coefficient measuring device (AFT-200, Daiei Kagaku Seiki Seisakusho Co., Ltd.). (Manufactured by Mitsui Chemicals Co., Ltd.) was used in the environment of 23° C. and a humidity of 50 RH%. The measurement was performed according to JIS K7125:1999. The measurement results were as shown in Table 1 below.

  Further, as a comparative control, a general polyester film 4 (E-5100, manufactured by Toyobo Co., Ltd.) was prepared, and the film physical properties were measured in the same manner as above. The measurement results are also shown in Table 1.

  As is clear from Table 1, polyethylene terephthalate films (biomass PET films) 1 and 2 synthesized using biomass-derived ethylene glycol are polyester films (PET films) produced from raw materials obtained from conventional fossil fuels. ) It can be seen that it has physical properties comparable to those of 3 and 4.

Example 1
<Preparation 1 of laminated body>
Aluminum vapor deposition was performed on one surface of the biomass PET film 1 (thickness 12 μm) obtained as described above (vapor deposition conditions... Vapor deposition source: aluminum, vacuum degree in vapor deposition chamber: 2×10 ⁻³ mbar, Vacuum degree in the winding chamber: 3×10 ⁻² mbar, film transport speed: 350 m/min, film thickness: 450Å). In addition, another sheet of the biomass PET film 1 (thickness 12 μm) obtained as described above is further prepared (referred to as a biomass PET film 1′), one surface is subjected to corona treatment, and the corona-treated surface is printed. Layers (pattern and white press) were formed. Then, the vapor-deposited surface of the biomass PET film 1 and the printed surface of the biomass PET film 1′ were attached by dry lamination. Further, the other surface of the biomass PET film 1 (the surface opposite to the vapor deposition surface) and a general linear low-density polyethylene film (Mitsui Chemicals Tohcello KK: TUFC-D, thickness 80 μm). And were laminated by dry lamination to obtain a laminated film. The printing ink used was NEW LP Super manufactured by Toyo Ink Co., Ltd. A urethane adhesive (manufactured by Mitsui Chemicals, Inc.: Takelac A-515V/Takenate A-5) was used for sticking by dry lamination, and the coating amount when dried was adjusted to 3.5 g/m ² . After bonding, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a standing pouch having an outer dimension of 120 mm×190 mm, a folding width of 35 mm, and a seal width of 5 mm at the outer peripheral portion was prepared.

Example 2
<Production of laminated body 2>
(1) The biomass PET film 1 (thickness 12 μm) obtained as described above was prepared, and one surface thereof was subjected to corona treatment. The corona-treated biomass PET film 1 was mounted on a delivery roll of a winding-type vacuum vapor deposition device, and then this was fed out, and aluminum was used as a vapor deposition source on the corona-treated surface of the biomass PET film 1 to obtain oxygen. While supplying gas, a vapor deposition film of aluminum oxide having a film thickness of 200Å was formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating system.
(Deposition conditions)
Degree of vacuum in vapor deposition chamber: 2×10 ⁻⁴ mbar
Degree of vacuum in the winding chamber: 2×10 ⁻² mbar
Electron beam power: 25 kW
Film transport speed: 240 m/min
Deposition surface: Corona treated surface
(2) Next, to a mixed solution of polyvinyl alcohol, isopropyl alcohol, and ion-exchanged water of composition a prepared according to the composition table below, ethyl silicate of composition b, a silane coupling agent, isopropyl alcohol, A hydrolysis solution containing hydrochloric acid and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
Composition table a
Polyvinyl alcohol 2.30
Isopropyl alcohol 2.70
H ₂ O 51.20
b
Ethyl silicate 16.60
Silane coupling agent 0.20
Isopropyl alcohol 3.90
0.5N hydrochloric acid aqueous solution 0.50
H ₂ O 22.60
Total 100.00 (wt%)
(3) Next, the vapor-deposited aluminum oxide surface is coated with the above-prepared gas barrier composition (barrier coating solution), and then heat treated at a drying temperature of 180° C. and a line speed of 100 m/min, A gas barrier coat layer having a thickness of 0.3 μm (dry state) was formed to produce a gas barrier laminate film. The vapor-deposited surface of the aluminum oxide vapor-deposited PET film thus obtained was bonded to a general nylon film (manufactured by Toyobo Co., Ltd.: Harden N1200, thickness 15 μm) by dry lamination. Further, a general linear low-density polyethylene film (Mitsui Chemicals Tohcello Co., Ltd.: TUFC-D, thickness 80 μm) was laminated on the nylon film by dry lamination to obtain a laminated film. . A urethane-based adhesive (Takelac A-515V/Takenate A-5, manufactured by Mitsui Chemicals, Inc.) was used for bonding by dry lamination, and the coating amount when dried was adjusted to 3.5 g/m ² . After bonding, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a standing pouch having an outer dimension of 120 mm×190 mm, a folding width of 35 mm, and a seal width of 5 mm at the outer peripheral portion was prepared.

Comparative Example 1
<Preparation of laminated body 3>
One surface of the general PET film 4 (thickness 12 μm) prepared above was subjected to corona treatment, and a printing layer (pattern and white press) was formed on the corona-treated surface. Then, the printed surface of the PET film 4 and the vapor-deposited surface of the general aluminum vapor-deposited PET film 5 (thickness 12 μm) prepared above were attached by dry lamination. Furthermore, the surface of the aluminum vapor-deposited PET film 5 opposite to the vapor-deposited surface and a general linear low-density polyethylene film (Mitsui Chemicals Tohcello: TUX FC-D, thickness 80 μm) are dry laminated. It stuck and the laminated film was obtained. The printing ink used was NEW LP Super manufactured by Toyo Ink Co., Ltd. A urethane adhesive (manufactured by Mitsui Chemicals, Inc.: Takelac A-515V/Takenate A-5) was used for sticking by dry lamination, and the coating amount when dried was adjusted to 3.5 g/m ² . After bonding, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a standing pouch having an outer dimension of 120 mm×190 mm, a folding width of 35 mm, and a seal width of 5 mm at the outer peripheral portion was prepared.

Comparative example 2
<Fabrication of laminated body 4>
Aluminum oxide was vapor-deposited and a gas barrier coat layer was formed on a general PET film (E-5100, manufactured by Toyobo Co., Ltd., thickness 12 μm) in the same manner as in Example 2 above. The vapor-deposited surface of the aluminum oxide vapor-deposited PET film thus obtained and a general nylon film (Hayden N1200, manufactured by Toyobo Co., Ltd., thickness 15 μm) were laminated by dry lamination. Furthermore, a general linear low-density polyethylene film (Mitsui Chemicals Tohcello Co., Ltd.: TUFC-D, thickness 80 μm) was laminated on the nylon film by dry lamination to obtain a laminated film. .. A urethane adhesive (manufactured by Mitsui Chemicals, Inc.: Takelac A-515V/Takenate A-5) was used for sticking by dry lamination, and the coating amount when dried was adjusted to 3.5 g/m ² . After bonding, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a standing pouch having an outer dimension of 120 mm×190 mm, a folding width of 35 mm, and a seal width of 5 mm at the outer peripheral portion was prepared.

<Evaluation of laminated body>
Each of the laminated films obtained in Example 1 and Comparative Example 1 was cut out into a test piece with a width of 15 mm and a length of 200 mm. The PET film and the polyethylene film were peeled off, and the T-time peeling strength was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.). The tensile speed in this measurement was 50 mm/min. The measurement results were as shown in Table 2 below.

Each of the laminated films obtained in Example 1 and Comparative Example 1 was cut out into a test piece with a width of 15 mm and a length of 200 mm. The seal layer surfaces of the test piece were bonded together by heat sealing. The peeled strength at T was measured on the adhered sample using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.). In this measurement, the sealing pressure was 30 N/cm ² , the sealing time was 1 second, the sealing temperature was 170° C., and the pulling speed was 300 mm/min. The measurement was performed according to JIS Z1707. The measurement results were as shown in Table 2 below.

  Each of the laminated films obtained in Example 1 and Comparative Example 1 was used in an environment of a temperature of 23° C. and a humidity of 60 RH% with an oxygen permeability measuring device (OX-TRAN, manufactured by MOCON). Then, the oxygen permeability was measured. The measurement results were as shown in Table 2 below.

  Each of the laminated films obtained in Example 1 and Comparative Example 1 was subjected to a water vapor permeability measuring device (PERMATRAN, MOCON) under an environment of a temperature of 40° C. and a humidity of 90 RH%. The water vapor permeability was measured. The measurement results were as shown in Table 2 below.

Each standing pouch obtained in Example 1 and Comparative Example 1 was filled with 80 cc of water, and then the opening (upper edge) was sealed to prepare a water-containing standing pouch. The standing pouch containing water was dropped upright from a height of 50 cm to perform a drop impact test. The measurement results were as shown in Table 2 below.

For each laminated film obtained in Example 2 and Comparative Example 2, the laminate strength, seal strength, and barrier value (oxygen permeability and water vapor permeability) were measured under the same conditions as above, and a drop impact test was conducted. .. The measurement results were as shown in Table 3 below.

  As is clear from Tables 2 and 3, the barrier film having a base material layer made of a polyethylene terephthalate film synthesized using biomass-derived ethylene glycol has a barrier property having a base material layer made of an existing polyester film. It can be seen that it has physical properties comparable to those of the film.

10 Laminated body 11 Base material layer 12 Deposition layer 13 Resin layer 14 Adhesive layer 15 Printing layer 16 Resin layer 20 Laminated body 21 Base material layer 22 Deposition layer 23 Resin layer 24 Adhesive layer 25 Resin layer

Claims (14)

A barrier film having a substrate layer and a vapor deposition layer formed on at least one surface of the substrate layer,
The base material layer is made of a biaxially stretched resin film,
The biaxially stretched resin film has a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived terephthalic acid as a dicarboxylic acid unit, and a biomass polyester resin and a fossil-fuel-derived ethylene glycol as a diol unit, and a fossil-fuel-derived resin film. A terephthalic acid as a dicarboxylic acid unit, and a polyester resin made of a fossil fuel-derived raw material,
90 mass% or less of the biomass polyester resin is contained in the biaxially stretched resin film,
A barrier film, wherein the vapor deposition layer is a vapor deposition film of silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, or an oxide thereof.   The barrier film according to claim 1, further comprising a gas barrier coating film on the vapor deposition layer. 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, and 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.), at least one kind of alkoxide represented by polyvinyl alcohol resin, and The barrier film according to claim 2, containing an ethylene/vinyl alcohol copolymer.   The resin film according to claim 1, wherein the resin film further comprises a recycled polyester resin containing a fossil fuel-derived raw material having fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The barrier film according to any one of items.   The barrier film according to claim 4, wherein the resin film contains 5 to 45% by mass of the recycled polyester.   The barrier property according to any one of claims 1 to 5, wherein the content of biomass-derived carbon measured by radioactive carbon (C14) is 10 to 19% with respect to the total carbon in the resin composition. the film.   The barrier film according to any one of claims 1 to 6, wherein the vapor deposition layer is made of a vapor deposition film of aluminum, aluminum oxide, or silicon oxide.   A laminated film using the barrier film according to any one of claims 1 to 7.   A packaging bag comprising the laminated film according to claim 8.   A sheet molded product, comprising the laminated film according to claim 8.   A label material comprising the laminated film according to claim 8.   A lid member comprising the laminated film according to claim 8.   A laminated tube comprising the laminated film according to claim 8.   A packaged product comprising the laminated film according to claim 8.