JP2015036208A - Barrier film, and laminate film and package made from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film having excellent barrier properties, and a laminate film and a package made from the same.SOLUTION: A barrier film 10 includes a substrate layer 11, a vapor deposition layer 12, and a gas barrier coating film 13. The substrate layer 11 is formed of a resin composition mainly composed of a polyester including a diol unit and a dicarboxylic acid unit. The diol unit includes ethylene glycol derived from a biomass. The dicarboxylic acid unit includes dicarboxylic acid derived from fossil fuel. The vapor deposition layer 12 includes aluminum oxide made by PVD method, having a thickness of 30 to 100Å.

Description

  The present invention relates to a barrier film, and particularly relates to a barrier film using a biomass-derived polyester resin as a base film material, and a laminated film and a package using the same.

  Conventionally, as a packaging material having gas barrier properties, a gas barrier film provided with an aluminum foil layer on one surface of a substrate made of a resin film, or an inorganic oxide thin film such as silicon oxide or aluminum oxide instead of an aluminum foil layer Gas barrier films provided with layers are known. Such an inorganic oxide thin film layer is usually formed by a chemical vapor deposition method (hereinafter also referred to as a CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or a vacuum. It can be formed using physical vapor deposition methods (hereinafter also referred to as PVD methods) such as vapor deposition, sputtering, ion plating, and ion cluster beam methods. In consideration of gas barrier properties, it is preferable to form an inorganic oxide thin film layer by a CVD method such as a plasma chemical vapor deposition method (for example, Patent Document 1).

  Moreover, as a base material widely used for packaging materials, resin films made of polyester resins, polyolefin resins, polyamide resins and the like are used. Among them, polyester is widely used in various industrial applications such as packaging containers because it is excellent in mechanical properties, chemical stability, heat resistance, transparency, and the like and inexpensive. By the way, polyester is obtained by polycondensation of a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is esterified using ethylene glycol and terephthalic acid as raw materials. It is produced by a polycondensation reaction after the reaction. These raw materials are produced from petroleum, which is a fossil resource, for example, ethylene glycol is produced industrially from ethylene and terephthalic acid is produced industrially from xylene. In recent years, with regard to such materials derived from fossil fuels, there has been an increasing trend to use petroleum substitute raw materials for various purposes in consideration of the environment, and it is desired to move away from fossil fuels. In recent years, biomass plastics using biomass-derived raw materials have been put into practical use rapidly, and PET and the like using biomass-derived materials as part of the raw materials have begun to be put into practical use.

  Moreover, it has also been proposed to use PET using a biomass-derived material as described above as a packaging material. For example, Patent Document 2 uses ethylene glycol derived from biomass and dicarboxylic acid derived from fossil fuel. A barrier film using a film (biomass-derived PET film) made of PET (biomass-derived PET) formed by containing at least a part of the obtained polyester has been proposed.

JP 2003-038773 A JP 2012-96469 A

  In order to replace the barrier film using the biomass-derived PET film as described above with a film (fossil fuel-derived PET film) made of conventional fossil fuel-derived PET (fossil fuel-derived PET), The function of the barrier film used, that is, the gas barrier performance, should be equal to or higher than that of the barrier film using conventional fossil fuel-derived PET.

  The present inventors examined the barrier properties of a barrier film using a resin composition containing biomass-derived polyester as a main component as a base film material. In the barrier film using fossil fuel-derived PET, a vapor deposition layer is used. In contrast, there is no significant difference in gas barrier performance depending on the formation method of the film, whereas in the case of a barrier film using a resin composition containing biomass-derived polyester as a main component, the gas barrier performance depends on the vapor deposition method used to form the vapor deposition layer. It has been found that there is a significant effect on And when the present inventors form a vapor deposition layer in the barrier film obtained using the resin composition which contains polyester derived from biomass as a main component, the direction which formed the vapor deposition layer by PVD method is CVD method. The knowledge that the gas barrier performance of the obtained barrier film was remarkably improved was obtained. The present invention is based on this finding.

  Accordingly, an object of the present invention is to provide a barrier film using a resin composition containing a biomass-derived polyester having excellent gas barrier properties as a main component, and a laminated film and a package using the same.

  The barrier film according to the present invention includes a base material layer, a vapor deposition layer provided on at least one of the base material layers, and a gas barrier coating provided on a surface of the vapor deposition layer opposite to the base material layer side. A base material layer comprising a resin composition comprising a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, wherein the diol unit is a biomass-derived ethylene glycol. The dicarboxylic acid unit is made of fossil fuel-derived dicarboxylic acid, the vapor deposition layer is made of aluminum oxide by physical vapor deposition, and the vapor deposition layer has a thickness of 30 to 100 mm. To do.

  In the present invention, the resin composition contains 50 to 95% by mass of a polyester in which the diol unit is biomass-derived ethylene glycol and the dicarboxylic acid unit is a dicarboxylic acid derived from petrochemical fuel, based on the entire resin composition. It is preferable to contain.

  In the present invention, the dicarboxylic acid preferably contains terephthalic acid.

In the present invention, the gas barrier coating film has a general formula: R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) and a polyvinyl alcohol It is preferable to obtain a sol composition comprising a resin and / or an ethylene / vinyl alcohol copolymer by gelation.

  A laminated film according to another aspect of the present invention includes the above-described barrier film and a sealant layer provided on at least one surface side of the barrier film.

  In the present invention, it is preferable that a support is further provided, and the support is provided between the barrier film and the sealant layer or on the base material layer side of the barrier film.

  A pouch or lid according to another aspect of the present invention is a pouch or lid made of the above-described laminated film, wherein a sealant layer is disposed in the innermost layer of the laminated film.

  A standing pouch according to another aspect of the present invention is a standing pouch having a trunk portion and a bottom portion, wherein the trunk portion is made of the above-mentioned laminated film, and a sealant layer is disposed in the innermost layer of the laminated film. is there.

  A laminated tube according to another aspect of the present invention is a laminated tube comprising: a head portion including a shoulder portion and a spout portion; and a cylindrical body portion connected to the shoulder portion of the head portion. Is formed of a laminated film, and the laminated film includes a first sealant layer, a barrier film, and a second sealant layer in order from the inner layer side, and the barrier film is the above-described barrier film. .

  In the present invention, it is preferable that the laminated film further comprises a support.

  The liquid container according to another aspect of the present invention is a liquid container comprising a laminated film, wherein the laminated film is sequentially from the inner layer side, from the first sealant layer, the barrier film, the polyolefin resin layer, and the paper substrate. And a second sealant layer, and the barrier film is the barrier film described above.

  A paper cup according to another aspect of the present invention is a paper cup provided with a body part and a bottom part provided at one end of the body part, wherein the body part and / or the bottom part is made of a laminated film, and the laminated film is on the inner layer side. In order, a support comprising a sealant layer, a barrier film, a polyolefin resin layer, and a paper substrate is provided, and the barrier film is the above-described barrier film.

  According to the present invention, vapor deposition made of aluminum oxide by physical vapor deposition is performed on a base material layer made of a resin composition containing as a main component a polyester obtained using a diol unit containing biomass-derived ethylene glycol. By providing the layer, an environmental load is reduced and a barrier film having excellent barrier properties can be realized.

It is a fragmentary sectional view which shows simply the structure of the barrier film which concerns on embodiment of this invention. It is a fragmentary sectional view which shows simply the structure of the laminated film to which the barrier film which concerns on embodiment of this invention is applied. It is a figure which shows simply an example of a structure of a standing pouch. It is a fragmentary sectional view of the laminated film which forms a trunk part. It is a fragmentary sectional view which shows an example of the other structure of the laminated | multilayer film which forms a trunk | drum. It is a figure which shows an example of a pillow bag simply. It is a figure which shows an example of a 3 way seal bag simply. It is a figure which shows an example of a 4-way seal bag simply. It is a fragmentary sectional view showing an example of a tube container simply. It is a fragmentary sectional view of the laminated film which forms the cylindrical trunk | drum of a tube container. It is a fragmentary sectional view showing an example of other composition of a lamination film which forms a cylindrical body part of a tube container. It is a perspective view which shows an example of a liquid paper container. It is a fragmentary sectional view which shows an example of a structure of the laminated | multilayer film used for a liquid paper container. It is the perspective view which excised a part of paper cup. It is a fragmentary sectional view which shows an example of a structure of the laminated | multilayer film used for the trunk | drum of a paper cup. It is explanatory drawing which showed an example of the outline of the manufacturing method of a paper cup.

  DESCRIPTION OF EMBODIMENTS Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments) will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art and those that are substantially the same. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined. For convenience of explanation of the layer structure and the like, in the example shown below, the explanation will be made with a drawing in which the base material layer is arranged below, but the present invention is not necessarily used in this arrangement. In the following description, one of the layers in the thickness direction may be referred to as “up” or “up”, and the other of the layers in the thickness direction may be referred to as “down” or “down”.

<Barrier film>
The barrier film according to the embodiment of the present invention will be described. FIG. 1 is a partial cross-sectional view schematically showing the configuration of a barrier film according to an embodiment of the present invention. As shown in FIG. 1, the barrier film 10 includes a base material layer 11, a vapor deposition layer 12, and a gas barrier coating film 13. The barrier film 10 is configured by laminating a base material layer 11, a vapor deposition layer 12, and a gas barrier coating film 13 in the order of the base material layer 11, the vapor deposition layer 12, and the gas barrier coating film 13.

[Base material layer]
The base material layer 11 is made of a resin composition containing polyester described below as a main component.

(polyester)
The polyester is obtained by copolymerizing a diol unit and a dicarboxylic acid unit. In the polyester used in the present invention, the diol unit contains biomass-derived ethylene glycol, and the dicarboxylic acid unit consists of fossil fuel-derived dicarboxylic acid.

  Biomass-derived ethylene glycol uses ethanol (biomass ethanol) produced from biomass as a raw material. Biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide. Moreover, you may use the biomass ethylene glycol marketed, for example, the biomass ethylene glycol marketed by India Glycol company can be used conveniently.

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

  Specific examples of the aliphatic dicarboxylic acid include chains having usually 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. Or alicyclic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid derivatives include lower alkyl esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of the aliphatic dicarboxylic acids, and cyclic acid anhydrides of the aliphatic dicarboxylic acids such as succinic anhydride. . Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and those having succinic acid as a main component are particularly preferable. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferable.

  These dicarboxylic acids can be used singly or in combination of two or more.

  The polyester may be a copolymer polyester obtained by adding a copolymer component as the third component in addition to the diol unit and the dicarboxylic acid unit. Specific examples of the copolymer component include bifunctional oxycarboxylic acids, trifunctional or higher polyhydric alcohols, trifunctional or higher polyhydric carboxylic acids and / or their anhydrides, and 3 Examples include at least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids. Among these copolymer components, a bifunctional and / or trifunctional or higher functional oxycarboxylic acid is particularly preferably used because a copolymer polyester having a high polymerization degree tends to be easily produced. Among them, the use of a tri- or higher functional oxycarboxylic acid is most preferable because a polyester having a high degree of polymerization can be easily produced with a very small amount without using a chain extender (coupling agent) described later.

  The polyester may be a high molecular weight polyester obtained by chain extension (coupling) of these copolyesters. As a coupling agent, a carbonate compound, a diisocyanate compound, or the like can be used, and the amount thereof is usually 10 mol% for carbonate bonds and urethane bonds for 100 mol% of all monomer units constituting the polyester. Hereinafter, it is 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, and dicyclohexyl. Examples include carbonate. 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, and xylylene. Known diisocyanates such as range isocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like can be mentioned.

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

  The amount of the diol unit used in the production of the polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof, but in general, esterification and / or transesterification and / or polycondensation reaction It is used in an excess of 0.1 to 20 mol% because there is a distillation inside.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction.

  Examples of the polymerization catalyst generally include compounds containing a Group 1 to Group 14 metal element excluding hydrogen and carbon in the periodic table. 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, alkoxy salt, organic sulfonate, or β-diketonate salt, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof. Among these, titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium-containing metal compounds and mixtures thereof are preferable, and titanium compounds, zirconium compounds and germanium compounds are particularly preferable. In addition, since the polymerization rate of the catalyst is high when it is melted or dissolved during polymerization, the catalyst is preferably a liquid at the time of polymerization, or a compound that dissolves in an ester low polymer or polyester.

  The titanium compound is preferably a tetraalkyl titanate, specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples include benzyl titanate and mixed titanates thereof. In addition, 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 triethanolamate, butyl titanate dimer and the like are also preferably used. Furthermore, titanium oxide and composite oxides containing titanium and silicon are 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), particularly tetra-n-butyl titanate, polyhydroxy titanium stearate Rate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titania / silica composite oxide (eg, Acordis Industrial Fiber) The product name “C-94” manufactured by ers Inc.) is preferable.

  Specific examples of the zirconium compound include zirconium tetraacetate, zirconium acetylate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, and polyhydroxyzirconium. Examples include stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. Further, zirconium oxide or a complex oxide containing, for example, zirconium and silicon may be used. Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate acetate, zirconium ammonium oxalate, potassium potassium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxy Zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide are preferred.

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

  The amount of the catalyst used in the case of using a metal compound as the polymerization catalyst is such that the lower limit is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30,000 ppm or less, preferably 1 as the amount of metal relative to the produced polyester. 1,000 ppm or less, more preferably 250 ppm or less, and particularly preferably 130 ppm or less. If too much catalyst is used, this is not only economically disadvantageous, but also lowers the thermal stability of the polymer. When the amount of the catalyst used is too small, the polymerization activity is lowered, and accordingly, the decomposition of the polymer is easily induced during the production of the polymer. As the amount of catalyst used, the amount of terminal carboxyl groups of the polyester to be produced is reduced as the amount used is reduced, and therefore the amount of catalyst used is preferably reduced.

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

  In the above production process, a coupling agent may be added to the reaction system. After completion of polycondensation, the coupling agent is added to the reaction system without solvent in a uniform molten state, and reacted with the polyester obtained by polycondensation.

  High molecular weight polyesters using these coupling agents can be produced using known methods. After the polycondensation is completed, the coupling agent is added to the reaction system without solvent in a uniform molten state and reacted with the polyester obtained by polycondensation. Specifically, the terminal group obtained by catalyzing a dicarboxylic acid unit and a diol unit has a hydroxyl group substantially, and a mass average molecular weight (Mw) is 20,000 or more, preferably 40,000 or more. By reacting the above-mentioned coupling agent with the polyester prepolymer, a polyester resin having a higher molecular weight can be obtained. If the prepolymer has an Mw of 20,000 or more, it is not affected by the remaining catalyst even under severe conditions such as a molten state by using a small amount of a coupling agent. High molecular weight polyesters can be produced.

  The obtained polyester may be solidified after solidification as necessary in order to further increase the degree of polymerization and remove oligomers such as cyclic trimers. Specifically, after the polyester is chipped and dried, the polyester is pre-crystallized by heating at a temperature of 100 to 180 ° C. for 1 to 8 hours, and subsequently, an inert gas at a temperature of 190 to 230 ° C. It is performed by heating for 1 to several tens of hours in an atmosphere or under reduced pressure.

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

  Various additives can be added to the manufactured polyester or to the manufactured polyester as long as the properties are not impaired. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, and ions. Examples include exchange agents and coloring pigments. It is preferable that an additive is added in 5-50 mass% with respect to the whole polyester resin composition, Preferably it is 5-20 mass%.

  In addition to the above-described polyester, the resin composition constituting the base material layer 11 may include a resin that reuses a piece that is generated when the polyester is formed into a film to produce a film. As the polyester used for such reuse, in addition to the above-described polyester containing biomass-derived diol units, polyesters comprising conventional petrochemically derived diol units and dicarboxylic acid units may be used. By using such recycled polyester, the environmental load can be further reduced.

It is preferable that the resin composition containing polyester contains 10 to 19% of biomass-derived carbon content based on measurement of radioactive carbon (C14) with respect to the total carbon in the polyester. Since carbon dioxide in the atmosphere contains C14 at a constant ratio (105.5 pMC), the C14 content in plants that grow by incorporating 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, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all the carbon atoms in the polyester. In the present invention, in the case where the content of C14 in the polyester was P _C14, the content of P _{bio Bio} carbon from biomass, defined as the following equation (1).
P _bio (%) = P _C14 /105.5×100 (1)

For example, since PET is a polymer in which ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms are polymerized at a molar ratio of 1: 1, when only biomass-derived ethylene glycol is used, The content P _bio of the biomass-derived carbon is 20%. In this embodiment, it is preferable that the content of carbon derived from biomass by radioactive carbon (C14) measurement is 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 biomass in the resin composition is preferably closer to 20%, but from the viewpoint of problems in film production processes and physical properties, the resin composition is recycled as described above. Since it is preferable to include polyester and additives, the actual upper limit is 18%.

That is, when only biomass-derived ethylene glycol is used, the biomass-derived carbon content P _bio in the polyester is 20%, and the biomass-derived carbon content is based on the total carbon in the resin composition. Therefore, the polyester obtained using ethylene glycol derived from biomass as the diol unit and dicarboxylic acid derived from the petrochemical fuel as the dicarboxylic acid unit is 50 ( = 10% / 20%) mass% to 95 (= 19% / 20%) mass% means that it is preferably contained.

  As the base material layer 11, a film obtained by forming the above-described resin composition into a film can be used. In order to use the resin composition as a resin film, a conventional method of processing a resin composition made of polyester into a film can be used. For example, a resin film is manufactured by shape | molding a resin composition in a sheet form with a well-known melt extruder etc., and cooling the molded object (sheet-like molded object) shape | molded in the sheet form then. Specifically, after drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature equal to or higher than the melting point of the polyester (Tm) to Tm + 70 ° C. to melt the resin composition, for example, A resin film can be formed by extruding into a sheet form from a die such as a T-die, and then rapidly cooling and solidifying the extruded sheet-shaped formed body with a rotating cooling drum or the like.

  As a melt extruder, well-known extruders, such as a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, can be used according to the objective.

  A resin film is obtained by extending | stretching a sheet-like molded object at least to the uniaxial direction of MD (Machine Direction) direction or TD (Transverse Direction) direction. The MD direction is the extrusion direction when the sheet-like molded body is extruded using a melt extruder, and the TD direction is the extrusion direction when the sheet-like molded body is extruded using a melt extruder. The directions are orthogonal. A known stretching method can be used as a method of stretching the sheet-like molded body. For example, the sheet-shaped molded body is stretched in a uniaxial or biaxial direction by longitudinal uniaxial stretching, longitudinal uniaxial multistage stretching, transverse uniaxial stretching, longitudinal and transverse sequential biaxial stretching, longitudinal and transverse simultaneous biaxial stretching, or a combination thereof. .

  The resin film is preferably formed by biaxial stretching. When forming a resin film by biaxially stretching the sheet-shaped molded body, for example, the sheet-shaped molded body extruded on the cooling drum as described above, followed by heating by roll heating, infrared heating, etc. Stretch in the machine direction. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 to 100 ° C. The ratio of longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the resin film. When the draw ratio is less than 2.5, the thickness unevenness of the resin film becomes large and it is difficult to obtain a good resin film.

  The longitudinally stretched resin film is subsequently stretched in the transverse direction and sequentially subjected to heat fixing and heat relaxation treatment steps. Thereby, it becomes a biaxially stretched film. The transverse stretching is usually performed in a temperature range of 50 to 100 ° C. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this application. If it is less than 2.5 times, the thickness unevenness of the resin film becomes large and it is difficult to obtain a good resin film, and if it exceeds 5.0 times, breakage tends to occur during film formation.

  A heat setting treatment is subsequently performed after the transverse stretching, and a preferable temperature range for heat setting is Tg + 70 to Tm-10 ° C. of polyester. The heat setting time is preferably 1 to 60 seconds. Furthermore, for applications that require a low thermal shrinkage rate, heat relaxation treatment may be performed as necessary.

Although the thickness of the resin film obtained as mentioned above is arbitrary according to the use, it is 3-100 micrometers normally, Preferably it is 5-50 micrometers. Breaking strength of such a resin film is 5 to 35 kg / mm ² at 5~40kg / ^mm 2, TD direction MD direction. The breaking elongation of the resin film is 50 to 350% in the MD direction and 50 to 300% in the TD direction. Further, the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1 to 5%. Thus, a resin film is equivalent to the physical property of the polyester film manufactured only from the material derived from the conventional fossil fuel.

[Deposition layer]
The vapor deposition layer 12 is a vapor deposition film provided on one (upper) surface of the base material layer 11 and made of aluminum oxide (aluminum oxide). The vapor deposition layer 12 functions as a layer having a gas barrier function that prevents permeation of oxygen gas, water vapor, and the like. By providing the base material layer 11 made of biomass-derived polyester resin with a vapor deposition layer 12 formed using a physical vapor deposition (PVD) method and a gas barrier coating film 13 to be described later, oxygen gas, water vapor, etc. It is possible to impart or improve a gas barrier property that prevents permeation of water. Two or more vapor deposition layers 12 may be provided. When it has two or more vapor deposition layers 12, each may have the same composition or different compositions. Further, one or more vapor deposition layers 12 may be provided on the other (lower) surface of the base material layer 11. One or more vapor deposition layers 12 may be provided on both surfaces of the base material layer 11.

  In the present embodiment, the vapor deposition layer 12 is formed using a PVD method such as a vacuum vapor deposition method, an oxidation reaction vapor deposition method, a sputtering method, an ion plating method, and an ion cluster beam method. Note that the vapor deposition layer formed by using the PVD method does not include an organic substance, that is, a carbon component. Therefore, in this embodiment, the vapor deposition layer formed using the PVD method is a vapor deposition layer that does not contain an organic substance, that is, a carbon component.

  The vacuum evaporation method is a method in which a metal or metal oxide is used as a raw material (evaporation material), is heated and vaporized, and is vapor-deposited on the surface of the base material layer 11. The oxidation reaction vapor deposition method is a method in which a metal or a metal oxide is used as a raw material, oxygen is introduced and oxidized, and this is deposited on the surface of the base material layer 11. Further, the oxidation reaction vapor deposition method may be a plasma-assisted type in which the oxidation reaction is supported by plasma. In the above method, as a method for heating the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam (EB) heating method, or the like can be used.

The vapor deposition layer 12 is formed of aluminum oxide (aluminum oxide). As the vapor deposition layer 12, it is preferable to use an amorphous thin film of aluminum oxide. Specifically, the vapor deposition layer 12 is an amorphous thin film of aluminum oxide represented by the formula AlO _X (wherein X represents a number in the range of 0.5 to 1.5). As the vapor deposition layer 12, a non-crystalline thin film of aluminum oxide in which the value of X decreases in the depth direction from the film surface toward the inner surface can be used. The amorphous thin film of aluminum oxide is represented by the formula AlO _X (where X represents a number in the range of 0.5 to 1.5), and in the depth direction from the thin film surface toward the inner surface. It is preferable that the value of X is increasing. In the present embodiment, as the value of X in the above formula, a value of X = 0.5 or more can be basically used. However, in the present embodiment, X = 1. When it is less than 0, since coloring is intense and it is inferior to transparency, it is preferable to use the thing of X = 1.0 or more. Moreover, since the thing of X = 1.5 is a thing in which Al and oxygen were completely oxidized, the thing to X = 1.5 can be used as an upper limit. In addition, when the value of X in said formula is 0, it is a perfect inorganic simple substance (pure substance), and is not transparent.

  Note that the rate of decrease in the value of X is determined by using a surface analyzer such as an X-ray photoelectron spectrometer (XPS) or a secondary ion mass spectrometer (SIMS) in the depth direction. This can be confirmed by performing elemental analysis of the vapor deposition layer 12 using a method of analyzing by ion etching or the like.

The amorphous thin film of aluminum oxide can be formed using, for example, a take-up vacuum deposition apparatus. When an amorphous thin film of aluminum oxide is formed using a roll-up type vacuum deposition apparatus, the vacuum degree of the vacuum chamber is preferably 10 ⁰ to 10 ⁻⁵ mbar, more preferably 10 ⁻¹ to 10 ⁻⁴ mbar. preferable. The degree of vacuum of the vapor deposition chamber is preferably 10 ⁻² to 10 ⁻⁸ mbar before introducing oxygen, more preferably 10 ⁻³ to 10 ⁻⁷ mbar, and 10 ⁻¹ to 10 ⁻⁶ after introducing oxygen. mbar is preferable, and 10 ⁻² to 10 ⁻⁵ mbar is more preferable. As a conveyance speed of the base material layer 11, 10-800 m / min is preferable and 50-600 m / min is more preferable. The amount of oxygen introduced varies depending on the size of the vapor deposition machine.

  If the oxidation degree of the aluminum oxide is too high, the film quality to be formed becomes hard, so that the vapor deposition layer 12 is liable to crack, and if the oxidation degree of the aluminum oxide is too low, the transparency is lowered. Therefore, during the vapor deposition of aluminum oxide on the base material layer 11 or immediately after the vapor deposition, the ultraviolet ray (wavelength 366 nm) transmittance of the vapor deposition layer 12 is preferably in the range of 85 to 96%, more preferably in the range of 87 to 94%. In addition, the film thickness of the vapor deposition layer 12 is preferably in the range of 150 to 600 mm in consideration of suitability for processing. Moreover, when the vapor deposition layer 12 consists of silicon oxide, the film thickness of the vapor deposition layer 12 should be in the range of 50 to 300 mm in consideration of suitability for post-processing, using a mixture of silicon monoxide and silicon as a raw material. preferable.

  In this embodiment, the film thickness of the vapor deposition layer 12 provided on the base material layer 11 is 30-100 mm. If it is less than 30 mm, the gas barrier property may be insufficient even when the gas barrier coating film 13 is used in combination. On the other hand, if it exceeds 100%, gas barrier performance may not be maintained when a gas barrier film is used for a package. The reason for this is not clear, but if the thickness of the vapor deposition layer (alumina) 12 exceeds 100 mm, the flexibility is lowered, and when used for an application such as a package, cracks or pinholes are formed in a part of the vapor deposition layer 12. It is considered that the gas barrier property is reduced. The thickness of the vapor deposition layer 12 is preferably in the range of 40 to 90 mm, more preferably 50 to 80 mm. In addition, the film thickness of the vapor deposition layer 12 can be measured with a fundamental parameter method, for example using a fluorescent X-ray-analysis apparatus (Brand name: RIX2000 type | mold, Rigaku Corporation make). Moreover, as a means to change the film thickness of the vapor deposition layer 12, it can carry out by the method of changing the deposition rate of the vapor deposition layer 12, the method of changing the speed | rate of vapor deposition, etc.

  When forming the vapor deposition layer 12 in the base material layer 11, it is preferable to give the surface of the base material layer 11 a corona discharge process, a flame process, etc. previously. By performing these treatments, the adhesive strength between the base material layer 11 and the vapor deposition layer 12 can be improved. Thereby, the base material layer 11 and the vapor deposition layer 12 can be stuck firmly, and generation | occurrence | production of the delamination (delamination) etc. can be suppressed. The corona discharge treatment can be performed by using a known corona discharge treatment device and passing the paper substrate through the generated corona atmosphere. The frame processing can be performed by using a known frame processing device and burning the surface of the paper substrate with fire.

  In addition to corona discharge treatment and flame treatment, the surface of the base material layer 11 may be subjected to plasma treatment with an inert gas in advance. Thereby, when the vapor deposition layer 12 is formed on the surface of the base material layer 11, the adhesion between the base material layer 11 and the vapor deposition layer 12 is improved, the base material layer 11 and the vapor deposition layer 12 are firmly adhered, Generation | occurrence | production of delamination (delamination) etc. can be suppressed. In addition, the surface of the base material layer 11 is subjected to plasma treatment immediately before the vapor deposition layer 12 is formed on the base material layer 11 using the PVD method, thereby removing moisture, dust and the like on the surface of the base material layer 11. Surface treatments such as surface smoothing and activation can be performed.

  Examples of the plasma treatment method include a plasma surface treatment method for modifying the surface of the base material layer 11 using a plasma gas generated by ionizing the gas by arc discharge on the surface of the base material layer 11. Can be used. Specifically, an inert gas such as nitrogen gas, argon gas, helium gas, or the like is used as a plasma gas, and the surface of the base material layer 11 can be plasma-treated by a plasma surface treatment method. As the plasma gas, a mixed gas obtained by further adding oxygen gas to the above inert gas may be used.

  As the above plasma treatment, it is preferable to perform the plasma treatment in consideration of conditions such as plasma output, plasma gas type, plasma gas supply amount, treatment time, and the like. As a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used. In the plasma treatment, a plasma treatment surface can be formed using an atmospheric pressure plasma treatment method or the like.

[Gas barrier coating film]
The gas barrier coating film 13 is a layer that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The gas barrier coating film 13 has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer greater than or equal to 0, m represents an integer greater than or equal to 1, n + m represents the valence of M), and the polyvinyl alcohol as described above. And a gas barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. .

  The gas barrier coating film 13 is prepared by a step of preparing the gas barrier composition and, on the vapor deposition layer 12 provided on one surface of the base material layer 11, through a surface treated with oxygen gas as necessary. Then, the step of coating the gas barrier composition to provide a coating film, and the base material layer 11 provided with the coating film at 20 ° C. to 180 ° C. and the base material layer 11 Heat treatment is performed for 10 seconds to 10 minutes at a temperature equal to or lower than the melting point, and on the vapor deposition layer 12 provided on one surface of the base material layer 11, if necessary, through the plasma treatment surface with oxygen gas, the above-mentioned It can be manufactured by a process including a process of forming the gas barrier coating film 13.

  In the present embodiment, the gas barrier coating film 13 is formed by laminating two or more gas barrier compositions prepared as described above on the vapor deposition layer 12 provided on one surface of the base material layer 11. May be. Thus, a composite polymer layer in which two or more gas barrier coating films 13 are stacked can be formed and manufactured.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As a condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a 2 to 6 mer is used.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , as the metal atom represented by M, silicon, zirconium, titanium, aluminum, and the like can be used. In the present embodiment, examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, 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, i -Propyl group, n-butyl group, sec-butyl group, and the like. In the present embodiment, these alkyl groups may be the same or different in the same molecule.

In the present embodiment, 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 alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group). In the above, as Ra, methyl group, ethyl group, n-propyl group, n-butyl group, and others are used. Specific examples of the alkoxysilane include, for example, tetramethoxysilane (Si (OCH ₃ ) ₄ ), tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), and tetrapropoxysilane (Si (OC ₃ H ₇ ) _4. ), Tetrabutoxysilane (Si (OC ₄ H ₉ ) ₄ ), and the like.

In the present embodiment, examples of the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, the general formula Rb _n Si (ORc) _4-m (where, n is Represents an integer of 0 or more, 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. Alkylalkoxysilanes can also be used. Specific examples of the alkylalkoxysilane include, 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 ), etc. can be used. Said alkoxysilane, alkylalkoxysilane, etc. can be used individually or in mixture of 2 or more types. In the present embodiment, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present embodiment, as the alkoxide represented by the 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 ), tetraipropoxyzirconium (Zr (iso-OC ₃ H). ₇ ) ₄ ), tetra-n-butoxyzirconium (Zr (OC ₄ H ₉ ) ₄ ), etc. can be used.

Moreover, in this embodiment, as an alkoxide represented by said general formula R _< ¹ _> nM (OR _< ² _> ) _m , the titanium alkoxide whose M is Ti can be used, for example. Specific examples of the titanium alkoxide include, for example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxytitanium (Ti (OC ₂ H ₅ ) ₄ ), and tetraisopropoxytitanium (Ti (iso-OC ₃ H ₇ ). ₄ ), tetra-n-butoxytitanium (Ti (OC ₄ H ₉ ) ₄ ), etc. can be used.

Moreover, in this embodiment, as an alkoxide represented by said general formula R _< ¹ _> nM (OR _< ² _> ) _m , the aluminum alkoxide whose M is Al can be used, for example. Specific examples of the 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 ), etc. can be used.

  In the present embodiment, the above alkoxides may be used as a mixture of two or more thereof. In particular, by using a mixture of alkoxysilane and zirconium alkoxide, it is possible to improve the toughness, heat resistance and the like of the resulting barrier film, and avoid a decrease in the retort resistance of the film during stretching. . The amount of the zirconium alkoxide used is in the range of 10 parts by mass or less with respect to 100 parts by mass of the alkoxysilane, and preferably about 5 parts by mass. In the above, when it exceeds 10 parts by mass, the gas barrier coating film 13 is easily gelled, and the brittleness of the film is increased, and the gas barrier coating film 13 is easily peeled off when the base film is coated. This is not preferable because of the tendency.

  Further, by using a mixture of alkoxysilane and titanium alkoxide, there is an advantage that the thermal conductivity of the obtained gas barrier coating film 13 is lowered and the heat resistance of the barrier film 10 is remarkably improved. In the above, the usage-amount of a titanium alkoxide is 5 mass parts or less with respect to 100 mass parts of said alkoxysilane, Preferably, 3 mass parts is preferable. In the above, if it exceeds 5 parts by mass, the brittleness of the gas barrier coating film 13 increases, and when the base material layer 11 is coated, the gas barrier coating film 13 tends to peel off, which is not preferable.

  Next, as the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer for forming the gas barrier coating film 13, a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer is used alone. Or a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer. By using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, physical properties such as gas barrier properties, water resistance, weather resistance, and the like of the gas barrier coating film 13 can be remarkably improved. In particular, by using a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, in addition to the above physical properties such as gas barrier properties, water resistance, and weather resistance, a gas barrier after heat-resistant water and hydrothermal treatment It is possible to form the gas barrier coating film 13 which is remarkably excellent in properties and the like.

  When a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is, as a mass ratio, polyvinyl alcohol-based resin: ethylene / vinyl alcohol copolymer. = 10: 0.05 to 10: 6 is preferable, and it is more preferable to use at a blending ratio of about 10: 1.

  Content with a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 mass parts with respect to 100 mass parts of total amounts of said alkoxide, Preferably, it is 20-200. It is preferable to prepare a gas barrier composition at a blending ratio of mass parts. In the above, when it exceeds 500 parts by mass, the brittleness of the gas barrier coating film 13 is increased, and the water resistance and weather resistance of the resulting barrier film 10 tend to be lowered. If it is less than 1, it is not preferable because gas barrier properties are lowered.

  As the polyvinyl alcohol resin, those obtained by saponifying polyvinyl acetate can be generally used. As the above-mentioned polyvinyl alcohol-based resin, partially saponified polyvinyl alcohol resin in which several tens of percent of acetic acid groups remain, or completely saponified polyvinyl alcohol in which acetic acid groups do not remain, or OH groups have been modified. A modified polyvinyl alcohol resin may be used and is not particularly limited. Specific examples of the above-mentioned polyvinyl alcohol resin include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (ken) manufactured by Kuraray Co., Ltd. Degree of conversion = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. Specifically, it includes from partially saponified products in which several tens mol% of acetic acid groups remain to completely saponified products in which acetic acid groups remain only several mol% or no acetic acid groups remain. The degree of saponification is not particularly limited, but is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Things are 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.

  When preparing the gas barrier composition, for example, a silane coupling agent may be added. As said silane coupling agent, known organic reactive group containing organoalkoxysilane can be used. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used. Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like can be used. The above silane coupling agents may be used alone or in combination of two or more. In this embodiment, the usage-amount of the above silane coupling agents can be used within the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If the silane coupling agent is used in an amount of 20 parts by mass or more, the rigidity and brittleness of the gas barrier coating film 13 are increased, and the insulating property and workability of the gas barrier coating film 13 tend to decrease, which is not preferable.

  As a sol-gel method catalyst, mainly a polycondensation catalyst, used in preparing the gas barrier composition, a tertiary amine that 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 this embodiment, N, N-dimethylbenzylamine is particularly preferably used. The amount used is 0.01 to 1.0 part by mass, preferably about 0.03 part by mass, per 100 parts by mass of the total amount of alkoxide and silane coupling agent.

  The acid used in preparing the gas barrier composition is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent, or the like. As said acid, mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, organic acids, such as an acetic acid and tartaric acid, and others can be used, for example. The amount of the acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent. Is preferred.

  Moreover, when preparing said gas-barrier composition, water is 0.1-100 mol with respect to 1 mol of total molar amounts of said alkoxide, Preferably, it is used in the ratio of 0.8-2 mol. it can. When the amount of the water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked, resulting in low density and porosity. Such a porous polymer is not preferable because the gas barrier property of the barrier film cannot be improved. On the other hand, when the amount of water is less than 0.8 mol, the hydrolysis reaction tends to hardly proceed, which is not preferable.

  As an organic solvent used when preparing said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol etc. are mentioned, for example. Furthermore, in the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in a state of being dissolved in a coating solution containing the alkoxide or the silane coupling agent. Therefore, the type of the organic solvent is appropriately selected. When a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. In the present embodiment, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, one commercially available as Soarnol (trade name) can be used. The amount of the organic solvent used is usually 30 per 100 parts by mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. It is -500 mass parts.

<Manufacturing method of barrier film>
Next, an example of the manufacturing method of the barrier film 10 will be described. First, the vapor deposition layer 12 made of aluminum oxide is formed on one surface of the base material layer 11 using the PVD method. Next, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel 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, a polycondensation reaction gradually proceeds in the gas barrier composition (coating liquid). Next, the gas barrier composition (coating liquid) is applied on the vapor deposition layer 12 provided on one surface of the base material layer 11 and dried. As a method for applying the gas barrier composition, for example, application 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 can be used. By using this coating means, the gas barrier coating film 13 having a film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed by one or a plurality of coatings, Under normal circumstances, condensation is performed by heating and drying at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C., for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. The gas barrier coating film 13 can be formed. Moreover, when applying a gas-barrier composition as needed, a primer agent etc. can also be apply | coated on the vapor deposition layer 12 previously. Further, pretreatment such as corona discharge treatment, flame treatment, plasma treatment, and the like can be optionally performed.

  Next, by the above drying, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer proceeds, and the coating film becomes It is formed. Further, preferably, the above coating operation is repeated to laminate a plurality of coating films composed of two or more layers.

  Next, the laminate coated with the coating liquid is 20 ° C. to 180 ° C. and a temperature not higher than the melting point of the base material layer 11, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to A gas barrier coating film 13 made of the above gas barrier composition (coating liquid) is formed on the vapor deposition layer 12 formed on one surface of the base material layer 11 by heat treatment for 10 minutes, and thereby barrier properties are achieved. The film 10 can be manufactured. Thus obtained barrier film 10 is excellent in gas barrier properties.

  In the present embodiment, as described above, when the ethylene / vinyl alcohol copolymer or the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are not used in combination, that is, only the polyvinyl alcohol resin is used. In the case of producing a barrier film by using, in order to improve the gas barrier property after the hot water treatment, for example, a gas barrier composition produced by using a polyvinyl alcohol resin in advance is applied. 1 coating layer (first gas barrier coating film) is formed, and then a gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied onto the first coating layer. A second coating layer (second gas barrier coating film) may be formed to form a composite layer thereof. Thereby, the gas barrier property of the barrier property film obtained can be improved.

  Also, a coating layer formed from a gas barrier composition containing the above-mentioned ethylene / vinyl alcohol copolymer, or a gas barrier composition containing a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. The applied layer may be formed by laminating a plurality of layers. The gas barrier property of the barrier film thus obtained can be improved.

  In addition to the vapor deposition layer 12 and the gas barrier coating film 13, the barrier film 10 is appropriately coated with an inert gas on the surface of the gas barrier coating film 13 as necessary. Plasma treatment, plasma treatment with oxygen gas, primer treatment, or the like may be performed in any order as appropriate.

  As described above, the barrier film 10 includes the vapor-deposited layer 12 having a predetermined thickness formed by the PVD method on the base material layer 11 made of a resin composition containing a biomass-derived polyester as a main component, and the gas barrier coating film 13. And can have excellent barrier properties. Thereby, the barrier film 10 can have a barrier property equal to or higher than a barrier film using a PET film made of a fossil fuel-derived raw material. Moreover, since the barrier film 10 can form the base material layer 11 by the layer which consists of a carbon neutral material, compared with the barrier film manufactured from the raw material obtained from the conventional fossil fuel, the usage-amount of fossil fuel is reduced. This can greatly reduce the environmental load.

The barrier film 10 is useful as a packaging material because it has the excellent characteristics as described above. In particular, the barrier film 10 blocks and prevents permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc. Since it has excellent gas barrier properties, it can be suitably used as a barrier substrate constituting a food packaging film. In particular, when used for so-called gas-filled packaging filled with O ₂ , H ₂ O or the like, the excellent gas barrier property is extremely effective for holding the filled gas. Further, even when used in a gas-filled package 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 10 is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and has extremely excellent gas barrier properties.

<Laminated film>
Next, the laminated film to which the barrier film 10 is applied will be described. FIG. 2 is a cross-sectional view schematically showing the configuration of a laminated film to which a barrier film according to an embodiment of the present invention is applied. As illustrated in FIG. 2, the laminated film 20 </ b> A includes a barrier film 10 and a sealant layer 21, and is configured by laminating the sealant layer 21 on the surface of the gas barrier coating film 13 of the barrier film 10. . By providing the sealant layer 21 on the surface of the barrier film 10, a package having excellent gas barrier properties as described later can be obtained.

  In the embodiment shown in FIG. 2, the laminated film 20 </ b> A has a configuration in which the sealant layer 21 is laminated on the surface of the gas barrier coating film 13 of the barrier film 10. 11 may be configured such that the sealant layer 21 is laminated on the surface opposite to the surface on which the vapor deposition layer 12 is laminated, and on the surface of the gas barrier coating film 13 of the barrier film 10. Further, a sealant layer may be provided on both the surface of the base material layer 11 opposite to the surface on which the vapor deposition layer 12 is laminated.

  In the embodiment shown in FIG. 2, the laminated film 20 </ b> A includes the barrier film 10 and the sealant layer 21. However, the present invention is not limited to this, and the barrier film 10 and the sealant layer are not limited thereto. 21, as will be described later, between the barrier film 10 and the sealant layer 21, the surface of the sealant layer 21 opposite to the surface on which the barrier film 10 is laminated, or the barrier film 10. Depending on the form of the package, another layer may be provided on the surface opposite to the surface on which the sealant layer 21 is laminated.

[Sealant layer]
As shown in FIG. 2, the sealant layer 21 is provided on the surface of the gas barrier coating film 13 of the barrier film 10. The sealant layer 21 is a layer formed of a heat-sealable resin film that can be fused to each other by heat.

  The material for forming the sealant layer 21 is not particularly limited as long as it is a resin that can be fused to each other by heat. Specifically, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high Density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), ethylene-α-olefin copolymer polymerized using metallocene catalyst, ethylene / polypropylene random or block copolymer resin, polypropylene , Ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methacrylic acid Methyl copolymer (EMMA), ionomer resin, heat sealable ethylene Vinyl alcohol resin or copolymerized resin Methylpentene resin, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene, polypropylene or cyclic olefin copolymer, polyolefin resin such as acrylic acid, methacrylic resin Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. And the like. These may be used alone or as a mixture of two or more. The sealant layer 21 can be used as a resin film or sheet as described above, or a coating film thereof.

  When polyethylene is used as a material for forming the sealant layer 21, a raw material obtained by polymerizing ethylene derived from biomass in addition to ethylene obtained from fossil fuel may be used.

  Here, the ethylene derived from biomass is produced using biomass ethanol as a raw material. The method for producing biomass-derived ethylene is not particularly limited, and can be obtained by a conventionally known method. Biomass-derived ethylene can be produced using biomass ethanol as a raw material, but it is particularly preferable to use biomass-derived fermented ethanol obtained from a plant raw material. A plant raw material is not specifically limited, A conventionally well-known plant can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

  In the present embodiment, biomass-derived fermented ethanol refers to ethanol that has been purified after contacting a microorganism-producing product or a product derived from the crushed product thereof with a culture solution containing a carbon source obtained from plant raw materials. . For the purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and azeotropically or removing water by membrane separation or the like can be mentioned.

  In order to obtain biomass-derived ethylene, at this stage, advanced purification such as the total amount of impurities in ethanol being 1 ppm or less may be further performed.

  When ethylene is obtained by a dehydration reaction of ethanol, a catalyst is usually used, but this catalyst is not particularly limited, and a conventionally known catalyst can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated. For example, γ-alumina is preferable.

  Since the dehydration reaction of ethanol is an endothermic reaction, it is usually carried out under heating conditions. The heating temperature is not limited as long as the reaction proceeds at a commercially useful reaction rate, but the lower limit is preferably a temperature of 100 ° C or higher, more preferably 250 ° C or higher, and even more preferably 300 ° C or higher. The upper limit is not particularly limited, but is preferably 500 ° C. or lower, more preferably 400 ° C. or lower, from the viewpoint of energy balance and equipment.

  The reaction pressure is not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst is easily separated is suitable, but a liquid phase suspension bed, a fluidized bed, or the like may be used.

  In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in ethanol supplied as a raw material. Generally, when performing a dehydration reaction, it is preferable that there is no water in view of water removal efficiency. However, in the case of dehydration reaction of ethanol using a solid catalyst, it has been found that in the absence of water, the production of other olefins, particularly butene, tends to increase. If a small amount of water is not present, it is assumed that ethylene dimerization after dehydration cannot be suppressed. The lower limit of the allowable water content is 0.1% by mass or more, preferably 0.5% by mass or more. Although an upper limit is not specifically limited, From a viewpoint of a mass balance and a heat balance, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20% or less.

  By performing the dehydration reaction of ethanol in this way, a mixed part of ethylene, water and a small amount of unreacted ethanol can be obtained. However, since ethylene is a gas at room temperature or lower at 5 MPa or less, gas and liquid separation from these mixed parts Ethylene can be obtained by removing water and ethanol. This method can be performed by a known method.

  The ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time, etc. are not particularly limited except that the operating pressure at this time is normal pressure or higher.

  When the raw material is ethanol derived from biomass, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, as well as carbon dioxide gas that is a decomposition product thereof, enzyme decomposition products, It contains trace amounts of nitrogen-containing compounds such as amines and amino acids, which are impurities, and ammonia, which is a decomposition product thereof. Depending on the use of ethylene, these trace amounts of impurities may cause a problem and may be removed by purification. The purification method is not particularly limited, and can be performed by a conventionally known method. Suitable purification operations include, for example, an adsorption purification method. The adsorbent used is not particularly limited, and a conventionally known adsorbent can be used. For example, a high surface area material is preferable, and the type of adsorbent is selected according to the type and amount of impurities in ethylene obtained by dehydration of biomass-derived ethanol.

  In addition, you may use caustic water treatment together as a refinement | purification method of the impurity in ethylene. When caustic water treatment is performed, it is preferably performed before adsorption purification. In this case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

  By using polyethylene obtained by polymerizing ethylene derived from biomass thus obtained as a material constituting the sealant layer 21, a layer made of a carbon neutral material can be used. The combined use with the polyester obtained from the raw material can further reduce the amount of fossil fuel used and can reduce the environmental burden.

  Commercially available ethylene may be used as biomass-derived ethylene, for example, “C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min)” made by Braschem Co. A low density polyethylene resin can be used.

  In this embodiment, the sealant layer 21 is a single layer, but two or more sealant layers 21 may be provided. When two or more sealant layers 21 are included, each may have the same composition or a different composition.

  As thickness of the sealant layer 21, 20-200 micrometers is preferable and 30-130 micrometers is more preferable.

  Examples of the method of laminating the sealant layer 21 on the upper surface side (inner surface side) of the barrier film 10 include a dry lamination method and a melt extrusion lamination method. Moreover, when performing said lamination | stacking, pre-treatments, such as a corona treatment, an ozone treatment, a flame treatment, etc., can be given to a film as needed. Of these, the dry lamination method is more preferable because of its excellent adhesive strength.

[Other layers]
The laminated film 20 </ b> A may have at least one layer other than the barrier film 10 and the sealant layer 21. Examples of other layers include a support, a resin layer, and a printing layer. When two or more other layers are included, each may have the same composition or a different composition. These other layers can be laminated together via an adhesive layer by a dry lamination method or via an adhesive resin layer by a melt extrusion lamination method.

The adhesive layer can be formed by applying an adhesive used for laminating (laminating adhesive) on the surface of a layer to be laminated (for example, a resin layer) and drying it. Examples of laminating adhesives include one-part or two-part cured or non-cured vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, and rubber. Other types of adhesives such as a solvent type, an aqueous type, and an emulsion type can be used. As a coating method of the above laminating adhesive, for example, a laminated film is constituted by a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, and other methods. It can apply | coat to the application surface of a layer. The coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry) are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry) is more preferable.

  The adhesive resin layer is formed by a melt extrusion lamination method using a thermoplastic resin. The thermoplastic resin that can be used for the adhesive resin layer includes low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, and ethylene / α-olefin polymerized using metallocene catalyst. Polymer 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 -Graft polymerization of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, ester monomer on methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin, or Copolymerized resin, maleic anhydride to polyolefin resin Such as shift-modified resin can be used. These materials can be used alone or in combination of two or more.

  Also, one or both surfaces of the laminated film 20A have chemical functions, electrical functions, magnetic functions, mechanical functions, friction / abrasion / lubricating functions, optical functions, thermal functions, biocompatibility, etc. Secondary processing can be performed for the purpose of imparting surface functions and the like. Examples of secondary processing include, for example, embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical Vapor deposition, coating, etc.). Further, the laminated film 20A can be subjected to laminating processing (dry laminating or extrusion laminating), bag making processing, and other post-processing processing to produce a molded product such as a package.

  Thus, the laminated film 20A is a film provided with the barrier film 10, and since the barrier film 10 has excellent barrier properties, an excellent gas barrier can be obtained by using the laminated film according to the present invention as a packaging material. It is possible to realize a packaging body having properties.

<Packaging body>
The laminated film 20A is formed by providing, as a two-layer structure, a vapor deposition layer 12 formed using a PVD method and a gas barrier coating film 13 thereon on a base material layer 11 made of a biomass-derived PET film. Since the vapor deposition layer 12 having high barrier properties can be formed even if the film thickness of the vapor deposition layer 12 is thin, it can be suitably used as a package. Examples of the package include a packaged product (packaging bag), a lid material, a laminate tube, a liquid container, a paper cup, and various label materials. As packaging bags, for example, standing pouch type, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type And various forms of packaging bags such as a square bottom seal type and a gusset type. The thickness of the laminated film can be appropriately determined according to the application. For example, it is used in the form of a film having a thickness of 30 to 300 μm, preferably 35 to 180 μm. An example of the package to which the laminated film is applied will be described below. In addition, in this embodiment, although each layer other than the sealant layer 21 of the package illustrated below is made into one layer, it is not limited to this, You may have two or more layers. Moreover, although the package body illustrated below is provided with the printing layer, it is not limited to this, The printing layer does not need to be provided.

[Standing pouch]
A standing pouch to which the above-described laminated film of the present invention is applied will be described. FIG. 3 is a diagram schematically illustrating an example of a configuration of a standing pouch. As shown in FIG. 3, the standing pouch 30 includes two body parts (side sheet) 31 and a bottom part (bottom sheet) 32. In the standing pouch 30, the side sheet 31 and the bottom sheet 32 are configured as separate members. The standing pouch 30 is a package formed by bag making so that the sealant layer of the laminated film constituting the side sheet 31 becomes the innermost layer.

  The side sheet 31 can be formed using a laminated film. FIG. 4 is a partial cross-sectional view of the laminated film forming the body portion. As shown in FIG. 4, the laminated film 20B forming the side sheet 31 includes a sealant layer 21, a support 33, a printing layer 34, and a barrier film 10, and includes the sealant layer 21, the support 33, the printing layer 34, The barrier film 10 is laminated in this order from the inner surface side to the outer surface side. The barrier film 10 is configured by laminating the base material layer 11, the vapor deposition layer 12, and the gas barrier coating film 13 in this order from the outer surface side to the inner surface side of the side sheet 31. The standing pouch 30 is manufactured by heat-sealing and bonding the sealant layers 21 of the side sheets 31 to each other.

(Support)
The support 33 supports the laminated film of the present embodiment described above, such as a stretched polyester resin layer, a stretched polyamide resin layer, a stretched polyolefin resin layer, and a paper base material (paper layer). As long as it can improve the impact resistance and the like, it is not particularly limited, and it can be formed using a known material. Further, a material derived from bimass may be used as the support 33. Moreover, the support body 33 can use these layers individually or in combination of 2 or more layers.

  As the polyester-based resin layer that can be used as the support 33, a biomass-derived polyester can be used in addition to a conventionally known fossil fuel-derived polyester. The polyester-based resin layer may be a layer formed by mixing a resin material containing a conventional fossil fuel-derived raw material and a resin material containing a biomass-derived raw material.

  In addition, in order to improve adhesiveness, you may use what contains a sulfonic acid group containing dicarboxylic acid as a dicarboxylic acid component. Examples of the sulfonic acid group-containing dicarboxylic acid include a sulfonic acid metal salt-containing dicarboxylic acid. Examples of the dicarboxylic acid containing a sulfonic acid metal salt include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- [4-sulfophenoxy] isophthalic acid. And salts (alkali metal salts, alkaline earth metal salts, etc.). In particular, from the viewpoint of obtaining good adhesion and deformation resistance, it is preferable to use sodium sulfoterephthalic acid or 5-sodium sulfoisophthalic acid. In the sulfone group-containing polyester, the copolymerization ratio of the sulfonic acid group-containing dicarboxylic acid is preferably 0.5 to 10 mol% with respect to the total acid component. Further, the intrinsic viscosity is preferably 0.3 to 0.8 dl / g.

  Depending on the application of the standing pouch 30, various polyester resins can be used, and a mixture of two or more kinds may be used. For example, when polyester is used, a support having excellent thermal dimensional stability, fragrance retention and heat resistance can be obtained. Moreover, when using a sulfone group containing polyester, the coextruded film which has high interlayer adhesive strength is obtained.

  The polyester resin layer may contain various additives such as a lubricant as required.

  Moreover, as a polyamide-type resin layer which can be used as the support body 33, although an aliphatic polyamide may be mainly used, you may contain other polyamide components, for example, an aromatic polyamide. Examples of the aliphatic polyamide include hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis (amino Aliphatic and alicyclic diamines such as methyl) cyclohexane and bis (p-aminocyclohexylmethane), and dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and the like Aliphatic polyamides obtained by polycondensation reaction with derivatives, polyamide resins obtained by condensation of ε-aminocaproic acid, 11-aminoundecanoic acid, polyamide resins obtained from lactam compounds such as ε-caprolactam, ω-laurolactam, Or a mixture of these It can be used. Specifically, for example, an aliphatic polyamide resin such as nylon 6, nylon 6,6, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon MXD6 can be used. Among them, suitable aliphatic polyamides include nylon 6, nylon 6,6, nylon-6 / 6,6 and the like. Examples of the two or more aliphatic polyamides include combinations of nylon 6 and nylon 6/6, 6 in any ratio.

  When a polyester resin layer or a polyamide resin layer is formed as the support 33, in order to improve the adhesion of the support 33 to the sealant layer 21, between the support 33 and the sealant layer 21, You may provide the modified polyolefin resin layer which consists of modified polyolefin. The modified polyolefin is modified by a method such as replacing a part of the main component polyolefin with another substance (monomer) by copolymerization or cocondensation, or reacting an appropriate substance (monomer) locally. Polyolefin resin. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene- Vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, polyethylene resin Or an acid-modified polyolefin resin obtained by modifying a polyolefin resin such as a polypropylene resin with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid or other unsaturated carboxylic acid.

  A preferable modified polyolefin is a copolymer having a structure in which a polyolefin segment and a segment having a polarity other than olefin are bonded in a block shape and / or a graft shape and / or a random shape, such as a propylene-based polyolefin segment. A copolymer of ethylene and a segment containing lactic acid as a constituent component, a copolymer of an ethylene-based polyolefin segment and a segment containing an acrylic acid unit as a constituent component, a propylene-based polyolefin segment and a segment containing an acrylic acid unit as a constituent component A copolymer etc. are mentioned. Specifically, for example, ADMER SE800, SF740, SF731, and SF730 manufactured by Mitsui Chemicals, Inc. can be used as the maleic anhydride-modified polyolefin resin.

  In addition to the above, as a material derived from bigus constituting the support 33, a commercially available polylactic acid film may be used. For example, a polylactic acid film sold by Mitsui Chemicals, Inc. Can be used for

  Further, as the paper layer that can be used as the support 33, any paper can be used depending on the desired rigidity and the like, for example, high-quality paper, imitation paper, art paper, coated paper, pure white roll paper, special white paper In addition to bifurcated kraft paper and bleached kraft paper, label paper and cup base paper with improved water resistance can be used.

The thickness of the paper layer is in the range of 50 to 200 g / m ² , more preferably 75 to 120 g / m ² . If the thickness of the paper layer is less than 50 g / m ² , the support 33 is insufficiently rigid because it is too thin. Further, when the thickness of the paper layer exceeds 200 g / m ² , the rigidity of the support 33 becomes too high, and there is a concern about the problem of high cost and processability.

  By forming the support 33 using a resin material containing a biomass-derived raw material, the support 33 becomes carbon neutral. When the support 33 is made of a paper base material (paper layer), the laminated film is formed of a layer made of carbon neutral resin because the base material layer 11 and the support 33 are made of carbon neutral resin. A laminated film having two or more can be produced. Thereby, the usage-amount of the fossil fuel used for formation of the support body 33 can be reduced significantly, and an environmental load can be reduced.

  As a method for forming the support 33, a conventionally known method can be used, and it is not particularly limited. The support 33 may be formed by extruding and laminating these materials, or as a film formed in advance using a T-die method or an inflation method, using a dry laminating method or the like as a printed layer 34. May be laminated.

(Print layer)
The printing layer 34 can be provided as necessary. For example, as shown in FIG. 4, the printing layer 34 can be provided between the barrier film 10 and the support 33. The print layer 34 is a desired arbitrary print such as a character, a pattern, a figure, a symbol, a pattern, etc. for displaying decoration, contents, display of a best-before period, display of a manufacturer, a seller, etc. It is a layer that forms a pattern. The print layer 34 may be provided on the entire surface or may be provided on a part thereof.

  The printing layer 34 can be formed using conventionally known pigments and dyes, and contains one or more ordinary ink vehicles as a main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, One or more additives such as light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, etc. are optionally added, and colorants such as dyes and pigments are further added. An ink composition obtained by adding and sufficiently kneading with a solvent, a diluent or the like can be used.

  As the above-mentioned ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic acid resin, natural resin Resin, hydrocarbon resin, polyvinyl chloride resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin, One or more of melamine resin, aminoalkyd resin, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber, etc. can be used in combination.

  The formation method of the printing layer 34 is not specifically limited, For example, normal printing methods, such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc., can be used. Using such a method for forming the printing layer 34, the printing layer 34 can be formed by printing a desired printing pattern on the outer surface side of the support 33 with the ink composition.

The coating amount of the ink composition is preferably 1μm~8μm position in the dry state after coating, and more preferably 2g / m ² ~3g / m ² in the coating unit.

  It is preferable to form the print layer 34 after performing surface treatment on the print layer forming side of the support 33 in advance. Examples of such surface treatment include corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, and other pretreatments. is there. In addition, a primer coating agent, an undercoat agent, an anchor coating agent, or the like can be arbitrarily applied in advance and surface-treated.

  In this embodiment, the printing layer 34 is provided between the barrier film 10 and the support 33. However, when the support 33 is transparent, the printing layer 34 is the sealant layer 21 and the support. 33 may be provided.

  As the bottom sheet 32 of the standing pouch 30, a stretched nylon film having a vapor deposition layer, a laminated film having a sealant layer laminated, or the like can be used.

  The standing pouch 30 can be manufactured by a conventionally known manufacturing method. For example, the two side sheets 31 are overlapped with the side sheets 31 facing each other so that the sealant layer 21 is the innermost layer. The bottom sheet 32 is inserted between the two side sheets 31, and the side sheet 31 and the bottom sheet 32 are heat sealed.

  As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  Since the standing pouch 30 is excellent in barrier properties, it is suitable for packaging chemical products, pharmaceuticals, quasi-drugs, cosmetics, foods and the like containing an organic compound as an active ingredient, for example, as an outer bag of a patch or liquid It can be suitably used as a standing pouch for use in refill contents such as detergents, liquid softeners, and liquid soaps. Further, the standing pouch 30 is excellent in barrier properties, and thus is suitable for packaging bags that require high impact resistance, such as a standing pouch that needs to be filled with a large volume of liquid.

  Further, the laminated film 20B forming the side sheet 31 is not limited to the layer configuration as shown in FIG. 4 and may have the layer configuration shown in FIG. Moreover, according to the material which comprises the support body 33, you may change each layer suitably in arbitrary positions, for example, as shown in FIG. 5, the laminated film 20C which forms the side sheet 31 is the sealant layer 21, The barrier film 10, the support 33, and the printing layer 34 are provided, and the laminated film 20C is formed by laminating the sealant layer 21, the barrier film 10, the support 33, and the printing layer 34 in this order from the inner surface to the outer surface. A layer structure may be used. The barrier film 10 is configured by laminating the base layer 11, the vapor deposition layer 12, and the gas barrier coating film 13 in this order from the outer surface side to the inner surface side of the side sheet 31.

  Moreover, according to the form which heat-seals a laminated | multilayer film, it can be set as various packaging bags other than a standing pouch. FIG. 6 is a diagram schematically illustrating an example of a pillow bag, FIG. 7 is a diagram schematically illustrating an example of a three-way seal bag, and FIG. 8 is a diagram schematically illustrating an example of a four-way seal bag. is there. In addition, in FIGS. 6-8, the heat seal location is displayed by hatching. As shown in FIG. 6, the pillow bag 41 is formed so that the sealant layer 21 of the laminated films 20 </ b> A to 20 </ b> C as shown in FIGS. It is obtained by heat sealing and bonding. Further, as shown in FIG. 7, the three-sided seal bag 42 is formed so that the sealant layer 21 of the laminated films 20A to 20C as shown in FIGS. It is obtained by heat-sealing and bonding the three sides of ~ 20C. Further, as shown in FIG. 8, the four-side seal bag 43 is formed into a bag so that the sealant layer 21 of the laminated films 20A to 20C as shown in FIGS. Can be obtained by heat-sealing and adhering.

[Cover material]
A lid material can be formed using the laminated film of the present embodiment. The lid material is a case where the support 33 constituting the laminated film is constituted by a paper layer, and can be formed using laminated films 20A to 20C having a layer structure as shown in FIGS. 2, 4 and 5. it can.

  Since the lid material has excellent barrier properties, it is heated in cup-shaped packaging containers, especially instant foods that are poured with hot water such as cup ramen and cup fried noodles, foods heated in a microwave oven, and other instant foods. It can be suitably used as a lid for packaging containers for sealing contents such as beverages, beverages heated in a microwave oven, snack confectionery, confectionery, and jelly.

[Tube container]
In this embodiment, a tube container can be formed using the above laminated film. FIG. 9 is a partial cross-sectional view schematically showing an example of a tube container. As shown in FIG. 9, the tube container 50 includes a head 51 and a cylindrical body 52.

  The head 51 includes a hollow conical shoulder 53 and a spout 54 and is integrally formed.

  The cylindrical body 52 is connected to the shoulder 53 of the head 51. The cylindrical trunk | drum 52 can be formed using a laminated film. FIG. 10 is a partial cross-sectional view of a laminated film that forms the cylindrical body of the tube container. As shown in FIG. 10, the laminated film 20D forming the cylindrical body 52 includes the first sealant layer 21A, the barrier film 10, the printing layer 34, and the second sealant layer 21B, and the first sealant. The layer 21 </ b> A, the barrier film 10, the printing layer 34, and the second sealant layer 21 </ b> B are laminated in this order from the inner surface side to the outer surface side of the cylindrical body portion 52. The barrier film 10 is configured by laminating the base material layer 11, the vapor deposition layer 12, and the gas barrier coating film 13 in this order from the inner surface side to the outer surface side of the cylindrical body portion 52.

  The cylindrical body 52 is produced by superimposing the first sealant layer 21A and the second sealant layer 21B on both ends of the cylindrical body 52, and heat-sealing and welding the overlapped portions. . The cylindrical body 52 has a head 51 connected to the upper part of one opening thereof. In addition, the both ends of the cylindrical trunk | drum 52 are not limited to the method of superimposing the 1st sealant layer 21A and the 2nd sealant layer 21B, Even if it overlaps the 2nd sealant layer 21B. Good.

  As a heat sealing method, a conventionally known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or a flame seal can be used.

  An example of the manufacturing method of the tube container 50 is demonstrated. The head 51 is connected to one opening of the cylindrical body 52 by, for example, a normal method such as compression molding. Thereafter, the contents are filled from the other open end connected to the head portion 51 of the cylindrical body 52, and the open end is thermally welded to form the bottom seal portion 55. Thereby, the tube container 50 filled and packaged with the contents can be obtained. The cap 56 attached to the spout portion 54 is attached by various methods such as screwing or fitting, for example, corresponding to the shape of the spout portion 54.

  Since the tube container 50 has excellent barrier properties, the volume of contents such as toothpaste, cosmetics, glue, paste hot pepper, paste wasabi, cream, paint, cartilage, pharmaceuticals, and other conventionally known products can be reduced. Since it can suppress, it can be used conveniently as a tube container.

  Further, the laminated film 20D forming the cylindrical body 52 is not limited to the layer configuration as shown in FIG. 10, and the layer configuration of the laminated film 20D can be arbitrarily adjusted as appropriate. An example of another layer configuration of the laminated film forming the laminated film forming the cylindrical body 52 is shown in FIG. As shown in FIG. 11, the laminated film 20E forming the cylindrical body portion 52 is provided with a polyolefin resin layer 57 between the gas barrier coating film 13 and the printing layer 34, and the printing layer 34 and the second sealant layer. You may provide the support body 33 between 21B.

  The polyolefin-based resin layer 57 is a polyethylene-based, polypropylene-based, or cyclic polyolefin-based resin, or a copolymer resin, a modified resin, a mixture (including alloy), or a plurality of layers containing these resins as a main component. It is a laminated body. Examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), ethylene- Vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer Polymers (EMMA), ionomer resins, ethylene-propylene copolymers, cyclic polyolefins such as polymethylpentene, polybutene, and polynorbornene, and polyolefin resins such as polyethylene and polypropylene can be used. Moreover, in order to improve the adhesion between layers, the above-mentioned polyolefin resin is modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Resin etc. can be applied. These resins can be used alone or in combination.

  For polyolefin resins, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties Various plastic compounding agents and additives can be added for the purpose of improving and modifying electrical characteristics, strength, etc. The amount of addition can be from a very small amount to several tens of percent. Depending on the case, it can be added arbitrarily. In the above, as general additives, for example, coloring of lubricants, plasticizers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, dyes, pigments, etc. An agent or the like can be used, and a modifying resin can also be used.

  The thickness of the polyolefin-based resin layer 57 can be appropriately set within a range of usually 5 to 800 μm, preferably 10 to 500 μm. If the thickness is less than this range, the moisture barrier property is insufficient, and if it is more than this range, the quality becomes excessive and the moldability also deteriorates.

  In the case where the polyolefin resin layer 57 is laminated on the surface of the gas barrier coating film 13 by a melt extrusion lamination method using a polyolefin resin having a polar group such as the acid-modified polyolefin resin as described above, an anchor coat is used. The polyolefin resin layer 57 can be laminated without performing a surface treatment such as an agent.

[Liquid paper container]
In this embodiment, a liquid paper container can be formed using the above-described laminated film. FIG. 12 is a perspective view showing an example of a liquid paper container. As shown in FIG. 12, the liquid paper container 60 has a square cylindrical body 61 including a side surface, a square plate-shaped bottom portion 62, and an upper portion 63.

  The upper part 63 includes a pair of opposed inclined plates 63a and a pair of folding portions 64 that are located between the inclined plates 63a and are folded between the inclined plates 63a. The pair of inclined plates 63a is provided with a margin 65 at each upper end, and the pair of inclined plates 63a are bonded to each other by a margin 65 provided at each upper end. The spout 66 is attached to one inclined plate 63a of the pair of inclined plates 63a. In the present embodiment, as shown in FIG. 12, a spout 66 may be provided in the inclined plate 63a, and the spout 66 may be sealed with a cap 67, but the present invention is not limited to this. For example, the embodiment may not include the spout 66 and the cap 67 in the inclined plate 63a.

  Such a liquid paper container 60 is a gobeltop type liquid paper container, and stores therein drinking water such as liquor, shochu, wine, milk, juice and the like. The cap 67 is removed from the spout 66 and the contents such as drinking water are taken out from the liquid paper container 60.

  The liquid paper container 60 can be formed using a laminated film. FIG. 13 is a cross-sectional view showing an example of the configuration of a laminated film used in a liquid paper container. As shown in FIG. 13, the laminated film 20F forming the liquid paper container 60 includes a first sealant layer 21A, a barrier film 10, a polyolefin resin layer 57, a support 33, a second sealant layer 21B, and printing. The first sealant layer 21A, the barrier film 10, the polyolefin resin layer 57, the support 33, the second sealant layer 21B, and the print layer 34 from the inner surface side to the outer surface side of the liquid paper container 60. The layers are laminated in this order. The barrier film 10 is configured by laminating the base material layer 11, the vapor deposition layer 12, and the gas barrier coating film 13 in this order from the inner surface side to the outer surface side of the liquid paper container 60.

As the support 33, the paper base (paper layer) as described above can be used. As described above, the paper base material constituting the support 33 is, for example, cardboard, ivory paper, paper board such as manila ball, milk carton base paper, cup base paper, synthetic paper, clay coated paper, kraft paper, high quality paper, etc. Known papers can be used. The amount of paper support 33 may be suitably determined depending on the form of a liquid sheet container 60 is ^{usually, 100g / m 2 ~500g / m} 2.

  Further, before laminating the second sealant layer 21 </ b> B on the support 33, the surface of the support 33 may be subjected to corona discharge treatment, flame treatment, or the like. By performing these treatments, the adhesive strength between the layers can be improved. The corona discharge treatment can be performed by using a known corona discharge treatment device and passing the paper substrate through the generated corona atmosphere. The frame processing can be performed by using a known frame processing device and burning the surface of the paper substrate with fire.

  Next, an example of a method for manufacturing the liquid paper container 60 will be described. The liquid paper container 60 can be manufactured by a conventionally known method using the above-described materials. Specifically, the second sealant layer 21B is formed on one surface of the paper base material layer 61 by using an extrusion coating method with a material for forming the second sealant layer 21B. Next, a print layer 34 on which information is printed is printed and provided on the second sealant layer 21B. Next, the base material layer 11 on which the vapor deposition layer 12 and the gas barrier coating film 13 are formed is supplied to the other surface of the paper base material layer 71, and between the paper base material layer 71 and the barrier film 10, The resin material constituting the polyolefin resin layer 57 is melt-extruded to form the polyolefin resin layer 57. Next, an anchor coating agent is applied on the base material layer 11. Next, the sealant film constituting the first sealant layer 21A is supplied to form the first sealant layer 21A. The laminated film thus obtained is wound up.

  The resulting laminated film 20F can be boxed to produce liquid paper containers 60 having various shapes such as a gable top type and a brick type.

  In the present embodiment, after the print layer 34 is printed on the second sealant layer 21B, the polyolefin resin layer 57 is provided between the paper base material layer 71 and the barrier film 10. However, the method for manufacturing the liquid paper container 60 is not limited to this, and after the printing layer 34 is printed on the second sealant layer 21B, the paper base material layer 71, the barrier film 10 and Before the polyolefin-based resin layer 57 is provided between the two, the flow direction of the paper base material layer 71 and the flow direction of the paper base material layer 71 are inline or off-line with respect to the paper base material layer 71 provided with the second sealant layer 21B. Perforation may be made in the orthogonal direction to form a trunk cut line 72 and a connecting cut line 73 as shown in FIG.

  Since the liquid paper container 60 has excellent barrier properties, alcohol such as sake, shochu and wine, milk beverages such as milk, foods such as soft drinks such as orange juice and tea, chemicals such as car wax, shampoo and detergent. It can be suitably used as a packaging paper container for all liquids such as products.

[Paper cup]
A paper cup can be formed using the laminated film of this embodiment described above. FIG. 14 is a perspective view in which a part of the paper cup is cut out. As shown in FIG. 14, the paper cup 80 has a flange portion 81 at the top and is provided at a cylindrical barrel portion 82 that gradually increases in diameter toward the opening, and a lower end (one end) of the barrel portion 82. And a bottom portion 83. The body portion 82 is provided with a flange portion 81 whose upper end is rounded outward. Note that the paper cup 80 is sealed by attaching a lid material along the flange portion 81 of the body portion 82 after the contents are stored. The lid member preferably has a gas barrier property, and a conventionally known lid member having a gas barrier property can also be used, and a lid member formed using the above-described laminated film of the present invention is used. You can also

  The trunk | drum 82 can be formed using a laminated film. FIG. 15 is a partial cross-sectional view showing an example of a configuration of a laminated film used in the body portion of the paper cup. As shown in FIG. 15, the laminated film 20 </ b> G forming the body portion 82 includes the sealant layer 21, the barrier film 10, the polyolefin resin layer 57, the support 33, and the printing layer 34. The film 10, the polyolefin resin layer 57, the support 33, and the printing layer 34 are laminated in this order from the inner surface side to the outer surface side of the body portion 82. The barrier film 10 is configured by laminating the base material layer 11, the vapor deposition layer 12, and the gas barrier coating film 13 in this order from the inner surface side to the outer surface side of the body portion 82.

As the support 33, the paper base (paper layer) as described above can be used. The basis weight of the support 33 is preferably 200 to 300 g / m ^{2 in view} of cup molding.

  Specifically, the laminated film 20G forming the body 82 is a laminated film in which low density polyethylene as the sealant layer 21, barrier film 10, low density polyethylene as the polyolefin resin layer 57, and the support 33 are laminated in this order. A film can be used. Also, as with the body portion 82, the bottom 83 is also a laminated film in which low-density polyethylene as the sealant layer 21, the barrier film 10, the low-density polyethylene as the polyolefin-based resin layer 57, and the support 33 are laminated in this order. Can be used.

  In the present embodiment, the laminated film 20G is provided with the printing layer 34 on the outer surface side of the support 33, but is not limited to this, and the outer surface side of the printing layer 34 or the support 33 and the printing layer 34 is not limited thereto. Further, a sealant layer 21 may be provided between the two.

  FIG. 16 is an explanatory view showing an example of an outline of a paper cup manufacturing method. As shown in FIG. 16, the printed layer 34 of the body blank 82 ′ cut out in a fan shape from the laminated body of FIG. 15 and given a predetermined contour is positioned outside, and the printed layer 34 is positioned inside. These are rounded into a cylindrical shape and bonded together by heat sealing in a state where both end portions 82a 'are overlapped. As a result, a body pasting portion 85 is formed in the body portion 2.

  Further, a bottom blank 83 'is cut out in a circular shape from a cup base paper (not shown), and the outer peripheral edge of the bottom blank 83' is bent downward to form a bent portion 83a '. The bottom blank 83 'may be cut out from the laminated film 20G.

  Next, a bottom blank 83 'that has been molded is placed below the barrel blank 82' that has been processed into a cylindrical shape. Then, the lower end portion of the trunk blank 82 ′ is bent so that the bent portion 83 a ′ of the bottom blank 83 ′ is wrapped by the lower end of the trunk blank 82 ′. While maintaining this state, the portion where the bent portion 83a ′ of the bottom blank 83 ′ and the lower end portion of the body blank 82 ′ overlap is melted with hot air, and these are integrated by applying a predetermined pressure to the portion. To do. Then, the paper cup 80 is completed by forming the flange part 81 in the upper end part of the trunk | drum 82. FIG. The laminated film 20G forming the body 82 is laminated in the order of the sealant layer 21, the barrier film 10, the polyolefin resin layer 57, the support 33, and the printing layer 34 from the inner surface side to the outer surface side of the paper cup 80. The print layer 34 is configured to be located on the outermost side.

  Since the paper cup 80 has excellent barrier properties, it is a container for storing snacks, instant foods that are poured with hot water, foods heated in a microwave oven, other instant foods, heated beverages, beverages heated in a microwave oven, etc. Can be suitably used.

  In this embodiment, although the case where the trunk | drum 82 was formed using laminated | multilayer film 20G was demonstrated, it is not limited to this, Only the bottom part 83 or the trunk | drum 82 and the bottom part 83 uses laminated | multilayer film 20G. It may be formed.

  Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited by these examples.

<Example 1>
[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) were supplied as a slurry to the reaction vessel, and the esterification reaction was carried out at 240 ° C. for 5 hours by a conventional direct weight method. Thereafter, 0.013 parts by mass of trimethyl phosphate (manufactured by Aldrich) 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 280 ° C., and then the degree of vacuum was lowered to 200 Pa while maintaining the polymerization temperature of 280 ° C. to synthesize a polymer. The reaction time was 3 hours. The synthesized polymer was discharged into running water in the form of strands and pelletized by a pelletizer. The obtained pellets were dried at 160 ° C. for 5 hours and then solid-phase 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. When the obtained polymer was subjected to differential thermal analysis (apparatus: Shimadzu DSC-60, measurement condition: helium gas, heated at 6 ° C./min), the glass transition temperature was 69 ° C., which was derived from fossil fuel. It was equivalent to known PET obtained from the raw material. Moreover, when the radiation-made carbon measurement of obtained biomass-derived PET was performed, the content of biomass-derived carbon by radioactive carbon (C14) measurement was 16%.

[Preparation of by-mass PET film]
Master batch by melting and kneading 90 parts by mass of polyethylene terephthalate pellets obtained as described above and fossil fuel-derived polyethylene terephthalate containing 600 ppm of porous silica having an average particle size of 1.0 to 4.0 μm as a lubricant. Was made. Next, 60 parts by mass of the polyethylene terephthalate pellets obtained as described above, 30 parts by mass of recycled PET (re-pelleted loss part in the manufacturing process such as ear loss during film formation), and 10 parts by mass of the master batch The dried portion was supplied to an extruder, melted at 285 ° C., extruded into a sheet form from a T die, and cooled and solidified with a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched at a magnification of 3.5 times in the longitudinal direction at a speed of the low speed drive roll of 6.5 m / min and a speed of the high speed drive roll of 22 m / min. A biaxially stretched polyester film having a thickness of 12.13 μm was obtained by stretching in the transverse direction at a magnification of 3.5 times.

(Radio-made carbon measurement)
When the carbon production measurement of the biaxially stretched polyester film (biomass PET film) obtained as described above was performed, the content of biomass-derived carbon by radioactive carbon (C14) measurement was 14%.

[Preparation of barrier film]
First, a biomass PET film (thickness: 12 μm) obtained as described above was prepared, and one surface was subjected to corona treatment. The biomass PET film subjected to the corona treatment is mounted on a take-out roll of a take-up type vacuum deposition apparatus, and then this is fed out, and aluminum gas is used as a deposition source on the corona-treated surface of the biomass PET film, and oxygen gas is supplied. While supplying, a barrier film 10 having a layer structure as shown in FIG. 1 is formed by forming an aluminum oxide vapor deposition layer having a thickness of 80 mm under the following vapor deposition conditions by a PVD method using an electron beam (EB) heating method. Produced.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ⁻⁴ mbar
Electron beam power: 25kW

  Subsequently, immediately after forming the aluminum oxide vapor deposition layer, the surface of the vapor deposition layer was subjected to plasma treatment with a mixed gas of oxygen gas and argon gas using a glow discharge plasma generator.

  Next, the barrier treatment liquid prepared as described below was coated on the plasma-treated surface of the aluminum oxide vapor deposition layer formed by the PVD method, and then heat-treated to obtain a thickness of 0.3 μm (in the dry operation state). A barrier film was produced by forming a gas barrier coating film.

  The barrier coating liquid described above was prepared according to the following composition table, mixed with a composition a consisting of polyvinyl alcohol, isopropyl alcohol, and ion-exchanged water, composition b, ethyl silicate, silane coupling agent, isopropyl alcohol. Then, a hydrolyzed solution composed of hydrochloric acid and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

<Comparative Example 1>
A biomass PET film (thickness 12 μm) obtained as described above was prepared, and one side was subjected to corona treatment. The biomass PET film subjected to the corona treatment is mounted on the feeding roll of the plasma chemical vapor deposition apparatus, and then this is fed out. The silicon oxide having a film thickness of 120 mm is deposited on the corona treatment surface of the biomass PET film according to the following deposition conditions. The deposited layer was formed.
(Deposition conditions)
Raw material: Hexamethyldisiloxane Introduced gas amount: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 1.5: 1.0 (unit: slm)
Degree of vacuum in the vacuum chamber: 2 × 10 ⁻³ mbar
Cooling / electrode drum power supply: 6kW

  Subsequently, immediately after the silicon oxide vapor deposition layer was formed, the surface of the vapor deposition layer was subjected to plasma treatment with a mixed gas of oxygen gas and argon gas using a glow discharge plasma generator.

  Next, a gas barrier coating film having a thickness of 0.3 μm (in a dry operation state) is formed on the plasma-treated surface of the silicon oxide vapor deposition film formed by the CVD method in the same manner as in Example 1 to produce a barrier film. did.

<Comparative example 2>
The same as Example 1 except that instead of the biomass PET film (thickness 12 μm) of Example 1, a general petrochemically derived PET film (“E-5100”, manufactured by Toyobo Co., Ltd., thickness 12 μm) was used. Thus, a barrier film was produced.

<Comparative Example 3>
The same as Comparative Example 1 except that instead of the biomass PET film of Comparative Example 1 (thickness 12 μm), a general petrochemically derived PET film (“E-5100”, manufactured by Toyobo Co., Ltd., thickness 12 μm) was used. Thus, a barrier film was produced.

  Table 2 below shows the types of the PET films of Example 1 and Comparative Examples 1 to 3 and the method of forming the vapor deposition layer.

<Evaluation>
As barrier properties of the laminated films obtained in Example 1 and Comparative Examples 1 to 3, oxygen permeability and water vapor permeability were measured.

(Measurement of oxygen permeability)
Each laminated film obtained in Example 1 and Comparative Examples 1 to 3 was subjected to an oxygen permeability measurement device (Oxtran (OX-TRAN), manufactured by MOCON) in an environment of a temperature of 23 ° C. and a humidity of 60 RH%. Was used to measure oxygen permeability. The measurement results are shown in Table 2 below. In addition, the case where oxygen permeability was 1.0 or less was evaluated as favorable. In Table 2, “−” indicates a case where measurement has not been performed.

(Measurement of water vapor permeability)
Each laminated film obtained in Example 1 and Comparative Examples 1 to 3 was subjected to a water vapor permeability measuring machine (Permatran, manufactured by MOCON) in an environment of a temperature of 40 ° C. and a humidity of 90 RH%. Used to measure the water vapor permeability. The measurement results are shown in Table 2 below. In addition, the case where water vapor permeability was 2.0 or less was evaluated as favorable.

  As is clear from Table 2, the barrier film in which the vapor deposition layer is formed on the biomass PET film by using the PVD method is the barrier film in which the vapor deposition layer is formed on the biomass PET film by using the CVD method. It was confirmed that the base material layer composed of the derived PET film has a higher barrier property than the barrier film in which the vapor deposition layer is formed using PVD or CVD.

<Example 2>
[Production of standing pouch]
A printed layer was formed on the surface of the gas barrier coating film of the barrier film produced in Example 1. Next, the printing surface of the barrier film and the biaxially stretched nylon film (support) were bonded using a dry laminating method. Furthermore, a biaxially stretched nylon film and a linear low density polyethylene film (sealant layer) were bonded using a dry laminating method to obtain a laminated film 1. The laminated film 1 has a base material layer, a vapor deposition layer, a gas barrier coating film, a printing layer, an adhesive layer, a biaxially stretched nylon film, an adhesive layer, and a linear low density polyethylene film sequentially laminated from the outer surface. It is a thing.

  In addition, a laminated film 2 in which a biaxially stretched nylon film, a silicon oxide vapor-deposited layer, a gas barrier coating film, an adhesive layer, and a linear low-density polyethylene film were laminated in order from the outer surface was prepared. Note that the vapor deposition layer of silicon oxide is formed using the CVD method, and the vapor deposition layer formed using the CVD method is a vapor deposition layer containing an organic substance, that is, a carbon component. A standing pouch shown in FIG. 3 was produced using the laminated film 1 as a side sheet and the laminated film 2 as a bottom sheet.

<Example 3>
[Production of pillow bag]
A printed layer was formed on the surface of the gas barrier coating film of the barrier film produced in Example 1. Next, a laminated film 3 was obtained by laminating a polypropylene film (sealant layer) on the printed layer surface of the barrier film using a dry laminating method. The laminated film 3 is obtained by sequentially laminating a base material layer, a vapor deposition layer, a gas barrier coating film, a printing layer, an adhesive layer, and a polypropylene film from the outer surface. Using the laminated film 3, a pillow bag shown in FIG.

DESCRIPTION OF SYMBOLS 10 Barrier film 11 Base material layer 12 Deposition layer 13 Gas barrier coating film 20A-20G Laminated film 21 Sealant layer 21A First sealant layer 21B Second sealant layer 30 Standing pouch 31 Body (side sheet)
32 Bottom (bottom sheet)
33 Support 34 Print Layer 41 Pillow Bag 42 3-way Seal Bag 43 4-way Seal Bag 50 Tube Container 51 Head 52 Cylindrical Body 53 Shoulder 54 Outlet Portion 55 Bottom Seal Portion 56 Cap 57 Polyolefin Resin Layer 60 Liquid Paper container 61 Body 62 Bottom 63 Upper 63a Inclined plate 64 Folding part 65 Margin 66 Spout 67 Cap 71 Paper base material layer 72 Body cut line 73 Connection cut line 80 Paper cup 81 Flange part 82 Body 82 'Body blank 82a 'Both ends 83 Bottom 83' Bottom blank 83a 'Bent part 85

Claims (12)

A barrier film comprising: a base material layer; a vapor deposition layer provided on at least one of the base material layers; and a gas barrier coating film provided on a surface opposite to the base material layer side of the vapor deposition layer. Because
The base material layer comprises a resin composition comprising, as a main component, a polyester composed of a diol unit and a dicarboxylic acid unit,
The diol unit comprises biomass-derived ethylene glycol;
The dicarboxylic acid unit comprises a dicarboxylic acid derived from a fossil fuel;
The said vapor deposition layer consists of aluminum oxide by a physical vapor deposition method, The thickness of the said vapor deposition layer is 30-100cm, The barrier film characterized by the above-mentioned.   The said resin composition contains 50-95 mass% of polyesters whose said diol unit is biomass-derived ethylene glycol and whose dicarboxylic acid unit is dicarboxylic acid derived from petrochemical fuel with respect to the whole resin composition. 2. The barrier film according to 1.   The barrier film according to claim 1 or 2, wherein the dicarboxylic acid contains terephthalic acid. The gas barrier coating film has a general formula: R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), at least one alkoxide represented by: The barrier film according to any one of claims 1 to 4, which is obtained by gelling a sol composition comprising an ethylene / vinyl alcohol copolymer. The barrier film according to any one of claims 1 to 4,
A sealant layer provided on at least one surface side of the barrier film;
A laminated film comprising: Further comprising a support,
The laminated film according to claim 5, wherein the support is provided between the barrier film and the sealant layer or on the substrate layer side of the barrier film. In the pouch or lid material comprising the laminated film according to claim 5 or 6,
A pouch or lid material in which a sealant layer is disposed on the innermost layer of the laminated film. In a standing pouch with a torso and a bottom,
The trunk portion is made of the laminated film according to claim 5 or 6,
A standing pouch in which a sealant layer is disposed on the innermost layer of the laminated film. In a laminated tube comprising a head composed of a shoulder and a spout, and a cylindrical body connected to the shoulder of the head,
The cylindrical body is made of a laminated film,
The laminated film comprises, in order from the inner layer side, a first sealant layer, a barrier film, and a second sealant layer,
The laminated tube whose said barrier film is a barrier film as described in any one of Claims 1-4.   The laminated tube according to claim 11, wherein the laminated film further comprises a support. In a liquid container made of a laminated film,
The laminated film comprises, in order from the inner layer side, a first sealant layer, a barrier film, a polyolefin-based resin layer, a support made of a paper substrate, and a second sealant layer,
The container for liquids whose said barrier film is a barrier film as described in any one of Claims 1-4. In a paper cup provided with a trunk and a bottom provided at one end of the trunk,
The trunk and / or the bottom is made of a laminated film,
The laminated film comprises, in order from the inner layer side, a support comprising a sealant layer, a barrier film, a polyolefin resin layer, and a paper substrate,
The paper cup whose said barrier film is the barrier film as described in any one of Claims 1-4.