Laminated film, laminate, and package

Abstract

To provide a laminated film which can reduce an environmental load and is not inferior to a laminated film using a conventional base material layer manufactured from a fossil fuel-derived raw material in terms of physical properties such as gas barrier properties and mechanical characteristics, and to provide a laminate and a package including the laminated film.SOLUTION: The laminated film of the present disclosure includes at least a base material layer and a vapor deposition film, in which the base material layer contains a polyester composed of a diol unit and a dicarboxylic acid unit, the diol unit contains ethylene glycol obtained from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide as a raw material, and the vapor deposition film is a vapor deposition film of a metal or a metal oxide.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to laminate films, laminates, and packages. [Background technology]

[0002] Polyesters are widely used in various industrial applications due to their excellent mechanical properties, chemical stability, heat resistance, transparency, etc., and their low cost. Polyesters are obtained by polycondensation of diol units and dicarboxylic acid units. For example, polyethylene terephthalate is produced by esterifying ethylene glycol and terephthalic acid as raw materials, followed by polycondensation. These raw materials are produced from petroleum, a fossil fuel. For example, ethylene glycol is industrially produced from ethylene, and terephthalic acid is industrially produced from xylene.

[0003] In recent years, with growing calls for the creation of a circular economy, there has been a desire to move away from fossil fuels in the materials sector, just as there is in energy. Therefore, the production of polyester from raw materials other than fossil fuels, such as biomass, is being considered. Biomass is a non-exhaustible resource, an industrial resource derived from the constituent materials of living organisms. The carbon contained in biomass comes from carbon dioxide absorbed from the atmosphere through photosynthesis during the growth process of living organisms. Therefore, even if carbon dioxide is emitted when biomass is burned, it is thought that the amount of carbon dioxide in the atmosphere does not increase overall. For this reason, biomass is attracting attention as a carbon-neutral renewable energy source. Recently, the practical application of biomass plastics made from these biomass raw materials has progressed rapidly, and attempts have been made to produce polyester, a general-purpose polymer material, from these biomass raw materials (for example, Patent Documents 1 and 2). By using polyester produced from biomass-derived raw materials (biomass polyester) instead of polyester produced using fossil fuel-derived raw materials, it becomes possible to reduce the amount of fossil fuel used and the environmental burden.

[0004] Bioethanol, which is used to produce biomass polyester, can be produced by sugar fermentation from molasses, a non-edible raw material. However, it is known from experience that the yield of crops such as sugarcane is greatly affected by weather factors. Therefore, there are concerns that climate change will make it difficult to stably procure sugarcane, the raw material for bioethanol. Ethanol, which is also used as a raw material for plastics, has been produced from resources that are neither fossil fuels nor biomass. For example, ethanol has been produced by microbial fermentation using carbon monoxide present in exhaust gases emitted from steel mills and factories as a raw material (see, for example, Patent Document 3). Ethylene glycol has also been produced by electrolyzing carbon dioxide present in exhaust gases emitted from steel mills and factories (see, for example, Patent Document 4). Furthermore, the production of polyesters from these compounds has also been considered. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2011-527348 [Patent Document 2] Special Publication No. 2012-519748 [Patent Document 3] Special Publication No. 2011-512869 [Patent Document 4] Japanese Patent Application Publication No. 2018-123390 Summary of the Invention [Problem to be solved by the invention]

[0006] Polyester films, which are components of laminate films, have been produced from polyesters produced from fossil fuel-derived raw materials or from polyesters produced from biomass raw materials. However, it was unclear whether laminate films produced from polyesters produced using ethanol produced from carbon monoxide gas or ethylene glycol produced from carbon dioxide gas would exhibit gas barrier properties and mechanical properties similar to those of conventional laminate films.

[0007] Therefore, an object of the present disclosure is to provide a laminated film that can reduce the environmental impact and is comparable in physical properties such as gas barrier properties and mechanical properties to laminated films that use conventional substrate layers produced from raw materials derived from fossil fuels. Another object of the present disclosure is to provide a laminate including the laminate film, and a package including the laminate. [Means for solving the problem]

[0008] The inventors have discovered that a laminated film having a substrate layer manufactured using ethylene glycol, which is made from carbon monoxide gas or carbon dioxide gas as a raw material, is comparable in physical properties such as gas barrier properties and mechanical properties to laminated films having conventional substrate layers manufactured from raw materials derived from fossil fuels. The present disclosure was completed based on this finding and through further investigation.

[0009] The present disclosure is solved by the following embodiments. <1> A laminated film comprising at least a substrate layer and a vapor-deposited film, the substrate layer contains a polyester composed of a diol unit and a dicarboxylic acid unit, the diol unit contains ethylene glycol produced from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide; The laminated film, wherein the vapor-deposited film is a vapor-deposited film of a metal or a metal oxide. <2> The dicarboxylic acid unit includes at least one selected from the group consisting of terephthalic acid derived from a fossil fuel, terephthalic acid derived from biomass, and terephthalic acid derived from carbon dioxide gas. <1> The laminated film according to claim 1. <3> The content of carbon dioxide molecules in the substrate layer is 1.1 × 10 18 pcs / g or more 3.0×10 18 pieces / g or less, <1> or <2> The laminated film according to claim 1. <4> The content of water molecules in the base layer is 8.6×10 19 pcs / g or more 2.5×10 20 pieces / g or less, <1> ~ <3> 10. The laminated film according to claim 9, wherein the thickness of the laminated film is 100 nm or more. <5> a surface coating layer is further provided between the substrate layer and the vapor-deposited film, the surface coating layer contains a resin material having a polar group; <1> ~ <4> 10. The laminated film according to claim 9, wherein the thickness of the laminated film is 100 nm or more. <6> the substrate layer, the vapor-deposited film, and the gas barrier coating film in this order; the gas barrier coating film contains an alkoxide and at least one water-soluble polymer selected from the group consisting of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer; <1> ~ <5> 10. The laminated film according to claim 9, wherein the thickness of the laminated film is 100 nm or more. <7> <1> ~ <6> A laminate comprising the laminate film according to any one of the above and a sealant layer. <8> Further comprising a support; the support is a stretched polyester resin layer, a stretched polyamide resin layer, or a stretched polypropylene resin layer; <7> The laminate according to claim 1. <9> The support, the base layer, the vapor-deposited film, and the sealant layer are provided in this order. <8> The laminate according to claim 1. <10> <7> ~ <9> A package comprising the laminate described in any one of the above. [Effects of the Invention]

[0010] The present disclosure can provide a laminate film that can reduce the environmental impact and is comparable in physical properties, such as gas barrier properties and mechanical properties, to laminate films that use conventional substrate layers produced from raw materials derived from fossil fuels. The present disclosure also provides a laminate including the laminate film, and a package including the laminate. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a cross-sectional view simply illustrating an example of the configuration of a laminated film according to the present disclosure. [Figure 2] 1 is a cross-sectional view simply illustrating an example of the configuration of a laminated film according to the present disclosure. [Figure 3] 1 is a cross-sectional view simply illustrating an example of the configuration of a laminated film according to the present disclosure. [Figure 4] FIG. 1 is a cross-sectional view simply illustrating an example of the configuration of a laminate according to the present disclosure. [Figure 5] FIG. 1 is a cross-sectional view simply illustrating an example of the configuration of a laminate according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Laminated film] A laminate film according to the present disclosure includes a substrate layer and a vapor-deposited film on at least one surface of the substrate layer. For example, as shown in FIG. 1, a laminate film 15 according to the present disclosure includes a substrate layer 10 and a vapor-deposited film 11 on at least one surface of the substrate layer 10. In the embodiment shown in Figure 1, the laminated film 15 is configured to have a vapor-deposited film 11 above the surface of the base material layer 10, but the laminated film 15 may also be configured to have a vapor-deposited film 11 below the surface of the base material layer 10, or may be configured to have a vapor-deposited film 11 on both the above and below surfaces of the base material layer 10.

[0013] One embodiment of the laminate film according to the present disclosure further includes a surface coating layer between the substrate layer and the vapor-deposited film. For example, as shown in Figure 2, a laminate film 15 includes a substrate layer 10, a surface coating layer 13 on at least one surface of the substrate layer 10, and a vapor-deposited film 11 on the surface coating layer 13.

[0014] One embodiment of the laminate film according to the present disclosure further includes a gas barrier coating film on the vapor-deposited film. For example, as shown in Fig. 3, a laminate film 15 includes a base layer 10, a vapor-deposited film 11 on at least one surface of the base layer 10, and a gas barrier coating film 12 on the vapor-deposited film 11.

[0015] The components of the laminated film according to the present disclosure will be described below in order, starting with the polyester that is the constituent material of the base layer.

[0016] [polyester] The substrate layer of the laminated film according to the present disclosure contains a polyester composed of diol units and dicarboxylic acid units, and the diol units contain ethylene glycol derived from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide. The term "polyester" refers to a polymer formed by ester bonds. Such polyesters are typically obtained by polycondensation of diol units and dicarboxylic acid units. That is, the polyester contained in the base layer is obtained by a polycondensation reaction using ethylene glycol as a diol unit and dicarboxylic acid as a dicarboxylic acid unit, which are derived from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide as raw materials.

[0017] [Ethylene glycol made from carbon monoxide gas] Ethylene glycol using carbon monoxide gas as a raw material can be produced from ethanol using carbon monoxide gas as a raw material. For example, ethylene glycol using carbon monoxide gas as a raw material can be obtained by, for example, producing ethanol using carbon monoxide gas as a raw material and then converting it into ethylene oxide using a conventionally known method.

[0018] <Microbial fermentation> Ethanol, which is made from carbon monoxide gas, can be obtained by microbial fermentation.

[0019] Microbial fermentation is carried out, for example, in a fermenter filled with a culture solution containing water and microorganisms. A feed gas containing carbon monoxide gas is supplied into the fermenter, and the carbon monoxide gas is converted into ethanol inside the fermenter. The feed gas may contain carbon dioxide, nitrogen, oxygen, etc. in addition to carbon monoxide.

[0020] The fermenter is preferably a continuous fermentation apparatus, and may be any of agitation type, airlift type, bubble column type, loop type, open bond type, and photobio type. The raw material gas and the culture solution may be continuously supplied to the fermenter, but it is not necessary to supply the raw material gas and the culture solution simultaneously, and the raw material gas may be supplied to a fermenter to which the culture solution has been previously supplied. The raw material gas is generally blown into the fermenter through a sparger or the like.

[0021] The culture medium is not particularly limited as long as it has an appropriate composition for culturing microorganisms, but is a liquid containing water as the main component and nutrients (e.g., vitamins, phosphoric acid, etc.) dissolved or dispersed in this water.

[0022] The temperature of the fermenter is preferably controlled to 40° C. or less. By controlling the temperature to 40° C. or less, the microorganisms in the fermenter do not die, and ethanol is efficiently produced by the raw material gas coming into contact with the microorganisms. The temperature of the fermenter is more preferably 38°C or lower, and in order to enhance the activity of the microorganisms, is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher.

[0023] The microorganism (species) that ferments the feed gas is not particularly limited as long as it can produce ethanol by microbial fermentation of the feed gas using carbon monoxide as the main feedstock. For example, the microorganism (species) is preferably one that produces ethanol from the feed gas through the fermentation action of gas-utilizing bacteria. Among gas-utilizing bacteria, the genus Clostridium is preferred, and Clostridium autoethanogenum is more preferred, from the viewpoints of gas utilization and culture stability. Examples are provided in more detail below.

[0024] Gas-utilizing bacteria include both eubacteria and archaebacteria. Examples of true bacteria include bacteria of the genus Clostridium, Moorella, Acetobacterium, Carboxydocella, Rhodopseudomonas, Eubacterium, Butyribacterium, Oligotropha, Bradyrhizobium, and the aerobic hydrogen-oxidizing bacteria Larsotonia.

[0025] On the other hand, examples of archaea include bacteria of the genus Methanobacterium, bacteria of the genus Methanobrevibacter, bacteria of the genus Methanocalculus, bacteria of the genus Methanococcus, bacteria of the genus Methanosarcina, bacteria of the genus Methanosphaera, bacteria of the genus Methanothermobacter, Metha Examples include bacteria of the genus Nothrix, bacteria of the genus Methanoculleus, bacteria of the genus Methanofollis, bacteria of the genus Methanogenium, bacteria of the genus Methanospirillium, bacteria of the genus Methanosaeta, bacteria of the genus Thermococcus, bacteria of the genus Thermofilum, bacteria of the genus Arcaheoglobus, and the like. Among these, as archaea, bacteria of the genus Methanosarcina, bacteria of the genus Methanococcus, bacteria of the genus Methanothermobacter, bacteria of the genus Methanothrix, bacteria of the genus Thermococcus, bacteria of the genus Thermofilum, and bacteria of the genus Archaeoglobus are preferred.

[0026] Furthermore, due to their excellent ability to assimilate carbon monoxide and carbon dioxide, archaea are preferably bacteria of the genus Methanosarcina, Methanothermobactor, or Methanococcus, with Methanosarcina or Methanococcus being particularly preferred. Specific examples of Methanosarcina bacteria include Methanosarcina barkeri, Methanosarcina mazei, and Methanosarcina acetivorans.

[0027] Among the gas-utilizing bacteria listed above, it is preferable to select and use bacteria with high ethanol production capacity, such as Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans, Moorella thermoacetica, and Acetobacterium woodii.

[0028] Ethanol produced by microbial fermentation is obtained, for example, as an ethanol-containing liquid mixed with a culture solution. Ethanol can be separated from this ethanol-containing liquid using a separation device. Examples of separation devices include solid-liquid separators, distillation devices, and separation membranes, but it is preferable to use a solid-liquid separator and a distillation device in combination. Below, we will specifically explain the separation process performed using a solid-liquid separator and a distillation device in combination.

[0029] The ethanol-containing liquid obtained by microbial fermentation is separated in a solid-liquid separation device into a solid component mainly composed of microorganisms and a liquid component containing ethanol. The ethanol-containing liquid obtained by microbial fermentation contains, in addition to the target ethanol, microorganisms contained in the fermenter and their dead bodies as solid components, so solid-liquid separation is performed to remove these. Examples of solid-liquid separation devices include filters, centrifuges, and devices that use solution precipitation. The solid-liquid separation device may also be a device (e.g., a heat drying device) that evaporates the liquid component containing ethanol from the ethanol-containing liquid and separates it from the solid component. In this case, the liquid component containing the target ethanol may be entirely evaporated, or the liquid component may be partially evaporated so that the target ethanol is preferentially evaporated.

[0030] The liquid component separated by solid-liquid separation is further distilled in a distillation apparatus to separate the target product, ethanol. Separation by distillation allows for the production of large amounts of highly purified ethanol through simple operations. When distillation is performed, a known distillation apparatus such as a distillation column may be used. Furthermore, the distillation is performed, for example, so that the distillate contains the target product, ethanol, at a high purity, while the bottoms (i.e., the distillation residue) contains water as the main component (for example, 70% by mass or more, preferably 90% by mass or more). By performing the distillation in this manner, the target product, ethanol, and water can be largely separated.

[0031] The temperature inside the distillation apparatus during ethanol distillation is not particularly limited, but is preferably 100° C. or lower, more preferably 95° C. or lower, and preferably 70° C. or higher. By setting the temperature inside the distillation apparatus within the above range, ethanol can be reliably separated from other components such as water. The pressure inside the distillation apparatus during ethanol distillation may be normal pressure, but is preferably less than atmospheric pressure, more preferably 60 kPa or more and 150 kPa or less (gauge pressure). By setting the pressure inside the distillation apparatus within this range, the ethanol separation efficiency can be improved, and the ethanol yield can be increased.

[0032] [Ethylene glycol made from carbon dioxide gas] Ethylene glycol can be produced from carbon dioxide gas by electrolysis. A method for producing ethylene glycol from carbon dioxide gas by electrolysis will be described below.

[0033] <Electrolysis> Electrolysis can be carried out, for example, using an electrolysis cell comprising an anode, a cathode, and an ion exchange membrane positioned to separate the anode and the cathode.

[0034] The anode causes an oxidation reaction of water (H2O) to produce oxygen (O2) and hydrogen ions (H +) or hydroxide ions (OH - ) to generate oxygen (O2) and water (H2O). On the other hand, the cathode reacts with the hydrogen ions (H + ) and electrons (e - ) to reduce carbon dioxide (CO2) and to produce carbon compounds such as ethylene glycol (C2H6O2). In this way, by reducing carbon dioxide on the cathode side of the electrolytic cell, ethylene glycol can be produced using carbon dioxide as a raw material.

[0035] The anode is preferably mainly composed of a catalytic material capable of reducing the overvoltage of the reaction that oxidizes water or hydroxide ions. Examples of such catalytic materials include metals such as platinum (Pt), palladium (Pd), and nickel (Ni), alloys and intermetallic compounds containing these metals, binary metal oxides such as manganese oxide (Mn-O), iridium oxide (Ir-O), nickel oxide (Ni-O), cobalt oxide (Co-O), iron oxide (Fe-O), tin oxide (Sn-O), indium oxide (In-O), ruthenium oxide (Ru-O), lithium oxide (Li-O), and lanthanum oxide (La-O), ternary metal oxides such as Ni-Co-O, Ni-Fe-O, La-Co-O, Ni-La-O, and Sr-Fe-O, quaternary metal oxides such as Pb-Ru-Ir-O and La-Sr-Co-O, and metal complexes such as Ru complexes and Fe complexes.

[0036] The cathode is preferably made of a catalytic material capable of reducing the overvoltage of the carbon dioxide reduction reaction. Examples of such catalytic materials include metals such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), titanium (Ti), cadmium (Cd), zinc (Zn), indium (In), gallium (Ga), lead (Pb), and tin (Sn), metal materials such as alloys and intermetallic compounds containing at least one of these metals, carbon materials such as carbon (C), graphene, CNT (carbon nanotubes), fullerene, and Ketjenblack, and metal complexes such as Ru complexes and Re complexes.

[0037] [Diol unit] The diol unit used in the present disclosure does not have to be limited to ethylene glycol made from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide. That is, ethylene glycol made from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide may be used in combination with another diol. Even when used in combination with another diol, the present disclosure aims to reduce the environmental impact as long as ethylene glycol made from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide is used.

[0038] Other diols include diols derived from fossil fuels and diols derived from biomass.

[0039] As the fossil fuel-derived diol, a compound having two or more, preferably two to eight hydroxyl groups per molecule can be used. Specifically, the fossil fuel-derived diol is not particularly limited and conventionally known compounds can be used, such as polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, and 3-methyl-1,5-pentanediol. These may be used alone or in combination of two or more.

[0040] Examples of biomass-derived diols that can be used include aliphatic diols obtained from plant materials such as corn, sugarcane, cassava, and sago palm. Examples of biomass-derived aliphatic diols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), and hexamethylene glycol, all of which can be obtained from plant materials by the following methods. These may be used alone or in combination.

[0041] Biomass-derived polypropylene glycol is produced by a fermentation method in which glucose is obtained by decomposing plant raw materials, via 3-hydroxypropylaldehyde (HPA) from glycerol. Compared to polypropylene glycol produced by the EO production method, polypropylene glycol produced by a biomethod such as the fermentation method is preferable in terms of safety, as useful by-products such as lactic acid can be obtained, and production costs can be kept low. Biomass-derived butylene glycol can be produced by producing glycol from plant raw materials, fermenting the glycol, obtaining succinic acid, and then hydrogenating the resulting succinic acid. Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

[0042] [Dicarboxylic acid unit] The dicarboxylic acid unit of the polyester is, for example, a dicarboxylic acid derived from a fossil fuel, and examples of the dicarboxylic acid derived from a fossil fuel include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof, without limitation. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, butyl esters, etc. Among these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as a derivative of aromatic dicarboxylic acid. Specific examples of aliphatic dicarboxylic acids include linear or alicyclic dicarboxylic acids typically having 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. Derivatives of aliphatic dicarboxylic acids include lower alkyl esters of the above aliphatic dicarboxylic acids, such as methyl esters, ethyl esters, propyl esters, and butyl esters, as well as cyclic acid anhydrides of the above aliphatic dicarboxylic acids, such as succinic anhydride. Among these, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferred, with those containing succinic acid as the main component being particularly preferred. More preferred derivatives of aliphatic dicarboxylic acids include methyl esters of adipic acid and succinic acid, or a mixture thereof.

[0043] Furthermore, the dicarboxylic acid units of the polyester may be derived from biomass. Examples of biomass-derived dicarboxylic acids that can be used include aliphatic dicarboxylic acids obtained from plant materials such as renewable plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, as well as regenerated oils obtained by recycling waste cooking oils containing these oils as a main component. Examples of biomass-derived aliphatic dicarboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced by alkaline pyrolysis of ricinoleic acid obtained from castor oil, with heptyl alcohol as a by-product. Furthermore, biomass-derived aromatic dicarboxylic acids can be produced by, for example, producing isobutanol from corn, sugars, or wood, converting the isobutanol into isobutylene, dimerizing the isobutane to produce isooctene, synthesizing p-xylene through radical cleavage, recombination, and cyclization, and then oxidizing the resulting p-xylene (WO 2009 / 079213). When a biomass-derived dicarboxylic acid is used as the dicarboxylic acid unit, in the present disclosure, it is particularly preferable to use biomass-derived terephthalic acid.

[0044] The dicarboxylic acid unit of the polyester may be a dicarboxylic acid produced from carbon dioxide gas. An example of a dicarboxylic acid produced from carbon dioxide gas is terephthalic acid, which is produced from carbon dioxide gas. Terephthalic acid produced from carbon dioxide gas can be produced, for example, by using a composite catalyst containing chromium oxide and a specific H-ZSM-5 zeolite to produce p-xylene from carbon dioxide gas and hydrogen gas as raw materials, and then oxidizing the p-xylene (Japanese Patent Laid-Open Publication No. 2019-205969).

[0045] These dicarboxylic acids can be used alone or in combination of two or more.

[0046] The polyester may be a copolymerized polyester containing the diol unit and dicarboxylic acid unit, as well as a third copolymerization component. Specific examples of the copolymerization component include a bifunctional oxycarboxylic acid, and at least one polyfunctional compound selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polycarboxylic acid and / or its anhydride, and a trifunctional or higher oxycarboxylic acid for forming a crosslinked structure. Among these copolymerization components, bifunctional and / or trifunctional or higher oxycarboxylic acids are particularly preferred because they tend to facilitate the production of copolymerized polyesters with a high degree of polymerization. Among these, the use of trifunctional or higher oxycarboxylic acids is most preferred because a very small amount of the oxycarboxylic acid can easily produce a polyester with a high degree of polymerization without the need for a chain extender, as described below.

[0047] The polyester may also be a high-molecular-weight polyester obtained by chain-extending (coupling) these copolymer polyesters. Chain extenders such as carbonate compounds and diisocyanate compounds can also be used, but the amount thereof is usually 10 mol % or less, preferably 5 mol % or less, and more preferably 3 mol % or less of carbonate bonds and urethane bonds relative to 100 mol % of all monomer units constituting the polyester.

[0048] Specific examples of carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, dicyclohexyl carbonate, etc. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can also be used.

[0049] Specific examples of the diisocyanate compound include known diisocyanates such as 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0050] The polyester used in the present disclosure can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, it can be produced by a general melt polymerization method in which an esterification reaction and / or transesterification reaction between the above-mentioned diol unit and dicarboxylic acid unit is carried out, followed by a polycondensation reaction under reduced pressure, or by a known solution heating dehydration condensation method using an organic solvent.

[0051] The amount of diol used in producing the polyester is substantially equimolar to 100 moles of the dicarboxylic acid or its derivative. However, since distillates are generally produced during the esterification and / or transesterification reaction and / or polycondensation reaction, the diol is generally used in an excess of 0.1 mol % or more and 20 mol % or less.

[0052] The polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and the catalyst may be added when the raw materials are charged or when pressure reduction is initiated.

[0053] Polymerization catalysts typically include compounds containing metal elements from Groups 1 to 14 of the periodic table, excluding hydrogen and carbon. Specific examples include compounds containing organic groups, such as carboxylates, alkoxy salts, organic sulfonates, or β-diketonate salts, containing 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, as well as inorganic compounds, such as oxides and halides, of the aforementioned metals, and mixtures thereof. Among these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium, or calcium, or mixtures thereof, are preferred, with titanium compounds, zirconium compounds, or germanium compounds being particularly preferred. Furthermore, because a catalyst in a molten or dissolved state during polymerization increases the polymerization rate, it is preferred that the catalyst be liquid during polymerization or soluble in an ester oligomer or polyester.

[0054] 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, tetrabenzyl titanate, or a mixture thereof. Titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide)acetylacetonate, titanium bis(ammonium lactate)dihydroxide, titanium bis(ethylacetoacetate)diisopropoxide, titanium (triethanolamine)isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamine, 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, tetra-n-butyl titanate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate, titanium lactate, butyl titanate dimer, titanium oxide, and titania / silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) are preferred, and tetra-n-butyl titanate, polyhydroxytitanium stearate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, and titania / silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) are particularly preferred.

[0055] Specific examples of zirconium compounds include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate, and mixtures thereof. Zirconium oxide and composite oxides containing, for example, zirconium and silicon may also be used. Among these, zirconyl diacetate, zirconium tris(butoxy)stearate, zirconium tetraacetate, zirconium acetate hydroxide, ammonium zirconium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide are preferred.

[0056] Specific examples of germanium compounds include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. From the viewpoints of cost and availability, germanium oxide, tetraethoxygermanium, and tetrabutoxygermanium are preferred, with germanium oxide being particularly preferred.

[0057] When a metal compound is used as a polymerization catalyst, the amount of catalyst used, expressed as the amount of metal relative to the polyester produced, is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30,000 ppm or less, preferably 1,000 ppm or less, more preferably 250 ppm or less, and particularly preferably 130 ppm or less. If the amount of catalyst used is too large, not only is it economically disadvantageous but the thermal stability of the polymer is reduced, while if the amount is too small, the polymerization activity is reduced, which makes it more likely that the polymer will decompose during polymer production. As for the amount of catalyst used here, the method of reducing the amount of catalyst used is a preferred embodiment, because the amount of terminal carboxyl groups in the polyester produced is reduced as the amount of catalyst used is reduced.

[0058] The reaction temperature for the esterification reaction and / or transesterification reaction between diol units and dicarboxylic acid units is usually in the range of 150°C to 260°C, and the reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon. The reaction pressure is usually normal pressure to 10 kPa, and the reaction time is usually 1 hour to 10 hours.

[0059] In the above-mentioned production process, a chain extender (coupling agent) may be added to the reaction system. After the polycondensation is completed, the chain extender is added to the reaction system in a homogeneous molten state without a solvent, and reacted with the polyester obtained by polycondensation.

[0060] High-molecular-weight polyesters using these chain extenders (coupling agents) can be produced using known techniques. After polycondensation is complete, the chain extender is added to the reaction system in a homogeneous, molten state without a solvent and reacted with the polyester obtained by polycondensation. Specifically, a polyester with a higher molecular weight can be obtained by reacting the chain extender with a polyester prepolymer obtained by catalytically reacting a diol with a dicarboxylic acid, which has substantially hydroxyl end groups and a mass-average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more. A prepolymer with a mass-average molecular weight of 20,000 or more can be produced with the use of a small amount of coupling agent without being affected by residual catalyst, even under harsh conditions such as a molten state, and therefore without forming gel during the reaction.

[0061] [Base material layer] The substrate layer of the laminated film according to the present disclosure is a film containing the above-described polyester, i.e., a film containing a polyester using ethylene glycol derived from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide (hereinafter also referred to as "gas-derived polyester"). From the viewpoint of reducing the environmental impact, the content of the gas-derived polyester in the base layer is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more. The content of the gas-derived polyester in the base layer is 100% by mass or less, with 99% by mass or less being practical and 97% by mass or less being more practical.

[0062] Because the base layer contains gas-derived polyester, the carbon dioxide molecule content in the base layer tends to be higher than that of films using conventional fossil fuel-derived polyester. For example, the carbon dioxide molecule content in the base layer is 1.1 x 10 18 It is preferable that the number of particles is 1.5×10 18 More preferably, it is 2.0 × 10 18It is more preferable that the carbon dioxide molecule content in the substrate layer is 3.0×10 18 It is preferable that the number of particles is less than 2.7 × 10 18 It is more preferable that the number of particles is 2.4×10 18 It is more preferable that the number is not more than 1 / g. The content of carbon dioxide molecules in the substrate layer is measured by thermal desorption mass spectrometry (TDS-MS), specifically by the method described in the Examples below.

[0063] In addition, the water molecule content in the base layer tends to be higher than that of conventional films using polyester derived from fossil fuels. For example, the water molecule content in the base layer is 8.6 × 10 19 It is preferable that the number of particles is 9.0 × 10 19 More preferably, it is 1.0 × 10 20 The content of water molecules in the base layer is more preferably 2.5×10 20 It is preferable that the number of particles is less than 2.0 × 10 20 It is more preferable that the number of particles is less than 1.5 × 10 20 It is more preferable that the number is not more than 1 / g. The content of water molecules in the substrate layer is measured by thermal desorption spectrometry-mass spectrometry (TDS-MS), specifically by the method described in the Examples below.

[0064] The substrate layer may contain various additives as long as the properties of the present disclosure are not impaired. Examples of additives include plasticizers, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather resistance agents, antistatic agents, thread friction reducers, mold release agents, antioxidants, ion exchange agents, and color pigments. The content of these additives is, for example, 5% by mass or more and 50% by mass or less.

[0065] To obtain a substrate layer by processing polyester into a film, a conventional method for forming a film from polyester can be used. Specifically, gas-derived polyester pellets are dried and then fed into a melt extruder heated to a temperature above the melting point (Tm) of the pellets and below Tm + 70°C. The pellets are melted and extruded into a sheet from a die such as a T-die. The extruded sheet is then rapidly cooled and solidified on a rotating cooling drum, etc., to form a substrate layer. The substrate layer obtained in this manner is composed of a single layer. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, etc. can be used depending on the purpose.

[0066] The substrate layer is preferably biaxially stretched. The biaxial stretching can be carried out by a conventionally known method, and may be sequential biaxial stretching or simultaneous biaxial stretching. Sequential biaxial stretching and simultaneous biaxial stretching will be described below.

[0067] [Sequential biaxial stretching] In the sequential biaxial stretching, the film extruded onto the cooling drum as described above is stretched in the machine direction, and then the film is stretched in the transverse direction. The longitudinal stretching is usually performed by varying the peripheral speed of rolls, and may be performed in one step or in multiple steps using multiple pairs of rolls. The longitudinal stretching ratio is preferably 2.0 times or more, more preferably 2.5 times or more, and preferably 15.0 times or less, more preferably 7.0 times or less, even more preferably 5.0 times or less, and even more preferably 4.2 times or less. This can suppress variations in optical properties such as in-plane retardation. The stretching temperature is preferably 50° C. or higher, more preferably 80° C. or higher, and even more preferably 95° C. or higher, and is preferably 120° C. or lower, more preferably 115° C. or lower, and even more preferably 110° C. or lower, thereby making it possible to suppress variations in optical properties such as in-plane retardation.

[0068] The transverse stretching is usually performed using a tenter method, in which the film is conveyed while being held at both ends with clips, and stretched in the transverse direction. The stretching ratio in the transverse direction is preferably 2 times or more, more preferably 2.5 times or more, and is preferably 15 times or less, more preferably 5 times or less. This can suppress variations in optical properties such as in-plane retardation. The stretching temperature is preferably 50° C. or higher, more preferably 90° C. or higher, and even more preferably 95° C. or higher, and is preferably 120° C. or lower, more preferably 110° C. or lower, and even more preferably 105° C. or lower, thereby making it possible to suppress variations in optical properties such as in-plane retardation.

[0069] The film sequentially biaxially stretched as described above is preferably heat-treated in a tenter at a temperature equal to or higher than the stretching temperature and lower than the melting point to impart flatness and dimensional stability. Specifically, heat setting is preferably carried out at a temperature of 120°C or higher, more preferably 190°C or higher, and preferably 235°C or lower, more preferably 225°C or lower. Furthermore, from the viewpoint of suppressing variations in optical properties such as in-plane retardation, it is preferable to perform post-heat treatment stretching of 1% to 10% in the first half of the heat treatment. This can suppress variations in optical properties such as in-plane retardation. After the heat treatment, the film is slowly cooled to room temperature and then wound up. If necessary, a relaxation treatment or the like may be performed during the heat treatment or slow cooling. The relaxation rate during the heat treatment is preferably 0.5% or more, more preferably 0.8% or more, even more preferably 1% or more, and preferably 5% or less, more preferably 3% or less, even more preferably 2.5% or less, and even more preferably 2% or less. This can suppress variations in optical properties such as in-plane retardation. The relaxation rate during slow cooling is preferably 0.5% or more, and preferably 3% or less, more preferably 2% or less, even more preferably 1.5% or less, and even more preferably 1.0% or less. This can suppress variations in optical properties such as in-plane retardation. From the viewpoint of flatness, the temperature during slow cooling is preferably 80°C or more, more preferably 90°C or more, and even more preferably 100°C or more, and preferably 150°C or less, more preferably 130°C or less, and even more preferably 120°C or less.

[0070] [Simultaneous biaxial stretching] In simultaneous biaxial stretching, the film extruded onto the cooling drum as described above is introduced into a simultaneous biaxial tenter, and while both ends of the film are held with clips, the film is conveyed and stretched simultaneously and / or stepwise in the machine and cross directions. Simultaneous biaxial stretching machines include pantograph, screw, drive motor, and linear motor types, but drive motor and linear motor types are preferred, as they allow the stretching ratio to be changed as desired and relaxation treatment to be performed at any desired location.

[0071] The area ratio of the simultaneous biaxial stretching is preferably 2 times or more, more preferably 3 times or more, even more preferably 6 times or more, even more preferably 10 times or more, and is preferably 50 times or less, more preferably 30 times or less, even more preferably 25 times or less, even more preferably 20 times or less, and particularly preferably 15 times or less, thereby making it possible to suppress variations in optical properties such as in-plane retardation. In the case of simultaneous biaxial stretching, it is preferable to make the stretching ratios in the machine direction and the cross direction the same and to make the stretching speeds approximately equal in order to suppress in-plane orientation differences.

[0072] The stretching temperature for simultaneous biaxial stretching is preferably 50° C. or higher, more preferably 90° C. or higher, and even more preferably 100° C. or higher, and is preferably 160° C. or lower, more preferably 150° C. or lower, and even more preferably 140° C. or lower, thereby making it possible to suppress variations in optical properties such as in-plane retardation.

[0073] The simultaneously biaxially stretched film is preferably subsequently heat-treated in a heat-setting chamber in a tenter at a temperature equal to or higher than the stretching temperature and lower than the melting point in order to impart flatness and dimensional stability. The heat-treatment conditions are the same as those after the successive biaxial stretching.

[0074] The thickness of the substrate layer is optional depending on the application, but is usually 5 μm or more and 500 μm or less. The breaking strength of such a film is 1 kg / mm ​​in the MD direction. 2 More than 40kg / mm 2 Below, 1kg / mm ​​in the TD direction2 More than 35kg / mm 2 The elongation at break is 10% or more and 350% or less in the MD direction and 3% or more and 300% or less in the TD direction. Thus, the substrate layer of the laminate according to the present disclosure has properties equivalent to those of substrate layers produced from conventional fossil fuel-derived materials or biomass-derived materials.

[0075] Although the substrate layer 10 shown in FIG. 1 is configured as a single layer, the substrate layer provided in the laminate of the present disclosure is not limited to a single layer configuration and may be configured as a multilayer configuration. When the substrate layer is configured as a multilayer configuration, it is sufficient that at least one layer contains a gas-derived polyester, and the other layers do not need to contain a gas-derived polyester. Examples of polyesters that constitute layers that do not contain a gas-derived polyester include at least one selected from the group consisting of fossil fuel-derived polyesters, biomass-derived polyesters, and recycled polyesters. Note that recycled polyester refers to polyester that has been recycled by collecting used products such as containers that have been shipped to the market.

[0076] The substrate layer can be subjected to secondary processing for the purpose of imparting surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, biocompatibility, etc. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, and surface treatments (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.).

[0077] [Vapor deposition film] The vapor-deposited film provided in the laminate film according to the present disclosure is a vapor-deposited film of a metal or metal oxide. The vapor-deposited film can be formed by a conventionally known method using a conventionally known metal or metal oxide, and its composition and formation method are not particularly limited. The presence of a vapor-deposited film in the laminate film can impart or improve gas barrier properties that prevent the transmission of oxygen gas, water vapor, etc., and light-blocking properties that prevent the transmission of visible light, ultraviolet light, etc. The laminate film may have two or more vapor-deposited film layers. When two or more vapor-deposited film layers are present, the layers may have the same composition or different compositions.

[0078] Examples of vapor-deposited films that can be used include vapor-deposited films of metals such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y). Alternatively, vapor-deposited films of oxides of the above metals can be used. Vapor-deposited films of aluminum, aluminum oxide, and silicon oxide are particularly suitable for packaging materials.

[0079] Metal oxides are expressed as, for example, SiO X , AlO X MO etc. X(Note that in the formula, M represents a metal element, and the value of X varies depending on the metal element.) The range of X is silicon (Si) from 0 to 2, aluminum (Al) from 0 to 1.5, magnesium (Mg) from 0 to 1, calcium (Ca) from 0 to 1, potassium (K) from 0 to 0.5, tin (Sn) from 0 to 2, sodium (Na) from 0 to 0.5, boron (B) from 0 to 1.5, titanium (Ti) from 0 to 2, lead (Pb) from 0 to 1, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X = 0, the material is a completely pure metal (substance) and is not transparent. The upper limit of the range of X is the value when the material is completely oxidized. Silicon (Si) and aluminum (Al) are preferably used as packaging materials, with silicon (Si) having an x ​​range of 1.0 or more and 2.0 or less, and aluminum (Al) having an x ​​range of 0.5 or more and 1.5 or less.

[0080] In the present disclosure, the thickness of the vapor-deposited film of the metal or metal oxide as described above varies depending on the type of metal or metal oxide used, but is preferably 50 Å or more, more preferably 100 Å or more, and is preferably 2000 Å or less, more preferably 1000 Å or less. More specifically, when the vapor-deposited film is an aluminum vapor-deposited film, the film thickness is preferably 50 Å or more, more preferably 100 Å or more, and is preferably 600 Å or less, more preferably 450 Å or less. When the vapor-deposited film is an aluminum oxide or silicon oxide vapor-deposited film, the film thickness is preferably 50 Å or more, more preferably 100 Å or more, and is preferably 500 Å or less, more preferably 300 Å or less.

[0081] Examples of methods for forming a vapor-deposited film include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0082] As one aspect of the present disclosure, the vapor-deposited film will be described in further detail below.

[0083] A vapor deposition film of a metal oxide such as silicon oxide can be formed on one surface of a substrate layer by low-temperature plasma chemical vapor deposition using a vapor deposition monomer gas such as an organosilicon compound as a raw material, an inert gas such as argon gas or helium gas as a carrier gas, and oxygen gas or the like as an oxygen supply gas, and utilizing a low-temperature plasma generator or the like. In the above, the low-temperature plasma generator can be, for example, a high-frequency plasma generator, a pulse wave plasma generator, a microwave plasma generator, or the like. To obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

[0084] The vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organic silicon compound is formed by a chemical reaction between the vapor deposition monomer gas such as an organic silicon compound and oxygen gas, and the reaction product adheres tightly to the surface of the substrate layer to form a thin film that is dense and highly flexible. The vapor deposition film is usually formed by a compound represented by the general formula SiO X (wherein X is a number between 0 and 2) As the vapor-deposited film of silicon oxide, from the viewpoints of transparency, barrier properties, etc., the vapor-deposited film of silicon oxide is preferably a film of silicon dioxide represented by the general formula SiO X (where X is a number between 1.3 and 1.9.) In the above, the value of X varies depending on the molar ratio of the vapor deposition monomer gas and oxygen gas, the plasma energy, etc., but generally, as the value of X decreases, the gas permeability decreases, but the film itself becomes yellowish and its transparency decreases.

[0085] The silicon oxide vapor-deposited film is primarily composed of silicon oxide and further contains, via chemical bonding or the like, at least one compound consisting of one or more elements selected from the group consisting of carbon, hydrogen, silicon, and oxygen. Examples of the compound include compounds having a C-H bond, compounds having a Si-H bond, compounds in which carbon units are graphite-like, diamond-like, fullerene-like, or the like, and raw organosilicon compounds or their derivatives. More specifically, examples include hydrocarbons having a CH moiety, hydrosilica such as SiH silyl and SiH silylene, and hydroxyl group derivatives such as SiH OH silanol. In addition to the above, the type and amount of compounds contained in the silicon oxide vapor-deposited film can be varied by changing the conditions of the vapor deposition process. The content of the above compounds in the silicon oxide vapor-deposited film is preferably 0.1% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 20% by mass or less. If the content is less than 0.1% by mass, the impact resistance, extensibility, flexibility, etc. of the silicon oxide vapor-deposited film will be insufficient, and it will be prone to scratches, cracks, etc. when bent, etc., making it difficult to stably maintain high barrier properties. On the other hand, if the content exceeds 50% by mass, the barrier properties will decrease.

[0086] Furthermore, in the present disclosure, it is preferable that the content of the above-mentioned compounds in the silicon oxide vapor-deposited film decreases from the surface of the silicon oxide vapor-deposited film in the depth direction, which has the advantage that the impact resistance and the like are improved at the surface of the silicon oxide vapor-deposited film by the above-mentioned compounds, and on the other hand, the content of the above-mentioned compounds is low at the interface with the substrate layer, thereby strengthening the tight adhesion between the substrate layer and the silicon oxide vapor-deposited film.

[0087] The physical properties of the silicon oxide vapor deposition film can be confirmed by performing elemental analysis of the silicon oxide vapor deposition film using a surface analysis device such as an X-ray photoelectron spectroscopy (XPS) or a secondary ion mass spectroscopy (SIMS) and analyzing the film by ion etching in the depth direction.

[0088] In the present disclosure, the thickness of the silicon oxide vapor deposition film is preferably 50 Å or more, more preferably 100 Å or more, and preferably 4000 Å or less, more preferably 1000 Å or less. If the film thickness exceeds 4000 Å, cracks and the like are likely to occur. If the film thickness is less than 50 Å, it becomes difficult to achieve the barrier effect. In the above, the film thickness can be measured by the fundamental parameter method using an X-ray fluorescence analyzer (model name: RIX2000) manufactured by Rigaku Corporation. In addition, in the above, means for changing the film thickness of the silicon oxide vapor deposition film include increasing the volume rate of the vapor deposition film, i.e., increasing the amounts of monomer gas and oxygen gas, and slowing down the vapor deposition rate.

[0089] Next, in the above, examples of vapor deposition monomer gases that can be used, such as organosilicon compounds, for forming a vapor-deposited film of a metal oxide such as silicon oxide, include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane.

[0090] From the viewpoints of ease of handling and the properties of the continuous film formed, it is preferable to use 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as the raw material among the above-mentioned organosilicon compounds. In addition, in the above, for example, argon gas, helium gas, etc. can be used as the inert gas.

[0091] Next, in the present disclosure, the metal oxide vapor deposition film formed by the physical vapor deposition method will be described in more detail. As the metal oxide vapor deposition film formed by the physical vapor deposition method, for example, a metal oxide vapor deposition film can be formed using a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method.

[0092] Specifically, in the present invention, the deposited film can be formed by using a vacuum deposition method in which a metal or metal oxide is used as a raw material, heated to vaporize it, and then deposited on the surface of a substrate layer; an oxidation reaction deposition method in which a metal or metal oxide is used as a raw material, oxidized by introducing oxygen, and then deposited on the surface of a substrate layer; or a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is assisted by plasma. In the above, the deposition material can be heated by, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), etc.

[0093] As the vapor-deposited film of metal oxide by the physical vapor deposition method, it is preferable to use, for example, an amorphous thin film of aluminum oxide, more specifically, a thin film of the formula AlO X (wherein X is a number in the range of 0.5 to 1.5), and the value of X decreases in the depth direction from the surface of the film toward the inside. Alternatively, in the present disclosure, the amorphous thin film of aluminum oxide may be an amorphous thin film of aluminum oxide represented by the formula AlO X(wherein X is a number in the range of 0.5 to 1.5), and the value of X in the amorphous aluminum oxide thin film increases in the depth direction from the surface toward the inside of the film. In the present disclosure, the value of X in the above formula is basically 0.5 or more, but in the present disclosure, X of 1.0 or more is preferably used because X of less than 1.0 results in severe coloration and poor transparency, and X of 1.5 or more is used because aluminum and oxygen are completely oxidized in an X of 1.5, so that X of 1.5 or less can be used as the upper limit.

[0094] Next, in the present disclosure, the thickness of the amorphous thin film of aluminum oxide is preferably 10 Å or more, more preferably 60 Å or more, and is preferably 3000 Å or less, more preferably 1000 Å or less.

[0095] In the present disclosure, an amorphous thin film of aluminum oxide can be formed using a winding vacuum deposition apparatus. In the deposition, the vacuum degree of the vacuum chamber is preferably 10 -5 mbar or more, more preferably 10 -4 mbar or more, preferably 10 0 mbar or less, more preferably 10 -1 The vacuum level in the deposition chamber is preferably 10 mbar or less before oxygen is introduced. -8 mbar or more, more preferably 10 -7 mbar or more, preferably 10 -2 mbar or less, more preferably 10 -3 After oxygen is introduced, the pressure is preferably 10 -6 mbar or more, more preferably 10 -5 mbar or more, preferably 10 -1 mbar or less, more preferably 10 -2The pressure is preferably 10 m / min or more, more preferably 50 m / min or more, and is preferably 800 m / min or less, more preferably 600 m / min or less. The amount of oxygen introduced varies depending on the size of the deposition machine.

[0096] In the present disclosure, in the thin film layer made of a metal oxide by physical vapor deposition, the ultraviolet (366 nm wavelength) transmittance of the aluminum oxide vapor deposition film during and immediately after deposition is preferably 85% or more, more preferably 87% or more, and also preferably 96% or less, more preferably 94% or less. If the ultraviolet transmittance is too low, transparency decreases. Furthermore, an aluminum oxide vapor deposition film with too high an ultraviolet transmittance has a high degree of oxidation of aluminum oxide, and the formed film becomes hard, making it prone to cracking. The thickness of the aluminum oxide vapor deposition film is preferably 150 Å or more and 600 Å or less, taking into account suitability for post-processing. Furthermore, as the deposited film made of silicon oxide, a deposited film of silicon oxide made by physical vapor deposition using a mixture of silicon monoxide and silicon as raw materials and having a film thickness in the range of 50 Å to 300 Å, in consideration of suitability for post-processing, is preferred.

[0097] In the present disclosure, when a metal oxide vapor deposition film is formed on a substrate layer, it is preferable to provide a plasma-treated surface or the like by subjecting the surface of the substrate layer to plasma treatment with an inert gas in advance, from the viewpoint of improving adhesion between the surface of the substrate layer and the surface of the metal oxide vapor deposition film, and ultimately firmly adhering the two to prevent delamination or the like.

[0098] In the present disclosure, the plasma-treated surface using an inert gas will be described. Such a plasma-treated surface can be formed by using a plasma surface treatment method, which performs surface modification on one surface of a substrate layer using a plasma gas generated by ionizing a gas by arc discharge. That is, in the present disclosure, the plasma-treated surface can be formed by performing plasma treatment using a plasma surface treatment method that uses an inert gas such as nitrogen gas, argon gas, or helium gas as the plasma gas. In the present disclosure, a mixed gas obtained by further adding oxygen gas to the above inert gas can also be used as the plasma gas.

[0099] Furthermore, in the present disclosure, when forming a plasma-treated surface using an inert gas, it is desirable to perform the plasma treatment in-line, for example, immediately before forming a metal oxide vapor deposition film by physical vapor deposition or chemical vapor deposition, because this removes moisture, dust, etc. from the surface of the substrate layer and enables surface treatment such as smoothing and activation of the surface.

[0100] Furthermore, in the present disclosure, the above-mentioned plasma treatment is preferably performed as a plasma discharge treatment, taking into consideration conditions such as plasma output, type of plasma gas, supply amount of plasma gas, and treatment time. Furthermore, in the present disclosure, plasma can be generated using, for example, a device such as a direct current glow discharge, a high-frequency discharge, or a microwave discharge. Furthermore, in the present disclosure, a plasma-treated surface can also be formed using an atmospheric pressure plasma treatment method or the like.

[0101] Furthermore, when producing a laminated film having a surface coating layer as described below, a vapor deposition film can be formed on the surface coating layer in the same manner as described above, thereby producing a laminated film having a surface coating layer between the substrate layer and the vapor deposition film.

[0102] [Surface coating layer] The laminate film according to the present disclosure may further include a surface coating layer between the substrate layer and the vapor-deposited film. The surface coating layer is a layer containing a resin material having a polar group. By including this surface coating layer, a vapor-deposited film having high adhesion can be formed on the surface coating layer, thereby improving gas barrier properties. Furthermore, a package produced using a laminate including this surface coating layer has high lamination strength. In one embodiment, the surface coating layer may be provided on the substrate layer, i.e., the surface coating layer may be adjacent to the substrate layer.

[0103] The surface coating layer contains a resin material having a polar group. In the present disclosure, a polar group refers to a group containing one or more heteroatoms. Examples of polar groups include ester groups, epoxy groups, hydroxyl groups, amino groups, amide groups, carboxyl groups, carbonyl groups, carboxylic anhydride groups, sulfone groups, thiol groups, and halogen groups. Among these, from the viewpoint of lamination properties of the packaging body, carboxyl groups, carbonyl groups, ester groups, hydroxyl groups, and amino groups are preferred, and carboxyl groups and hydroxyl groups are more preferred.

[0104] As the resin material having a polar group, polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, polyamide such as nylon 6, nylon 6,6, MXD nylon, amorphous nylon, polyurethane, etc. are preferred. By using such a resin material, the adhesion of the vapor-deposited film formed on the surface coating layer can be significantly improved, and the gas barrier properties thereof can be effectively improved.

[0105] In one embodiment, the resin material having a polar group is preferably a hydroxyl group-containing (meth)acrylic resin, which can improve the heat resistance of the laminated film and can prevent the gas barrier properties from deteriorating even after the laminated film is subjected to a retort treatment or a boiling treatment.

[0106] In one embodiment of the present disclosure, the hydroxyl group-containing (meth)acrylic resin used to form the surface coating layer is a polymer of a neutral monomer and a hydroxyl group-containing (meth)acrylic monomer. Examples of neutral monomers include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, styrene, vinyl toluene, and vinyl acetate. Examples of the hydroxyl group-containing (meth)acrylic monomer include 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0107] The glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin is preferably 50° C. or higher, more preferably 70° C. or higher. The glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin is preferably 200° C. or lower, more preferably 150° C. or lower. By adjusting the glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin to 50° C. or higher, blocking resistance can be improved. By setting the glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin to 200°C or less, the reactivity of an isocyanate compound can be improved when the hydroxyl group-containing (meth)acrylic resin is used together with an isocyanate compound to form a surface coating layer. In the present disclosure, Tg can be measured in accordance with JIS K7121:2012 (Method for measuring transition temperature of plastics). Specifically, Tg can be determined by measuring a DSC curve at a heating rate of 10°C / min using a differential scanning calorimetry (DSC) device.

[0108] The number average molecular weight of the hydroxyl group-containing (meth)acrylic resin is preferably 10,000 or more, and the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin is preferably 100,000 or less. By adjusting the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin to 10,000 or more, blocking resistance can be improved. By adjusting the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin to 100,000 or more, the ease of forming the surface coating layer can be improved. In the present disclosure, the number average molecular weight can be measured by gel permeation chromatography (GPC). In GPC measurement, the number average molecular weight of a polymer is generally measured in terms of standard polystyrene.

[0109] The hydroxyl value of the hydroxyl group-containing (meth)acrylic resin is preferably 20 mg KOHL / g or more, more preferably 30 mg KOHL / g or more, and preferably 200 mg KOHL / g or less, more preferably 150 mg KOHL / g or less. By making the hydroxyl value of the hydroxyl group-containing (meth)acrylic resin 20 mg KOHL / g or more, the reactivity of an isocyanate compound can be improved when the hydroxyl group-containing (meth)acrylic resin is used together with the isocyanate compound to form the surface coating layer. By setting the hydroxyl value of the hydroxyl group-containing (meth)acrylic resin to 200 mg KOHL / g or less, the amount of isocyanate compound used can be reduced, thereby reducing production costs. In the present disclosure, the hydroxylation can be measured in accordance with JIS K0070:1992 (Test methods for oxidation, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products).

[0110] In the present disclosure, the surface coating layer can be formed using a water-based emulsion or a solvent-based emulsion. Specific examples of water-based emulsions include polyamide-based emulsions, polyethylene-based emulsions, and polyurethane-based emulsions. Specific examples of solvent-based emulsions include polyester-based emulsions.

[0111] The content of the resin material having a polar group in the surface coating layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0112] The surface coating layer may contain a resin material other than the resin material having a polar group, as long as the characteristics of the present invention are not impaired. In one embodiment of the present disclosure, the surface coating layer may include an isocyanate compound. The surface coating layer may contain additives, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins, etc., as long as the properties of the present disclosure are not impaired.

[0113] The ratio of the thickness of the surface coating layer to the total thickness of the substrate layer and the surface coating layer is preferably 0.08% or more, more preferably 0.2% or more, even more preferably 1% or more, and even more preferably 3% or more. The ratio of the thickness of the surface coating layer to the total thickness of the substrate layer and the surface coating layer is preferably 20% or less, more preferably 10% or less. By setting the ratio of the thickness of the surface coating layer to the total thickness of the base layer and the surface coating layer to 0.08% or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the package can be further improved. By setting the ratio of the thickness of the surface coating layer to the total thickness of the base layer and the surface coating layer to 20% or less, the film-forming properties and processability of the surface coating layer can be further improved, and the recyclability of packaging materials produced using the laminate film according to the present disclosure can be improved.

[0114] The thickness of the surface coating layer is preferably 0.02 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and even more preferably 0.2 μm or more. The thickness of the surface coating layer is preferably 10 μm or less, and more preferably 5 μm or less. By making the thickness of the surface coating layer 0.02 μm or more, the adhesion of the vapor-deposited film can be further improved, the gas barrier properties can be further improved, and the laminate strength of the package can be further improved. By setting the thickness of the surface coating layer to 10 μm or less, the film-forming property and processability of the surface coating layer can be further improved, and the recyclability of packaging materials produced using the laminate film according to the present disclosure can be improved.

[0115] A laminate consisting of a base layer and a surface coating layer can be produced offline. Specifically, a resin composition containing a predetermined polyester is formed into a film using a T-die method, an inflation method, or the like, to form a resin film, which is then stretched, and a coating liquid for forming a coat is applied to the resin film and dried. Furthermore, a laminate consisting of a substrate layer and a surface coating layer can be produced in-line. Specifically, a resin composition containing a predetermined polyester is formed into a film using a T-die method, an inflation method, or the like, to form a resin film, which is then stretched in the machine direction (MD), a coating liquid for forming a coat is applied to the resin film, dried, and then stretched in the transverse direction (TD). Note that stretching in the transverse direction may be performed first. Furthermore, stretching in both the machine direction and the transverse direction may be performed before or after applying the coating liquid for forming a coat.

[0116] [Gas barrier coating film] The laminated film according to the present disclosure may further include a gas barrier coating film on the vapor deposition film. The gas barrier coating film may include a compound represented by the general formula R 1 n M(OR 2 ) m (wherein, R 1 and R 2each independently represents 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 the valence of M. and at least one water-soluble polymer (hereinafter simply referred to as "water-soluble polymer") selected from the group consisting of polyvinyl alcohol resins and ethylene-vinyl alcohol copolymers, and further comprising a step of preparing a gas barrier composition by polycondensation using a sol-gel method in the presence of a sol-gel catalyst, an acid, water, and an organic solvent; a step of applying the gas barrier composition by polycondensation using a sol-gel method onto a vapor-deposited film made of a metal oxide provided on one side of a base layer, if necessary via a surface that has been plasma-treated with oxygen gas, to form a coating film; and a step of heat-treating the laminated film provided with the coating film at a temperature of 20°C to 180°C and not more than the melting point of the base layer for 10 seconds to 10 minutes, to form a gas barrier coating film made of the gas barrier composition onto the vapor-deposited film made of a metal oxide provided on one side of the base layer, if necessary via a surface that has been plasma-treated with oxygen gas.

[0117] In the present disclosure, the gas barrier coating film may be a compound represented by the general formula R 1 n M(OR 2 ) m and a water-soluble polymer, and further comprising a sol-gel catalyst, an acid, water, and an organic solvent to prepare a gas barrier composition which is polycondensed by a sol-gel method, and then using this to form two or more gas barrier coating films of the gas barrier composition on a vapor-deposited film of a metal oxide provided on one side of a base layer, thereby forming a composite polymer layer in which two or more gas barrier coating films of the gas barrier composition are layered.

[0118] In the above, the gas barrier coating film is formed by the general formula R 1 n M(OR 2 ) mAs the alkoxide represented by the formula (I), at least one of a partial hydrolyzate of an alkoxide and a hydrolysis condensate of an alkoxide can be used. Furthermore, the partial hydrolyzate of the alkoxide does not necessarily have to have all of the alkoxy groups hydrolyzed, and may be one in which one or more alkoxy groups are hydrolyzed or a mixture thereof. Furthermore, as the hydrolysis condensate, a dimer or higher of a partially hydrolyzed alkoxide, specifically a dimer or higher and a hexamer or lower, can be used.

[0119] The general formula R 1 n M(OR 2 ) m In the alkoxide represented by the formula (I), silicon, zirconium, titanium, aluminum, and the like can be used as the metal atom represented by M. In the present disclosure, preferred metals include silicon and titanium. In the present disclosure, the alkoxide can be used alone or as a mixture of two or more alkoxides of different metal atoms in the same solution.

[0120] In addition, the above general formula R 1 n M(OR 2 ) m In the alkoxide represented by the formula 1 Specific examples of the organic group represented by the general formula R include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-hexyl, n-octyl, and the like. 1 n M(OR 2 ) m In the alkoxide represented by the formula 2 Specific examples of the organic group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, etc. In the present disclosure, these alkyl groups may be the same or different in the same molecule.

[0121] In the present disclosure, the above general formula R 1 n M(OR 2 ) m As the alkoxide represented by the formula (I), it is preferable to use, for example, 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, Ra may be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or the like. Specific examples of the alkoxysilane include tetramethoxysilane Si(OCH3)4, tetraethoxysilane Si(OC2H5)4, tetrapropoxysilane Si(OC3H7)4, tetrabutoxysilane Si(OC4H9)4, and the like.

[0122] As the polyvinyl alcohol resin for forming the gas barrier coating film, a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer can be used in combination. The use of a water-soluble polymer can significantly improve the physical properties of the gas barrier coating film, such as gas barrier property, water resistance, and weather resistance. In particular, in the present disclosure, the use of a polyvinyl alcohol resin in combination with an ethylene-vinyl alcohol copolymer can form a gas barrier coating film that is remarkably excellent in hot water resistance and gas barrier property after hot water treatment, in addition to the above-mentioned physical properties such as gas barrier property, water resistance, and weather resistance.

[0123] In the present disclosure, when a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer are used in combination, the weight ratio of the polyvinyl alcohol resin to the ethylene-vinyl alcohol copolymer is preferably 10:0.05 or more and 10:6 or less, and a weight ratio of 10:1 is more preferred.

[0124] In the present disclosure, the content of the water-soluble polymer is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and preferably 500 parts by mass or less, more preferably 200 parts by mass or less, relative to 100 parts by mass of the total amount of the alkoxide. If the content exceeds 500 parts by mass, the brittleness of the gas barrier coating film increases, and the water resistance and weather resistance of the resulting gas barrier laminate film tend to decrease. If the content is less than 5 parts by mass, the gas barrier properties decrease.

[0125] In the present disclosure, the polyvinyl alcohol resin and / or ethylene-vinyl alcohol copolymer can generally be a polyvinyl alcohol resin obtained by saponifying polyvinyl acetate. The polyvinyl alcohol resin may be a partially saponified polyvinyl alcohol resin in which several tens of percent of acetate groups remain, a fully saponified polyvinyl alcohol in which no acetate groups remain, or a modified polyvinyl alcohol resin in which OH groups have been modified, but is not particularly limited. Specific examples of the polyvinyl alcohol resin include RS-110 (saponification degree = 99%, polymerization degree = 1000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (saponification degree = 40%, polymerization degree = 2000) manufactured by the same company, and Gohsenol NM-14 (saponification degree = 99%, polymerization degree = 1400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

[0126] Furthermore, in the present disclosure, the ethylene-vinyl alcohol copolymer may be a saponified copolymer of ethylene and vinyl acetate, i.e., a copolymer obtained by saponifying an ethylene-vinyl acetate random copolymer. Specifically, the saponification degree ranges from partially saponified products, in which several tens of mol% of acetate groups remain, to fully saponified products, in which only a few mol% of acetate groups remain, or even no acetate groups remain. While not particularly limited, from the viewpoint of gas barrier properties, the saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. Furthermore, the content of repeating units derived from ethylene in the ethylene-vinyl alcohol copolymer (hereinafter also referred to as "ethylene content") is generally 0 to 50 mol%, preferably 20 to 45 mol%. Specific examples of the ethylene-vinyl alcohol copolymer include EVAL EP-F101 (ethylene content: 32 mol%) manufactured by Kuraray Co., Ltd. and Soarnol D2908 (ethylene content: 29 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

[0127] Next, in this disclosure, a gas barrier composition that forms a gas barrier coating film that constitutes the laminate film according to the present disclosure will be described. Such a gas barrier composition can be a compound represented by the general formula R 1 n M(OR 2 ) m and the water-soluble polymer as described above, and are further subjected to polycondensation by a sol-gel method in the presence of a sol-gel catalyst, an acid, water, and an organic solvent to prepare a gas barrier composition.

[0128] When preparing the gas barrier composition, for example, a silane coupling agent or the like can also be added. Known organoalkoxysilanes containing organic reactive groups can be used as the silane coupling agent. In the present disclosure, organoalkoxysilanes having epoxy groups are particularly suitable, and examples of the silane coupling agents that can be used include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. One or more of the above-mentioned silane coupling agents may be used in combination. In the present disclosure, the amount of the silane coupling agent used may be in the range of 1 to 20 parts by mass per 100 parts by mass of the alkoxysilane. If 20 parts by mass or more is used, the rigidity and brittleness of the gas barrier coating film formed tend to increase, and the insulating properties and processability of the gas barrier coating film tend to decrease.

[0129] Next, the sol-gel catalyst, primarily a polycondensation catalyst, used in the gas barrier composition is a tertiary amine that is substantially insoluble in water and soluble in organic solvents. Examples of suitable catalysts include N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. In the present disclosure, N,N-dimethylbenzylamine is particularly suitable. Its amount is preferably 0.01 to 1.0 parts by mass, e.g., 0.03 parts by mass, per 100 parts by mass of the total amount of the alkoxide and silane coupling agent. The acid used in the gas barrier composition is primarily a catalyst for hydrolysis of the sol-gel catalyst, primarily the alkoxide and the silane coupling agent. Examples of suitable acids include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid. The amount of the acid used is preferably 0.001 mole or more and 0.05 mole or less, for example 0.01 mole, based on the total molar amount of the alkoxide and the alkoxide portion (for example, silicate portion) of the silane coupling agent.

[0130] Furthermore, water can be used in the gas barrier composition. The amount of water is preferably 0.1 mol or more, more preferably 0.8 mol or more, and preferably 100 mol or less, more preferably 2 mol or less, per mol of the total molar amount of the alkoxide. If the amount of water exceeds 100 mol, the polymer obtained from the alkoxysilane and metal alkoxide will become spherical particles, and these spherical particles will be three-dimensionally crosslinked to form a low-density, porous polymer. Such a porous polymer will not be able to improve the gas barrier properties of the laminate film. If the amount of water is less than 0.1 mol, the hydrolysis reaction will tend to proceed more slowly.

[0131] Examples of organic solvents that can be used in the gas barrier composition include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, and others. Furthermore, in the gas barrier composition, the water-soluble polymer is preferably dissolved in a coating solution containing the alkoxide, silane coupling agent, and the like, and therefore the type of organic solvent is appropriately selected. When a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer are used in combination, n-butanol is preferably used. In the present disclosure, the ethylene-vinyl alcohol copolymer solubilized in a solvent can be, for example, a commercially available product under the trade name Soarnol. The amount of the organic solvent used is typically 30 to 500 parts by mass per 100 parts by mass of the total amount of the alkoxide, silane coupling agent, water-soluble polymer, acid, and sol-gel catalyst.

[0132] Next, the laminated film according to the present disclosure can also be produced, for example, as follows. First, a gas barrier composition (coating liquid) is prepared by mixing an alkoxide such as the alkoxysilane, a silane coupling agent, a water-soluble polymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a metal alkoxide. Next, a polycondensation reaction gradually progresses within the gas barrier composition (coating liquid). Next, the gas barrier composition (coating liquid) is applied by a conventional method onto a vapor-deposited film of a metal oxide provided on one side of a substrate layer, and then dried. The drying process then progresses polycondensation of the alkoxide such as the alkoxysilane, the metal alkoxide, the silane coupling agent, and the water-soluble polymer, forming a coating film. Furthermore, the above coating process is preferably repeated to laminate multiple coating films consisting of two or more layers. Finally, the substrate layer coated with the coating liquid is heat-treated at a temperature of preferably 20°C or higher, more preferably 50°C or higher, and below the melting point of the substrate layer, preferably 180°C or lower, more preferably 160°C or lower, for 10 seconds to 10 minutes to form one or more gas barrier coating films of the gas barrier composition (coating liquid) on the vapor-deposited film made of metal oxide formed on one side of the substrate layer, thereby producing a laminate film according to the present disclosure. The laminate film according to the present disclosure obtained in this manner has excellent gas barrier properties.

[0133] In the present disclosure, the laminate film according to the present disclosure is produced by using an ethylene-vinyl alcohol copolymer, or both a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer, instead of a polyvinyl alcohol resin, and carrying out coating, drying, and heat treatment in the same manner as described above, and has the advantage of further improving the gas barrier property after hot water treatment such as boiling treatment or retort treatment.

[0134] Furthermore, in the present disclosure, when an ethylene-vinyl alcohol copolymer or a combination of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer is not used as described above, i.e., when a laminate film according to the present disclosure is produced using only a polyvinyl alcohol resin, the gas barrier property after hot water treatment can be improved, for example, by first applying a gas barrier composition using a polyvinyl alcohol resin to form a first coating layer, and then applying a gas barrier composition containing an ethylene-vinyl alcohol copolymer on top of that coating layer to form a second coating layer, thereby forming a composite layer of these layers, which makes it possible to improve the gas barrier property of the laminate film according to the present disclosure.

[0135] Furthermore, forming a plurality of coating layers formed from a gas barrier composition containing the above-mentioned ethylene-vinyl alcohol copolymer, or a gas barrier composition containing a combination of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer, can also be an effective means for improving the gas barrier properties of the laminate film according to the present disclosure.

[0136] In the present disclosure, the vapor-deposited metal oxide film and the gas barrier coating film form chemical bonds, hydrogen bonds, coordinate bonds, etc., for example, through hydrolysis and co-condensation reactions, improving adhesion between the vapor-deposited metal oxide film and the gas barrier coating film, and the synergistic effect of the two layers can exhibit better gas barrier properties. Examples of methods for applying the gas barrier composition include applying it once or multiple times using a coating means such as roll coating (e.g., gravure roll coater), spray coating, spin coating, dipping, brush coating, bar coating, or applicator to form a coating film. Subsequent heating and drying induces condensation, forming a gas barrier coating film. The drying temperature is preferably 50°C or higher, more preferably 70°C or higher, and preferably 300°C or lower, more preferably 200°C or lower. The drying time is preferably 0.005 minutes or higher, more preferably 0.01 minutes or higher, and preferably 60 minutes or shorter, more preferably 10 minutes or shorter. The thickness of the coated film after drying is preferably 0.01 μm or more, more preferably 0.1 μm or more, and preferably 30 μm or less, more preferably 10 μm or less. If necessary, when applying the gas barrier composition, a primer or the like can be applied in advance to the vapor-deposited film made of a metal oxide, or a pretreatment such as a corona discharge treatment or a plasma treatment can be optionally performed.

[0137] As described above, the laminate film according to the present disclosure may have a substrate layer on one side thereof, and may have laminated thereon, in this order, a plasma-treated surface using an inert gas, a vapor-deposited film made of a metal oxide, a plasma-treated surface using an oxygen gas or a primer agent layer, and a gas barrier coating film.

[0138] [Laminate] A laminate according to the present disclosure includes a laminate film according to the present disclosure and a sealant layer. For example, as shown in Fig. 4, a laminate 20 according to the present disclosure includes a laminate film 15 and a sealant layer 21. In the embodiment shown in Fig. 3, the laminate 20 has the sealant layer 21 laminated on the surface of the vapor-deposited film 11 of the laminate film 15. However, the laminate 20 may also have the sealant layer 21 laminated on the surface of the base layer 10 of the laminate film 15, or may have the sealant layer 21 laminated on both surfaces of the laminate film 15.

[0139] One embodiment of the laminate according to the present disclosure further includes a support. For example, as shown in Fig. 5, the laminate 20 includes a lamination film 15, a sealant layer 21, and a support 33. More specifically, the laminate 20 includes the support 33, a base layer 10, a vapor-deposited film 11, and the sealant layer 21, in this order.

[0140] Furthermore, the laminate according to the present disclosure may have at least one other layer, in addition to the sealant layer and the support, such as a printed layer, a metal foil, an adhesive layer, an adhesive resin layer, etc. When two or more other layers are included, they may have the same composition or different compositions. The sealant layer, the support and other layers will be described below.

[0141] [Sealant layer] The sealant layer is a layer formed of a film of a heat-sealable resin that can be fused to each other by heat. The material constituting the sealant layer is not particularly limited as long as it is a resin that can be fused to each other by heat, and examples thereof include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-α-olefin copolymers polymerized using a metallocene catalyst, random or block copolymers of ethylene and polypropylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene Examples of suitable resins include polyolefin resins such as ethylene-methyl methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ionomer resins, heat-sealable ethylene-vinyl alcohol resins, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, and cyclic olefin copolymers; acid-modified polyolefin resins obtained by modifying polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid; polyvinyl acetate resins; poly(meth)acrylic resins; and polyvinyl chloride resins. Among these, low-density polyethylene, linear low-density polyethylene, and polypropylene are preferred. These resins may be used alone or in combination. The sealant layer may be a film or sheet of the above resin, or a coating film thereof.

[0142] When polyethylene is used as the material constituting the sealant layer 21, in addition to ethylene obtained from fossil fuels, polymerized ethylene derived from biomass may also be used as the raw material. Examples of biomass-derived ethylene that can be used include those described in JP 2012-251006 A. By using polyethylene obtained by polymerizing biomass-derived ethylene as the material constituting the sealant layer, a layer made of a carbon-neutral material can be formed. Therefore, by using polyethylene obtained by polymerizing biomass-derived ethylene in combination with the gas-derived polyester described above, the amount of fossil fuel used can be further reduced significantly, thereby reducing the environmental impact.

[0143] As the polyethylene obtained by polymerizing biomass-derived ethylene, a commercially available product may be used, for example, a sugarcane-derived linear low-density polyethylene resin "C4LL-LL118 (d=0.916, MFR=1.0 g / 10 min)" manufactured by Braskem.

[0144] 4 and 5, the laminate 20 has one sealant layer, but two or more sealant layers may be provided. When two or more sealant layers are provided, the respective sealant layers may have the same composition or different compositions.

[0145] The thickness of the sealant layer is preferably 20 μm or more, more preferably 30 μm or more, and is preferably 200 μm or less, more preferably 130 μm or less.

[0146] Examples of methods for laminating a sealant layer on one side of the laminate (e.g., the inner surface when made into a packaging bag) include dry lamination and melt extrusion lamination. Furthermore, when carrying out the lamination, the film may be subjected to pretreatment such as corona treatment, ozone treatment, and flame treatment, as needed. Among these, dry lamination is more preferred because it provides excellent adhesive strength.

[0147] Furthermore, the laminate according to the present disclosure is not limited to a configuration including only a laminate film and a sealant layer, and as long as it includes these layers, the laminate may include at least one other layer in addition to the laminate film and sealant layer. For example, as shown in Fig. 5, a laminate 20 may include a support 33 on the surface of the laminate film 15 opposite to the surface on which the sealant layer 21 is laminated.

[0148] [Support] The support is not particularly limited and can be formed using any known material, such as an oriented polyester resin layer, an oriented polyamide resin layer, an oriented polyolefin resin layer, or a paper layer (paper substrate), as long as it can support the laminate and improve the strength characteristics and impact resistance of the laminate. Furthermore, a biomass-derived material may also be used as the support. Furthermore, the support can be formed using one of these layers alone or in combination of two or more layers.

[0149] The stretched polyester resin layer that can be used as the support can be a conventionally known fossil fuel-derived polyester, a biomass-derived polyester, or a gas-derived polyester. The stretched polyester resin layer may also be a layer made of a mixture of a resin material containing a conventional fossil fuel-derived raw material and a resin material containing a biomass-derived raw material.

[0150] To improve adhesion, a dicarboxylic acid component containing a sulfonic acid group may be used. Examples of sulfonic acid group-containing dicarboxylic acids include metal sulfonate-containing dicarboxylic acids. Examples of metal sulfonate-containing dicarboxylic acids include metal salts (alkali metal salts, alkaline earth metal salts, etc.) of sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5-[4-sulfophenoxy]isophthalic acid. In particular, from the viewpoint of achieving 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 mol % or more and 10 mol % or less based on the total acid components. Furthermore, the intrinsic viscosity is preferably 0.3 dL / g or more and 0.8 dL / g or less.

[0151] Depending on the intended use of the package including the laminate of the present disclosure, various polyester resins can be used for the stretched polyester resin layer, and a mixture of two or more polyester resins may also be used. For example, when polyester is used, a support having excellent thermal dimensional stability, aroma retention, and heat resistance can be obtained. Furthermore, when a sulfonic acid group-containing polyester is used, a coextruded film having high interlayer adhesive strength can be obtained.

[0152] The stretched polyester resin layer may contain various additives such as a lubricant, if necessary.

[0153] The stretched polyamide resin layer usable as the support may be primarily made of aliphatic polyamide, but may also contain other polyamide components, such as aromatic polyamides. Examples of aliphatic polyamides that can be used include aliphatic polyamides obtained by polycondensation of aliphatic or alicyclic diamines such as hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, and bis(p-aminocyclohexylmethane) with dicarboxylic acids or derivatives thereof such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid; polyamide resins obtained by condensation of ε-aminocaproic acid, 11-aminoundecanoic acid, and the like; polyamide resins obtained from lactam compounds such as ε-caprolactam and ω-laurolactam; and mixtures thereof. Specifically, aliphatic polyamide resins such as polyamide 6, polyamide 6,6, polyamide 9, polyamide 11, polyamide 12, polyamide 6 / 66, polyamide 66 / 610, and MXD6 can be used. Among these, preferred aliphatic polyamides include polyamide 6, polyamide 6,6, and polyamide 6 / 6,6. Examples of two or more aliphatic polyamides include a combination of polyamide 6 and polyamide 6 / 6,6 in any ratio.

[0154] Examples of stretched polyolefin resin layers that can be used as the support include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), ethylene-α-olefin copolymers polymerized using a metallocene catalyst, and random or block copolymers of ethylene and polypropylene. Of these, stretched polypropylene resin layers using polypropylene are preferred.

[0155] When a stretched polyester resin layer or a stretched polyamide resin layer is used as the support, a modified polyolefin resin layer made of a modified polyolefin may be provided between the support and the sealant layer to improve adhesion between the support and the sealant layer. Modified polyolefin is a polyolefin resin modified by substituting a part of the main component polyolefin with another substance (monomer) by copolymerization or co-condensation, or by locally reacting an appropriate substance (monomer). Examples of such resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-α-olefin copolymers polymerized using a metallocene catalyst, polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ionomer resins, ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-propylene copolymer, methylpentene polymer, polyethylene, polyethylene-based resins, and acid-modified polyolefin-based resins such as polyolefin-based resins modified with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids. It goes without saying that the above-mentioned polyethylene-based resins can also be those using the above-mentioned biomass-derived ethylene as a monomer unit.

[0156] Preferred modified polyolefins are copolymers having a structure in which polyolefin segments and polar non-olefin segments are bonded in a block, graft, and / or random manner, such as copolymers of propylene-based polyolefin segments and segments containing lactic acid as constituent components, copolymers of ethylene-based polyolefin segments and segments containing acrylic acid units as constituent components, copolymers of propylene-based polyolefin segments and segments containing acrylic acid units as constituent components, etc. Specifically, examples of maleic anhydride-modified polyolefin resins that can be used include Admer SE800, SF740, SF731, and SF730 manufactured by Mitsui Chemicals, Inc.

[0157] In addition to the above, commercially available polylactic acid films may also be used as biomass-derived materials for the support. For example, polylactic acid films sold by Mitsui Chemicals Tohcello Co., Ltd. can be suitably used.

[0158] Furthermore, as a paper layer (paper substrate) that can be used as a support, any paper can be used depending on the desired rigidity, etc., and known papers such as high-quality paper, construction paper, art paper, coated paper, pure white roll paper, kraft paper, label paper with enhanced water resistance, paperboard such as cup base paper, card paper, ivory paper, and manila cardboard, milk carton base paper, cup base paper, synthetic paper, and clay-coated paper can be used.

[0159] The thickness of the above-mentioned stretched polyester resin layer or the like serving as a support may be adjusted appropriately depending on the intended use of the laminate. For example, when the laminate is used as a packaging material for an application requiring rigidity, a thick support can be used.

[0160] Furthermore, by forming the support using a resin material containing raw materials derived from biomass, the support becomes a layer made of a carbon-neutral resin. By forming a laminate with a base layer and a support made of a layer made of a carbon-neutral resin, it is possible to manufacture a laminate having two or more layers containing a carbon-neutral resin. This allows for a significant reduction in the amount of fossil fuel used to form the support, thereby reducing the environmental burden.

[0161] The method for forming the support is not particularly limited and may be a conventionally known method. The support may be formed by extrusion lamination of these materials, or may be formed in advance as a film by a T-die method, an inflation method, or the like, and then laminated on the printing layer by dry lamination, or the like.

[0162] [Print layer] A printed layer can be provided as needed, for example, between the laminated film and the support. The printed layer is a layer on which any printed pattern such as letters, pictures, figures, symbols, designs, etc. is formed for decoration, indication of contents, indication of expiration date, indication of manufacturer, seller, etc. The printed layer may be provided on the entire surface or on a part of the surface.

[0163] The printing layer can be formed using conventionally known pigments or dyes, and an ink composition can be used which contains one or more ordinary ink vehicles as the main component, optionally containing one or more additives such as plasticizers, stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, and fillers as needed, and further containing a colorant such as a dye or pigment, and which is thoroughly kneaded with a solvent, diluent, etc.

[0164] The ink vehicle may be one or more of known ones, such as linseed oil, tung oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin-modified resin, shellac, alkyd resin, phenolic resin, maleic acid resin, natural 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, melamine resin, aminoalkyd resin, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc.

[0165] The method for forming the printed layer is not particularly limited, and can be, for example, a conventional printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. Using such a method for forming a printed layer, the ink composition can be printed onto the outer surface side of the support in a desired pattern to form a printed layer.

[0166] The thickness of the printed layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, and is preferably 8 μm or less, more preferably 5 μm or less.

[0167] The printing layer is preferably formed after a surface treatment has been previously performed on the side of the support on which the printing layer is to be formed. Such surface treatments include pretreatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, and oxidation treatment using chemicals. Alternatively, the surface may be treated in advance by optionally applying a primer coating agent, undercoating agent, anchor coating agent, or the like.

[0168] [Metal foil] The metal foil is obtained by rolling a metal such as aluminum foil, copper foil, etc. By including a metal foil in the laminate, the gas barrier properties can be further improved.

[0169] The metal constituting the metal foil is not particularly limited, and examples thereof include aluminum, copper, magnesium, and the like.

[0170] The thickness of the metal foil is preferably 3 μm or more, more preferably 5 μm or more, and is preferably 50 μm or less, more preferably 10 μm or less. By making the thickness of the metal foil 3 μm or more, the gas barrier property can be further improved.

[0171] The metal foil can be laminated on any layer via an adhesive resin layer, which will be described later.

[0172] [Adhesive layer] The adhesive layer used when bonding two layers by dry lamination can be formed by applying an adhesive used for lamination (laminating adhesive) to the surface of the layer to be laminated and drying it. Examples of laminating adhesives that can be used include one-component or two-component curing or non-curing vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, and rubber adhesives, including solvent-based, water-based, and emulsion-based adhesives. The laminating adhesive can be applied to the coating surface of the layer constituting the laminate by, for example, direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, Fountain coating, transfer roll coating, or other methods. The thickness of the adhesive layer is preferably 0.5 μm or more, more preferably 1 μm or more. This ensures sufficient adhesive strength. Furthermore, the thickness of the adhesive layer is preferably 10 μm or less, more preferably 5 μm or less. This reduces the likelihood of misalignment during lamination.

[0173] [Adhesive resin layer] The adhesive resin layer provided when bonding two layers by melt extrusion lamination is formed by melt extrusion lamination using a thermoplastic resin. The thermoplastic resin that can be used for the adhesive resin layer is a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, or a copolymer resin, modified resin, or mixture (including alloy) containing these resins as the main component. Examples of polyolefin resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), ethylene-α-olefin copolymers polymerized using a metallocene catalyst, random or block copolymers of ethylene and polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, and ionomer resins. To improve interlayer adhesion, acid-modified polyolefin resins obtained by modifying the above polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid can also be used. Furthermore, resins obtained by graft-polymerizing or copolymerizing unsaturated carboxylic acids, unsaturated carboxylic anhydrides, and ester monomers onto polyolefin resins can also be used. These materials can be used alone or in combination of two or more. Examples of cyclic polyolefin-based resins that can be used include cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbornene. These resins can be used alone or in combination of two or more. It goes without saying that the polyethylene-based resins mentioned above can be those that use the above-mentioned biomass-derived ethylene as a monomer unit.

[0174] Various plastic compounding agents and additives can be added to the adhesive resin layer as needed, for example, to improve or modify the film's processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, release properties, flame retardancy, mildew resistance, electrical properties, strength, etc., and the amount added can be any amount ranging from a trace amount to several tens of percent depending on the purpose. Common additives that can be used in the above include, for example, lubricants, plasticizers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, UV absorbers, light stabilizers, colorants (dyes, pigments, etc.), and even modifying resins can be used.

[0175] The thickness of the adhesive resin layer can be set appropriately, and is preferably 5 μm or more, more preferably 10 μm or more, and is preferably 800 μm or less, more preferably 500 μm or less. If the thickness is less than the lower limit, the moisture barrier properties will be insufficient, and if it is more than the upper limit, the quality will be excessive and moldability will also be reduced. The adhesive resin layer may have a single layer structure or a multi-layer structure.

[0176] In addition, when a polyolefin resin having a polar group, such as the acid-modified polyolefin resin described above, is used as the adhesive resin layer and the adhesive resin layer is laminated on the base material layer 10 by a melt extrusion lamination method, the adhesive resin layer can be laminated without performing surface treatment such as an anchor coating agent.

[0177] As such, the laminate according to the present disclosure comprises a base layer and a sealant layer, and the base layer is formed from a layer made of a carbon-neutral material and is highly hygienic. Therefore, by using the base layer in the laminate, it is possible to reduce the amount of fossil fuel used for the entire laminate, thereby achieving a laminate that is highly effective in reducing CO2 emissions and is highly hygienic.

[0178] Furthermore, one or both surfaces of the laminate may be subjected to secondary processing for the purpose of imparting surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, biocompatibility, etc. Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, surface treatments (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.), etc. Furthermore, the laminate may be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-processing processes to produce packages, etc. In particular, as described above, the laminate according to the present disclosure aims to reduce the amount of fossil fuel used, has a high effect in reducing CO2 emissions, and has excellent gas barrier properties, and is therefore useful as a packaging material for food and the like, and can be suitably used, for example, as a packaging film for packaging bodies. [Example]

[0179] The present disclosure will be described in more detail below using examples, but the present disclosure is not limited to the following examples.

[0180] [Preparation of polyester film A] We prepared pellets (intrinsic viscosity: 0.61 dL / g) of polyethylene terephthalate (PET) using ethylene glycol derived from carbon monoxide gas as the diol unit and terephthalic acid derived from fossil fuels as the dicarboxylic acid unit. Hereinafter, these pellets will also be referred to as pellet A. After drying, pellets A were fed to an extruder, melted at 260°C, extruded into a sheet form from a T-die, and cooled and solidified by a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was held in an 88°C environment for 1 minute, and then stretched simultaneously in the machine direction and transverse direction at a stretching rate of 100 mm / min to a stretching ratio of 3.6 times in area. In this way, a polyester film A having a thickness of 12 μm was obtained.

[0181] [Preparation of polyester film B] We prepared pellets (intrinsic viscosity: 0.65 dL / g) of polyethylene terephthalate (PET) using ethylene glycol derived from carbon monoxide gas as the diol unit and terephthalic acid derived from fossil fuels as the dicarboxylic acid unit. Hereinafter, these pellets will also be referred to as pellet B. A polyester film B having a thickness of 12 μm was obtained in the same manner as in the polyester film A, except that pellets B were used instead of pellets A.

[0182] [Preparation of polyester film C] Pellets (intrinsic viscosity: 0.61 dL / g) made of polyethylene terephthalate (PET) were prepared using fossil fuel-derived ethylene glycol as the diol unit and fossil fuel-derived terephthalic acid as the dicarboxylic acid unit. These pellets are hereinafter also referred to as pellets C. A polyester film C having a thickness of 12 μm was obtained in the same manner as in the polyester film A, except that pellets C were used instead of pellets A.

[0183] [Preparation of polyester film D] Pellets (intrinsic viscosity: 0.65 dL / g) made of polyethylene terephthalate (PET) were prepared using fossil fuel-derived ethylene glycol as the diol unit and fossil fuel-derived terephthalic acid as the dicarboxylic acid unit. These pellets are hereinafter also referred to as pellets D. A polyester film D having a thickness of 12 μm was obtained in the same manner as in the polyester film A, except that pellets D were used instead of pellets A.

[0184] [Haze measurement] A test piece measuring 50 mm long x 50 mm wide was cut out from each of the polyester films A to D. The haze of each test piece was measured using a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.) under an environment of a temperature of 23°C and a relative humidity of 50% RH. The measurement was performed in accordance with JIS K7136:2000. The smaller the haze, the more transparent the polyester film. The results are shown in Table 1.

[0185] [Measurement of tensile strength and tensile elongation] For each of the polyester films A to D, test specimens measuring 200 mm in the machine direction (MD) and 15 mm in the transverse direction (TD) were cut out. The tensile strength and tensile elongation in the machine direction were measured for each test specimen using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.) at a temperature of 23°C and a relative humidity of 50% RH. The test was performed at a pulling speed of 300 mm / min. Further, test pieces measuring 15 mm in the longitudinal direction and 200 mm in the transverse direction were cut out, and the tensile strength and tensile elongation in the transverse direction of each test piece were measured in the same manner as above. The results are shown in Table 1.

[0186] [Measurement of carbon dioxide and water molecule content] Four test pieces measuring 10 mm long x 3 mm wide were cut out from each of the polyester films A to D. The total mass of the four test pieces was approximately 35 mg. Thermal desorption spectrometry-mass spectrometry (TDS-MS) was performed under the following conditions to measure the content of carbon dioxide molecules and water molecules in the polyester film. The results are shown in Table 1. (Measurement conditions) ·Device name: Denshi Kagaku EMD-WA1000S / W type Four specimens were heated on the SiC stage. Ionization method: Electron Ionization (EI) Measurement mode: SCAN mode Measurement mass range (m / z): 1 to 200 ·Heating conditions: 50℃~100℃ Heating rate: 10℃ / min Holding temperature and holding time: 100°C for 30 minutes

[0187] [Table 1]

[0188] As is clear from Table 1 above, polyester films A and B, although made from polyesters containing ethylene glycol as a diol unit derived from carbon monoxide gas, exhibit physical properties comparable in transparency and mechanical properties to films made from conventional polyesters containing ethylene glycol as a diol unit derived from fossil fuels. Furthermore, it was found that films made from polyesters containing ethylene glycol as a diol unit, which is derived from carbon monoxide gas, contained more carbon dioxide molecules and water molecules than films made from polyesters containing ethylene glycol as a diol unit derived from fossil fuels.

[0189] [Example 1-1] An aluminum vapor-deposited film having a thickness of 450 Å was formed on one surface of the polyester film A serving as the base layer, to obtain a laminated film of Example 1-1. The vapor-deposited film formation conditions were as follows. (Formation conditions) Vapor deposition source: Aluminum Vacuum level in deposition chamber: 2×10 -3 mbar Vacuum level in the winding chamber: 3 x 10 -2 mbar Film conveying speed: 350m / min

[0190] [Example 1-2] A hydroxyl group-containing (meth)acrylic resin (number average molecular weight 25,000, glass transition temperature 99°C, hydroxyl value 80 mg KOHL / g) was diluted with a mixed solvent of methyl ketone and ethyl acetate (mixing ratio 1:1) to a solids concentration of 10 mass % to prepare the base resin. An ethyl acetate solution containing tolylene diisocyanate (solid content 75% by mass) was added to the base resin as a curing agent to obtain a solution for forming a surface coating layer. The amount of the curing agent used was 10 parts by mass per 100 parts by mass of the base resin. The solution for forming the surface coating layer prepared as described above was applied to one side of the polyester film B serving as the base layer, and dried to form a surface coating layer having a thickness of 0.5 μm. An aluminum vapor-deposited film having a thickness of 450 Å was formed on the surface coating layer, to obtain a laminated film of Example 1-2. The vapor-deposited film formation conditions were the same as those in Example 1-1.

[0191] [Comparative Example 1-1] A laminated film of Comparative Example 1-1 was obtained in the same manner as in Example 1-1, except that Polyester Film C was used instead of Polyester Film A.

[0192] [Comparative Example 1-2] A laminated film of Comparative Example 1-2 was obtained in the same manner as in Example 1-1, except that Polyester Film D was used instead of Polyester Film B.

[0193] [Oxygen permeability measurement] Test pieces were obtained by cutting out the laminated films of Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2. The test pieces were set in an oxygen permeability measuring device (product name: OX-TRAN2 / 20, manufactured by MOCON) so that the substrate layer side of the test piece was the oxygen supply side. The oxygen permeability (unit: cc / m) was measured in accordance with JIS K 7126-2:2006 (constant pressure method) under an environment of a temperature of 23°C and a relative humidity of 90%. 2 ·day·atm) was measured.

[0194] [Water vapor permeability measurement] Test pieces were obtained by cutting out the laminated films of Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2. The test pieces were set in a water vapor transmission rate measuring device (product name: PERMATRAN-w 3 / 33, manufactured by MOCON) so that the substrate layer side of the test piece was the water vapor supply side. The water vapor transmission rate (unit: g / m) was measured in accordance with JIS K 7129:2008 (Method B) under an environment of a temperature of 40°C and a relative humidity of 90%. 2 ·day) was measured.

[0195] The results are shown in Table 2 together with the layer structures of the laminated films of Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2.

[0196] [Table 2]

[0197] As is clear from Table 2 above, Examples 1-1 and 1-2, which are laminate films using polyesters whose diol units are ethylene glycol derived from carbon monoxide gas, have equivalent oxygen permeability and water vapor permeability to Comparative Examples 1-1 and 1-2, which are laminate films using conventional polyesters whose diol units are ethylene glycol derived from fossil fuels, and therefore exhibit comparable physical properties in terms of gas barrier properties.

[0198] [Example 2-1] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polypropylene film (product name: P2161, thickness 20 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, the printed layer-forming surface of the biaxially oriented polypropylene film and the vapor-deposited film-forming surface of the laminated film of Example 1-1 were sandwich-laminated via a 15 μm thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). The substrate layer surface of the laminate thus obtained was sandwich laminated with an unstretched polypropylene film (product name: TAF513, thickness 18 μm, manufactured by Okamoto Corporation) via a 15 μm thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). In this way, a laminate of Example 2-1 was obtained, in which the support, printed layer, adhesive resin layer, vapor-deposited film, base material layer, adhesive resin layer and sealant layer were laminated in this order. The primary use of the laminate of Example 2-1 is as a snack packaging bag.

[0199] [Example 2-2] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polypropylene film (product name: P2161, thickness 20 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ester adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the layer was attached to the surface of the laminated film of Example 1-1 on which the vapor-deposited film had been formed. Next, an ester adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the laminated film, and a linear low-density polyethylene film (product name: MTNST, thickness 60 μm, manufactured by Futamura Chemical Co., Ltd.) was attached to the substrate layer. In this way, a laminate of Example 2-2 was obtained in which the support, printed layer, adhesive layer, vapor-deposited film, base layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 2-2, the thickness of each adhesive layer was 3 μm. The main use of the laminate of Example 2-2 is as a sprinkle wrapper.

[0200] [Example 2-3] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (product name: E5102, thickness 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the layer was attached to the surface of the laminated film of Example 1-1 on which the vapor-deposited film had been formed. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the laminated film, and a linear low-density polyethylene film (product name: MTNST, thickness 60 μm, manufactured by Futamura Chemical Co., Ltd.) was attached to the substrate layer. In this way, a laminate of Example 2-3 was obtained, in which the support, printed layer, adhesive layer, vapor-deposited film, base layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 2-3, the thickness of each adhesive layer was 3 μm. The main application of the laminate of Example 2-3 is a coffee bag.

[0201] [Example 2-4] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (product name: E5102, thickness 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the layer was attached to the surface of the laminated film of Example 1-1 on which the vapor-deposited film had been formed. The substrate layer surface of the laminate thus obtained was sandwich laminated with a high-density polyethylene film (product name: HD (white), milky white, thickness 60 μm, manufactured by Dai Nippon Printing Co., Ltd.) via a 20 μm-thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). The high-density polyethylene film side of the laminate thus obtained was sandwich-laminated with aluminum foil (10 μm thick, manufactured by Toyo Aluminum Co., Ltd.) via a 20 μm thick adhesive resin layer formed by melt-extrusion of ethylene-methacrylic acid copolymer (trade name: N0908C, manufactured by Dow Mitsui Polychemicals Co., Ltd.). The aluminum foil surface of the laminate thus obtained was sandwich-laminated with a linear low-density polyethylene film (product name: L-100N, thickness: 50 μm, manufactured by Aicello Co., Ltd.) via a 35 μm-thick adhesive resin layer formed by melt-extrusion of an ethylene-methacrylic acid copolymer (product name: N0908C, manufactured by Dow Mitsui Polychemicals Co., Ltd.). An adhesive resin layer was formed on the surface of the biaxially stretched polyethylene terephthalate film of the laminate thus obtained by melt-extruding low-density polyethylene (product name: CE4009, manufactured by Sumitomo Chemical Co., Ltd.) to a thickness of 20 μm, and a sealant layer was formed on the surface of this adhesive resin layer by melt-extruding low-density polyethylene (product name: LC602A, manufactured by Japan Polyethylene Co., Ltd.) to a thickness of 30 μm. In this way, a laminate of Example 2-4 was obtained, in which a sealant layer, adhesive resin layer, support, printed layer, adhesive layer, vapor-deposited film, base material layer, adhesive resin layer, support, adhesive resin layer, metal foil, adhesive resin layer, and sealant layer were laminated in this order. The main application of the laminates of Examples 2-4 is laminate tubes.

[0202] [Example 2-5] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (product name: E5102, thickness 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, the printed layer-forming surface of the biaxially stretched polyethylene terephthalate film and the vapor-deposited film-forming surface of the laminated film of Example 1-1 were sandwich-laminated via a 15 μm thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). The substrate layer surface of the laminate thus obtained was sandwich laminated with a linear low-density polyethylene film (product name: MTNST, thickness 40 μm, manufactured by Futamura Chemical Co., Ltd.) via a 15 μm thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). In this way, a laminate of Example 2-5 was obtained in which the support, printed layer, adhesive resin layer, vapor-deposited film, base material layer, adhesive resin layer and sealant layer were laminated in this order. The main use of the laminates of Examples 2-5 is as a sprinkle bag or a coffee bag.

[0203] [Example 2-6] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially oriented nylon film (product name: N1102, thickness: 15 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the layer was attached to the surface of the laminated film of Example 1-1 on which the vapor-deposited film had been formed. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the laminated film, and a linear low-density polyethylene film (product name: MTNST, thickness 40 μm, manufactured by Futamura Chemical Co., Ltd.) was attached to the substrate layer. In this way, the laminate of Example 2-6 was obtained, in which the support, printed layer, adhesive layer, vapor-deposited film, base layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 2-6, the thickness of the adhesive layer was 3 μm in all cases. The main use of the laminates of Examples 2-6 is as refill containers.

[0204] [Example 2-7] A laminate of Example 2-7 was obtained in the same manner as in Example 2-5, except that an unstretched polypropylene film (product name: RS512, thickness 30 μm, manufactured by Idemitsu Unitech Co., Ltd.) was used instead of the linear low-density polyethylene film. The main application of the laminates of Examples 2-7 is individual coffee packaging.

[0205] [Example 2-8] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (product name: E5102, thickness 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the layer was bonded to the surface of the laminated film of Example 1-1 on which the vapor-deposited film was formed. The thickness of the adhesive layer formed by bonding was 3 μm. Next, a solvent-free ether-based adhesive (product name: A246A / A248B, manufactured by Mitsui Chemicals, Inc.) was applied to the substrate layer of the laminated film, and it was then bonded to a linear low-density polyethylene film (product name: MTNST, thickness 40 μm, manufactured by Futamura Chemical Co., Ltd.) The adhesive layer formed by bonding had a thickness of 1 μm. In this way, a laminate of Example 2-8 was obtained, in which the support, printed layer, adhesive layer, vapor-deposited film, base material layer, adhesive layer and sealant layer were laminated in this order. The main application of the laminates of Examples 2-8 is individual coffee packaging.

[0206] [Example 2-9] A laminate of Example 2-9 was obtained in the same manner as in Example 2-3, except that an unstretched polypropylene film (product name: GLC, thickness 60 μm, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was used instead of the linear low-density polyethylene film. The main application of the laminates of Examples 2-9 is individual coffee packaging.

[0207] [Laminate strength measurement] For each of the laminates of Examples 2-1 to 2-3 and 2-5 to 2-9, the lamination strength between the laminate film and the support was measured in accordance with JIS Z 0238:1998. Specifically, the laminate was cut into a rectangular shape so that the transverse length of the base layer constituting the laminate film was 15 mm and the machine direction length of the base layer constituting the laminate film was greater than the transverse length, yielding a test specimen. The laminate film and the support were partially peeled off from the resulting test specimen. The laminate film and the support of the test specimen were clamped and held in the chucks of a tensile tester (trade name: Tensilon STA-1150, manufactured by A&D Co., Ltd.). The test specimen was then pulled 10 mm in the vertical direction at 50 mm / min using a T-peel tester, and the average tensile strength was measured. The same operation was tried 10 times, and the average of the 10 measured values ​​was taken as the lamination strength (unit: N / 15 mm width) between the laminated film and the support. For the laminate of Example 2-4, the lamination strength between the laminate film and the biaxially stretched polyethylene terephthalate film was measured in the same manner. The results are shown in Table 3 together with the layer structures and main uses of the laminates of Examples 2-1 to 2-9.

[0208] [Table 3]

[0209] As is clear from the above Examples 2-1 to 2-9, it is possible to produce a laminate from a laminate film using a polyester in which ethylene glycol is used as a diol unit and carbon monoxide gas is used as a raw material. Furthermore, the laminate strength measured for the laminates of Examples 2-1 to 2-9 was equivalent to the laminate strength measured for laminates using conventional polyesters in which fossil fuel-derived ethylene glycol was used as the diol unit, and it was found that the laminates of Examples 2-1 to 2-9 exhibited physical properties that were comparable in terms of mechanical properties.

[0210] [Example 3-1] Using a continuous vapor deposition film-forming device that had a pretreatment section with an oxygen plasma pretreatment device installed and a film-forming section separated from each other, the substrate layer polyester film A was applied to one side of the substrate layer. In the pretreatment section, tension was applied to the substrate layer by roll-to-roll movement, and plasma was introduced from a plasma supply nozzle under the following conditions to perform oxygen plasma pretreatment. In the continuously transported film-forming section, a 12 nm thick aluminum oxide vapor deposition film was formed (PVD method) on the oxygen plasma-treated surface using a reactive resistance heating method as the heating means for the vacuum vapor deposition method under the following conditions, thereby obtaining the laminated film of Example 3-1. (Formation conditions) (Oxygen plasma pretreatment conditions) Plasma intensity: 200W·sec / m 2 Plasma formation gas ratio: oxygen:argon = 2:1 Voltage applied between pretreatment drum and plasma supply nozzle: 340V (Film formation conditions) Conveying speed: 400m / min Oxygen gas supply: 20,000 sccm

[0211] [Example 3-2] The solution for forming a surface coating layer prepared in the same manner as in Example 1-2 was applied to one surface of the polyester film A serving as the base layer and dried to form a surface coating layer having a thickness of 0.5 μm. An aluminum oxide vapor-deposited film having a thickness of 12 nm was formed on the surface coating layer, to obtain a laminated film of Example 3-2. The vapor-deposited film formation conditions were the same as those in Example 3-1.

[0212] [Example 3-3] A hydrolysis liquid consisting of ethyl silicate, a silane coupling agent, isopropyl alcohol, hydrochloric acid, and ion-exchanged water (composition b) was added to a mixed liquid consisting of polyvinyl alcohol, isopropyl alcohol, and ion-exchanged water (composition a) prepared according to the composition table shown below, and the mixture was stirred to obtain a colorless and transparent barrier coating liquid. Composition table a Polyvinyl alcohol 2.30 Isopropyl alcohol 2.70 Wednesday 51.20 b Ethyl silicate 16.60 Silane coupling agent 0.20 Isopropyl alcohol 3.90 0.5N hydrochloric acid solution 0.50 Wednesday 22.60 Total 100.00(wt%) The barrier coating liquid (gas barrier composition) prepared as described above was coated onto the aluminum oxide vapor deposition film of the laminated film of Example 3-1, and the film was heat-treated at a drying temperature of 180°C and a line speed of 100 m / min to form a gas barrier coating film with a thickness of 0.3 μm (in a dry state), thereby obtaining the laminated film of Example 3-3.

[0213] [Example 3-4] A barrier coating liquid prepared in the same manner as in Example 3-3 was coated onto the aluminum oxide vapor-deposited film of the laminated film of Example 3-2, and the film was heat-treated at a drying temperature of 180°C and a line speed of 100 m / min to form a gas barrier coating film with a thickness of 0.3 μm (in a dry state), thereby obtaining the laminated film of Example 3-4.

[0214] [Examples 3-5] A silicon oxide vapor deposition film having a thickness of 20 nm was formed on one side of the polyester film A serving as the substrate layer using an induction heating vacuum deposition apparatus equipped with a plasma gun in a roll-to-roll manner while applying tension to the substrate (PVD method), to obtain the laminated film of Example 3-5. The vapor deposition film formation conditions were as follows: (Formation conditions) (Plasma irradiation conditions) Line speed: 30m / min ·Vacuum degree: 1.7×10 -2 Pa Output: 5.7kw Acceleration voltage: 151V Ar gas flow rate: 7.5 sccm (Film formation conditions) Deposition material: SiO Reactive gas: O2 Reaction gas flow rate: 100sccm

[0215] [Examples 3-6] The solution for forming a surface coating layer prepared in the same manner as in Example 1-2 was applied to one surface of the polyester film A serving as the base layer and dried to form a surface coating layer having a thickness of 0.5 μm. A silicon oxide vapor-deposited film having a thickness of 20 nm was formed on the surface coating layer, to obtain a laminated film of Example 3-6. The vapor-deposited film formation conditions were the same as those in Example 3-5.

[0216] [Examples 3-7] A barrier coating liquid prepared in the same manner as in Example 3-3 was coated onto the silicon oxide vapor-deposited film of the laminated film of Example 3-5, and the film was heat-treated at a drying temperature of 180°C and a line speed of 100 m / min to form a gas barrier coating film with a thickness of 0.3 μm (in a dry state), thereby obtaining the laminated film of Example 3-7.

[0217] [Examples 3-8] A barrier coating liquid prepared in the same manner as in Example 3-3 was coated onto the silicon oxide vapor-deposited film of the laminated film of Example 3-6, and the film was heat-treated at a drying temperature of 180°C and a line speed of 100 m / min to form a gas barrier coating film with a thickness of 0.3 μm (in a dry state), thereby obtaining the laminated film of Example 3-8.

[0218] [Comparative Example 3-1] A laminated film of Comparative Example 3-1 was obtained in the same manner as in Example 3-1, except that Polyester Film C was used instead of Polyester Film A.

[0219] [Comparative Example 3-2] A laminated film of Comparative Example 3-2 was obtained in the same manner as in Example 3-2, except that Polyester Film C was used instead of Polyester Film A.

[0220] [Comparative Example 3-3] A laminated film of Comparative Example 3-3 was obtained in the same manner as in Example 3-3, except that Polyester Film C was used instead of Polyester Film A.

[0221] [Comparative Example 3-4] A laminated film of Comparative Example 3-4 was obtained in the same manner as in Example 3-4, except that Polyester Film C was used instead of Polyester Film A.

[0222] [Comparative Example 3-5] A laminated film of Comparative Example 3-5 was obtained in the same manner as in Example 3-5, except that Polyester Film C was used instead of Polyester Film A.

[0223] [Comparative Example 3-6] A laminated film of Comparative Example 3-6 was obtained in the same manner as in Example 3-6, except that Polyester Film C was used instead of Polyester Film A.

[0224] [Comparative Example 3-7] A laminated film of Comparative Example 3-7 was obtained in the same manner as in Example 3-7, except that Polyester Film C was used instead of Polyester Film A.

[0225] [Comparative Example 3-8] A laminated film of Comparative Example 3-8 was obtained in the same manner as in Example 3-8, except that Polyester Film C was used instead of Polyester Film A.

[0226] [Oxygen permeability measurement] Test pieces were obtained by cutting out the laminated films of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-8. The test pieces were set in an oxygen permeability measuring device (product name: OX-TRAN2 / 20, manufactured by MOCON) so that the substrate layer side of the test piece was the oxygen supply side. The oxygen permeability (unit: cc / m) was measured in accordance with JIS K 7126-2:2006 (constant pressure method) under an environment of a temperature of 23°C and a relative humidity of 90%. 2 ·day·atm) was measured.

[0227] [Water vapor permeability measurement] Test pieces were obtained by cutting out the laminated films of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-8. The test pieces were set in a water vapor transmission rate measuring device (product name: PERMATRAN-w 3 / 33, manufactured by MOCON) so that the substrate layer side of the test piece was the water vapor supply side. The water vapor transmission rate (unit: g / m) was measured in accordance with JIS K 7129:2008 (Method B) under an environment of a temperature of 40°C and a relative humidity of 90%. 2 ·day) was measured.

[0228] The results are shown in Tables 4 and 5 together with the layer structures of the laminated films of Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-8.

[0229] [Table 4]

[0230] [Table 5]

[0231] As is clear from Tables 4 and 5 above, Examples 3-1 to 3-8, which are laminated films using polyesters whose diol units are ethylene glycol derived from carbon monoxide gas, have equivalent oxygen permeability and water vapor permeability to Comparative Examples 3-1 to 3-8, which are laminated films using conventional polyesters whose diol units are ethylene glycol derived from fossil fuels, and therefore exhibit comparable physical properties in terms of gas barrier properties.

[0232] [Example 4-1] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (product name: E5202, thickness 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, the printed layer-forming surface of the biaxially stretched polyethylene terephthalate film and a low-density polyethylene film (product name: DNW-20 Blue, milky white, thickness 100 μm, manufactured by Dai Nippon Printing Co., Ltd.) were sandwich laminated together via a 25 μm thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Nippon Polyethylene Co., Ltd.). Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the low-density polyethylene film, and the film was bonded to the surface of the laminated film of Example 3-1 on which the vapor-deposited film had been formed. The thickness of the adhesive layer formed by bonding was 3 μm. The substrate layer surface of the laminate thus obtained was sandwich laminated with a linear low-density polyethylene film (product name: SP100AS, thickness 80 μm, manufactured by Dai Nippon Printing Co., Ltd.) via a 25 μm thick adhesive resin layer formed by melt extrusion of an ethylene-methacrylic acid copolymer (product name: N0908C, manufactured by Dow Mitsui Polychemicals Co., Ltd.). The biaxially stretched polyethylene terephthalate film side of the laminate thus obtained was sandwich laminated with a linear low-density polyethylene film (product name: L-100N, thickness 80 μm, manufactured by Aicello Co., Ltd.) via a 25 μm thick adhesive resin layer formed by melt extrusion of low-density polyethylene (product name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). In this way, a laminate of Example 4-1 was obtained, in which a sealant layer, an adhesive resin layer, a support, a printed layer, an adhesive resin layer, a support, an adhesive layer, a vapor-deposited film, a base layer, an adhesive resin layer, and a sealant layer were laminated in this order. The main application of the laminate of Example 4-1 is a laminate tube.

[0233] [Example 4-2] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to the vapor-deposited film-formed surface of the laminated film of Example 3-1 to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and a biaxially oriented nylon film (product name: N1202, thickness 15 μm, manufactured by Toyobo Co., Ltd.) was attached to it. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied to the biaxially oriented nylon film, and the film was then bonded to a linear low-density polyethylene film (product name: EP-7R, thickness 60 μm, manufactured by Dai Nippon Printing Co., Ltd.). In this way, a laminate of Example 4-2 was obtained, in which the substrate layer, vapor-deposited film, printed layer, adhesive layer, support, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 4-2, the thickness of each adhesive layer was 3 μm. The main application of the laminate of Example 4-2 is as a refill container.

[0234] [Example 4-3] The laminate of Example 4-3 was obtained in the same manner as in Example 4-2, except that an unstretched polypropylene film (product name: ZK207, thickness 60 μm, manufactured by Toray Film Processing Co., Ltd.) was used instead of the linear low-density polyethylene film. The primary use of the laminate of Example 4-3 is in microwave packaging.

[0235] [Example 4-4] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to the vapor-deposited film-formed surface of the laminated film of Example 3-1 to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and a biaxially oriented polypropylene film (product name: P2161, thickness 20 μm, manufactured by Toyobo Co., Ltd.) was attached to it. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied to the base layer of the laminated film, and a linear low-density polyethylene film (product name: MTNST, thickness 40 μm, manufactured by Futamura Chemical Co., Ltd.) was attached to the base layer. In this way, a laminate of Example 4-4 was obtained in which the support, adhesive layer, printed layer, vapor-deposited film, base layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 4-4, the thickness of each adhesive layer was 3 μm. The primary use of the laminate of Example 4-4 is as a deep-draw lid.

[0236] [Examples 4-5] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to the vapor-deposited film-formed surface of the laminated film of Example 3-1 to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, an ether-based adhesive (product name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and then it was laminated with a linear low-density polyethylene film (product name: MTNST, thickness: 40 μm, manufactured by Futamura Chemical Co., Ltd.) The adhesive layer formed by lamination was 3 μm thick. In this way, a laminate of Example 4-5 was obtained in which the substrate layer, the vapor-deposited film, the printed layer, the adhesive layer, and the sealant layer were laminated in this order. The main use of the laminate of Example 4-5 is for packaging wet tissues or pickles.

[0237] [Examples 4-6] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polypropylene film (product name: P2161, thickness 20 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the layer was bonded to the surface of the laminated film of Example 3-1 on which the vapor-deposited film was formed. The thickness of the adhesive layer formed by bonding was 3 μm. A low-density polyethylene (product name: LC600A, manufactured by Nippon Polyethylene Co., Ltd.) and a linear low-density polyethylene (product name: 15100C, manufactured by Prime Polymer Co., Ltd.) were co-extruded onto the substrate layer surface of the laminate obtained in this manner to form an adhesive resin layer having a thickness of 15 μm and a sealant layer having a thickness of 30 μm. In this way, the laminates of Examples 4-6 were obtained, in which the support, printed layer, adhesive layer, vapor-deposited film, base material layer, adhesive resin layer and sealant layer were laminated in this order. The main use of the laminates of Examples 4-6 is for packaging dried bonito flakes.

[0238] [Examples 4-7] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to the vapor-deposited film-formed surface of the laminated film of Example 3-1 to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied to the printed layer, and a low-density polyethylene film (product name: SR-WN2 White, milky white, thickness 130 μm, manufactured by Dai Nippon Printing Co., Ltd.) was attached to it. Next, an ester adhesive (product name: RU-004 / H-1, manufactured by Rock Paint Co., Ltd.) was applied to the base layer of the laminated film, and it was then bonded to a low-density polyethylene film (product name: SR-WN2AS, thickness 130 μm, manufactured by Dai Nippon Printing Co., Ltd.). In this way, the laminate of Example 4-7 was obtained, in which the sealant layer, adhesive layer, substrate layer, vapor-deposited film, printed layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 4-7, the thickness of the adhesive layer was 3 μm in each case. The main application of the laminates of Examples 4 to 7 is laminate tubes.

[0239] [Examples 4-8] The laminate of Example 4-8 was obtained in the same manner as in Example 4-3, except that a biaxially oriented polyethylene terephthalate film (product name: E5202, thickness 12 μm, manufactured by Toyobo Co., Ltd.) was used instead of the biaxially oriented nylon film, and a 70 μm thick unstretched polypropylene film was used. The primary use of the laminates of Examples 4-8 is in microwave packaging.

[0240] [Examples 4-9] Two sheets of the laminated film of Example 3-1 were prepared. A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied to the vapor-deposited film surface of the first laminate film by gravure roll coating to form a printed layer. The thickness of the printed layer when dried was 1 μm. Next, an ester adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied onto the printed layer, and the printed layer was then bonded to the surface of the second laminated film on which the vapor-deposited film had been formed. Next, an ester adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the second laminated film, and a linear low-density polyethylene film (product name: XMTN, thickness 80 μm, manufactured by Futamura Chemical Co., Ltd.) was attached to the substrate layer. In this way, the laminate of Example 4-9 was obtained, in which the substrate layer, vapor-deposited film, printed layer, adhesive layer, vapor-deposited film, substrate layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 4-9, the thickness of the adhesive layer was 3 μm in all cases. The main application of the laminates of Examples 4-9 is packaging of artificial dialysis drugs.

[0241] [Examples 4-10] A laminate of Example 4-10 was obtained in the same manner as in Example 4-9, except that a biaxially stretched nylon film (product name: N1202, thickness 15 μm, manufactured by Toyobo Co., Ltd.) was used instead of the second laminate film. The primary uses for the laminates of Examples 4-10 are as refill containers, ink packaging or aerosol spray containers.

[0242] [Laminate strength measurement] For each of the laminates of Examples 4-2 to 4-4, 4-6, 4-8 and 4-10, the lamination strength between the laminate film and the support was measured in accordance with JIS Z 0238:1998. Specifically, the laminate was cut into a rectangular shape so that the transverse length of the base layer constituting the laminate film was 15 mm and the machine direction length of the base layer constituting the laminate film was greater than the transverse length, yielding a test specimen. The laminate film and the support were partially peeled off from the resulting test specimen. The laminate film and the support of the test specimen were clamped and held in the chucks of a tensile tester (trade name: Tensilon STA-1150, manufactured by A&D Co., Ltd.). The test specimen was then pulled 10 mm in the vertical direction at 50 mm / min using a T-peel tester, and the average tensile strength was measured. The same operation was tried 10 times, and the average of the 10 measured values ​​was taken as the lamination strength (unit: N / 15 mm width) between the laminated film and the support. For the laminate of Example 4-1, the lamination strength between the laminate film and a low-density polyethylene film (trade name: DNW-20 blue, milky white, thickness 100 μm, manufactured by Dai Nippon Printing Co., Ltd.) was measured in the same manner. For the laminate of Example 4-5, the lamination strength between the laminate film and a linear low-density polyethylene film (trade name: MTNST, thickness 40 μm, manufactured by Futamura Chemical Co., Ltd.) was measured in the same manner. For the laminates of Examples 4-7, the lamination strength between the laminate film and a low-density polyethylene film (product name: SR-WN2 White, milky white, thickness 130 μm, manufactured by Dai Nippon Printing Co., Ltd.) was similarly measured. For the laminates of Examples 4-9, the lamination strength between the two laminated films was similarly measured. Table 6 shows the results together with the layer structures and main uses of the laminates of Examples 4-1 to 4-10.

[0243] [Table 6]

[0244] As is clear from the above Examples 4-1 to 4-10, it is possible to produce a laminate from a laminate film using a polyester in which ethylene glycol is used as a diol unit and carbon monoxide gas is used as a raw material. Furthermore, the laminate strength measured for the laminates of Examples 4-1 to 4-10 was equivalent to the laminate strength measured for laminates using conventional polyesters in which fossil fuel-derived ethylene glycol was used as the diol unit, indicating that the laminates of Examples 4-1 to 4-10 exhibit comparable physical properties in terms of mechanical properties. [Explanation of symbols]

[0245] 10 Base material layer 11 Vapor-deposited film 12 Gas barrier coating film 13 Surface coating layer 15 Laminated film 20 laminate 21 Sealant layer 33 Support

Claims

1. A laminated film comprising at least a substrate layer and a vapor-deposited film, the substrate layer contains a polyester composed of a diol unit and a dicarboxylic acid unit, the diol unit contains ethylene glycol produced from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide; The laminated film, wherein the vapor-deposited film is a vapor-deposited film of a metal or a metal oxide.

2. The laminate film according to claim 1, wherein the dicarboxylic acid unit comprises at least one selected from the group consisting of terephthalic acid derived from fossil fuels, terephthalic acid derived from biomass, and terephthalic acid derived from carbon dioxide gas.

3. The content of carbon dioxide molecules in the substrate layer is 1.1 × 10 １８ pieces / g or more 3.0×10 １８ The laminated film according to claim 1 or 2, wherein the number of particles per gram is not more than 1 / g.

4. The content of water molecules in the base layer is 8.6 × 10 １９ pieces / g or more 2.5×10 ２０ The laminated film according to claim 1 or 2, wherein the number of particles per gram is not more than 1 / g.

5. a surface coating layer is further provided between the substrate layer and the vapor-deposited film, The laminated film according to claim 1 or 2, wherein the surface coating layer contains a resin material having a polar group.

6. the substrate layer, the vapor-deposited film, and the gas barrier coating film in this order; 3. The laminate film according to claim 1, wherein the gas barrier coating film contains an alkoxide and at least one water-soluble polymer selected from the group consisting of polyvinyl alcohol resins and ethylene-vinyl alcohol copolymers.

7. A laminate comprising the laminate film according to claim 1 or 2 and a sealant layer.

8. Further comprising a support; The laminate according to claim 7, wherein the support is a stretched polyester resin layer, a stretched polyamide resin layer, or a stretched polypropylene resin layer.

9. The laminate according to claim 8 , comprising the support, the base layer, the vapor-deposited film, and the sealant layer in this order.

10. A package comprising the laminate of claim 7.

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