Ethylene glycol, polyester, polyester pellets, molded article, film, fibers, fiber article, molded article, preform, polyester film, laminated film, laminate, and package

Abstract

In the present invention, ethylene glycol is obtained by using at least one gas selected from the group consisting of carbon monoxide and carbon dioxide as a raw material.

Description

Ethylene glycol, polyester, polyester pellets, moldings, films, fibers, textile products, moldings, preforms, polyester films, laminated films, laminates and packaging materials

[0001] The present disclosure relates to ethylene glycol, polyester, polyester pellets, molded articles, films, fibers, textile products, molded articles, preforms, polyester films, laminated films, laminates, and packaging.

[0002] Ethylene glycol is widely used in various applications, such as as a raw material for polymers and as a moisturizing agent. Ethylene glycol is industrially produced from ethylene, which is obtained from petroleum, a fossil fuel. For example, ethylene oxide is produced from ethylene by the chlorohydrin method or a silver-catalyzed oxidation method, and then ethylene glycol is produced by hydrolyzing the ethylene oxide.

[0003] In recent years, with growing calls for the creation of a recycling-oriented society, there has been a desire to move away from fossil fuels in the materials field, just as there has been in the energy field. Therefore, the use of non-fossil fuel raw materials, such as biomass, has been considered. Biomass is a non-exhaustible industrial resource derived from the constituent substances of living organisms. Because the carbon contained in biomass is derived from carbon dioxide absorbed from the atmosphere through photosynthesis during the growth process of living organisms, even if carbon dioxide is emitted by burning biomass, it is thought that the overall amount of carbon dioxide in the atmosphere does not increase. Therefore, biomass has attracted attention as a carbon-neutral renewable energy source. Recently, the practical application of ethylene glycol derived from biomass has progressed rapidly, and attempts have been made to produce resins such as polyester from ethylene glycol derived from biomass (biomass ethylene glycol) (e.g., Patent Documents 1 and 2). Using biomass ethylene glycol instead of ethylene glycol produced from fossil fuel-derived raw materials can reduce fossil fuel consumption and reduce environmental impact.

[0004] Bioethanol, which is used to produce biomass ethylene glycol, can be produced by sugar fermentation from blackstrap molasses of sugarcane, a non-edible raw material. However, it is known from experience that the yield of crops such as sugarcane is significantly affected by meteorological factors. Therefore, there are concerns that climate change will make it difficult to stably procure sugarcane, the raw material for bioethanol. To address these concerns, organic compounds such as ethanol have been produced from resources that are neither fossil fuels nor biomass. For example, ethanol has been produced by microbial fermentation using carbon monoxide, which is present in exhaust gases from steel mills and factories (see, for example, Patent Document 3). Carbon dioxide has also been reduced using an electrolytic cell to produce hydrocarbons such as ethane and ethylene (see, for example, Patent Document 4). Using these organic compounds instead of organic compounds produced from fossil fuel-derived raw materials can also reduce fossil fuel consumption and reduce environmental impact.

[0005] JP 2011-527348 A JP 2012-519748 A JP 2011-512869 A JP 2012-112001 A

[0006] Therefore, an object of the present disclosure is to provide ethylene glycol, which can reduce the environmental impact, produced from carbon monoxide gas or carbon dioxide gas through microbial fermentation or reduction using an electrolytic cell. Another object of the present disclosure is to provide a polyester using the ethylene glycol. Another object of the present disclosure is to provide polyester pellets containing the polyester. Another object of the present disclosure is to provide a molded article of the polyester. Another object of the present disclosure is to provide a preform used in producing the molded article. Another object of the present disclosure is to provide a polyester film containing the polyester. Another object of the present disclosure is to provide a laminate including the polyester film and a packaging product including the laminate. Another object of the present disclosure is to provide a laminate film having a base layer containing the polyester. Another object of the present disclosure is to provide a laminate including the laminate film and a packaging product including the laminate.

[0007] The present inventors have found that ethylene glycol can be produced from ethanol produced by microbial fermentation using carbon monoxide gas as a raw material. The present inventors have also found that ethylene glycol can be produced by reducing carbon dioxide gas by electrolysis. The present disclosure was completed based on these findings and through further investigation.

[0008] The present disclosure solves the problems described above by the following embodiments: <1> Ethylene glycol produced from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide. <2> A method for producing ethylene glycol using a gas containing at least one carbon dioxide molecule in an amount of 2.2×10 １８ pieces / g or more 1.5×10 １９<1> The ethylene glycol according to <1>, having an intrinsic viscosity of 0.50 dL / g or more and 0.90 dL / g or less. <3> The ethylene glycol according to <1> or <2>, having a Kjeldahl nitrogen content of 700 μg / g or less. <4> A polyester comprising diol units and dicarboxylic acid units, wherein the diol units are the ethylene glycol according to any one of <1> to <3>. <5> The polyester according to <4>, wherein the dicarboxylic acid units are 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. <6> Polyester pellets comprising the polyester according to <4> or <5>, having an intrinsic viscosity of 0.50 dL / g or more and 0.90 dL / g or less. <7> The polyester pellets according to <6>, having a Kjeldahl nitrogen content of 260 μg / g or less. <8> The polyester pellets according to <6>, having a carbon dioxide molecule content of 4.8 x 10 １７ pieces / g or more 3.0×10 １８ <9> The polyester pellet according to <6> or <7>, wherein the water molecule content is 1.8×10 / g or less. １９ pieces / g or more 1.0×10 ２０The polyester pellets according to any one of <6> to <8>, wherein the number of particles / g or less is 1. <10> A molded article using the polyester pellets according to any one of <6> to <9>. <11> A film using the polyester pellets according to any one of <6> to <9>. <12> A fiber using the polyester pellets according to <6>. <13> The fiber according to <12>, wherein the polyester pellets have a heat of fusion of 8 J / g or more during a second heating cycle, as measured by differential scanning calorimetry (DSC) in accordance with JIS K7122:2012. <14> The fiber according to <12> or <13>, wherein the polyester pellets have a heat of solidification of 7 J / g or more during a second cooling cycle, as measured by differential scanning calorimetry (DSC) in accordance with JIS K7122:2012. <15> The fiber according to any one of <12> to <14>, wherein the Kjeldahl nitrogen content in the polyester pellets is 90 μg / g or less. <16> The content of hydrogen molecules in the polyester pellets is 7.5 × 10 １７ <17> A textile product using the fiber according to any one of <12> to <16>. <18> A molded article of the polyester according to <4> or <5>. <19> A polyester having a carbon dioxide molecule content of 9.2 x 10 or less. １７ pieces / g or more 3.0×10 １８ <20> The molded article according to <18> or <19>, having a Kjeldahl nitrogen content of 18 μg / g or less. <21> The molded article according to any one of <18> to <20>, which is a container. <22> A preform used for producing the molded article according to <21>. <23> A polyester film comprising the polyester according to <4> or <5>. <24> A polyester film having a carbon dioxide molecule content of 1.1 x 10 １８ pieces / g or more 3.0×10 １８ <25> The polyester film according to <23>, wherein the water molecule content is 8.6×10 / g or less. １９ pieces / g or more 2.5×10 ２０<26> A laminate comprising the polyester film according to any one of <23> to <25>. <27> A laminate film comprising at least a substrate layer and a vapor-deposited film, wherein the substrate layer contains the polyester according to <4> or <5>, and the vapor-deposited film is a vapor-deposited film of a metal or a metal oxide. <28> The content of carbon dioxide molecules in the substrate layer is 1.1 x 10 １８ pieces / g or more 3.0×10 １８ <29> The laminated film according to <27>, wherein the content of water molecules in the base layer is 8.6×10 １９ pieces / g or more 2.5×10 ２０The laminate film according to <27> or <28>, having a density of 1 / 200 or less per 1000 particles / g. <30> The laminate film according to any one of <27> to <29>, further comprising a surface coating layer between the base layer and the vapor-deposited film, wherein the surface coating layer contains a resin material having a polar group. <31> The laminate film according to any one of <27> to <30>, comprising, in this order, the base layer, the vapor-deposited film, and a gas barrier coating film, wherein 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. <32> A laminate comprising the laminate film according to any one of <27> to <31> and a sealant layer. <33> The laminate according to <32>, further comprising a support, wherein the support is a stretched polyester resin layer, a stretched polyamide resin layer, or a stretched polypropylene resin layer. <34> The laminate according to <33>, comprising, in this order, the support, the base material layer, the vapor-deposited film, and the sealant layer. <35> A laminate comprising at least the polyester film according to any one of <23> to <25> and a sealant layer. <36> The laminate according to <35>, in which the resin constituting the sealant layer is low-density polyethylene, linear low-density polyethylene, or polypropylene. <37> The laminate according to <35> or <36>, further comprising a barrier layer between the polyester film and the sealant layer. <38> The laminate according to <37>, in which the barrier layer is a metal foil. <39> A package comprising the laminate according to any one of <32> to <38>.

[0009] The present disclosure can provide ethylene glycol that can reduce environmental impact. The present disclosure can also provide a polyester using the ethylene glycol. The present disclosure can also provide polyester pellets containing the polyester. The present disclosure can also provide a molded article of the polyester. The present disclosure can also provide a preform used in producing the molded article. The present disclosure can also provide a polyester film containing the polyester. The present disclosure can also provide a laminate including the polyester film and a packaging product including the laminate. The present disclosure can also provide a laminate film including a substrate layer containing the polyester. The present disclosure can also provide a laminate including the laminate film and a packaging product including the laminate.

[0010] FIG. 1 is a schematic diagram showing the configuration of a reduction catalyst used in the production of ethylene glycol according to the present disclosure. FIG. 2 is a schematic diagram showing in detail an example of the configuration of the reduction catalyst of FIG. 1. FIG. 3 is a cross-sectional view showing the structure of a photochemical reaction cell used in the production of ethylene glycol according to the present disclosure. FIG. 4 is a cross-sectional view showing an example of the operating principle of the photochemical reaction cell of FIG. 3. FIG. 5 is a cross-sectional view showing another example of the operating principle of the photochemical reaction cell of FIG. 3. FIG. 6 is a perspective view showing the structure of a chemical reaction device used in the production of ethylene glycol according to the present disclosure. FIG. 7 is a cross-sectional view showing another example of the structure of a chemical reaction device used in the production of ethylene glycol according to the present disclosure. FIG. 8 is a cross-sectional view showing another example of the structure of a chemical reaction device used in the production of ethylene glycol according to the present disclosure. FIG. 9 is a schematic half-sectional view showing an embodiment of a preform used in the production of a molded body according to the present disclosure. FIG. 10 is a schematic half-sectional view showing an embodiment of a molded body according to the present disclosure. FIG. 11 is a perspective view showing a spoon, which is an embodiment of a molded product according to the present disclosure. FIG. 12 is a cross-sectional view showing, in simplified form, an example of the configuration of a polyester film according to the present disclosure. FIG. 13 is a cross-sectional view showing, in simplified form, an example of the configuration of a laminate including a polyester film according to the present disclosure. FIG. 14 is a perspective view showing, in simplified form, an example of a standing pouch. FIG. 1 is a cross-sectional view showing, in a simplified manner, an example of the configuration of a laminate that forms a side sheet of a standing pouch. FIG. 2 is a cross-sectional view showing, in a simplified manner, an example of another configuration of a laminate that forms a side sheet of a standing pouch. FIG. 3 is a front view showing, in a simplified manner, an example of a pillow bag. FIG. 4 is a front view showing, in a simplified manner, an example of a three-sided sealed bag. FIG. 5 is a front view showing, in a simplified manner, an example of a four-sided sealed bag. FIG. 6 is a partial cross-sectional view showing, in a simplified manner, an example of a tube container. FIG. 7 is a cross-sectional view showing, in a simplified manner, an example of the configuration of a laminate that forms the cylindrical body of a tube container. FIG. 8 is a cross-sectional view showing, in a simplified manner, an example of another configuration of a laminate that forms the cylindrical body of a tube container. FIG. 9 is a perspective view showing, in a simplified manner, an example of a liquid-carrying paper container. FIG. 10 is a cross-sectional view showing, in a simplified manner, an example of a configuration of a laminate that forms a liquid-carrying paper container. FIG. 11 is a perspective view showing, in a simplified manner, an example of a paper cup with a portion cut away. FIG. 12 is a cross-sectional view showing, in a simplified manner, an example of the configuration of a laminate that forms the body of a paper cup. FIG. 13 is an explanatory view showing, in outline, an example of a method for manufacturing a paper cup. FIG. 14 is a cross-sectional view showing, in a simplified manner, an example of the configuration of a laminate film according to the present disclosure.Fig. 1 is a cross-sectional view simply showing an example of the configuration of a laminate film according to the present disclosure; Fig. 2 is a cross-sectional view simply showing an example of the configuration of a laminate film according to the present disclosure; Fig. 3 is a cross-sectional view simply showing an example of the configuration of a laminate according to the present disclosure; Fig. 4 is a cross-sectional view simply showing an example of the configuration of a laminate according to the present disclosure.

[0011] [Ethylene glycol] In the present disclosure, "ethylene glycol" refers to pure ethylene glycol (chemical formula: HOCH ２ CH ２ The term "ethylene glycol" does not refer to ethylene glycol (represented by the general formula (III) and OH), but rather refers to a composition containing impurities (contaminant components) that are inevitably contained in ethylene glycol produced through synthesis or purification.

[0012] The ethylene glycol according to the present disclosure is produced from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide. By using the ethylene glycol according to the present disclosure instead of conventional ethylene glycol derived from fossil fuels, it is possible to reduce the amount of fossil fuel used and to alleviate the environmental burden.

[0013] The Kjeldahl nitrogen content of the ethylene glycol according to the present disclosure tends to be lower than that of conventional ethylene glycol derived from fossil fuels. For example, the Kjeldahl nitrogen content of the ethylene glycol according to the present disclosure is preferably 700 μg / g or less, more preferably 560 μg / g or less, and even more preferably 330 μg / g or less. Furthermore, the Kjeldahl nitrogen content of the ethylene glycol according to the present disclosure is 0 μg / g or more, practically 10 μg / g or more, and more practically 30 μg / g or more. In the present disclosure, Kjeldahl nitrogen refers to nitrogen quantified in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). Specific methods for measuring the Kjeldahl nitrogen content are described in the Examples below.

[0014] Furthermore, the carbon dioxide molecule content in the ethylene glycol according to the present disclosure tends to be higher than that of conventional ethylene glycol derived from fossil fuels. For example, the carbon dioxide molecule content in the ethylene glycol according to the present disclosure is 2.2 × 10 １８ It is preferable that the number of particles is 2.8×10 １８ More preferably, the number is 3.8 × 10 １８ It is more preferable that the carbon dioxide molecule content in the ethylene glycol of the present disclosure is 1.5 × 10 １９ It is preferable that the number of particles is 1.2 × 10 １９ It is more preferable that the number of particles is 1.0 × 10 １９ The carbon dioxide molecule content in ethylene glycol is measured by thermal desorption mass spectrometry (TDS-MS). Specifically, it is measured by the method described in the Examples below.

[0015] Among the ethylene glycols disclosed herein, ethylene glycol made from carbon monoxide gas as a raw material can be produced from ethanol made from carbon monoxide gas as a raw material. Below, we will explain each of ethanol made from carbon monoxide gas as a raw material, ethylene glycol made from carbon monoxide gas as a raw material, and ethylene glycol made from carbon dioxide gas as a raw material.

[0016] [Ethanol from Carbon Monoxide Gas] Ethanol from carbon monoxide gas can be obtained by microbial fermentation. Hereinafter, a method for producing ethanol from carbon monoxide gas by microbial fermentation will be described.

[0017] <Microbial Fermentation> 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. Note that the feed gas may contain carbon dioxide, nitrogen, oxygen, etc. in addition to carbon monoxide.

[0018] The fermenter is preferably a continuous fermentation apparatus, and may be any of a stirring type, airlift type, bubble column type, loop type, open bond type, and photobio type. The raw material gas and culture solution may be continuously supplied to the fermenter, but it is not necessary to supply the raw material gas and culture solution simultaneously; 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 via a sparger or the like.

[0019] 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.

[0020] 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 are not killed, and ethanol is efficiently produced by contacting the raw material gas with the microorganisms. The temperature of the fermenter is more preferably 38° C. or less, and in order to enhance the activity of the microorganisms, it is preferably 10° C. or more, more preferably 20° C. or more, and even more preferably 30° C. or more.

[0021] 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-assimilating bacteria. Among gas-assimilating bacteria, the genus Clostridium is preferred, and Clostridium autoethanogenum is more preferred, from the viewpoints of gas assimilation ability and culture stability. Examples are provided in more detail below.

[0022] Gas-assimilating bacteria include both eubacteria and archaea. Examples of eubacteria include bacteria of the genus Clostridium, Moorella, Acetobacterium, Carboxydocella, Rhodopseudomonas, Eubacterium, Butyribacterium, Oligotropha, Bradyrhizobium, and aerobic hydrogen-oxidizing bacteria of the genus Larsotonia.

[0023] 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.

[0024] 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.

[0025] It is preferable to select and use bacteria with high ethanol production ability from among the above-mentioned gas-utilizing bacteria, such as Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans, Moorella thermoacetica, and Acetobacterium woodii.

[0026] 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.

[0027] 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 using 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, all of the liquid component containing the target ethanol may be evaporated, or the liquid component may be partially evaporated so that the target ethanol is preferentially evaporated.

[0028] 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 large amounts of ethanol to be purified to high purity through a simple operation. When performing distillation, a known distillation apparatus such as a distillation column may be used. Furthermore, the distillation is performed, for example, such 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 (e.g., 70% by mass or more, preferably 90% by mass or more). By operating in this manner, the target product, ethanol, and water can be largely separated.

[0029] 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 higher and 150 kPa or lower (gauge pressure). Setting the pressure inside the distillation apparatus within the above range can improve the ethanol separation efficiency and increase the ethanol yield.

[0030] [Ethylene Glycol Using Carbon Monoxide Gas as a Raw Material] 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, ethanol obtained as described above is heated in the presence of a catalyst to produce ethylene through an intramolecular dehydration reaction. Next, ethylene is oxidized using a silver catalyst in a gas-phase catalytic reaction of ethylene to produce a gas containing ethylene oxide. It is known that the gas-phase catalytic reaction of ethylene produces not only ethylene oxide but also small amounts of organic acids such as formic acid and acetic acid, and aldehyde compounds such as formaldehyde and acetaldehyde as by-products. Therefore, the gas produced by the gas-phase catalytic reaction of ethylene contains organic acids and aldehyde compounds in addition to ethylene oxide. The produced gas is washed with water, and the ethylene oxide is absorbed into the water and separated from the produced gas. The resulting aqueous ethylene oxide solution is supplied to a distillation column to strip the ethylene oxide, and a high-concentration aqueous ethylene oxide solution is recovered as the overhead distillate.

[0031] The high-concentration aqueous ethylene oxide solution is then sent to a reactor. The reaction to produce ethylene glycol from ethylene oxide is typically carried out at a reaction temperature of 150°C to 180°C and a reaction pressure of 2.5 MPa or less. The amount of water in the aqueous ethylene oxide solution is appropriately adjusted. In general, it is preferable to use an ethylene oxide concentration of 9% by mass to 13% by mass. The water content of the produced aqueous ethylene glycol solution is removed in a dehydration tower or the like.

[0032] Next, vacuum distillation is performed to fractionate ethylene glycol from diethylene glycol, triethylene glycol, etc., to obtain ethylene glycol from carbon monoxide gas. A vacuum distillation column is used for vacuum distillation. The temperature during fractional distillation of ethylene glycol is preferably 125°C or higher, more preferably 135°C or higher, and preferably 225°C or lower, more preferably 195°C or lower. The pressure during fractional distillation of ethylene glycol is preferably 10 hPa or higher, more preferably 15 hPa or higher, and preferably 550 hPa or lower, more preferably 79 hPa or lower. Within the above temperature and pressure ranges, ethylene glycol can be efficiently purified by fractional distillation.

[0033] [Ethylene glycol produced from carbon dioxide gas] Ethylene glycol produced from carbon dioxide gas can be obtained by electrolysis using a chemical reaction device that uses a specific reduction catalyst. First, the reduction catalyst will be described.

[0034] <Reduction Catalyst> The reduction catalyst comprises a current collector having a metal layer on its surface, and an organic molecule bound to the surface of the metal layer and containing a quaternary nitrogen cation, represented by any one of the following general formulas I to V:

[0035]

[0036] In general formulas I to V, R １ is a primary, secondary or tertiary amino group. ２ and R ３ may be the same or different and each independently represents H or a primary, secondary or tertiary amino group. p, q, r and n each independently represents an integer of 1 to 12. Y is a reactive functional group, and X － indicates a counter anion.

[0037] A reduction catalyst according to a first embodiment will be described below with reference to FIGS. 1 and 2. FIG. 1 is a diagram showing the configuration of the reduction catalyst 1, and FIG. 2 is a diagram showing an example of the configuration of the reduction catalyst 1 in detail. As shown in FIG. 1, the reduction catalyst 1 includes a current collector 101 and organic molecules 112 containing quaternary nitrogen cations. The current collector 101 has a metal layer 102 on its surface. The organic molecules 112 containing quaternary nitrogen cations are bonded to the metal layer 102 to form a monolayer (self-assembled monolayer: SAM). Hereinafter, the organic molecules containing quaternary nitrogen cations will be referred to as modified organic molecules.

[0038] The current collector 101 is made of an electrically conductive material and may be, for example, a stainless steel substrate.

[0039] The metal layer 102 on the surface of the current collector 101 contains at least one metal selected from the group consisting of Au, Ag, Cu, Zn, Pt, Fe, Ti, Ni, Sn, In, and Bi. The metal layer 102 may contain components other than metals, but is preferably made of metal only. The metal layer 102 and the current collector 101 may be made of the same material. In this case, the metal constituting the metal layer 102 may also serve as the current collector 101.

[0040] The metal contained in the metal layer 102 functions as a catalyst that activates the reduction reaction. In order to improve catalytic activity, the metal contained in the metal layer 102 is preferably in the form of fine particles.

[0041] The average particle size of the metal microparticles contained in the metal layer 102 is preferably 1 nm or more and 300 nm or less. If the average particle size is 300 nm or less, the catalytic activity efficiency can be increased. Furthermore, it is difficult to manufacture metal microparticles with an average particle size of less than 1 nm. It is more preferable that the average particle size of the metal microparticles is 150 nm or less, as this further improves the catalytic activity efficiency. The metal microparticles may be primary particles with an average particle size of 50 nm or less, or may be secondary particles formed by agglomeration of such primary particles.

[0042] The modified organic molecule 112 has a skeleton 110 containing a quaternary nitrogen cation, a reactive functional group 109 located at one end, and an amino group 111 located at the other end. The quaternary nitrogen cation contained in the modified organic molecule 112 is at least one cation selected from an alkylammonium cation, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, and an imidazolium cation. As described below, the quaternary nitrogen cation is preferably an imidazolium cation because of its high effect of improving reduction activity.

[0043] The skeleton 110 is composed of a quaternary nitrogen cation and an alkyl group that is a substituent of the cation. The number of carbon atoms in the alkyl group corresponds to p, q, r, and n in general formulas I to V, and each is independently an integer of 1 to 12. In general formulas I to V, when p, q, r, and n are 1 to 12, the quaternary nitrogen cation and the amino group, and the quaternary nitrogen cation and the metal layer 102 are not too far apart, and as will be described later, the quaternary nitrogen cation can have the effect of improving the reduction efficiency. It is more preferable that p, q, r, and n are integers of 2 to 6.

[0044] The reactive functional group 109 corresponds to Y in the general formulae I to V. The reactive functional group 109 has affinity for the metal layer 102 and chemically bonds to the metal layer 102. This immobilizes the modified organic molecule 112 to the metal layer 102. The reactive functional group 109 is preferably a functional group capable of forming a covalent bond with the metal layer 102, and is preferably selected from, for example, a thiol group, a disulfide group, and a thiocyanate group. A thiol group is more preferable because of its excellent bonding strength.

[0045] The amino group 111 is R in general formulas I to V. １ and optionally R ２ and R ３ The amino group 111 may be a primary, secondary, or tertiary amino group. When the amino group is a secondary or tertiary amino group, its substituents may be one or two C １ ~C １２Preferably, the alkyl group has the carbon atoms of 12 or less. When the alkyl group has 12 or less carbon atoms, the distance between the quaternary nitrogen cation and the amino group is not too great, and as will be described later, the amino group can have the effect of improving the reduction efficiency. More preferably, the alkyl group has 2 or more and 6 or less carbon atoms. The amino group 111 may form a salt with hydrofluoric acid, hydrochloric acid, hydrobromic acid, iodic acid, sulfuric acid, nitric acid, phosphoric acid, or the like.

[0046] The modified organic molecule 112 is a group represented by the general formulas I to V, where X － Specifically, it forms an ammonium salt, a piperidinium salt, a pyrrolidinium salt, a pyridinium salt, or an imidazolium salt. Note that the counter anion is omitted in Figure 1. In Figure 2, a bromide ion is shown as the counter anion.

[0047] Counter anions include, but are not limited to, fluoride ions, chloride ions, bromide ions, iodide ions, HCO ３ － , B.F. ４ － , P.F. ６ － , C.F. ３ COO － , C.F. ３ SO ３ － , NO ３ － , SCN － , N (CN) ２ － , C(CN) ３ － (CF ３ SO ２ ) ３ C － , bis(trifluoromethoxysulfonyl)imide anion, bis(trifluoromethoxysulfonyl)imide anion, bis(perfluoroethylsulfonyl)imide anion, and the like.

[0048] Examples of the modified organic molecule 112 include the following molecules: 1-(2-mercaptoethyl)-3-aminomethylimidazolium bromide, 1-(3-mercaptopropyl)-3-aminomethylimidazolium bromide, 1-(4-mercaptobutyl)-3-aminomethylimidazolium bromide, 1-(5-mercaptopentyl)-3-aminomethylimidazolium bromide, 1-(6-mercaptohexyl)-3-aminomethylimidazolium bromide, imidazolium bromide, 1-(8-mercaptooctyl)-3-aminomethylimidazolium bromide, 1-(9-mercaptononyl)-3-aminomethylimidazolium bromide, 1-(10-mercaptodecyl)-3-aminomethylimidazolium bromide, 1-(11-mercaptoundecyl)-3-aminomethylimidazolium bromide, 1-(12-mercaptododecyl)-3-aminomethylimidazolium bromide, 1-(2-mercaptoethyl)-3-(2-aminoethyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(3-aminopropyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(4-aminobutyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(5-aminopentyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(6-aminohexyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(8-aminooctyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(9-aminononyl)imidazolium bromide imidazolium bromide, 1-(2-mercaptoethyl)-3-(10-aminodecyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(11-aminoundecyl)imidazolium bromide, 1-(2-mercaptoethyl)-3-(12-aminododecyl)imidazolium bromide, 1-(4-mercaptobutyl)-3-(2-methylaminoethyl)imidazolium bromide, 1-(6-mercaptohexyl)-3-(3-dimethylaminopropyl)imidazolium bromide, 1-(8-mercaptohexyl)-3-(4-ethylmethylaminobutyl)imidazolium bromide,1-(2-mercaptoethyl)-4-aminomethylpyridinium bromide, 1-(3-mercaptopropyl)-4-aminomethylpyridinium bromide, 1-(4-mercaptobutyl)-4-aminomethylpyridinium bromide, 1-(5-mercaptopentyl)-4-aminomethylpyridinium bromide, 1-(6-mercaptohexyl)-4-aminomethylpyridinium bromide, 1-(8-mercaptooctyl)-4-aminomethylpyridinium bromide 1-(9-mercaptononyl)-4-aminomethylpyridinium bromide, 1-(10-mercaptodecyl)-4-aminomethylpyridinium bromide, 1-(11-mercaptoundecyl)-4-aminomethylpyridinium bromide, 1-(12-mercaptododecyl)-4-aminomethylpyridinium bromide, 1-(2-mercaptoethyl)-4-(2- 1-(2-mercaptoethyl)-4-(3-aminopropyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(4-aminobutyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(5-aminopentyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(6-aminohexyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(6-aminohexyl)pyridinium bromide 1-(2-mercaptoethyl)-4-(8-aminooctyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(9-aminononyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(10-aminodecyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(11-aminoundecyl)pyridinium bromide, 1-(2-mercaptoethyl)-4-(12-aminododecyl)pyridinium bromide, 1-(5-mercaptopentyl)-4-(3-methylaminopropyl)pyridinium bromide, 1-(9-mercaptononyl)-4-(4-dimethylaminobutyl)pyridinium bromide, 1-(11-mercaptoundecyl)-4-(6-ethylmethylaminohexyl)pyridinium bromide,1-(2-mercaptoethyl)-1-aminomethylpyrrolidinium bromide, 1-(3-mercaptopropyl)-1-aminomethylpyrrolidinium bromide, 1-(4-mercaptobutyl)-1-aminomethylpyrrolidinium bromide, 1-(5-mercaptopentyl)-1-aminomethylpyrrolidinium bromide, 1-(6-mercaptohexyl)-1-aminomethylpyrrolidinium bromide, 1-(8-mercaptooctyl)-1-aminomethylpyrrolidinium bromide , 1-(9-mercaptononyl)-1-aminomethylpyrrolidinium bromide, 1-(10-mercaptodecyl)-1-aminomethylpyrrolidinium bromide, 1-(11-mercaptoundecyl)-1-aminomethylpyrrolidinium bromide, 1-(12-mercaptododecyl)-1-aminomethylpyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(2-aminoethyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(3-aminopropyl ) pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(4-aminobutyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(6-aminohexyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(8-aminooctyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(9-aminononyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(10-aminodecyl)pyrrolidinium bromide, 1- (2-mercaptoethyl)-1-(11-aminoundecyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(12-aminododecyl)pyrrolidinium bromide, 1-(2-mercaptoethyl)-1-(4-methylaminobutyl)pyrrolidinium bromide, 1-(3-mercaptopropyl)-1-(8-dimethylaminooctyl)pyrrolidinium bromide, 1-(4-mercaptobutyl)-1-(9-ethylmethylaminononyl)pyrrolidinium bromide,1-(2-mercaptoethyl)-1-aminomethylpiperidinium bromide, 1-(3-mercaptopropyl)-1-aminomethylpiperidinium bromide, 1-(4-mercaptobutyl)-1-aminomethylpiperidinium bromide, 1-(5-mercaptopentyl)-1-aminomethylpiperidinium bromide, 1-(6-mercaptohexyl)-1-aminomethylpiperidinium bromide, 1-(8-mercaptooctyl)-1-aminomethylpiperidinium bromide, 1-(9-mercaptononyl)-1-aminomethylpiperidinium bromide, 1-(10-mercaptodecyl)-1-aminomethylpiperidinium bromide, 1-(11-mercaptoundecyl)-1-aminomethylpiperidinium bromide, 1-(12-mercaptododecyl)-1-aminomethylpiperidinium bromide, 1-(2-mercaptoethyl)-1-(2-aminoethyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(3-aminopropyl)piperidine 1-(2-mercaptoethyl)-1-(4-aminobutyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(6-aminohexyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(8-aminooctyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(9-aminononyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(10-aminodecyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(11-aminodecyl)piperidinium bromide 1-(2-mercaptoethyl)-1-(11-aminoundecyl)piperidinium bromide, 1-(2-mercaptoethyl)-1-(12-aminododecyl)piperidinium bromide, 1-(10-mercaptodecyl)-1-(9-methylaminononyl)piperidinium bromide, 1-(11-mercaptoundecyl)-1-(10-dimethylaminodecyl)piperidinium bromide, 1-(12-mercaptododecyl)-1-(12-ethylmethylaminododecyl)piperidinium bromide,2-mercaptoethyl-(aminomethyl)dimethylammonium bromide, 3-mercaptopropyl-(aminomethyl)dimethylammonium bromide, 4-mercaptobutyl-(aminomethyl)dimethylammonium bromide, 5-mercaptopentyl-(aminomethyl)dimethylammonium bromide, 6-mercaptohexyl-(aminomethyl)dimethylammonium bromide, 8-mercaptooctyl-(aminomethyl)dimethylammonium bromide, 9-mercaptononyl-(aminomethyl)dimethylammonium bromide, 10-mercaptodecyl-(aminomethyl)dimethylammonium bromide, 11-mercaptoundecyl-(aminomethyl)dimethylammonium bromide, 12-mercaptododecyl-(aminomethyl)dimethylammonium bromide, 2-mercaptoethyl-(3-aminopropyl)dimethylammonium bromide, 2-mercaptoethyl-(4-aminobutyl)dimethylammonium bromide, 2-mercaptoethyl-(5-aminopentyl)dimethylammonium bromide, 2-mercaptoethyl-(6-aminohexyl)dimethylammonium bromide, 2-mercaptoethyl-(8-aminooctyl)dimethylammonium bromide, 2-mercaptoethyl-(9-aminononyl)dimethylammonium bromide, 2-mercaptoethyl-(10-aminodecyl)dimethylammonium bromide, 2-mercaptoethyl-(11-aminoundecyl)dimethylammonium bromide, 2-mercaptoethyl-(12-aminododecyl)dimethylammonium bromide, 5-mercaptopentyl-(8-methylaminononyl)ethylmethylammonium bromide, 6-mercaptohexyl-(6-dimethylaminohexyl)methylpropylammonium bromide, and 8-mercaptooctyl-(4-ethylmethylaminobutyl)butylhexylammonium bromide.

[0049] Next, a method for manufacturing the reduction catalyst 1 will be described. First, a metal layer 102 is formed on the surface of the current collector 101. As a method for this, a known vacuum film formation method such as a sputtering method, a vapor deposition method, or an ALD (Atomic Layer Deposition) method can be used.

[0050] Next, the reactive functional groups 109 are bonded to the metal layer 102, thereby immobilizing the modified organic molecules 112 on the metal layer 102. Known methods can be used for this. For example, a method of bringing the current collector 101 provided with the metal layer 102 into contact with a solution in which the modified organic molecules 112 are dissolved, a method of evaporating the modified organic molecules 112 in a high vacuum to form a film on the surface of the current collector 101, a method of spraying the modified organic molecules 112 onto the surface of the current collector 101 by spraying, etc. can be used.

[0051] In the method using a solution in which the modified organic molecules 112 are dissolved, the modified organic molecules 112 chemically adsorbed to the metal layer 102 spontaneously form aggregates due to the van der Waals forces and hydrophobic interactions between the adsorbed molecules. The dense aggregation of the adsorbed molecules forms a monolayer with uniform orientation.

[0052] Any solvent capable of dissolving organic molecules may be used as the solvent for dissolving the modified organic molecules 112. For example, the solvent may be selected from alcohols such as ethanol, and aromatic or aliphatic organic solvents such as toluene and hexane. Ethanol is preferred because it has high solubility for the modified organic molecules 112 and is easy to handle.

[0053] An example of a method for immobilizing the modified organic molecules 112 on the metal layer 102 will be described in more detail. First, a preparation solution in which the modified organic molecules 112 are dissolved is prepared. Next, the current collector 101 on which the metal layer 102 has been formed is immersed in this preparation solution. The immersion time is set to several minutes to several hours. This allows the modified organic molecules 112 to be immobilized on the surface of the metal layer 102. Conditions such as the concentration of the modified organic molecules 112, the immersion time, and the immersion temperature can be appropriately changed depending on the structure of the modified organic molecules 112, etc. These conditions affect the state of formation of a monolayer made of the modified organic molecules 112.

[0054] If the concentration of the preparation solution is too low, it takes a long time to form a monolayer. On the other hand, if the concentration is too high, there is a risk that further molecules will be adsorbed onto the monolayer, resulting in the formation of a laminated film. Therefore, the concentration of the modified organic molecules 112 is preferably 0.1 mM or more and 100 mM or less, and more preferably 1 mM or more and 10 mM or less.

[0055] The immersion time is preferably sufficient to form a dense and uniformly oriented monolayer, and is preferably from 1 minute to 100 hours, and more preferably from 12 hours to 72 hours.

[0056] The temperature of the preparation solution during immersion affects the formation of a dense and uniformly oriented monolayer, so it is desirable that the temperature be between room temperature (25°C) and 60°C, taking into consideration the vapor pressure and boiling point of the solvent.

[0057] The immobilization of the modified organic molecules 112 on the surface of the metal layer 102 can be confirmed by a known electrochemical method or surface analysis method. As an electrochemical method, cyclic voltammetry can be used. A specific example will be described below. First, 1 mM potassium hexacyanoferrate (III) (K ３ [Fe(CN) ６ ]) or 1 mM hexaammineruthenium(III) chloride ([Ru(NH ３ ) ６ ]Cl ３ A 0.2 M potassium chloride (KCl) aqueous solution containing the modified organic molecules 112 is prepared. The electrochemical response of the current collector 101 is measured in this aqueous solution before and after the step of adsorbing the modified organic molecules 112, and the results are compared.

[0058] As an electrochemical response, a reaction current due to an electrochemical redox reaction of hexacyanoiron(III) anions or hexaammineruthenium(III) cations is measured. The reaction current for the current collector 101 to which the modified organic molecules 112 are immobilized is reduced compared to the reaction current for the current collector 101 to which the modified organic molecules 112 are not immobilized. This is because the immobilization of the modified organic molecules 112 on the metal layer 102 inhibits the redox reaction of the hexacyanoiron(III) anions or hexaammineruthenium(III) cations. In this way, by measuring the reaction current, it is possible to indirectly confirm that the modified organic molecules 112 have been immobilized.

[0059] A Fourier transform infrared spectrophotometer (FT-IR) using the reflectance method can be used as a surface analysis method. This method allows for highly sensitive measurement of the infrared spectra of the thin film and molecular adsorbed species on the surface of the current collector 101. In other words, information on the structure of the organic molecules, particularly the functional groups, can be obtained. X-ray photoelectron spectroscopy (XPS) can also be used as a surface analysis method. This method allows for measurement of the modified organic molecules 112 and, if the modified organic molecules 112 have anions, the composition of the anions. Furthermore, a contact angle meter can be used to determine the presence or absence of the modified organic molecules 112 based on differences in water wettability.

[0060] Next, as a reduction reaction in the reduction catalyst 1, CO ２ The reduction of CO is taken as an example. ２ In the elementary reaction of reduction, CO ２ is reduced to CO by a one-electron reduction reaction. ２ This reaction requires a large overvoltage. This overvoltage is an energy loss, which causes a decrease in the energy conversion efficiency. ２ Along with the reduction reaction, a side reaction of water and hydrogen ions occurs, generating hydrogen. This side reaction produces CO ２ The faradaic efficiency of the reduction reaction decreases. However, the reduction catalyst 1 can achieve a high reduction efficiency.

[0061] In the reduction catalyst 1, the quaternary nitrogen cation is CO ２ and form a reaction intermediate. ２ Therefore, the reduction catalyst 1 can convert CO with low energy. ２ This allows a reduction reaction to occur. As a result, the energy conversion efficiency of the reduction catalyst can be improved. Furthermore, the quaternary nitrogen cation has the effect of inhibiting water and hydrogen ions from approaching the metal layer 102. Therefore, the quaternary nitrogen cation can impart reaction selectivity to the reduction reaction in the metal layer 102. In other words, it is possible to suppress the generation of hydrogen due to side reactions and improve the faradaic efficiency.

[0062] The amino group of the modified organic molecule 112 is２ It reacts with the molecule to form carbonate, so there is no CO required for the reduction reaction. ２ The amino group can attract molecules and supply them to the quaternary nitrogen cations and the metal layer 102. ２ It forms salts with carboxylic acids (e.g., formic acid, acetic acid, oxalic acid, etc.) produced by reduction, which has the effect of promoting multi-electron reduction reactions in which reduction occurs continuously, thereby improving the reduction efficiency.

[0063] The reduction catalyst 1 can use carbon dioxide as a reduction raw material. The reduction product changes depending on the interaction between the quaternary nitrogen cation, the metal layer 102, and the reduction raw material. For example, when CO ２ When used, carbon monoxide (CO), formic acid (HCOOH), formaldehyde (HCHO), methanol (CH ３ OH), acetic acid (CH ３ COOH), acetaldehyde (CH ３ CHO), ethanol (CH ３ CH ２ OH), oxalic acid ((COOH) ２ ), glycolic acid (C ２ H ２ O ３ ), glycolaldehyde (C ２ H ２ O ２ ), and ethylene glycol (HOCH ２ CH ２ However, reduction catalyst 1 can produce ethylene glycol with high selectivity.

[0064] <Photochemical Reaction Cell> Next, the photochemical reaction cell provided in the chemical reaction device will be described with reference to FIGS.

[0065] The photochemical reaction cell includes an oxidation catalyst layer, a reduction catalyst layer containing a reduction catalyst, and a power supply element connected to the oxidation catalyst layer and the reduction catalyst layer. The power supply element preferably includes a semiconductor layer that separates charges using light energy, and a solar cell, for example, can be used. The semiconductor layer is preferably disposed between the oxidation catalyst layer and the reduction catalyst layer.

[0066] Fig. 3 is a cross-sectional view showing the structure of the photochemical reaction cell 30. As shown in Fig. 3, the photochemical reaction cell 30 is a laminate in which a reduction catalyst layer 20, a substrate 11, a reflective layer 12, a reduction electrode layer 13, a multi-junction solar cell 17, an oxidation electrode layer 18, and an oxidation catalyst layer 19 are laminated in this order. In the photochemical reaction cell 30, the side with the reduction catalyst layer 20 is the back surface, and the side with the oxidation catalyst layer 19 is the front surface onto which light is incident.

[0067] The substrate 11 is provided to support the photochemical reaction cell and increase its mechanical strength. The substrate 11 is made of a conductive material. For example, the substrate 11 can be made of a metal plate made of a metal selected from the group consisting of Au, Ag, Cu, Pt, Zn, Fe, Ti, Sn, In, Bi, and Ni, or an alloy plate containing at least one of these metals. An alloy plate such as SUS can be used as the alloy plate. Alternatively, the substrate 11 can be made of a conductive resin or the like. The substrate 11 can also be made of a semiconductor substrate such as Si or Ge. The substrate 11 can also be made of an ion exchange membrane.

[0068] The reflective layer 12 is formed on the surface of the substrate 11. The reflective layer 12 is made of a material capable of reflecting light. For example, the reflective layer 12 can be made of a metal layer or a distributed Bragg reflector layer made of a semiconductor multilayer film. The reflective layer 12 is disposed between the substrate 11 and the multi-junction solar cell 17. Therefore, the reflective layer 12 can reflect light that is not absorbed in the multi-junction solar cell 17 and allow it to enter the multi-junction solar cell 17 again. This can improve the light absorption rate of the multi-junction solar cell 17.

[0069] The reduction electrode layer 13 is disposed on the reflective layer 12 and is sandwiched between the reflective layer 12 and an n-type semiconductor layer (an n-type amorphous silicon layer 14a described later) of the multi-junction solar cell 17. Therefore, the reduction electrode layer 13 is preferably composed of a material capable of forming ohmic contact with the n-type semiconductor layer. The reduction electrode layer 13 may be composed of, for example, a metal such as Ag, Au, Al, or Cu, or an alloy containing at least one of these metals. Alternatively, the reduction electrode layer 13 may be composed of a transparent conductive oxide such as ITO (indium tin oxide), zinc oxide (ZnO), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), or ATO (antimony-doped tin oxide). The reduction electrode layer 13 may also have, for example, a laminated structure of a metal and a transparent conductive oxide, a composite structure of a metal and another conductive material, or a composite structure of a transparent conductive oxide and another conductive material.

[0070] The multi-junction solar cell 17 is disposed on the reduction electrode layer 13. Starting from the reduction electrode layer 13, a first solar cell 14, a second solar cell 15, and a third solar cell 16 are stacked in this order. All of these solar cells use pin junction semiconductors. The first solar cell 14, the second solar cell 15, and the third solar cell 16 each have different light absorption wavelengths. By stacking these solar cells in a planar configuration, the multi-junction solar cell 17 can absorb sunlight over a wide range of wavelengths. This allows for more efficient utilization of solar energy. Furthermore, because the solar cells are connected in series, a high open-circuit voltage can be obtained.

[0071] The first solar cell 14 comprises, in order from the reduction electrode layer 13 side, an n-type amorphous silicon (a-Si) layer 14a, an intrinsic amorphous silicon germanium (a-SiGe) layer 14b, and a p-type microcrystalline silicon (μc-Si) layer 14c. The a-SiGe layer 14b is a layer that absorbs light in the short wavelength region of about 400 nm. Therefore, in the first solar cell 14, charge separation occurs due to light energy in the short wavelength region.

[0072] The second solar cell 15 comprises, in order from the reduction electrode layer 13 side, an n-type a-Si layer 15a, an intrinsic a-SiGe layer 15b, and a p-type μc-Si layer 15c. The a-SiGe layer 15b is a layer that absorbs light in the intermediate wavelength region of about 600 nm. Therefore, in the second solar cell 15, charge separation occurs due to light energy in the intermediate wavelength region.

[0073] The third solar cell 16 includes, in order from the reduction electrode layer 13 side, an n-type a-Si layer 16a, an intrinsic a-Si layer 16b, and a p-type μc-Si layer 16c. The a-Si layer 16b is a layer that absorbs light in the long wavelength region of about 700 nm. Therefore, in the third solar cell 16, charge separation occurs due to light energy in the long wavelength region.

[0074] In the multi-junction solar cell 17, charge separation occurs due to light of each wavelength region. That is, holes are separated to the positive electrode side (front side) and electrons are separated to the negative electrode side (back side). This causes an electromotive force to be generated in the multi-junction solar cell 17.

[0075] While the multi-junction solar cell 17 described here is configured with a stacked structure of three solar cells, the present invention is not limited thereto, and a multi-junction solar cell configured with a stacked structure of two or four or more solar cells may also be used. Alternatively, a single solar cell may be used instead of the multi-junction solar cell 17. Furthermore, while the solar cell using a pin junction semiconductor has been described, a solar cell using a pn junction semiconductor may also be used. Furthermore, a semiconductor layer made of, for example, GaAs, GaInP, AlGaInP, CdTe, CuInGaSe, or the like may also be used. Furthermore, various forms such as single crystal, polycrystalline, and amorphous may be used as the semiconductor layer.

[0076] The oxide electrode layer 18 is disposed on the multi-junction solar cell 17 and is sandwiched between the p-type semiconductor layer of the multi-junction solar cell 17 and the oxidation catalyst layer 19. The oxide electrode layer 18 is preferably composed of a transparent material capable of making ohmic contact with the p-type semiconductor layer. The oxide electrode layer 18 is composed of a transparent conductive oxide such as ITO (indium tin oxide), zinc oxide (ZnO), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), or ATO (antimony-doped tin oxide). The oxide electrode layer 18 may also have, for example, a structure in which a metal and a transparent conductive oxide are stacked, a structure in which a metal and another conductive material are combined, or a structure in which a transparent conductive oxide and another conductive material are combined.

[0077] The oxidation catalyst layer 19 is disposed on the positive electrode side of the multi-junction solar cell 17 and is formed on the oxidation electrode layer 18. When the pH of the electrolyte is lower than 7 (pH<7), the oxidation catalyst layer 19 is formed by oxidation of H ２ Oxidize O ２ and H ＋ On the other hand, if the pH of the electrolyte is greater than 7 (pH>7), OH － Oxidize to O ２ and H ２ Therefore, the oxidation catalyst layer 19 is made of a material that reduces the activation energy for the oxidation reaction. ２ O or OH － It is made of a material that reduces the overvoltage that occurs when the reaction involves oxidizing and extracting electrons.

[0078] Examples of such materials include 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), and ruthenium oxide (Ru—O); ternary metal oxides such as Ni—Co—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.

[0079] The form of the oxidation catalyst layer 19 is not limited to a thin film, but may be a lattice, particle, or wire shape.

[0080] In the photochemical reaction cell 30, irradiated light passes through the oxidation catalyst layer 19 and the oxidation electrode layer 18 to reach the multi-junction solar cell 17. Therefore, the oxidation electrode layer 18 and the oxidation catalyst layer 19 arranged on the light irradiated side are optically transparent to the irradiated light. More specifically, the transmittance of the oxidation electrode layer 18 and the oxidation catalyst layer 19 on the irradiated side is at least 10% or more, and more preferably 30% or more, of the amount of irradiated light.

[0081] The reduction catalyst layer 20 is disposed on the negative electrode side of the multi-junction solar cell 17 and is formed on the back surface of the substrate 11. The reduction catalyst layer 20 is ２ The reduction catalyst layer 20 reduces the reducing raw materials such as carbon monoxide, formic acid, formaldehyde, methane, methanol, acetic acid, acetaldehyde, ethanol, ethylene glycol, etc. to generate carbon compounds. For this reason, the reduction catalyst layer 20 is made of a material that reduces the activation energy for reducing the reducing raw materials.

[0082] The reduction catalyst 1 described above is applied as such a reduction catalyst layer 20. That is, the reduction catalyst layer 20 includes a current collector 101 and organic molecules 112 containing quaternary nitrogen cations. The current collector 101 may be used as the substrate 11.

[0083] Furthermore, a conductive protective layer may be disposed on the surface of the multi-junction solar cell 17, or between the electrode layer and the catalyst layer on the light-irradiated side (between the oxidation electrode layer 18 and the oxidation catalyst layer 19 in the photochemical reaction cell 30). The protective layer prevents corrosion of the multi-junction solar cell 17 in the oxidation-reduction reaction. As a result, the life of the multi-junction solar cell 17 can be extended. The protective layer may also be optically transparent as required. Examples of the protective layer include TiO ２ , ZrO ２ , Al ２ O ３ , SiO ２ , or HfO ２ The thickness of the dielectric thin film is preferably 10 nm or less, more preferably 5 nm or less, in order to obtain conductivity by the tunnel effect.

[0084] 4 and 5 are cross-sectional views for explaining the operating principle of the photochemical reaction cell 30. In these figures, the reflective layer 12, the reduction electrode layer 13, and the oxidation electrode layer 18 are omitted.

[0085] As shown in Figures 4 and 5, when light L is incident from the front side (the oxidation electrode layer 18 side), the incident light passes through the oxidation catalyst layer 19 (and the oxidation electrode layer 18) and reaches the multi-junction solar cell 17. When the multi-junction solar cell 17 absorbs light, photoexcited electrons and their corresponding holes are generated, and then they are separated. Specifically, in each solar cell (the first solar cell 14, the second solar cell 15, and the third solar cell 16), the photoexcited electrons move to the n-type semiconductor layer side (the reduction catalyst layer 20 side), and the holes generated as pairs of the photoexcited electrons move to the p-type semiconductor layer side (the oxidation catalyst layer 19 side). That is, charge separation occurs. As a result, an electromotive force is generated in the multi-junction solar cell 17.

[0086] Photoexcited electrons generated in the multi-junction solar cell 17 are used in a reduction reaction in the reduction catalyst layer 20, which is the negative electrode. Holes are used in an oxidation reaction in the oxidation catalyst layer 19, which is the positive electrode.

[0087] An example in which the electrolyte is an acidic solution with a pH of less than 7 is shown in FIG. 4. In the vicinity of the oxidation catalyst layer 19, the reaction of the following formula (1) occurs: ２ O is oxidized to O ２ and H ＋ and electrons are generated. ＋ moves to the reduction catalyst layer 20 side via an ion migration path described later. In the vicinity of the reduction catalyst layer 20, the reaction of the following formula (2) occurs. That is, CO ２ However, the H who moved ＋ and electrons to form carbon monoxide (CO) and H ２ O is produced. ２ O → 4H ＋ +O ２ +4e － ...(1) 2CO ２ +4H ＋ +4e － → 2CO + 2H ２O 2 (2) On the other hand, an example in which the electrolyte is a basic solution with a pH greater than 7 is shown in FIG. 5. In the vicinity of the oxidation catalyst layer 19, the reaction of the following formula (3) occurs: OH － is oxidized to O ２ and H ２ O and electrons are generated. In the vicinity of the reduction catalyst layer 20, the reaction of the following formula (4) occurs: CO ２ Is H ２ It undergoes a reduction reaction that receives electrons along with O, producing carbon monoxide (CO) and OH － The OH produced on the reduction catalyst layer 20 side is － moves to the oxidation catalyst layer 19 side via an ion migration path described later. － → O ２ +2H ２ O+4e － ...(3) 2CO ２ +2H ２ O+4e － → 2CO + 4OH － ... (4) The multi-junction solar cell 17 must have an open-circuit voltage equal to or greater than the potential difference between the standard oxidation-reduction potential of the oxidation reaction occurring in the oxidation catalyst layer 19 and the standard oxidation-reduction potential of the reduction reaction occurring in the reduction catalyst layer 20. For example, when the pH of the reaction solution is 0, the standard oxidation-reduction potential of the oxidation reaction in formula (1) is +1.23 [V], and the standard oxidation-reduction potential of the reduction reaction in formula (2) is −0.1 [V]. Therefore, the open-circuit voltage of the multi-junction solar cell 17 must be 1.33 [V] or greater.

[0088] More preferably, the open-circuit voltage needs to be equal to or greater than the potential difference including the overvoltage. More specifically, for example, when the overvoltages of the oxidation reaction in formula (1) and the reduction reaction in formula (2) are each 0.2 [V], the open-circuit voltage is preferably 1.73 [V] or greater.

[0089] The reduction reactions in the above formulas (2) and (4) are ２ The reduction reaction from CO to CO is shown, but is not limited to this. ２ From HCOOH, HCHO, CH ４ , C.H. ３ OH, C ２ H５ OH, HOCH ２ CH ２ A reduction reaction to OH or the like can also occur. ＋ or OH － Therefore, H generated in the oxidation catalyst layer 19 ＋ When the OH produced in the reduction catalyst layer 20 cannot move to the reduction catalyst layer 20 of the counter electrode, － When H cannot move to the oxidation catalyst layer 19 of the counter electrode, the overall reaction efficiency decreases. ＋ Or OH － By providing an ion transfer path for transferring H ＋ Or OH － Therefore, high photoreaction efficiency can be achieved.

[0090] <Chemical Reaction Device> Next, a chemical reaction device using the above-mentioned photochemical reaction cell will be described with reference to Figures 6 to 9. Here, the oxidation-reduction reaction (the above formulas (1) and (2)) in the case of an acidic solution in which the electrolyte pH is less than 7 will be described as an example. In the case of a basic solution in which the electrolyte pH is greater than 7, the oxidation-reduction reaction according to the above formulas (3) and (4) occurs.

[0091] Fig. 6 is a perspective view showing the structure of a chemical reaction device 200 according to this embodiment. Fig. 7 is a cross-sectional view showing the structure of the chemical reaction device 200. The chemical reaction device 200 comprises a photochemical reaction cell 30, an electrolytic cell 31 that houses the photochemical reaction cell, and an electrolytic cell flow path 41 that is connected to the electrolytic cell 31 as an ion migration path. Note that the ion migration path is omitted in Fig. 6. As described above, the photochemical reaction cell 30 comprises a stack of an oxidation catalyst layer 19, a reduction catalyst layer 20, a multi-junction solar cell 17 formed therebetween, and a substrate 11.

[0092] The electrolytic bath 31 includes an oxidation reaction electrolytic bath 31a in which an oxidation catalyst layer 19 is disposed, and a reduction reaction electrolytic bath 31b in which a reduction catalyst layer 20 is disposed. In the oxidation reaction electrolytic bath 31a, H ２ O is oxidized to O ２ and H ＋In the reduction reaction electrolytic cell 31b, CO is generated by the reduction catalyst layer 20. ２ is reduced to CO and H ２ O is produced. These two electrolytic cells are separated by the substrate 11 of the photochemical reaction cell 30. In this example, the end of the substrate 11 protrudes beyond the ends of the multi-junction solar cell 17, the oxidation catalyst layer 19, and the reduction catalyst layer 20, but this is not limiting, and the substrate 11, the multi-junction solar cell 17, the oxidation catalyst layer 19, and the reduction catalyst layer 20 may be flat plates with the same area.

[0093] Separate electrolytes can be supplied to the electrolytic bath 31 a for oxidation reaction and the electrolytic bath 31 b for reduction reaction. An electrolytic bath flow path 41, which allows ions to move, connects the electrolytic bath 31 a for oxidation reaction and the electrolytic bath 31 b for reduction reaction.

[0094] In this way, with the configuration including the electrolytic cell flow path 41, H generated on the oxidation catalyst layer 19 side ＋ can be transferred to the reduction catalyst layer 20, and this H ＋ This allows carbon dioxide to be decomposed on the reduction catalyst layer 20 side, thereby achieving high photoreaction efficiency.

[0095] The electrolytic cell flow path 41 will be described in more detail. The electrolytic cell flow path 41 is provided, for example, on the side of the electrolytic cell 31. One end of the electrolytic cell flow path 41 is connected to the electrolytic cell 31a for the oxidation reaction, and the other end is connected to the electrolytic cell 31b for the reduction reaction. In other words, the electrolytic cell flow path 41 connects the electrolytic cell 31a for the oxidation reaction and the electrolytic cell 31b for the reduction reaction. This allows ions to move between the oxidation catalyst layer 19 and the reduction catalyst layer 20.

[0096] An ion exchange membrane 43 is filled in a portion of the electrolytic cell flow path 41, and only specific ions are allowed to pass through the ion exchange membrane 43. This allows only specific ions to move while separating the electrolyte between the oxidation reaction electrolytic cell 31a and the reduction reaction electrolytic cell 31b.

[0097] The ion exchange membrane 43 is a proton exchange membrane, and is used to exchange H generated in the oxidation reaction electrolytic cell 31a. ＋The proton exchange membrane may be a cation exchange membrane such as Nafion or Flemion, or an anion exchange membrane such as Neosepta or Selemion.

[0098] Instead of the ion exchange membrane 43, a material such as agar that allows ions to move and separates the electrolyte may be used. For example, a salt bridge may be used. In general, the use of a proton-exchange solid polymer membrane, such as Nafion, can improve ion migration performance.

[0099] Furthermore, a circulation mechanism 42 such as a pump may be provided in the electrolytic cell flow path 41. By promoting the circulation of the electrolyte by the circulation mechanism 42, ions (H ＋ ) can be improved. Alternatively, two electrolytic cell flow paths 41 may be provided, and a circulation mechanism 42 provided in at least one of them may be used to move ions from the electrolytic cell 31 a for the oxidation reaction to the electrolytic cell 31 b for the reduction reaction via one electrolytic cell flow path 41, and from the electrolytic cell 31 b for the reduction reaction to the electrolytic cell 31 a for the oxidation reaction via the other electrolytic cell flow path 41. Alternatively, multiple circulation mechanisms 42 may be provided. Alternatively, multiple (three or more) electrolytic cell flow paths 41 may be provided to reduce ion diffusion and circulate ions more efficiently.

[0100] By creating a liquid flow using the circulation mechanism 42, it is possible to prevent the generated gas bubbles from remaining on the electrode surface or the surface of the electrolytic cell, thereby suppressing the decrease in efficiency and light intensity distribution caused by the scattering of sunlight by the bubbles.

[0101] Furthermore, light irradiation can generate heat on the surface of the multi-junction solar cell 17. This heat can generate a temperature difference in the electrolyte, which can be used to generate convection and circulate ions more efficiently. In this case, ion migration can be promoted more than ion diffusion.

[0102] A temperature adjustment mechanism 44 for adjusting the temperature of the electrolyte may be provided in the electrolytic cell flow path 41 or the electrolytic cell 31. By controlling the temperature using the temperature adjustment mechanism 44, it is possible to control the solar cell performance and catalyst performance. For example, by making the temperature of the reaction system uniform, it is possible to stabilize and improve the performance of the solar cell and catalyst. It is also possible to prevent temperature rise for system stability. Temperature control can change the selectivity of the solar cell and catalyst, and also control the products.

[0103] The oxidation reaction electrolytic cell 31a is filled with an electrolytic solution containing an arbitrary electrolyte. The oxidation catalyst layer 19 is immersed in this electrolytic solution. The electrolytic solution is H ２ It is preferable that the catalyst promotes the oxidation reaction of O. For example, ２ A liquid containing O is used.

[0104] The reduction reaction electrolytic cell 31b is filled with an electrolytic solution. The reduction catalyst layer 20 is immersed in the electrolytic solution. The electrolytic solution is a CO ２ It reduces the reduction potential of CO ２ Absorbs CO ２ It is preferable to have an absorbent, e.g., CO ２ A liquid containing

[0105] An example of the electrolyte filling the reduction reaction electrolytic cell 31b is a solution containing a cation such as an imidazolium ion or a pyridinium ion and BF ４ － or PF ６ －Examples of the amine include ionic liquids or aqueous solutions thereof, which are composed of salts with anions such as methylamine, imidazole, or pyridine and remain in a liquid state over a wide temperature range. Furthermore, examples of the amine include solutions of amines such as ethanolamine, imidazole, or pyridine, or aqueous solutions thereof. The amine may be a primary amine, secondary amine, or tertiary amine. Examples of primary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, and hexylamine. In any of the primary amines, secondary amines, and tertiary amines, the hydrocarbon group substituting the amine may be an alcohol group or may be substituted with a halogen. Examples of these include methanolamine, ethanolamine, and chloromethylamine. The hydrocarbon group substituting the amine may have an unsaturated bond.

[0106] Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, methylethylamine, and methylpropylamine.

[0107] Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trimethanolamine, triethanolamine, tripropanolamine, tributanolamine, tripropanolamine, trihexanolamine, methyldiethylamine, and methyldipropylamine.

[0108] Ions such as imidazolium ions and pyridinium ions can be used as cations in ionic liquids. Examples of imidazolium ions include 1-ethyl-3-methylimidazolium ion, 1-methyl-3-propylimidazolium ion, 1-butyl-3-methylimidazole ion, 1-methyl-3-pentylimidazolium ion, and 1-hexyl-3-methylimidazolium ion. These imidazolium ions may be substituted at the 2-position, and examples thereof include 1-ethyl-2,3-dimethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl-2,3-dimethylimidazolium ion, 1,2-dimethyl-3-pentylimidazolium ion, and 1-hexyl-2,3-dimethylimidazolium ion. Examples of pyridinium ions include methylpyridinium, ethylpyridinium, propylpyridinium, butylpyridinium, pentylpyridinium, and hexylpyridinium, etc. In both imidazolium ions and pyridinium ions, the alkyl group may be substituted, and an unsaturated bond may be present.

[0109] The anions of ionic liquids include fluoride ions, chloride ions, bromide ions, iodide ions, and BF ４ － , P.F. ６ － , C.F. ３ COO － , C.F. ３ SO ３ － , NO ３ － , SCN － , (CF ３ SO ２ ) ３ C － , bis(trifluoromethoxysulfonyl)imide, bis(trifluoromethoxysulfonyl)imide, bis(perfluoroethylsulfonyl)imide, etc. Also usable are zwitterions in which the cation and anion of an ionic liquid are linked by a hydrocarbon.

[0110] The temperatures of the electrolytic solution filling the electrolytic bath 31a for oxidation reaction and the electrolytic solution filling the electrolytic bath 31b for reduction reaction may be the same or different depending on the environment in which they are used. ２ In this case, the temperature of the electrolyte is higher than the atmospheric temperature, for example, 30°C or higher and 150°C or lower, more specifically, 40°C or higher and 120°C or lower.

[0111] The reduction catalyst 1 in the first embodiment is used as the reduction catalyst layer 20. A reduction potential is applied to the metal layer 102 of the reduction catalyst. Therefore, among the components of the electrolyte, CO ２ ions (e.g., bicarbonate ions) or physically dissolved CO ２ is subjected to electrostatic attraction in the vicinity of the quaternary nitrogen cations contained in the metal layer 102 and the modified organic molecules 112 immobilized on its surface. ２ The metal layer 102 and the quaternary nitrogen cations form an electric double layer at the catalyst / electrolyte interface.

[0112] At this interface, CO ２ In the reduction reaction electrolytic cell 31b, the CO ２ is reduced to produce carbon compounds. ２ are carbon monoxide (CO), formic acid (HCOOH), formaldehyde (HCHO), and methanol (CH ３ OH), acetic acid (CH ３ COOH), acetaldehyde (CH ３ CHO) ethanol (CH ３ CH ２ OH), and ethylene glycol (HOCH ２ CH ２ OH) and as a side reaction, water (H ２ O) is reduced to hydrogen (H ２ ) can also be generated.

[0113] When carbon dioxide undergoes a two-electron reduction reaction, formic acid is produced in addition to carbon monoxide. When formic acid undergoes a two-electron reduction reaction, formaldehyde is produced. Furthermore, when formaldehyde undergoes a two-electron reduction reaction, methanol is produced. When methanol is produced using the reduction catalyst 1, formic acid or formaldehyde may be selected as the reduction raw material in addition to carbon dioxide. Therefore, it is desirable that the electrolyte in the reduction reaction electrolytic cell 31b has absorbed therein at least one reduction raw material selected from carbon dioxide, formic acid, and formaldehyde. For example, the electrolyte in the reduction reaction electrolytic cell 31b may be a sodium bicarbonate solution.

[0114] Furthermore, when carbon dioxide undergoes a two-electron reduction reaction, oxalic acid may be produced. When oxalic acid undergoes a two-electron reduction reaction, glycolic acid is produced. Furthermore, when glycolic acid undergoes a two-electron reduction reaction, glyoxal or glycolic acid is produced. Furthermore, when glyoxal or glycolic acid undergoes a two-electron reduction reaction, glycolaldehyde is produced. Furthermore, when glycolaldehyde undergoes a two-electron reduction reaction, ethylene glycol is produced. When ethylene glycol is produced using the reduction catalyst 1, oxalic acid, glycolic acid, or glycolaldehyde may be selected as the reduction raw material in addition to carbon dioxide. Therefore, the electrolyte in the reduction reaction electrolytic cell 31b may have absorbed therein at least one reduction raw material selected from oxalic acid, glycolic acid, or glycolaldehyde.

[0115] When carbon dioxide undergoes an eight-electron reduction reaction, acetic acid may be produced. When acetic acid undergoes an eight-electron reduction reaction, acetaldehyde is produced. Furthermore, when acetaldehyde undergoes an eight-electron reduction reaction, ethanol is produced. When ethanol is produced using the reduction catalyst 1, acetic acid or acetaldehyde may be selected as the reduction raw material in addition to carbon dioxide. Therefore, the electrolytic solution in the reduction reaction electrolytic cell 31b may have absorbed therein at least one reduction raw material selected from carbon dioxide, acetic acid, and acetaldehyde.

[0116] As described above, the reaction in which carbon dioxide is reduced to produce formic acid, formaldehyde, and methanol, the reaction in which carbon dioxide is reduced to produce oxalic acid, glycolic acid, glyoxal or glycolic acid, glycolaldehyde, and ethylene glycol, and the reaction in which carbon dioxide is reduced to produce acetic acid, acetaldehyde, and ethanol depend on the density of the modified organic molecules 112 in the reduction catalyst 1. For example, when the density of the modified organic molecules 112 relative to the metal layer 102 is 1×10 １１ atoms / cm ２ In the following cases, a reaction occurs in which formic acid, formaldehyde, and methanol are mainly produced: １２ atoms / cm ２ 10 above １５ atoms / cm ２ In the following cases, a reaction occurs in which acetic acid, acetaldehyde, and ethanol are produced in addition to formic acid, formaldehyde, and methanol. １３ atoms / cm ２ 10 above １５ atoms / cm ２ In the following cases, reactions occur that produce mainly acetic acid, acetaldehyde, and ethanol.

[0117] The bonding state and molecular density of the modified organic molecules 112 can be calculated based on the analysis results of X-ray photoelectron spectroscopy (XPS). The analysis conditions can be as follows. The detection angle refers to the angle between the normal to the sample and the axis of the detector input lens. Model used: Quantera-SXM manufactured by PHI Corporation. X-ray source: Single crystal spectroscopic AlKα ray. Output: 50 W. Analysis area: φ200 μm. Pass energy: Wide scan - 280.0 eV (1.0 eV / step). Narrow scan - 69.0 eV (0.125 eV / step). Detection angle: 45°. Charge neutralization electron gun: Ar. ＋ , e －Used together: As a charge correction (horizontal axis energy correction), the C--C / H bond component of the C1s spectrum is adjusted to 284.80 eV.

[0118] The bond density (molecular density) of the modified organic molecules 112 is calculated by the following formula (6) using the number of Au atoms per unit area estimated by the following formula (5) and the number of S atoms (S / Au) normalized by the number of Au atoms from the semi-quantitative analysis results.

[0119] Au (atoms / cm ２ ) = Density (g / cm ３ ) × detection depth (nm) × N / Mw (5) Molecular density (atoms / cm ２ )=Au(atoms / cm ２ ) × S / Au (atomic ratio) (6) where the density is 19.3 g / cm ３ , the detection depth is 5 nm, N is Avogadro's number (atoms / mol), and Mw is 197 g / mol.

[0120] The reaction in which carbon dioxide is reduced in the reduction catalyst 1 to produce ethylene glycol via oxalic acid, glycolic acid, or glycolaldehyde selectively occurs when the electrode is maintained at a reduction potential. That is, when the electrode is maintained at a reduction potential, the orientation of the modified organic molecules 112 becomes uniform, thereby causing the reaction to produce ethylene glycol. The electrolysis conditions for maintaining the electrode at a reduction potential are as follows: in a three-electrode cell using an electrode substrate as the working electrode, silver / silver chloride as the reference electrode, and platinum as the counter electrode, a potential of −0.8 V to −1.3 V is applied to the working electrode for preferably 5 hours or more, more preferably 3 hours or more, and even more preferably 1 hour or more. The orientation of the modified organic molecules 112 can be observed using a scanning tunneling microscope (STM).

[0121] Next, modified examples of the chemical reaction device according to this embodiment will be described. Fig. 8 is a cross-sectional view showing the structure of a chemical reaction device 210. Fig. 9 is a cross-sectional view showing the structure of a chemical reaction device 220. Below, structures different from the above-described chemical reaction device 200 will be described.

[0122] As shown in FIG. 8, the chemical reaction device 210 includes a photochemical reaction cell 30, an electrolytic cell 31 containing the photochemical reaction cell 30, and an opening 51 formed in the substrate 11 as an ion migration path.

[0123] The opening 51 is provided so as to penetrate the end of the substrate 11 from the electrolytic bath 31a for oxidation reaction to the electrolytic bath 31b for reduction reaction. An ion exchange membrane 43 is filled in a part of the opening 51, and the electrolytic bath 31a for oxidation reaction and the electrolytic bath 31b for reduction reaction are separated by the substrate 11 and the ion exchange membrane 43. The ion exchange membrane 43 allows only specific ions to pass through.

[0124] With this configuration, it is possible to separate the electrolyte between the oxidation reaction electrolytic bath 31 a and the reduction reaction electrolytic bath 31 b , and to allow only specific ions to move through the ion exchange membrane 43 .

[0125] 9, the chemical reaction device 220 includes a photochemical reaction cell 30, an electrolytic cell 31 containing the photochemical reaction cell 30, and an opening 52 formed as an ion migration path. The opening 52 is provided so as to penetrate the reduction catalyst layer 20, the substrate 11, the multi-junction solar cell 17, and the oxidation catalyst layer 19 from the oxidation reaction electrolytic cell 31a side to the reduction reaction electrolytic cell 31b side.

[0126] An ion exchange membrane 43 is filled in a part of the opening 52, and the electrolytic bath 31 a for the oxidation reaction and the electrolytic bath 31 b for the reduction reaction are separated by the substrate 11 and the ion exchange membrane 43. The ion exchange membrane 43 allows only specific ions to pass through.

[0127] With this configuration, it is possible to separate the electrolyte between the oxidation reaction electrolytic bath 31 a and the reduction reaction electrolytic bath 31 b , and to allow only specific ions to move through the ion exchange membrane 43 .

[0128] In the chemical reaction device 220 of FIG. 9, the ion exchange membrane 43 is installed only in a part of the opening 52, but the ion exchange membrane 43 may be installed over the entire opening 52.

[0129] [Uses of Ethylene Glycol] The ethylene glycol according to the present disclosure can be used as a solvent or antifreeze. Furthermore, the ethylene glycol according to the present disclosure can be used as a raw material for producing ethylene glycol compound derivatives or polyesters. Hereinafter, polyesters will be described as an example of the use of the ethylene glycol according to the present disclosure.

[0130] [Polyester] The polyester according to the present disclosure is composed of diol units and dicarboxylic acid units, and is obtained by polycondensation using ethylene glycol according to the present disclosure as the diol units and dicarboxylic acid as the dicarboxylic acid units. That is, in the polyester according to the present disclosure, the diol units are ethylene glycol produced from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide.

[0131] <Diol Unit> The diol unit used in the polyester does not have to be only the ethylene glycol according to the present disclosure. That is, ethylene glycol made from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide as a raw material may be used in combination with another diol. Even when used in combination with another diol, the use of ethylene glycol made from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide as a raw material can reduce the environmental impact.

[0132] Other diols include diols derived from fossil fuels and diols derived from biomass.

[0133] 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.

[0134] 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.

[0135] Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant raw materials. Compared to polypropylene glycol produced by the EO production method, biomethods such as the fermentation method described above are preferable in that useful by-products such as lactic acid are obtained from a safety perspective, and production costs can be kept low. Biomass-derived butylene glycol can be produced from biomass-derived succinic acid. Specifically, biomass-derived succinic acid can be obtained by producing glycol from plant raw materials and fermenting this glycol. Biomass-derived butylene glycol can be produced by adding water to biomass-derived succinic acid. Biomass-derived ethylene glycol can be produced, for example, via ethylene from bioethanol obtained by a conventional method.

[0136] <Dicarboxylic Acid Unit> The dicarboxylic acid unit of the polyester according to the present disclosure may be, for example, a dicarboxylic acid derived from a fossil fuel. Examples of fossil fuel-derived dicarboxylic acids include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof, without limitation. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid. Examples of aromatic dicarboxylic acid derivatives include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Among these, terephthalic acid is preferred, and examples of aromatic dicarboxylic acid derivatives include dimethyl terephthalate. Examples of aliphatic dicarboxylic acids include chain 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. In addition, the derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of the above aliphatic dicarboxylic acids, and 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, and those containing succinic acid as the main component are particularly preferred.As the derivatives of aliphatic dicarboxylic acids, methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferred.

[0137] Furthermore, the dicarboxylic acid used in the dicarboxylic acid unit may be a biomass-derived dicarboxylic acid. Examples of biomass-derived dicarboxylic acids 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, and regenerated oils obtained by recycling waste cooking oils containing these oils as the 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. Examples of biomass-derived aromatic dicarboxylic acids include biomass-derived terephthalic acid. Biomass-derived terephthalic acid can be produced, for example, by producing isobutanol from corn, sugars, or wood, converting the isobutanol to isobutylene, dimerizing this to produce isooctene, synthesizing p-xylene through radical cleavage, recombination, and cyclization, and then oxidizing this (WO 2009 / 079213). When a biomass-derived dicarboxylic acid is used as the dicarboxylic acid unit, the present disclosure particularly prefers the use of biomass-derived terephthalic acid.

[0138] Furthermore, the dicarboxylic acid used in the dicarboxylic acid unit may be a dicarboxylic acid derived from carbon dioxide gas. Terephthalic acid derived from carbon dioxide gas can be used as the dicarboxylic acid derived from carbon dioxide gas. Terephthalic acid derived from carbon dioxide gas can be produced, for example, by producing p-xylene from carbon dioxide gas and hydrogen gas as raw materials using a composite catalyst containing chromium oxide and a specific H-ZSM-5 zeolite, and then oxidizing the p-xylene (see JP 2019-205969 A).

[0139] These dicarboxylic acids may be used alone or in combination of two or more.

[0140] The polyester may be a copolymer polyester containing the diol unit and dicarboxylic acid unit, as well as a copolymerization component as a third 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 a trifunctional or higher oxycarboxylic acid is most preferred because it allows the production of polyesters with a high degree of polymerization with a very small amount without the need for a chain extender, as described below.

[0141] 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, and 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.

[0142] 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 derived from the same or different hydroxy compounds such as phenols and alcohols can also be used.

[0143] 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.

[0144] The polyester according to the present disclosure can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, the polyester can be produced by a general melt polymerization method in which esterification reaction and / or transesterification reaction of the above-mentioned diol unit and dicarboxylic acid unit are performed, followed by polycondensation under reduced pressure, or by a known solution heating dehydration condensation method using an organic solvent.

[0145] The amount of diol used in producing the polyester is substantially equimolar to 100 moles of the dicarboxylic acid or a derivative thereof. 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.

[0146] The polycondensation 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 added before the polycondensation, and the catalyst may be added when the raw materials are charged or when the pressure reduction is started.

[0147] Examples of polymerization catalysts include compounds containing metal elements from Groups 1 to 14 of the periodic table, excluding hydrogen and carbon. Specific examples include compounds containing an organic group, 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, and calcium, and mixtures thereof, are preferred, with titanium compounds, zirconium compounds, and germanium compounds being particularly preferred. Furthermore, because the polymerization rate increases when the catalyst is in a molten or dissolved state during polymerization, it is preferable that the catalyst be liquid during polymerization or soluble in an ester oligomer or polyester.

[0148] 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, and mixed titanates 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.

[0149] 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.

[0150] 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.

[0151] 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 also the thermal stability of the polymer decreases, while if it is too small, the polymerization activity decreases, and as a result, decomposition of the polymer is easily induced during polymer production. As for the amount of catalyst used here, the method of reducing the amount of catalyst used is a preferred embodiment, since the amount of terminal carboxyl groups in the polyester produced decreases as the amount used decreases.

[0152] The reaction temperature for the esterification reaction and / or transesterification reaction of the diol unit and the dicarboxylic acid unit 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.

[0153] In the above-described 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 using a solvent, and is reacted with the polyester obtained by the polycondensation.

[0154] 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 the use of 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 terminal hydroxy 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 by using a small amount of coupling agent without being affected by residual catalyst, even under harsh conditions such as a molten state, and therefore can produce a high-molecular-weight polyester without forming a gel during the reaction.

[0155] [Polyester pellets] The polyester pellets according to the present disclosure can be obtained by molding the polyester obtained as described above using a known method. For example, the polyester can be extracted in the form of a strand from a polymerization reactor and pelletized using a fixed or rotary cutter or pelletizer while or after cooling with water or air. The shape of the molded pellets can be cylindrical with a circular or elliptical cross section, or spherical.

[0156] After the polyester is pelletized, solid-state polymerization may be carried out as necessary to further increase the degree of polymerization or to remove oligomers such as cyclic trimers. Specifically, the polyester is pelletized and dried, and then heated at a temperature of 100° C. to 180° C. for 1 hour to 8 hours to pre-crystallize the polyester, followed by heating at a temperature of 190° C. to 230° C. under an inert gas flow or under reduced pressure for 1 hour to several tens of hours.

[0157] The diameter of the polyester pellets is adjusted by adjusting the diameter of the outlet from the polymerization reactor, the strand withdrawal speed, the take-up speed, the cutting speed, etc. Specifically, the diameter is adjusted by adjusting the pressure in the polymerization reactor when the polymer is withdrawn or by adjusting the cutting speed of the rotary strand cutter.

[0158] The diameter of the obtained polyester pellets has a lower limit (minimum diameter) of usually 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, and most preferably 1 mm or more, and an upper limit (maximum diameter) of 20 mm or less, preferably 10 mm or less, more preferably 7 mm or less, and most preferably 4 mm or less. If the diameter is too small, degradation due to hydrolysis during pellet storage tends to become significant, and if the diameter is too large, poor bite during molding tends to result in unevenness in the product. Here, the diameter of the polyester pellet refers to the diameter or length of the cross section of the polyester pellet. Furthermore, the cross section of the polyester pellet refers to the cross section where the cross-sectional area of ​​the polyester pellet is maximum.

[0159] In the polyester pellets according to the present disclosure, the proportion of powder particles having a maximum diameter of less than 1 mm is preferably 2.0% by weight or less, and more preferably 1.0% by weight or less. If the proportion of powder particles having a maximum diameter of less than 1 mm is high, these powder particles will not bite into the molding machine screw during melt molding, resulting in a long residence time in the molding machine. In addition, their large surface area makes them prone to thermal degradation, which will be mixed into the molded product as foreign matter such as discoloration or lumps, leading to problems such as a decrease in the mechanical strength of the molded product and poor appearance.

[0160] The intrinsic viscosity of the polyester pellets according to the present disclosure is 0.50 dL / g or more and 0.90 dL / g or less, preferably 0.60 dL / g or more and 0.85 dL / g or less, and more preferably 0.65 dL / g or more and 0.80 dL / g or less. If the intrinsic viscosity is less than 0.50 dL / g, the molded article, film, fiber, or textile product produced using the polyester pellets may lack the required mechanical properties. On the other hand, if the intrinsic viscosity exceeds 0.90 dL / g, productivity is impaired in the raw material production process, molded article production process, film production process, fiber production process, and textile product production process. The preferred value of the intrinsic viscosity of the polyester pellets according to the present disclosure varies depending on the application of the polyester pellets. For example, when the polyester pellets are used for a molded article, the intrinsic viscosity of the polyester pellets is preferably 0.70 or more, more preferably 0.75 or more, and preferably 0.85 or less, more preferably 0.80 or less. When the polyester pellets are used for a film, the intrinsic viscosity of the polyester pellets is preferably 0.55 or more, more preferably 0.60 or more, and is preferably 0.70 or less, more preferably 0.65 or less. The intrinsic viscosity of the polyester pellets according to the present disclosure is a value calculated from the melt viscosity measured at 35°C using a phenol / tetrachloroethane solvent (component ratio: 3 / 2).

[0161] Polyester pellets with a desired intrinsic viscosity can be obtained by adjusting the polycondensation temperature, polycondensation pressure, polycondensation time, solid-state polymerization temperature, solid-state polymerization pressure, solid-state polymerization time, etc. The higher the polycondensation temperature, the higher the intrinsic viscosity of the resulting polyester pellets tends to increase, while the lower the polycondensation temperature, the lower the intrinsic viscosity of the resulting polyester pellets tends to decrease. The higher the polycondensation pressure, the higher the intrinsic viscosity of the resulting polyester pellets tends to increase, while the lower the polycondensation pressure, the lower the intrinsic viscosity of the resulting polyester pellets tends to decrease. The longer the polycondensation time, the higher the intrinsic viscosity of the resulting polyester pellets tends to increase, while the shorter the polycondensation time, the lower the intrinsic viscosity of the resulting polyester pellets tends to decrease. The higher the solid-state polymerization temperature, the higher the intrinsic viscosity of the resulting polyester pellets tends to increase, while the lower the solid-state polymerization temperature, the lower the intrinsic viscosity of the resulting polyester pellets tends to decrease. The higher the solid-state polymerization pressure, the higher the intrinsic viscosity of the resulting polyester pellets tends to increase, while the lower the solid-state polymerization pressure, the lower the intrinsic viscosity of the resulting polyester pellets tends to decrease. The longer the solid-state polymerization time, the more the intrinsic viscosity of the resulting polyester pellets tends to increase, and the shorter the solid-state polymerization time, the more the intrinsic viscosity of the resulting polyester pellets tends to decrease.

[0162] The polyester pellets according to the present disclosure tend to have a higher heat of fusion during the second heating and a higher heat of solidification during the second heating, as measured by differential scanning calorimetry (DSC) in accordance with JIS K7122:2012 (Method for measuring heat of transition of plastics), compared to conventional fossil fuel-derived polyester pellets. For example, the heat of fusion during the second heating, as measured by DSC in accordance with JIS K7122:2012, is preferably 8 J / g or more, more preferably 11 J / g or more, and even more preferably 13 J / g or more. Furthermore, the heat of fusion during the second heating, as measured by DSC in accordance with JIS K7122:2012, is preferably 25 J / g or less, more preferably 20 J / g or less, and even more preferably 15 J / g or less. For example, the heat of solidification of the polyester pellets according to the present disclosure during the second cooling cycle, as measured by DSC in accordance with JIS K7122:2012, is preferably 7 J / g or more, more preferably 9 J / g or more, and even more preferably 12 J / g or more. Furthermore, the heat of solidification of the polyester pellets according to the present disclosure during the second cooling cycle, as measured by DSC in accordance with JIS K7122:2012, is preferably 25 J / g or less, more preferably 20 J / g or less, and even more preferably 15 J / g or less. A specific method for DSC measurement is performed using a differential scanning calorimeter according to the method described in the Examples below.

[0163] The Kjeldahl nitrogen content of the polyester pellets according to the present disclosure tends to be lower than that of conventional polyester pellets derived from fossil fuels. For example, the Kjeldahl nitrogen content of the polyester pellets according to the present disclosure is preferably 260 μg / g or less, more preferably 230 μg / g or less, even more preferably 200 μg / g or less, even more preferably 90 μg / g or less, particularly preferably 80 μg / g or less, and particularly preferably 75 μg / g or less. Furthermore, the Kjeldahl nitrogen content of the polyester pellets according to the present disclosure is 0 μg / g or more, practically 10 μg / g or more, more practically 30 μg / g or more, even more practically 100 μg / g or more, and even more practically 150 μg / g or more. In the present disclosure, Kjeldahl nitrogen refers to nitrogen quantified in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). The specific method for measuring the Kjeldahl nitrogen content is the method described in the Examples below.

[0164] The content of carbon dioxide molecules in the polyester pellets according to the present disclosure tends to be higher than that in conventional polyester pellets derived from fossil fuels. For example, the content of carbon dioxide molecules in the polyester pellets according to the present disclosure is 4.8×10 １７ It is preferable that the number of particles is 7.0 × 10 １７ More preferably, it is 1.0 × 10 １８ The content of carbon dioxide molecules in the polyester pellets according to the present disclosure is more preferably 3.0 × 10 １８ It is preferable that the number of particles is 2.0 × 10 １８ More preferably, it is 1.5 × 10 １８ The carbon dioxide molecule content in the polyester pellets is measured by thermal desorption / desorption mass spectrometry (TDS-MS). Specifically, the measurement is performed by the method described in the examples below.

[0165] Furthermore, the polyester pellets according to the present disclosure tend to have a higher water molecule content than conventional polyester pellets derived from fossil fuels. For example, the water molecule content of the polyester pellets according to the present disclosure is 1.8×10 １９ It is preferable that the number of particles is 2.0 × 10 １９ More preferably, the number is 4.0 × 10 １９ The content of water molecules in the polyester pellets according to the present disclosure is more preferably 1.0×10 ２０ It is preferable that the number of particles is 7.5×10 １９ More preferably, it is 5.0 × 10 １９ The water molecule content in the polyester pellets is measured by thermal desorption spectrometry-mass spectrometry (TDS-MS). Specifically, it is measured by the method described in the examples below.

[0166] Furthermore, the content of hydrogen molecules in the polyester pellets according to the present disclosure tends to be smaller than that in conventional polyester pellets derived from fossil fuels. For example, the content of hydrogen molecules in the polyester pellets according to the present disclosure is 7.5×10 １７ It is preferable that the number of particles is 7.0 × 10 １７ More preferably, it is 6.6 × 10 １７ The content of hydrogen molecules in the polyester pellets according to the present disclosure is more preferably 0 or more and more preferably 1.0 × 10 or less. １７ It is practical to have a density of 3.0 × 10 １７ It is more practical to have a hydrogen molecule content of at least 1 / g. The hydrogen molecule content in the polyester pellets is measured by thermal desorption mass spectrometry (TDS-MS). Specifically, it is measured by the method described in the examples below.

[0167] Various additives may be added during the production process of polyester pellets or to the produced polyester pellets to the extent that the properties of the pellets are not impaired, and examples of such 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, color pigments, etc. These additives are added in an amount of 5 to 50% by mass based on the total mass of the polyester pellets.

[0168] The polyester pellets according to the present disclosure can be used to produce molded articles or films, as described below. The polyester pellets according to the present disclosure can also be used to produce fibers or fiber products, as described below. However, the uses of the polyester pellets according to the present disclosure are not limited thereto, and they do not necessarily have to be used to produce fibers.

[0169] [Molded Product] The molded product according to the present disclosure is made using the polyester pellets described above. Examples of molded products include compression molded products, injection molded products, blow molded products, and thermoformed products. Specific containers include, for example, bottles, vials, cups, trays, and packs. To process the polyester pellets into a molded product, a conventional method for processing polyester pellets into a molded product can be used. An example of a method for processing polyester pellets into a bottle will be described below.

[0170] The polyester pellets are melted and injected using an injection molding machine to produce a preform 30X as shown in FIG.

[0171] The preform 30X shown in Figure 10 includes a mouth 31X, a body 32X connected to the mouth 31X, and a bottom 33X connected to the body 32X. Of these, the mouth 31X corresponds to the mouth 41X of a bottle 40X (described later) and has substantially the same shape as the mouth 41X. The body 32X corresponds to the neck 44X, shoulder 48X, and body 42X of the bottle 40X and has a substantially cylindrical shape. The bottom 33X corresponds to the bottom 43X of the bottle 40X and has a substantially hemispherical shape.

[0172] In one embodiment, the mouth 31X includes a threaded portion 34X that corresponds to the threaded portion 46X of the bottle 40X onto which the cap is screwed, a cap 35X provided below the threaded portion 34X, and a support ring 36X that is provided below the cap 35X and corresponds to the support ring 47X of the bottle 40X. The shape of the mouth 31X may be a conventionally known shape.

[0173] The cross-sectional thickness of the body portion 32X of the preform 30X according to the present disclosure is preferably 1.3 mm or more, more preferably 1.7 mm or more. On the other hand, the cross-sectional thickness of the body portion 32X of the preform 30X is preferably 4.7 mm or less, more preferably 4.0 mm or less. By setting the cross-sectional thickness of the body portion 32X of the preform 30X within the above range, a molded product according to the present disclosure can be manufactured. Note that the cross-sectional thickness of the body portion 32X of the preform 30X refers to the cross-sectional thickness at the point where the cross-sectional thickness of the body portion 32X of the preform 30X is smallest.

[0174] Next, the preform is heated and subjected to biaxial stretch blow molding in a blow molding die, thereby forming a bottle as shown in FIG.

[0175] The bottle 40X shown in Figure 11 has a mouth 41X, a substantially cylindrical body 42X, and a bottom 43X. The body 42X is provided below and continuous with the mouth 41X. The bottom 43X is provided below and continuous with the body 42X. A neck 44X is located between the mouth 41X and the body 42X. A shoulder 48X is located between the neck 44X and the body 42X.

[0176] A threaded portion 46X for screwing a cap (not shown) is provided on the outer periphery of the mouth portion 41X. An annular support ring 47X protruding outward is provided on the outer periphery of the mouth portion 41X below the threaded portion 46X.

[0177] As described above, the body 42X is substantially cylindrical. The body 42X has a plurality of horizontal grooves 45X formed therein. The horizontal cross section of the shoulder 48X is substantially circular, and the area of ​​the horizontal cross section of the shoulder 48X gradually increases from the neck 44X side toward the body 42X side.

[0178] A heel portion 49X is formed on the radially outer portion of the bottom portion 43X. The heel portion 49X is provided in an annular shape over the entire circumferential area of ​​the bottom portion 43X. The heel portion 49X is the thinnest portion of the bottom portion 43X that is stretched during blow molding.

[0179] The size of the bottle 40X is not limited, and the bottle may be of any size. The full capacity of the bottle 40X may be, for example, 100 mL or more, 200 mL or more, or 300 mL or more. The full capacity of the bottle 40X may be, for example, 600 mL or less, 550 mL or less, or 530 mL or less.

[0180] Furthermore, the thickness of the heel portion 49X of the bottom portion 43X is not limited to, but may be, for example, 0.07 mm or more, 0.08 mm or more, or 0.09 mm or more. The thickness of the heel portion 49X may be, for example, 0.30 mm or less, 0.25 mm or less, or 0.20 mm or less. By making the thickness of the heel portion 49X 0.30 mm or less, the weight of the bottle 40X can be reduced. On the other hand, by making the thickness of the heel portion 49X 0.07 mm or more, the bottom portion 43X can be prevented from popping out and becoming permanently deformed when the bottle 40X is placed in a vending machine or dropped.

[0181] From the viewpoint of bottle strength, the cross-sectional thickness of the body 42X of the bottle 40X is preferably 0.05 mm or more, more preferably 0.10 mm or more. On the other hand, from the viewpoint of reducing the amount of polyester used, the cross-sectional thickness of the body 42X of the bottle 40X is preferably 0.54 mm or less, more preferably 0.50 mm or less. The cross-sectional thickness of the body 42X of the bottle 40X refers to the cross-sectional thickness at the point where the cross-sectional thickness of the bottle 40X is smallest in the body 42X.

[0182] In the bottle according to one embodiment of the present disclosure, the ratio of volume to mass (volume / mass) is preferably 5 mL / g or more, more preferably 8 mL / g or more, from the viewpoint of bottle formability, while the volume / mass ratio is preferably 50 mL / g or less, more preferably 45 mL / g or less, from the viewpoint of bottle strength.

[0183] The bottle according to one embodiment of the present disclosure may have a single-layer structure or a multi-layer structure having two or more layers. When the bottle has a multi-layer structure, the layers may have the same composition or different compositions.

[0184] In one embodiment, the bottle may have a vapor-deposited film on its surface, thereby improving the gas barrier properties of the bottle. The vapor-deposited film may be located on either the inner or outer surface of the bottle, but is preferably located on the inner surface.

[0185] Examples of the vapor-deposited film include vapor-deposited films made of metals such as aluminum, inorganic oxides such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide, organosilicon compounds such as hexamethyldisiloxane, and hard carbon films such as diamond-like carbon (DLC) films. Note that the hard carbon film made of DLC is a hard carbon film also called an i-carbon film or a hydrogenated amorphous carbon film (a-C:H), and is a hard carbon film that can be used in the SP ３ It is an amorphous carbon film that is mainly composed of bonds.

[0186] The thickness of the vapor-deposited film is not particularly limited, and can be, for example, 1 nm or more and 150 nm or less.

[0187] The deposition film can be formed by a conventionally known method. Examples include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, as well as chemical vapor deposition (CVD) methods such as plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. The thickness of the deposition film can be measured at the body of the bottle, and refers to the cross-sectional thickness of the deposition film at the point where the cross-sectional thickness is smallest. When the deposition film is multilayered, the thickness of the deposition film is the sum of the thicknesses of all the deposition films.

[0188] [Film] The film according to the present disclosure uses the polyester pellets described above. To process the polyester pellets into a film, a conventional method for forming a film from polyester pellets can be employed. Specifically, the polyester pellets described above are dried and then fed into a melt extruder heated to a temperature above the melting point of the polyester pellets (Tm) to Tm + 70°C to melt the polyester pellets. The molten polyester pellets are extruded into a sheet through a die such as a T-die. The extruded sheet is rapidly cooled and solidified using a rotating cooling drum or the like. In this manner, a film 1X as shown in FIG. 12 can be formed. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose. In this disclosure, the term "film" refers to any of a sheet, a film, a film-like material, and a sheet-like material, and does not have any particular meaning.

[0189] The film according to the present disclosure is preferably biaxially stretched. Biaxial stretching can be performed 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.

[0190] [Sequential Biaxial Stretching] In sequential biaxial stretching, the film extruded onto the cooling drum as described above is stretched in the longitudinal direction, and then the film is stretched in the transverse direction. The longitudinal stretching is usually performed by the difference in peripheral speed of rolls, and may be performed in one stage or in multiple stages using multiple pairs of rolls. The longitudinal stretching ratio is preferably 2.0 times or more, more preferably 2.5 times or more, and also 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 more, more preferably 80°C or more, even more preferably 95°C or more, and preferably 120°C or less, more preferably 115°C or less, and even more preferably 110°C or less. This can suppress variations in optical properties such as in-plane retardation.

[0191] 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 transverse stretching ratio is preferably 2 times or more, more preferably 2.5 times or more, and also 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 more, more preferably 90°C or more, even more preferably 95°C or more, and preferably 120°C or less, more preferably 110°C or less, and even more preferably 105°C or less. This can suppress variations in optical properties such as in-plane retardation.

[0192] The film sequentially biaxially stretched as described above is preferably subjected to heat treatment 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. Specifically, heat setting is preferably performed 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 heat treatment post-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 higher, more preferably 0.8% or higher, even more preferably 1% or higher, and preferably 5% or lower, more preferably 3% or lower, even more preferably 2.5% or lower, and even more preferably 2% or lower. 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 is 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 makes it possible to 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, 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.

[0193] [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 longitudinal and transverse directions. Simultaneous biaxial stretching machines include pantograph type, screw type, drive motor type, and linear motor type, but drive motor type or linear motor type is preferred, as they can arbitrarily change the stretching ratio and perform relaxation treatment at any location.

[0194] 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. This makes 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 transverse direction the same and to make the stretching speeds approximately equal in order to suppress in-plane orientation differences.

[0195] 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.

[0196] 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.

[0197] The thickness of the film according to the present disclosure may vary depending on the application, but is typically 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 Over 40 kg / mm ２ Below, 1 kg / mm ​​in the TD direction ２ 35kg / mm ​​or more ２ The film according to the present disclosure has properties equivalent to those of polyester films produced from conventional fossil fuel-derived or biomass-derived materials, and the breaking elongation is 10% or more and 350% or less in the MD direction and 3% or more and 300% or less in the TD direction.

[0198] The film according to the present disclosure can also 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, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.), etc.

[0199] The film according to the present disclosure can be suitably used for applications such as laminates, packaging materials, various label materials, lid materials, sheet molded products, and laminate tubes.

[0200] [Fibers] The fibers according to the present disclosure are made using the polyester pellets described above. The fibers according to the present disclosure may be in any form, such as long fibers (filaments) or short fibers (staples). In the case of long fibers, they may be monofilaments consisting of one single yarn, or multifilaments consisting of multiple single yarns. In the case of short fibers, there are no limitations on the cut length or the number of crimps. The cross-sectional shape of the fibers according to the present disclosure can be not only round, but also a wide variety of cross-sectional shapes such as flat, Y-shaped, T-shaped, hollow, rice-field shaped, and well shaped.

[0201] The fineness of the fiber may be appropriately set depending on the application, and for long fibers for clothing, a value of 8 dtex or more and 150 dtex or less is practically preferred. Furthermore, the strength is preferably 1.5 cN / dtex or more for clothing, but by taking measures such as combining it with other fibers when producing fabrics, a value of 1.5 cN / dtex or less can be used without any problems. The elongation may be appropriately set depending on the application, and from the viewpoint of processability when processed into fabrics, it is preferably 25% or more and 60% or less. When post-processing is performed, it is preferable to set the elongation to 60% or more and 250% or less.

[0202] The polyester pellets can be processed into fibers by a conventional method for processing polyester pellets into fibers. Hereinafter, a melt spinning method, which is an example of a method for processing polyester pellets into fibers, will be described.

[0203] The polyester pellets used as raw materials are melted, metered and transported using a gear pump, and discharged from a spinneret. The yarn is cooled to room temperature by blowing cooling air onto it using a yarn cooling device such as a chimney, oiled and concentrated using an oiling device, entangled using a fluid entangling nozzle device, passed through a take-up roller and a stretching roller, and stretched according to the ratio of the peripheral speeds of the take-up roller and the stretching roller, thereby processing it into a fiber. Furthermore, the yarn may be heat-set using a stretching roller and wound up on a winder (winding device). Alternatively, the peripheral speeds of the take-up roller and the stretching roller may be set to the same, and the yarn may be wound up on a winder running at the same speed to produce an unstretched yarn, which is then stretched in a separate process.

[0204] The fibers can be subjected to post-processing such as false twisting and twisting, and can be woven and knitted in the same manner as ordinary fibers.

[0205] [Textile Products] The fibers according to the present disclosure can be made into textile products according to known methods. Examples of textile products using the fibers according to the present disclosure include gauze, filters, carpets, automotive interior materials, clothing, woven fabrics, knitted fabrics, pile fabrics, nonwoven fabrics, spun yarns, batting, etc. Furthermore, textile products according to the present disclosure may have any weave or knit structure, and suitable weaves include plain weave, twill weave, satin weave, or variations thereof, warp knitting, weft knitting, circular knitting, lace knitting, or variations thereof.

[0206] [Molded Article] The molded article according to the present disclosure is obtained by molding the polyester described above. Examples of molded articles include compression molded articles, injection molded articles, blow molded articles, and thermoformed articles. The molded article also includes containers for storing articles. Specific examples of containers include bottles, vials, cups, trays, and packs. Examples of molded articles other than containers include pellets, films, sheets, chopsticks, cutlery, and the like. Specific examples of cutlery include knives, forks, and spoons. To process polyester into a molded article, a conventional method for processing polyester into a molded article can be used.

[0207] The Kjeldahl nitrogen content of the molded article according to the present disclosure tends to be lower than that of molded articles made from conventional fossil fuel-derived polyesters. For example, the Kjeldahl nitrogen content of the molded article according to the present disclosure is preferably 18 μg / g or less, more preferably 16 μg / g or less, and even more preferably 15 μg / g or less. Furthermore, the Kjeldahl nitrogen content of the molded article according to the present disclosure is 0 μg / g or more, practically 1 μg / g or more, and more practically 3 μg / g or more. In the present disclosure, Kjeldahl nitrogen refers to nitrogen quantified in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). Specific methods for measuring the Kjeldahl nitrogen content are described in the Examples below.

[0208] Furthermore, the content of carbon dioxide molecules in the molded article according to the present disclosure tends to be higher than that in molded articles made from conventional fossil fuel-derived polyesters. For example, the content of carbon dioxide molecules in the molded article according to the present disclosure is 9.2 × 10 １７ It is preferable that the number of particles is 9.4×10 １７ More preferably, it is 9.6 × 10 １７ It is more preferable that the carbon dioxide molecule content in the molded article according to the present disclosure is 3.0 × 10 １８ It is preferable that the number of particles is 2.7×10 １８ More preferably, it is 2.5 × 10 １８ The carbon dioxide molecule content in the polyester resin layer is measured by thermal desorption spectrometry-mass spectrometry (TDS-MS). Specifically, it is measured by the method described in the examples below.

[0209] [Container] An example of a container that is one embodiment of the molded article according to the present disclosure is a bottle 40X shown in Fig. 11. Fig. 11 is a front view showing one embodiment of the molded article according to the present disclosure. Details of bottle 40X are the same as those described above, and therefore will not be described here.

[0210] [Preform] In this specification, a preform refers to a preform prior to blow molding into a container. The preform according to the present disclosure is used to manufacture a container, which is one embodiment of the present disclosure. Therefore, the preform according to the present disclosure is composed of a polyester using ethylene glycol as a diol unit and dicarboxylic acid as a dicarboxylic acid unit, which is derived from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide. By configuring the preform in this manner, a molded article according to the present disclosure can be manufactured. Note that the polyester contained in the preform according to the present disclosure can be the same as that used in the molded article according to the present disclosure.

[0211] An example of a preform according to the present disclosure is a preform 30X shown in Fig. 10. Fig. 10 is a schematic half cross-sectional view showing one embodiment of the preform 30X according to the present disclosure. Details of the preform 30X are the same as those described above, and therefore will not be described here.

[0212] [Spoon] The structure of a spoon, which is one embodiment of the molded product according to the present disclosure, will be described below with reference to FIG.

[0213] The spoon 50X comprises a measuring portion 51X and a handle portion 52X. The measuring portion 51X and the handle portion 52X are both integrally formed by polyester injection molding. The tip of the measuring portion 51X is rounded. The width of the handle portion 52X gradually increases toward its end. A measuring space 53X that opens upward is formed in the measuring portion 51X.

[0214] The thicknesses of the measuring portion 51X and the handle portion 52X may be the same or different. As an example, the thickness of the measuring portion 51X is 1.2 mm, and the thickness of the handle portion 52X is 1.4 mm. The thicknesses of the measuring portion 51X and the handle portion 52X can be designed appropriately depending on the weight of the object to be measured using the spoon 50X. The dimensions of the measuring portion 51X and the handle portion 52X can also be designed appropriately.

[0215] [Polyester Film] The polyester film according to the present disclosure is a film containing the polyester according to the present disclosure. That is, the film contains a polyester (hereinafter also referred to as "gas-derived polyester") using ethylene glycol derived from at least one gas selected from the group consisting of carbon monoxide and carbon dioxide. From the viewpoint of reducing the environmental load, the content of the gas-derived polyester in the polyester film is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more. Furthermore, the content of the gas-derived polyester in the polyester film is 100% by mass or less, with 99% by mass or less being practical and 97% by mass or less being more practical.

[0216] Since the polyester film according to the present disclosure contains a gas-derived polyester, the content of carbon dioxide molecules in the polyester film tends to be higher than that of films using conventional fossil fuel-derived polyester. For example, the content of carbon dioxide molecules in the polyester film according to the present disclosure is 1.1 × 10 １８ It is preferable that the number of particles is 1.5×10 １８ More preferably, the number is 2.0 × 10 １８ The content of carbon dioxide molecules in the polyester film according to the present disclosure is more preferably 3.0 × 10 １８ It is preferable that the number of particles is 2.7×10 １８ More preferably, it is 2.4 × 10 １８ The carbon dioxide molecule content in the polyester film is measured by thermal desorption / mass spectrometry (TDS-MS). Specifically, it is measured by the method described in the examples below.

[0217] Furthermore, the content of water molecules in the polyester film according to the present disclosure tends to be higher than that in films using conventional polyesters derived from fossil fuels. For example, the content of water molecules in the polyester film according to the present disclosure is 8.6×10 １９It 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 polyester film according to the present disclosure is more preferably 2.5×10 ２０ It is preferable that the number of particles is 2.0 × 10 ２０ More preferably, it is 1.5 × 10 ２０ The content of water molecules in the polyester film is measured by thermal desorption spectrometry-mass spectrometry (TDS-MS). Specifically, it is measured by the method described in the examples below.

[0218] The polyester film 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, 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.

[0219] To obtain the polyester film of the present disclosure by processing polyester into a film shape, 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 through a die such as a T-die. The extruded sheet is then rapidly cooled and solidified on a rotating cooling drum or the like to form a polyester film 10Y as shown in FIG. 14. The polyester film 10Y thus obtained is composed of a single layer. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

[0220] The polyester film according to the present disclosure is preferably biaxially stretched. The biaxial stretching can be performed by a conventionally known method, and may be sequential biaxial stretching or simultaneous biaxial stretching. Details of sequential biaxial stretching and simultaneous biaxial stretching are the same as those described above, and therefore will not be described here.

[0221] The thickness of the polyester film 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 Over 40 kg / mm ２ Below, 1 kg / mm ​​in the TD direction ２ 35kg / mm ​​or more ２ The polyester film according to the present disclosure has properties equivalent to those of polyester films produced from conventional fossil fuel-derived or biomass-derived materials, and 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.

[0222] While the polyester film 10Y shown in Figure 14 is composed of a single layer, the polyester film of the present disclosure is not limited to a single layer configuration and may be composed of a multilayer configuration. When the polyester film of the present disclosure is composed of a multilayer configuration, at least one layer needs to contain a gas-derived polyester, and the other layers may not contain a gas-derived polyester. Examples of polyesters constituting 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 recycled by collecting used products such as containers shipped to the market.

[0223] The polyester film according to the present disclosure 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, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.), etc.

[0224] The polyester film according to the present disclosure can be suitably used for applications such as laminates, packaging, various label materials, lid materials, sheet molded products, laminated tubes, etc. Hereinafter, laminates, packaging, stand-up pouches, lid materials, tube containers, liquid paper containers, and paper cups will be described as examples of applications of the polyester film according to the present disclosure.

[0225] [Laminate] A laminate according to the present disclosure includes a polyester film according to the present disclosure. For example, a laminate according to the present disclosure includes a polyester film according to the present disclosure and a sealant layer provided on one or both surfaces of the polyester film according to the present disclosure. For example, a laminate according to the present disclosure includes at least a polyester film and a sealant layer. FIG. 15 is a cross-sectional view showing a simplified example of the configuration of a laminate according to the present disclosure. As shown in FIG. 15, a laminate 20A includes a polyester film 10Y and a sealant layer 21Y, with the sealant layer 21Y laminated above the polyester film 10Y. Note that in the embodiment shown in FIG. 15, the laminate 20A is configured such that the sealant layer 21Y is laminated above the surface of the polyester film 10Y. However, the laminate 20A may also be configured such that the sealant layer 21Y is laminated below the surface of the polyester film 10Y, or such that the sealant layer 21Y is laminated on both the upper and lower surfaces of the polyester film 10Y.

[0226] In addition to the sealant layer 21Y, the laminate 20A may have at least one other layer above and / or below the surface of the polyester film 10Y, such as a barrier layer, a support, a resin layer, a printed layer, an adhesive layer, an adhesive resin layer, etc. The other layers will be described later.

[0227] [Sealant Layer] The sealant layer 21Y is provided above the polyester film 10Y of the laminate 20A, for example, as shown in Fig. 15. The sealant layer 21Y is a layer formed of a film of a heat-sealable resin that can be fused to each other by heat.

[0228] The material for forming the sealant layer 21Y 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 copolymer polymerized using a metallocene catalyst, ethylene-polypropylene random copolymer (random polypropylene), ethylene-polypropylene block copolymer (block polypropylene), polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-acrylic acid copolymer (EAA), and ethylene-α-olefin copolymer (ethylene-α-olefin copolymer). Examples of suitable resins include polyolefin resins such as ethyl acrylate copolymer (EEA), ethylene-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 as a mixture of two or more. The sealant layer 21Y can be a film or sheet of the above resins, or a coating film thereof.

[0229] When polyethylene is used as the material for forming the sealant layer 21Y, 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 include those described in JP 2012-251006 A. By using polyethylene obtained by polymerizing biomass-derived ethylene as the material for forming the sealant layer 21Y, a layer made of a carbon-neutral material can be formed. Therefore, by using polyethylene in combination with the gas-derived polyester described above, the amount of fossil fuel used can be further reduced, thereby further reducing the environmental impact.

[0230] 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 Corporation may be used.

[0231] 15, the laminate 20A has one sealant layer 21Y, but two or more sealant layers 21Y may be provided. When two or more sealant layers 21Y are provided, the respective sealant layers may have the same composition or different compositions.

[0232] The thickness of the sealant layer 21Y 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.

[0233] 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.

[0234] 15 includes a polyester film 10Y and a sealant layer 21Y, the present invention is not limited thereto, and as long as the laminate 20A includes these layers, the laminate 20A may include at least one other layer in addition to the polyester film 10Y and the sealant layer 21Y. For example, the laminate 20A may include other layers between the polyester film 10Y and the sealant layer 21Y, on the surface of the sealant layer 21Y opposite to the surface on which the polyester film 10Y is laminated, or on the surface of the polyester film 10Y opposite to the surface on which the sealant layer 21Y is laminated, depending on the application of the laminate.

[0235] Examples of other layers include a barrier layer, a support, a resin layer, a printing layer, an adhesive layer, and an adhesive resin layer. When two or more other layers are included, the other layers may have the same composition or different compositions. These other layers can be laminated to each other via an adhesive layer by dry lamination or via an adhesive resin layer by melt extrusion lamination.

[0236] [Barrier Layer] The laminate preferably further includes a barrier layer. The position at which the barrier layer is provided is not particularly limited as long as the effects of the present disclosure are achieved, but the barrier layer is preferably provided between the polyester film and the sealant layer.

[0237] The barrier layer functions as a gas barrier layer that prevents the permeation of gases such as oxygen gas, or a water vapor barrier layer that prevents the permeation of water vapor. Examples of barrier layers that can be used include a layer made of a metal foil obtained by rolling a metal such as aluminum foil, a layer made of a vapor-deposited film of a metal such as aluminum, a layer made of a vapor-deposited film of an inorganic oxide such as alumina, a layer made of a gas barrier coating film, and a saponified ethylene-vinyl acetate copolymer (EVOH). Furthermore, when the barrier layer is formed of a layer made of a vapor-deposited film of an inorganic oxide such as alumina, a layer made of the gas barrier coating film may be provided on at least one side of the layer made of a vapor-deposited film of an inorganic oxide to impart or improve gas barrier properties. The barrier layer can be formed by a conventionally known method, and its composition and formation method are not particularly limited. Examples of metal foils and vapor-deposited films that can be used to form the barrier layer include those described in JP 2012-96469 A. The gas barrier coating film contains one or more alkoxides and a polyvinyl alcohol resin and / or an ethylene-vinyl alcohol copolymer, and is obtained by polycondensation using a sol-gel method. For example, the one described in JP 2012-96469 A can be used. As the EVOH constituting the barrier layer, for example, the one described in JP 2008-307847 A can be used. Two or more barrier layers may be provided. When two or more barrier layers are provided, they may have the same composition or different compositions. Furthermore, one or more barrier layers may be provided on each of the two surfaces of the polyester film 10Y.

[0238] [Support] The support is not particularly limited and can be formed using a known material, such as a stretched polyester resin layer, a stretched polyamide resin layer, a stretched 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.

[0239] 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.

[0240] 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 sulfoterephthalate 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 relative to the total acid components. Furthermore, the intrinsic viscosity is preferably 0.3 dL / g or more and 0.8 dL / g or less.

[0241] Depending on the intended use of the package including the laminate of the present disclosure, various polyester-based resins can be used for the stretched polyester resin layer, and a mixture of two or more types 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.

[0242] The stretched polyester resin layer may contain various additives such as a lubricant, if necessary.

[0243] 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 nylon 6, nylon 6,6, nylon 9, nylon 11, nylon 12, nylon 6 / 66, nylon 66 / 610, and nylon MXD6 can be used. Among these, preferred aliphatic polyamides include nylon 6, nylon 6,6, and nylon-6 / 6,6. Examples of two or more aliphatic polyamides include a combination of nylon 6 and nylon 6 / 6,6 in any ratio.

[0244] 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, a stretched polypropylene resin layer using polypropylene is preferred.

[0245] When a stretched polyester resin layer or a stretched polyamide resin layer is used as the support, a modified polyolefin resin layer made of modified polyolefin may be provided between the support and the sealant layer 21Y in order to improve adhesion between the support and the sealant layer 21Y. The modified polyolefin is a polyolefin resin modified by substituting a part of the polyolefin, which is the main component, with another substance (monomer) by copolymerization or co-condensation, or by locally reacting an appropriate substance (monomer). Examples of the polyethylene resin 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 polyethylene-based resins can also be those using the above-mentioned biomass-derived ethylene as a monomer unit.

[0246] Preferred modified polyolefins are copolymers having a structure in which polyolefin segments and polar segments other than olefins 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, the maleic anhydride-modified polyolefin resins that can be used include Admer SE800, SF740, SF731, and SF730 manufactured by Mitsui Chemicals, Inc.

[0247] 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.

[0248] 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.

[0249] The thickness of the 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.

[0250] Furthermore, by forming the support using a resin material containing biomass-derived raw materials, the support becomes a layer made of a carbon-neutral resin. By forming a laminate with the polyester film 10Y and a support having a layer made of a carbon-neutral resin, a laminate having two or more layers containing a carbon-neutral resin can be manufactured. This allows for a significant reduction in the amount of fossil fuel used to form the support, thereby reducing the environmental impact.

[0251] 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.

[0252] [Printed Layer] A printed layer can be provided as needed, for example, between the polyester film 10Y 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, expiration date, manufacturer, seller, etc. The printed layer may be provided on the entire surface or on a part of the surface.

[0253] 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.

[0254] 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.

[0255] 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.

[0256] The thickness of the printing 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.

[0257] 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.

[0258] [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.

[0259] The metal constituting the metal foil is not particularly limited, and examples thereof include aluminum, copper, magnesium, and the like.

[0260] 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.

[0261] The metal foil can be laminated on any layer via an adhesive resin layer, which will be described later.

[0262] [Adhesive Layer] The adhesive layer provided 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-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, and rubber-based solvent-based, water-based, or emulsion-based adhesives. Examples of coating methods for the laminating adhesive include direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, Fountain coating, transfer roll coating, and other methods for application to the coating surfaces of the layers constituting the laminate. 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.

[0263] [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-based resin, a polypropylene-based resin, a cyclic polyolefin-based resin, or a copolymer resin, modified resin, or mixture (including alloy) containing these resins as the main component. Examples of polyolefin resins that can be used 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. Acid-modified polyolefin resins obtained by modifying the above-mentioned polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid to improve interlayer adhesion can also be used. Furthermore, resins obtained by graft polymerizing or copolymerizing unsaturated carboxylic acids, unsaturated carboxylic acid 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 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 resins mentioned above can be those that use the above-mentioned biomass-derived ethylene as a monomer unit.

[0264] 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. The amount added can be any amount from a trace amount to several tens of percent depending on the purpose. In the above, typical additives that can be used include, for example, lubricants, plasticizers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, UV absorbers, light stabilizers, colorants (dyes, pigments, etc.), and further, modifying resins can also be used.

[0265] The thickness of the adhesive resin layer can be set appropriately, preferably 5 μm or more, more preferably 10 μm or more, and also preferably 800 μm or less, more preferably 500 μm or less. If the thickness is less than the lower limit, the moisture barrier property 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.

[0266] 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 polyester film 10Y by a melt extrusion lamination method, the adhesive resin layer can be laminated without performing surface treatment such as an anchor coating agent.

[0267] In addition, 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 processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing to produce packages, etc.

[0268] As described above, the laminate 20A is a film including the polyester film 10Y and the sealant layer 21Y. The polyester film 10Y is formed of a layer made of a carbon-neutral material and has excellent hygiene. Therefore, by using the polyester film 10Y in the laminate 20A, the amount of fossil fuel used for the laminate 20A as a whole can be reduced, and CO ２ It is possible to realize a laminate that has a high emission reduction effect and is highly hygienic.

[0269] In addition, 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, and biocompatibility. Examples of secondary processing include embossing, painting, bonding, 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.). Furthermore, the laminate may be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-processing processes to produce a package or the like. Packages will be described below.

[0270] <Packaging> As described above, the laminate including the polyester film according to the present disclosure aims to reduce the amount of fossil fuel used and to reduce CO ２Because of its high emission reduction effect and excellent hygiene, it is useful as a packaging material for food and the like, and can be suitably used, for example, as a packaging film for packaging. Examples of packaging include packaging bags, lids, laminated tubes, liquid containers, paper cups, and various label materials. Examples of packaging bags include various types of packaging bags, such as standing pouches, side seals, two-sided seals, three-sided seals, four-sided seals, envelope seals, palm seals (pillow seals), pleated seals, flat bottom seals, square bottom seals, and gusset seals. The thickness of the laminate can be determined appropriately depending on the application, and is preferably 30 μm or more, more preferably 35 μm or more, and preferably 300 μm or less, more preferably 180 μm or less. An example of a packaging product using a laminate comprising a polyester film according to the present disclosure is described below. In this disclosure, each layer of the packaging body exemplified below, except for the sealant layer 21Y, is a single layer, but this is not limited to this and may have two or more layers. Also, while the packaging body exemplified below includes a printed layer, this is not limited to this and may not include a printed layer.

[0271] [Standing Pouch] A case where a laminate including a polyester film according to the present disclosure is applied to a standing pouch will be described. FIG. 16 is a perspective view showing a simplified example of a standing pouch. As shown in FIG. 16, the standing pouch 30Y is composed of two side sheets 31Y and one bottom sheet 32Y. In the standing pouch 30Y, the side sheets 31Y and the bottom sheet 32Y are composed of separate members. The standing pouch 30Y is a package formed by bag manufacturing such that the sealant layer of the laminate constituting the side sheet 31Y is the innermost layer. Note that, in the present disclosure, the side sheets 31Y and the bottom sheet 32Y of the standing pouch 30Y are composed of separate members, but this is not limited thereto, and the side sheets 31Y and the bottom sheet 32Y may be composed of the same member.

[0272] The side sheet 31Y can be formed using a laminate including a polyester film according to the present disclosure. Figure 17 is a cross-sectional view illustrating a simplified example of the configuration of a laminate forming the side sheet 31Y. As shown in Figure 17, the laminate 20B forming the side sheet 31Y can include, for example, a sealant layer 21Y, a support 33Y, a printing layer 34Y, and a polyester film 10Y, and can be constructed by laminating the sealant layer 21Y, the support 33Y, the printing layer 34Y, and the polyester film 10Y in this order from the inner surface to the outer surface. The standing pouch 30Y is produced by heat-sealing and bonding the sealant layers 21Y of the side sheet 31Y together. The laminate 20B may also include the barrier layer between any of the layers forming the laminate 20B, such as between the polyester film 10Y and the printing layer 34Y.

[0273] In this embodiment, the printing layer 34Y is provided between the polyester film 10Y and the support 33Y, but if the support 33Y is transparent, the printing layer 34Y may be provided between the sealant layer 21Y and the support 33Y.

[0274] Furthermore, in this embodiment, the side sheet 31Y is formed using a laminate comprising a polyester film according to the present disclosure, but this is not limited to this, and the bottom sheet 32Y may be formed using a laminate comprising a polyester film according to the present disclosure, or both the side sheet 31Y and the bottom sheet 32Y may be formed using laminates comprising a polyester film according to the present disclosure.

[0275] Furthermore, the laminate 20B forming the side sheet 31Y is not limited to the layer structure shown in Fig. 17, but may have the layer structure shown in Fig. 15, or may include other layers as described above. Furthermore, the positions of the layers may be changed as appropriate depending on the material constituting the support 33Y. For example, as shown in Fig. 18, the laminate 20C forming the side sheet 31Y may include a sealant layer 21Y, a polyester film 10Y, a support 33Y, and a printed layer 34Y, and the laminate 20C may have a layer structure in which the sealant layer 21Y, polyester film 10Y, support 33Y, and printed layer 34Y are stacked in this order from the inner surface to the outer surface. Furthermore, the laminate 20C may also include the barrier layer between any of the layers constituting the laminate 20C, such as between the polyester film 10Y and the sealant layer 21Y.

[0276] The standing pouch 30Y can be manufactured using a conventionally known manufacturing method, for example, by stacking two side sheets 31Y facing each other so that the sealant layer 21Y is the innermost layer, inserting a bottom sheet 32Y between the two side sheets 31Y, and heat-sealing the side sheet 31Y and the bottom sheet 32Y.

[0277] Heat sealing can be performed by any known method, such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, or ultrasonic sealing.

[0278] The standing pouch 30Y can be suitably used as a packaging bag for filling liquids, for packaging chemical products, pharmaceuticals, quasi-drugs, cosmetics, food, etc., for example, as an outer bag for patches, or as a standing pouch used for refill contents such as liquid detergent, liquid fabric softener, liquid soap, etc.

[0279] Furthermore, depending on the heat-sealing configuration of the laminate, various packaging bags other than stand-up pouches can be produced. Fig. 19 is a simplified front view of an example of a pillow bag, Fig. 20 is a simplified front view of an example of a three-sided sealed bag, and Fig. 21 is a simplified front view of an example of a four-sided sealed bag. In Figs. 19-21, heat-sealed areas are indicated by hatching. The pillow bag 41Y shown in Fig. 19 is obtained by producing a bag with the sealant layer 21Y of the laminates 20A-20C shown in Figs. 15, 17, and 18 as the innermost layer, and then heat-sealing and bonding two opposing sides of the laminate. The three-sided sealed bag 42Y shown in Fig. 20 is obtained by producing a bag with the sealant layer 21Y of the laminates 20A-20C shown in Figs. 15, 17, and 18 as the innermost layer, and then heat-sealing and bonding three sides of the laminates 20A-20C. In addition, the four-sided sealed bag 43Y shown in Figure 21 is obtained by manufacturing a bag so that the sealant layer 21Y of the laminates 20A to 20C as shown in Figures 15, 17, and 18 is the innermost layer, and then heat-sealing and adhering the four sides of the laminates 20A to 20C.

[0280] [Lid Material] Next, a case where a lid material is formed using a laminate including a polyester film according to the present disclosure will be described. The lid material is a case where the support 33Y constituting the laminate is composed of a paper layer, and can be formed using laminates 20A to 20C having layer configurations such as those shown in Figures 15, 17, and 18.

[0281] The lid material can be suitably used as a lid material for cup-shaped packaging containers, in particular for packaging containers for sealing contents such as instant foods such as cup ramen and cup yakisoba that can be eaten by pouring hot water over them, foods to be heated in a microwave oven and other ready-to-eat foods, heated beverages, beverages to be heated in a microwave oven, snacks, confectionery, jellies, etc.

[0282] [Tube Container] Next, a tube container formed using a laminate including a polyester film according to the present disclosure will be described. Fig. 22 is a partial cross-sectional view showing a simplified example of a tube container. As shown in Fig. 22, a tube container 50Y includes a head portion 51Y and a cylindrical body portion 52Y.

[0283] The head portion 51Y is composed of a hollow conical shoulder portion 53Y and a spout portion 54Y, which are integrally formed.

[0284] The cylindrical body 52Y is connected to the shoulder 53Y of the head 51Y. The cylindrical body 52Y can be formed using a laminate. FIG. 23 is a simplified cross-sectional view illustrating an example of the configuration of a laminate forming the cylindrical body of a tube container. As shown in FIG. 23, the laminate 20D forming the cylindrical body 52Y includes a first sealant layer 21A, a polyester film 10Y, a printed layer 34Y, and a second sealant layer 21B, and is configured by laminating the first sealant layer 21A, the polyester film 10Y, the printed layer 34Y, and the second sealant layer 21B in this order from the inner surface to the outer surface of the cylindrical body 52Y. The laminate 20D may also include the barrier layer between any of the layers forming the laminate 20D, such as between the polyester film 10Y and the printed layer 34Y.

[0285] Furthermore, the layer structure of the laminate 20D forming the tubular body 52Y is not limited to that shown in FIG. 23 , and the layer structure of the laminate 20D can be adjusted as appropriate. Another example of the layer structure of the laminate forming the tubular body 52Y is shown in FIG. 24 . As shown in FIG. 24 , the laminate 20E forming the tubular body 52Y is the same as the laminate 20D shown in FIG. 23 , except that an adhesive resin layer 55Y is provided between the polyester film 10Y and the printed layer 34Y, and a support 33Y is provided between the printed layer 34Y and the second sealant layer 21B. The laminate 20E may also include the barrier layer between any of the layers forming the laminate 20E, such as between the polyester film 10Y and the adhesive resin layer 55Y.

[0286] The cylindrical body 52Y is produced by overlapping the first sealant layer 21A and the second sealant layer 21B at both ends of the cylindrical body 52Y and heat-sealing and fusing the overlapped portions. The cylindrical body 52Y has a head 51Y connected to the top of one opening. Note that the method for overlapping the both ends of the cylindrical body 52Y is not limited to overlapping the first sealant layer 21A and the second sealant layer 21B, and the second sealant layers 21B may also be overlapped.

[0287] Heat sealing can be performed by a conventionally known method such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing, or flame sealing.

[0288] An example of a manufacturing method for the tube container 50Y will be described. The head 51Y is connected to one opening of the cylindrical body 52Y by a conventional method such as compression molding. The contents are then filled into the other open end of the cylindrical body 52Y connected to the head 51Y, and the open end is heat-sealed to form a bottom seal 56Y. This allows for the tube container 50Y to be filled and packaged with the contents. A cap can be attached to the spout 54Y by various methods, such as by screwing or fitting, depending on the shape of the spout 54Y.

[0289] The tube container 50Y can be suitably used as a tube container for, for example, toothpaste, cosmetics, glue, mustard paste, wasabi paste, cream, paint, cartilage, medicines, and other conventionally known products.

[0290] [Liquid-holding paper container] Next, a case where a liquid-holding paper container is formed using a laminate including a polyester film according to the present disclosure will be described. Fig. 25 is a perspective view showing an example of a liquid-holding paper container. As shown in Fig. 25, the liquid-holding paper container 60Y has a rectangular cylindrical body 61Y including a side surface, a rectangular plate-shaped bottom 62Y, and an upper portion 63Y.

[0291] The upper portion 63Y has a pair of opposing inclined plates 63a and a pair of folded portions 64Y that are located between the inclined plates 63a and are folded between the inclined plates 63a. A margin 65Y is provided at the upper end of each of the pair of inclined plates 63a, and the pair of inclined plates 63a are adhered to each other by the margin 65Y provided at the upper end of each of the pair of inclined plates 63a. A spout may be attached to one of the pair of inclined plates 63a, and the spout may be sealed with a cap.

[0292] The liquid-carrying paper container 60Y can be formed using a laminate. Figure 26 is a cross-sectional view showing an example of the configuration of a laminate used in the liquid-carrying paper container. As shown in Figure 26, the laminate 20F forming the liquid-carrying paper container 60Y includes a first sealant layer 21A, a polyester film 10Y, an adhesive resin layer 55Y, a paper layer 66Y, a second sealant layer 21B, and a printed layer 34Y. The first sealant layer 21A, the polyester film 10Y, the adhesive resin layer 55Y, the paper layer 66Y, the second sealant layer 21B, and the printed layer 34Y can be stacked in this order from the inner surface to the outer surface of the liquid-carrying paper container 60Y. The laminate 20F may also include the barrier layer between any of the layers constituting the laminate 20F, such as between the polyester film 10Y and the adhesive resin layer 55Y. For example, the polyester film 10Y may be provided with a layer made of a metal vapor deposition film, a layer made of an inorganic oxide vapor deposition film, and a layer made of a gas barrier coating film.

[0293] Any paper can be used for the paper layer 66Y 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, water-resistant label paper, cup base paper, card paper, ivory paper, paperboard such as manila cardboard, milk carton base paper, cup base paper, synthetic paper, clay-coated paper, etc. can be used.

[0294] Furthermore, before laminating the second sealant layer 21B on the paper layer 66Y, the surface of the paper layer 66Y may be subjected to corona discharge treatment, flame treatment, or the like. These treatments can improve the adhesive strength between the layers. Corona discharge treatment can be performed by passing the paper layer through a corona atmosphere generated by a known corona discharge treatment device. Flame treatment can be performed by using a known flame treatment device to heat the surface of the paper layer with fire.

[0295] The liquid paper container 60Y can be manufactured using the above-mentioned laminate by a conventionally known method. For example, the laminate can be boxed to manufacture liquid paper containers 60Y of various shapes, such as gable top type and brick type.

[0296] The liquid paper container 60Y can be suitably used as a paper container for all types of liquids, including alcoholic beverages such as sake, shochu, and wine, dairy drinks such as milk, foods such as soft drinks like orange juice and tea, and chemical products such as car wax, shampoo, and detergent.

[0297] [Paper Cup] A paper cup formed using a laminate including a polyester film according to the present disclosure will be described. FIG. 27 is a perspective view of a paper cup with a portion cut away. As shown in FIG. 27, a paper cup 70Y includes a cylindrical body 72Y having a flange 71Y at the top and a diameter that gradually widens toward the opening, and a bottom 73Y provided at the lower end (one end) of the body 72Y. The body 72Y has a flange 71Y whose upper end is rounded outward. After the contents are placed inside the paper cup 70Y, a lid is attached along the flange 71Y of the body 72Y to seal it. The lid preferably has gas barrier properties, and conventionally known lids with gas barrier properties can also be used.

[0298] The body 72Y can be formed using a laminate including a polyester film according to the present disclosure. Figure 28 is a cross-sectional view showing an example of the configuration of a laminate used in the body of a paper cup. As shown in Figure 28, the laminate 20G forming the body 72Y includes a sealant layer 21Y, a polyester film 10Y, an adhesive resin layer 55Y, a paper layer 66Y, and a printed layer 34Y. The sealant layer 21Y, the polyester film 10Y, the adhesive resin layer 55Y, the paper layer 66Y, and the printed layer 34Y can be stacked in this order from the inner surface to the outer surface of the body 72Y. The laminate 20G may also include a barrier layer between any of the layers constituting the laminate 20G, such as between the polyester film 10Y and the adhesive resin layer 55Y. For example, the polyester film 10Y may be provided with a layer of a metal vapor deposition film, a layer of an inorganic oxide vapor deposition film, and a layer of a gas barrier coating film.

[0299] The laminate 20G forming the trunk 72Y can be, for example, a laminate in which a low-density polyethylene resin layer as the sealant layer 21Y, a polyester film 10Y, a low-density polyethylene resin layer as the adhesive resin layer 55Y, and a support 33Y are laminated in this order. Similarly to the trunk 72Y, the bottom 73Y can also be a laminate in which a low-density polyethylene resin layer as the sealant layer 21Y, a polyester film 10Y, a low-density polyethylene resin layer as the adhesive resin layer 55Y, and a paper layer 66Y are laminated in this order.

[0300] In this embodiment, the laminate 20G has a printed layer 34Y on the outer surface side of the paper layer 66Y, but this is not limited to this, and a sealant layer 21Y may also be provided on the outer surface side of the printed layer 34Y or between the paper layer 66Y and the printed layer 34Y.

[0301] An example of a schematic manufacturing method for a paper cup is shown in Figure 29. As shown in Figure 29, a body blank 72' is cut out in a fan shape from the laminate 20G shown in Figure 28 and given a predetermined outline, and rolled into a cylindrical shape with the printed layer 34Y on the outside and the printed layer 34Y on the inside, and both end portions 72a' are overlapped and bonded together by heat sealing. This forms a body adhesive portion 75Y on the body 72Y.

[0302] In addition, a circular bottom blank 73' is cut out from a cup base paper (not shown), and the outer peripheral edge of the bottom blank 73' is bent downward to form a bent portion 73a'. The bottom blank 73' may also be cut out from the laminate 20G.

[0303] Next, the formed bottom blank 73' is placed under the cylindrically processed body blank 72'. The lower end of the body blank 72' is then bent so that the bent portion 73a' of the bottom blank 73' is wrapped around the lower end of the body blank 72'. While maintaining this state, the overlapping portion of the bent portion 73a' of the bottom blank 73' and the lower end of the body blank 72' are melted with hot air, and a predetermined pressure is applied to this portion to integrate them. A flange portion 71Y is then formed at the upper end of the body 72Y, thereby completing the paper cup 70Y. The laminate 20G forming the body 72Y is configured by layering the sealant layer 21Y, polyester film 10Y, adhesive resin layer 55Y, paper layer 66Y, and printed layer 34Y in this order from the inner surface to the outer surface of the paper cup 70Y, with the printed layer 34Y being positioned outermost.

[0304] The paper cup 70Y can be suitably used as a paper container for snacks, instant foods that can be made into a meal by pouring hot water over them, foods that can be heated in a microwave oven, other instant foods, heated drinks, drinks that can be heated in a microwave oven, etc.

[0305] In this embodiment, the case where the body portion 72Y is formed by the laminate 20G has been described, but this is not limited to this, and only the bottom portion 73Y, or both the body portion 72Y and the bottom portion 73Y may be formed by the laminate 20G.

[0306] [Laminate Film] A laminate film according to the present disclosure includes a base layer and a vapor-deposited film on at least one surface of the base layer. For example, as shown in Fig. 30, a laminate film 15Z according to the present disclosure includes a base layer 10Z and a vapor-deposited film 11Z on at least one surface of the base layer 10Z. In the embodiment shown in Fig. 30, the laminate film 15Z includes the vapor-deposited film 11Z above the surface of the base layer 10Z. However, the laminate film 15Z may also include the vapor-deposited film 11Z below the surface of the base layer 10Z, or may include the vapor-deposited film 11Z on both the upper and lower surfaces of the surface of the base layer 10Z.

[0307] 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 Fig. 31, a laminate film 15Z includes a substrate layer 10Z, a surface coating layer 13Z on at least one surface of the substrate layer 10Z, and a vapor-deposited film 11Z on the surface coating layer 13Z.

[0308]

[0013] For example, as shown in Fig. 32, a laminate film 15Z includes a base layer 10Z, a vapor-deposited film 11Z on at least one surface of the base layer 10Z, and a gas-barrier coated film 12Z on the vapor-deposited film 11Z.

[0309] [Base layer] The base layer of the laminate film according to the present disclosure is a film containing the polyester according to the present disclosure. That is, it is a film containing a gas-derived polyester. The details of the characteristics of the base layer of the laminate film according to the present disclosure are the same as those of the polyester film according to the present disclosure, so description thereof will be omitted here.

[0310] [Vapor-deposited 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 laminate film having a vapor-deposited 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.

[0311] 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.

[0312] Metal oxides are expressed as, for example, SiO Ｘ , AlO Ｘ MO etc. Ｘ (In the formula, M represents a metal element, and the value of X varies depending on the metal element.) The range of X is as follows: silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1.5, titanium (Ti) is 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is 0 to 1.5. In the above, when X = 0, it is a complete metal element (pure substance) and is not transparent, and the upper limit of the range of X is the value when it is completely oxidized. Silicon (Si) and aluminum (Al) are preferably used as packaging materials, and for silicon (Si), the range of X is 1.0 or more and 2.0 or less, and for aluminum (Al), the range of X is 0.5 or more and 1.5 or less.

[0313] In the present disclosure, the film 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 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 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 preferably 500 Å or less, more preferably 300 Å or less.

[0314] Examples of methods for forming the vapor-deposited film include physical vapor deposition methods (PVD methods) such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods (CVD methods) such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0315] As one aspect of the present disclosure, the vapor-deposited film will be described in further detail below.

[0316] 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.

[0317] The vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound is formed by a chemical reaction between the vapor deposition monomer gas such as an organosilicon 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 of silicon oxide is usually formed by a vapor deposition monomer gas such as an organosilicon 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. Ｘ (wherein X is a number between 0 and 2) As the vapor-deposited film of silicon oxide, a film of 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 the 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 deteriorates.

[0318] The silicon oxide vapor deposition film is primarily composed of silicon oxide and further contains at least one compound consisting of one or more elements selected from the group consisting of carbon, hydrogen, silicon, and oxygen, bonded by chemical bonding or the like. Examples of the compound include compounds having a C-H bond, compounds having a Si-H bond, compounds in which the carbon unit is graphite-like, diamond-like, fullerene-like, or the like, or the raw material organosilicon compound or its derivatives. More specifically, hydrocarbons having a CH3 moiety, SiH ３ Silyl, SiH ２ Hydrosilica such as silylene, SiH ２Examples of suitable compounds include hydroxyl group derivatives such as 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 scratches, cracks, etc. will easily occur due to bending, etc., making it difficult to stably maintain high barrier properties. If the content exceeds 50% by mass, the barrier properties will be reduced.

[0319] 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.

[0320] The above-mentioned physical properties 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.

[0321] 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. The film thickness can be measured by the fundamental parameter method using an X-ray fluorescence analyzer (model RIX2000) manufactured by Rigaku Corporation. Examples of ways to change the film thickness of the silicon oxide vapor deposition film include increasing the volumetric velocity of the vapor deposition film, i.e., increasing the amounts of monomer gas and oxygen gas, or slowing the vapor deposition rate.

[0322] Next, in the above, examples of vapor deposition monomer gases such as organosilicon compounds that form 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.

[0323] 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.

[0324] 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.

[0325] Specifically, in the present disclosure, the vapor deposition film can be formed using a vacuum deposition method in which a metal or metal oxide is used as a raw material, heated to vaporize it, and then vaporized on the surface of a substrate layer; an oxidation reaction vapor deposition method in which a metal or metal oxide is used as a raw material, oxidized by introducing oxygen, and then vaporized on the surface of a substrate layer; or a plasma-assisted oxidation reaction vapor deposition method in which the oxidation reaction is assisted by plasma. In the above, the vapor deposition material can be heated by, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), or the like.

[0326] 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 inner surface of the thin 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 is a value in which aluminum and oxygen are completely oxidized, so X of 1.5 or less can be used as the upper limit.

[0327] Next, in the present disclosure, the film 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.

[0328] 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 conveying speed of the substrate layer 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, etc., varies depending on the size of the deposition machine, etc.

[0329] 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. Taking post-processing suitability into consideration, the thickness of the aluminum oxide vapor deposition film is preferably 150 Å or more and 600 Å or less. Furthermore, as a silicon oxide vapor deposition film, a silicon oxide vapor deposition film made by physical vapor deposition using a mixture of silicon monoxide and silicon as raw materials and having a thickness in the range of 50 Å or more and 300 Å or less is preferred, taking post-processing suitability into consideration.

[0330] 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 previously subjecting the surface of the substrate layer to plasma treatment using an inert gas, 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 (delamination) or the like.

[0331] In the present disclosure, a 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, in which one surface of a substrate layer is modified using a plasma gas generated by ionizing a gas using an arc discharge. That is, in the present disclosure, a 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 containing the above-mentioned inert gas and oxygen gas can also be used as the plasma gas.

[0332] 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.

[0333] 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.

[0334] 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 base layer and the vapor deposition film.

[0335] [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 with 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. That is, the surface coating layer may be adjacent to the substrate layer.

[0336] 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.

[0337] Preferred resin materials having a polar group include polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, polyamides such as nylon 6, nylon 6,6, MXD nylon, and amorphous nylon, polyurethane, etc. Use of such resin materials can significantly improve the adhesion of the vapor-deposited film formed on the surface coating layer, and can effectively improve its gas barrier properties.

[0338] 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 laminate film and can prevent deterioration of the gas barrier properties of the laminate film even after retort treatment or boiling treatment.

[0339] 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 the neutral monomer 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.

[0340] 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 setting 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 lower, the reactivity of an isocyanate compound used together with the hydroxyl group-containing (meth)acrylic resin to form a surface coating layer can be improved. 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.

[0341] The number average molecular weight of the hydroxyl group-containing (meth)acrylic resin is preferably 10,000 or more. The number average molecular weight of the hydroxyl group-containing (meth)acrylic resin is preferably 100,000 or less. By setting the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin to 10,000 or more, blocking resistance can be improved. By setting the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin to 100,000 or more, ease of formation of a 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 the polymer is generally measured in terms of standard polystyrene.

[0342] 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. The hydroxyl value of the hydroxyl group-containing (meth)acrylic resin is preferably 200 mg KOHL / g or less, more preferably 150 mg KOHL / g or less. By setting the hydroxyl value of the hydroxyl group-containing (meth)acrylic resin to 20 mg KOHL / g or more, the reactivity of an isocyanate compound when used together with the hydroxyl group-containing (meth)acrylic resin to form a surface coating layer can be improved. 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, 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).

[0343] 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.

[0344] 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.

[0345] The surface coating layer may contain a resin material other than the resin material having a polar group, as long as the properties of the present disclosure are not impaired. In one embodiment of the present disclosure, the surface coating layer may contain an isocyanate compound. As long as the properties of the present disclosure are not impaired, the surface coating layer may contain additives. Examples of additives include crosslinking agents, antioxidants, antiblocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0346] 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 substrate layer and the surface coating layer to 0.08% or more, the adhesion of the vapor-deposited film can be further improved, and the gas barrier property can be further improved. In addition, 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 substrate layer and the surface coating layer to 20% or less, the film-forming property and processability of the surface coating layer can be further improved. In addition, the recyclability of packages produced using the laminate film according to the present disclosure can be improved.

[0347] 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, 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, and the gas barrier property can be further improved. In addition, the laminate strength of the package can be further improved. By making the thickness of the surface coating layer 10 μm or less, the film-forming property and processability of the surface coating layer can be further improved. In addition, the recyclability of packages produced using the laminate film according to the present disclosure can be improved.

[0348] A laminate consisting of a substrate layer and a surface coating layer can be produced offline. Specifically, a resin composition containing a predetermined polyester is formed into a resin film using a T-die method, an inflation method, or the like, and then stretched. A coating liquid for forming a coating is applied to the resin film, and then the film is dried. A laminate consisting of a substrate layer and a surface coating layer can also be produced in-line. Specifically, a resin composition containing a predetermined polyester is formed into a resin film using a T-die method, an inflation method, or the like, and then stretched in the machine direction (MD direction). A coating liquid for forming a coating is applied to the resin film, dried, and then stretched in the transverse direction (TD direction). Stretching in the transverse direction may be performed first. Stretching in both the machine direction and the transverse direction may be performed before or after applying the coating liquid for forming a coating.

[0349] [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 to be polycondensed by 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 to be polycondensed by 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 provide 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.

[0350] 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.

[0351] In the above, the compound of 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.

[0352] 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, for example, silicon and titanium. In addition, in the present disclosure, the alkoxide can be used alone or by mixing two or more alkoxides of different metal atoms in the same solution.

[0353] 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, and n-octyl. 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, and the like. In the present disclosure, these alkyl groups may be the same or different in the same molecule.

[0354] In the present disclosure, the above general formula R １ｎ M (OR ２ ) ｍ As the alkoxide represented by the formula: Si(ORa), for example, it is preferable to use an alkoxysilane in which M is Si. As the alkoxysilane, the alkoxysilane represented by the 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(OCH ３ ) ４ , tetraethoxysilane Si(OC ２ H ５ ) ４ , tetrapropoxysilane Si(OC ３ H ７ ) ４ , tetrabutoxysilane Si(OC ４ H ９ ) ４ , and others can be used.

[0355] 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 significantly 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.

[0356] In the present disclosure, when a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer are used in combination, the blending ratio thereof, by weight, is preferably polyvinyl alcohol resin:ethylene-vinyl alcohol copolymer=10:0.05 or more and 10:6 or less, and a blending ratio of 10:1 is more preferable.

[0357] 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 it 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 also tend to decrease. If it is less than 5 parts by mass, the gas barrier properties decrease.

[0358] In the present disclosure, the polyvinyl alcohol resin and / or ethylene-vinyl alcohol copolymer may 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, and 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.

[0359] Furthermore, in the present disclosure, the ethylene-vinyl alcohol copolymer may be a saponified product of a copolymer of ethylene and vinyl acetate, i.e., a product obtained by saponifying an ethylene-vinyl acetate random copolymer. Specifically, the saponification degree ranges from a partially saponified product in which several tens of mol% of acetate groups remain to a completely saponified product 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, it is preferable to use an ethylene-vinyl alcohol copolymer having a content of repeating units derived from ethylene (hereinafter also referred to as the "ethylene content") of typically 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.

[0360] 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 may 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.

[0361] 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 thereof 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 above-mentioned silane coupling agent used is within the range of 1 part by mass to 20 parts by mass per 100 parts by mass of the above-mentioned alkoxysilane. Using 20 parts by mass or more tends to increase the rigidity and brittleness of the formed gas barrier coating film, and also tends to decrease the insulating properties and processability of the gas barrier coating film.

[0362] 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. Furthermore, the acid used in the gas barrier composition is used as a catalyst for the sol-gel process, primarily a catalyst for hydrolysis of the alkoxide, silane coupling agent, and the like. 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.

[0363] 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.

[0364] 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 liquid 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 combined total of the alkoxide, silane coupling agent, water-soluble polymer, acid, and sol-gel catalyst.

[0365] Next, the laminate 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, polycondensation gradually progresses in the gas barrier composition (coating liquid). Next, the gas barrier composition (coating liquid) is applied by a conventional method onto a vapor-deposited film made of a metal oxide provided on one side of a substrate layer, and then dried. Then, as a result of the drying, polycondensation of the alkoxide such as the alkoxysilane, the metal alkoxide, the silane coupling agent, and the water-soluble polymer progresses, forming a coating film. Furthermore, preferably, the above coating operation is 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 at a temperature 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. The laminate film according to the present disclosure obtained in this manner has excellent gas barrier properties.

[0366] 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.

[0367] 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 coating a gas barrier composition using a polyvinyl alcohol resin to form a first coating layer, and then coating the first coating layer with a gas barrier composition containing an ethylene-vinyl alcohol copolymer 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.

[0368] 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.

[0369] In the present disclosure, the vapor-deposited film made of a metal oxide and the gas barrier coating film form chemical bonds, hydrogen bonds, coordinate bonds, etc., for example, through a hydrolysis / co-condensation reaction, improving the adhesion between the vapor-deposited film made of a metal oxide 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. Subsequently, the composition is heated and dried to cause condensation, thereby 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. Furthermore, 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.

[0370] 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.

[0371] [Laminate] One embodiment of 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. 33, a laminate 20Z according to the present disclosure includes a laminate film 15Z and a sealant layer 21Z. In the embodiment shown in Fig. 33, the laminate 20Z includes a sealant layer 21Z laminated on a surface of a vapor-deposited film 11Z of a laminate film 15Z. However, the laminate 20Z may also include a sealant layer 21Z laminated on a surface of a base layer 10Z of a laminate film 15Z, or a sealant layer 21Z laminated on both surfaces of a laminate film 15Z.

[0372]

[0013] One embodiment of the laminate according to the present disclosure further includes a support. For example, as shown in Fig. 34, a laminate 20Z includes a laminate film 15Z, a sealant layer 21Z, and a support 33Z. More specifically, the laminate 20Z includes, in this order, a support 33Z, a base layer 10Z, a vapor-deposited film 11Z, and a sealant layer 21Z.

[0373] Furthermore, one embodiment of the laminate according to the present disclosure may have at least one other layer, such as a printed layer, a metal foil, an adhesive layer, or an adhesive resin layer, in addition to the sealant layer and the support. When two or more other layers are included, the other layers may have the same composition or different compositions. The details of the characteristics of the sealant layer, the support, and the other layers are the same as those described above, and therefore will not be described here.

[0374] 33 and 34, the laminate 20Z 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.

[0375] Furthermore, one embodiment of 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 the laminate includes these layers, the laminate may include at least one other layer in addition to the laminate film and the sealant layer. For example, as shown in Fig. 34, a laminate 20Z may include a support 33Z on the surface of a laminate film 15Z opposite to the surface on which a sealant layer 21Z is laminated.

[0376] One embodiment of the laminate according to the present disclosure includes a substrate layer and a sealant layer. The substrate layer is formed of a layer made of a carbon-neutral material and has excellent hygiene. Therefore, by using the substrate layer in the laminate, the amount of fossil fuel used for the entire laminate can be reduced, and CO ２ It is possible to realize a laminate that has a high emission reduction effect and is highly hygienic.

[0377] 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, and biocompatibility. 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.). Furthermore, the laminate may be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-processing processes to manufacture packages and the like. In particular, one embodiment of the laminate according to the present disclosure, as described above, aims to reduce the amount of fossil fuel used and to reduce CO ２ Because of its high emission reduction effect and excellent gas barrier properties, it is useful as a packaging material for food and the like, and can be suitably used, for example, as a packaging film for packaging bodies.

[0378] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples.

[0379] [Example 1-1] A medium containing the following components in 1 L of distilled water was prepared as a medium for microbial fermentation. (Medium composition) MgCl ２ ・6H ２ 0.5 g of HCl, 0.2 g of NaCl, 160 mL of 100 mM sodium phosphate buffer, pH 6.0, and NH ４ Cl 0.6g ・85% H ３ P.O. ４0.05mL ・KCl 0.15g ・Trace metal complex solution (LS06) 10mL ・Vitamin B complex solution (LS03) 10mL ・1000mg / L Resazurin 1mL ・FeCl ３ 0.0025 g cysteine ​​HCl monohydrate 0.75 g agarose 15 g 100 mM sodium phosphate buffer (NaH ２ P.O. ４ 13.2g and Na ２ HPO ４ ・7H ２ 1.1 g of 0 was dissolved in 1 L of water.

[0380] A Clostridium autoethanogenum culture was prepared as a culture for microbial fermentation. The Clostridium autoethanogenum in the culture was obtained from the German Resource Centre for Biological Materials (DSMZ), and the accession number assigned to the bacterium is DSMZ10061.

[0381] 4.9 L of the above medium was placed in a 5 L continuous stirred tank reactor. The headspace of the continuous stirred tank reactor was filled with 95% CO, 5% CO at atmospheric pressure. ２ The reactor was switched to a continuous stirred tank reactor (CST) and inoculated with 100 mL of Clostridium autoethanogenum culture. The reactor was maintained at 37°C and stirred at 200 rpm at the beginning of the culture and at 400 rpm during the growth phase. During stirring, the pH of the culture was maintained at 5.5 by automatic addition of 5 M NaOH.

[0382] Sterile serum bottles with a volume of 234 mL were filled with steel mill waste gas (composition: 53% CO, 18% CO ２ , 26%N ２ , 3% H ２) three times, then evacuated to a vacuum of -5 psi. 50 mL of the culture medium was directly transferred into a serum bottle. While maintaining the reaction temperature at 37°C using a shaking incubator, the head space of the serum bottle was filled with the waste gas and pressurized to 25 psig. The culture medium was cultured at 37°C with shaking. After 5 hours, the ethanol concentration in the culture medium was 1.675 g / L, confirming that ethanol was produced by microbial fermentation.

[0383] The culture solution after microbial fermentation was separated into solid and liquid components using a solid-liquid separation filter device under conditions of a culture solution introduction pressure of 200 kPa or more. The liquid component was then introduced into a distillation apparatus equipped with a heater using 170°C steam. After the temperature at the bottom of the distillation column was raised to 101°C within 15 minutes, the liquid component was introduced from the middle of the distillation column. During continuous operation, the column was operated continuously under conditions of 101°C at the bottom, 99°C at the middle, and 91°C at the top, at a flow rate of 15 sec / L, to purify ethanol.

[0384] γ-Al ２ O ３ Purified ethanol was supplied at 10 L / H to a multi-tube externally heated isothermal reactor packed with 1.5 L of catalyst (3 mmΦ×3 mmH), and the pressure was 10 kg / cm. ２ G. The reaction was carried out at a temperature of 370°C for 500 hours, and ethylene was produced by intramolecular dehydration of ethanol.

[0385] The produced ethylene was introduced into an ethylene oxidation reactor and catalytically oxidized with a molecular oxygen-containing gas in the presence of a silver catalyst to obtain a reaction product gas containing ethylene oxide. The reaction product gas containing ethylene oxide was supplied to the bottom of an ethylene oxide absorption tower, and water was introduced from the top of the ethylene oxide absorption tower and brought into countercurrent contact with the reaction product gas, thereby absorbing the ethylene oxide in the reaction product gas into the water. The unabsorbed gas near the top of the ethylene oxide absorption tower was circulated to the ethylene oxidation reactor. The bottom liquid of the ethylene oxide absorption tower was supplied to the top of an ethylene oxide stripper tower, which had a top pressure of 0.045 MPa (gauge) and a bottom temperature of 115°C. A portion of the bottom liquid of the ethylene oxide absorption tower was circulated to the ethylene oxide absorption tower. The stripped vapor near the top of the ethylene oxide stripper tower was condensed in a condenser, and a portion was refluxed to the ethylene oxide stripper tower and a portion was supplied to the ethylene oxide dehydration tower. Vapor near the top of the ethylene oxide dehydration tower was condensed in a condenser, a portion of the condensate was refluxed to the dehydration tower, and the remainder of the condensate was supplied to the light fraction separation tower. Vapor near the top of the light fraction separation tower was sent to the condenser, and the condensate was refluxed to the light fraction separation tower. The bottom liquid of the light fraction separation tower was supplied to the ethylene oxide rectification tower. Ethylene oxide vapor near the top of the ethylene oxide rectification tower was condensed in a condenser, a portion was refluxed to the ethylene oxide rectification tower, and the remainder was withdrawn as ethylene oxide.

[0386] The extracted ethylene oxide was added to the bottom liquid of the ethylene oxide dehydration column and supplied to a hydration reactor. The reaction was carried out at a pressure of 1.8 MPa (gauge) and a reaction temperature of 150°C, yielding a 15.2% by mass ethylene glycol aqueous solution. The ethylene glycol aqueous solution was supplied to a first evaporator operated at a top pressure of 0.41 MPa (gauge) and a bottom liquid temperature of 153°C. The bottom liquid of the first evaporator was supplied to a second evaporator operated at a top pressure of 0.17 MPa (gauge) and a bottom temperature of 136°C. The bottom liquid of the second evaporator was supplied to a third evaporator operated at a top pressure of 0.07 MPa (gauge) and a bottom temperature of 124°C. The bottom liquid of the third evaporator was supplied to a fourth evaporator operated at a top pressure of -0.03 MPa (gauge) and a bottom temperature of 105°C. The bottom liquid of the fourth evaporator was supplied to an ethylene glycol dehydration column, where moisture was removed, and then supplied to an ethylene glycol distillation column. Ethylene glycol was separated from the top of the ethylene glycol distillation column, thus obtaining the ethylene glycol of Example 1-1.

[0387] Example 1-2: A stainless steel substrate (150 mm x 250 mm, 150 μm thick) was used as a current collector, and a metal layer of Au was formed on its surface by sputtering. The metal layer had a uniform thickness in the surface direction, measuring 100 nm. The current collector with the metal layer formed thereon was immersed in 10 mL of an ethanol solution containing 1 mM of 1-(2-mercaptoethyl)-4-(3-aminopropyl)-pyridinium bromide for 48 hours, thereby immobilizing modified organic molecules on the surface of the metal layer. A three-electrode cell was fabricated using the reduction catalyst thus prepared. Specifically, a three-electrode cell was constructed using the reduction catalyst as the working electrode, an Ag / AgCl electrode as the reference electrode, and a Pt electrode as the counter electrode, using an H-shaped cell. The Pt electrode was placed in a cell separated by a glass filter.

[0388] Next, 5% NaHCO ３ 100% CO in aqueous solution ２ CO gas is bubbled into the solution and absorbed. ２ CO until the concentration reaches saturation ２ was dissolved. ３ CO absorbed in aqueous solution ２The gas concentrations at the inlet and outlet were measured, and when they reached the same concentration, the concentration in the aqueous solution was determined to have reached saturation. ３ The aqueous solution was placed in a CO ２ Absorbent and CO ２ It was used as a reducing electrolyte.

[0389] In a three-electrode cell, constant current electrolysis was carried out so that the potential applied to the working electrode was −1.2 V versus Ag / AgCl. The electrolysis time was 60 minutes. During the electrolysis, 100% CO was supplied to the electrolysis chamber of the working electrode. ２ Gas was bubbled through the mixture, and the mixture was stirred at a stirring speed of 800 rpm using a magnetic stirrer.

[0390] Next, the ethylene glycol produced by constant-current electrolysis was purified. Specifically, the electrolytic solution was removed from the three-electrode cell and supplied to a first evaporator operated at a top pressure of 0.41 MPa (gauge) and a bottom temperature of 153°C. The bottom liquid from the first evaporator was supplied to a second evaporator operated at a top pressure of 0.17 MPa (gauge) and a bottom temperature of 136°C. The bottom liquid from the second evaporator was supplied to a third evaporator operated at a top pressure of 0.07 MPa (gauge) and a bottom temperature of 124°C. The bottom liquid from the third evaporator was supplied to a fourth evaporator operated at a top pressure of −0.03 MPa (gauge) and a bottom temperature of 105°C. The bottom liquid from the fourth evaporator was supplied to an ethylene glycol dehydration column, where moisture was removed, and then supplied to an ethylene glycol distillation column. Ethylene glycol was separated from the top of the ethylene glycol distillation column. In this manner, the ethylene glycol of Example 1-2 was obtained.

[0391] Comparative Example 1-1 An aqueous solution of ethylene oxide derived from a fossil fuel was diluted with water to prepare an aqueous solution of ethylene oxide with an ethylene oxide to water mass ratio of 10:1. The aqueous solution of ethylene oxide was charged into a reactor and heated at a temperature of 200°C and a pressure of about 35 kg / cm. ２ Ethylene oxide and water were reacted under the conditions of 1.0 G to obtain an approximately 15% aqueous ethylene glycol solution. The obtained aqueous ethylene glycol solution was concentrated and completely dehydrated, and then charged into a distillation column. Nitrogen gas was introduced into the top of the distillation column at a concentration of 15 Nm ２Ethylene glycol was separated and purified under a reduced pressure of 20 mmHg while blowing in ethylene glycol at a flow rate of about 10,000 kg / Hr. Ethylene glycol of Comparative Example 1-1 was obtained at a distillation rate of about 10,000 kg / Hr.

[0392] [Measurement of Kjeldahl nitrogen content] For each of the ethylene glycols of Examples 1-1 and 1-2 and Comparative Example 1-1, the Kjeldahl nitrogen content in the ethylene glycol was measured in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). The results are shown in Table 1.

[0393] [Measurement of Carbon Dioxide Molecular Content] For each of the ethylene glycols in Examples 1-1 and 1-2 and Comparative Example 1-1, 35 mg was weighed on a SiC stage to prepare a sample. Thermal desorption mass spectrometry (TDS-MS) was performed under the following measurement conditions to measure the carbon dioxide molecular content of the sample. The results are shown in Table 1. (Measurement conditions) - Device name: EMD-WA1000S / W model manufactured by Denshi Kagaku - Sample heated on SiC stage - Ionization method: electron ionization (EI) - Measurement mode: SCAN mode - Measurement mass range (m / z): 1 to 200 - Heating conditions: 50°C to 100°C - Heating rate: 10°C / min - Holding temperature and holding time: 30 minutes at 100°C

[0394]

[0395] As is clear from Table 1 above, ethylene glycol made from carbon monoxide gas or carbon dioxide gas has a lower Kjeldahl nitrogen content than ethylene glycol derived from fossil fuels. Also, ethylene glycol made from carbon monoxide gas or carbon dioxide gas has a higher carbon dioxide molecule content than ethylene glycol derived from fossil fuels.

[0396] Example 2-1: 62 parts by mass of ethylene glycol from Example 1-1 and 83 parts by mass of fossil fuel-derived terephthalic acid were fed as a slurry to a reaction vessel, and an esterification reaction was carried out at 240°C for 5 hours using a conventional direct polymerization method. Subsequently, 0.013 parts by mass of trimethyl phosphate (manufactured by Aldrich) was added (15 mmol% relative to the acid component), followed by a polymerization reaction under high-temperature vacuum conditions. First, the vacuum was increased to 4000 Pa and the polymerization temperature to 280°C over 40 minutes. Then, while maintaining the polymerization temperature at 280°C, the vacuum was reduced to 200 Pa and a melt polymerization reaction was carried out for 3 hours to synthesize a polyester. The synthesized polyester was discharged into flowing water in the form of a strand and pelletized using a pelletizer. The pellets were dried at 160°C for 5 hours and then solid-phase polymerized at 205°C under a nitrogen atmosphere and a vacuum of 50 Pa. When the melt viscosity reached a value corresponding to an intrinsic viscosity of 0.61, the pellets were discharged to obtain polyester pellets of Example 2-1. After drying, the polyester pellets of Example 2-1 were fed to an extruder, melted at 260°C, extruded into a sheet from a T-die, and cooled and solidified with a cooling roll to obtain an unstretched sheet. The unstretched sheet was then held for 1 minute in an 88°C environment and then simultaneously stretched at a speed of 100 mm / min in both the longitudinal and transverse directions at an area stretching ratio of 3.6 times, to obtain a polyester film of Example 2-1 having a thickness of 12 μm.

[0397] [Example 2-2] A polyester pellet and a polyester film of Example 2-2 were obtained in the same manner as in Example 2-1, except that the time point at which the pellets were discharged in the solid-state polymerization was changed from the time point at which the melt viscosity reached a value corresponding to an intrinsic viscosity of 0.61 to the time point at which the melt viscosity reached a value corresponding to an intrinsic viscosity of 0.65.

[0398] Comparative Example 2-1 A polyester pellet and a polyester film of Comparative Example 2-1 were obtained in the same manner as in Example 2-1, except that ethylene glycol derived from a fossil fuel was used instead of ethylene glycol derived from carbon monoxide gas.

[0399] Comparative Example 2-2 A polyester pellet and a polyester film of Comparative Example 2-2 were obtained in the same manner as in Example 2-2, except that ethylene glycol derived from a fossil fuel was used instead of ethylene glycol derived from carbon monoxide gas.

[0400] [Measurement of Intrinsic Viscosity] Using a phenol / tetrachloroethane (component ratio: 3 / 2) solvent, the melt viscosity of each of the polyester pellets of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2 was measured at 35°C, and the intrinsic viscosity was calculated from the melt viscosity. The results are shown in Table 2.

[0401] [Measurement of the Contents of Carbon Dioxide Molecules and Water Molecules in Polyester Pellets] Each of the polyester pellets of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2 was cut to obtain a 35 mg test piece. The test piece was subjected to thermal desorption mass spectrometry (TDS-MS) under the following measurement conditions to measure the contents of carbon dioxide molecules and water molecules contained in the polyester pellets. The results are shown in Table 2. (Measurement Conditions) - Apparatus name: EMD-WA1000S / W model manufactured by Denshi Kagaku Co., Ltd. - Test piece heated on a SiC stage - Ionization method: electron ionization (EI) - Measurement mode: SCAN mode - Measurement mass range (m / z): 1 to 200 - Heating conditions: 50°C to 100°C - Heating rate: 10°C / min - Holding temperature and holding time: 30 minutes at 100°C

[0402] [Haze Measurement] Test pieces measuring 50 mm length x 50 mm width were cut out from each of the polyester films of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2. Using a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.), the haze of each test piece was measured 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 excellent the transparency of the film. The results are shown in Table 2.

[0403] [Measurement of Tensile Strength and Tensile Elongation] For each of the polyester films of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2, test specimens measuring 200 mm in the longitudinal direction (machine flow direction, MD) and 15 mm in the transverse direction (width direction, TD) were cut out. Using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.), the longitudinal tensile strength and longitudinal tensile elongation of each test specimen were measured at a temperature of 23°C and a relative humidity of 50% RH. The measurement was performed at a pulling speed of 300 mm / min. Furthermore, test specimens measuring 15 mm in the longitudinal direction and 200 mm in the transverse direction were cut out, and the transverse tensile strength and transverse tensile elongation of each test specimen were measured in the same manner as described above. The results are shown in Table 2.

[0404] [Measurement of the Content of Carbon Dioxide Molecules and Water Molecules in Polyester Films] Four test pieces measuring 10 mm long x 3 mm wide were cut out from each of the polyester films of Examples 1 and 2 and Comparative Examples 1 and 2. The total mass of the four test pieces was approximately 35 mg. Thermal desorption spectrometry (TDS-MS) was performed under the following measurement conditions to measure the content of carbon dioxide molecules and water molecules contained in the polyester films. The results are shown in Table 2. (Measurement conditions) - Instrument name: EMD-WA1000S / W model manufactured by Denshi Kagaku Co., Ltd. - Four test pieces were heated on a SiC stage - Ionization method: electron ionization (EI) - Measurement mode: SCAN mode - Measurement mass range (m / z): 1 to 200 - Heating conditions: 50°C to 100°C - Heating rate: 10°C / min - Holding temperature and holding time: 30 minutes at 100°C

[0405]

[0406] As is clear from Table 2 above, the polyester pellets according to the present disclosure have a higher content of carbon dioxide molecules and water molecules than conventional polyester pellets using fossil fuel-derived ethylene glycol. Furthermore, it can be seen that the polyester film according to the present disclosure, even though made from a polyester containing ethylene glycol as a diol unit derived from carbon monoxide gas, exhibits physical properties comparable in terms of transparency and mechanical properties to films made from conventional polyesters containing fossil fuel-derived ethylene glycol as a diol unit. It can also be seen that the polyester film according to the present disclosure has a higher content of carbon dioxide molecules and water molecules than films made from polyesters containing fossil fuel-derived ethylene glycol as a diol unit.

[0407] <Preparation of Polyester Pellets for Molded Article and Molded Article> [Example 2-3] The polyester pellets of Example 2-3 were obtained in the same manner as in Example 2-1, except that the time point for discharging the pellets during solid-state polymerization was changed from when the melt viscosity corresponding to an intrinsic viscosity of 0.61 was reached to when the melt viscosity corresponding to an intrinsic viscosity of 0.77 was reached. The polyester pellets of Example 2-3 were fed into an injection molding machine and melted at 290°C, and the melt was then injected to produce the preform shown in FIG. 10. The body of the preform had a thickness of 3.5 mm and a basis weight of 22 g. The preform was then heated to 110°C and subjected to biaxial stretch blow molding in a blow molding die to produce a bottle with a full capacity of 600 mL as shown in FIG. 11. The cross-sectional thickness of the bottle body was 0.28 mm. In this manner, the molded article of Example 2-3 in the form of a bottle was obtained.

[0408] [Example 2-4] Polyester pellets and a molded article of Example 2-4 were obtained in the same manner as in Example 2-1, except that the time point at which the pellets were discharged in the solid-state polymerization was changed from the time point at which the melt viscosity reached a value corresponding to an intrinsic viscosity of 0.61 to the time point at which the melt viscosity reached a value corresponding to an intrinsic viscosity of 0.79.

[0409] [Example 2-5] The polyester pellets of Example 2-3 were fed into an injection molding machine and melted at 290°C, and the molten material was then injected to produce the spoon shown in Figure 13. The thickness of the measuring part and the thickness of the handle were both 1.5 mm. In this way, a molded article in the form of a spoon of Example 2-5 was obtained.

[0410] Comparative Example 2-3 Polyester pellets and a molded article of Comparative Example 2-3 were obtained in the same manner as in Example 2-3, except that ethylene glycol derived from a fossil fuel was used instead of ethylene glycol derived from carbon monoxide gas.

[0411] Comparative Example 2-4 Polyester pellets and a molded article of Comparative Example 2-4 were obtained in the same manner as in Example 2-4, except that ethylene glycol derived from a fossil fuel was used instead of ethylene glycol derived from carbon monoxide gas.

[0412] Comparative Example 2-5 A molded article of Comparative Example 2-5 was obtained in the same manner as in Example 2-5, except that the polyester pellets of Comparative Example 2-3 were used instead of the polyester pellets of Example 2-3.

[0413] [Measurement of Intrinsic Viscosity] Using a phenol / tetrachloroethane (component ratio: 3 / 2) solvent, the melt viscosity of each of the polyester pellets of Examples 2-3 and 2-4 and Comparative Examples 2-3 and 2-4 was measured at 35°C, and the intrinsic viscosity was calculated from the melt viscosity. The results are shown in Table 3.

[0414] [Measurement of Kjeldahl nitrogen content in polyester pellets] For each of the polyester pellets of Examples 2-3 and 2-4 and Comparative Examples 2-3 and 2-4, the Kjeldahl nitrogen content in the polyester pellets was measured in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). The results are shown in Table 3.

[0415] [Measurement of Carbon Dioxide Molecular Content in Polyester Pellets] Each of the polyester pellets of Examples 2-3 and 2-4 and Comparative Examples 2-3 and 2-4 was cut to obtain a 35 mg test piece. The test piece was subjected to thermal desorption mass spectrometry (TDS-MS) under the following measurement conditions to measure the carbon dioxide molecular content contained in the polyester pellet. The results are shown in Table 3. (Measurement Conditions) - Apparatus name: EMD-WA1000S / W model manufactured by Denshi Kagaku Co., Ltd. - Test piece heated on SiC stage - Ionization method: electron ionization (EI) - Measurement mode: SCAN mode - Measurement mass range (m / z): 1 to 200 - Heating conditions: 50°C to 100°C - Heating rate: 10°C / min - Holding temperature and holding time: 30 minutes at 100°C

[0416] [Measurement of Kjeldahl nitrogen content in molded body and molded article] Test pieces were cut out from each of the molded body of Example 2-3, the molded article of Example 2-5, the molded body of Comparative Example 2-3, and the molded article of Comparative Example 2-5, and the Kjeldahl nitrogen content contained in the test pieces was measured in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). Note that the lower detection limit for Kjeldahl nitrogen content is 10 μg / g, and since Kjeldahl nitrogen was not detected in Example 2-5, the Kjeldahl nitrogen content in the molded article of Example 2-5 was determined to be less than 10 μg / g. The results are shown in Table 3.

[0417] [Measurement of carbon dioxide molecule content in molded body and molded article] Test pieces with a mass of 35 mg were cut out from each of the molded body of Example 2-3, the molded article of Example 2-5, the molded body of Comparative Example 2-3, and the molded article of Comparative Example 2-5. Thermal desorption mass spectrometry (TDS-MS) was performed under the following measurement conditions to measure the carbon dioxide molecule content of the test pieces. The results are shown in Table 3. (Measurement conditions) - Device name: EMD-WA1000S / W model manufactured by Denshi Kagaku - Four test pieces were heated on a SiC stage - Ionization method: electron ionization (EI) - Measurement mode: SCAN mode - Measurement mass range (m / z): 1 to 200 - Heating conditions: 50°C to 100°C - Heating rate: 10°C / min - Holding temperature and holding time: 30 minutes at 100°C

[0418] [Measurement of Buckling Strength] Each of the molded articles of Examples 2-3 and 2-4 and Comparative Examples 2-3 and 2-4 was filled with 600 mL of water as the liquid content, then sealed with a cap. A buckling strength test was performed with each molded article in an upright position. A top load tester (buckling test device) EH-1000 manufactured by Ebic Corporation was used to measure the buckling strength. The molded article was placed upright on a support table, the detection head was moved downward, and a load was applied from above the opening of the molded article at a constant speed. The maximum load at which the molded article reached a so-called yield state was taken as the buckling strength. The higher the buckling strength, the better the mechanical properties of the molded article. The results are shown in Table 3.

[0419] [Impact resistance test] Ten molded articles from each of Example 2-5 and Comparative Example 2-5 were prepared, and each molded article was dropped horizontally from a height of 1.5 m 10 times and evaluated based on the following evaluation criteria. The results are shown in Table 1. (Evaluation criteria) A: None of the 10 molded articles were broken, and the molded articles had excellent mechanical properties. B: One or more of the 10 molded articles were broken, and the molded articles did not have excellent mechanical properties.

[0420]

[0421] As is clear from Table 3 above, the polyester pellets according to the present disclosure have a lower Kjeldahl nitrogen content and a higher carbon dioxide molecule content than conventional polyester pellets using ethylene glycol derived from fossil fuels. It is also clear that molded articles using the polyester pellets according to the present disclosure exhibit physical properties comparable in terms of mechanical properties to conventional molded articles made from polyesters containing ethylene glycol derived from fossil fuels as diol units.

[0422] As is clear from Table 3 above, the molded articles according to the present disclosure, even though they are molded articles of polyesters containing ethylene glycol as diol units derived from carbon monoxide gas, exhibit physical properties comparable in terms of mechanical properties to molded articles of conventional polyesters containing ethylene glycol derived from fossil fuels as diol units. Furthermore, it can be seen that molded articles and articles of polyesters containing ethylene glycol as diol units derived from carbon monoxide gas have a lower Kjeldahl nitrogen content and a higher carbon dioxide molecule content than molded articles and articles of polyesters containing ethylene glycol as diol units derived from fossil fuels.

[0423] [Example 3-1] The polyester pellets of Example 2-2 were dried, then fed to an extruder, melted at 290°C, and spun from a spinneret with 192 holes. The spun yarn was passed through a 300 mm long heating cylinder at an ambient temperature of 350°C, cooled by blowing cooling air at 25°C from the side, and a spinning oil was applied using an oiling roller. The amount of spinning oil applied was such that the oil pickup after drawing was 0.5%. The yarn was taken up by a take-up roller at a speed of 660 m / min to obtain an undrawn fiber.

[0424] The obtained undrawn fiber was continuously preheated to 100°C using a preheating roller without being wound up, and then drawn 3.5 times between the preheating roller and the drawing roller. The surface temperature of the drawing roller was then adjusted to 140°C, and the fiber was preheated to facilitate further drawing, and the fiber was drawn 1.43 times between the drawing roller and the heating roller. The surface temperature of the heating roller was set to 257°C. The drawn fiber was subjected to a relaxation heat treatment between the heating roller and the relaxation roller at a relaxation rate of 11%, and then wound on a winder at a speed of 3,300 m / min. In this way, the fiber of Example 3-1 was obtained.

[0425] The fibers of Example 3-1 were used for the warp and weft, and the warp yarns along the longitudinal direction and the weft yarns along the width direction were alternately crossed to form a plain weave on a loom into a 30 cm x 30 cm gauze. In this way, the gauze of Example 3-1 was obtained.

[0426] [Comparative Example 3-1] The polyester pellets of Comparative Example 3-1, the fiber of Comparative Example 3-1, and the gauze of Comparative Example 3-1 were obtained in the same manner as in Example 3-1, except that the polyester pellets of Comparative Example 2-2 were used instead of the polyester pellets of Example 2-2.

[0427] [Measurement of Intrinsic Viscosity] Using a phenol / tetrachloroethane (component ratio: 3 / 2) solvent, the melt viscosity of each of the polyester pellets of Example 3-1 and Comparative Example 3-1 was measured at 35° C., and the intrinsic viscosity was calculated from the melt viscosity. The results are shown in Table 4.

[0428] [Differential Scanning Calorimetry (DSC)] For each of the polyester pellets used in Example 3-1 and Comparative Example 3-1, measurement was carried out under a nitrogen gas atmosphere using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, product name: DSC7000X) in accordance with JIS K7122:2012 (Method for measuring the heat of transition of plastics). The measurement sample was 15 mg of polyester pellets shredded with a razor. In this case, the measurement sample was held at 0°C for 5 minutes, then heated from 0°C to 300°C at a heating rate of 10°C / min (first heating), held at 300°C for 1 minute, and then cooled from 300°C to 0°C at a cooling rate of 10°C / min (first cooling), and held at 0°C for 5 minutes. The sample was then heated again from 0°C to 300°C at a heating rate of 10°C / min (second heating), held at 300°C for 1 minute, and then cooled from 300°C to 0°C at a cooling rate of 10°C / min (second cooling), and held at 0°C for 5 minutes. The sample was then heated from 0°C to 25°C at a heating rate of 10°C / min. This resulted in DSC curves for the second heating and second cooling periods. The heat of fusion and the heat of solidification were calculated from the areas enclosed by the baseline (the line connecting the start and end points of the ridge from base to base) and the peaks in the DSC curve. The flow rate of nitrogen gas was 20 mL / min. The results are shown in Table 4.

[0429] [Measurement of Kjeldahl nitrogen content] For each of the polyester pellets used in Example 3-1 and Comparative Example 3-1, the Kjeldahl nitrogen content in the polyester pellets was measured in accordance with JIS K0102:2019 44.1 (Kjeldahl method) and 44.2 (indophenol blue absorptiometry). The results are shown in Table 4.

[0430] [Measurement of hydrogen molecule content] Each of the polyester pellets used in Example 3-1 and Comparative Example 3-1 was cut to obtain a 35 mg test piece. The test piece was subjected to thermal desorption mass spectrometry (TDS-MS) under the following measurement conditions to measure the content of hydrogen molecules contained in the polyester pellet. The results are shown in Table 4. (Measurement conditions) - Device name: EMD-WA1000S / W model manufactured by Denshi Kagaku Co., Ltd. - Test piece heated on SiC stage - Ionization method: electron ionization (EI) - Measurement mode: SCAN mode - Measurement mass range (m / z): 1 to 200 - Heating conditions: 50°C to 100°C - Heating rate: 10°C / min - Holding temperature and holding time: held at 100°C for 30 minutes

[0431]

[0432] As is clear from Table 4 above, pellets of polyester containing carbon monoxide-derived ethylene glycol as a diol unit have larger heats of fusion and heats of solidification in DSC than pellets of polyester containing fossil fuel-derived ethylene glycol as a diol unit. Also clear from Table 4 above, pellets of polyester containing carbon monoxide-derived ethylene glycol as a diol unit have lower Kjeldahl nitrogen content and hydrogen molecule content than pellets of polyester containing fossil fuel-derived ethylene glycol as a diol unit.

[0433] [Example 4-1] An aluminum vapor-deposited film having a thickness of 450 Å was formed on one side of the polyester film of Example 2-1, which was the base layer, to obtain a laminated film of Example 4-1. The vapor-deposited film formation conditions were as follows. (Formation conditions) Vapor deposition source: aluminum Vacuum degree in vapor deposition chamber: 2 x 10 －３mbar Vacuum degree in the winding chamber: 3 x 10 －２ mbar Film conveying speed: 350 m / min

[0434] Example 4-2 A hydroxyl-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% by weight to prepare a base resin. An ethyl acetate solution containing tolylene diisocyanate (solids content 75% by weight) was added to the base resin as a curing agent to obtain a surface coating layer-forming solution. The amount of curing agent used was 10 parts by weight per 100 parts by weight of the base resin. The surface coating layer-forming solution prepared as above was applied to one side of the polyester film of Example 2-2, which served as the base layer, and dried to form a 0.5 μm-thick surface coating layer. A 450 Å-thick aluminum vapor-deposited film was formed on the surface coating layer to obtain the laminated film of Example 4-2. The vapor-deposited film formation conditions were the same as those of Example 4-1.

[0435] Comparative Example 4-1 A laminated film of Comparative Example 4-1 was obtained in the same manner as in Example 4-1, except that the polyester film of Comparative Example 2-1 was used instead of the polyester film of Example 2-1.

[0436] Comparative Example 4-2 A laminated film of Comparative Example 4-2 was obtained in the same manner as in Example 4-2, except that the polyester film of Comparative Example 2-2 was used instead of the polyester film of Example 2-2.

[0437] [Measurement of oxygen permeability] Test specimens were obtained by cutting out the laminated films of Examples 4-1 and 4-2 and Comparative Examples 4-1 and 4-2. The test specimens 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 specimen 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.

[0438] [Measurement of Water Vapor Permeability] Test specimens were obtained by cutting out the laminated films of Examples 4-1 and 4-2 and Comparative Examples 4-1 and 4-2. The test specimens were set in a water vapor permeability measuring device (product name: PERMATRAN-w 3 / 33, manufactured by MOCON) so that the substrate layer side of the test specimen was the water vapor supply side. The water vapor permeability (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.

[0439] The results are shown in Table 5 together with the layer structures of the laminated films of Examples 4-1 and 4-2 and Comparative Examples 4-1 and 4-2.

[0440]

[0441] As is clear from Table 5 above, Examples 4-1 and 4-2, which are laminate films using polyesters containing ethylene glycol, which is produced from carbon monoxide gas as a raw material, as diol units, have equivalent oxygen permeability and water vapor permeability to Comparative Examples 4-1 and 4-2, which are laminate films using conventional polyesters containing ethylene glycol, which is produced from fossil fuels, as diol units, and therefore exhibit physical properties that are comparable in terms of gas barrier properties.

[0442] Example 5-1 A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied to one side of a biaxially oriented polypropylene film (product name: P2161, thickness: 20 μm, manufactured by Toyobo Co., Ltd.) by gravure roll coating to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, the printed layer-formed side of the biaxially oriented polypropylene film and the vapor-deposited film-formed side of the laminated film of Example 4-1 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, the laminate of Example 5-1 was obtained, in which the support, printed layer, adhesive resin layer, vapor-deposited film, substrate layer, adhesive resin layer, and sealant layer were laminated in this order. The main use of the laminate of Example 5-1 is snack packaging.

[0443] Example 5-2 A urethane-based printing ink (trade name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polypropylene film (trade name: P2161, thickness: 20 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The dried thickness of the printed layer was 1 μm. Next, an ester-based adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the printed layer, and the resulting laminate was bonded to the vapor-deposited film-formed surface of the laminate film of Example 4-1. Next, an ester-based adhesive (trade name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the laminate film, and the resulting laminate was bonded to a linear low-density polyethylene film (trade name: MTNST, thickness: 60 μm, manufactured by Futamura Chemical Co., Ltd.). In this way, the laminate of Example 5-2 was obtained, in which the support, printed layer, adhesive layer, vapor-deposited film, substrate layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 5-2, the thickness of the adhesive layer was 3 μm in all cases. The main use of the laminate of Example 5-2 is as a sprinkle wrapper.

[0444] Example 5-3 A urethane-based printing ink (trade name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (trade name: E5102, thickness: 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, an ether-based adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the printed layer, and the laminated film of Example 4-1 was bonded to the vapor-deposited film-formed surface. Next, an ether-based adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the laminated film, and the laminated film was bonded to a linear low-density polyethylene film (trade name: MTNST, thickness: 60 μm, manufactured by Futamura Chemical Co., Ltd.). In this way, a laminate of Example 5-3 was obtained, in which the support, printing layer, adhesive layer, vapor-deposited film, base layer, adhesive layer, and sealant layer were laminated in this order. In the laminate of Example 5-3, the thickness of each adhesive layer was 3 μm. The main use of the laminate of Example 5-3 is as a coffee bag.

[0445] Example 5-4: A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied to one side of a biaxially oriented polyethylene terephthalate film (product name: E5102, thickness: 12 μm, manufactured by Toyobo Co., Ltd.) by gravure roll coating 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 to the printed layer and bonded to the vapor-deposited film-formed side of the laminated film of Example 4-1. 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 Corporation). The high-density polyethylene film surface of the thus obtained laminate was sandwiched 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 an ethylene-methacrylic acid copolymer (trade name: N0908C, manufactured by Mitsui Dow Polychemicals Co., Ltd.). The aluminum foil surface of the thus obtained laminate was sandwiched with a linear low-density polyethylene film (trade name: L-100N, 50 μm thick, manufactured by Aicello Co., Ltd.) via a 35 μm thick adhesive resin layer formed by melt extrusion of an ethylene-methacrylic acid copolymer (trade name: N0908C, manufactured by Mitsui Dow Polychemicals Co., Ltd.). An adhesive resin layer was formed by melt extrusion of low-density polyethylene (trade name: CE4009, manufactured by Sumitomo Chemical Co., Ltd.) to a thickness of 20 μm onto the biaxially oriented polyethylene terephthalate film surface of the thus obtained laminate. 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 5-4 was obtained, in which the sealant layer, adhesive resin layer, support, printed layer, adhesive layer, vapor-deposited film, substrate layer, adhesive resin layer, support, adhesive resin layer, metal foil, adhesive resin layer, and sealant layer were laminated in this order. The main use of the laminate of Example 5-4 is a laminate tube.

[0446] [Example 5-5] A urethane-based printing ink (product name: Finart BM, manufactured by DIC Graphics Corporation) was applied to one side of a biaxially oriented polyethylene terephthalate film (product name: E5102, thickness: 12 μm, manufactured by Toyobo Co., Ltd.) by gravure roll coating to form a printed layer. The dried thickness of the printed layer was 1 μm. Next, the printed layer-formed side of the biaxially oriented polyethylene terephthalate film and the vapor-deposited film-formed side of the laminated film of Example 4-1 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 (trade 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 (trade name: LC600A, manufactured by Japan Polyethylene Co., Ltd.). In this way, the laminate of Example 5-5 was obtained, in which the support, printed layer, adhesive resin layer, vapor-deposited film, substrate layer, adhesive resin layer, and sealant layer were laminated in this order. The main use of the laminate of Example 5-5 is as a sprinkle wrapper or coffee wrapper.

[0447] [Example 5-6] A urethane-based printing ink (trade name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially oriented nylon film (trade name: N1102, thickness: 15 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The dried thickness of the printed layer was 1 μm. Next, an ether-based adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the printed layer, and the laminated film of Example 4-1 was bonded to the vapor-deposited film-formed surface. Next, an ether-based adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the substrate layer of the laminated film, and the laminated film was bonded to a linear low-density polyethylene film (trade name: MTNST, thickness: 40 μm, manufactured by Futamura Chemical Co., Ltd.). In this way, the laminate of Example 5-6 was obtained, in which the support, the printing layer, the adhesive layer, the vapor-deposited film, the base material layer, the adhesive layer, and the sealant layer were laminated in this order. In the laminate of Example 5-6, the thickness of the adhesive layer was 3 μm in all cases. The main use of the laminate of Example 5-6 is as a refill container.

[0448] [Example 5-7] A laminate of Example 5-7 was obtained in the same manner as in Example 5-5, 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 use of the laminate of Example 5-7 is individual coffee packaging.

[0449] [Example 5-8] A urethane-based printing ink (trade name: Finart BM, manufactured by DIC Graphics Corporation) was applied by gravure roll coating to one side of a biaxially stretched polyethylene terephthalate film (trade name: E5102, thickness: 12 μm, manufactured by Toyobo Co., Ltd.) to form a printed layer. The dry thickness of the printed layer was 1 μm. Next, an ether-based adhesive (trade name: RU-3600 / H-689, manufactured by Rock Paint Co., Ltd.) was applied to the printed layer, and the laminated film of Example 4-1 was bonded to the vapor-deposited film-formed surface. The adhesive layer formed by bonding was 3 μm thick. Next, a solvent-free ether-based adhesive (trade name: A246A / A248B, manufactured by Mitsui Chemicals, Inc.) was applied to the substrate layer of the laminated film, and the laminated film was bonded to a linear low-density polyethylene film (trade name: MTNST, thickness: 40 μm, manufactured by Futamura Chemical Co., Ltd.). The thickness of the adhesive layer formed by lamination was 1 μm. In this way, the laminates of Examples 5-8 were obtained, in which the support, printed layer, adhesive layer, vapor-deposited film, base layer, adhesive layer, and sealant layer were laminated in this order. The main use of the laminates of Examples 5-8 is individual coffee packaging.

[0450] Example 5-9 A laminate of Example 5-9 was obtained in the same manner as in Example 5-3, 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 use of the laminate of Example 5-9 is individual coffee packaging.

[0451] [Measurement of Laminate Strength] For each of the laminates of Examples 5-1 to 5-3 and 5-5 to 5-9, the laminate 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, thereby obtaining a test specimen. In the obtained test specimen, the laminate film and the support were partially peeled off. The laminate film and the support of the test specimen were each clamped and held with the chuck of a tensile tester (trade name: Tensilon STA-1150, manufactured by A&D Co., Ltd.). Then, the test specimen was 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 repeated 10 times, and the average of the 10 measurements was taken as the laminate strength (unit: N / 15 mm width) between the laminate film and the support. For the laminate of Example 5-4, the laminate strength between the laminate film and the biaxially stretched polyethylene terephthalate film was measured in the same manner. The results are shown in Table 6, along with the layer structures and main uses of the laminates of Examples 5-1 to 5-9.

[0452]

[0453] As is clear from Examples 5-1 to 5-9 above, laminates can be produced from laminate films using polyesters containing ethylene glycol as a diol unit, which are produced using carbon monoxide gas as a raw material. Furthermore, the laminate strengths measured for the laminates of Examples 5-1 to 5-9 are equivalent to those measured for laminates using conventional polyesters containing ethylene glycol as a diol unit, which is derived from fossil fuels. This shows that the laminates of Examples 5-1 to 5-9 exhibit comparable physical properties in terms of mechanical properties.

[0454] Example 6-1: Using a continuous vapor deposition film-forming apparatus having a pretreatment section in which an oxygen plasma pretreatment device was placed and a film-forming section separated from each other, oxygen plasma pretreatment was performed on one side of the polyester film of Example 2-1, which was the base layer. In the pretreatment section, plasma was introduced from a plasma supply nozzle under the following conditions in a roll-to-roll manner while applying tension to the base layer, thereby performing 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 under the following conditions using a reactive resistance heating method as a heating means for vacuum deposition, thereby obtaining the laminated film of Example 6-1. (Formation conditions) (Oxygen plasma pretreatment conditions) Plasma intensity: 200 W sec / m ２ Plasma formation gas ratio: oxygen:argon = 2:1. Voltage applied between pretreatment drum and plasma supply nozzle: 340 V (film formation conditions). Transport speed: 400 m / min. Oxygen gas supply amount: 20,000 sccm.

[0455] [Example 6-2] The surface coating layer forming solution prepared in the same manner as in Example 4-2 was applied to one side of the polyester film of Example 2-1, which was the base layer, and dried to form a surface coating layer ...

Claims

1. Ethylene glycol produced using at least one gas selected from the group consisting of carbon monoxide and carbon dioxide as a raw material.

2. The carbon dioxide molecule content is 2.2 x 10 １８ pieces / g or more 1.5×10 １９ The ethylene glycol according to claim 1, wherein the molecular weight is 1 / g or less.

3. Ethylene glycol according to claim 1 or 2, having a Kjeldahl nitrogen content of 700 μg / g or less.

4. A polyester comprising a diol unit and a dicarboxylic acid unit, wherein the diol unit is the ethylene glycol according to any one of claims 1 to 3.

5. The polyester according to claim 4, wherein the dicarboxylic acid unit is 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.

6. A polyester pellet comprising the polyester according to claim 4 or 5, the intrinsic viscosity of which is 0.50 dL / g or more and 0.90 dL / g or less.

7. The polyester pellet according to claim 6, having a Kjeldahl nitrogen content of 260 μg / g or less.

8. The carbon dioxide molecule content is 4.8 x 10 １７ pieces / g or more 3.0×10 １８ The polyester pellet according to claim 6 or 7, wherein the number of particles per gram is not more than 1.

9. The water molecule content is 1.8 x 10 １９ pieces / g or more 1.0×10 ２０ The polyester pellet according to any one of claims 6 to 8, wherein the number of pellets per gram is not more than 1.

10. A molded article using the polyester pellets according to any one of claims 6 to 9.

11. A film using the polyester pellets according to any one of claims 6 to 9.

12. Fibers made from the polyester pellets according to claim 6.

13. The fiber according to claim 12, wherein the heat of fusion of the polyester pellets during the second heating step, as measured by differential scanning calorimetry (DSC) in accordance with JIS K7122:2012, is 8 J / g or more.

14. The fiber according to claim 12 or 13, wherein the heat of solidification of the polyester pellets during the second cooling step, as measured by differential scanning calorimetry (DSC) in accordance with JIS K7122:2012, is 7 J / g or more.

15. The fiber according to any one of claims 12 to 14, wherein the polyester pellets have a Kjeldahl nitrogen content of 90 μg / g or less.

16. The content of hydrogen molecules in the polyester pellets is 7.5×10 １７ The fiber according to any one of claims 12 to 15, wherein the number of particles per gram is less than or equal to 100 particles / g.

17. A textile product using the fiber according to any one of claims 12 to 16.

18. A molded article of the polyester according to claim 4 or 5.

19. The carbon dioxide molecule content is 9.2 x 10 １７ pieces / g or more 3.0×10 １８ The molded article according to claim 18, having a particle size of 1 / g or less.

20. The molded article according to claim 18 or 19, having a Kjeldahl nitrogen content of 18 μg / g or less.

21. The molded article according to any one of claims 18 to 20, which is a container.

22. A preform for use in producing the molded article according to claim 21.

23. A polyester film comprising the polyester of claim 4 or 5.

24. The carbon dioxide molecule content is 1.1 x 10 １８ pieces / g or more 3.0×10 １８ The polyester film according to claim 23, wherein the molecular weight is 1 / g or less.

25. The water molecule content is 8.6 x 10 １９ pieces / g or more 2.5×10 ２０ The polyester film according to claim 23 or 24, wherein the molecular weight is 1 / g or less.

26. A laminate comprising the polyester film according to any one of claims 23 to 25.

27. A laminated film comprising at least a base layer and a vapor-deposited film, wherein the base layer contains the polyester according to claim 4 or 5, and the vapor-deposited film is a vapor-deposited film of a metal or a metal oxide.

28. The content of carbon dioxide molecules in the base layer is 1.1 x 10 １８ pieces / g or more 3.0×10 １８ The laminated film according to claim 27, wherein the number of particles per gram is less than or equal to 100 particles.

29. 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 27 or 28, wherein the number of particles per gram is not more than 1.

30. The laminate film according to any one of claims 27 to 29, further comprising a surface coating layer between the base layer and the vapor-deposited film, the surface coating layer containing a resin material having a polar group.

31. A laminate film according to any one of claims 27 to 30, comprising, in this order, the base layer, the vapor deposition film, and a gas barrier coating film, the gas barrier coating film containing an alkoxide and at least one water-soluble polymer selected from the group consisting of polyvinyl alcohol resins and ethylene-vinyl alcohol copolymers.

32. A laminate comprising the laminate film according to any one of claims 27 to 31 and a sealant layer.

33. The laminate according to claim 32, further comprising a support, said support being an oriented polyester resin layer, an oriented polyamide resin layer or an oriented polypropylene resin layer.

34. The laminate according to claim 33, comprising, in this order, the support, the base material layer, the vapor-deposited film, and the sealant layer.

35. A laminate comprising at least the polyester film according to any one of claims 23 to 25 and a sealant layer.

36. The laminate according to claim 35, wherein the resin constituting the sealant layer is low-density polyethylene, linear low-density polyethylene, or polypropylene.

37. The laminate of claims 35 or 36, further comprising a barrier layer between the polyester film and the sealant layer.

38. The laminate of claim 37, wherein the barrier layer is a metal foil.

39. A package comprising a laminate according to any one of claims 32 to 38.

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