Gas barrier resin compositions, molded articles, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup containers, dish containers, blow-molded containers, fuel containers, bottle containers, tubing, multilayer tubing and paper containers

Abstract

A gas barrier resin composition is provided that, although using biomass-derived raw materials, still possesses high gas barrier properties and molding processability comparable to those derived from fossil fuels. Molded articles, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, disc-shaped containers, blow-molded containers, fuel containers, bottle containers, pipes, multilayer pipes, and paper containers using this gas barrier resin composition are also provided. One gas barrier resin composition comprises an ethylene-ethylene ester copolymer saponified compound, wherein the ethylene and ethylene esters used as raw materials for the ethylene-ethylene ester copolymer saponified compound are biomass-derived.

Description

Technical Field

[0001] This invention relates to gas barrier resin compositions, molded articles, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, disc-shaped containers, blow-molded containers, fuel containers, bottle containers, pipes, multilayer pipes, and paper containers. Prior Technology

[0002] Gas barrier materials made from resins with excellent gas-barrier properties (gas barrier properties) are widely used in various applications such as containers, films, sheets, and pipes. Known resins with excellent gas barrier properties include polyamide, polyester, polyvinylidene chloride, acrylonitrile copolymer, polyvinylidene fluoride, polytrifluoroethylene chloride, and ethylene-vinyl ester copolymer saponification. For example, Patent Document 1 describes an invention of a multilayer plastic container having at least one gas barrier resin layer selected from polyamide, polyester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, fluorinated resin, and silicone resin.

[0003] On the other hand, in recent years, with the goal of a circular society, the need for biodegradable plastics made from carbon-neutral biomass-derived raw materials has been gradually increasing. However, it is known that biomass-derived synthetic resins have inferior performance compared to synthetic resins derived from fossil fuels. For example, Patent Document 2 describes conventional biomass-derived polyolefin and other film materials as having insufficient quality in terms of adhesion, processability, and durability, and describes an invention for a resin film to improve this deficiency, which includes a biomass-derived resin layer containing a specific composition of biomass-derived resin. Furthermore, Patent Document 3 describes films made by replacing petroleum-derived resin with biomass-derived resin as having reduced impact resistance, and describes an invention for a laminated film to improve this deficiency, which includes an intermediate layer containing biomass-derived biopolyethylene, fossil fuel-derived polyethylene, and propylene-based block copolymer resin. Furthermore, Patent Document 4 discloses an invention concerning a laminate having a layer of carbon-neutralized polyester resin film using biomass ethylene glycol, and exemplifies an ethylene-ethylene copolymer saponified resin as a gas barrier resin, which is disclosed as a resin composed of raw materials derived from fossil fuels. Because this laminate in Patent Document 4 contains both biomass-derived resin and fossil fuel-derived resin, it is limited to being a biodegradable plastic. [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2007-137506 [Patent Document 2] International Publication No. 2014 / 065380 [Patent Document 3] International Publication No. 2018 / 163835 [Patent Document 4] Japanese Patent Application Publication No. 2012-096410 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] In applications of gas barrier materials, there is a growing demand for the commercialization of gas barrier resins synthesized from biomass-derived raw materials. However, as mentioned above, biomass-derived synthetic resins generally exhibit inferior performance compared to fossil fuel-derived synthetic resins. Therefore, replacing conventional fossil fuel-derived gas barrier resins with biomass-derived resins raises concerns about a reduction in the crucial gas barrier properties and processability. Consequently, there is a desire to develop biomass-derived resins that possess superior gas barrier properties and processability comparable to fossil fuel-derived resins.

[0007] The present invention was made based on the above circumstances, and its object is to provide a gas barrier resin composition that, although using biomass-derived raw materials, still has high gas barrier properties and molding processability that are no less than those derived from fossil fuels, as well as molded articles, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, disc-shaped containers, blow-molded containers, fuel containers, bottle containers, pipes, multilayer pipes and paper containers using the gas barrier resin composition. [Methods used to solve problems]

[0008] The inventors have discovered that in a gas barrier resin, an ethylene-ethylene ester copolymer saponified product synthesized using biomass-derived raw materials as monomers has high gas barrier properties and molding processability comparable to those synthesized using fossil fuel-derived raw materials as monomers, thereby achieving the present invention.

[0009] That is, the present invention is achieved by providing the following: [1] A gas barrier resin composition comprising an ethylene-ethylene ester copolymer saponified product, wherein the ethylene and ethylene esters in the raw materials of the ethylene-ethylene ester copolymer saponified product are derived from biomass; [2] As in [1], the gas barrier resin composition wherein the biomass of the above-mentioned ethylene-ethylene ester copolymer saponified product exceeds 99%; [3] Gas barrier resin compositions such as [1] or [2] have a biomass degree exceeding 99%; [4] Any gas barrier resin composition as described in [1] to [3], wherein the sulfur compound contains sulfur compounds with a sulfur atom content of more than 0 ppm and less than 100 ppm; [5] The gas barrier resin composition as in [4], wherein the sulfur compound is dimethyl sulfide or dimethyl sulfide; [6] The gas barrier resin composition of any one of [1] to [5], wherein the ethylene-ethylene copolymer saponified comprises: ethylene-ethylene copolymer saponified (X), and ethylene-ethylene copolymer saponified (Y) with a melting point lower than that of the ethylene-ethylene copolymer saponified (X); [7] The gas barrier resin composition as described in [6], wherein the mass ratio (X / Y) of the above-mentioned ethylene-vinyl ester copolymer saponified product (X) to the above-mentioned ethylene-vinyl ester copolymer saponified product (Y) is 60 / 40 or more and 95 / 5 or less; [8] A gas barrier resin composition such as [6] or [7], wherein the difference (XY) between the melting points of the above-mentioned ethylene-ethylene copolymer saponified product (X) and the above-mentioned ethylene-ethylene copolymer saponified product (Y) is 15°C or more. [9] The gas barrier resin composition of any one of [1] to [8] contains a carboxylic acid with a concentration of 30 ppm to 1000 ppm when converted to carboxylate groups;

[10] A gas barrier resin composition as described in any of [1] to [9], wherein the composition contains metal ions at a concentration of 1 ppm to 1000 ppm;

[11] The gas barrier resin composition of any one of [1] to

[10] contains a phosphoric acid compound with a phosphoric acid content of more than 1 ppm and less than 200 ppm in terms of phosphorus atoms;

[12] The gas barrier resin composition of any one of [1] to

[11] , wherein the boron compound contains a boron compound with a boron atom content of 5 ppm to 5000 ppm;

[13] A molded body comprising: a layer formed of a gas barrier resin composition as described in any one of [1] to

[12] ;

[14] The molded body as in

[13] further comprises a thermoplastic resin layer;

[15] A thin film or sheet having a molded body as described in

[13] or

[14] ;

[16] A packaging material having a film or sheet as described in

[15] ;

[17] An industrial film or sheet having a molded body as shown in

[13] or

[14] ;

[18] A thermoformed container having a molded body as shown in

[13] or

[14] ;

[19] A cup-shaped container, which is a thermoformed container as described in

[18] ;

[20] A tray-shaped container having the features of a thermoformed container as described in

[18] ;

[21] A blow-molded container having a molded body as shown in

[13] or

[14] ;

[22] A fuel container having the blow-formed container as described in

[21] ;

[23] A bottle container having the blow-forming container as described in

[21] ;

[24] A tube having a molded body as described in

[13] or

[14] ;

[25] A multilayer tube having a molded body as shown in

[13] or

[14] ;

[26] A paper container having a molded body as shown in

[13] or

[14] . [Invention Effects]

[0010] According to the present invention, a gas barrier resin composition that, although using biomass-derived raw materials, still possesses high gas barrier properties and molding processability comparable to those derived from fossil fuels, can be provided. Furthermore, molded bodies, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, disc-shaped containers, blow-molded containers, fuel containers, bottle containers, pipes, multilayer pipes, and paper containers using the gas barrier resin composition can be provided. Simple Explanation of the Diagram

[0011] [Figure 1] Figure 1 is a schematic perspective view showing one embodiment of the present invention, namely a cup-shaped container. [Figure 2] Figure 2 is a cross-sectional view of the cup-shaped container in Figure 1. [Figure 3] Figure 3 is a schematic diagram used to illustrate the manufacturing method of the cup-shaped container in Figure 1. [Figure 4] Figures 4(A) to 4(D) are schematic diagrams used to illustrate the manufacturing method of the cup-shaped container in Figure 1. Implementation

[0012] <Gas Barrier Resin Composition>

[0013] The gas barrier resin composition of this invention is a gas barrier resin composition comprising an ethylene-vinyl ester copolymer saponified product (ethylene-vinyl alcohol copolymer; hereinafter also referred to as "EVOH"), wherein the ethylene and ethylene ester of the raw materials (raw material monomers) of the aforementioned EVOH are derived from biomass (hereinafter, EVOH containing raw materials derived from biomass in the gas barrier resin composition of this invention is also referred to as "biomass-derived EVOH"). This gas barrier resin composition has an extremely low environmental impact due to the use of biomass-derived raw materials. Furthermore, since EVOH is selected as the gas barrier resin in this gas barrier resin composition, even when synthesized using biomass-derived raw materials, EVOH can still exhibit the same high gas barrier properties and molding processability as EVOH synthesized solely from raw materials derived from fossil fuels. Moreover, EVOH with the same structure refers to EVOH with the same degree of polymerization, the same ratio of each structural unit, the same degree of denaturation, and the same degree of saponification.

[0014] The fact that ethylene and ethylene esters used as raw materials are derived from biomass can be confirmed by measuring biobase content. Biobase content refers to an indicator of the proportion of raw materials derived from biomass; in this specification, it is determined by measuring the concentration of radiocarbon (14C) obtained using an accelerator mass analyzer (AMS). Specifically, biobase content can be measured according to the method described in ASTM D6866-18.

[0015] "Biomass" refers to organic resources derived from plants and animals, after the removal of fossil fuels (fossil resources). Biomass can be organic resources derived from plants.

[0016] The gas barrier resin composition of this invention can also be traced using the concentration of radioactive carbon (¹⁴C) in the company's products. Organisms ingest radioactive carbon (¹⁴C) from the atmosphere during their activities, thus containing a certain amount. However, if they cease activity, they stop ingesting new ¹⁴C, resulting in a decrease in the ¹⁴C ratio relative to total carbon. Furthermore, it is known that when plants fix carbon, a phenomenon called isotope identification occurs, and the ¹⁴C ratio relative to total carbon varies among different plants. It is also known that the ¹⁴C ratio relative to total carbon varies depending on the origin and age, and different raw materials with different ¹⁴C ratios relative to total carbon can be obtained depending on the biomass used as raw material. For example, by varying the ratios of different raw materials with different ¹⁴C ratios relative to total carbon, it becomes possible to obtain EVOH with a specific ¹⁴C ratio relative to total carbon. By investigating this ¹⁴C ratio relative to total carbon, it becomes possible to trace the EVOH (gas barrier resin composition) manufactured by the company.

[0017] EVOH is used in a wide range of applications, and it is the supplier's responsibility to supply high-quality products to the market. Furthermore, for brand building, methods for distinguishing one's own products from those of other companies are required. For example, the EVOH used in the gas barrier layer of commercially available packaging containers is formed by thermoforming. Due to the heat exposure during thermoforming, the ethylene-vinyl ester copolymer saponification can form a gel that is insoluble in solvents. Therefore, even if the packaging containers are recycled, the EVOH used is extracted with a solvent, and the molecular weight is measured, it is often difficult to accurately measure the molecular weight. Therefore, simply analyzing the molded product is insufficient to determine whether it is one's own company's EVOH.

[0018] EVOH has undergone numerous distribution channels and is used as a packaging material for food, pharmaceuticals, industrial chemicals, and pesticides, in the form of films, sheets, and containers. Furthermore, leveraging its barrier, heat-insulating, and stain-resistant properties, it is also used in automotive fuel tanks, tire tubing, agricultural films, geomembranes, and shoe cushioning materials. However, when using EVOH materials, especially after disposal, it becomes difficult to determine which factory or production line the resin or its packaging containers originated from. It also makes it difficult to track the quality of the company's products during or after use, the environmental impact after disposal, or their biodegradability in the ground.

[0019] One method for tracking self-produced products is to add a tracking agent to EVOH. However, adding a tracking agent can lead to increased costs or reduced performance of EVOH. In this context, using the concentration of radiocarbon (14C) to track self-produced products is a very useful feature.

[0020] The gas barrier resin composition of this invention is a resin composition that has the function of inhibiting gas permeation. Under conditions of 20°C-65%RH, the upper limit of the oxygen permeation rate of the gas barrier resin composition of this invention, measured according to the method described in JIS K7126-2 (isobaric method; 2006), is preferably 100 mL·20 μm / (m2·day·atm), more preferably 50 mL·20 μm / (m2·day·atm), and even more preferably 10 mL·20 μm / (m2·day·atm), 1 mL·20 μm / (m2·day·atm), or 0.5 mL·20 μm / (m2·day·atm).

[0021] (Derived from biomass EVOH) The biomass-derived EVOH contained in the gas barrier resin composition of the present invention is derived from the ethylene and ethylene ester monomers. By including biomass-derived EVOH, the biomass-derived EVOH of the gas barrier resin composition of the present invention can be improved, thereby reducing the environmental impact.

[0022] Biomass-derived EVOH is obtained by saponification of a copolymer of biomass-derived ethylene and ethylene esters. The production and saponification of the ethylene-ethylene ester copolymer, which is a precursor to biomass-derived EVOH, can be carried out using the same known methods as those used for the production and saponification of fossil fuel-derived ethylene-ethylene ester copolymers. As the ethylene ester, vinyl carboxylic acid esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl decanoate, vinyl laurate, vinyl stearate, vinyl tert-valerate, and vinyl tert-carbonate can be used, with vinyl acetate being preferred.

[0023] Ethylene derived from biomass can be manufactured using known methods such as purifying bioethanol from biomass feedstocks and performing dehydration reactions. Biomass feedstocks can be waste-based, unused, or resource-based, including, for example, cellulosic crops (pulp, kenaf, wheat straw, rice straw, old paper, papermaking residue, etc.), wood, charcoal, compost, natural rubber, cotton, sugarcane, soybean residue, oils (rapeseed oil, cottonseed oil, soybean oil, coconut oil, castor oil, etc.), carbohydrate-based crops (corn, taro, wheat, rice, rice husk, rice bran, old rice, cassava, sago, etc.), bagasse, buckwheat, soybeans, essential oils (pine root oil, orange oil, eucalyptus oil, etc.), pulping black liquor, and vegetable oil residues.

[0024] There are no particular limitations on the method for producing bioethanol. For example, the biomaterials can be pretreated as necessary (pressured hot water treatment, acid treatment, alkali treatment, saccharification using saccharifying enzymes), and then fermented by yeast to produce bioethanol. The bioethanol can then be purified through distillation and dehydration. When performing saccharification during bioethanol production, either continuous saccharification and fermentation (stages of saccharification and fermentation) or parallel saccharification and fermentation (simultaneous saccharification and fermentation) can be used. From a production efficiency perspective, parallel saccharification and fermentation is preferable for producing bioethanol.

[0025] Commercially available bio-based ethylene can be used, such as bio-based ethylene derived from sugarcane produced by Braskem SA.

[0026] Examples of biomass-derived ethylene esters include those manufactured using biomass-derived ethylene. Methods for manufacturing biomass-derived ethylene esters include, for example, a common industrial method using a palladium catalyst to react ethylene with acetic acid and oxygen molecules. Furthermore, in biomass-derived ethylene esters, the portion derived from carboxylic acids such as acetic acid (acetic acid group) can be derived from biomass or fossil fuels. That is, biomass-derived ethylene esters can be manufactured using biomass-derived ethylene and carboxylic acids derived from either biomass or fossil fuels. This is because the portion derived from carboxylic acids in ethylene-ethylene ester copolymers is largely removed through saponification, and since the removed carboxylic acids can be reused in synthesis, there is almost no impact from a carbon neutrality perspective.

[0027] The lower limit of ethylene content in biomass-derived EVOH is preferably 20 mol%, more preferably 23 mol%, and even better than 25 mol%. If the ethylene content in biomass-derived EVOH is above 20 mol%, there is a tendency for improved processability and long-term usability. The upper limit of ethylene content in biomass-derived EVOH is preferably 60 mol%, more preferably 55 mol%, and even better than 50 mol%. If the ethylene content in biomass-derived EVOH is below 60 mol%, there is a tendency for better gas barrier properties. The ethylene content of EVOH can be determined by nuclear magnetic resonance (NMR).

[0028] The lower limit of the degree of saponification of bio-derived EVOH is preferably 90 mol%, more preferably 95 mol%, and even more preferably 99 mol%. If the degree of saponification of bio-derived EVOH is above 90 mol%, the gas barrier properties, molding processability, and long-term serviceability of the gas barrier resin composition of the present invention tend to become better. Furthermore, the upper limit of the degree of saponification of bio-derived EVOH can be 100 mol%, or 99.97 mol% or 99.94 mol%. The degree of saponification of EVOH can be calculated by measuring the peak area of ​​hydrogen atoms contained in the ethylene ester structure and the peak area of ​​hydrogen atoms contained in the vinyl alcohol structure using 1H-NMR.

[0029] The biomass basis of biomass-derived EVOH is preferably above 99%, with above 99.5% being even better, and 100% is also acceptable. Since there are cases where some raw materials are mixed with fossil fuel-derived materials, the biomass basis may be lower than 100%. However, from the perspective of reducing environmental impact, the biomass basis of biomass-derived EVOH is preferably within the above range.

[0030] The biomass-derived EVOH may contain units derived from monomers other than ethylene, ethylene esters, and their saponifications, without hindering the purpose of this invention. When the biomass-derived EVOH contains the aforementioned units derived from other monomers, the upper limit of the content of these units relative to the total structural units of the biomass-derived EVOH is preferably 30 mol%, more preferably 20 mol%, 10 mol%, even more preferably 5 mol%, and sometimes 1 mol%. Furthermore, when the biomass-derived EVOH contains the aforementioned units derived from other monomers, the lower limit of its content may be 0.05 mol% or 0.10 mol. Other monomers mentioned above include, for example, alkenes such as propylene, butene, pentene, and hexene; 3-acetylated 1-propene, 3-acetylated 1-butene, 4-acetylated 1-butene, 3,4-diacetylated 1-butene, 3-acetylated 4-methyl-1-butene, 4-acetylated 2-methyl-1-butene, 4-acetylated 3-methyl-1-butene, 3,4-acetylated 2-methyl-1-butene, 4-acetylated 1-pentene, 5-acetylated 1-pentene, 4,5-acetylated 1-pentene, 4-acetylated 1-hexene, 5-acetylated 1-hexene, 6-acetylated 1-hexene, 5,6-acetylated 1-hexene, etc. Alkenes with ester groups, such as 1,3-diethoxy-2-methylenepropane, or their saponifications; unsaturated acids, such as acrylic acid, methacrylic acid, crotonic acid, and isoconic acid, or their anhydrides, salts, or mono- or dialkyl esters; nitriles, such as acrylonitrile and methacrylonitrile; acetylamines, such as acrylamide and methacrylamide; olefin sulfonic acids, such as vinyl sulfonic acid, allyl sulfonic acid, and methyl allyl sulfonic acid, or their salts; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, γ-methacryloxypropylmethoxysilane, and other vinyl silane compounds; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, etc.

[0031] Biomass-derived EVOH can also be denatured by methods such as carbamate, acetalization, cyanoethylation, and oxyalkylation.

[0032] When biomass-derived EVOH has other monomer units or other modified groups, biomass-derived EVOH can also have the structural unit (modified group) shown in the following formula (I).

[0033]

[0034] [In formula (I), X represents a hydrogen atom, a methyl group, or a group represented by R2 -OH. R1 and R2 each independently represent a single bond, an alkyl group having 1 to 9 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms. The aforementioned alkyl and alkoxy groups may also contain hydroxyl, alkoxy, or halogen atoms.]

[0035] The X group is preferably represented by a hydrogen atom or a group indicated by R2-OH, and more preferably by a group indicated by R2-OH.

[0036] The alkyl and alkoxy groups used as R1 or R2 may also contain hydroxyl, alkoxy, or halogen atoms. R1 and R2 are preferably alkyl or alkoxy groups having 1 to 5 carbon atoms, and more preferably alkyl or alkoxy groups having 1 to 3 carbon atoms.

[0037] As specific examples of the building unit (variant base) shown in Equation (I), examples can be given such as the building units (variant bases) shown in Equations (II), (III) and (IV) below.

[0038]

[0039] [In formula (II), R3 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group may also contain a hydroxyl, alkoxy, or halogen atom.]

[0040]

[0041] [In formula (III), R5 is synonymous with X in formula (I). R6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may also contain a hydroxyl, alkoxy, or halogen atom.]

[0042]

[0043] In formula (IV), R7 and R8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydroxyl group. Furthermore, some or all of the hydrogen atoms in the aforementioned alkyl or cycloalkyl groups may be replaced by hydroxyl, alkoxy, or halogen atoms.

[0044] In this invention, R1 in formula (I) may be a single bond, and X may be a hydroxymethyl group (R3 and R4 in formula (II) may be hydrogen atoms). By using biomass-derived EVOH having this building block (modified group), there is a tendency to improve secondary processing properties such as stretchability and thermoforming properties without significantly deteriorating gas barrier properties. When biomass-derived EVOH contains the above-mentioned building block (modified group), the lower limit of its content is preferably 0.1 mol%, more preferably 0.4 mol%, and even more preferably 1.0 mol%. On the other hand, from the viewpoint of achieving good gas barrier properties, the upper limit of the content of the above-mentioned building block (modified group) is preferably 20 mol%, more preferably 10 mol%, even more preferably 8 mol%, and particularly preferably 5 mol%.

[0045] In this invention, R1 in formula (I) may be a hydroxymethylene group, and X may be a hydrogen atom (R5 and R6 in formula (III) may be hydrogen atoms). By using biomass-derived EVOH having this structural unit (modified group), there is a tendency to improve secondary processing properties such as stretchability and thermoforming properties without significantly deteriorating gas barrier properties. When biomass-derived EVOH contains the above-mentioned structural unit (modified group), the lower limit of its content is preferably 0.1 mol%, more preferably 0.4 mol%, and even more preferably 1.0 mol%. On the other hand, from the viewpoint of achieving good gas barrier properties, the upper limit of the content of the above-mentioned structural unit (modified group) is preferably 20 mol%, more preferably 10 mol%, even more preferably 8 mol%, and particularly preferably 5 mol%.

[0046] In this invention, R1 in formula (I) can also be a methylmethyleneoxy group, and X can be a hydrogen atom. By using biomass-derived EVOH having this structural unit (modified group), there is a tendency to improve secondary processing properties such as stretchability and thermoforming properties without significantly deteriorating gas barrier properties. Furthermore, the aforementioned methylmethyleneoxy group is its oxygen atom bonded to the carbon atom of the main chain. That is, in formula (IV), it is preferable that one of R7 and R8 is a methyl group, and the other is a hydrogen atom. When the biomass-derived EVOH contains the aforementioned structural unit (modified group), the lower limit of its content is preferably 0.1 mol%, more preferably 0.5 mol%, more preferably 1.0 mol%, and particularly preferably 2.0 mol%. On the other hand, from the viewpoint of achieving good gas barrier properties, the upper limit of the content of the aforementioned building blocks (modified groups) is preferably 20 mol%, preferably 15 mol%, and even better 10 mol%.

[0047] Biomass-derived EVOH can be used alone or in combination with two or more types.

[0048] When using two or more bio-derived EVOHs, it is preferable to use two or more bio-derived EVOHs with different melting points. By using two or more bio-derived EVOHs with different melting points, there is a tendency to exhibit excellent molding processability. The gas barrier resin composition of the present invention includes EVOH(X) and EVOH(Y) with a lower melting point than the aforementioned EVOH(X) as bio-derived EVOHs. From the viewpoint of making the molding processability even better, the mass ratio (X / Y) of EVOH(X) is preferably 60 / 40 or more and 95 / 5 or less.

[0049] (EVOH(X)) EVOH(X) is an EVOH with a higher melting point than EVOH(Y), and is generally the EVOH with the highest melting point among the biomass-derived EVOH contained in the gas barrier resin composition of the present invention. The gas barrier resin composition of the present invention tends to have excellent gas barrier properties by including EVOH(X). The lower limit of the melting point of EVOH(X) is preferably 150°C, more preferably 155°C, and even more preferably 160°C. The upper limit of the melting point of EVOH(X) is preferably 200°C. If the melting point of EVOH(X) is within the above range, the gas barrier properties of the gas barrier resin composition of the present invention tend to become better.

[0050] From the viewpoint of achieving good processability and long-term usability, the lower limit of the ethylene content in EVOH(X) is preferably 20 mol%, more preferably 22 mol%, and even better than 24 mol%. Furthermore, from the viewpoint of increasing the melting point and achieving good gas barrier properties, the upper limit of the ethylene content in EVOH(X) is preferably 50 mol%, more preferably 48 mol%, and even better than 46 mol%.

[0051] The lower limit of the degree of saponification of EVOH(X) is preferably 90 mol%, more preferably 95 mol%, and even more preferably 99 mol%. If the degree of saponification of EVOH(X) is above 90 mol%, the gas barrier properties, molding processability, and long-term serviceability of the gas barrier resin composition of the present invention tend to become better. Furthermore, the upper limit of the degree of saponification of EVOH(X) can be 100 mol%, or 99.97 mol% or 99.94 mol%.

[0052] EVOH(X) may contain monomer units other than ethylene, ethylene esters and their saponifications described in the above-mentioned biomass-derived EVOH, without hindering the purpose of the present invention. From the viewpoint of maintaining the gas barrier properties of the gas barrier resin composition of the present invention, it is preferable not to contain other monomer units. When EVOH(X) contains the above-mentioned other monomer units, the content of EVOH(X) relative to the total structural units is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 1 mol% or less.

[0053] (EVOH(Y)) EVOH(Y) is a bio-derived EVOH with a lower melting point than EVOH(X). The gas barrier resin composition of the present invention, by including EVOH(Y), tends to exhibit excellent molding and processability. The lower limit of the melting point of EVOH(Y) is preferably 100°C, more preferably 105°C, and even more preferably 110°C. The upper limit of the melting point of EVOH(Y) is preferably 180°C. If the melting point of EVOH(Y) is within the above range, the gas barrier properties of the gas barrier resin composition of the present invention tend to become better.

[0054] From the perspective of lowering the melting point and improving molding processability and long-term usability, the lower limit of the ethylene content in EVOH(Y) is preferably 30 mol%, more preferably 32 mol%, and even more preferably 34 mol%. Furthermore, from the perspective of improving gas barrier properties, the upper limit of the ethylene content in EVOH(Y) is preferably 60 mol%, more preferably 58 mol%, and even more preferably 56 mol%.

[0055] The lower limit of the degree of saponification of EVOH(Y) is preferably 90 mol%, more preferably 95 mol%, and even more preferably 99 mol%. If the degree of saponification of EVOH(Y) is higher than 90 mol%, the gas barrier properties, molding processability, and long-term serviceability of the gas barrier resin composition of the present invention tend to become better. Furthermore, the upper limit of the degree of saponification of EVOH(Y) can be 100 mol%, or 99.97 mol%, or 99.94 mol%. Moreover, from the viewpoint of improving molding processability, the lower limit of the degree of saponification of EVOH(Y) can be 70 mol%, or 80 mol%, and the upper limit of the degree of saponification of EVOH(Y) can be 98 mol.

[0056] EVOH(Y) may contain monomer units (structural units) other than ethylene, ethylene esters and their saponifications described in the above-mentioned biomass-derived EVOH, without hindering the purpose of the present invention. From the viewpoint of lowering the melting point of EVOH(Y) and improving the molding and processability of the gas barrier resin composition of the present invention, it is preferable that EVOH(Y) contains other monomer units (structural units). When EVOH(Y) contains other monomer units, the lower limit of the content of EVOH(Y) relative to the total structural units is preferably 0.1 mol%, and more preferably 0.3 mol%. Furthermore, the upper limit of the above content is preferably 15 mol%, and more preferably 10 mol%. There are no particular limitations on other monomer units (structural units), but the structural units described in formula (I) above are preferred, the structural units of formulas (II), (III) or (IV) above are preferred, and formula (IV) above is even more preferred. EVOH(Y) tends to have excellent molding and processability by including the other monomer units (construction units) mentioned above.

[0057] The difference in ethylene unit content (YX) between EVOH(Y) and EVOH(X) is preferably 5 mol% or more, preferably 7 mol% or more, and even more preferably 10 mol% or more. However, the aforementioned difference in ethylene unit content (YX) can also be 25 mol% or less. If the difference in ethylene unit content (YX) is within the above range, it tends to exhibit good gas barrier properties and improved moldability.

[0058] The melting point difference (XY) between EVOH(X) and EVOH(Y) is preferably above 15°C, and more preferably above 18°C. This melting point difference (XY) can be below 100°C or below 50°C. If the melting point difference (XY) is within the above range, it tends to exhibit good gas barrier properties and improved molding processability.

[0059] The mass ratio (X / Y) of EVOH(X) to EVOH(Y) is preferably 60 / 40 or higher, and more preferably 65 / 35 or higher. Furthermore, the mass ratio (X / Y) is preferably 95 / 5 or lower, and more preferably 90 / 10 or lower. If the mass ratio (X / Y) is within the above range, it tends to exhibit good gas barrier properties and improved molding processability.

[0060] (EVOH(Z)) The gas barrier resin composition of this invention may also contain EVOH(Z), which has a lower melting point than EVOH(Y). If the gas barrier resin composition contains EVOH(Z), it tends to exhibit excellent molding and processability. The suitable state of EVOH(Z) is the same as that of EVOH(Y), except that its melting point is lower than that of EVOH(Y).

[0061] According to JIS K7210:1999, the lower limit of the melt flow rate (MFR) of biomass-derived EVOH at 190°C and 2160g load is preferably 0.1 g / 10, more preferably 0.5 g / 10, and even more preferably 1.0 g / 10. On the other hand, the upper limit of the MFR of biomass-derived EVOH is preferably 30 g / 10, more preferably 20 g / 10, and even more preferably 15 g / 10. If the MFR of biomass-derived EVOH at 190°C and 2160g load is within the above range, there is a tendency for improved molding processability.

[0062] The lower limit of the melting point of biomass-derived EVOH is preferably 135℃, preferably 150℃, and even better than 155℃. EVOH derived from biomass tends to have excellent gas barrier properties if its melting point is above 135℃. The upper limit of the melting point of biomass-derived EVOH is preferably 200℃, preferably 190℃, and even better than 185℃. EVOH derived from biomass tends to have improved molding processability if its melting point is below 200℃.

[0063] The lower limit of the proportion of biomass-derived EVOH in the total resin composition of the gas barrier resin of the present invention is preferably 80% by mass, more preferably 90% by mass, even more preferably 95% by mass, particularly preferably 98% by mass, and may also be 99% by mass. The resin composition of the gas barrier resin of the present invention may be substantially composed solely of biomass-derived EVOH, or may be composed solely of biomass-derived EVOH. Furthermore, the lower limit of the proportion of biomass-derived EVOH in the gas barrier resin composition of the present invention is preferably 80% by mass, more preferably 90% by mass, even more preferably 95% by mass, particularly preferably 98% by mass, and may also be 99% by mass. The gas barrier resin composition of the present invention may also be substantially composed solely of biomass-derived EVOH.

[0064] From the viewpoint of tracking products from the company, the gas barrier resin composition of the present invention preferably contains sulfur compounds exceeding 0 ppm to 100 ppm in terms of sulfur atoms. Furthermore, the inventors have learned that sulfur compounds with a sulfur atom content of less than 100 ppm do not substantially affect the performance of the gas barrier resin composition; therefore, sulfur compounds are suitable as tracking agents. The upper limit of the sulfur compound content is preferably 50 ppm, more preferably 5 ppm, more preferably 3 ppm, and particularly preferably 1.5 ppm. The lower limit of the sulfur compound content can be 0.0001 ppm, 0.001 ppm, 0.01 ppm, 0.05 ppm, or 0.1 ppm. When using biomass-derived raw materials, there may be cases where EVOH containing organic sulfur compounds contained in the biomass raw materials is obtained. On the other hand, EVOH derived from fossil fuels undergoes desulfurization during petroleum naphtha cracking, thus containing less sulfur compounds compared to EVOH derived from biomass. Therefore, when using this biomass-derived EVOH, tracking the biomass-derived EVOH becomes easier by comparing the content of sulfur compounds. In particular, the gas barrier resin composition of the present invention, as a sulfur compound, becomes easier to track when it contains organic sulfur compounds, including dimethyl sulfide or dimethyl sulfide. Furthermore, from the viewpoint of tracking products from the company, it is preferable that the biomass-derived ethylene and biomass-derived vinyl esters used as raw materials, as well as the obtained EVOH, are not subjected to excessive purification to ensure that the content of sulfur compounds is below the detection limit.

[0065] (Other ingredients) The gas barrier resin composition of this invention is preferably rich in carboxylic acid. The presence of carboxylic acid in the gas barrier resin composition of this invention improves melt molding properties and coloring resistance at high temperatures. In particular, the increased pH buffering capacity of the gas barrier resin composition improves coloring resistance to acidic or alkaline substances, and a pKa of the carboxylic acid in the range of 3.5 to 5.5 is preferred.

[0066] When the gas barrier resin composition of the present invention contains carboxylic acid, the lower limit of its content is preferably 30 ppm (converted to carboxylate ions), and more preferably 100 ppm. On the other hand, the upper limit of the carboxylic acid content is preferably 1000 ppm, and more preferably 600 ppm. If the carboxylic acid content is above 30 ppm, there is a tendency for improved resistance to coloring at high temperatures. On the other hand, if the carboxylic acid content is below 1000 ppm, there is a tendency for improved melt molding properties. The carboxylic acid content can be calculated by titrating an extract obtained by extracting 10 g of the resin composition in 50 ml of pure water at 95°C for 8 hours. Here, the content of carboxylic acid in the resin composition does not take into account the content of carboxylates present in the above-mentioned extract. Furthermore, carboxylic acid may also exist as carboxylate ions.

[0067] Examples of carboxylic acids include monovalent and polyvalent carboxylic acids, which can be composed of one or more types. When both monovalent and polyvalent carboxylic acids are included, the melt-forming properties and colorfastness at high temperatures of the gas barrier resin composition can be further improved. Furthermore, polyvalent carboxylic acids may also have three or more carboxyl groups. In this case, the colorfastness of the gas barrier resin composition of the present invention can be further enhanced.

[0068] A monovalent carboxylic acid is a compound containing one carboxyl group within its molecule. A pKa value in the range of 3.5 to 5.5 is preferred for monovalent carboxylic acids. Examples of such monovalent carboxylic acids include formic acid (pKa = 3.77), acetic acid (pKa = 4.76), propionic acid (pKa = 4.85), butyric acid (pKa = 4.82), hexanoic acid (pKa = 4.88), decanoic acid (pKa = 4.90), lactic acid (pKa = 3.86), acrylic acid (pKa = 4.25), methacrylic acid (pKa = 4.65), benzoic acid (pKa = 4.20), and 2-naphthoic acid (pKa = 4.17). These carboxylic acids may also have hydroxyl, amino, or halogen atoms as substituents, provided their pKa is within the range of 3.5 to 5.5. Acetic acid is preferred due to its high safety and ease of handling.

[0069] Polyvalent carboxylic acids refer to compounds with two or more carboxyl groups in their molecules. In this case, it is preferable that the pKa of at least one carboxyl group is in the range of 3.5 to 5.5. Examples of such polyvalent carboxylic acids include oxalic acid (pKa2=4.27), succinic acid (pKa1=4.20), fumaric acid (pKa2=4.44), malic acid (pKa2=5.13), glutaric acid (pKa1=4.30, pKa2=5.40), adipic acid (pKa1=4.43, pKa2=5.41), pimelic acid (pKa1=4.71), phthalic acid (pKa2=5.41), isophthalic acid (pKa2=4.46), p-phthalic acid (pKa1=3.51, pKa2=4.82), citric acid (pKa2=4.75), tartaric acid (pKa2=4.40), glutamic acid (pKa2=4.07), and aspartic acid (pKa=3.90).

[0070] The gas barrier resin composition of the present invention preferably contains more phosphoric acid compounds. When the gas barrier resin composition of the present invention contains phosphoric acid compounds, the lower limit of its content is preferably 1 ppm (equivalent to phosphate), and more preferably 3 ppm. On the other hand, the upper limit of the above content is preferably 200 ppm (equivalent to phosphate), and more preferably 100 ppm. If phosphoric acid compounds are contained within this range, the thermal stability of the gas barrier resin composition of the present invention can be improved. In particular, the generation of gel-like impurities or discoloration during long-term melt molding can be suppressed. As phosphoric acid compounds, various acids such as phosphoric acid and aphosphoric acid, or their salts, can be used. The phosphate can be in any form of a first phosphate, a second phosphate, or a third phosphate. Examples of cations for phosphates include alkali metals and alkaline earth metals. Specifically, examples of phosphoric acid compounds include sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

[0071] The gas barrier resin composition of the present invention is preferably rich in boron compounds. When the gas barrier resin composition of the present invention contains boron compounds, the lower limit of its content is preferably 5 ppm (equivalent to boron atoms), and more preferably 100 ppm. On the other hand, the upper limit of the above content is preferably 5000 ppm (equivalent to boron atoms), and more preferably 1000 ppm. If boron compounds are present within this range, the thermal stability of the gas barrier resin composition of the present invention during melt molding can be improved, and the formation of gel-like impurities can be suppressed. Furthermore, the mechanical properties of the obtained molded article can also be improved. These effects are presumably due to the chelate interaction between EVOH and the boron compounds. Examples of boron compounds include boric acid, borate esters, borate salts, and boron hydride. Specifically, examples of boric acids include, for example, orthoboric acid (H3BO3), metaboric acid, and tetraboric acid; examples of borate esters include, for example, trimethyl borate and triethyl borate; and examples of borate salts include, for example, alkali metal salts of the aforementioned boric acids, alkaline earth metal salts, and borax.

[0072] The gas barrier resin composition of the present invention is preferably rich in metal ions. When the gas barrier resin composition of the present invention contains metal ions, the interlayer adhesion is excellent when formed into a multilayer molded body, i.e., a multilayer structure. The reason for the improved interlayer adhesion is not clear, but it is believed that when the layers composed of the gas barrier resin composition and adjacent layers contain molecules with functional groups capable of reacting with the hydroxyl groups of EVOH, the bonding reaction between the two is accelerated by the metal ions. Furthermore, controlling the ratio of metal ions to the aforementioned carboxylic acid can also improve the melt molding properties or colorfastness of the gas barrier resin composition of the present invention.

[0073] When the gas barrier resin composition of the present invention contains metal ions, the lower limit of its content is preferably 1 ppm, more preferably 100 ppm, and even more preferably 150 ppm. On the other hand, the upper limit of the metal ion content is preferably 1000 ppm, more preferably 400 ppm, and even more preferably 350 ppm. If the metal ion content is 1 ppm or more, there is a tendency for the interlayer adhesion of the obtained multilayer structure to become better. On the other hand, if the metal ion content is 1000 ppm or less, there is a tendency for the colorfastness to become better.

[0074] Examples of metal ions include monovalent metal ions, divalent metal ions, and other transition metal ions, which may consist of one or more types. Monovalent and divalent metal ions are preferred.

[0075] Alkali metal ions are preferred as monovalent metal ions, such as lithium, sodium, potassium, rubidium, and cesium ions. From an industrial perspective, sodium or potassium ions are preferred due to their ease of acquisition. Furthermore, alkali metal salts that impart alkali metal ions can be categorized as aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, and metal complexes. Among these, aliphatic carboxylates and phosphates are preferred because they are readily available; specifically, sodium acetate, potassium acetate, sodium phosphate, and potassium phosphate are preferred.

[0076] As for the metal ions, it is preferable to include divalent metal ions. If the metal ions include divalent metal ions, for example, the thermal degradation of EVOH during the recycling and reuse of trimmed material is suppressed, and the formation of gel and impurities in the obtained molded body is also suppressed. Examples of divalent metal ions include beryllium, magnesium, calcium, strontium, barium, and zinc ions; from an industrial perspective, magnesium, calcium, or zinc ions are preferred. Furthermore, examples of divalent metal salts that impart divalent metal ions include carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, and metal complexes, with carboxylates being preferred. As for the carboxylic acids constituting the carboxylates, carboxylic acids with 1 to 30 carbon atoms are preferred; specific examples include acetic acid, stearic acid, lauric acid, octacoate, docosanoic acid, octanoic acid, sebacic acid, castor oil, myristic acid, palmitic acid, etc., with acetic acid and stearic acid being particularly preferred.

[0077] If the gas barrier resin composition of the present invention does not impede the scope of the present invention, it may also contain other components such as anti-caking agents, processing aids, resins other than EVOH, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, anti-static agents, lubricants, colorants, fillers, surfactants, desiccants, oxygen absorbers, crosslinking agents, and reinforcing agents for various fibers.

[0078] Examples of anti-caking agents include oxides, nitrides, and nitride oxides of elements selected from silicon, aluminum, magnesium, zirconium, cerium, tungsten, and molybdenum. Among these, silicon oxide is preferred due to its ease of acquisition. The gas barrier resin composition of the present invention improves its barrier resistance by including an anti-caking agent.

[0079] Examples of processing aids include fluorinated processing aids such as Kynar (trademark) manufactured by Arkema and Dynamar (trademark) manufactured by 3M. The gas barrier resin composition of this invention, by including processing aids, tends to prevent the adhesion of contaminants to the mold lip.

[0080] Resins other than EVOH include, for example, various polyolefins (polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymers, copolymers of ethylene with α-olefins having 4 or more carbon atoms, copolymers of polyolefins with anhydrous maleic acid, ethylene-vinyl ester copolymers, ethylene-acrylate copolymers, or modified polyolefins modified by grafting unsaturated carboxylic acids or their derivatives), various polyamides (nylon 6, nylon 6.6, nylon 6 / 66 copolymers, nylon 11, nylon 12, poly(m-phenylene adipamide), etc.), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate, and modified polyvinyl alcohol resins).

[0081] Examples of stabilizers used to improve melt stability include hydrotalcite compounds, hindered phenolic and hindered amine heat stabilizers, and metal salts of higher aliphatic carboxylic acids (e.g., calcium stearate, magnesium stearate, etc.). When the gas barrier resin composition of the present invention contains a stabilizer, its content is preferably 0.001 to 1% by mass.

[0082] Examples of antioxidants include 2,5-di-t-butyl-hydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis-(6-t-butylphenol), 2,2'-methylene-bis-(4-methyl-6-t-butylphenol), octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, and 4,4'-thiobis-(6-t-butylphenol).

[0083] Examples of UV absorbers include ethylene-2-cyano-3',3'-diphenyl acrylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone.

[0084] Examples of plasticizers include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, waxes, fluidized paraffin, and phosphate esters.

[0085] Examples of anti-static agents include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, and carbowax.

[0086] Examples of lubricants include ethylene distearamide and butyl stearate.

[0087] Examples of colorants include carbon black, phthalocyanine, quinacridone, indoline, azo pigments, and iron oxide red (bengala).

[0088] Examples of fillers include glass fiber, asbestos, vallastonite, and calcium silicate.

[0089] Examples of desiccants include phosphates (with the above-mentioned phosphates removed), sodium borate, sodium sulfate, sodium chloride, sodium nitrate, sugar, silica gel, bentonite, molecular sieves, and superabsorbent resins.

[0090] From the viewpoint of preventing the formation of pores during molding and processing, the water content of the gas barrier resin composition of the present invention is preferably 3.0 parts by weight or less, more preferably 1.0 parts by weight or less, even more preferably 0.5 parts by weight or less, and particularly preferably 0.3 parts by weight or less, relative to a total of 100 parts by weight of EVOH derived from biomass.

[0091] The gas barrier resin composition of this invention contains biomass-derived impurities, such as EVOH derived from biomass. While various impurities are possible, it tends to contain at least a number of metals such as iron and nickel.

[0092] (Biobase degree of gas barrier resin composition) The biomass content of the gas barrier resin composition of the present invention is preferably above 99%, more preferably above 99.5%, and can also be 100%. Furthermore, the biomass content of this gas barrier resin composition refers to the value measured taking into account other resins and other components besides EVOH. When the biomass content of the gas barrier resin composition of the present invention is within the above-mentioned range, it is preferable due to its extremely low environmental impact.

[0093] The method for including the other components mentioned above in the gas barrier resin composition of the present invention is not particularly limited, and it can be manufactured by melt-blending other components and additives with biomass-derived EVOH. Each component can be in a solid state such as powder, or can be blended into a melt, or blended into a solute contained in a solution or a dispersion medium contained in a dispersion. As solutions and dispersions, aqueous solutions and aqueous dispersions are suitable, respectively. Melt-blending can be performed using known mixing or blending equipment such as a kneader-ruder, extruder, mixing roller, or closed-type mixer. The temperature range during melt-blending can be appropriately adjusted according to the melting point of the biomass-derived EVOH or each component, typically 150~250°C. Alternatively, several components can be added to the biomass-derived EVOH beforehand, and then other necessary components can be added as described above and melt-blended to manufacture the product. As a method for pre-adding several components to biomass-derived EVOH, an example is impregnating the biomass-derived EVOH into granules or powder in a solution of dissolved added components. An aqueous solution is suitable as the solution.

[0094] <Molded Body> A molded body having a layer formed from the gas barrier resin composition of the present invention (hereinafter also referred to as "gas barrier resin composition layer") is a suitable embodiment of the present invention. The gas barrier resin composition of the present invention can also be made into a single-layer molded body, and can also be a molded body (laminated body) having a thermoplastic resin layer. The thermoplastic resin layer refers to a layer in which thermoplastic resin is the main component. Furthermore, the molded body of the present invention can also have an adhesive resin layer (adhesive layer). An adhesive resin layer refers to a layer in which adhesive resin, anchor coating agent, or adhesive is the main component. Here, "main component" means that the proportion of this component is more than 50% by mass, preferably more than 90% by mass. The molded body of the present invention can also have other layers.

[0095] Therefore, the molded body of the present invention can also be made into a multi-layered structure (laminated body). The lower limit of the number of layers of the molded body of the present invention is 1, preferably 2, and more preferably 3. Furthermore, the upper limit of the number of layers of the molded body is, for example, 1000, 100, 20, or 10. The molded body has a low environmental impact and has good gas barrier properties, appearance, and molding processability. The applications of the molded body using the gas barrier resin composition of the present invention are wide-ranging, including, for example, films, sheets, containers, bottles, tanks, pipes, and hoses.

[0096] As specific forming methods, films, sheets, tubes, and hoses can be formed by extrusion molding, container shapes can be formed by injection molding, and hollow containers such as bottles or tanks can be formed by hollow molding or rotational molding. Examples of hollow molding include extrusion hollow molding, which involves forming a preform by extrusion molding and then blowing it into shape, and injection hollow molding, which involves forming a preform by injection molding and then blowing it into shape. The manufacture of flexible packaging materials or containers is suitable for methods such as forming packaging materials like multilayer films by extrusion molding, and thermoforming pre-formed multilayer sheets by extrusion molding to create container-shaped packaging materials.

[0097] The aforementioned multilayer structure is a multilayer structure having at least one gas-barrier resin composition layer and further having a thermoplastic resin layer. This multilayer structure is typically obtained by laminating the gas-barrier resin composition layer with other layers (thermoplastic resin layers). As part of the layer composition of this multilayer structure, a layer composed of resin other than the gas-barrier resin composition of this invention is designated as layer x, the gas-barrier resin composition layer as layer y, and the adhesive resin layer as layer z. Examples include x / y, x / y / x, x / z / y, x / z / y / z / x, x / y / x / y / x, x / z / y / z / x / z / y / z / x, etc. When multiple x, y, and z layers are provided, their types can be the same or different. Furthermore, a layer of recycled resin composed of waste materials such as trimming material generated during molding can also be provided, or the recycled resin can be mixed with layers composed of other resins. From the perspective of formability and cost, the thickness of each layer in a multilayer film is typically 2 to 20% of the thickness of the y-layer relative to the total thickness.

[0098] From a processability perspective, thermoplastic resins are preferred as the resins used in the aforementioned x-layer. Examples of thermoplastic resins include various polyolefins (polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymers, copolymers of ethylene with α-olefins having 4 or more carbon atoms, copolymers of polyolefins with anhydrous maleic acid, ethylene-vinyl ester copolymers, ethylene-acrylate copolymers, or modified polyolefins grafted with unsaturated carboxylic acids or their derivatives), various polyamides (nylon 6, nylon 6.6, nylon 6 / 66 copolymers, nylon 11, nylon 12, poly(m-phenylene adipamide), etc.), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate, and modified polyvinyl alcohol resins). The thermoplastic resin layer can be non-stretched, or it can be stretched or calendered uniaxially or biaxially. Among them, polyolefins are preferred in terms of moisture resistance, mechanical properties, economy, and heat sealability, while polyamide or polyester are preferred in terms of mechanical properties and heat resistance.

[0099] The adhesive resin used in the aforementioned z-layer is an adhesive resin, preferably a thermoplastic resin. For example, a carboxylic acid-modified polyolefin is suitable as the adhesive resin. Here, carboxylic acid-modified polyolefin refers to a polyolefin copolymer containing an unsaturated carboxylic acid or its anhydride (such as anhydrous maleic acid) as a copolymerizing component; or a graft copolymer obtained by grafting an unsaturated carboxylic acid or its anhydride onto a polyolefin.

[0100] The aforementioned Z-layer system can also utilize adhesives, anchoring agents, etc. Anchoring agents and adhesives can be resins, or substances other than resins such as low-molecular-weight compounds, or can be composed of multiple components. A Z-layer can be formed by applying these and drying as necessary. Surface treatments such as corona discharge treatment of the coating surface before coating can improve adhesion. There are no particular limitations on the adhesive; for example, a two-component reactive polyurethane adhesive that reacts a mixture of polyisocyanate and polyol components is preferred. Furthermore, adhesion can be further improved by adding a small amount of a known silane coupling agent. Suitable examples of silane coupling agents include those having reactive groups such as isocyanate groups, epoxy groups, amino groups, urea groups, and mercapto groups.

[0101] The aforementioned multi-layered structure may also include a paper substrate layer. The paper substrate used as the paper substrate layer can be any paper with various properties such as shaping, bending resistance, rigidity, flexural strength, etc., depending on the intended use of the paper container. Examples include bleached or unbleached paper with strong sizing properties as the main strength material, or various types of paper such as pure white roll paper, kraft paper, paperboard, processed paper, or milk carton paper. The paper substrate layer may also be a combination of multiple layers of such paper. The paper substrate layer has a basis weight of 80-600 g / m², preferably 100-450 g / m², and a thickness of 110-860 μm, preferably 140-640 μm. If the paper substrate layer is thinner than this, the strength of the container will be insufficient; if it is thicker, the rigidity will become too high, potentially making it difficult to process. Furthermore, the paper substrate can be printed using conventional printing methods to create, for example, text, graphics, symbols, and other desired designs.

[0102] Methods for obtaining multilayer structures include, for example, co-extrusion molding, co-extrusion hollow molding, co-injection molding, extrusion lamination, co-extrusion lamination, dry lamination, and solution coating. Furthermore, multilayer structures obtained by such methods can be further processed by vacuum deep drawing, blow molding, or pressure molding, followed by reheating to achieve the desired molded structure. Alternatively, multilayer structures can be obtained by uniaxial or biaxial stretching after reheating within a range below the melting point of EVOH using methods such as roll stretching, scaling stretching, or expansion stretching. The methods described later for manufacturing films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, disc-shaped containers, blow-molded containers, fuel containers, bottle containers, pipes, multilayer pipes, and paper containers are also included in the form of the molding method of the present invention.

[0103] Examples of single-layer or multi-layer molded bodies using the gas barrier resin composition of the present invention include containers (bags, cups, tubes, trays, bottles, etc.), fuel containers, pipes, fibers, food and beverage packaging materials, container filling materials, medical infusion bags, tire tubing, shoe cushioning materials, inner bag materials for bag-in-box packaging, tanks for storing organic liquids, pipes for transporting organic liquids, hot water pipes for greenhouses (hot water pipes for geothermal heating, etc.), packaging materials for cosmetics, packaging materials for dental care, packaging materials for pharmaceuticals, packaging sub-parts (caps, stoppers for bag-in-box packaging, etc.), pesticide bottles, agricultural films (greenhouse films, soil fumigation films), grain storage bags, geotextile films, outer bags for vacuum insulation panels, wallpaper or cosmetic panels, and gas tanks for hydrogen, oxygen, etc. A portion of these examples are described below.

[0104] <film or sheet> The film or sheet of the present invention comprises the molded body of the present invention. A film refers to a "soft, film-like substance with an average thickness of less than 250 μm," and a sheet refers to a "soft, sheet-like substance with an average thickness of 250 μm or more." The distinction between film and sheet is also the same in industrial applications of "film or sheet." Hereinafter, "film or sheet" will also be referred to as "film, etc." The film, etc. of the present invention can be a film, etc., composed of the molded body of the present invention. That is, one embodiment of the molded body of the present invention can be a film, etc. The film, etc. of the present invention has low environmental impact and good gas barrier properties, appearance, and processability. The film, etc. of the present invention can be a single-layer film composed only of a gas barrier resin composition layer, or it can be a multi-layer film. The average thickness of the film, etc. of the present invention is preferably, for example, 1 μm or more but less than 300 μm, and more preferably 5 μm or more but less than 100 μm. The film, etc. of the present invention is suitable for use as various packaging materials, etc.

[0105] The arithmetic mean roughness (Ra) of at least one surface of the thin film of the present invention, as measured according to JIS B0601, is preferably 1.0 μm or less, more preferably 0.8 μm or less, even more preferably 0.6 μm or less, and particularly preferably 0.4 μm or less. The arithmetic mean roughness (Ra) of at least one surface of the thin film of the present invention is preferably 0.05 μm or more, more preferably 0.10 μm or more, even more preferably 0.15 μm or more, and particularly preferably 0.20 μm or more. When the arithmetic mean roughness (Ra) of at least one surface of the thin film of the present invention is within the above-mentioned range, the fracture resistance is excellent.

[0106] The average length (RSm) of the contour curve element of at least one surface of the thin film of the present invention, as measured according to JIS B0601, is preferably 1000 μm or less, more preferably 800 μm or less, more preferably 600 μm or less, and particularly preferably 400 μm or less. The average length (RSm) of the contour curve element of at least one surface of the thin film of the present invention is preferably 50 μm or more, more preferably 100 μm or more, more preferably 150 μm or more, and particularly preferably 200 μm or more. When the average length (RSm) of the contour curve element of at least one surface of the thin film of the present invention is within the above-mentioned range, the fracture resistance is excellent. Furthermore, JIS B0601 refers, for example, to JIS B0601:2001.

[0107] The films of the present invention can be unstretched films, but stretched films are preferred. Stretching increases strength and other properties. Furthermore, when the films of the present invention are stretched films, the generation of stripe-like unevenness that may occur during stretching is less, resulting in better appearance and gas barrier properties. Also, the films of the present invention can be heat-shrinkable films.

[0108] (Manufacturing methods for thin films, etc.) The films and the like of the present invention can be manufactured using known methods. There are no particular limitations on the method for forming the films and the like, and examples include melt processing, solution processing, and calendering, with melt processing being preferred. Examples of melt processing include T-die processing (casting) and inflation processing, with casting being preferred. In particular, it is preferable to manufacture the films using a casting molding step that involves melting and extruding the resin composition constituting the films and the like of the present invention onto a casting roller, and a step that stretches the unstretched film and the like obtained from the aforementioned resin composition. The melting temperature in the melt processing varies depending on the melting point of the gas-barrier resin composition according to the present invention, and is preferably in the range of 150 to 300°C.

[0109] Stretching can be uniaxial or biaxial, with biaxial stretching being preferred. Biaxial stretching can be either sequential biaxial stretching or simultaneous biaxial stretching. The lower limit of the area-converted stretching ratio is preferably 6 times, and more preferably 8 times. The upper limit of the stretching ratio is preferably 15 times, and more preferably 12 times. Stretching ratios within the above ranges can improve the film's thickness uniformity, gas barrier properties, and mechanical strength. Furthermore, the stretching temperature can be, for example, between 60°C and 120°C.

[0110] The method for manufacturing films, etc., according to the present invention may include a heat treatment step on the stretched film, etc., after the stretching step. The heat treatment temperature is usually set to a temperature higher than the stretching temperature, and can be, for example, above 120°C and below 200°C.

[0111] The films of this invention are suitable for use as materials for various packaging containers, such as food packaging containers, pharmaceutical packaging containers, industrial drug packaging containers, and pesticide packaging containers. Furthermore, heat-shrinkable films and industrial films, described later, are also included in one embodiment of the films of this invention.

[0112] Packaging Materials The packaging material of this invention comprises the film or sheet of this invention. The packaging material of this invention can be a packaging material composed of the film or sheet of this invention. That is, one embodiment of the molded body of this invention can be a packaging material. The packaging material of this invention has low environmental impact and also exhibits good gas barrier properties, appearance, and processability.

[0113] The packaging material of the present invention can be a single-layer film or a multi-layer film. Furthermore, the multi-layer film may also have layers formed other than resin, such as paper layers or metal layers. The packaging material of the present invention can be directly in the shape of a film or sheet, or it can be a film or sheet that has undergone secondary processing. Examples of packaging materials obtained through secondary processing include (1) cup-shaped containers obtained by vacuum forming, air-forming, vacuum-air-forming, or thermoforming of the film or sheet; (2) bottles or cup-shaped containers obtained by stretching and blowing the film or sheet; and (3) bag-shaped containers obtained by heat-sealing the film or sheet. Moreover, the secondary processing method is not limited to the methods exemplified above; other known secondary processing methods besides those described above, such as air-forming, can be used appropriately.

[0114] The packaging material of this invention is used to package industrial materials such as food, beverages, pesticides, pharmaceuticals, medical devices, machine parts, and precision materials, as well as clothing. In particular, the packaging material of this invention is preferably used in applications requiring relative oxygen barrier properties, where the interior of the packaging material is replaced by various functional gases. The packaging material of this invention is formed into various forms depending on the application, such as stand-up pouches, vacuum packaging bags, bags with spouts, laminated tubular containers, and container lids.

[0115] Vacuum Packaging Bags The packaging material of this invention can be a vacuum packaging bag. As an example of a vacuum packaging bag, such as a bag-shaped container, it includes a film or similar material as a spacer separating the contents from the outside, and the inside is in a depressurized state. In the vacuum packaging bag, for example, two films of this invention are overlapped, and the edges of the two films are sealed to each other. In the vacuum packaging bag, multi-layered films are preferred as the spacer. The vacuum packaging bag can be manufactured using a nozzle or chamber-type vacuum packaging machine.

[0116] This vacuum packaging bag is used for applications where packaging under vacuum is desired, such as the preservation of food and beverages. Furthermore, this vacuum packaging bag can also be used as outer packaging material for vacuum insulation.

[0117] <Industrial films or sheets> The industrial film or sheet (industrial film or industrial sheet) of the present invention is a molded body comprising a single-layer or multi-layer film of the present invention. The industrial film of the present invention may be an industrial film or the like constructed from the molded body of the present invention. That is, one embodiment of the molded body of the present invention may be an industrial film or the like. The industrial film or the like of the present invention has low environmental impact and also exhibits good gas barrier properties, appearance, and processability. Specific examples of industrial films or the like include agricultural films, landfill films, and building films.

[0118] The industrial films of the present invention are preferably multilayer films. As the thermoplastic resin layer, a hydrophobic thermoplastic resin is preferred to prevent a decrease in the gas barrier performance of the resin composition layer due to moisture. Specifically, examples include polyolefin resins such as linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, ultra-low-density linear polyethylene, medium-density polyethylene, and high-density polyethylene; polyethylene resins such as ethylene-α-olefin copolymers; polypropylene; polypropylene resins such as ethylene-propylene (block and random) copolymers and propylene-α-olefin (α-olefin with 4-20 carbon atoms); polybutene; and grafted polyolefins modified by grafting unsaturated carboxylic acids or their esters onto these polyolefins. Cyclic polyolefin resins; ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, polyester resins, polyamide resins, polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene, vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, chlorinated polypropylene, etc., halogenated polyolefins, aromatic or aliphatic polyketides, etc., among which polyolefin resins are preferred in terms of mechanical strength or molding processability, and polyethylene and polypropylene are particularly good.

[0119] Regarding the melt viscosity of the aforementioned hydrophobic thermoplastic resin, the lower limit of the melt flow rate (MFR) at 210°C and 2160g load is preferably 1.0 g / 10 parts, and more preferably 2.0 g / 10 parts; the upper limit is preferably 100 g / 10 parts, and more preferably 60 g / 10 parts. By using a hydrophobic thermoplastic resin composition with this melt viscosity, it is possible to obtain good multilayer films with no layer disorder.

[0120] As for the layer structure of the industrial film, etc. of the present invention, when the layer composed of resin other than the gas barrier resin composition of the present invention is designated as layer x, the gas barrier resin composition layer is designated as layer y, and the adhesive resin layer is designated as layer z, the layer structure can be illustrated as follows. In the layer structure, the layer further to the left represents the outermost layer (the side exposed to the external environment). 5 layers y / z / x / z / y, x / z / y / z / x, x / z / y / z / y 6 layers x / z / y / z / x / x 7 layers x / z / y / z / y / z / x, x / x / z / y / z / x / x

[0121] Especially for the purpose of preventing the reduction of oxygen barrier properties caused by moisture, it is preferable to use a gas barrier resin composition layer as the intermediate layer and a thermoplastic resin layer as the outer layer, with x / z / y / z / x, x / x / z / y / z / x / x, etc. being more preferred.

[0122] The thickness of the industrial film, etc., of the present invention is generally 5-5 mm, preferably 10-4.5 mm, more preferably 15-4 mm, and particularly preferably 20-3.5 mm. Furthermore, the thickness of the hydrophobic resin composition layer, etc., in the industrial film, etc., is not particularly limited, but is generally 0.5-2.5 mm, preferably 1-2 mm, and particularly preferably 1-1.5 mm. The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1-20% of the total layer thickness, more preferably 2-18%, and even more preferably 3-15%.

[0123] Examples of building films and the like mentioned above include wallpaper. Wallpaper, as one embodiment of the industrial film of the present invention, has low environmental impact and excellent productivity.

[0124] Examples of landfill films include geomembranes and landfill sheets. Geomembranes refer to thin sheets used as waterproofing structures in waste disposal sites. Landfill sheets are thin sheets used to prevent the spread of hazardous substances from industrial waste, for example, they can be used to prevent the spread of radon gas.

[0125] In the aforementioned agricultural films, from the viewpoint of enabling long-term outdoor use, it is preferable that the gas barrier resin composition includes antioxidants or UV stabilizers (UV absorbers, light stabilizers, colorants), etc. The aforementioned agricultural films are preferably multilayer films, and as a thermoplastic resin layer, to prevent the gas barrier performance of the gas barrier resin composition layer from decreasing due to moisture, a hydrophobic thermoplastic resin is preferred.

[0126] Thermoplastic resin layers are preferably incorporating UV-resistant agents or adhesive components. Examples of UV-resistant agents include UV absorbers, light stabilizers, and colorants.

[0127] Compared to the aforementioned hydrophobic thermoplastic resin, the amount of the aforementioned UV-resistant agent incorporated into the hydrophobic thermoplastic resin is typically 1-10% by mass, preferably 2-8% by mass, and particularly preferably 3-5% by mass. If the amount incorporated is less than the above range, the hydrophobic thermoplastic resin becomes more prone to degradation due to ultraviolet radiation. On the other hand, if the amount incorporated is greater than the above range, the mechanical strength of the hydrophobic thermoplastic resin will decrease.

[0128] Examples of adhesive components include aliphatic saturated hydrocarbon resins such as polyisobutylene, or alicyclic saturated hydrocarbon resins. The amount of these components relative to the hydrophobic thermoplastic resin is typically 1-30% by mass, preferably 2-20% by mass, and particularly preferably 3-15% by mass. If the amount is appropriate, the films are easily sealed by being pressed together when packaged with agricultural films. If the amount is less than the above range, gaps are created between the films, allowing air to easily penetrate, thus reducing the long-term shelf life of the contents. Conversely, if the amount exceeds the above range, it can cause blockage of multiple film layers, making it impossible to roll out from the film-forming rollers.

[0129] Regarding the thickness of the aforementioned agricultural films, the total thickness is typically 5–200 μm, preferably 10–150 μm, more preferably 15–100 μm, and particularly preferably 20–50 μm. Furthermore, the thickness of the thermoplastic resin layer (hydrophobic resin composition layer, etc.) in the agricultural films is not particularly limited, but is typically 0.5–200 μm, preferably 1–100 μm, and particularly preferably 1–10 μm. The thickness of the gas barrier resin composition layer is not particularly limited, but is 1–20% of the total layer thickness, preferably 2–18%, and more preferably 3–15%.

[0130] As for storage silos using the aforementioned agricultural films, there are no particular limitations. Examples include covered storage silos, silage pits, bag storage silos, tubular storage silos, and stacked storage silos, with covered storage silos being particularly suitable.

[0131] In manufacturing covered storage silos, the hay is first shaped to the desired volume using machinery such as a roll baler. Then, the shaped hay is wrapped with agricultural film using machinery such as a baler and sealed. Since residual air during sealing can affect the quality of the contents, it is best to apply tension to the agricultural film while simultaneously rolling it up to ensure a tight seal between the contents and the film.

[0132] The aforementioned agricultural films are used for various purposes such as greenhouse films, soil fumigation films, silage films, storage bags, and grain preservation bags.

[0133] <Pipes> The pipe of this invention comprises the molded body of this invention. The pipe of this invention can be a pipe constructed from the molded body of this invention. That is, one embodiment of the molded body of this invention can be a pipe. The pipe of this invention has low environmental impact, and also exhibits good gas barrier properties, appearance, and processability.

[0134] The manufacturing method of the pipe of the present invention is not particularly limited. For example, it can be formed directly into a pipe shape by melt molding such as co-extrusion molding, co-injection molding, or extrusion coating; it can be formed into a pipe shape by hot melting of the film or sheet of the present invention; it can be formed into a pipe shape by laminating the film or sheet of the present invention with an adhesive.

[0135] Multi-layer pipe The multilayer tubing system of the present invention comprises the molded body of the present invention. The multilayer tubing of the present invention can be a multilayer tubing constructed from the molded body of the present invention. That is, one embodiment of the molded body of the present invention can be a multilayer tubing. The multilayer tubing of the present invention has low environmental impact and also exhibits good gas barrier properties, appearance, and processability. From the viewpoint of suppressing oxidative degradation under long-term use, the multilayer tubing system of the present invention preferably contains an antioxidant in the gas barrier resin composition. As the aforementioned antioxidant, from the viewpoint of suppressing oxidative degradation from use at high temperatures, compounds having hindered amine groups and / or compounds having hindered phenolic groups are preferred.

[0136] As a multilayer tube, the layer structure of the molded body described above can be adopted. When multilayer tubes are used as pipes for hot water circulation, they are generally composed of three layers: a thermoplastic resin layer as the outermost layer, a gas barrier resin composition layer, and another thermoplastic resin layer. This is because by adding the co-extrusion coating equipment for the gas barrier resin composition and adhesive resin of this invention to an existing production line for manufacturing single-layer tubes such as cross-linked polyolefins, it is easy to transform it into a production line for manufacturing multilayer tubes of this invention, and in fact, many tube manufacturers adopt this structure.

[0137] Placing polyolefin layers on both sides of the gas barrier resin layer, using it as an intermediate layer, is effective in preventing damage to the gas barrier resin layer. However, in the case of multilayer pipes used as hot water circulation pipes for geothermal systems, the risk of damage to the gas barrier resin layer from physical impacts is relatively low since they are usually buried under the floor. Therefore, from a gas barrier perspective, it is ideal to place the gas barrier resin layer on the outermost layer. Since gas barrier resins exhibit significant humidity dependence, their barrier properties decrease under high humidity conditions. Placing the gas barrier resin layer on the outermost layer is advantageous because it is located furthest from the inner surface of the pipe in contact with water, making it the most advantageous layer configuration from the perspective of the multilayer pipe's barrier performance. On the other hand, placing the EVOH layer on the outermost layer generally exposes it to direct air contact, making it susceptible to oxidative degradation. In this environment, when using gas barrier resin compositions containing compounds with hindered amine groups and / or antioxidants with hindered phenol groups, since the outermost layer is configured to be resistant to oxidation and degradation even at high temperatures, it will more effectively provide multilayer tubes with good barrier properties and reduced cracking caused by oxidation and degradation.

[0138] Furthermore, in the case where the multilayer pipe system of the present invention is used in the heat-insulating multilayer pipe of a district heating and cooling system, it is preferable to have a three-layer structure consisting of a thermoplastic resin layer, an adhesive resin layer, and a gas barrier resin layer, with the gas barrier resin composition layer disposed inside the thermoplastic resin layer (hereinafter referred to as laminate 1), or from the viewpoint of preventing damage to layer (1), it is preferable to have a five-layer structure consisting of a thermoplastic resin layer, an adhesive resin layer, a gas barrier resin composition layer, an adhesive resin layer, and a thermoplastic resin layer (hereinafter referred to as laminate 2).

[0139] There are no particular limitations on the composition of the multilayer insulated pipes in district heating and cooling systems, etc. For example, it is preferable to arrange the above-mentioned composite material 1 or 2 in the following order: inner pipe from the inside, insulation foam layer covering the inner pipe, and outer layer.

[0140] The type (material), shape, and size of the pipe used for the inner tube are not particularly limited as long as they can transport heat media such as gases or liquids. They can be appropriately selected according to the type of heat medium, the purpose of the piping material, and its usage. Specifically, metals such as steel, stainless steel, and aluminum, polyolefins (polyethylene, cross-linked polyethylene (PEX), polypropylene, poly-1-butene, poly-4-methyl-1-pentene, etc.), and the above-mentioned laminates 1 or 2 are also suitable. Among these, cross-linked polyethylene (PEX) is also suitable.

[0141] Thermal insulation foam systems can use materials such as polyurethane foam, polyethylene foam, polystyrene foam, phenolic foam, and polyisocyanurate foam. From the perspective of improving thermal insulation performance, polyurethane foam is more suitable.

[0142] As a foaming agent for thermal insulation foam, various alternatives to chlorofluorocarbons, such as chlorofluorocarbon gas, water, chlorinated hydrocarbons, hydrocarbons, and carbon dioxide are used. From the perspective of foaming effect and environmental impact, hydrocarbons, specifically n-pentane and cyclopentane, are suitable.

[0143] One method for manufacturing insulated multilayer tubes includes, for example, placing an inner tube for transporting the heat medium inside a tubular outer layer, fixing the inner tube with a spacer to form a double tube, and then injecting various foaming agents into the gap between the inner tube and the outer layer to allow it to foam and cure. The material of the spacer is not particularly limited, but polyethylene or polyurethane is preferred to reduce damage to the inner tube and outer layer caused by the spacer.

[0144] (Manufacturing methods for multilayer tubes, etc.) The following describes a method for manufacturing a multilayer tube, which may also be applicable to other molded bodies (films, sheets, etc.). The multilayer tube system of this invention can be manufactured, for example, by co-extruding a gas barrier resin composition and an adhesive resin onto a single-layer tube such as a cross-linked polyolefin. When performing co-extrusion coating of the gas barrier resin composition and adhesive resin onto a single-layer tube, a molten film of the gas barrier resin composition and adhesive resin can be simply coated onto the single-layer tube. However, there is a possibility that the adhesion between the tube and the coating layer is insufficient, leading to the possibility that the coating layer peels off during long-term use and loses its gas barrier properties. As a countermeasure, flame treatment and / or corona discharge treatment of the surface of the tube to be coated before coating is effective.

[0145] Other multilayer molding methods for manufacturing multilayer pipes include co-extrusion molding, which involves simultaneously extruding molten resin fluids in layers within an extruder using an extruder with the corresponding number and type of resin layers. Dry lamination and other multilayer molding methods can also be employed.

[0146] The manufacturing method of multilayer tubes should ideally include a cooling step using water at 10-70°C immediately after molding. That is, after melt molding, the gas barrier resin layer should be cooled with water at 10-70°C to solidify before it hardens. If the cooling water temperature is too low, the gas barrier resin layer at the bend in subsequent secondary processing steps, where the multilayer tube is bent, is prone to cracking due to deformation. The exact reasons for this increased susceptibility to cracking are unclear, but it is presumed to be due to residual stress in the molded product. From this perspective, a cooling water temperature of 15°C or higher is preferable, and 20°C or higher is even better. On the other hand, even if the cooling water temperature is too high, the gas barrier resin layer at the bend during secondary processing is still prone to cracking due to deformation. The exact reasons for this are not fully understood, but it is presumed to be due to excessive crystallinity of the gas barrier resin layer. From this perspective, a cooling water temperature below 60°C is preferable, and below 50°C is even better.

[0147] By secondary processing of the multilayer tube obtained by the above method, various molded bodies can be obtained. As for the secondary processing method, there are no particular limitations, and known secondary processing methods can be used. For example, a method in which the multilayer tube is heated to 80~160°C and deformed into the desired shape, and then processed by fixing it for 1 minute to 2 hours.

[0148] <Thermoformed Containers> The thermoformed container of the present invention comprises the molded body of the present invention. The thermoformed container of the present invention can be a thermoformed container constructed from the molded body of the present invention. That is, one embodiment of the molded body of the present invention can be a thermoformed container. The thermoformed container of the present invention has low environmental impact and good gas barrier properties, appearance, and processability. The thermoformed container of the present invention is used in applications requiring oxygen barrier properties, such as in various fields of food, cosmetics, pharmaceuticals, and toiletries. This thermoformed container is formed by thermoforming, for example, a single-layer or multi-layer film or sheet, to create a container with a receiving portion.

[0149] (Storage Department) The storage section is the part used to store the contents of food and other items. The shape of this storage section is determined by the shape of the contents. Specifically, the thermoformed container is formed as, for example, a cup-shaped container, a plate-shaped container, a bag-shaped container, a bottle-shaped container, a bag-shaped container, etc.

[0150] As an indicator, the shape of the storage compartment can be represented by the draw ratio (S). Here, the draw ratio (S) refers to the value calculated by dividing the deepest part of the container by the diameter of the circle inscribed in the container's opening with its largest diameter. That is, a larger draw ratio (S) indicates a deeper container, and a smaller value indicates a shallower container. For example, a cup-shaped thermoformed container has a large draw ratio (S), while a plate-shaped container has a small draw ratio (S). Furthermore, the diameter of the circle inscribed in the opening is, for example, the diameter of the circle when the opening of the storage compartment is circular, the minor axis (minor diameter) when it is elliptical, and the length of the short side when it is rectangular.

[0151] The appropriate value for the stretch ratio (S) varies depending on the thickness of the film or sheet. In the case where the thermoforming container of the present invention is formed by thermoforming a film, a stretch ratio (S) of 0.2 or higher is preferred, 0.3 or higher is more preferred, and 0.4 or higher is even more preferred. On the other hand, when the thermoforming container is formed by thermoforming a sheet, a stretch ratio (S) of 0.3 or higher is preferred, 0.5 or higher is more preferred, and 0.8 or higher is even more preferred.

[0152] In this thermoformed container, the lower limit of the thickness ratio (I / O) between the total thickness I of other layers laminated on one side of the gas barrier resin composition layer and the total thickness O of other layers laminated on the other side of the gas barrier resin composition layer is preferably 1 / 99, and more preferably 30 / 70. Furthermore, the upper limit of the aforementioned I / O is preferably 70 / 30, and more preferably 55 / 45. Moreover, the thickness of the entire layer or a single layer of the thermoformed container is the average thickness obtained by observing and measuring samples cut from multiple locations of the thermoformed container using a slicing machine under an optical microscope.

[0153] The lower limit for the overall average thickness of the thermoformed container is preferably 300 μm, more preferably 500 μm, and even more preferably 700 μm. The upper limit for the overall average thickness of the thermoformed container is preferably 10000 μm, more preferably 8500 μm, and even more preferably 7000 μm. Furthermore, the overall average thickness refers to the thickness of the entire layer within the housing of the thermoformed container. If the overall average thickness exceeds the above-mentioned upper limit, the manufacturing cost of the thermoformed container will increase. On the other hand, if the overall average thickness does not meet the above-mentioned upper limit, there is a concern that rigidity cannot be maintained, and the thermoformed container becomes easily damaged.

[0154] (Manufacturing method of multi-layer thin sheets used in thermoformed containers) This describes a method for manufacturing a multilayer sheet, one of the single-layer or multi-layer films used in the manufacture of thermoformed containers. The multilayer sheet can be formed using a co-extrusion molding apparatus. For example, the gas barrier resin composition or other resins forming each layer can be fed into separate extruders, and co-extrusion can be performed using these extruders to form a multilayer sheet with a specified layer structure.

[0155] The extrusion molding of each layer is carried out by operating an extruder equipped with a single-screw extruder at a specified temperature. The temperature of the extruder forming the gas barrier resin composition layer is set to, for example, 170°C or higher and 260°C or lower. Furthermore, the temperature of the extruder forming the thermoplastic resin layer, the adhesive resin layer, and the recyclable layer is set to, for example, 150°C or higher and 260°C or lower.

[0156] (Thermoforming) The thermoforming container of this invention can be formed by heating multiple layers of thin sheets to soften them and then shaping them into a mold shape. Examples of thermoforming methods include those using vacuum or compressed air, and, if necessary, using plugs to form the mold shape (direct method, overhang method, air-lubricating method, snapback method, plug-assist method, etc.), and methods involving pressure molding. Various molding conditions, such as molding temperature, vacuum level, compressed air pressure, and molding speed, are appropriately set according to the plug shape or mold shape, and the properties of the raw resin.

[0157] The molding temperature is not particularly limited as long as it is sufficient to soften the resin for molding. The suitable temperature range varies depending on the composition of the multilayer sheets, etc. Furthermore, this heating temperature is usually lower than the melting point of the resin. Specifically, the lower limit of the heating temperature for multilayer sheets is usually 50°C, preferably 60°C, and even more preferably 70°C. The upper limit of the heating temperature is, for example, 180°C, but can also be 160°C.

[0158] (Layer structure of thermoformed containers) The thermoformed container of the present invention only needs to have at least one gas barrier resin composition layer, which can be composed of a single layer or multiple layers. When the thermoformed container has multiple layers, the layer composition can be appropriately set according to the application, etc.

[0159] When the thermoformed container of the present invention is composed of multiple layers, it is preferable to place the thermoplastic resin layer on the outermost layer. When the layer composed of resin other than the gas-barrier resin composition of the present invention is designated as layer x, the gas-barrier resin composition layer as layer y, and the adhesive resin layer as layer z, from the viewpoint of impact resistance, x / z / y / z / x is preferable from the inner surface of the receiving portion towards the outer surface. Furthermore, as a layer configuration including a recyclable layer, examples include... (Inner surface) x / z / y / z / recycling layer / x (outer surface) (Inner surface) x / recycle layer / z / y / z / recycle layer / x(outer surface) (Inner surface) recycling layer / z / y / z / recycling layer (outer surface) etc. Furthermore, the layer configuration can also be replaced by a layer configuration with a recyclable layer instead of a thermoplastic resin layer. Furthermore, when multiple x, y, z and recyclable layers are used respectively, the resins constituting the individual layers can be the same or different.

[0160] <Cup-shaped container> Secondly, regarding the thermoformed container of the present invention, the cup-shaped container shown in Figures 1 and 2 will be used as an example for specific description. However, the cup-shaped container is only one example of a thermoformed container, and the following description of the cup-shaped container is not intended to limit the scope of the present invention.

[0161] The cup-shaped container 1 shown in Figures 1 and 2 comprises a cup body 2 as a storage section and a flange 3. The cup-shaped container 1 is used by the user to store contents in the cup body 2 and seal the opening 4 of the cup body 2 with a cap 7 on the flange 3. Examples of the cap 7 include resin films, metal foils, and metal-resin composite films; among these, a metal-resin composite film with a metal layer laminated on top of a resin film is preferred. Examples of resin films include polyethylene films and polyethylene terephthalate films. The metal layer is not particularly limited, but metal foils and metal deposition layers are preferred; from the viewpoint of gas barrier properties and productivity, aluminum foil is preferred.

[0162] The cup-shaped container 1 is typically obtained by thermoforming multiple layers of thin sheets. These multiple layers typically include at least a gas-barrier resin composition layer, and preferably other layers are laminated onto this gas-barrier resin composition layer. Examples of these other layers include, for instance, a thermoplastic resin layer, an adhesive resin layer, and a recyclable layer. Specific examples of the layer structure of the multiple sheets are as described above.

[0163] (Manufacturing method of cup-shaped container) As shown in Figure 3, the cup-shaped container 1 is manufactured by heating a continuous multi-layer thin sheet 21 with a heating device 30 to soften it, and then thermoforming it using a mold device 40.

[0164] (Heating device) The heating device 30 is equipped with a pair of heaters (heater 31 and heater 32), and the space between the heaters 31 and heater 32 is designed to allow a continuous multilayer sheet 21 to pass through. Furthermore, the heating device 30 can also be a device that heats by means of thermal pressure.

[0165] (Mold assembly) The mold assembly 40 is suitable for thermoforming using the pressure-assisted molding method, and includes a lower mold 50 and an upper mold 51 housed within a cavity (not shown). The lower mold 50 and upper mold 51 are each individually movable in the vertical direction, and in the separated state, a continuous multi-layered sheet 21 can pass through between them. The lower mold 50 has a plurality of recesses 52 for forming a cup-shaped container 1. The upper mold 51 has a plurality of plugs 53 protruding toward the lower mold 50. The plurality of plugs 53 are positioned at positions corresponding to the plurality of recesses 52 of the lower mold 50. Each plug 53 can be inserted into its corresponding recess 52.

[0166] (Thermoforming) First, as shown in Figures 3 and 4(A), the continuous multilayer sheet 21, which is softened by the heating device 30, is subjected to tension by moving the lower mold 50 upward, causing it to adhere closely to the lower mold 50 and slightly lifting the continuous multilayer sheet 21. Second, as shown in Figure 4(B), the plug 53 is inserted into the recess 52 by moving the upper mold 51 downward.

[0167] Next, as shown in Figure 4(C), the upper mold 51 is moved upward to separate the plug 53 from the recess 52, and a vacuum is applied to the cavity (not shown), causing the continuous multi-layered sheets 21 to adhere tightly to the inner surface of the recess 52. Then, the molding part is cooled by air jetting, thus fixing the shape. Next, as shown in Figure 4(D), the cavity (not shown) is opened to the atmosphere, and the lower mold 50 is moved downward to demold the lower mold 50, thereby obtaining a one-piece molded article. By cutting this one-piece molded article, the cup-shaped container 1 shown in Figures 1 and 2 is obtained.

[0168] Other embodiments of thermoformed containers The thermoformed container of this invention is not limited to the above-described form; a disc-shaped container is also included in the thermoformed container of this invention. The disc-shaped container can also be manufactured using the same method as the cup-shaped container described above. This disc-shaped container is suitable for use as a food tray, etc.

[0169] <Blow-formed containers> The blow-molded container of this invention comprises the molded body of this invention. The blow-molded container of this invention can be a blow-molded container constructed from the molded body of this invention. That is, one embodiment of the molded body of this invention can be a blow-molded container. The blow-molded container of this invention has low environmental impact and also exhibits good barrier properties, appearance, and processability. The blow-molded container of this invention can be used in various containers requiring gas barrier properties, oil resistance, etc.

[0170] In the blow-molded container of the present invention, when the layer composed of resin other than the gas barrier resin composition of the present invention is designated as layer x, the gas barrier resin composition layer as layer y, and the adhesive resin layer as layer z, a layer structure can be adopted, for example, from the inner surface of the container toward the outer surface of the container, such as (inner)x / z / y / z / recovery layer / x(outer), (inner)x / z / y / z / x(outer), (inner)x / recovery layer / z / y / z / recovery layer / x(outer), (inner)recovery layer / z / y / z / recovery layer / x(outer), etc. Furthermore, a structure including a recovery layer can be used instead of the adhesive resin layer. When multiple x, y, z, and recovery layers are individually configured, the resins constituting the individual layers can be the same or different.

[0171] The blow-molded container of the present invention is preferably manufactured by a manufacturing method that includes a step of blow molding using a gas barrier resin composition. Blow molding can be performed by known methods such as direct blow molding, injection blow molding, sheet blow molding, and free blow molding.

[0172] Specifically, for example, gas barrier resin particles forming a gas barrier resin composition layer and various resins forming other layers as necessary are used. The process involves blow molding using a blow molding machine at a temperature of 100°C to 400°C, followed by cooling at a mold temperature of 10°C to 30°C for 10 seconds to 30 minutes. This allows for the formation of a blow-molded hollow container. The heating temperature during blow molding can be 150°C or higher, or 180°C or 200°C or higher. Furthermore, this heating temperature can be above the melting point of the gas barrier resin composition. On the other hand, the upper limit of this heating temperature can be 350°C, or 300°C or 250°C. The blow-molded container of this invention can be used in various applications such as fuel containers or various bottles.

[0173] <Fuel Container> The blow-molded container of this invention can be used as a fuel container. The fuel container of this invention can also include a filter, a residual meter, baffles, etc. Because of its blow-molded construction, the fuel container of this invention has a low environmental impact and good barrier properties, appearance, and processability, making it suitable for use as a fuel container. Here, "fuel container" refers to fuel containers mounted on automobiles, locomotives, ships, aircraft, generators, industrial or agricultural machinery, etc., or portable fuel containers for refueling such fuel containers, and containers for storing fuel. Furthermore, examples of fuel include gasoline, especially oxygenated gasoline blended with methanol, ethanol, or MTBE, as well as heavy oil, light oil, kerosene, etc. Among these, the fuel container of this invention is particularly suitable for use as a fuel container for oxygenated gasoline.

[0174] <Bottle Container> The blow-formed container of this invention can be used as a bottle container. The bottle container of this invention can also be further equipped with components other than the blow-formed container of this invention, such as a covering film and a cap. The molding method of the bottle container of this invention can be, for example, direct blow molding and injection blow molding. Because the blow-formed container of this invention, molded into a bottle shape, has a low environmental impact and good barrier properties, appearance, and processability, it is suitable for use as a bottle container for food, cosmetics, etc.

[0175] <Paper Containers> The paper container of this invention comprises the molded body of this invention. The paper container of this invention can be a paper container constructed from the molded body of this invention. That is, one embodiment of the molded body of this invention can be a paper container. The paper container is constructed from a molded body containing a paper substrate and is made by processing it into the shape of a carton or cup, etc. This paper container can preserve various beverages for a long time.

[0176] Forming systems that include paper substrates, for example, can form films at high speeds by using T-die extrusion coating.

[0177] <Other Implementation Forms> This invention is not limited to the embodiments described above. Any of the molded bodies, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, disc-shaped containers, blow-molded containers, fuel containers, bottle containers, pipes, and multilayer pipes of this invention may be, for example, a single-layer structure consisting only of a gas barrier layer formed from a gas barrier resin composition, or a multilayer structure consisting of a plurality of gas barrier resin compositions. [Example]

[0178] The present invention will be illustrated in more detail below with examples, but the invention is not limited to these examples.

[0179] [Evaluation Method] (1) Ethylene content and saponification degree of EVOH The synthesized EVOH particles were dissolved in dimethyl silane (DMSO)-d6 containing tetramethylsilane as an internal standard and tetrafluoroacetic acid (TFA) as an additive. The ethylene content and degree of saponification were measured using 500MHz 1H-NMR (JMTC-400 / 54 / SS, manufactured by Nippon Electronics Corporation) at 80°C. The peaks in the above-measured spectra are classified as follows. 0.6~1.9ppm: Methylene protons (4H) of ethylene units, methylene protons (2H) of vinyl alcohol units, and methylene protons (2H) of vinyl acetate units. 1.9~2.0 ppm: Methyl proton (3H) of vinyl acetate unit 3.1~4.2 ppm: Methylene proton (1H) of vinyl alcohol unit (2) Melting point of EVOH For the synthesized EVOH particles, the melting point was determined by measuring the peak temperature at a rate of 10°C / min from 30°C to 250°C using a differential scanning calorimeter "Q2000" manufactured by TA Instruments.

[0180] (3) Quantitative analysis of carboxylic acids 20 g of the synthesized EVOH particles or the gas barrier resin composition particles obtained in the examples and comparative examples were added to 100 mL of deionized water in a 200 mL Erlenmeyer flask with a stopper. A cooling condenser was attached, and the mixture was stirred and extracted at 95°C for 6 hours. The extracted solution was titrated with NaOH at N / 50 using phenolphthalein as an indicator to quantify the content of carboxylic acid as a carboxylate group. Furthermore, in samples containing phosphorus compounds, the content of phosphorus compounds measured using the evaluation method described later was added to calculate the amount of carboxylic acid.

[0181] (4) Quantitative analysis of metal ions, phosphoric acid compounds and boron compounds 0.5 g of the synthesized EVOH particles or the gas barrier resin composition particles obtained in the examples and comparative examples were placed in a Teflon (registered trademark) pressure vessel, and 5 mL of concentrated nitric acid was added. The vessel was allowed to decompose at room temperature for 30 minutes. After 30 minutes, the vessel was capped and heated at 150°C for 10 minutes using a wet decomposition apparatus (Actac's "MWS-2"), followed by heating at 180°C for 5 minutes. The decomposition was then carried out, followed by cooling to room temperature. The treated solution was transferred to a 50 mL volumetric flask (TPX) and purified water was added to the aforementioned mark. Elemental analysis of the solution was performed using an ICP-C spectrophotometer (Perkin Elmer's "OPTIMA4300DV") to determine the atomic conversions of the metal ions, phosphorus compounds, and boron compounds contained in the EVOH particles or gas barrier resin composition particles.

[0182] (5) Biobase For the EVOH particles obtained from the synthesis and the gas barrier resin composition particles obtained from the examples and comparative examples, the concentration of radiocarbon (14C) was measured by an accelerator mass analyzer (AMS) according to the method described in ASTM D6866-18, and the biomass was calculated based on the principle of radiocarbon dating.

[0183] (6) Evaluation of monolayer thin films (6-1) Evaluation of the disadvantages of single-layer thin film fabrication A single-screw extruder (D2020 of Toyo Seiki Manufacturing Co., Ltd.; D(mm)=20, L / D=20, compression ratio=3.0, screw: full stroke) was used to produce a single-layer film with an average thickness of 20 μm from gas barrier resin composition particles obtained in the examples and comparative examples. The conditions at this time are as follows. (Conditions for a single-shaft extrusion unit) Extrusion temperature: 210℃ Screw rotation speed: 40 rpm Mold width: 30cm Take-up roll temperature: 80℃ Take-up roller speed: 3.1 m / min Under the above conditions, continuous operation was performed to produce a single-layer film. For each film produced 30 minutes after the start of operation, the number of defects per 17 cm of film length was counted. The counting of the above defects was performed using a film defect inspection device (Frontier System's "AI-10"). Furthermore, the inspection camera in the film defect inspection device was set such that its lens position was 195 mm away from the film surface. Film defects were classified as "Good (A)" if the number of defects was less than 50, "Fairly Good (B)" if the number of defects was more than 50 but less than 200, and "Defective (C)" if the number of defects was more than 200.

[0184] (6-2) Evaluation of the appearance of single-layer thin films For films produced 30 minutes after the start of operation, the appearance (stripes) is evaluated visually according to the following evaluation criteria. Additionally, a roller is manufactured to wind 100m of film onto a paper tube, and the appearance (coloration) of the roller's ends due to yellowing is evaluated visually according to the following evaluation criteria. (Evaluation Criteria for Stripes) Good (A): No stripes detected Good (B): Stripes confirmed Defect (C): Most stripes detected (Evaluation criteria for coloring at the roller end) Good (A): Colorless Good (B): Yellowing Undesirable (C): Significant yellowing

[0185] (7) Oxygen penetration Using the gas barrier resin composition particles obtained in the examples and comparative examples, a 20 μm thick monolayer film was formed under the following conditions. After adjusting the humidity at 20°C / 65%RH, the oxygen transmittance was measured using an oxygen transmittance measuring device (Modern Control's "OX-Tran2 / 20") at 20°C / 65%RH. Furthermore, this measurement was performed according to JIS K 7126-2 (isobaric method; 2006). (Fabrication of a single-layer thin film) Using a single-spindle extrusion unit (D2020 from Toyo Seiki Manufacturing Co., Ltd., D(mm)=20, L / D=20, compression ratio=3.0, screw: full stroke), a single-layer film with a thickness of 20μm was produced from the gas barrier resin composition particles described above. The extrusion conditions are as follows. Extrusion temperature: 210℃ Mold width: 30cm Take-up roll temperature: 80℃ Screw rotation speed: 40 rpm Take-up roller speed: 3.1 m / min

[0186] (8) Evaluation of multilayer thin films (8-1) Evaluation of the appearance of multilayer thin films Using the gas barrier resin composition particles obtained in the examples and comparative examples, multilayer films (polyethylene layer / adhesive resin layer / gas barrier resin composition layer / adhesive resin layer / polyethylene layer, thickness (μm): 60 / 10 / 10 / 10 / 60) were formed using three types of 5-layer co-extruders under the following conditions. The polyethylene used was "Novatec (trademark) UF943" manufactured by Nippon Polyethylene Co., Ltd., and the adhesive resin used was "Admer (trademark) NF528" manufactured by Mitsui Chemicals Co., Ltd. (Extruder conditions) Extrusion temperatures for each resin: Supply section / Compression section / Metering section / Die = 170℃ / 170℃ / 210℃ / 210℃ Polyethylene extruder: 32φ single-shaft extruder, GT-32-A type (manufactured by the Plastics Engineering Research Institute of Co., Ltd.) Adhesive resin extruder: 25φ single-shaft extruder, P25-18-AC type (manufactured by Osaka Seiki Co., Ltd.) Extruder for gas barrier resin composition: 20φ single-shaft extruder, ME type CO-EXT testing machine (manufactured by Toyo Seiki Co., Ltd.) T-mold: 300mm wide, 3 types, 5 layers (manufactured by the Plastics Engineering Research Institute of [Company Name]) Temperature of cooling roller: 50℃ Winding speed: 4m / min For multilayer films produced 30 hours after initial operation, visual evaluation is performed to check for streaks according to the following evaluation criteria. Additionally, a roller is manufactured to wind 100m of multilayer film onto a paper tube, and the ends of the roller are visually evaluated for yellowing according to the following evaluation criteria. (Evaluation Criteria for Stripes) A (Good): No stripes detected. B (Good): Stripes detected C (Poor): Most stripes detected (Evaluation criteria for coloring at the roller end) A (Good): Colorless B (Good): Yellowing C (Poor): Significant yellowing

[0187] (8-2) Measurement of oxygen penetration After adjusting the humidity of the multilayer film produced 30 minutes after the start of operation in (8-1) at 20°C and 65%RH, the oxygen penetration was measured using an oxygen penetration measuring device (Mocon Modern Controls.inc's "OX-Tran2 / 20") at 20°C and 65%RH, according to the method described in JIS K 7126-2 (isobaric method; 2006).

[0188] (9) Evaluation of thermoformed containers Using gas barrier resin composition particles, polypropylene (Novatec PP EA7AD manufactured by Nippon Polypropylene Co., Ltd.), and adhesive resin (Admer QF551 manufactured by Mitsui Chemicals Co., Ltd.), obtained in the examples and comparative examples, multilayer sheets (polypropylene / adhesive resin / gas barrier resin composition / adhesive resin / polypropylene, thickness (μm): 368 / 16 / 32 / 16 / 368) were produced using three types of 5-layer co-extrusion apparatuses under the following conditions. (Extruder conditions) Extrusion temperatures for each resin: Supply section / Compression section / Metering section / Die = 150℃ / 150℃ / 210℃ / 210℃ Extruder for polypropylene resin: 32φ single-shaft extruder, GT-32-A type (manufactured by the Plastics Engineering Research Institute, Inc.) Adhesive resin extruder: 25φ single-shaft extruder, P25-18-AC type (manufactured by Osaka Seiki Co., Ltd.) Extruder for EVOH resin composition: 20φ extruder, ME type CO-EXT experimental machine (manufactured by Toyo Seiki Co., Ltd.) T-mold: 300mm wide, 3 types, 5 layers (manufactured by the Plastics Engineering Research Institute of [Company Name]) Temperature of cooling roller: 80℃ Winding speed: 1m / min Multi-layer sheets produced after 30 minutes of operation were used in a thermoforming machine (Asano Manufacturing Co., Ltd.: Vacuum Air Compression Deep Drawing Molding Machine "FX-0431-3"). The sheet temperature was set to 160°C, and the multi-layer sheets were thermoformed into a round cup shape (mold shape: upper 75mm φ, lower 60mm φ, depth 75mm, draw ratio S=1.0) using compressed air (pressure 5kgf / cm2) to obtain a thermoformed container. The forming conditions are as follows. Heater temperature: 400℃ Plug: 45φ×65mm Mold temperature: 40℃ The appearance of the thermoformed container with the obtained cup shape is visually confirmed and evaluated according to the following criteria. (Evaluation criteria for appearance) Good (A): No spots or localized thickness deviations were found. Good (B): Some spots and localized thickness deviations were detected. Defect (C): Significant spots and localized thickness deviations were identified.

[0189] (10) Evaluation of stripes in blow-formed containers Using EVOH resin composition particles, high-density polyethylene (HI-ZEX 8200B manufactured by Priman Polymer Co., Ltd.), and adhesive resin (ADMER GT-6A manufactured by Mitsui Chemicals Co., Ltd.), a blow molding container was made from three types of six-layer preforms (inner) high-density polyethylene layer / adhesive resin layer / gas barrier resin composition layer / adhesive resin layer / high-density polyethylene layer / high-density polyethylene layer (outer) at 210°C using a Suzuki Kogyo TB-ST-6P blow molding machine. Furthermore, in the manufacturing of the blow-molded container, the container is cooled at 15°C for 20 seconds to form a 3L blow-molded container with an average thickness of 1000μm ((inner) high-density polyethylene layer / adhesive resin layer / gas barrier resin composition layer / adhesive resin layer / high-density polyethylene layer / high-density polyethylene layer (outer) = (inner) 340μm / 50μm / 40μm / 50μm / 400μm / 120μm (outer)). The average diameter of the bottom surface of this blow-molded container is 100mm, and the average height is 400mm. The blow-molded container was evaluated using visual inspection and circumferential cross-sectional microscopy after 30 minutes of operation. (Evaluation Criteria for Stripes) A (Good): No stripes were found. B (Fair): Stripes were confirmed. C (Poor): A large number of stripes were confirmed.

[0190] (11) Fuel penetration Using the gas barrier resin composition granules obtained from the use examples and comparative examples, high-density polyethylene ("HI-ZEX (trademark) 8200B" manufactured by Prime Polymer Co., Ltd.), and an adhesive resin ("ADMER (trademark) GT-6A" of Mitsui Chemicals, Inc.), a multilayer film (polyethylene / adhesive resin / gas barrier resin composition / adhesive resin / polyethylene) was produced using the three 5-layer coextrusion device and extruder conditions used in (5) above. The layer structure of the multilayer film is such that the polyethylene resin in the inner and outer layers is 90 μm, the adhesive resin is 10 μm each, and the gas barrier resin composition layer in the middle layer is 20 μm. For the obtained multilayer film, the penetration of a model fuel was measured using a flow-type gas / vapor permeability measuring device (GTR-30XFKE) of GTR-TEC Co., Ltd. The multilayer film was conditioned at 20°C and 65% RH for 1 month, and the measurement was carried out at 60°C. The model fuel used was CE10 gasoline, the composition of which is toluene / isooctane / ethanol = 45 / 45 / 10 mass%.

[0191] [Preparation of vinyl acetate synthesis catalyst] 23 g (water absorption amount 19.7 g) of silica spherical carrier HSV-I (spherical diameter 5 mm, specific surface area 160 m2 / g, water absorption rate 0.75 g / g) manufactured by Shanghai Haiyuan Chemical Technology Co., Ltd. was impregnated with an aqueous solution equivalent to the water absorption amount of the carrier containing 1.5 g of an aqueous solution of sodium tetrachloropalladate containing 56 mass% and 1.5 g of an aqueous solution of tetrachloroauric acid tetrahydrate containing 17 mass%, and then immersed in 40 mL of an aqueous solution containing 2.5 g of sodium metasilicate nonahydrate, and left standing for 20 hours. Then, 3.3 mL of an aqueous solution of 52 mass% hydrazine hydrate was added, and after standing at room temperature for 4 hours, it was washed with water until chloride ions disappeared, and dried at 110°C for 4 hours. The obtained palladium / gold / support composition was immersed in 60 mL of a 1.7 mass% acetic acid aqueous solution and left standing overnight. Subsequently, it was washed with water overnight and dried at 110°C for 4 hours. Thereafter, it was impregnated with an aqueous solution equivalent to the water absorption amount of the carrier containing 2 g of potassium acetate, and the vinyl acetate synthesis catalyst was obtained by drying at 110°C for 4 hours.

[0192] [Synthesis of vinyl acetate] <Synthesis example of VAM1> 3 mL of the above vinyl acetate synthesis catalyst was diluted with 75 mL of glass beads and filled into a reaction tube made of SUS316L (inner diameter 22 mm, length 480 mm). At a temperature of 150 °C and a pressure of 0.6 MPaG, a gas mixture in the ratio of ethylene / oxygen / water / acetic acid / nitrogen = 47.3 / 6.1 / 5.6 / 26.3 / 14.7 (mol%) was passed through at a flow rate of 20 NL / hour for reaction to synthesize vinyl acetate (VAM1). The ethylene used was bio-based ethylene (produced by Braskem S.A., bio-based ethylene from sugarcane), and a gas cylinder filled with this ethylene was used (ethylene purity 96.44%, internal volume 29.502 L, internal pressure 1.8234 MPa). Also, the acetic acid used was bio-based acetic acid (produced by Godavari Biorefineries Ltd., bio-based acetic acid from sugarcane), which was vaporized at 220 °C and introduced into the reaction system as vapor.

[0193] <Synthesis of VAM2 - VAM3> Except for changing the raw material ethylene and acetic acid as described in Table 1 to those from bio-based and / or fossil fuel sources, the other steps were the same as those for VAM1 to synthesize each vinyl acetate of VAM2 - VAM3.

[0194] Moreover, the following raw materials were used as the raw materials for synthesizing vinyl acetate. · Bio-based ethylene: Produced by Braskem S.A., bio-based ethylene from sugarcane · Fossil fuel-based ethylene: Produced by Air Liquide Industrial Gases Co., Ltd., fossil fuel-based ethylene · Bio-based acetic acid: Produced by Godavari Biorefineries Ltd., bio-based acetic acid from sugarcane · Fossil fuel-based acetic acid: Produced by FUJIFILM Wako Pure Chemical Corporation, fossil fuel-based acetic acid

[0195]

Table 1

[0196] [Synthesis of EVOH] <Production of EVOH (A1) Granules> (Polymerization of Ethylene-Vinyl Acetate Copolymer) Into a 250 L pressurized reaction tank equipped with a jacket, a stirrer, a nitrogen inlet, an ethylene inlet, and an initiator addition port, 105 kg of VAM1 and 32.3 kg of methanol (hereinafter, sometimes referred to as MeOH) were placed. After heating to 65 °C, nitrogen purging was carried out for 30 minutes to replace the inside of the reaction tank with nitrogen. Then, ethylene was pressurized and introduced so that the reaction tank pressure (ethylene pressure) became 3.67 MPa. The ethylene used was bio-based ethylene (produced by Braskem S.A., bio-based ethylene from sugarcane). After adjusting the temperature inside the reaction tank to 65 °C, 16.8 g of 2,2’-azobis(2,4-dimethylvaleronitrile) (“V-65” from Wako Pure Chemical Industries, Ltd.) as an initiator was added as a methanol solution to initiate polymerization. During polymerization, the ethylene pressure was maintained at 3.67 MPa and the polymerization temperature was maintained at 65 °C. After 3 hours, when the polymerization rate of Vac reached 45%, cooling was carried out to stop polymerization. The reaction tank was opened to remove ethylene, and then nitrogen gas was bubbled to completely remove ethylene. Then, unreacted VAc was removed under reduced pressure, and a 20 mass% MeOH solution was prepared by adding MeOH to the ethylene vinyl acetate copolymer.

[0197] (Saponification and Washing) 250 kg of a 20% (w / w) MeOH solution from the ethylene-vinyl acetate copolymer jacket was placed into a 500 L reaction tank equipped with a stirrer, nitrogen inlet, reflux cooler, and solution addition port. Nitrogen was blown into the solution while the temperature was simultaneously raised to 60 °C. 4 kg of sodium hydroxide was added to prepare a 2-equivalent MeOH solution. After the sodium hydroxide addition was complete, the system temperature was maintained at 60 °C for 2 hours to allow the saponification reaction to proceed. After 2 hours, another 4 kg of sodium hydroxide was added using the same method, and heating and stirring continued for another 2 hours. Subsequently, 14 kg of acetic acid was added to stop the saponification reaction, and 50 kg of ion-exchanged water was added. Heating and stirring were continued, and MeOH and water were distilled off the reaction tank to concentrate the reaction solution. After 3 hours, another 50 kg of ion-exchanged water was added to precipitate EVOH. The precipitated EVOH was collected and pulverized using a mixer. The obtained EVOH powder was added to a 1 g / L acetic acid aqueous solution (liquid ratio 20: 10 kg powder to 200 L of ion-exchange water) and stirred and washed for 2 hours. This was then dehydrated, and the powder was again added to a 1 g / L acetic acid aqueous solution (liquid ratio 20) and stirred and washed for 2 hours. This dehydrated powder was repeated three times, adding the powder to ion-exchange water (liquid ratio 20) and stirring and washing for 2 hours, followed by dehydration for purification. The powder was then dried at 60°C for 16 hours to obtain 25 kg of crude EVOH.

[0198] (Manufacturing of EVOH aqueous particles) 25 kg of the obtained coarsely dried EVOH was placed in a 100 L stirred tank equipped with a jacket, a mixer, and a reflux cooler. 20 kg of water and 20 g of MeOH were added, and the mixture was heated to 70 °C to dissolve. The solution was then passed through a 3 mm diameter glass tube and extruded into a mixture cooled to 5 °C with a water / MeOH weight ratio of 90 / 10, causing it to precipitate in strands. These strands were then cut into granules using a strand cutter to obtain hydrated EVOH particles. These hydrated EVOH particles were then added to a 1 g / L acetic acid aqueous solution (liquid ratio 20) and stirred for 2 hours. After dehydration, the acetic acid aqueous solution was replaced, and the same operation was repeated. The ethanol was washed with acetic acid aqueous solution and then dehydrated three times. The mixture was then immersed in ion-exchange water (bath ratio 20) and stirred for 2 hours before dehydration for purification. This yielded water-containing particles of EVOH, containing the catalyst residue from the saponification reaction and the MeOH used in the precipitation process after removal. The water content of the obtained EVOH particles was measured using a Mettler HR73 halogen moisture meter, and was found to be 110% by mass.

[0199] (Manufacture of EVOH (A1) Granules) The obtained water-containing EVOH granules are put into an aqueous solution containing sodium acetate, acetic acid, phosphoric acid and boric acid (bath ratio 20), stirred periodically and immersed for 4 hours. Moreover, the concentrations of each component are adjusted so that the content of each component in the obtained EVOH (A1) granules will be as described in Table 2. After immersion, liquid is removed, and EVOH (A1) granules containing sodium acetate, acetic acid, phosphoric acid and boric acid are obtained by drying at 80°C for 3 hours and at 130°C for 7.5 hours under air.

[0200] <Production of Each Granule of EVOH (A2) to EVOH (A6), EVOH (B1) to (B5)> Except for changing the types of ethylene and vinyl acetate as raw materials (raw monomers) and the contents of phosphoric acid compounds and boron compounds as described in Table 2, and appropriately changing the usage amounts of ethylene and vinyl acetate, EVOH (A2) granules to EVOH (A6) granules and EVOH (B1) to EVOH (B5) granules are produced using the same method as that for EVOH (A1) granules. Ethylene derived from fossil fuels is the ethylene manufactured by Air Liquide Industrial Gases Co., Ltd.

[0201] According to the methods described in the above evaluation methods (1) to (5), the ethylene unit content, saponification degree, melting point, quantification of carboxylic acid, metal ions, quantification of phosphoric acid compounds and boron compounds, and measurement of biobased degree are respectively carried out on EVOH (A1) granules to EVOH (A6) granules and EVOH (B1) to EVOH (B5) granules. The results are shown in Table 2.

[0202]

[0203] [Examples] <Example 1> Using a twin-screw extruder ("2D25W" manufactured by Toyo Seiki Seisakusho Co., Ltd., 25 mm φ, die temperature 220°C, screw rotation speed 100 rpm), the EVOH (A1) granules are extruded and granulated under a nitrogen atmosphere to obtain the gas barrier resin composition granules of Example 1.

[0204] According to the evaluation methods (3) to (8), (10) and (11) described above, the gas barrier resin composition particles obtained in Example 1 were subjected to quantitative analysis of carboxylic acid, quantitative analysis of metal ions, phosphoric acid compounds and boron compounds, biomass degree, evaluation of single-layer films, oxygen permeability, evaluation of multilayer films, evaluation of striations in blown gas molded containers, and measurement or evaluation of fuel permeability. The results are shown in Tables 3 and 4. Furthermore, the ethylene unit content and saponification degree in Table 3 are further substantiated by the results in Table 2.

[0205] <Examples 2, 4-6, Comparative Examples 1, 3-5> Except for changing the type of EVOH used to that described in Table 3, the gas barrier resin composition particles of Examples 2, 4-6 and Comparative Examples 1, 3-5 were prepared and evaluated using the same method as in Example 1. The results are shown in Tables 3 and 4.

[0206] <Example 3, Comparative Example 2> Except for changing the type and mass ratio of EVOH used as described in Table 3, the gas barrier resin components of Example 3 and Comparative Example 2 were prepared using the same method as in Example 1. Measurements or evaluations of carboxylic acid, metal ions, phosphoric acid compounds, and boron compounds, biomass degree, single-layer film evaluation, oxygen permeability, multilayer film evaluation, and thermoformed container evaluation were performed according to the evaluation methods (3) to (9) described above. The results are shown in Tables 3 and 4. Furthermore, the ethylene unit content and saponification degree in Table 3 are further representations of the results in Table 2.

[0207] According to the method described below, sulfur compounds were measured in the gas barrier resin composition particles obtained in Examples 1-6 and Comparative Examples 1-5. The results (content and types of sulfur compounds converted from sulfur atoms) are shown in Table 3. Measurement of Sulfur Compound Content The quantification of sulfur compounds was performed using a trace nitrogen and sulfur analyzer (TS-2100H type) manufactured by Mitsubishi Analytical Technology, and the measurement conditions were set as follows. Heater temperature: Inlet 900℃, Outlet 900℃ Gas flow rates: 300 ml / min each for Ar and O2 [Analysis System NSX-2100] Measurement mode: TS Specifications: SD-210 Measurement time (timer): 540 seconds (9 minutes) PMT Sensitivity: High Concentration The identification of sulfur compounds was performed using gas chromatography (GC) and gas chromatography-mass spectrometry (GC / MS). A flame photometric detector (FPD), which exhibits high sensitivity for trace amounts of sulfur and phosphorus compounds, was used as the detector for GC. Identification was achieved by analyzing the observed mass composition of the sulfur compounds based on the retention time after detection.

[0208] <Example 7 and Comparative Example 6> (Evaluation of co-extruded coated paper) Using cardboard (500μm thick, 400g / m2 basis weight) as the substrate, a three-layer, five-co-extruded coating was applied to the substrate. The co-extruded structure consisted of low-density polyethylene / adhesive layer / gas barrier resin composition layer / adhesive layer / low-density polyethylene / cardboard, with a thickness configuration of 20 / 5 / 5 / 5 / 20 / 500μm. The equipment used included a low-density polyethylene extruder, an EVOH extruder, an adhesive layer extruder, and a feed block and T-die for confluencing and distributing the resin supplied from the individual extruders. The low-density polyethylene used was linear low-density polyethylene (Ultozex 2022L manufactured by Priman Polymer Co., Ltd.), and the adhesive layer was anhydrous maleic acid-modified polypropylene (Admer QF-500 manufactured by Mitsui Chemicals Co., Ltd.). The temperature conditions of the feed block and T-die were set to 250°C, and the take-up speed was set to 300 m / min. The co-extruded coated paper produced after 30 minutes of operation was visually evaluated for the presence or absence of striations on the co-extruded coated surface according to the following evaluation criteria. (Evaluation Criteria for Stripes) A (Good): No stripes were found. B (Good): Stripes detected C (Poor): Most stripes detected

[0209] The results of evaluating the co-extruded coated paper using the gas barrier resin composition particles of Example 5 and Comparative Example 4 as gas barrier resin compositions are respectively recorded as Example 7 and Comparative Example 6. The stripe evaluation of Example 7 and Comparative Example 6 is A.

[0210]

[0211]

[0212] As shown in Tables 3 and 4, it has been demonstrated that the gas barrier resin compositions of Examples 1 to 6, although using raw materials derived from biomass, still have high gas barrier properties and molding processability that are not inferior to those derived solely from fossil fuels (gas barrier resin compositions of Comparative Examples 1 to 5), and this performance is not attributable to the so-called biomass or fossil fuel raw materials.

[0213] <Example 8> For Example 3 above, the traceability of a thermoformed container obtained after 30 minutes of operation using the evaluation method (9) described above was evaluated. Specifically, the EVOH layer of the obtained thermoformed container was taken out as a traceability sample. According to the method described in the evaluation method (5) above, the biomass degree of the taken-out EVOH layer was measured to be 100%, which is consistent with the value obtained from the gas barrier resin composition particles of Example 3, confirming that it has traceability. Furthermore, when measuring and identifying the sulfur compound content of the taken-out EVOH layer, it was confirmed that the sulfur compound content was 1.2 ppm in terms of sulfur atoms, and the sulfur compound was dimethyl sulfide, which is consistent with the value obtained from the gas barrier resin composition particles of Example 3, and it has traceability.

[0214] 1: Cup-shaped container 2: cup body 3: Flange portion 4: Opening 5: Inner surface 6: Outer surface 7: Cover 21: Continuous multilayer thin film 30: Heating device 31, 32: Heaters 40: Mold device 50: Lower mold 51: Upper mold 52: concave part 53: Plug

Claims

1. A gas barrier resin composition comprising an ethylene-ethylene ester copolymer saponified compound, wherein the ethylene and ethylene esters in the raw materials of the ethylene-ethylene ester copolymer saponified compound are derived from biomass, and the composition contains sulfur compounds at a concentration of 0.1 ppm to 100 ppm in terms of sulfur atoms.

2. The gas barrier resin composition of claim 1, wherein the biomass of the ethylene-ethylene ester copolymer saponified product exceeds 99%.

3. The gas barrier resin composition of claim 1 or 2 has a biomass degree of more than 99%.

4. The gas barrier resin composition as claimed in claim 1 or 2, wherein the sulfur compound is dimethyl sulfide or dimethyl sulfide.

5. The gas barrier resin composition of claim 1 or 2, wherein the ethylene-ethylene copolymer saponified comprises: ethylene-ethylene copolymer saponified (X), and ethylene-ethylene copolymer saponified (Y) with a melting point lower than that of the ethylene-ethylene copolymer saponified (X).

6. The gas barrier resin composition of claim 5, wherein the mass ratio (X / Y) of the ethylene-ethylene copolymer saponified product (X) to the ethylene-ethylene copolymer saponified product (Y) is 60 / 40 or more and 95 / 5 or less.

7. The gas barrier resin composition of claim 5, wherein the difference (XY) between the melting points of the ethylene-ethylene copolymer saponified product (X) and the ethylene-ethylene copolymer saponified product (Y) is 15°C or more.

8. The gas barrier resin composition as requested in item 1 or 2, containing carboxylic acid in an amount of 30 ppm to 1000 ppm when converted to carboxylate.

9. The gas barrier resin composition as claimed in item 1 or 2, containing metal ions of 1 ppm to 1000 ppm.

10. The gas barrier resin composition as claimed in item 1 or 2, containing a phosphoric acid compound at a concentration of 1 ppm to 200 ppm in terms of phosphorus atoms.

11. The gas barrier resin composition as claimed in item 1 or 2, containing boron compounds at a concentration of 5 ppm to 5000 ppm in boron atom conversion.

12. A molded article comprising: a layer formed of a gas barrier resin composition as claimed in any one of claims 1 to 11.

13. The molded body of claim 12, further comprising a thermoplastic resin layer.

14. A film having a molded body as claimed in claim 12 or 13.

15. A sheet having the shaped body as claimed in claim 12 or 13.

16. A packaging material having a film as claimed in claim 14 or a sheet as claimed in claim 15.

17. A thermoformed container having a molded body as claimed in claim 12 or 13.

18. A cup-shaped container having the thermoformed container as claimed in claim 17.

19. A disc-shaped container having the thermoformed container as claimed in claim 17.

20. A blow-molded container having a molded body as claimed in claim 12 or 13.

21. A fuel container having the blow-formed container as claimed in claim 20.

22. A bottle container having the blow-formed container as claimed in claim 20.

23. A pipe having a molded body as claimed in claim 12 or 13.

24. A multilayer tube having a molded body as claimed in claim 12 or 13.

25. A paper container having a molded body as claimed in claim 12 or 13.

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