WO2022004691A1

WO2022004691A1 - Gas barrier resin composition, molded body, film or sheet, packaging material, film or sheet for industrial uses, heat molded container, cup shaped container, tray shaped container, blow molded container, fuel container, bottle container, tube, multilayer pipe and paper container

Info

Publication number: WO2022004691A1
Application number: PCT/JP2021/024450
Authority: WO
Inventors: 正和中谷; 瑞子尾下
Original assignee: 株式会社クラレ
Priority date: 2020-06-30
Filing date: 2021-06-29
Publication date: 2022-01-06
Also published as: TW202208488A; JPWO2022004691A1

Abstract

The present invention provides: a gas barrier resin composition which uses a starting material derived from biomass and still has high gas barrier properties and high formability equivalent to those of materials derived from fossil fuels; and a molded body, a film or sheet, a packaging material, a film or sheet for industrial uses, a heat molded container, a cup shaped container, a tray shaped container, a blow molded container, a fuel container, a bottle container, a tube, a multilayer pipe and a paper container, each of which uses the above-described gas barrier resin composition. A gas barrier resin composition that contains a saponified ethylene-vinyl ester copolymer, wherein the ethylene and the vinyl ester, which are starting materials of the saponified ethylene-vinyl ester copolymer, are derived from biomass.

Description

Gas barrier resin composition, molded body, film or sheet, packaging material, industrial film or sheet, thermoformed container, cup-shaped container, tray-shaped container, blow molded container, fuel container, bottle container, tube, multi-layer pipe and paper container

The present invention relates to a gas barrier resin composition, a molded body, a film or sheet, a packaging material, an industrial film or sheet, a thermoformed container, a cup-shaped container, a tray-shaped container, a blow molded container, a fuel container, a bottle container, a tube, and a multilayer. Regarding pipes and paper containers.

Gas barrier materials using resins with excellent ability to block gases such as oxygen (gas barrier properties) are widely used in various applications such as containers, films, sheets, and pipes. As the resin having excellent gas barrier properties, polyamide, polyester, polyvinylidene chloride, acrylonitrile copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-vinyl ester copolymer sakenized product and the like are known. 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, fluorine-containing resin and silicone resin. ..

On the other hand, in recent years, with the aim of creating a sound material-cycle society, demand for bioplastics using carbon-neutral biomass-derived raw materials is increasing. However, it is known that the synthetic resin derived from biomass may be inferior in performance to the synthetic resin derived from fossil fuel. For example, Patent Document 2 states that conventional film materials such as biomass-derived polyolefins do not have sufficient qualities such as adhesion, processability, and durability, and a biomass-derived resin for improving such points. Described is an invention of a resin film comprising a biomass-derived resin layer having a specific composition including. Further, Patent Document 3 states that a film in which a petroleum-derived resin is replaced with a biomass-derived resin may have reduced impact resistance and the like, and a biomass-derived biomass polyethylene for improving such a point. The present invention describes the invention of a laminated film having an intermediate layer containing polyethylene derived from fossil fuel and a propylene-based block copolymer resin. Further, Patent Document 4 describes an invention relating to a laminate having a layer made of a carbon-neutral polyester resin film using biomass ethylene glycol, and an ethylene-vinyl ester copolymer saken product is exemplified as a gas barrier resin. However, this ethylene-vinyl ester copolymer saken product is shown as a resin made of a raw material derived from fossil fuel. Such a laminate of Patent Document 4 is limited as a bioplastic because a biomass-derived resin and a fossil fuel-derived resin coexist.

Japanese Unexamined Patent Publication No. 2007-137506 International Publication No. 2014/065380 International Publication No. 2018/163835 Japanese Unexamined Patent Publication No. 2012-096410

In the use of gas barrier materials, it is expected that gas barrier resins synthesized using biomass-derived raw materials will be commercialized. However, as described above, the performance of the biomass-derived synthetic resin may be inferior to that of the fossil fuel-derived synthetic resin. Therefore, when the conventional fossil fuel-derived gas barrier resin is replaced with the biomass-derived gas barrier resin, There is concern that the most important gas barrier properties and molding processability will deteriorate. Therefore, it is desired to develop a biomass-derived resin having excellent gas barrier properties and molding processability comparable to those of fossil fuel-derived resins.

The present invention has been made based on the above circumstances, and an object thereof is a gas barrier having high gas barrier properties and molding processability comparable to those derived from fossil fuels while using raw materials derived from biomass. Resin composition, and molded bodies, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, tray-shaped containers, blow-molded containers, fuel containers, bottle containers using this gas barrier resin composition. , Tubes, multi-layer pipes and paper containers.

The present inventor has synthesized an ethylene-vinyl ester copolymer saken product, which is a kind of gas barrier resin, using a raw material derived from biomass as a monomer and a raw material derived from fossil fuel as a monomer. It has been found that it has a high gas barrier property and molding processability comparable to those of the conventional one having the same structure, and the present invention has been completed.

That is, the present invention
[1] A gas barrier resin composition containing an ethylene-vinyl ester copolymer saponified product and in which ethylene and vinyl ester, which are raw materials for the above-mentioned ethylene-vinyl ester copolymer saken product, are derived from biomass;
[2] The gas barrier resin composition of [1], wherein the ethylene-vinyl ester copolymer saken product has a biobase degree of more than 99%;
[3] The gas barrier resin composition of [1] or [2] having a biobase degree of more than 99%;
[4] The gas barrier resin composition according to any one of [1] to [3], which contains a sulfur compound in an amount of more than 0 ppm and 100 ppm or less in terms of sulfur atom.
[5] The gas barrier resin composition of [4], wherein the sulfur compound is dimethyl sulfide or dimethyl sulfoxide;
[6] The ethylene-vinyl ester copolymer kenide has a lower melting point than the ethylene-vinyl ester copolymer kenide (X) and the ethylene-vinyl ester copolymer kenide (X). The gas barrier resin composition according to any one of [1] to [5], which comprises the ester copolymer saponified product (Y);
[7] The mass ratio (X / Y) of the ethylene-vinyl ester copolymer saponified product (X) and the ethylene-vinyl ester copolymer saken product (Y) is 60/40 or more and 95/5 or less. , [6] gas barrier resin composition;
[8] The difference in melting point (XY) between the ethylene-vinyl ester copolymer saken product (X) and the ethylene-vinyl ester copolymer saken product (Y) is 15 ° C. or higher [6]. Or the gas barrier resin composition of [7];
[9] The gas barrier resin composition according to any one of [1] to [8], which contains carboxylic acid in an amount of 30 ppm or more and 1000 ppm or less in terms of carboxylic acid root;
[10] The gas barrier resin composition according to any one of [1] to [9], which contains 1 ppm or more and 1000 ppm or less of metal ions;
[11] The gas barrier resin composition according to any one of [1] to [10], which comprises 1 ppm or more and 200 ppm or less of a phosphoric acid compound in terms of phosphorus atom.
[12] The gas barrier resin composition according to any one of [1] to [11], which contains a boron compound in an amount of 5 ppm or more and 5000 ppm or less in terms of boron atom;
[13] A molded product comprising a layer formed from the gas barrier resin composition according to any one of [1] to [12];
[14] The molded product of [13] further comprising a thermoplastic resin layer;
[15] A film or sheet comprising the molded product of [13] or [14];
[16] A packaging material comprising the film or sheet of [15];
[17] An industrial film or sheet comprising the molded article of [13] or [14];
[18] A thermoformed container comprising the molded body of [13] or [14];
[19] A cup-shaped container provided with the thermoformed container of [18];
[20] A tray-shaped container provided with the thermoformed container of [18];
[21] A blow-molded container comprising the molded product of [13] or [14];
[22] A fuel container provided with the blow-molded container of [21];
[23] A bottle container comprising the blow-molded container of [21];
[24] A tube comprising the molded product of [13] or [14];
[25] Multilayer pipe comprising the molded body of [13] or [14];
[26] A paper container comprising the molded product of [13] or [14];
Is achieved by providing.

According to the present invention, a gas barrier resin composition having high gas barrier properties and molding processability comparable to those derived from fossil fuels while using a raw material derived from biomass, and a molded product using this gas barrier resin composition. A film or sheet, a packaging material, an industrial film or sheet, a heat-molded container, a cup-shaped container, a tray-shaped container, a blow-molded container, a fuel container, a bottle container, a tube, a multi-layer pipe and a paper container can be provided.

FIG. 1 is a schematic perspective view showing a cup-shaped container according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of the cup-shaped container of FIG. FIG. 3 is a schematic diagram for explaining a method for manufacturing the cup-shaped container of FIG. 4 (A) to 4 (D) are schematic views for explaining a method for manufacturing the cup-shaped container of FIG. 1.

<Gas barrier resin composition>
The gas barrier resin composition of the present invention contains an ethylene-vinyl ester copolymer saken compound (ethylene-vinyl alcohol copolymer; hereinafter also referred to as "EVOH"), and is an ethylene which is a raw material (raw material monomer) of the above-mentioned EVOH. The vinyl ester is derived from biomass (hereinafter, EVOH whose raw material is derived from biomass, which is contained in the gas barrier resin composition of the present invention is also referred to as "EVOH derived from biomass"), is a gas barrier resin composition. Since the gas barrier resin composition uses a raw material derived from biomass, the environmental load is extremely low. Further, in the gas barrier resin composition, EVOH is selected and used as the gas barrier resin, and even when EVOH is synthesized using a raw material derived from biomass, it is the same as that synthesized only from the raw material derived from fossil fuel. It can exhibit high gas barrier properties and molding processability equivalent to EVOH of the structure. Note that EVOH having the same structure means EVOH having the same degree of polymerization, content ratio of each structural unit, presence / absence of denaturation, degree of saponification, and the like.

It can be confirmed by measuring the degree of biobase that the ethylene and vinyl esters used as raw materials are derived from biomass. The biobase degree is an index showing the ratio of biomass-derived raw materials, and in the present specification, it is the biobase carbon content obtained by measuring the concentration ^{of radioactive carbon (14 C) by an accelerator mass spectrometer (AMS).} .. The degree of biobase can be specifically measured according to the method described in ASTM D6866-18.

"Biomass" is a resource that is an organic substance derived from animals and plants, excluding fossil fuels (fossil resources). Biomass may be a resource that is an organic matter derived from plants.

The gas barrier resin composition of the present invention can also be used to track its own products by utilizing the concentration ^{of radiocarbon (14 C).} Organisms take up and contain a certain amount ^{of radiocarbon (14} C) in the atmosphere during their activity, but when the activity is stopped, the uptake of ^{new 14} C stops and the ratio ^{of 14 C to total carbon decreases.} It is also known that a phenomenon called isotope sorting occurs when plants fix carbon, and ^{the ratio of 14} C to total carbon differs depending on the plant species. ^{It is known that the ratio of 14} C to total carbon varies depending on the place of origin and age, and a raw material having a ^{ratio of 14} C to total carbon can be obtained depending on the biomass used as a raw material. For example, by changing the raw material ratio ^{of 14} C to different total carbons, it is possible to obtain EVOH with a ratio of ¹⁴ C to specific total carbons, and by examining this ratio ^{of 14 C to total carbons, it is possible to obtain EVOH.} It is possible to track EVOH (gas barrier resin composition) manufactured in-house.

EVOH is used in a wide range of applications, and it is the supplier's responsibility to supply high-quality products to the market. There is also a need for a way to distinguish between our own products and those of other companies for branding. For example, EVOH used in the gas barrier layer of a commercially available packaging container is formed into a packaging container by thermoforming, but the ethylene-vinyl ester copolymer saken product is a gel insoluble in a solvent due to the thermal history received during thermoforming. May form. Therefore, even if the packaging container is collected, the EVOH used is extracted with a solvent, and the molecular weight is to be measured, it is often difficult to accurately measure the molecular weight. Therefore, it is not possible to determine whether or not it is EVOH of the company only by analyzing the molded product.

EVOH is used in films, sheets, containers, etc. as a packaging material for foods, pharmaceuticals, industrial chemicals, pesticides, etc. through many distribution channels. It is also used in fuel tanks for automobiles and other vehicles, tube materials for tires, agricultural films, geomembranes, cushioning materials for shoes, etc., taking advantage of its barrier properties, heat retention properties, stain resistance, and the like. When these materials in which EVOH is used are further discarded, it is difficult to determine from which factory and which production line the such resin and the packaging container after use thereof are manufactured. In addition, it is difficult to conduct a quality survey of the company's products during or after use, and to track the environmental impact after disposal and the degradability into the ground.

As one of the tracking methods for in-house products, for example, a method of adding a tracer substance to EVOH can be considered. However, the addition of a tracer may cause an increase in cost and a decrease in EVOH performance. Against this background, ^{being able to track in-house products using the concentration of radiocarbon (14} C) can be said to be a very useful effect.

The gas barrier resin composition of the present invention is a resin composition having a function of suppressing gas permeation. The upper limit of the oxygen permeation rate of the gas barrier resin composition of the present invention measured according to the method described in JIS K 7126-2 (isopressure method; 2006) under 20 ° C.-65% RH conditions is 100 mL / 20 μm /. ^(m 2 · day · atm) are preferred, more preferably ^{50mL · 20μm / (m 2 ·} day · atm), 10mL · 20μm / (m 2 · day · atm), 1mL · 20μm / (m 2 · day · atm), or ^{0.5mL · 20μm / (m 2 ·} day · atm) it is more preferred.

(Biomass-derived EVOH)
The biomass-derived EVOH contained in the gas barrier resin composition of the present invention is an EVOH in which ethylene and vinyl esters, which are raw material monomers, are derived from biomass. Since the biomass-derived EVOH contains a biomass-derived raw material, the biobase degree of the gas barrier resin composition of the present invention can be increased and the environmental load can be reduced.

Biomass-derived EVOH is obtained by saponification of a copolymer of biomass-derived ethylene and vinyl ester. The production and saponification of an ethylene-vinyl ester copolymer as a precursor of biomass-derived EVOH can be carried out by a known method similar to the production and saponification of a conventional fossil fuel-derived ethylene-vinyl ester copolymer. can. As the vinyl ester, for example, a carboxylic acid vinyl ester such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate, vinyl versatic acid can be used. It can be made, and vinyl acetate is preferable.

Biomass-derived ethylene can be produced by a known method, for example, by purifying bioethanol from a biomass raw material and performing a dehydration reaction. As the biomass raw material, waste type, unused type, resource crop type and the like can be used, for example, cellulose type crops (pulp, kenaf, straw, rice straw, used paper, papermaking residue, etc.), wood, charcoal, compost. , Natural rubber, cotton, sugar cane, okara, oil (rapeseed oil, cottonseed oil, soybean oil, coconut oil, castor oil, etc.), carbohydrate-based crops (corn, potatoes, wheat, rice, rice husks, rice bran, old rice, cassaba, sago palm) , Bagasse, buckwheat, soybean, essential oil (pine root oil, orange oil, eucalyptus oil, etc.), pulp black liquor, vegetable oil residue, etc. can be used.

The method for producing bioethanol is not particularly limited, and for example, the biomass raw material is pretreated (pressurized hot water treatment, acid treatment, alkali treatment, saccharification treatment using a saccharifying enzyme) as necessary, and then yeast fermentation. After producing bioethanol, the bioethanol can be purified through a distillation step and a dehydration step. When saccharification is performed during the production of bioethanol, sequential saccharification fermentation in which saccharification and fermentation are carried out in stages may be used, or parallel saccharification fermentation in which saccharification and fermentation are carried out at the same time may be used, but the production efficiency is improved. From the viewpoint, it is preferable to produce bioethanol by parallel saccharification fermentation.

Commercially available biomass-derived ethylene may be used, for example, Braskem S. A. Bioethylene derived from sugar cane can be used.

Examples of the biomass-derived vinyl ester include vinyl esters produced using biomass-derived ethylene. Examples of the method for producing vinyl ester derived from biomass include a method of reacting ethylene with acetic acid and oxygen molecules using a palladium catalyst, which is a general industrial production method. Further, in the biomass-derived vinyl ester, the portion (acyl group) derived from a carboxylic acid such as acetic acid may be derived from biomass or may be derived from fossil fuel. That is, the biomass-derived vinyl ester may be produced by using biomass-derived ethylene and a biomass-derived or fossil fuel-derived carboxylic acid. Most of the carboxylic acid-derived portion of the ethylene-vinyl ester copolymer is desorbed by saponification, and the desorbed carboxylic acid can be used again for synthesis, so that there is almost no effect from the viewpoint of carbon neutrality. This is because.

The lower limit of the ethylene unit content of biomass-derived EVOH is preferably 20 mol%, more preferably 23 mol%, still more preferably 25 mol%. When the ethylene unit content of biomass-derived EVOH is 20 mol% or more, molding processability, long-run property and the like tend to be improved. The upper limit of the ethylene unit content of biomass-derived EVOH is preferably 60 mol%, more preferably 55 mol%, still more preferably 50 mol%. When the ethylene unit content of biomass-derived EVOH is 60 mol% or less, the gas barrier property tends to be better. The ethylene unit content of EVOH can be determined by a nuclear magnetic resonance (NMR) method.

The lower limit of the saponification degree of biomass-derived EVOH is preferably 90 mol%, more preferably 95 mol%, still more preferably 99 mol%. When the saponification degree of biomass-derived EVOH is 90 mol% or more, the gas barrier property, molding processability, and long-run property of the gas barrier resin composition of the present invention tend to be better. Further, the upper limit of the saponification degree of the biomass-derived EVOH may be 100 mol%, and may be 99.97 mol% or 99.94 mol%. The degree of saponification of EVOH can be ^{calculated by performing 1} H-NMR measurement and measuring the peak area of hydrogen atoms contained in the vinyl ester structure and the peak area of hydrogen atoms contained in the vinyl alcohol structure.

The biobase degree of biomass-derived EVOH is preferably more than 99%, more preferably more than 99.5%, and may be 100%. Since some fossil fuel-derived raw materials may be mixed with the raw materials, the biobase degree may be less than 100%, but from the viewpoint of reducing the environmental load, the biobase degree of biomass-derived EVOH should be within the above range. Is preferable.

The biomass-derived EVOH may have a unit derived from a monomer other than ethylene, vinyl ester and a saponified product thereof, as long as the object of the present invention is not impaired. When the biomass-derived EVOH has a unit derived from the other monomer, the upper limit of the content of the unit derived from the other monomer to the total structural unit of the biomass-derived EVOH is preferably 30 mol%, preferably 20 mol%. More preferably, 10 mol% is even more preferred, 5 mol% is even more preferred, and 1 mol% is even more preferred. When the biomass-derived EVOH has a unit derived from the other monomer, the lower limit of its content may be 0.05 mol% or 0.10 mol%. The other monomers include, for example, alkenes such as propylene, butylene, pentene, and hexene; 3-allyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-diasiloxy. -1-Buten, 3-Aryloxy-4-methyl-1-butene, 4-Achilloxy-2-methyl-1-butene, 4-Aryloxy-3-methyl-1-butene, 3,4-diasiloxy-2-methyl -1-Buten, 4-Acyloxy-1-Penten, 5-Acyloxy-1-Penten, 4,5-Diacyloxy-1-Penten, 4-Acyloxy-1-hexene, 5-Acyloxy-1-Hexene, 6-Acyloxy Alkenes having ester groups such as -1-hexene, 5,6-diasiloxy-1-hexene, 1,3-diacetoxy-2-methylenepropane, or alkenes thereof; Unsaturated acid or its anhydride, salt, mono or dialkyl ester, etc .; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfone such as vinyl sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid. Acids or salts thereof; vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, γ-methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, Examples include vinylidene chloride.

Biomass-derived EVOH may be post-denatured by methods such as urethanization, acetalization, cyanoethylation, and oxyalkyleneization.

When the biomass-derived EVOH has a modifying group such as another monomer unit, the biomass-derived EVOH may have a structural unit (modifying group) represented by the following formula (I).

[In the formula (I), X represents a group represented by hydrogen atom, methyl group, or ^R 2 -OH. R ¹ and R ² each independently represent a single bond, an alkylene group having 1 to 9 carbon atoms or an alkylene oxy group having 1 to 9 carbon atoms, and the alkylene group and the alkylene oxy group are hydroxyl groups, alkoxy groups or halogen atoms. May include. ]

X is preferably a group represented by hydrogen or ^R 2 -OH, more preferably a group represented by ^R 2 -OH.

The ^{alkylene group and alkyleneoxy group used as R 1} or R ² may contain a hydroxyl group, an alkoxy group or a halogen atom. R ¹ and R ² are preferably an alkylene group or an alkyleneoxy group having 1 to 5 carbon atoms, and more preferably an alkylene group or an alkyleneoxy group having 1 to 3 carbon atoms.

Specific examples of the structural unit (modifying group) represented by the formula (I) include the following structural units (modifying group) represented by the formulas (II), (III), and (IV). Can be mentioned.

[In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hydroxyl group, an alkoxy group or a halogen atom. ]

[In formula (III), R ⁵ is synonymous with X in formula (I). R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may contain a hydroxyl group, an alkoxy group or a halogen atom. ]

[In formula (IV), R ⁷ and R ⁸ 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. Further, a part or all of the alkyl group and the hydrogen atom of the cycloalkyl group may be substituted with a hydroxyl group, an alkoxy group or a halogen atom.

In the present invention, R ¹ in the formula (I) may be a single bond, and X may be a hydroxymethyl group (R ³ and R ⁴ in the formula (II) are hydrogen atoms). By using biomass-derived EVOH having this structural unit (modifying group), secondary processability such as stretchability and thermoformability tends to be improved without significantly deteriorating the gas barrier property. When the biomass-derived EVOH contains the structural unit (modifying group), the lower limit of the content is preferably 0.1 mol%, more preferably 0.4 mol%, still more preferably 1.0 mol%. On the other hand, the upper limit of the content of the structural unit (modifying group) is preferably 20 mol%, more preferably 10 mol%, further preferably 8 mol%, and particularly preferably 5 mol% from the viewpoint of improving the gas barrier property. ..

In the present invention, R ¹ in the formula (I) may be a hydroxymethylene group, and X may be a hydrogen atom (R ⁵ and R ⁶ in the formula (III) are hydrogen atoms). By using biomass-derived EVOH having this structural unit (modifying group), secondary processability such as stretchability and thermoformability tends to be improved without significantly deteriorating the gas barrier property. When the biomass-derived EVOH contains the structural unit (modifying group), the lower limit of the content is preferably 0.1 mol%, more preferably 0.4 mol%, still more preferably 1.0 mol%. On the other hand, the upper limit of the content of the structural unit (modifying group) is preferably 20 mol%, more preferably 10 mol%, further preferably 8 mol%, and particularly preferably 5 mol% from the viewpoint of improving the gas barrier property. ..

In the present invention, R ¹ is a methyl methylene group of in the formula (I), X may be a hydrogen atom. By using biomass-derived EVOH having this structural unit (modifying group), secondary processability such as stretchability and thermoformability tends to be improved without significantly deteriorating the gas barrier property. Further, in the above-mentioned methylmethyleneoxy group, an oxygen atom is bonded to a carbon atom in the main chain. That is, in the formula (IV), ^{it is preferable that one of R 7} and R ⁸ is a methyl group and the other is a hydrogen atom. When the biomass-derived EVOH contains the structural unit (modifying group), the lower limit of the content is preferably 0.1 mol%, more preferably 0.5 mol%, still more preferably 1.0 mol%. 0 mol% is particularly preferred. On the other hand, the upper limit of the content of the structural unit (modifying group) is preferably 20 mol%, more preferably 15 mol%, still more preferably 10 mol% from the viewpoint of improving the gas barrier property.

Biomass-derived EVOH may be used alone or in combination of two or more.

When two or more types of biomass-derived EVOH are used in combination, it is preferable to use two or more types of biomass-derived EVOH having different melting points. By using two or more kinds of biomass-derived EVOH having different melting points, it tends to show excellent molding processability. The gas barrier resin composition of the present invention contains EVOH (X) as biomass-derived EVOH and EVOH (Y) having a melting point lower than that of EVOH (X), and the mass of EVOH (X) and EVOH (Y). It is preferable that the ratio (X / Y) is 60/40 or more and 95/5 or less from the viewpoint of further improving the molding processability.

(EVOH (X))
EVOH (X) is an EVOH having a melting point higher than that of EVOH (Y), and is usually an EVOH having the highest melting point among the biomass-derived EVOH contained in the gas barrier resin composition of the present invention. When the gas barrier resin composition of the present invention contains EVOH (X), it tends to have excellent gas barrier properties. 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. When the melting point of EVOH (X) is within the above range, the gas barrier property of the gas barrier resin composition of the present invention tends to be good.

The lower limit of the ethylene unit content of EVOH (X) is preferably 20 mol%, more preferably 22 mol%, still more preferably 24 mol%, from the viewpoint of good molding processability and long-run property. The upper limit of the ethylene unit content of EVOH (X) is preferably 50 mol%, more preferably 48 mol%, still more preferably 46 mol%, from the viewpoint of raising the melting point and improving the gas barrier property.

The lower limit of the saponification degree of EVOH (X) is preferably 90 mol%, more preferably 95 mol%, still more preferably 99 mol%. When the saponification degree of EVOH (X) is 90 mol% or more, the gas barrier property, molding processability and long-run property of the gas barrier resin composition of the present invention tend to be better. Further, the upper limit of the saponification degree of EVOH (X) may be 100 mol%, and may be 99.97 mol% or 99.94 mol%.

EVOH (X) may have a monomer unit other than the ethylene, vinyl ester and the saponified product described in the above-mentioned biomass-derived EVOH as long as the object of the present invention is not impaired. From the viewpoint of maintaining a high gas barrier property of the gas barrier resin composition, it is preferable not to have other monomer units. When EVOH (X) has the above other monomer units, the content of EVOH (X) with respect to all structural units is preferably 5 mol% or less, more preferably 3 mol% or less, and further preferably 1 mol% or less. preferable.

(EVOH (Y))
EVOH (Y) is a biomass-derived EVOH having a melting point lower than that of EVOH (X). When the gas barrier resin composition of the present invention contains EVOH (Y), it tends to exhibit excellent molding 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. When the melting point of EVOH (Y) is within the above range, the gas barrier property of the gas barrier resin composition of the present invention tends to be good.

The lower limit of the ethylene unit content of EVOH (Y) is preferably 30 mol%, more preferably 32 mol%, and further 34 mol% from the viewpoint of lowering the melting point and improving the molding processability and long-running property. preferable. The upper limit of the ethylene unit content of EVOH (Y) is preferably 60 mol%, more preferably 58 mol%, and even more preferably 56 mol% from the viewpoint of improving the gas barrier property.

The lower limit of the saponification degree of EVOH (Y) is preferably 90 mol%, more preferably 95 mol%, still more preferably 99 mol%. When the saponification degree of EVOH (Y) is 90 mol% or more, the gas barrier property, molding processability and long-run property of the gas barrier resin composition of the present invention tend to be better. Further, the upper limit of the saponification degree of EVOH (Y) may be 100 mol%, and may be 99.97 mol% or 99.94 mol%. Further, the lower limit of the saponification degree of EVOH (Y) may be 70 mol% or 80 mol% from the viewpoint of enhancing the molding processability, and the upper limit of the saponification degree of EVOH (Y) is. From the viewpoint of enhancing the moldability, it may be 98 mol%.

EVOH (Y) may have a monomer unit (structural unit) other than ethylene, vinyl ester and its saponified product described in the above-mentioned biomass-derived EVOH, as long as the object of the present invention is not impaired. When it is preferable that EVOH (Y) has another monomer unit (structural unit) from the viewpoint of lowering the melting point of EVOH (Y) and enhancing the molding processability of the gas barrier resin composition of the present invention. There is. When EVOH (Y) contains other monomer units, the lower limit of the content of EVOH (Y) with respect to all structural units is preferably 0.1 mol%, more preferably 0.3 mol%. The upper limit of the content is preferably 15 mol%, more preferably 10 mol%. The other monomer unit (structural unit) is not particularly limited, but is preferably the structural unit described in the above formula (I), and is of the above formula (II), formula (III) or formula (IV). It is more preferably a structural unit, and further preferably the above formula (IV). When EVOH (Y) contains the above-mentioned other monomer unit (structural unit), the molding processability tends to be excellent.

The ethylene unit content difference (YX) between EVOH (Y) and EVOH (X) is preferably 5 mol% or more, more preferably 7 mol% or more, still more preferably 10 mol% or more. Further, the ethylene unit content difference (YX) may be 25 mol% or less. When the ethylene unit content difference (YX) is in the above range, the moldability tends to be good while showing a good gas barrier property.

The melting point difference (XY) between EVOH (X) and EVOH (Y) is preferably 15 ° C. or higher, more preferably 18 ° C. or higher. The melting point difference (XY) may be 100 ° C. or lower, or 50 ° C. or lower. When the melting point difference (XY) is in the above range, the molding processability tends to be good while showing a good gas barrier property.

The mass ratio (X / Y) of EVOH (X) to EVOH (Y) is preferably 60/40 or more, and more preferably 65/35 or more. The mass ratio (X / Y) is preferably 95/5 or less, more preferably 90/10 or less. When the mass ratio (X / Y) is in the above range, the molding processability tends to be good while showing a good gas barrier property.

(EVOH (Z))
The gas barrier resin composition of the present invention may contain EVOH (Z) having a melting point lower than EVOH (Y). When the gas barrier resin composition contains EVOH (Z), it tends to exhibit excellent molding processability. A preferred embodiment of EVOH (Z) is similar to EVOH (Y), except that it has a lower melting point than EVOH (Y).

The lower limit of the melt flow rate (MFR) of biomass-derived EVOH measured in accordance with JIS K7210: 1999 at 190 ° C. and a load of 2160 g is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes. 1.0 g / 10 minutes is more preferable. On the other hand, the upper limit of the MFR of biomass-derived EVOH is preferably 30 g / 10 minutes, more preferably 20 g / 10 minutes, and even more preferably 15 g / 10 minutes. When the MFR of biomass-derived EVOH at 190 ° C. and a load of 2160 g is within the above range, the molding processability tends to increase.

The lower limit of the melting point of biomass-derived EVOH is preferably 135 ° C, more preferably 150 ° C, and even more preferably 155 ° C. When the melting point of biomass-derived EVOH is 135 ° C. or higher, the gas barrier property tends to be excellent. The upper limit of the melting point of the biomass-derived EVOH is preferably 200 ° C, more preferably 190 ° C, and even more preferably 185 ° C. When the melting point of biomass-derived EVOH is 200 ° C. or lower, the molding processability tends to increase.

The lower limit of the proportion of biomass-derived EVOH in all the resins constituting the gas barrier resin composition of the present invention is preferably 80% by mass, more preferably 90% by mass, further preferably 95% by mass, and particularly preferably 98% by mass. , 99% by mass, and the resin constituting the gas barrier resin composition of the present invention may be substantially only biomass-derived EVOH or may be only biomass-derived EVOH. 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, further preferably 95% by mass, particularly preferably 98% by mass, and 99% by mass. The gas barrier resin composition of the present invention may be substantially composed of only biomass-derived EVOH.

It is more preferable that the gas barrier resin composition of the present invention contains a sulfur compound in an amount of more than 0 ppm and 100 ppm in terms of sulfur atom from the viewpoint of tracking the company's product. Further, the inventors have found that a sulfur compound having a sulfur atom equivalent of 100 ppm or less does not substantially affect the performance of the gas barrier resin composition, and the sulfur compound is suitable as a tracer substance. The upper limit of the content of the sulfur compound is more preferably 50 ppm, further preferably 5 ppm, still more preferably 3 ppm, and particularly preferably 1.5 ppm. The lower limit of the content of the sulfur compound may be 0.0001 ppm, 0.001 ppm, 0.01 ppm, 0.05 ppm, or 0.1 ppm. When a raw material derived from biomass is used, EVOH containing an organic sulfur compound contained in the raw material of biomass may be obtained. On the other hand, since EVOH derived from fossil fuel is desulfurized during cracking of naphtha, the amount of sulfur compound is smaller than that of EVOH derived from biomass. Therefore, when such biomass-derived EVOH is used, it becomes easier to trace the biomass-derived EVOH by comparing the contents of the sulfur compounds. In particular, when the gas barrier resin composition of the present invention contains an organic sulfur compound as a sulfur compound, particularly dimethyl sulfide or dimethyl sulfoxide, tracking becomes easier. In addition, from the viewpoint of tracking the company's products, the content of the sulfur compound is the detection limit value for the biomass-derived ethylene and biomass-derived vinyl ester as raw materials and the obtained EVOH during the production of EVOH. It may be preferable not to carry out excessive purification as described below.

(Other ingredients)
The gas barrier resin composition of the present invention preferably further contains a carboxylic acid. When the gas barrier resin composition of the present invention contains a carboxylic acid, melt moldability and color resistance at high temperatures can be improved. In particular, the pH buffering capacity of the gas barrier resin composition is enhanced, and the coloring resistance to acidic substances and basic substances may be improved. Therefore, the pKa of the carboxylic acid is more preferably in the range of 3.5 to 5.5. preferable.

When the gas barrier resin composition of the present invention contains a carboxylic acid, the lower limit of the content is preferably 30 ppm, more preferably 100 ppm in terms of carboxylic acid root. On the other hand, the upper limit of the carboxylic acid content is preferably 1000 ppm, more preferably 600 ppm. When the content of the carboxylic acid is 30 ppm or more, the color resistance due to high temperature tends to be good. On the other hand, when the content of the carboxylic acid is 1000 ppm or less, the melt moldability tends to be good. The content of the carboxylic acid is calculated by titrating an extract obtained by extracting 10 g of the resin composition with 50 ml of pure water at 95 ° C. for 8 hours. Here, the content of the carboxylic acid salt present in the extract is not taken into consideration as the content of the carboxylic acid in the resin composition. Further, the carboxylic acid may exist as a carboxylic acid ion.

Examples of the carboxylic acid include monovalent carboxylic acid and polyvalent carboxylic acid, which may be composed of one kind or a plurality of kinds. When both a monovalent carboxylic acid and a polyvalent carboxylic acid are contained as the carboxylic acid, the melt moldability of the gas barrier resin composition and the coloring resistance at high temperatures may be further improved. Further, the multivalent carboxylic acid may have three or more carboxy groups. In this case, the coloring resistance of the gas barrier resin composition of the present invention may be further improved.

The monovalent carboxylic acid is a compound having one carboxy group in the molecule. The pKa of the monovalent carboxylic acid is preferably in the range of 3.5 to 5.5. 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), and caproic acid. (PKa = 4.88), caproic acid (pKa = 4.90), lactic acid (pKa = 3.86), acrylic acid (pKa = 4.25), methacrylic acid (pKa = 4.65), benzoic acid (pKa = 4.65). Examples thereof include pKa = 4.20) and 2-naphthoic acid (pKa = 4.17). These carboxylic acids may have substituents such as hydroxyl groups, amino groups and halogen atoms as long as pKa is in the range of 3.5 to 5.5. Of these, acetic acid is preferable because it is highly safe and easy to handle.

A polyvalent carboxylic acid is a compound having two or more carboxy groups in the molecule. In this case, the pKa of at least one carboxy group is preferably 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), and 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), terephthalic acid (pKa1 = 3.51, pKa2 = 4.82), succinic acid (pKa2 = 4.75), tartaric acid (pKa2 = 4.40), glutamate (pKa2). = 4.07), aspartic acid (pKa = 3.90), and the like.

The gas barrier resin composition of the present invention preferably further contains a phosphoric acid compound. When the gas barrier resin composition of the present invention contains a phosphoric acid compound, the lower limit of the content thereof is preferably 1 ppm in terms of phosphoric acid root, and more preferably 3 ppm. On the other hand, the upper limit of the content is preferably 200 ppm in terms of phosphoric acid root, and more preferably 100 ppm. If a phosphoric acid compound is contained in this range, the thermal stability of the gas barrier resin composition of the present invention may be improved. In particular, it may be possible to suppress the generation and coloring of gel-like lumps during melt molding for a long period of time. As the phosphoric acid compound, for example, various acids such as phosphoric acid and phosphoric acid and salts thereof can be used. The phosphate may be in the form of a first phosphate, a second phosphate, or a third phosphate. Examples of the cation species of phosphate include alkali metals and alkaline earth metals. Specific examples of the phosphoric acid compound include a phosphoric acid compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

The gas barrier resin composition of the present invention preferably further contains a boron compound. When the gas barrier resin composition of the present invention contains a boron compound, the lower limit of the content thereof is preferably 5 ppm, more preferably 100 ppm in terms of boron element. On the other hand, the upper limit of the content is preferably 5000 ppm, more preferably 1000 ppm in terms of boron atom. If a boron compound is contained in this range, the thermal stability of the gas barrier resin composition of the present invention during melt molding can be improved, and the generation of gel-like lumps may be suppressed. In some cases, the mechanical properties of the obtained molded product can be improved. It is speculated that these effects are due to the chelate interaction between EVOH and the boron compound. Examples of the boron compound include boric acid, borate ester, borate, and boron borohydride. Specifically, examples of boric acid include orthoboric acid (H ₃ BO ₃ ), metaboric acid, and tetraboric acid, and examples of boric acid esters include, for example, trimethyl borate and triethyl borate, boric acid. Examples of the salt include the above-mentioned alkali metal salts of boric acid, alkaline earth metal salts, and boric acid.

The gas barrier resin composition of the present invention preferably further contains metal ions. When the gas barrier resin composition of the present invention contains metal ions, the interlayer adhesiveness becomes excellent when a multi-layer molded body, that is, a multi-layer structure is formed. The reason for the improvement in interlayer adhesion is not clear, but if the layer adjacent to the layer made of the gas barrier resin composition contains a molecule having a functional group capable of reacting with the hydroxy group of EVOH, both of them are subjected to metal ions. It is considered that the bond formation reaction of is accelerated. Further, by controlling the content ratio of the metal ion and the above-mentioned carboxylic acid, the melt moldability and coloring resistance of the gas barrier resin composition of the present invention can be improved.

When the gas barrier resin composition of the present invention contains metal ions, the lower limit of the content is preferably 1 ppm, more preferably 100 ppm, still more preferably 150 ppm. On the other hand, the upper limit of the metal ion content is preferably 1000 ppm, more preferably 400 ppm, still more preferably 350 ppm. When the content of the metal ion is 1 ppm or more, the interlayer adhesiveness of the obtained multilayer structure tends to be good. On the other hand, when the content of the metal ion is 1000 ppm or less, the coloring resistance tends to be good.

Examples of the metal ion include a monovalent metal ion, a divalent metal ion, and other transition metal ions, which may be composed of one or more kinds. Of these, monovalent metal ions and divalent metal ions are preferable.

As the monovalent metal ion, an alkali metal ion is preferable, and examples thereof include lithium, sodium, potassium, rubidium and cesium ions, and sodium or potassium ion is preferable from the viewpoint of industrial availability. Examples of the alkali metal salt that gives alkali metal ions include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates and metal complexes. Of these, aliphatic carboxylates and phosphates are preferable because they are easily available, and specifically, sodium acetate, potassium acetate, sodium phosphate and potassium phosphate are preferable.

It may be preferable to include divalent metal ions as metal ions. When the metal ion contains a divalent metal ion, for example, thermal deterioration of EVOH when the trim is recovered and reused is suppressed, and the generation of gel and lumps in the obtained molded product may be suppressed. Examples of the divalent metal ion include ions of beryllium, magnesium, calcium, strontium, barium and zinc, but magnesium, calcium or zinc ions are preferable from the viewpoint of industrial availability. Examples of the divalent metal salt that gives a divalent metal ion include a carboxylate, a carbonate, a hydrochloride, a nitrate, a sulfate, a phosphate and a metal complex, and a carboxylate is preferable. The carboxylic acid constituting the carboxylic acid salt is preferably a carboxylic acid having 1 to 30 carbon atoms, and specifically, acetic acid, stearic acid, lauric acid, montanic acid, behenic acid, octyl acid, sebacic acid, ricinolic acid, and the like. Examples thereof include myristic acid and palmitic acid, and acetic acid and stearic acid are preferable.

The gas barrier resin composition of the present invention is, for example, an antistatic agent, a processing aid, a resin other than EVOH, a stabilizer, an antioxidant, an ultraviolet absorber, a plasticizer, as long as the effect of the present invention is not impaired. Other components such as antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, oxygen absorbers, cross-linking agents, and reinforcing agents such as various fibers may be contained.

Examples of the blocking inhibitor include oxides, nitrides, and nitride oxides of elements selected from silicon, aluminum, magnesium, zirconium, cerium, tungsten, molybdenum, etc. Among these, silicon oxide is preferable because of its availability. .. When the gas barrier resin composition of the present invention contains a blocking inhibitor, blocking resistance can be enhanced.

Examples of the processing aid include fluorine-based processing aids such as Arkema's Kynar (trademark) and 3M's Dynamer (trademark). When the gas barrier resin composition of the present invention contains a processing aid, it tends to be able to prevent adhesion to the eyes and eyes of the die lip.

Resins other than EVOH include, for example, various polyolefins (polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, ethylene-propylene copolymer, and the common weight of ethylene and α-olefin having 4 or more carbon atoms. Combines, copolymers of polyolefins and maleic anhydride, ethylene-vinyl ester copolymers, ethylene-acrylic acid ester copolymers, or modified polyolefins graft-modified with unsaturated carboxylic acids or derivatives thereof, etc.), various types Polyamide (nylon 6, nylon 6.6, nylon 6/66 copolymer, nylon 11, nylon 12, polymethoxylylen adipamide, etc.), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), poly Examples thereof include vinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate and modified polyvinyl alcohol resin.

Stabilizers for improving melt stability, etc. include hydrotalcite compounds, hindered phenol-based, hindered amine-based heat stabilizers, metal salts of higher aliphatic carboxylic acids (for example, calcium stearate, magnesium stearate, etc.) and the like. Can be mentioned. When the gas barrier resin composition of the present invention contains a stabilizer, the content thereof is preferably 0.001 to 1% by mass.

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, 4,4'-thiobis- (6-t-Butylphenol) and the like can be mentioned.

Examples of the ultraviolet absorber include ethylene-2-cyano-3', 3'-diphenylacrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (2'-hydroxy-3'-t. -Butyl-5'-methylphenyl) 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the like can be mentioned.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester and the like.

Examples of the antistatic agent include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbowax and the like.

Examples of the lubricant include ethylene bisstearoamide and butyl stearate.

Examples of the colorant include carbon black, phthalocyanine, quinacridone, indoline, azo pigments, red iron oxide and the like.

Examples of the filler include glass fiber, asbestos, ballastonite, calcium silicate and the like.

Examples of the desiccant include phosphate (excluding the above phosphate), sodium borate, sodium sulfate, sodium chloride, sodium nitrate, sugar, silica gel, bentonite, molecular sieve, highly water-absorbent resin and the like.

The water content of the gas barrier resin composition of the present invention is preferably 3.0 parts by mass or less, preferably 1.0 part by mass, based on 100 parts by mass of the total of biomass-derived EVOH from the viewpoint of preventing the generation of voids during molding. The following is more preferable, 0.5 parts by mass or less is further preferable, and 0.3 parts by mass or less is particularly preferable.

The gas barrier resin composition of the present invention may contain impurities derived from biomass caused by EVOH derived from biomass. It may contain various impurities, but it tends to contain at least a large amount of metals such as iron and nickel.

(Biobase degree of gas barrier resin composition)
The biobase degree of the gas barrier resin composition of the present invention is preferably more than 99%, more preferably more than 99.5%, and may be 100%. The biobase degree of this gas barrier resin composition means a value measured in consideration of other resins and the like contained in arbitrary components other than EVOH. When the biobase degree of the gas barrier resin composition of the present invention is within the above range, the environmental load is extremely low, which is preferable.

The method for incorporating the above-mentioned other components into the gas barrier resin composition of the present invention is not particularly limited, but it can be produced by melt-kneading other components and additives with biomass-derived EVOH. Each component may be blended in a solid state such as powder or as a melt, or may be blended as a solute contained in a solution or a dispersoid contained in a dispersion liquid. As the solution and the dispersion liquid, an aqueous solution and an aqueous dispersion liquid are suitable, respectively. For melt-kneading, a known mixing device or kneading device such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer can be used. The temperature range at the time of melt-kneading can be appropriately adjusted according to the biomass-derived EVOH used, the melting point of each component, and the like, and usually 150 to 250 ° C. is adopted. Further, some components may be added to the biomass-derived EVOH in advance, and then other necessary components may be melt-kneaded as described above to produce the product. As a method of pre-adding some components to biomass-derived EVOH, a method of immersing biomass-derived EVOH as pellets or powder in a solution in which the added components are dissolved can be exemplified. As the solution, an aqueous solution is suitable.

<Molded body>
A molded product provided with 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 preferred embodiment of the present invention. The gas barrier resin composition of the present invention may be a molded product having a single-layer structure, or may be a molded product (laminated product) having a thermoplastic resin layer. The thermoplastic resin layer is a layer containing a thermoplastic resin as a main component. Further, the molded product of the present invention may include an adhesive resin layer (adhesive layer). The adhesive resin layer means a layer containing an adhesive resin, an anchor coating agent, or an adhesive as a main component. Here, the "main component" means that the proportion of the component is more than 50% by mass, and is preferably 90% by mass or more. The molded product of the present invention may further include other layers.

As described above, the molded body of the present invention can also be a multi-layer structure (laminated body). The lower limit of the number of layers of the molded product of the present invention may be 1, but 2 is preferable, and 3 is more preferable. The upper limit of the number of layers of the molded product may be, for example, 1000, 100, 20 or 10. The molded product has a low environmental load and has good gas barrier properties, appearance, molding processability, and the like. The molded product using the gas barrier resin composition of the present invention has various uses, and examples thereof include films, sheets, containers, bottles, tanks, pipes, hoses and the like.

As a specific molding method, for example, films, sheets, pipes and hoses can be molded by extrusion molding, container shapes can be molded by injection molding, and hollow containers such as bottles and tanks can be molded by hollow molding or rotary molding. Examples of the hollow molding include extrusion hollow molding in which a parison is formed by extrusion molding and then blown to form the preform, and injection hollow molding in which a preform is formed by injection molding and then blown to form the preform. For the production of flexible packaging materials and containers, a method of forming a packaging material such as a multilayer film by extrusion molding and a method of thermoforming a multilayer sheet formed by extrusion molding into a container-shaped packaging material are preferably used.

The multilayer structure is a multilayer structure including at least one gas barrier resin composition layer and further including a thermoplastic resin layer. The multilayer structure is usually obtained by laminating a gas barrier resin composition layer and another layer (thermoplastic resin layer). As the layer structure of the multilayer structure, for example, if the layer made of a resin other than the gas barrier resin composition of the present invention is an x layer, the gas barrier resin composition layer is a y layer, and the adhesive resin layer is a z layer, for example, 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 And so on. When a plurality of x-layers, y-layers, and z-layers are provided, the types may be the same or different. Further, a layer using a recovery resin made of scrap such as trim generated during molding may be separately provided, or the recovery resin may be mixed with a layer made of another resin. In the thickness structure of each layer of the multilayer structure, the thickness ratio of the y layer to the total layer thickness is usually 2 to 20% from the viewpoint of moldability and cost.

As the resin used for the x layer, a thermoplastic resin is preferable from the viewpoint of workability and the like. Examples of the thermoplastic resin include various polyolefins (polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, ethylene-propylene copolymer, and a copolymer of ethylene and α-olefin having 4 or more carbon atoms. , Polypolymer of polyolefin and maleic anhydride, ethylene-vinyl ester copolymer, ethylene-acrylic acid ester copolymer, or modified polyolefin obtained by graft-modifying these with unsaturated carboxylic acid or a derivative thereof), various polyamides (Nylon 6, Nylon 6.6, Nylon 6/66 copolymer, Nylon 11, Nylon 12, Polymethoxylylen adipamide, etc.), Various polyesters (Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, etc.), Polychloride Examples thereof include vinyl, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate and modified polyvinyl alcohol resin. The thermoplastic resin layer may be unstretched, or may be uniaxially or biaxially stretched or rolled. Among them, polyolefin is preferable in terms of moisture resistance, mechanical properties, economy and heat sealability, and polyamide and polyester are preferable in terms of mechanical properties and heat resistance.

The adhesive resin used for the z layer is a resin having adhesiveness, and is preferably a thermoplastic resin having adhesiveness. As the adhesive resin, for example, a carboxylic acid-modified polyolefin is suitable. Here, the carboxylic acid-modified polyolefin is a polyolefin-based copolymer containing an unsaturated carboxylic acid or an anhydride thereof (maleic anhydride or the like) as a copolymerization component; or an unsaturated carboxylic acid or an anhydride thereof is grafted onto the polyolefin. Means the graft copolymer obtained in the above.

An adhesive, an anchor coating agent, or the like can also be used for the z layer. The anchor coating agent and the adhesive may be a resin, may be a non-resin such as a small molecule compound, or may be composed of a plurality of components. The z layer can be formed by applying these and drying them if necessary. Adhesiveness may be improved by performing surface treatment such as corona discharge treatment on the coated surface before coating. The adhesive is not particularly limited, and for example, it is preferable to use a two-component reaction type polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted. Further, the adhesiveness may be further enhanced by adding a small amount of a known silane coupling agent or the like. Preferable examples of the silane coupling agent include a silane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group and a mercapto group.

The multilayer structure may further have a paper base material layer. As the paper base material used for the paper base material layer, any paper having various types, bending resistance, rigidity, waist, strength, etc. can be used depending on the use of the paper container. For example, it is a main strength material, and bleached or unbleached paper having a strong size property, or various types of paper such as pure white roll paper, kraft paper, paperboard, processed paper, or milk base paper can be used. The paper base material layer may be a laminate of a plurality of these paper layers. The paper substrate layer has a basis weight of 80 to 600 g / m ² , preferably a basis weight of 100 to 450 g / m ² , and a thickness of 110 to 860 μm, preferably 140 to 640 μm. If the thickness of the paper base layer is thinner than the above range, the strength as a container is insufficient, and if the thickness of the paper base layer is thicker than the above range, the rigidity becomes too high and processing becomes difficult. obtain. In addition, for example, characters, figures, symbols, and other desired patterns can be arbitrarily formed on the paper base material layer by a normal printing method.

Examples of the method for obtaining a multi-layer structure include co-extrusion molding, co-extrusion hollow molding, co-injection molding, extrusion laminating, co-extrusion laminating, dry laminating, solution coating and the like. The multilayer structure obtained by such a method is further subjected to secondary processing molding after reheating by a method such as vacuum compressed air deep drawing molding, blow molding, press molding, etc., and the target molded body structure is performed. May be. Further, the multilayer structure is stretched by uniaxial or biaxial stretching after reheating within the range below the melting point of EVOH by a roll stretching method, a pantograph stretching method, an inflation stretching method, or the like. You can also get it. Methods for manufacturing films or sheets, packaging materials, industrial films or sheets, heat-molded containers, cup-shaped containers, tray-shaped containers, blow-molded containers, fuel containers, bottle containers, tubes, multi-layer pipes and paper containers, which will be described later, are also available. It is included in the form of the method for producing a molded product of the present invention.

As a single-layer or multi-layer molded body using the gas barrier resin composition of the present invention, containers (bags, cups, tubes, trays, bottles, etc.), fuel containers, pipes, fibers, food and drink packaging materials, container packings, etc. Materials, medical infusion bag materials, tire tube materials, shoe cushion materials, bag-in-box inner bag materials, organic liquid storage tank materials, organic liquid transport pipe materials, hot water pipe materials for heating (hot water for floor heating) (Pipe materials, etc.), cosmetic packaging materials, dental care packaging materials, pharmaceutical packaging materials, packaging material child parts (caps, bag-in-box cock parts, etc.), pesticide bottles, agricultural films (greenhouse films, soil) (Smoking film), grain storage bag, geomembrane, vacuum insulation board outer bag, wallpaper or decorative board, gas tank for hydrogen, oxygen, etc. can be mentioned. A part of the example will be specifically described below.

<Film or sheet>
The film or sheet of the present invention comprises a molded product of the present invention. The film means "a film-like soft film having an average thickness of less than 250 μm", and the sheet means "a thin plate-like soft film having an average thickness of 250 μm or more". The same applies to the distinction between film and sheet in industrial "film or sheet". Hereinafter, "film or sheet" is also referred to as "film or the like". The film or the like of the present invention may be a film or the like made of the molded product of the present invention. That is, one embodiment of the molded product of the present invention may be a film or the like. The film or the like of the present invention has a low environmental load, and has good gas barrier properties, appearance, and molding processability. The film or the like of the present invention may be a single-layer film composed of only the gas barrier resin composition layer, or may be a multilayer film. The average thickness of the film or the like of the present invention is preferably, for example, 1 μm or more and less than 300 μm, and more preferably 5 μm or more and less than 100 μm. The film or the like of the present invention can be suitably used as various packaging materials and the like.

The arithmetic average roughness (Ra) of at least one surface of the film or the like of the present invention measured in accordance with JIS B0601 is preferably 1.0 μm or less, more preferably 0.8 μm or less, and further preferably 0.6 μm or less. It is preferably 0.4 μm or less, and particularly preferably 0.4 μm or less. The arithmetic mean roughness (Ra) of at least one surface of the film or the like of the present invention is preferably 0.05 μm or more, more preferably 0.10 μm or more, further preferably 0.15 μm or more, and particularly preferably 0.20 μm or more. .. When the arithmetic average roughness (Ra) of at least one surface of the film or the like of the present invention is within the above range, the fracture resistance is excellent.

The average length (RSm) of at least one surface contour curve element measured according to JIS B0601 of the film of the present invention is preferably 1000 μm or less, more preferably 800 μm or less, further preferably 600 μm or less, and further preferably 400 μm. The following are particularly preferred. The average length (RSm) of the contour curve element of at least one surface of the film of the present invention is preferably 50 μm or more, more preferably 100 μm or more, further preferably 150 μm or more, and particularly preferably 200 μm or more. When the average length (RSm) of the contour curve element on at least one surface of the film or the like of the present invention is within the above range, the fracture resistance is excellent. The above-mentioned JIS B0601 represents JIS B0601: 2001.

The film or the like of the present invention may be an unstretched film or the like, but it is preferably stretched. The strength and the like are improved by being stretched. Further, when the film or the like of the present invention is a stretched film or the like, the appearance and gas barrier properties are also good because the occurrence of streak-like unevenness that may occur due to stretching is small. Further, the film or the like of the present invention may be a heat-shrinkable film or the like.

(Manufacturing method of film, etc.)
The film or the like of the present invention can be produced by a known method. The method for forming the film or the like is not particularly limited, and examples thereof include a melting method, a solution method, a calendar method, and the like, and the melting method is preferable. Examples of the melting method include a T-die method (cast method) and an inflation method, and the cast method is preferable. In particular, it is preferable to produce the product by a method including a cast molding step of melt-extruding the resin composition constituting the film or the like of the present invention onto a casting roll and a step of stretching an unstretched film or the like obtained from the resin composition. .. The melting temperature in the melting method varies depending on the melting point of the gas barrier resin composition of the present invention and the like, but is preferably about 150 to 300 ° C.

The stretching may be uniaxial stretching or biaxial stretching, and biaxial stretching is preferable. The biaxial stretching may be either sequential biaxial stretching or simultaneous biaxial stretching. The lower limit of the stretch ratio in terms of area is preferably 6 times, more preferably 8 times. The upper limit of the draw ratio is preferably 15 times, more preferably 12 times. When the draw ratio is within the above range, the uniformity of the thickness of the film or the like, the gas barrier property, and the mechanical strength can be improved. The stretching temperature can be, for example, 60 ° C. or higher and 120 ° C. or lower.

The method for producing a film or the like of the present invention may include a step of heat-treating the stretched film or the like after the stretching step. The heat treatment temperature is usually set to a temperature higher than the stretching temperature, and can be, for example, more than 120 ° C. and 200 ° C. or lower.

The film or the like of the present invention is suitably used as a material for various packaging containers such as food packaging containers, pharmaceutical packaging containers, industrial chemical packaging containers, and pesticide packaging containers. Further, a heat-shrinkable film or the like and an industrial film or the like, which will be described later, are also included in one embodiment of the film or the like of the present invention.

<Packaging material>
The packaging material of the present invention comprises the film or sheet of the present invention. The packaging material of the present invention may be a packaging material made of the film or sheet of the present invention. That is, one embodiment of the molded product of the present invention may be a packaging material. The packaging material of the present invention has a low environmental load, and has good gas barrier properties, appearance, and molding processability.

The packaging material of the present invention may be a single-layer film or the like, or may be a multilayer film or the like. Further, the multilayer film or the like may further have a layer formed from other than the resin, for example, a paper layer, a metal layer, or the like. The packaging material of the present invention may remain in the form of a film or sheet, or the film or sheet may be secondarily processed. Examples of the packaging material obtained by the secondary processing include (1) a tray cup-shaped container obtained by thermoforming a film or sheet by vacuum forming, vacuum forming, vacuum forming, or the like, (2) a film or. Examples thereof include a bottle obtained by performing stretch blow molding on a sheet, a cup-shaped container, (3) a bag-shaped container obtained by heat-sealing a film or a sheet, and the like. The secondary processing method is not limited to each of the methods exemplified above, and for example, a known secondary processing method other than the above such as blow molding can be appropriately used.

The packaging material of the present invention is used for packaging, for example, foods, beverages, chemicals such as pesticides and pharmaceuticals, medical equipment, machine parts, industrial materials such as precision materials, and clothing. In particular, the packaging material of the present invention is preferably used for applications that require a barrier property against oxygen and applications in which the inside of the packaging material is replaced by various functional gases. The packaging material of the present invention is formed in various forms depending on the application, for example, a vertical bag filling seal bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, a lid material for a container, and the like.

<Vacuum packaging bag>
The packaging material of the present invention may be a vacuum packaging bag. An example of a vacuum packaging bag is a bag-shaped container provided with a film or the like of the present invention as a partition wall separating the inside and the outside where the contents are packaged, and the inside is in a depressurized state. In the vacuum packaging bag, for example, the two films of the present invention are overlapped with each other, and the peripheral portions of the two films and the like are sealed to each other. In the vacuum packaging bag, the partition wall is preferably a multilayer film or the like. The vacuum packaging bag can be manufactured using a nozzle type or chamber type vacuum packaging machine.

The vacuum packaging bag is used for applications where it is desired to wrap in a vacuum state, for example, for storing foods, beverages, etc. Further, the vacuum packaging bag can also be used as an outer packaging material for a vacuum heat insulating body.

<Industrial film or sheet>
The industrial film or sheet of the present invention (industrial film or industrial sheet) comprises a molded body such as a single-layer or multilayer film of the present invention. The industrial film or the like of the present invention may be an industrial film or the like made of the molded product of the present invention. That is, one embodiment of the molded product of the present invention may be an industrial film or the like. The industrial film or the like of the present invention has a low environmental load, and has good gas barrier properties, appearance, and molding processability. Specific examples of industrial films and the like include agricultural films, landfill films and the like, architectural films and the like.

The industrial film or the like of the present invention is preferably a multilayer film or the like, and as the thermoplastic resin layer, a hydrophobic thermoplastic resin is preferably used for the purpose of preventing deterioration of the gas barrier performance of the gas barrier resin composition layer due to moisture. Be done. Specifically, polyolefin-based resins: linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, ultra-low-density linear polyethylene, medium-density polyethylene, polyethylene such as high-density polyethylene, and ethylene-α-. Polyolefin resins such as olefin copolymers, polypropylene, ethylene-propylene (block and random) copolymers, polypropylene resins such as propylene-α-olefin (α-olefins with 4 to 20 carbon atoms) copolymers, polybutene , Polypentene, etc .; grafted polyolefins obtained by graft-modifying these polyolefins with unsaturated carboxylic acids or esters thereof, cyclic polyolefin-based resins; ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid esters. Halogenized polyolefins such as copolymers, polyester resins, polyamide resins, polyvinyl chlorides, polyvinylidene chlorides, acrylic resins, polystyrenes, vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylenes, chlorinated polypropylenes, etc. Examples thereof include aromatic or aliphatic polyketones. Among them, polyolefin-based resins are preferable, and polyethylene and polypropylene are particularly preferable in terms of mechanical strength and moldability.

Regarding the melt viscosity of the hydrophobic thermoplastic resin, the lower limit of MFR under a load of 210 ° C. and 2160 g is preferably 1.0 g / 10 minutes, more preferably 2.0 g / 10 minutes. The upper limit is preferably 100 g / 10 minutes, more preferably 60 g / 10 minutes. By using such a hydrophobic thermoplastic resin composition having a melt viscosity, a good multilayer film or the like without layer disorder can be obtained.

As the layer structure of the industrial film or the like of the present invention, assuming that the layer made of a resin other than the gas barrier resin composition of the present invention is the x layer, the gas barrier resin composition layer is the y layer, and the adhesive resin layer is the z layer, the following The layer structure of can be exemplified. The layer structure on the left side indicates that the layer is on the outer side (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

In particular, for the purpose of preventing deterioration of the oxygen barrier property due to moisture, it is preferable to use a gas barrier resin composition layer as an intermediate layer and a thermoplastic resin layer as an outer layer, and x / z / y / z / x, x / x. Configurations such as / z / y / z / x / x are more preferable.

The total thickness of the industrial film or the like of the present invention is usually 5 to 5 mm, preferably 10 to 4.5 mm, more preferably 15 to 4 mm, and particularly preferably 20 to 3.5 mm. The thickness of the hydrophobic resin composition layer or the like in the industrial film or the like is not particularly limited, but is usually 0.5 to 2.5 mm, preferably 1 to 2 mm, and particularly preferably 1 to 1.5 mm. The thickness of the thermoplastic resin layer is not particularly limited, but is preferably in the range of 1 to 20%, preferably 2 to 18%, and more preferably 3 to 15% of the total layer thickness.

Examples of the above-mentioned architectural film include wallpaper. The wallpaper as an embodiment of the industrial film or the like of the present invention has a small environmental load and is excellent in productivity.

Examples of the landfill film and the like include geomembranes and landfill sheets. Geomembrane is a sheet used as a water shield for waste treatment plants. The landfill sheet is a sheet that prevents the diffusion of harmful substances generated from industrial waste and the like, and can be used, for example, to prevent the diffusion of radon gas.

In the above agricultural film and the like, it is preferable that the gas barrier resin composition contains an antioxidant or an ultraviolet resistant agent (ultraviolet absorber, light stabilizer, colorant) or the like from the viewpoint of enabling long-term outdoor use. .. The agricultural film or the like is preferably a multilayer film or the like, and as the thermoplastic resin layer, a hydrophobic thermoplastic resin is preferably used for the purpose of preventing deterioration of the gas barrier performance of the gas barrier resin composition layer due to moisture.

It is preferable that the thermoplastic resin layer contains an ultraviolet resistant agent and an adhesive component. Examples of the ultraviolet resistant agent include an ultraviolet absorber, a light stabilizer, a colorant and the like.

The blending amount of the above UV resistant agent with respect to the hydrophobic thermoplastic resin is usually 1 to 10% by mass, preferably 2 to 8% by mass, and particularly preferably 3 to 5% by mass with respect to the hydrophobic thermoplastic resin. When the blending amount is less than the above range, the hydrophobic thermoplastic resin is likely to be deteriorated by ultraviolet rays. On the other hand, when the blending amount is larger than the above range, the mechanical strength of the hydrophobic thermoplastic resin is lowered.

Examples of the adhesive component include an aliphatic saturated hydrocarbon resin such as polyisobutene and an alicyclic saturated hydrocarbon resin, and the blending amount with respect to the hydrophobic thermoplastic resin is usually 1 to 30% by mass, preferably 1 to 30% by mass. It is 2 to 20% by mass, particularly preferably 3 to 15% by mass. If the blending amount is appropriate, the films and the like are crimped to each other when wrapping with the agricultural film and the like, and the sealing is easily maintained. If the blending amount is less than the above range, gaps are generated between the films and the like, and air invades the inside, so that the long-term storage property of the contents deteriorates. Further, when the blending amount is larger than the above range, blocking of the multilayer film occurs and it becomes impossible to unwind from the film roll or the like.

The total thickness of the agricultural film or the like is usually 5 to 200 μm, preferably 10 to 150 μm, more preferably 15 to 100 μm, and particularly preferably 20 to 50 μm. The thickness of the thermoplastic resin layer (hydrophobic resin composition layer, etc.) in the agricultural film or the like is not particularly limited, but is usually 0.5 to 200 μm, preferably 1 to 100 μm, and particularly preferably 1 to 10 μm. be. The thickness of the gas barrier resin composition layer is not particularly limited, but is preferably in the range of 1 to 20%, preferably 2 to 18%, and more preferably 3 to 15% of the total layer thickness.

The form of the silo using the agricultural film or the like is not particularly limited, and examples thereof include a lap silo, a bunker silo, a bag silo, a tube silo, and a stack silo, but the silo is particularly suitable.

When making a wrap silo, first mold the grass to the desired capacity using a machine such as a roll baler. Then, the agricultural film or the like is wrapped around the molded grass using a machine such as a bale trumpet and sealed. Since the amount of residual air at the time of sealing affects the quality of the contents, it is preferable to apply tension to the agricultural film or the like and wind it while stretching the film to bring the film or the like into close contact with the contents.

The agricultural film and the like can be used for various purposes such as a greenhouse film, a soil fumigation film, a silage film, a silo bag, and a grain storage bag.

<Tube>
The tube of the present invention comprises the molded body of the present invention. The tube of the present invention may be a tube made of the molded product of the present invention. That is, one embodiment of the molded product of the present invention may be a tube. The tube of the present invention has a low environmental load, and has good gas barrier properties, appearance, and molding processability.

The method for producing the tube of the present invention is not particularly limited, and for example, a method of directly forming a tube by melt molding such as coextrusion molding, co-injection molding, extrusion coating, or heat welding of the film or sheet of the present invention. Examples thereof include a method of forming into a tube shape, a method of laminating the film or sheet of the present invention with an adhesive, and forming into a tube shape.

<Multi-layer pipe>
The multilayer pipe of the present invention comprises the molded body of the present invention. The multilayer pipe of the present invention may be a multilayer pipe made of the molded product of the present invention. That is, one embodiment of the molded product of the present invention may be a multi-layer pipe. The multi-layer pipe of the present invention has a low environmental load, and has good gas barrier properties, appearance, and molding processability. The multilayer pipe of the present invention preferably contains an antioxidant in the gas barrier resin composition from the viewpoint of suppressing oxidative deterioration in long-term use. The antioxidant is preferably a compound having a hindered amine group and / or a compound having a hindered phenol group from the viewpoint of suppressing oxidative deterioration in use at high temperatures.

As the layer structure of the multi-layer pipe, the layer structure of the above-mentioned molded body can be adopted. When the multilayer pipe is used as a hot water circulation pipe, a three-layer structure of a thermoplastic resin layer having a thermoplastic resin layer as the outermost layer / a gas barrier resin composition layer / a thermoplastic resin layer is generally adopted. This can be easily diverted to the production line of the multi-layer pipe of the present invention by adding the coextrusion coating equipment of the gas barrier resin composition of the present invention and the adhesive resin to the existing production line of a single-layer pipe such as crosslinked polyolefin. This is because many pipe manufacturers actually adopt this configuration.

Providing polyolefin layers or the like on both sides of the gas barrier resin composition layer and using the gas barrier resin composition layer as an intermediate layer is effective in preventing scratches on the gas barrier resin composition layer. However, when the multi-layer pipe is used as a hot water circulation pipe such as a floor heating pipe, it is usually buried under the floor, and the risk of damage to the gas barrier resin composition layer due to physical impact is relatively small. Rather, from the viewpoint of gas barrier properties, it is desirable to arrange the gas barrier resin composition layer on the outermost layer. Since the gas barrier resin composition shows a large humidity dependence and the barrier property is lowered under high humidity conditions, by arranging the gas barrier resin composition layer on the outermost layer, the gas barrier resin composition layer mainly comes into contact with water. It will be located at the farthest place from the inner surface of the pipe, and will have the most advantageous layer structure in terms of the barrier performance of the multi-layer pipe. On the other hand, when the EVOH layer is generally arranged on the outermost layer, it is easily affected by oxidative deterioration because it comes into direct contact with air. In such an environment, when a gas barrier resin composition containing a compound having a hindered amine group and / or an antioxidant having a hindered phenol group is used, it is arranged on the outermost layer which is less likely to be oxidatively deteriorated even at high temperatures. Therefore, the effect of providing a multi-layer pipe having a good barrier property and reducing the occurrence of cracks due to oxidative deterioration is more effectively exhibited.

Further, when the multilayer pipe of the present invention is used for a heat insulating multilayer pipe for district heating and cooling, the thermoplastic resin layer / adhesive resin layer / gas barrier resin composition in which the gas barrier resin composition layer is arranged inside the thermoplastic resin layer. From the viewpoint of preventing damage to the three-layer structure of the material layer (hereinafter, may be abbreviated as the laminated body 1) or the layer (1), the thermoplastic resin layer / adhesive resin layer / gas barrier resin composition layer / adhesiveness. It is preferable to have a five-layer structure of a resin layer / thermoplastic resin layer (hereinafter, may be abbreviated as laminate 2).

The configuration of the heat insulating multi-layer pipe for district heating and cooling is not particularly limited, but for example, the inner pipe, the heat insulating foam layer surrounding the inner pipe, and the

laminated body

1 or 2 as the outer layer are arranged in this order from the inside. Is preferable.

The type (material), shape and size of the pipe used for the inner pipe are not particularly limited as long as they can transport a heat medium such as gas or liquid, and the type of heat medium and the use and usage form of the piping material are not particularly limited. It can be appropriately selected according to the above. Specifically, metals such as steel, stainless steel, and aluminum, polyolefins (polyethylene, cross-linked polyethylene (PEX), polypropylene, poly1-butene, poly4-methyl-1-pentene, etc.), and the above-mentioned

laminate

1 or 2 and the like. Among these, cross-linked polyethylene (PEX) is preferably used.

Polyurethane foam, polyethylene foam, polystyrene foam, phenol foam, and polyisocyanurate foam can be used as the heat insulating foam, and polyurethane foam is preferably used from the viewpoint of improving heat insulating performance.

Freon gas, various alternative fluorocarbons, water, hydrocarbons chloride, hydrocarbons, carbon dioxide, etc. are used as foaming agents for heat insulating foams, but hydrocarbons, specifically n-, are used from the viewpoint of foaming effect and environmental impact. Pentane and cyclopentane are preferably used.

As a method for manufacturing a heat insulating multi-layer pipe, for example, an inner pipe for transporting a heat medium is placed in a pipe-shaped outer layer, the inner pipe is fixed with a spacer to form a double pipe, and then a gap between the inner pipe and the outer layer is formed. Examples thereof include a method of injecting various foam stock solutions into the foam to foam and solidify. The material of the spacer is not particularly limited, but polyethylene or polyurethane is preferable in order to reduce damage to the inner tube and the outer layer due to the spacer.

(Manufacturing method for multi-layer pipes, etc.)
Hereinafter, a method for manufacturing a multi-layer pipe will be described, but a part or all of this manufacturing method can be applied to other molded bodies (films, sheets, etc.). The multilayer pipe of the present invention can be produced, for example, by coextruding a gas barrier resin composition and an adhesive resin on a single-layer pipe such as crosslinked polyolefin as described above. When performing coextrusion coating of the gas barrier resin composition and the adhesive resin on the single-layer pipe, a film in which the gas barrier resin composition and the adhesive resin are melted may be simply coated on the single-layer pipe. The adhesive force between the pipe and the coat layer may be insufficient, and the coat layer may peel off and lose the gas barrier property during long-term use. As a countermeasure, it is effective to perform frame treatment and / or corona discharge treatment on the surface of the pipe to be coated before coating.

As another multi-layer molding method for manufacturing multi-layer pipes, a number of extruders corresponding to the types of resin layers are used, and simultaneous extrusion molding is performed in a layered state in which the flows of the melted resin are overlapped in the extruder. There is a method of carrying out by so-called coextrusion molding. Further, a multi-layer molding method such as dry lamination can also be adopted.

The method for manufacturing a multi-layer pipe may include a step of cooling with water at 10 to 70 ° C. immediately after molding. That is, it is desirable to solidify the gas barrier resin composition layer by cooling with water at 10 to 70 ° C. after melt molding and before the gas barrier resin composition layer solidifies. If the temperature of the cooling water is too low, cracks due to strain are likely to occur in the gas barrier resin composition layer at the bent portion when the multilayer pipe is bent in the subsequent secondary processing step. The details of the cause of the tendency for cracks to occur due to strain are not clear, but it is presumed that the residual stress in the molded product has an effect. From this viewpoint, the temperature of the cooling water is more preferably 15 ° C. or higher, further preferably 20 ° C. or higher. On the other hand, even if the temperature of the cooling water is too high, cracks due to strain are likely to occur in the gas barrier resin composition layer at the bent portion during the secondary processing. The details of this cause have not been fully elucidated, but it is presumed that the crystallinity of the gas barrier resin composition layer becomes too large. From this viewpoint, the temperature of the cooling water is more preferably 60 ° C. or lower, further preferably 50 ° C. or lower.

Various molded bodies can be obtained by secondary processing the multi-layer pipe obtained by the above method. The secondary processing method is not particularly limited, and a known secondary processing method can be appropriately used. For example, in a state where the multilayer pipe is heated to 80 to 160 ° C. and then deformed into a desired shape, 1 A method of processing by fixing for 2 minutes to 2 hours can be mentioned.

<Thermoforming container>
The thermoformed container of the present invention comprises the molded body of the present invention. The thermoformed container of the present invention may be a thermoformed container made of the molded body of the present invention. That is, one embodiment of the molded product of the present invention may be a thermoformed container. The thermoformed container of the present invention has a low environmental load, and has good gas barrier properties, appearance, and moldability. The thermoformed container of the present invention is used in various fields such as foods, cosmetics, medical chemicals, toiletries, etc., where oxygen barrier properties are required. The thermoformed container is formed as having an accommodating portion, for example, by thermoforming a single-layer or multi-layer film or sheet.

(Accommodation)
The storage part is a part that stores the contents such as food. The shape of this accommodating portion is determined according to the shape of the contents. Specifically, the thermoformed container is formed as, for example, a cup-shaped container, a tray-shaped container, a bag-shaped container, a bottle-shaped container, a pouch-shaped container, or the like.

The form of the accommodating portion can be expressed by the aperture ratio (S) as one index. Here, the aperture ratio (S) is a value obtained by dividing the depth of the deepest part of the container by the diameter of the circle having the maximum diameter inscribed in the opening of the container. That is, the aperture ratio (S) means that the larger the value, the deeper the bottom of the container, and the smaller the value, the shallower the bottom of the container. For example, when the thermoformed container is cup-shaped, the drawing ratio (S) is large, and when it is a tray, the drawing ratio (S) is small. The diameter of the inscribed maximum diameter circle is, for example, the diameter of the circle when the opening of the accommodating portion is circular, the minor diameter (minor axis length) when it is elliptical, and short when it is rectangular. The length of the side.

The suitable value of the aperture ratio (S) differs depending on the film or sheet thickness. When the thermoformed container is a film obtained by thermoforming, the drawing ratio (S) is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.4 or more. On the other hand, when the thermoformed container is a molded sheet, the drawing ratio (S) is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.8 or more.

In the thermoformed container, the total thickness I of the other layers laminated on one surface side of the gas barrier resin composition layer and the total thickness O of the other layers laminated on the other surface side of the gas barrier resin composition layer. As the lower limit of the thickness ratio (I / O) with, 1/99 is preferable, and 30/70 is more preferable. The upper limit of the I / O is preferably 70/30, more preferably 55/45. The thickness of all layers or a single layer of the thermoformed container is an average value of the thicknesses measured by observation with an optical microscope for samples cut out from a plurality of locations of the thermoformed container using a microtome.

The lower limit of 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 of the overall average thickness of the thermoformed container is preferably 10,000 μm, more preferably 8500 μm, and even more preferably 7,000 μm. The overall average thickness refers to the thickness of all layers in the housing portion of the thermoformed container. If the overall average thickness exceeds the above upper limit, the manufacturing cost of the thermoformed container increases. On the other hand, if the overall average thickness is less than the above upper limit, the rigidity cannot be maintained and the thermoformed container may be easily broken.

(Manufacturing method of multilayer sheet used for thermoformed container)
A method for manufacturing a multilayer sheet, which is one of a single-layer or multilayer film used for manufacturing a thermoformed container, will be described. The multilayer sheet can be formed by using a coextrusion molding apparatus. This multilayer sheet can be formed as having a predetermined layer structure by, for example, charging a gas barrier resin composition or another resin forming each layer into separate extruders and co-extruding them with these extruders.

Extrusion molding of each layer is performed by operating an extruder equipped with a uniaxial screw at a predetermined temperature. The temperature of the extruder that forms the gas barrier resin composition layer is, for example, 170 ° C. or higher and 260 ° C. or lower. The temperature of the extruder that forms the thermoplastic resin layer, the adhesive resin layer, and the recovery layer is, for example, 150 ° C. or higher and 260 ° C. or lower.

(Thermoforming)
The thermoformed container of the present invention can be formed by heating and softening a multilayer sheet or the like and then molding it into a mold shape. As the thermoforming method, for example, vacuum or compressed air is used, and if necessary, a plug is also used to form a mold shape (straight method, drape method, air slip method, snapback method, plug assist method, etc.), press molding. How to do it. Various molding conditions such as molding temperature, degree of vacuum, compressed air pressure, and molding speed are appropriately set according to the shape of the plug, the shape of the mold, the properties of the raw material resin, and the like.

The molding temperature is not particularly limited as long as the resin can be softened sufficiently for molding, and the suitable temperature range differs depending on the configuration of the multilayer sheet or the like. This heating temperature is usually lower than the melting point of the resin. The lower limit of the heating temperature of a specific multilayer sheet or the like is usually 50 ° C., preferably 60 ° C., more preferably 70 ° C. The upper limit of the heating temperature is, for example, 180 ° C., and may be 160 ° C.

(Layer composition of thermoformed container)
The thermoformed container of the present invention may be provided with at least a gas barrier resin composition layer, and may be composed of a single layer or a plurality of layers. When the thermoforming container has a plurality of layers, the layer structure may be appropriately set according to the intended use and the like.

When the thermoformed container of the present invention is composed of a plurality of layers, it is preferable to arrange the thermoplastic resin layer on the outermost layer. When the layer made of a resin other than the gas barrier resin composition of the present invention is the x layer, the gas barrier resin composition layer is the y layer, and the adhesive resin layer is the z layer, x / z from the inner surface to the outer surface of the accommodating portion. / Y / z / x is preferable from the viewpoint of impact resistance. The layer structure when the recovery layer is included is, for example, (inner surface) x / z / y / z / recovery layer / x (outer surface).
(Inner surface) x / recovery layer / z / y / z / recovery layer / x (outer surface),
(Inner surface) Recovery layer / z / y / z / Recovery layer (outer surface)
And so on. In these layer configurations, a layer configuration may be provided in which a recovery layer is provided instead of the thermoplastic resin layer. When a plurality of x, y, z and recovery layers are used, the resins constituting the respective layers may be the same or different.

<Cup-shaped container>
Next, the thermoformed container of the present invention will be specifically described by taking the cup-shaped container shown in FIGS. 1 and 2 as an example. However, the cup-shaped container is only an example of a thermoformed container, and the following description of the cup-shaped container does not limit the scope of the present invention.

The cup-shaped container 1 of FIGS. 1 and 2 includes a cup body 2 as an accommodating portion and a flange portion 3. The cup-shaped container 1 is used by accommodating the contents in the cup body 2 and sealing the lid 7 on the flange portion 3 so as to close the opening 4 of the cup body 2. Examples of the lid 7 include a resin film, a metal foil, a metal resin composite film, and the like, and among these, a metal resin composite film in which a metal layer is laminated on a resin film is preferable. Examples of the resin film include a polyethylene film and a polyethylene terephthalate film. The metal layer is not particularly limited, and a metal foil and a metal vapor deposition layer are preferable, and an aluminum foil is more preferable from the viewpoint of gas barrier property and productivity.

The cup-shaped container 1 is usually obtained by thermoforming a multilayer sheet. It is preferable that the multilayer sheet includes at least a gas barrier resin composition layer, and another layer is laminated on the gas barrier resin composition layer. Examples of the other layer include a thermoplastic resin layer, an adhesive resin layer, a recovery layer, and the like. Specific examples of the layer structure of the multilayer sheet are as described above.

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

(Heating device)
The heating device 30 includes a pair of heaters (heater 31 and heater 32), and the continuous multilayer sheet 21 can pass between the heater 31 and the heater 32. As the heating device 30, a device that is heated by a hot press can also be used.

(Mold device)
The mold device 40 is suitable for thermoforming by the plug assist method, and includes a lower mold 50 and an upper mold 51 housed in a chamber (not shown). The lower mold 50 and the upper mold 51 can be individually moved in the vertical direction, and the continuous multilayer sheet 21 can pass between the lower mold 50 and the upper mold 51 in a separated state. The lower mold 50 has a plurality of recesses 52 for forming the accommodating portion of the cup-shaped container 1. The upper die 51 includes a plurality of plugs 53 projecting toward the lower die 50. The plurality of plugs 53 are provided at positions corresponding to the plurality of recesses 52 of the lower mold 50. Each plug 53 can be inserted into the corresponding recess 52.

(Thermoforming)
First, as shown in FIGS. 3 and 4A, the continuous multilayer sheet 21 softened by the heating device 30 is brought into close contact with the lower mold 50 by moving the lower mold 50 upward, and the continuous multilayer sheet 21 is brought into close contact with the lower mold 50. Is slightly lifted to give tension to the continuous multilayer sheet 21. Next, as shown in FIG. 4B, the plug 53 is inserted into the recess 52 by moving the upper mold 51 downward.

Subsequently, as shown in FIG. 4C, the upper mold 51 is moved upward to separate the plug 53 from the recess 52, and then the inside of the chamber (not shown) is evacuated to draw the continuous multilayer sheet 21 into the recess 52. Adhere to the inner surface. After that, the shape is fixed by cooling the molded portion by injecting air. Subsequently, as shown in FIG. 4D, the inside of the chamber (not shown) is opened to the atmosphere and the lower mold 50 is moved downward to release the lower mold 50, whereby a primary molded product is obtained. By cutting this primary molded product, the cup-shaped container 1 shown in FIGS. 1 and 2 can be obtained.

<Other Embodiments of Thermoformed Container>
The thermoformed container of the present invention is not limited to the above-mentioned form, and the tray-shaped container is also included in the thermoformed container of the present invention. The tray-shaped container can also be manufactured by the same method as the cup-shaped container described above. The tray-shaped container is suitably used as a food tray or the like.

<Blow molded container>
The blow-molded container of the present invention includes the molded product of the present invention. The blow-molded container of the present invention may be a blow-molded container made of the molded product of the present invention. That is, one embodiment of the molded product of the present invention may be a blow molded container. The blow-molded container of the present invention has a low environmental load and has good barrier properties, appearance and molding processability. The blow-molded container of the present invention can be used for various containers that require gas barrier properties, oil resistance, and the like.

In the blow-molded container of the present invention, when the layer made of a resin other than the gas barrier resin composition of the present invention is an x layer, the gas barrier resin composition layer is a y layer, and the adhesive resin layer is a z layer, for example, from the inner surface of the container. (Inside) x / z / y / z / Recovery layer / x (outside), (inside) x / z / y / z / x (outside), (inside) x / recovery layer / toward the outer surface of the container Layer structures such as z / y / z / recovery layer / x (outside) and (inside) recovery layer / z / y / z / recovery layer (outside) can be adopted. It should be noted that a configuration may include a recovery layer instead of the adhesive resin layer, and in the case of an arrangement in which a plurality of x, y, z and recovery layers are used, the resins constituting the respective layers may be the same or different. good.

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

Specifically, for example, a gas barrier resin composition pellet forming a gas barrier resin composition layer and, if necessary, each resin forming each other layer are used and blown at a temperature of 100 ° C. to 400 ° C. by a blow molding machine. Mold and cool at a mold temperature of 10 ° C to 30 ° C for 10 seconds to 30 minutes. This makes it possible to mold a blow-molded hollow container. The heating temperature at the time of blow molding may be 150 ° C. or higher, and may be 180 ° C. or 200 ° C. or higher. Further, this heating temperature may be equal to or higher than the melting point of the gas barrier resin composition. On the other hand, the upper limit of this heating temperature may be 350 ° C., and may be 300 ° C. or 250 ° C. The blow-molded container of the present invention is used for various purposes such as a fuel container and various bottles.

<Fuel container>
The blow molded container of the present invention can be used as a fuel container. The fuel container of the present invention may include a filter, a fuel gauge, a baffle plate, and the like. Since the fuel container of the present invention is provided with the blow-molded container of the present invention, it has a low environmental load, good barrier properties, appearance and moldability, and is suitably used as a fuel container. Here, the fuel container is a fuel container mounted on an automobile, a motorcycle, a ship, an aircraft, a generator, industrial or agricultural equipment, or a portable fuel container for refueling these fuel containers, and further. Means a container for storing fuel. As a typical example, gasoline, particularly oxygen-containing gasoline blended with methanol, ethanol, MTBE, etc., is mentioned as a fuel, but heavy oil, light oil, kerosene, etc. are also included. Of these, the fuel container of the present invention is particularly preferably used as a fuel container for oxygen-containing gasoline.

<Bottle container>
The blow-molded container of the present invention can be used as a bottle container. The bottle container of the present invention may further include a structure other than the blow-molded container of the present invention, such as a cover film and a cap. Examples of the method for molding a bottle container of the present invention include direct blow molding and injection blow molding. The blow-molded container of the present invention molded into a bottle shape has a low environmental load and has good barrier properties, appearance, and molding processability, and is therefore preferably used for bottle containers for foods, cosmetics, and the like.

<Paper container>
The paper container of the present invention comprises the molded product of the present invention. The paper container of the present invention may be a paper container made of the molded product of the present invention. That is, one embodiment of the molded product of the present invention may be a paper container. The paper container is made of a molded body containing a paper base material, and is made by processing it into a shape such as a carton or a cup. Such a paper container can store various beverages and the like for a long period of time.

The molded product containing the paper substrate can be formed at a high speed by being formed by, for example, extrusion coating by the T-die method.

<Other embodiments>
The present invention is not limited to those described in the above embodiments. Any of the molded bodies, films or sheets, packaging materials, industrial films or sheets, thermoformed containers, cup-shaped containers, tray-shaped containers, blow-molded containers, fuel containers, bottle containers, tubes and multilayer pipes of the present invention, for example. , A single-layer structure composed of only a gas barrier layer formed of a gas barrier resin composition, a multi-layer structure composed of a gas barrier layer formed of a plurality of gas barrier resin compositions, and the like may be used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Evaluation method]
^{(1) Ethylene unit content and degree of saponification of EVOH Dimethyl sulfoxide (DMSO) -d 6} containing tetramethylsilane as an internal standard and tetrafluoroacetic acid (TFA) as an additive for the synthesized EVOH pellets. The ethylene unit content and the degree of saponification were measured at 80 ° C. using 1H-NMR (“JMTC-400 / 54 / SS” manufactured by JEOL Ltd.) at 500 MHz.
Each peak in the spectrum of the above measurement is assigned as follows.
0.6 to 1.9 ppm: Methylene proton (4H) in ethylene unit, methylene proton (2H) in vinyl alcohol unit, methylene proton in vinyl acetate unit (2H)
1.9-2.0 ppm: Methyl proton (3H) in vinyl acetate unit
3.1-4.2 ppm: Methine proton (1H) in vinyl alcohol unit
(2) Melting point of EVOH The EVOH pellets obtained by synthesis are measured by raising the temperature from 30 ° C to 250 ° C at a rate of 10 ° C / min using a differential scanning calorimeter “Q2000” manufactured by TA Instruments. The melting point was calculated from the peak temperature.

(3) Quantification of Carboxylic Acid 20 g of EVOH pellets obtained by synthesis or gas barrier resin composition pellets obtained in Examples and Comparative Examples and 100 mL of ion-exchanged water are put into a 200 mL triangular flask with a stopper, and a cooling condenser is used. Was added, and the mixture was stirred and extracted at 95 ° C. for 6 hours. The obtained extract was neutralized and titrated with N / 50 NaOH using phenolphthalein as an indicator, and the content of carboxylic acid in terms of carboxylic acid root was quantified. In the embodiment containing a phosphorus compound, the amount of carboxylic acid was calculated by taking into account the content of the phosphorus compound measured by the evaluation method described later.

(4) Quantitative determination of metal ions, phosphoric acid compounds and boron compounds 0.5 g of EVOH pellets obtained by synthesis or gas barrier resin composition pellets obtained in Examples and Comparative Examples were placed in a pressure vessel made of Teflon (registered trademark). It was added, 5 mL of concentrated nitric acid was added thereto, and the mixture was decomposed at room temperature for 30 minutes. After 30 minutes, the lid was closed, and the mixture was decomposed by heating at 150 ° C. for 10 minutes and then at 180 ° C. for 5 minutes using a wet decomposition device (“MWS-2” manufactured by Actac), and then cooled to room temperature. This treatment liquid was transferred to a 50 mL volumetric flask (manufactured by TPX) and scalpel-up with pure water. Elemental analysis of this solution was performed using an ICP emission spectrophotometer (PerkinElmer's "OPTIMA4300DV"), and the metal atom equivalent amount of metal ions and the phosphorus atom conversion of phosphorus compounds contained in EVOH pellets or gas barrier resin composition pellets. The amount and the boron atom equivalent amount of the boron compound were determined.

(5) Bio-based degree The EVOH pellets obtained by synthesis and the gas barrier resin composition pellets obtained in Examples and Comparative Examples are radioactive by an accelerator mass spectrometer (AMS) according to the method described in ASTM D6866-18. The concentration of carbon ( ¹⁴ C) was measured and the degree of biobase was calculated based on the principle of radiocarbon dating.

(6) Evaluation of single-layer film (6-1) Evaluation of defects in single-layer film formation Single-screw extruder (“D2020” by Toyo Seiki Seisakusho Co., Ltd .; D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight) was used to prepare a single-layer film having an average thickness of 20 μm from the gas barrier resin composition pellets obtained in Examples and Comparative Examples. Each condition at this time is as shown below.
(Conditions for single-screw extruder)
Extrusion temperature: 210 ° C
Screw rotation speed: 40 rpm
Die width: 30 cm
Pick-up roll temperature: 80 ° C
Take-up roll speed: 3.1 m / min A single-layer film was produced by continuous operation under the above conditions, and the number of defects per 17 cm of film length was counted for each film produced 30 minutes after the start of operation. The number of defects was counted using a film defect inspection device (“AI-10” manufactured by Frontier Systems). The detection camera in this film defect inspection device was installed so that the lens position was 195 mm from the film surface. The film-forming defects are "good (A)" when the number of defects is less than 50, "slightly good (B)" when the number of defects is 50 or more and less than 200, and "defective (C)" when the number of defects is 200 or more. Judged as.

(6-2) Evaluation of Appearance of Single-Layer Film The appearance (streak) of the film produced 30 minutes after the start of operation was visually evaluated according to the following evaluation criteria. Further, a roll in which 100 m of the film was wound around a paper tube was prepared, and the appearance (coloring) due to yellowing of the end of the roll was visually evaluated according to the following evaluation criteria.
(Streak evaluation criteria)
Good (A): No streak was observed Slightly good (B): Streak was confirmed Defective (C): Many streak was confirmed (evaluation criteria for coloring at the end of the roll)
Good (A): Colorless Slightly good (B): Yellowing Poor (C): Significant yellowing

(7) Oxygen permeability Using the gas barrier resin composition pellets obtained in Examples and Comparative Examples, a single-layer film having a thickness of 20 μm was formed under the following conditions, and humidity control was performed under the conditions of 20 ° C./65% RH. After that, the oxygen permeability was measured under the condition of 20 ° C./65% RH using an oxygen permeability measuring device (“OX-Tran2 / 20” of ModernControl). This measurement was carried out in accordance with JIS K 7126-2 (isopressure method; 2006).
(Making a single-layer film)
From the above gas barrier resin composition pellets using a single-screw extruder (“D2020” from Toyo Seiki Seisakusho Co., Ltd., D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight). A single-layer film having a thickness of 20 μm was produced. The extrusion conditions are as shown below.
Extrusion temperature: 210 ° C
Die width: 30 cm
Pick-up roll temperature: 80 ° C
Screw rotation speed: 40 rpm
Pick-up roll speed: 3.1 m / min

(8) Evaluation of multilayer film (8-1) Evaluation of appearance of multilayer film Using the gas barrier resin composition pellets obtained in Examples and Comparative Examples, using a 3 type 5-layer coextruder under the following conditions. , A multilayer film (polyethylene layer / adhesive resin layer / gas barrier resin composition layer / adhesive resin layer / polyethylene layer, thickness (μm): 60/10/10/10/60) was prepared. "Novatec (trademark) UF943" manufactured by Japan Polyethylene Corporation was used as the polyethylene, and "Admer (trademark) NF528" manufactured by Mitsui Chemicals, Inc. was used as the adhesive resin.
(Extruder conditions)
Extrusion temperature of each resin: Supply part / compression part / measuring part / die = 170 ℃ / 170 ℃ / 210 ℃ / 210 ℃
Polyethylene extruder: 32φ single-screw extruder, GT-32-A type (manufactured by Plastic Engineering Laboratory Co., Ltd.)
Adhesive resin extruder: 25φ single-screw extruder, P25-18-AC type (manufactured by Osaka Seiki Kogyo Co., Ltd.)
Extruder of gas barrier resin composition: 20φ single-screw extruder, laboratory machine ME type CO-EXT (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
T-die: 300 mm width for 3 types and 5 layers (manufactured by Plastic Engineering Laboratory Co., Ltd.)
Cooling roll temperature: 50 ° C
Pick-up speed: 4 m / min The presence or absence of streaks was visually evaluated for the multilayer film produced 30 minutes after the start of operation according to the following evaluation criteria. Further, a roll in which 100 m of the multilayer film was wound on a paper tube was prepared, and the presence or absence of yellowing at the end of the roll was visually evaluated according to the following evaluation criteria.
(Streak evaluation criteria)
A (good): No streak was observed B (slightly good): Streak was confirmed C (defective): Many streaks were confirmed (evaluation criteria for coloring at the end of the roll)
A (good): colorless B (slightly good): yellowing C (poor): markedly yellowing

(8-2) Measurement of Oxygen Permeability After adjusting the humidity of the multilayer film produced 30 minutes after the start of operation in (8-1) above under the conditions of 20 ° C. and 65% RH, an oxygen permeability measuring device (8-2). Oxygen permeation according to the method described in JIS K 7126-2 (isopressure method; 2006) using "OX-Tran2 / 20") of Mocon Modern Controls.inc under the conditions of 20 ° C. and 65% RH. The degree was measured.

(9) Evaluation of thermoformed container Gas barrier resin composition pellets obtained in Examples and Comparative Examples, polypropylene (“Novatec (trademark) PP EA7AD” manufactured by Nippon Polypro Co., Ltd.), and adhesive resin (“Mitsui Chemicals Co., Ltd.” Admer ™ QF551 ”), using a 3 type 5 layer coextruder, under the following conditions, multi-layer sheet (polypropylene / adhesive resin / gas barrier resin composition / adhesive resin / polypropylene, thickness (μm): 368/16/32/16/368) was created.
(Extruder conditions)
Extrusion temperature of each resin: Supply part / compression part / measuring part / die = 150 ℃ / 150 ℃ / 210 ℃ / 210 ℃
Polypropylene resin extruder: 32φ single-screw extruder, GT-32-A type (manufactured by Plastic Engineering Laboratory Co., Ltd.)
Adhesive resin extruder: 25φ single-screw extruder, P25-18-AC type (manufactured by Osaka Seiki Kogyo Co., Ltd.)
EVOH resin composition extruder: 20φ extruder, laboratory machine ME type CO-EXT (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
T-die: 300 mm width for 3 types and 5 layers (manufactured by Plastic Engineering Laboratory Co., Ltd.)
Cooling roll temperature: 80 ° C
Pick-up speed: 1 m / min Collect the multi-layer sheet produced 30 minutes after the start of operation, and use the obtained multi-layer sheet as a thermoforming machine (manufactured by Asano Manufacturing Co., Ltd .: vacuum compressed air deep drawing molding machine "FX-0431-3"". ), The sheet temperature is set to 160 ° C., and compressed air (atmospheric pressure 5 kgf / cm ² ) makes it into a round cup shape (mold shape: upper part 75 mmφ, lower part 60 mmφ, depth 75 mm, drawing ratio S = 1.0). By thermoforming, a thermoformed container was obtained. The molding conditions are shown below.
Heater temperature: 400 ° C
Plug: 45φ x 65mm
Mold temperature: 40 ° C
The appearance of the cup-shaped thermoformed container obtained visually was evaluated according to the following evaluation criteria.
(Appearance evaluation criteria)
Good (A): No unevenness or local unevenness was observed. Slightly good (B): Slight unevenness and local unevenness were confirmed. Defective (C): Significant unevenness and local unevenness were confirmed.

(10) Streak evaluation of blow-molded container EVOH resin composition pellets obtained in Examples and Comparative Examples, high-density polyethylene (“HIZEX ™ 8200B” manufactured by Prime Polymer Co., Ltd.), and adhesive resin (Mitsui Chemicals). (Inside) high-density polyethylene layer / adhesive resin layer / gas barrier resin at 210 ° C. using a blow molding machine TB-ST-6P manufactured by Suzuki Kosakusho Co., Ltd. using "ADMER (trademark) GT-6A"). A blow-molded container was prepared from 3 types of 6-layer parisons of composition layer / adhesive resin layer / high-density polyethylene layer / high-density polyethylene layer (outside). In the manufacture of blow-molded containers, the mold is cooled at a temperature of 15 ° C. for 20 seconds, and the average thickness of all layers is 1000 μm ((inside) high-density polyethylene layer / adhesive resin layer / gas barrier resin composition layer / adhesive resin. A 3L blow-molded container of layer / high-density polyethylene layer / high-density polyethylene layer (outside) = (inside) 340 μm / 50 μm / 40 μm / 50 μm / 400 μm / 120 μm (outside) was molded. The bottom surface average diameter of this blow molded container was 100 mm, and the average height was 400 mm. Blow-molded containers were collected 30 minutes after the start of operation, and streak evaluation was performed by visual inspection of the appearance and observation of a cross-sectional microscope in the circumferential direction.
(Streak evaluation criteria)
A (good): No streak was observed.
B (slightly good): Streak was confirmed.
C (defective): Many streaks were confirmed.

(11) Fuel permeability The gas barrier resin composition pellets obtained in Examples and Comparative Examples, high-density polyethylene (“HIZEX ™ 8200B” manufactured by Prime Polymer Co., Ltd.) and adhesive resin (“HIZEX ™ 8200B” manufactured by Prime Polymer Co., Ltd.) and adhesive resin (“Mitsui Chemicals Co., Ltd.” ADMER ™ GT-6A ”) and the multilayer film (polyethylene / adhesive resin / gas barrier resin composition / adhesion) using the 3 types and 5 layer co-extruder and extruder conditions used in (5) above. (Resin / polyethylene) was prepared. The layer structure of the multilayer film was 90 μm for the polyethylene resin of the inner and outer layers, 10 μm each for the adhesive resin, and 20 μm for the gas barrier resin composition layer of the intermediate layer. The permeability of the model fuel of the obtained multilayer film was measured using a GTR Tech flow-type gas / vapor transmittance measuring device (GTR-30XFKE). The multilayer film was humidity-controlled at 20 ° C. and 65% RH for 1 month, and the measurement was carried out at 60 ° C. CE10 gasoline was used as the model fuel, and its composition was toluene / isooctane / ethanol = 45/45/10% by mass.

[Preparation of vinyl acetate synthesis catalyst]
Silica sphere carrier HSV-I (sphere diameter 5 mm, specific surface area 160 m2 / g, water absorption rate 0.75 g / g) 23 g (water absorption 19.7 g) manufactured by Shanghai Haiyuan Chemical Technology Co., Ltd., 56 mass% sodium tetrachloroplazate After impregnating with an aqueous solution equivalent to the amount of water absorbed by the carrier containing 1.5 g of the aqueous solution and 1.5 g of the 17 mass% tetrachlorogold acid tetrahydrate aqueous solution, the mixture is immersed in 40 mL of the aqueous solution containing 2.5 g of sodium metasilicate 9hydrate. Then, it was allowed to stand for 20 hours. Subsequently, 3.3 mL of a 52 mass% hydrazine hydrate aqueous solution was added, and the mixture was allowed to stand at room temperature for 4 hours, washed with water until chloride ions disappeared, and dried at 110 ° C. for 4 hours. The obtained palladium / gold / carrier composition was immersed in 60 mL of a 1.7 mass% acetic acid aqueous solution and allowed to stand overnight. Then, it was washed with water overnight and dried at 110 ° C. for 4 hours. Then, 2 g of potassium acetate was impregnated into an aqueous solution corresponding to the amount of water absorbed by the carrier and dried at 110 ° C. for 4 hours to obtain a vinyl acetate synthesis catalyst.

[Synthesis of vinyl acetate]
<Synthesis example of VAM1>
The vinyl acetate synthesis catalyst 3 mL is diluted with 75 mL of glass beads and filled in a SUS316L reaction tube (inner diameter 22 mm, length 480 mm), and ethylene / oxygen / water / acetic acid / nitrogen = 47 at a temperature of 150 ° C. and a pressure of 0.6 MPaG. A gas mixed at a ratio of 3.3 / 6.1 / 5.6 / 26.3 / 14.7 (mol%) was circulated at a flow rate of 20 NL / hour, and a reaction was carried out to synthesize vinyl acetate (VAM1). As ethylene, ethylene derived from biomass (bioethylene derived from sugar cane manufactured by Braskem SA) is used, and a gas cylinder filled with this ethylene (ethylene purity 96.44%, internal volume 29.502 L, internal pressure 1.8234 MPa). )It was used. As acetic acid, biomass-derived acetic acid (Bioacetate derived from sugarcane produced by Godavari Biorefines Ltd.) was used, vaporized at 220 ° C., and then introduced into the reaction system by steam.

<Synthesis of VAM2 to VAM3>
As shown in Table 1, each vinyl acetate of VAM2 to VAM3 was synthesized by the same method as VAM1 except that the raw materials ethylene and acetic acid were changed to those derived from biomass and / or fossil fuel.

The following raw materials were used as the raw materials used for the synthesis of vinyl acetate.
-Biomass-derived ethylene: Braskem S. A. Manufactured by Satoukibi-derived bioethylene / fossil fuel-derived ethylene: Air Liquid Industrial Gas Co., Ltd., manufactured by Fossil Fuel-derived ethylene / biomass-derived acetic acid: Godavari Biorefines Ltd. Bioacetic acid derived from sugar cane, acetic acid derived from fossil fuel: Acetic acid derived from fossil fuel manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.

[Synthesis of EVOH]
<Preparation of EVOH (A1) pellets>
(Polymerization of ethylene-vinyl acetate copolymer)
105 kg of VAM1 and 32.3 kg of methanol (hereinafter, also referred to as MeOH) were charged into a 250 L pressurized reaction vessel equipped with a jacket, a stirrer, a nitrogen inlet, an ethylene inlet and an initiator addition port, and the temperature was 65 ° C. After the temperature was raised to the above temperature, nitrogen bubbling was performed for 30 minutes to replace the inside of the reaction vessel with nitrogen. Next, ethylene was boosted and introduced so that the reaction vessel pressure (ethylene pressure) was 3.67 MPa. As ethylene, ethylene derived from biomass (bioethylene derived from sugar cane, manufactured by Braskem SA) was used. After adjusting the temperature in the reaction vessel to 65 ° C., 16.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator is methanol. It was added as a solution and polymerization was started. During the 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%, the mixture was cooled to terminate the polymerization. After opening the reaction vessel and deethyleneing, nitrogen gas was bubbled to completely deethylene. Then, after removing the unreacted VAC under reduced pressure, MeOH was added to the ethylene-vinyl acetate copolymer to prepare a 20% by mass MeOH solution.

(Saponification and cleaning)
250 kg of a 20 mass% MeOH solution of the obtained ethylene-vinyl acetate copolymer jacket was placed in a 500 L reaction vessel equipped with a stirrer, a nitrogen inlet, a reflux condenser and a solution addition port, and 60 while blowing nitrogen into the solution. The temperature was raised to ° C., and 4 kg of sodium hydroxide was added as a MeOH solution having a concentration of 2 specified. After the addition of sodium hydroxide was completed, the saponification reaction was allowed to proceed by stirring for 2 hours while keeping the temperature inside the system at 60 ° C. After 2 hours had passed, 4 kg of sodium hydroxide was added again in the same manner, and heating and stirring were continued for 2 hours. Then, 14 kg of acetic acid was added to stop the saponification reaction, and 50 kg of ion-exchanged water was added. The reaction solution was concentrated by distilling MeOH and water out of the reaction vessel while heating and stirring. After 3 hours had passed, 50 kg of ion-exchanged water was further added to precipitate EVOH. EVOH precipitated by decantation was collected and ground with a mixer. The obtained EVOH powder was put into a 1 g / L acetic acid aqueous solution (bath ratio 20: ratio of 10 kg of powder to 200 L of ion-exchanged water) and washed by stirring for 2 hours. This was deflated, further added to a 1 g / L acetic acid aqueous solution (bath ratio 20), and stirred and washed for 2 hours. The deflated product was put into ion-exchanged water (bath ratio 20), stirred and washed for 2 hours, and the operation of deflating the liquid was repeated 3 times for purification. By drying this at 60 ° C. for 16 hours, 25 kg of a crudely dried EVOH was obtained.

(Manufacturing of EVOH hydrous pellets)
25 kg of the obtained crude EVOH was placed in a 100 L stirring tank equipped with a jacket, a stirrer and a reflux condenser, 20 kg of water and 20 g of MeOH were further added, and the temperature was raised to 70 ° C. to dissolve. This solution is extruded into a mixed solution of water / MeOH = 90/10 at a weight ratio cooled to 5 ° C. through a glass tube having a diameter of 3 mm to precipitate in a strand shape, and the strand is cut into a pellet shape with a strand cutter. A water-containing pellet of EVOH was obtained. The water-containing pellets of EVOH were put into an acetic acid aqueous solution (bath ratio 20) having a concentration of 1 g / L and washed by stirring for 2 hours. This was deflated, further added to a 1 g / L acetic acid aqueous solution (bath ratio 20), and stirred and washed for 2 hours. After the liquid was removed, the acetic acid aqueous solution was updated and the same operation was performed. After washing with an acetic acid aqueous solution and then deflated, the solution is put into ion-exchanged water (bath ratio 20), stirred and washed for 2 hours, and the operation of deflated is repeated 3 times to purify the catalyst during the saponification reaction. Water-containing pellets of EVOH were obtained from which the residue and MeOH used at the time of strand precipitation were removed. The water content of the obtained EVOH water-containing pellets was measured with a halogen moisture meter "HR73" manufactured by METTLER CORPORATION and found to be 110% by mass.

(Manufacturing of EVOH (A1) pellets)
The obtained water-containing pellets of EVOH were put into an aqueous solution (bath ratio 20) containing sodium acetate, acetic acid, phosphoric acid and boric acid, and immersed for 4 hours with regular stirring. The concentration of each component was adjusted so that the content of each component in the obtained EVOH (A1) pellet was as shown in Table 2. After soaking, the liquid is drained and dried in air at 80 ° C. for 3 hours and in air at 130 ° C. for 7.5 hours to obtain EVOH (A1) pellets containing sodium acetate, acetic acid, phosphoric acid and boric acid. rice field.

<Preparation of each pellet of EVOH (A2) to EVOH (A6) and EVOH (B1) to (B5)>
EVOH (A1) except that the types of ethylene and vinyl acetate as raw materials (raw material monomers) and the contents of phosphoric acid compounds and boron compounds were changed as shown in Table 2, and the amounts of ethylene and vinyl acetate used were changed as appropriate. ) EVOH (A2) pellets to EVOH (A6) pellets and EVOH (B1) to EVOH (B5) pellets were prepared in the same manner as the pellets. As the ethylene derived from fossil fuel, ethylene manufactured by Air Liquide Industrial Gas Co., Ltd. was used.

For each of the EVOH (A1) pellets to the EVOH (A6) pellets and the EVOH (B1) to the EVOH (B5) pellets, the ethylene unit content and the degree of saponification according to the methods described in the above evaluation methods (1) to (5). , Melting point, quantification of carboxylic acid, quantification of metal ion, phosphoric acid compound and boron compound, and measurement of biobase degree. The results are shown in Table 2.

[Example]
<Example 1>
EVOH (A1) pellets are extruded and pelletized in a nitrogen atmosphere using a twin-screw extruder (“2D25W” manufactured by Toyo Seiki Seisakusho Co., Ltd., 25 mmφ, die temperature 220 ° C., screw rotation speed 100 rpm), and Example 1 Gas barrier resin composition pellets were obtained.

With respect to the obtained gas barrier resin composition pellets of Example 1, quantification of carboxylic acid, metal ion, phosphoric acid compound and according to the methods described in the above evaluation methods (3) to (8), (10) and (11). Quantification of boron compounds, biobase degree, single layer film evaluation, oxygen permeability, multilayer film evaluation, streak evaluation of blow-molded container, and measurement or evaluation of fuel permeability were performed. The results are shown in Tables 3 and 4. The ethylene unit content and saponification degree in Table 3 are the results of Table 2 reprinted.

<Examples 2, 4 to 6, Comparative Examples 1, 3 to 5>
Each gas barrier resin composition pellet of Examples 2, 4 to 6 and Comparative Examples 1, 3 to 5 was prepared in the same manner as in Example 1 except that the type of EVOH used was changed as shown in Table 3. And evaluated. The results are shown in Tables 3 and 4.

<Example 3, Comparative Example 2>
The gas barrier resin composition pellets of Example 3 and Comparative Example 2 were prepared in the same manner as in Example 1 except that the type and mass ratio (ratio) of EVOH used were changed as shown in Table 3. According to the methods described in the above evaluation methods (3) to (9), quantification of carboxylic acid, quantification of metal ion, phosphoric acid compound and boron compound, biobase degree, single layer film evaluation, oxygen permeability, multilayer film evaluation, In addition, the evaluation of the thermoformed container was measured or evaluated. The results are shown in Tables 3 and 4. The ethylene unit content and saponification degree in Table 3 are the results of Table 2 reprinted.

The sulfur compounds of the gas barrier resin composition pellets obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were measured according to the method described below. The results (contents and types of sulfur compounds in terms of sulfur atoms) are shown in Table 3.
<Measurement of sulfur compound content>
The quantification of sulfur compounds was performed using a trace nitrogen sulfur analytical instrument (TS-2100H type) manufactured by Mitsubishi Analytech, and the measurement conditions were as follows.
Heater temperature: Inlet 900 ℃, Outlet 900 ℃
Gas flow rate: Ar, O ₂ 300 ml / min each
[Analysis system NSX-2100]
Measurement mode: TS
Parameters: SD-210
Measurement time (timer): 540 seconds (9 minutes)
PMT Sensitivity: High-concentration sulfur compounds were identified using gas chromatography (GC) and gas chromatography-mass spectrometry (GC / MS). As a GC detector, an FPD (flame light intensity detector), which is highly sensitive to trace amounts of sulfur compounds and phosphorus compounds, is used to analyze the mass components observed during the retention time when sulfur compounds are detected. By doing so, identification was performed.

<Example 7 and Comparative Example 6>
(Evaluation of co-extruded coated paper)
Using carton paper (thickness 500 μm, basis weight 400 g / m ² ) as a base material, coextrusion coating of 3 types and 5 layers was performed. The coextrusion structure is low density polyethylene / adhesive layer / gas barrier resin composition layer / adhesive layer / low density polyethylene / carton paper, and the thickness structure is 20/5/5/5/20/500 μm. A feed block and a T-shaped die were used to merge and distribute a low-density polyethylene extruder, an EVOH extruder, an adhesive layer extruder, and resins supplied from the respective extruders. The low-density polyethylene is linear low-density polyethylene ("Ultzex (trademark) 2022L" manufactured by Prime Polymer Co., Ltd.), and the adhesive layer is polypropylene modified with maleic anhydride ("Admer (Admer)" manufactured by Mitsui Chemicals, Inc. Trademark) QF-500 ") was used. At this time, the temperature conditions of the feed block and the T-shaped die were set to 250 ° C., and the pick-up speed was set to 300 m / min. With respect to the coextruded coated paper produced 30 minutes after the start of operation, the presence or absence of streaks on the coextruded coated surface side was visually evaluated according to the following evaluation criteria.
(Streak evaluation criteria)
A (good): No streak was observed B (slightly good): Streak was confirmed C (bad): Many streaks were confirmed

The results of coextrusion coated paper evaluation using each of the gas barrier resin composition pellets of Example 5 and Comparative Example 4 as the gas barrier resin composition are referred to as Example 7 and Comparative Example 6, respectively. The streak evaluation of Example 7 and Comparative Example 6 was A.

As shown in Tables 3 and 4, the gas barrier resin compositions of Examples 1 to 6 are only derived from fossil fuels while using raw materials derived from biomass (gas barrier resin compositions of Comparative Examples 1 to 5). ), It has high gas barrier properties and molding processability comparable to those of), and it is suggested that its performance is not due to raw materials such as biomass or fossil fuels.

<Example 8>
The traceability of Example 3 was evaluated using the thermoformed container 30 minutes after the start of operation obtained in the evaluation method (9) thermoformed container evaluation. Specifically, the EVOH layer of the obtained thermoformed container was taken out and used as a traceability sample. The biobase degree of the removed EVOH layer was measured according to the method described in the above evaluation method (5) and found to be 100%, which is consistent with the value obtained in the gas barrier resin composition pellet of Example 3 and has traceability. It was confirmed that. Further, when the sulfur compound content of the extracted EVOH layer was measured and identified, the sulfur compound was 1.2 ppm in terms of sulfur atom, the sulfur compound was dimethyl sulfide, and the gas barrier resin composition of Example 3 was obtained. It was confirmed that the value was consistent with the value obtained with the product pellet and that it had traceability.

1 Cup-shaped container 2 Cup body 3 Flange part 4 Opening 5 Inner surface 6 Outer surface 7 Lid 21 Continuous multi-layer sheet 30

Heating device

31, 32 Heater 40 Mold device 50 Lower mold 51 Upper mold 52 Recessed 53 Plug

Claims

Containing ethylene-vinyl ester copolymer saken product,
A gas barrier resin composition in which ethylene and vinyl ester, which are raw materials for the ethylene-vinyl ester copolymer saponified product, are derived from biomass.
The gas barrier resin composition according to claim 1, wherein the ethylene-vinyl ester copolymer saken product has a biobase degree of more than 99%.
The gas barrier resin composition according to claim 1 or 2, wherein the degree of biobase is more than 99%.
The gas barrier resin composition according to any one of claims 1 to 3, which contains a sulfur compound in an amount of more than 0 ppm and 100 ppm or less in terms of sulfur atom.
The gas barrier resin composition according to claim 4, wherein the sulfur compound is dimethyl sulfide or dimethyl sulfoxide.
The ethylene-vinyl ester copolymer saken product has a lower melting point than the ethylene-vinyl ester copolymer saken product (X) and the ethylene-vinyl ester copolymer saken product (X). The gas barrier resin composition according to any one of claims 1 to 5, which comprises a coalesced polymer (Y).
The claim that the mass ratio (X / Y) of the ethylene-vinyl ester copolymer saken product (X) and the ethylene-vinyl ester copolymer saken product (Y) is 60/40 or more and 95/5 or less. The gas barrier resin composition according to 6.
6. The gas barrier resin composition according to the above.
The gas barrier resin composition according to any one of claims 1 to 8, which contains carboxylic acid in an amount of 30 ppm or more and 1000 ppm or less in terms of carboxylic acid root.
The gas barrier resin composition according to any one of claims 1 to 9, which contains 1 ppm or more and 1000 ppm or less of metal ions.
The gas barrier resin composition according to any one of claims 1 to 10, which contains 1 ppm or more and 200 ppm or less of a phosphoric acid compound in terms of phosphorus atoms.
The gas barrier resin composition according to any one of claims 1 to 11, which contains a boron compound in an amount of 5 ppm or more and 5000 ppm or less in terms of boron atom.
A molded product comprising a layer formed from the gas barrier resin composition according to any one of claims 1 to 12.
The molded product according to claim 13, further comprising a thermoplastic resin layer.
A film or sheet comprising the molded product according to claim 13 or 14.
A packaging material comprising the film or sheet according to claim 15.
An industrial film or sheet comprising the molded product according to claim 13 or 14.
A thermoformed container comprising the molded product according to claim 13 or 14.
A cup-shaped container provided with the thermoformed container according to claim 18.
A tray-shaped container provided with the thermoformed container according to claim 18.
A blow-molded container comprising the molded product according to claim 13 or 14.
A fuel container comprising the blow-molded container according to claim 21.
A bottle container provided with the blow-molded container according to claim 21.
A tube comprising the molded product according to claim 13 or 14.
A multi-layer pipe comprising the molded body according to claim 13 or 14.
A paper container comprising the molded product according to claim 13 or 14.