JP2022032037A - Single-layer film, vapor-deposition film, multilayer film and heat seal film - Google Patents

Abstract

To provide: a single-layer film formed from a gas-barrier resin composition that has high gas barrier properties and sufficient long-run properties comparable to those of fossil fuel-derived ones, while using biomass-derived materials; and a vapor-deposition film, a multilayer film and a heat seal film including the single-layer film.SOLUTION: A single-layer film is formed from a gas-barrier resin composition. The gas-barrier resin composition contains one or more saponified ethylene-vinyl ester copolymers. Ethylene and vinyl ester, which are the materials for the one or more saponified ethylene-vinyl ester copolymer, are partially derived from biomass, with the balance being fossil fuel-derived ones.SELECTED DRAWING: None

Description

The present invention relates to a single layer film, a thin film, a multilayer film and a film for heat sealing.

Gas barrier materials using resins having 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, there is an increasing demand for bioplastics using biomass-derived raw materials such as carbon-neutral biomass. 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.

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

Also in the application of gas barrier materials, it is expected to commercialize gas barrier resins synthesized using raw materials derived from biomass. 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 property will be reduced. Therefore, it is desired to develop a biomass-derived resin having an excellent gas barrier property comparable to that of a fossil fuel-derived resin.

Further, the gas barrier resin may be molded into various shapes such as a container and a sheet by melt molding. For this reason, it is also important for the gas barrier resin to have a long-running property (long-term operation characteristic) in which defects and the like are unlikely to occur even if melt molding is continuously performed for a long period of time. Among various molded bodies, the gas barrier property and long-running property of the material used for the film are particularly important due to its shape, use, production form, and the like.

The present invention has been made based on the above circumstances, and an object thereof is to provide a high gas barrier property comparable to that derived from fossil fuel and a sufficient long-run property while using a raw material derived from biomass. It is an object of the present invention to provide a single-layer film formed from a gas barrier resin composition having the same, and a vapor-deposited film, a multilayer film and a heat-sealing film provided with the single-layer film.

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 was found that it has a high gas barrier property comparable to that of the conventional one having the same structure. On the other hand, regarding the long-run property, the ethylene-vinyl ester copolymer saken product synthesized by using the raw material derived from biomass as a monomer is inferior to the one synthesized by using the raw material derived from fossil fuel as a monomer, which is a gas barrier property. It was also found that it tends to be different from. For these reasons, the present inventors have found that an ethylene-vinyl ester copolymer saken product in which a raw material derived from biomass and a raw material derived from fossil fuel are used in combination is derived from fossil fuel while reducing the environmental load. The present invention has been completed by finding that it can exhibit a high gas barrier property similar to that using only the raw materials of the above and also has a sufficient long-running property.

That is, the present invention
[1] A single-layer film formed from a gas barrier resin composition, wherein the gas barrier resin composition contains one or more kinds of ethylene-vinyl ester copolymer kendies, and the above one or more kinds. Ethylene-vinyl ester copolymer A single-layer film in which a part of ethylene and vinyl ester, which are the raw materials of the saponified product, is derived from biomass and the rest is derived from fossil fuel;
[2] The above-mentioned one or more kinds of ethylene-vinyl ester copolymer saken products are the same as the ethylene-vinyl ester copolymer saken product (A) in which at least a part of ethylene and vinyl esters as raw materials is derived from biomass. , The monolayer film of [1] containing an ethylene-vinyl ester copolymer saponified product (B) derived from fossil fuel;
[3] The mass ratio (A / B) of the ethylene-vinyl ester copolymer saponified product (A) and the ethylene-vinyl ester copolymer saken product (B) is 1/99 to 99/1. [2] Single layer film;
[4] In the above-mentioned one or more kinds of ethylene-vinyl ester copolymer kendies, the ethylene-vinyl ester copolymer weight in which a part of ethylene and vinyl ester as raw materials is derived from biomass and the rest is derived from fossil fuel. The monolayer film of [1] containing the coalesced saponified product (A');
[5] The single-layer film according to any one of [1] to [4], wherein the above-mentioned one or more kinds of ethylene-vinyl ester copolymer saken products have a biobase degree of 1% or more and 99% or less.
[6] The single-layer film according to any one of [1] to [5], wherein the gas barrier resin composition has a biobase degree of 1% or more and 99% or less.
[7] The single-layer film according to any one of [1] to [6], wherein the gas barrier resin composition contains a sulfur compound in an amount of more than 0 ppm and 100 ppm or less in terms of sulfur atom.
[8] The monolayer film of [7], wherein the sulfur compound is dimethyl sulfide or dimethyl sulfoxide;
[9] The single-layer film according to any one of [1] to [8], wherein at least a part of ethylene in the above raw materials is derived from biomass;
[10] The single-layer film according to any one of [1] to [9], wherein at least a part of the vinyl ester in the above raw materials is derived from biomass;
[11] The single-layer film according to any one of [1] to [10], which is a stretched film;
[12] A vapor-deposited film comprising the single-layer film according to any one of [1] to [11] and at least one inorganic vapor-deposited layer laminated on at least one surface side of the single-layer film;
[13] A multilayer film comprising the single-layer film according to any one of [1] to [11] or the vapor-filmed film of [12];
[14] A heat-sealing film comprising the single-layer film according to any one of [1] to [11], the vapor-filmed film of [12], or the multilayer film of [13];
[15] The heat-sealing film of [14], wherein the single-layer film is provided on the outermost surface layer as a heat-sealing layer;
Is achieved by providing.

According to the present invention, a single-layer film formed from a gas barrier resin composition having a high gas barrier property comparable to that derived from fossil fuel and a sufficient long-run property while using a raw material derived from biomass, and the single layer film. A vapor-deposited film including a layer film, a multilayer film, and a heat-sealing film can be provided.

FIG. 1 is a graph showing the results of hot tack strength measurement in Examples.

<Gas barrier resin composition>
First, the gas barrier resin composition for forming the single-layer film of the present invention (hereinafter, may be simply referred to as “gas barrier resin composition”) will be described. The gas barrier resin composition contains one or more kinds of ethylene-vinyl ester copolymer kendies (ethylene-vinyl alcohol copolymer; hereinafter also referred to as "EVOH"), and one or more kinds of EVOH. A part of ethylene and vinyl ester which is a raw material (raw material polymer) is derived from biomass, and the rest of ethylene and vinyl ester which is the raw material (raw material monomer) is derived from fossil fuel. The gas barrier resin composition has a low environmental load because a raw material derived from biomass is partially used. 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 has the same structure synthesized only from the raw material derived from fossil fuel. It can exhibit the same high gas barrier property as EVOH. 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. Further, in the gas barrier resin composition, EVOH is also used with a raw material derived from fossil fuel, so that the long-run property is sufficient. Although the reason why the present invention exerts such an effect is not clear, when EVOH is synthesized using a raw material derived from biomass, it does not affect the gas barrier property but affects the long-run property in a trace amount and inevitably. It is presumed that some impurities are generated or mixed.

Here, the long-running property in the present specification can be evaluated by the method described in Examples, and can be comprehensively evaluated by the degree of defects, streaks, and coloring when the gas barrier resin composition is continuously formed into a film. However, depending on the application and the like, coloring may not be a particular problem. Therefore, it is evaluated that the long-running property is sufficient if, for example, there are few defects and streaks after continuous film formation for 10 hours.

It can be confirmed by measuring the degree of biobase that the ethylene and vinyl esters used as raw materials contain both biomass-derived and fossil fuel-derived. 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 radiocarbon ( ¹⁴ C) by an accelerator mass spectrometer (AMS). .. The biobase degree can be specifically measured according to the method described in ASTM D6866-18. That is, when the biobase degree of EVOH is usually more than 0% and less than 100%, it can be said that the ethylene and vinyl esters used as raw materials contain both biomass-derived and fossil fuel-derived.

"Biomass" refers to resources that are organic substances 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 used in the present invention can also be used to track its own products by utilizing the concentration of radiocarbon ( ^14C ). 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. Since almost no ¹⁴ C remains in the fossil fuel-derived raw material, it is possible to obtain EVOH with a ratio of ¹⁴ C to a specific total carbon by changing the ratio of the biomass-derived raw material to the fossil fuel-derived raw material, for example. By investigating the ratio of ¹⁴ C to total carbon, 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 bring 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 heat 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. The same is a concern for molded bodies and the like other than thermoformed containers.

EVOH has been used in films, sheets, containers and the like as packaging materials for foods, pharmaceuticals, industrial chemicals, pesticides and the like through many distribution channels. Further, by utilizing its barrier property, heat retention property, stain resistance and the like, it is also used for fuel tanks of vehicles such as automobiles, tube materials for tires, agricultural films, geomembranes, cushion materials for shoes 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 is a resin composition having a function of suppressing gas permeation. The upper limit of the oxygen permeation rate of the single layer film (gas barrier resin composition) of the present invention measured according to the method described in JIS K 7126-2 (isopressure method; 2006) under the condition of 20 ° C.-65% RH is , 100 mL · 20 μm / (m ² · day · atm), more preferably 50 mL · 20 μm / (m ² · day · atm), 10 mL · 20 μm / (m ² · day · atm), 1 mL · 20 μm / (m 2 · day · atm) m ² · day · atm) or 0.5 mL · 20 μm / (m ² · day · atm) is more preferred.

(EVOH)
Examples of the form of one or more kinds of EVOH contained in the gas barrier resin composition include the following forms (I) and (II).
(I) One of the forms (II) raw materials of ethylene and vinyl esters containing EVOH (A) in which at least a part of ethylene and vinyl esters as raw materials is derived from biomass and EVOH (B) derived from fossil fuels. A form containing EVOH (A') in which the portion is derived from biomass and the balance is derived from fossil fuel.

In one or more kinds of EVOH, a part of ethylene unit, vinyl alcohol unit and vinyl ester unit may be derived from biomass, and the rest may be derived from fossil fuel. That is, EVOH (A) may be EVOH in which at least a part of ethylene unit, vinyl alcohol unit and vinyl ester unit is derived from biomass. The EVOH (B) may be an EVOH derived from fossil fuels in all of ethylene units, vinyl alcohol units and vinyl ester units. In EVOH (A'), a part of ethylene unit, vinyl alcohol unit and vinyl ester unit may be derived from biomass, and the balance may be EVOH derived from fossil fuel.

(EVOH (A))
EVOH (A) is EVOH in which at least a part of ethylene and vinyl esters, which are raw material monomers, is derived from biomass. Since EVOH (A) contains a raw material derived from biomass, the biobase degree of the gas barrier resin composition and the single-layer film of the present invention can be increased, and the environmental load can be reduced.

EVOH (A) is obtained by saponification of a copolymer of ethylene and vinyl ester, which is at least partially derived from biomass. The production and saponification of the ethylene-vinyl ester copolymer as a precursor of EVOH (A) shall be carried out by the same known method as the production and saponification of the ethylene-vinyl ester copolymer derived from the conventional fossil fuel. Can be done. 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-based, unused-based, resource-based crop-based, etc. can be used, for example, cellulose-based crops (pulp, kenaf, straw, rice straw, used paper, papermaking residue, etc.), wood, charcoal, compost. , Natural rubber, cotton, sugar cane, okara, fats and oils (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) Etc.), 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. et al. 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 a 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, the biomass-derived vinyl ester may be a vinyl ester produced by using a biomass-derived carboxylic acid. If the saponification degree of EVOH (A) is not 100 mol%, the acyl group derived from biomass will remain.

The lower limit of the ethylene unit content of EVOH (A) is preferably 20 mol%, more preferably 23 mol%, still more preferably 25 mol%. When the ethylene unit content of EVOH (A) is 20 mol% or more, the long-run property tends to increase. The upper limit of the ethylene unit content of EVOH (A) is preferably 60 mol%, more preferably 55 mol%, still more preferably 50 mol%. When the ethylene unit content of EVOH (A) 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 EVOH (A) is preferably 90 mol%, more preferably 95 mol%, still more preferably 99 mol%. When the saponification degree of EVOH (A) is 90 mol% or more, the gas barrier property and the long-run property in the gas barrier resin composition tend to be better. Further, the upper limit of the saponification degree of EVOH (A) 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.

It is preferable that at least a part of ethylene and vinyl ester used as a raw material of EVOH (A) is derived from biomass, at least a part of vinyl ester is derived from biomass, and all of vinyl ester is derived from biomass. It is also good. Further, it is preferable that at least a part of ethylene, which is a raw material of EVOH (A), is derived from biomass, and all of ethylene may be derived from biomass. Further, it may be preferable that at least a part of the vinyl ester as a raw material of EVOH (A) and at least a part of ethylene are derived from biomass, and all of the vinyl ester and ethylene may be derived from biomass.

The lower limit of the ratio of the vinyl alcohol unit derived from biomass in the total vinyl alcohol units (condensate of vinyl ester units) constituting EVOH (A) is preferably 1 mol%, more preferably 5 mol%, and further 10 mol%. Preferably, 25 mol% or 45 mol% is even more preferable, 70 mol%, 90 mol% or 99 mol% may be used, and all vinyl alcohol units constituting EVOH (A) may be derived from biomass. good. The upper limit of the proportion of vinyl alcohol units derived from fossil fuels in the total vinyl alcohol units constituting EVOH (A) is preferably 99 mol%, more preferably 95 mol%, still more preferably 90 mol%, or 75 mol% or 55. More preferably, mol% is more preferably 30 mol%, 10 mol% or 1 mol%, and the total vinyl alcohol units constituting EVOH (A) do not contain vinyl alcohol units derived from fossil fuels. May be good. When the proportion of biomass-derived vinyl alcohol units in the total vinyl alcohol units constituting EVOH (A) is high, the degree of biobase in the gas barrier resin composition and the single-layer film of the present invention is increased, and the environmental load tends to be reduced. .. On the other hand, from the viewpoint of providing a gas barrier resin composition having an excellent balance between biobase degree and long-running property, the proportion of vinyl alcohol unit derived from biomass is preferably 5 mol% or more and 95 mol% or less, and 15 mol% or more and 85 mol%. The following is more preferable, 25 mol% or more and 75 mol% or less are further preferable, and 35 mol% or more and 65 mol% or less are particularly preferable.

The lower limit of the proportion of ethylene units derived from biomass in all ethylene units constituting EVOH (A) is preferably 1 mol%, more preferably 5 mol%, further preferably 10 mol%, and 25 mol% or 45 mol%. Even more preferably, it may be 70 mol%, 90 mol% or 99 mol%, and all ethylene units constituting EVOH (A) may be derived from biomass. The upper limit of the proportion of ethylene units derived from fossil fuels in all ethylene units constituting EVOH (A) is preferably 99 mol%, more preferably 95 mol%, further preferably 90 mol%, and 75 mol% or 55 mol%. Is even more preferable, and it may be 30 mol%, 10 mol% or 1 mol%, and the ethylene unit derived from fossil fuel may not be contained in the total ethylene unit constituting EVOH (A). When the proportion of biomass-derived ethylene units in all ethylene units constituting EVOH (A) is high, the degree of biobase in the gas barrier resin composition and the single-layer film of the present invention is increased, and the environmental load tends to be reduced. On the other hand, from the viewpoint of providing a gas barrier resin composition having an excellent balance between biobase degree and long-running property, the proportion of ethylene units derived from biomass is preferably 5 mol% or more and 95 mol% or less, and 15 mol% or more and 85 mol% or less. Is more preferable, 25 mol% or more and 75 mol% or less is further preferable, and 35 mol% or more and 65 mol% or less is particularly preferable.

The lower limit of the biobase degree of EVOH (A) is preferably 1%, more preferably 5%, further preferably 20%, and particularly preferably 40% from the viewpoint of reducing the environmental load of the single-layer film of the present invention. Further, the lower limit of the biobase degree of EVOH (A) may be 60%, 80% or 95%. The upper limit of the biobase degree of EVOH (A) may be 100%, but 99% is preferable, 95% is more preferable, and 85%, 75% or 65% is preferable from the viewpoint of good long-running property. May be even more preferred.

EVOH (A) 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 EVOH (A) has a unit derived from the other monomer, the upper limit of the content of the unit derived from the other monomer to all structural units of EVOH (A) is preferably 30 mol%, preferably 20 mol. % Is more preferred, 10 mol% is even more preferred, 5 mol% is even more preferred, and 1 mol% is even more preferred. When EVOH (A) 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 sulfones 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.

EVOH (A) may be post-modified by a method such as urethanization, acetalization, cyanoethylation, or oxyalkyleneization.

EVOH (A) may be used alone or in combination of two or more.

The lower limit of the melt flow rate (MFR) at 190 ° C. and 2160 g load of EVOH (A) measured according to JIS K7210: 1999 is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes. , 1.0 g / 10 minutes is more preferred. On the other hand, the upper limit of MFR of EVOH (A) is preferably 30 g / 10 minutes, more preferably 20 g / 10 minutes, and even more preferably 15 g / 10 minutes. When the MFR of EVOH (A) at 190 ° C. and a load of 2160 g is in the above range, the melt moldability is improved, and as a result, the long-running property tends to be improved.

The lower limit of the melting point of EVOH (A) is preferably 135 ° C., more preferably 150 ° C., and even more preferably 155 ° C. When the melting point of EVOH (A) is 135 ° C. or higher, the gas barrier property tends to be excellent. The upper limit of the melting point of EVOH (A) is preferably 200 ° C, more preferably 190 ° C, and even more preferably 185 ° C. When the melting point of EVOH (A) is 200 ° C. or lower, the melt moldability is good, and as a result, the long-run property tends to be enhanced.

(EVOH (B))
EVOH (B) is an EVOH derived from fossil fuels. Here, the EVOH derived from fossil fuel means EVOH synthesized by using a raw material derived from fossil fuel. That is, the EVOH (B) is an EVOH in which all of the raw material monomers, ethylene, vinyl ester, and other monomers used as needed, are derived from fossil fuels. In other words, EVOH (B) is EVOH synthesized without using a biomass-derived raw material. When the gas barrier resin composition contains EVOH (B), sufficient long-running property can be exhibited.

Specific and preferred embodiments of EVOH (B) are similar to EVOH (A), except that the raw material is derived from fossil fuels, i.e., the biobase degree is 0%. That is, the specific and suitable ethylene unit content, saponification degree, type and content derived from other monomers, MFR, melting point, etc. of EVOH (B) are the same as those of EVOH (A).

EVOH (B) may be used alone or in combination of two or more.

In the form (I) in which EVOH (A) and EVOH (B) are used in combination, the lower limit of the mass ratio (A / B) of EVOH (A) and EVOH (B) is preferably 1/99. / 95 is more preferred, 15/85 is even more preferred, and 40/60 is particularly preferred. By setting the mass ratio (A / B) to 1/99 or more, the biobase degree of the gas barrier resin composition and the single-layer film of the present invention can be increased and the environmental load can be reduced. From the viewpoint of further reducing the environmental load, the lower limit of the mass ratio (A / B) may be preferably 60/40 or 75/25. Further, the upper limit of the mass ratio (A / B) is preferably 99/1, more preferably 95/5, further preferably 85/15, and even more preferably 60/40 or 40/60. By setting the mass ratio (A / B) to 99/1 or less, the long-running property can be enhanced.

The ethylene unit content, saponification degree, MFR, melting point, etc. of EVOH (A) and EVOH (B) may be the same or different. From the viewpoint of enhancing performance such as long-running property, it is preferable that the ethylene unit content, saponification degree, MFR and melting point of EVOH (A) and EVOH (B) are the same or close to each other. The difference in ethylene unit content between EVOH (A) and EVOH (B) is preferably 6 mol% or less, more preferably 3 mol% or less, still more preferably 0 mol%. The difference in the degree of saponification between EVOH (A) and EVOH (B) is preferably 2 mol% or less, more preferably 1 mol% or less, still more preferably 0 mol%. The difference in MFR between EVOH (A) and EVOH (B) is preferably 2 g / 10 minutes or less, more preferably 1 g / 10 minutes or less, and even more preferably 0 g / 10 minutes. The difference in melting point between EVOH (A) and EVOH (B) is preferably 7 ° C. or lower, more preferably 3 ° C. or lower, and even more preferably 0 ° C.

(EVOH (A'))
In EVOH (A'), a part of ethylene and vinyl ester which are raw material monomers is derived from biomass, and the balance of ethylene and vinyl ester which is the raw material monomer is derived from fossil fuel. When the raw material of EVOH (A') contains a raw material derived from biomass, the degree of biobase in the gas barrier resin composition and the single-layer film of the present invention tends to be increased, and the environmental load tends to be reduced. Further, since the raw material of EVOH (A') contains a raw material derived from fossil fuel, the long-running property of the gas barrier resin composition can be improved.

EVOH (A') is obtained by saponification of a copolymer of ethylene and vinyl ester, partly derived from biomass and the rest derived from fossil fuel. The ethylene-vinyl ester copolymer, which is a precursor of EVOH (A'), can be produced and saponified by a conventionally known method except that a biomass-derived polymer is used as a part of the raw material.

Examples of biomass-derived ethylene and biomass-derived vinyl esters used for the synthesis of EVOH (A') are the same as those described above as those used for the synthesis of EVOH (A).

The specific and suitable conditions for the ethylene unit content and saponification degree of EVOH (A') are the same as those of EVOH (A) described above.

In ethylene and vinyl esters used as raw materials for EVOH (A'), it is preferable that at least a part of ethylene is derived from biomass, and all of ethylene may be derived from biomass. Further, it is preferable that at least a part of the vinyl ester which is a raw material of EVOH (A') is derived from biomass, and the whole vinyl ester may be derived from biomass.

The lower limit of the ratio of the vinyl alcohol unit derived from biomass in all the vinyl alcohol units (condensate of vinyl ester unit) constituting EVOH (A') is preferably 1 mol%, more preferably 5 mol%, and 10 mol%. More preferably, 25 mol% or 45 mol% is even more preferred, and it may be 70 mol%, 90 mol% or 99 mol%, and all vinyl alcohol units constituting EVOH (A') are derived from biomass. May be good. The upper limit of the ratio of the vinyl alcohol unit derived from fossil fuel to the total vinyl alcohol unit constituting EVOH (A') is preferably 99 mol%, more preferably 95 mol%, further preferably 90 mol%, or 75 mol% or 55 mol% is more preferable, and it may be 30 mol%, 10 mol% or 1 mol%, and the total vinyl alcohol units constituting EVOH (A') do not contain vinyl alcohol units derived from fossil fuels. May be. When the proportion of biomass-derived vinyl alcohol units in all vinyl alcohol units constituting EVOH (A') is high, the degree of biobase in the gas barrier resin composition and the single-layer film of the present invention is increased, and the environmental load tends to be reduced. Become. On the other hand, from the viewpoint of providing a gas barrier resin composition having an excellent balance between biobase degree and long-running property, the proportion of vinyl alcohol unit derived from biomass is preferably 5 mol% or more and 95 mol% or less, and 15 mol% or more and 85 mol%. The following is more preferable, 25 mol% or more and 75 mol% or less are further preferable, and 35 mol% or more and 65 mol% or less are particularly preferable.

The lower limit of the proportion of biomass-derived ethylene in all ethylene units constituting EVOH (A') is preferably 1 mol%, more preferably 5 mol%, still more preferably 10 mol%, and 25 mol% or 45 mol%. More preferably, it may be 70 mol%, 90 mol% or 99 mol%, and all ethylene units constituting EVOH (A') may be derived from biomass. The upper limit of the proportion of ethylene units derived from fossil fuels in all ethylene units constituting EVOH (A') is preferably 99 mol%, more preferably 95 mol%, further preferably 90 mol%, and 75 mol% or 55 mol. % Is even more preferably 30 mol%, 10 mol% or 1 mol%, and the total ethylene units constituting EVOH (A') may not contain ethylene units derived from fossil fuels. .. When the proportion of biomass-derived ethylene units in all ethylene units constituting EVOH (A') is high, the degree of biobase in the gas barrier resin composition and the single-layer film of the present invention is increased, and the environmental load tends to be reduced. On the other hand, from the viewpoint of providing a gas barrier resin composition having an excellent balance between biobase degree and long-running property, the proportion of ethylene units derived from biomass is preferably 5 mol% or more and 95 mol% or less, and 15 mol% or more and 85 mol% or less. Is more preferable, 25 mol% or more and 75 mol% or less is further preferable, and 35 mol% or more and 65 mol% or less is particularly preferable.

The lower limit of the biobase degree of EVOH (A') is preferably 1%, more preferably 5%, still more preferably 20%, and 40% from the viewpoint of reducing the environmental load of the gas barrier resin composition and the single-layer film of the present invention. % Is particularly preferable. Further, for example, in applications where particularly excellent long-running property is not required, the lower limit of the biobase degree of EVOH (A') may be 60% or 80%. On the other hand, the upper limit of the biobase degree of EVOH (A') is preferably 99%, more preferably 95%, and even more preferably 85%, 75% or 65% from the viewpoint of improving long-running property.

EVOH (A') may have a unit derived from a monomer other than ethylene, vinyl ester and a saponified product thereof, or may be post-denatured, as long as the object of the present invention is not impaired. .. Specific examples of the copolymerization component and post-modification are the same as those of EVOH (A) described above.

EVOH (A') may be used alone or in combination of two or more.

Preferable aspects of the melt flow rate (MFR) and melting point of EVOH (A') at 190 ° C. and 2160 g load measured according to JIS K7210: 1999 are the same as those of EVOH (A) described above.

The lower limit of the proportion of one or more EVOHs in all the resins constituting the gas barrier resin composition is preferably 80% by mass, more preferably 90% by mass, further preferably 95% by mass, and particularly preferably 98% by mass. Preferably, it may be 99% by mass, and the resin constituting the gas barrier resin composition may be substantially only one or more kinds of EVOH, or may be only one kind or two or more kinds of EVOH. good. The lower limit of the proportion of one or more EVOHs in the gas barrier resin composition 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 may be substantially composed of only one kind or two or more kinds of EVOH.

The lower limit of the biobase degree of one or more EVOHs contained in the gas barrier resin composition is preferably 1%, more preferably 5%, and further 20% from the viewpoint of reducing the environmental load of the gas barrier resin composition. It is preferable, and 40% is particularly preferable. Further, for example, in applications where particularly excellent long-running property is not required, the lower limit of the biobase degree of the entire EVOH may be 60% or 80%. On the other hand, the upper limit of the biobase degree of the whole EVOH is preferably 99%, more preferably 95%, 85%, 75%, 65%, 55%, 45%, 35% or 25% may be even more preferred.

The specific and suitable ranges of the ethylene unit content, saponification degree, MFR and melting point of one or more EVOHs contained in the gas barrier resin composition are the same as those of EVOH (A) described above.

It is more preferable that the gas barrier resin composition contains a sulfur compound of more than 0 ppm and 100 ppm or less in terms of sulfur atoms from the viewpoint of tracking the company's products. 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 0.3 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 compounds 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 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 preferably further contains a carboxylic acid. When the gas barrier resin composition contains a carboxylic acid, melt moldability and coloring 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 contains a carboxylic acid, the lower limit of the content thereof 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 color resistance of the single-layer film 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), capric 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 tartaric acid (pKa2 = 4.27), tartaric acid (pKa1 = 4.20), pimelic acid (pKa2 = 4.44), malic acid (pKa2 = 5.13), and the like. Glutaric acid (pKa1 = 4.30, pKa2 = 5.40), malic 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), citric acid (pKa2 = 4.75), tartaric acid (pKa2 = 4.40), glutamate (pKa2). = 4.07), asparagic acid (pKa = 3.90), and the like.

The gas barrier resin composition preferably further contains a phosphoric acid compound. When the gas barrier resin composition 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 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 phosphorous acid, salts thereof and the like 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 sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate and the like.

The gas barrier resin composition preferably further contains a boron compound. When the gas barrier resin composition contains a boron compound, the lower limit of the content thereof is preferably 5 ppm in terms of boron atom, more preferably 100 ppm. 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 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 single-layer film or the like 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 hydride. 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 preferably further contains metal ions. When the gas barrier resin composition contains metal ions, the interlayer adhesiveness becomes excellent when a multi-layer molded product, that is, a multi-layer film 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 of the gas barrier resin composition and the coloring resistance of the single-layer film of the present invention can be improved.

When the gas barrier resin composition 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 kind or a plurality of 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 the 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 gels and lumps such as the obtained single-layer film 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 carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates and metal complexes, and carboxylates are 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 is, for example, an antiblocking agent, a processing aid, a resin other than EVOH, a stabilizer, an antioxidant, an ultraviolet absorber, a plasticizer, and an antistatic agent as long as the effect of the present invention is not impaired. , Lubricants, colorants, fillers, surfactants, desiccants, oxygen absorbers, cross-linking agents, reinforcing agents such as various fibers and the like.

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 contains a blocking inhibitor, the blocking resistance of the single-layer film of the present invention can be enhanced.

Examples of the processing aid include fluorine-based processing aids such as Arkema's Kynar (registered trademark) and 3M's Dynamer (registered trademark). When the gas barrier resin composition contains a processing aid, it tends 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 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, phosphoric acid 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 and the like, 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 is preferably 3.0 parts by mass or less, preferably 1.0 part by mass, based on a total of 100 parts by mass of one or more types of EVOH from the viewpoint of preventing the generation of voids during molding. It is more preferably parts of parts or less, further preferably 0.5 parts by mass or less, and particularly preferably 0.3 parts by mass or less.

The gas barrier resin composition may contain impurities derived from biomass due to EVOH (A) or EVOH (A').

(Biobase degree of gas barrier resin composition)
The lower limit of the biobase degree of the gas barrier resin composition is preferably 1%, more preferably 5%, further preferably 20%, and particularly preferably 40% from the viewpoint of reducing the environmental load. Further, for example, in applications where particularly excellent long-running property is not required, the lower limit of the biobase degree of the gas barrier resin composition may be 60% or 80%. On the other hand, the upper limit of the biobase degree of the gas barrier resin composition is preferably 99%, more preferably 95%, 85%, 75%, 65%, 55%, 45%, 35% from the viewpoint of good long-running property. Or 25% may be more preferred. 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. Further, the biobase degree of this gas barrier resin composition is equal to the biobase degree of the single layer film of the present invention.

<Manufacturing method of gas barrier resin composition>
The method for producing the gas barrier resin composition is not particularly limited. For example, in the case of a gas barrier resin composition containing EVOH (A) and EVOH (B),
(1) A method of mixing (dry blending) EVOH (A) pellets, EVOH (B) pellets, and the above-mentioned other components as necessary, and melting and kneading the mixed pellets.
(2) After immersing the pellets of EVOH (A) and / or the pellets of EVOH (B) in a solution containing the above-mentioned other components as necessary, the pellets of EVOH (A) and the pellets of EVOH (B) A method of dry blending with pellets and melting and kneading them,
(3) The pellets of EVOH (A) and the pellets of EVOH (B) are dry-blended, and when they are melt-kneaded, an aqueous solution containing the above-mentioned other components is added in the middle of the extruder as needed. Method (4) A method of blending the molten resin of EVOH (A) and the molten resin of EVOH (B) in a molten state (other components are previously contained in EVOH (A) and / or EVOH (B), if necessary. Even if it is left untouched, it may be liquid-added in the extruder.)
And so on.

According to the manufacturing methods (1) to (4) above, the effect of reducing the environmental load and long-running property are achieved by adjusting the mixing ratio of EVOH (A) and EVOH (B) according to the application, performance, etc. It is possible to produce a gas barrier resin composition having a high gas barrier property while considering the balance with the above. Among these, it is preferable to include (1) a step of dry-blending and melt-kneading the pellets of EVOH (A) and the pellets of EVOH (B). For mixing the pellets with each other or mixing the pellets with other components, for example, a ribbon blender, a high-speed mixer conider, a mixing roll, an extruder, an intensive mixer or the like can be used.

Further, in the case of a gas barrier resin composition containing EVOH (A'), EVOH (A') is synthesized by a known method, and the obtained EVOH (A') is subjected to other methods as necessary. It can be produced by mixing the components of.

<Single layer film>
The single-layer film of the present invention is a film formed from a gas barrier resin composition. The method for producing a single-layer film of the present invention can be produced by a known method, 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. The melting temperature in the melting method varies depending on the melting point of the gas barrier resin composition and the like, but is preferably about 150 to 300 ° C.

The single-layer film of the present invention may be stretched or unstretched. When it is stretched, the gas barrier property, strength, and the like tend to improve. On the other hand, when it is unstretched, the heat-sealing property tends to be good. Therefore, when it is used as the film for heat sealing of the present invention described later, it is preferably unstretched.

The average thickness of the single-layer film of the present invention is, for example, preferably 1 μm or more and less than 300 μm, and more preferably 5 μm or more and less than 100 μm. The single-layer film of the present invention can be suitably used as various packaging materials and the like.

When the single-layer film of the present invention is a stretched film, the stretching may be at least uniaxially stretched, but biaxial stretching is preferable. The biaxial stretching may be either sequential biaxial stretching or simultaneous biaxial stretching. The stretching temperature can be, for example, 60 ° C. or higher and 120 ° C. or lower.

When the single-layer film of the present invention is stretched, a step of heat-treating the stretched single-layer film may be provided 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 single-layer film of the present invention can be used in the form of laminating another layer on at least one surface side. For example, the single-layer film of the present invention can be used for a vapor-deposited film in which at least one inorganic vapor-deposited layer is laminated on at least one surface of the single-layer film.

<Embedded film>
The vapor-filmed film of the present invention includes the single-layer film of the present invention and at least one inorganic vapor-deposited layer laminated on at least one surface side of the single-layer film. The inorganic vapor deposition layer is a layer made of an inorganic substance such as a metal or an inorganic oxide and having a gas barrier property against oxygen and water vapor. The gas barrier resin composition for forming the single-layer film of the present invention has a higher affinity for metals and inorganic oxides than ordinary thermoplastic resins, and can form a dense and defect-free inorganic vapor-deposited layer. Further, since the gas barrier resin composition has a gas barrier property, it is possible to suppress a decrease in the gas barrier property even when a defect occurs in the inorganic thin-film deposition layer due to bending or the like. The single-layer film used for the vapor-filmed film of the present invention is preferably a single-layer film (stretched film) stretched in at least one axial direction.

The inorganic vapor deposition layer is preferably either a metal vapor deposition layer containing aluminum as a main component or an inorganic oxide vapor deposition layer containing alumina or silica as a main component. A metal-deposited layer is preferable for imparting light-shielding properties, but inorganic oxidation is possible from the viewpoints of visibility of the contents as a packaging material, appropriate range, and suppression of gel and lumps when melt-molding the crushed material. A thin-film deposition layer is preferred.

The metal vapor deposition layer is generally a layer containing aluminum as a main component. The content of aluminum atoms in the metal vapor deposition layer is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more. The average thickness of the metal vapor deposition layer is preferably 120 nm or less, more preferably 100 nm or less, still more preferably 90 nm or less. The average thickness of the metal vapor deposition layer is preferably 25 nm or more, more preferably 35 nm or more, and even more preferably 45 nm or more. The average thickness of the metal-deposited layer is an average value of the thicknesses at any 10 points on the cross section of the metal-deposited layer measured by an electron microscope.

The inorganic oxide vapor deposition layer includes an inorganic oxide such as an oxide such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, or yttrium, preferably an alumina or silica vapor deposition film. Can be mentioned. The average thickness of the inorganic oxide-deposited layer is preferably 60 nm or less, more preferably 50 nm or less, still more preferably 40 nm or less. The average thickness of the inorganic oxide-deposited layer is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more. The average thickness of the inorganic oxide-deposited layer is an average value of the thicknesses at any 10 points on the cross section of the inorganic oxide-deposited layer measured by an electron microscope.

The average thickness of the inorganic thin-film deposition layer is preferably 120 nm or less, more preferably 100 nm or less, and even more preferably 90 nm or less. The average thickness of the inorganic thin-film deposition layer is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more. The average thickness of the inorganic thin-film deposition layer is an average value of the thicknesses at any 10 points on the cross section of the inorganic vapor-film deposition layer measured by an electron microscope.

The inorganic thin-film deposition layer can be vapor-deposited by a known physical vapor deposition method or chemical vapor deposition method. Specific examples thereof include a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion beam mixing method, a plasma CVD method, a laser CVD method, a MO-CVD method, a thermal CVD method, and the like, and a physical vapor deposition method is used. It is preferable, and it is particularly preferable to use the vacuum vapor deposition method. A protective layer (top coat layer) may be provided on the inorganic thin-film deposition layer, if necessary, as long as the effects of the present invention are not impaired. The upper limit of the surface temperature of the substrate during vapor deposition is preferably 60 ° C, more preferably 55 ° C, and even more preferably 50 ° C. The lower limit of the surface temperature of the substrate during vapor deposition is not particularly limited, but is preferably 0 ° C, more preferably 10 ° C, and even more preferably 20 ° C. The surface of the substrate may be plasma treated before the vapor deposition. A known method can be used for the plasma treatment, and atmospheric pressure plasma treatment is preferable. In the atmospheric pressure plasma treatment, nitrogen, helium, neon, argon, krypton, xenon, radon and the like are used as the discharge gas. Of these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because the cost can be reduced.

<Multilayer film>
The multilayer film of the present invention is a multilayer film including the single-layer film or the vapor-deposited film of the present invention. The lower limit of the number of layers of the multilayer film may be 2, but 3 is preferable. That is, the vapor-deposited film of the present invention having at least two layers is one aspect of the multilayer film of the present invention. The upper limit of the number of layers of the multilayer film may be, for example, 1000, 100, 20 or 10. The multilayer film is usually obtained by laminating another layer different from these on the single-layer film and the vapor-filmed film of the present invention. As the layer structure of the multilayer film, a layer made of a resin other than the gas barrier resin composition is an x layer, a gas barrier resin composition layer is a y layer, an adhesive resin layer is a z layer, and "/" is an adhesive layer or a direct laminate. It means, 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 the like can be mentioned. 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 composition of each layer of the multilayer film, the thickness ratio of the y layer to the total layer thickness is usually 2 to 20% from the viewpoint of moldability, cost and the like. The adhesive layer is a layer formed of an adhesive resin or other adhesive.

Further, in the above layer structure, the inorganic vapor deposition layer (v layer) may be laminated on one surface or both surface sides of the y layer (gas barrier resin composition layer). The layer structure of the multilayer film including the v layer, that is, the vapor-film deposition film, is, for example, x / y / v, x / v / y, x / v / y / v, x / y / v / x, x / v. / Y / v / x, x / z / v / y, x / z / y / v / z / x, x / z / v / y / v / z / x and the like can be mentioned. Yet another layer such as a paper substrate may be laminated on the multilayer film.

In the multilayer film of the present invention, it is preferable that at least one layer of the single-layer film of the present invention is provided as the outermost layer. Since the single-layer film of the present invention is formed from the gas barrier resin composition, the adsorption of scent components and the like can be effectively suppressed. That is, the single-layer film of the present invention has non-adsorptive properties to scent components and the like. Therefore, the multilayer film provided with the single-layer film of the present invention on the outermost layer is excellent in non-adsorption of fragrance components.

As the resin used for the x-layer, a thermoplastic resin is preferable from the viewpoint of processability 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 may be capable of adhering each layer, and for example, polyurethane-based or polyester-based one-component or two-component curable adhesives and carboxylic acid-modified polyolefins are 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.

Examples of the method for obtaining the multilayer film include extrusion laminating, dry laminating, solution coating and the like. The multilayer film obtained by such a method is further subjected to secondary processing molding after reheating by a method such as vacuum pressure air deep drawing molding, blow molding, press molding, etc. to obtain a desired molded body structure. It's okay. Further, the multilayer film is reheated in a range below the melting point of EVOH by a roll stretching method, a pantograph stretching method, an inflation stretching method, or the like, and then uniaxially or biaxially stretched to obtain a stretched multilayer film. You can also.

Molds using the single-layer film, vapor-deposited film or multilayer film of the present invention include containers (bags, cups, tubes, trays, bottles, etc.), fuel containers, pipes, fibers, food and beverage packaging materials, and container packing. Materials, medical infusion bag materials, tire tube materials, shoe cushion materials, bag-in-box inner bag materials, organic liquid storage tank materials, organic liquid transportation 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.

<Heat seal film>
The single-layer film, thin-film vapor-deposited film or multilayer film of the present invention is preferably a film for heat sealing. That is, the heat-sealing film of the present invention includes the single-layer film, the vapor-deposited film, or the multilayer film of the present invention. When the heat-sealing film of the present invention is a multilayer film, the specific layer structure may be the same as the layer structure of the multilayer film described above. In the heat-sealing film, the outermost layer functions as a heat-sealing layer. The heat-sealing layer may be a layer made of the single-layer film of the present invention (a layer formed of a gas barrier resin composition), or may be a layer formed of another thermoplastic resin or the like.

In the heat-sealing film, it is preferable that at least one layer of the single-layer film of the present invention is provided as the outermost layer. In such a form of a heat-sealing film, the single-layer film layer of the present invention can be used as a heat-sealing layer. As described above, the single-layer film of the present invention can effectively suppress the adsorption of scent components and the like. Therefore, the single-layer film of the present invention is a heat-sealing layer, and the packaging material using the heat-sealing film provided with the single-layer film on the outermost layer can efficiently retain the scent component of the contents. ..

In order for the single-layer film of the present invention to exhibit good heat-sealing properties, the lower limit of the average ethylene unit content of EVOH constituting the gas barrier resin composition is preferably 25 mol%, more preferably 30 mol%. 40 mol% is more preferred. The upper limit of the ethylene unit content is preferably 60 mol%, more preferably 55 mol%.

The heat-sealing film of the present invention has excellent non-adhesiveness to fragrance components and the like as described above when the single-layer film of the present invention is provided as a heat-sealing layer (outermost layer). It can be suitably used for packaging bags.

In the heat-sealing film of the present invention, the heat-sealing layers (outermost layers) face each other and are pressure-bonded for 1 second under the conditions of a temperature of 185 ° C. and a pressure of 0.1 MPa using a heat plate type heat sealer. Is preferably 10 N / 15 mm or more. The heat-sealed layers to be faced with each other may be the same or different. The heat-sealing film can obtain excellent heat-sealing strength by heat-sealing, and can be suitably used as a heat-sealing film for packaging bags having high aroma retention. The heat seal strength is a value measured in accordance with JIS-Z1707.

<Packaging bag>
The heat-sealing film of the present invention is formed into a container and a package (bag, cup, tube, tray, bottle, etc.) with the heat-sealing layer inside by heat-sealing the heat-sealing layers. be able to. As described above, the heat-sealing film of the present invention can be heat-sealed with high strength, and when the single-layer film of the present invention is provided as a heat-sealing layer, the heat-sealing layer is provided. Since the fragrance component is excellent in non-adsorption property, the above-mentioned packaging bag and the like obtained from this can exhibit excellent fragrance retention property.

The heat-sealing method is not particularly limited, and a known method can be used. Examples thereof include a heat-sealing method using a hot plate type heat sealer, an impulse sealer, an ultrasonic sealer, a frictional heat sealer, a dielectric heating sealer, or the like. The temperature at the time of heat sealing is not particularly limited, but it is preferable that the temperature is equal to or higher than the melting point of the heat-sealed layer (melting point + 30 ° C.) or lower from the viewpoint of heat sealing strength and prevention of poor appearance. The heat-sealing pressure is not particularly limited, but is preferably 0.01 MPa or more and 1.0 MPa or less from the viewpoint of heat-sealing strength and prevention of appearance defects. The heat-sealing time is not particularly limited, but is preferably 0.05 seconds or more and 5 seconds or less from the viewpoint of heat-sealing strength and productivity.

As described above, the moisture content of the heat-sealed layer of the heat-sealing film when the heat-sealing film of the present invention is heat-sealed to form a packaging bag or the like is 0.1% by mass or more and 4% by mass. The following is preferable, and more preferably 0.2% by mass or more and 3% by mass or less. By setting the moisture content of the heat-sealed layer at the time of heat sealing within the above range, it is possible to maintain the appearance of the sealed portion and suppress the decrease in sealing strength. When this moisture content exceeds the above upper limit, foaming is likely to occur due to vaporization of the moisture in the heat-sealing layer during heat sealing, and as a result, the appearance of the heat-sealing portion is deteriorated and the heat-sealing property is deteriorated. There is a risk of doing so. Further, when this moisture content is not more than the above lower limit, the non-adsorptive property immediately after molding the packaging bag or the like may decrease. If the content is filled immediately after molding, the aroma component derived from the content is likely to be adsorbed on the heat-sealed layer.

Examples of the contents (packaged object) in the packaging bag include foods, beverages, pharmaceuticals, cosmetics, fragrances, toiletry products and the like containing fragrance components, and in particular, a group consisting of confectionery, tea leaves, coffee, spices and cigarettes. It is preferable that it is at least one selected from the above. Since the packaging bag can be in a form having excellent fragrance-retaining properties as described above, it is particularly suitable as a packaging bag for the above-mentioned foods and the like that require fragrance-retaining properties.

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 methods]
(1) Ethylene unit content and degree of saponification of EVOH For the EVOH pellets obtained by synthesis and the gas barrier resin composition pellets obtained in Examples and Comparative Examples, tetramethylsilane was used as an internal standard and tetra was used as an additive. It is dissolved in dimethyl sulfoxide (DMSO) ^-d6 containing fluoroacetic acid (TFA), measured at 80 ° C. using 1H-NMR ("JMTC-400 / 54 / SS" manufactured by JEOL Ltd.) at 500 MHz, and ethylene. The unit content and the degree of saponification were measured.
Each peak in the spectrum of the above measurement is assigned as follows.
0.6 to 1.9 ppm: Methylene proton (4H) as an ethylene unit, methylene proton (2H) as a vinyl alcohol unit, methylene proton as a 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) 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.

(3) 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 measured with pure water. Elemental analysis of this solution was performed with 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.

(4) 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.

(5) Long-running evaluation (5-1) Single-layer film film-forming defect evaluation Single-screw extruder (“D2020” from Toyo Seiki Seisakusho Co., Ltd .; D (mm) = 20, L / D = 20, compression ratio = 3 A single-layer film having an average thickness of 20 μm was prepared from the gas barrier resin composition pellets obtained in Examples and Comparative Examples using 0.0, screw: full flight). Each condition at this time is as shown below.
(Conditions for single-screw extruder)
Extrusion temperature: 210 ° C
Screw rotation speed: 40 rpm
Dice 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 10 hours and 50 hours 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.

(5-2) Evaluation of Appearance of Single-Layer Film The appearance (streak) of the films produced 10 hours and 50 hours 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

(6) 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)
Using a single-screw extruder (Toyo Seiki Seisakusho's "D2020", D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight), the thickness is 20 μm from the above gas barrier resin composition pellets. A single-layer film was produced. The extrusion conditions are as shown below.
Extrusion temperature: 210 ° C
Dice width: 30 cm
Pick-up roll temperature: 80 ° C
Screw rotation speed: 40 rpm
Pick-up roll speed: 3.1 m / min

[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 VAM4>
As shown in Table 1, each vinyl acetate of VAM2 to VAM4 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 tank 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 60 ° 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 the obtained 20 mass% MeOH solution of the 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 (A10) and EVOH (B1) to EVOH (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 (A10) 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 pellets (A1) to pellets (A10) and pellets (B1) to pellets (B5), sulfur compounds 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 2.
<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]
<Example 1>
After dry-blending EVOH (A1) pellets and EVOH (B1) pellets at a mass ratio (A1 / B1) of 10/90, a twin-screw extruder (“2D25W” manufactured by Toyo Seiki Seisakusho Co., Ltd., 25 mmφ, die temperature 220 ° C., Extrusion was performed in a nitrogen atmosphere using a screw rotation speed of 100 rpm) to obtain gas barrier resin composition pellets of Example 1.

Regarding the obtained gas barrier resin composition pellets of Example 1, the ethylene unit content and the degree of saponification, the quantification of carboxylic acid, the metal ion, and the phosphoric acid compound were obtained according to the methods described in the above evaluation methods (1) to (6). And the quantification of boron compounds, the degree of biobase, long-running property and oxygen permeability were measured or evaluated. The results are shown in Table 3.

<Examples 2 to 21, Comparative Examples 1 to 6>
Each gas barrier resin composition pellet of Examples 2 to 21 and Comparative Examples 1 to 6 was changed 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. Was prepared and evaluated. The results are shown in Table 3.

As shown in Table 3, each of the gas barrier resin compositions of Examples 1 to 21 is derived only from fossil fuel (gas barrier resin composition of Comparative Example 2) while partially using a raw material derived from biomass. It had a high gas barrier property comparable to that of other materials. Further, each of the gas barrier resin compositions of Examples 1 to 21 had a film forming defect and a streak evaluation of A or B for the film produced 10 hours after the start of operation, and had sufficient long-running properties. ..

Further, from the results of Examples and Comparative Examples, it is said that in the gas barrier resin composition using EVOH, the gas barrier property does not depend on the biobase degree, whereas the long-run property tends to increase as the biobase degree decreases. It was confirmed that it has specific properties. For example, each of the gas barrier resin compositions of Examples 1, 2, 5 to 13, and 15 to 21 having a biobase degree of 65% or less has a film forming defect for films produced 10 hours and 50 hours after the start of operation. The evaluation of streak and roll end coloring was A or B, and it had a high long-running property.

<Non-adsorption test>
Using the gas barrier resin composition pellets obtained in Example 21 and Comparative Example 6, a single-layer film having a thickness of 30 μm was formed under the following conditions, and the non-adsorption characteristics of nicotine and methyl salicylate were evaluated.
(Making a single-layer film)
Using a single-screw extruder (Toyo Seiki Seisakusho's "D2020", D (mm) = 20, L / D = 20, compression ratio = 3.0, screw: full flight), the thickness is 30 μm from the above gas barrier resin composition pellets. A single-layer film was produced. The extrusion conditions are as shown below.
Extrusion temperature: 210 ° C
Dice width: 30 cm
Pick-up roll temperature: 80 ° C
Screw rotation speed: 40 rpm
Pick-up roll speed: 2.1 m / min (preparation of evaluation sample)
After weighing 40 mg of nicotine or methyl salicylate, the mixture was placed in a weighing bottle having a content of 50 cm ³ and a U-shaped SUS net was placed therein so as not to touch the adsorbed substance. One piece of film having a width of 1 cm and a length of 4 cm and a piece of film having a width of 1 cm and a length of 1 cm cut out from the above-mentioned 30 μm single-layer film was placed on this net plate, and left to stand in a 20 ° C. and 50% RH environment for 2 weeks. The adsorption amount was measured by the method shown below using a film piece having a size more suitable for the adsorption amount.
(Measurement of adsorption amount)
To measure the amount of adsorption, use a heat-desorbable gas chromatograph-mass spectrometer (TCT-GC / MS, TCT: "CP-4020" manufactured by Chromepack, GC / MS: "5793" manufactured by Azilent) as follows. The amount of adsorption was measured by the method of.
(Gas sampling method)
The film piece was put into a glass chamber heated to 80 ° C. A sample was obtained by collecting clean nitrogen from one side at a flow rate of 100 ml / min, attaching a Tenax collecting tube to the other side, and collecting the gas distilled out for 3 minutes.
(Gas desorption conditions)
The Tenax collection tube was heated to 250 ° C. and desorbed.
(GC introduction method)
After the desorbed gas was cold trapped at −130 ° C., it was heated to 250 ° C. and introduced into the entanglement to measure the adsorption amount.

As a result of the test, the adsorption amount of Example 21 was 301 ng / cm ^{2 for nicotine and 220 ng / cm 2 for} methyl salicylate. This value is equivalent to nicotine 313 ng / cm ² and methyl salicylate 208 ng / cm ² in Comparative Example 6 using a fossil fuel-derived raw material, and is derived from fossil fuel even when the single-layer film of the present invention is used. It was found that the non-adhesiveness was comparable to that of the case of using the raw material of.

<Heat fusion test>
A two-component adhesive (Mitsui Chemicals'"A-520" and "A-50") is applied to one side of a biaxially stretched polyester film with an average thickness of 12 μm (Toray's "Lumilar (registered trademark)"). Then, a multilayer film was produced by laminating a single-layer film having a thickness of 30 μm used for evaluation of non-adsorption characteristics on the coated surface. The average thickness of the adhesive layer was 4 μm.
Using the obtained multilayer film, a three-way seal pouch was prepared so that the single-layer films were overlapped with each other and heat-sealed, and the heat-sealing strength was measured. A three-way seal automatic filling and packaging machine (“KP-109” manufactured by Komak Co., Ltd.) was used to make the pouch, and the seal temperature was set to 180 ° C to continuously supply the multilayer film to a width of 80 mm and a length. A 70 mm three-way seal pouch was made at a bag making speed of 100 bags / minute. The heat seal strength was measured using a tensile tester (“AGS-H” manufactured by Shimadzu Corporation) under a 50% RH environment at 23 ° C. As a sample, a film piece was prepared by cutting the sealing surface (sealing width 8 mm) in the width direction of the pouch to a width of 15 mm, both ends were fixed with chucks, and the sealing strength when pulled at a tensile speed of 250 m / min was measured. ..
(Evaluation of hot tackiness)
A hot tack tester (manufactured by Teller Corporation) was used to evaluate the hot tack strength. A film piece having a width of 25 mm and a length of 300 mm was prepared from the above-mentioned multilayer film, and the hot tack strength when the film was sealed with a sealing temperature in the range of 100 ° C. to 160 ° C., a sealing pressure of 2.0 MPa, and a sealing time of 1 second was measured.

As a result of the heat fusion test, the seal strength of Example 21 was 16.0 N / 15 mm. It can be said that this strength is equivalent to the seal strength of 15.8 N / 15 mm in Comparative Example 6 using a raw material derived from fossil fuel. The hot tack strength measurement results are shown in FIG. As is clear from the measurement results of the hot tack strength, it was found that the single-layer film of the present invention exhibits heat-sealing properties comparable to those of the single-layer film using a raw material derived from fossil fuel.

(Evaluation of traceability)
As a result of measuring the sulfur compound content of the gas barrier resin composition pellet obtained in Example 1 and identifying the sulfur compound by the same method as the method for measuring EVOH (A) and EVOH (B) pellets, the sulfur compound The content of sulfur was 0.1 ppm in terms of sulfur atom, and the sulfur compound was dimethyl sulfide. The traceability was evaluated using the single-layer film obtained in the evaluation of the oxygen permeability of Example 1. Specifically, a part of the obtained single-layer film was cut out and used as a traceability sample. The biobase degree of the cut out single-layer film was measured according to the method described in the above evaluation method (4) and found to be 10%, which is consistent with the value obtained in the gas barrier resin composition pellet of Example 1 and has traceability. It was confirmed that there was. Moreover, the measurement of the sulfur compound content of the cut-out single-layer film and its identification were carried out by the same method as the above-mentioned method. The sulfur compound contained in the single-layer film is 0.1 ppm in terms of sulfur atom, and the sulfur compound is dimethyl sulfide, which is consistent with the value obtained in the gas barrier resin composition pellet of Example 1 and has traceability. Was confirmed.

Claims (15)

A single-layer film formed from a gas barrier resin composition, which is a single-layer film.
The gas barrier resin composition contains one or more ethylene-vinyl ester copolymer saken compounds.
A single-layer film in which a part of ethylene and vinyl ester, which are raw materials for the above-mentioned one or more kinds of ethylene-vinyl ester copolymer saken products, is derived from biomass, and the rest is derived from fossil fuel. The above-mentioned one or more kinds of ethylene-vinyl ester copolymer saken products
It contains ethylene-vinyl ester copolymer saken product (A) in which at least a part of ethylene and vinyl ester as a raw material is derived from biomass, and ethylene-vinyl ester copolymer saken product (B) derived from fossil fuel. , The single layer film according to claim 1. Claim 2 in which the mass ratio (A / B) of the ethylene-vinyl ester copolymer saponified product (A) and the ethylene-vinyl ester copolymer saken product (B) is 1/99 to 99/1. The single layer film described in. The above-mentioned one or more kinds of ethylene-vinyl ester copolymer saken products
The single-layer film according to claim 1, wherein a part of ethylene and vinyl ester as raw materials is derived from biomass, and the rest is derived from fossil fuel. The ethylene-vinyl vinyl ester copolymer saken product (A') is contained. The single-layer film according to any one of claims 1 to 4, wherein the ethylene-vinyl ester copolymer saponified product of one or more of the above has a biobase degree of 1% or more and 99% or less. The single-layer film according to any one of claims 1 to 5, wherein the gas barrier resin composition has a biobase degree of 1% or more and 99% or less. The single-layer film according to any one of claims 1 to 6, wherein the gas barrier resin composition contains a sulfur compound in an amount of more than 0 ppm and 100 ppm or less in terms of sulfur atoms. The single layer film according to claim 7, wherein the sulfur compound is dimethyl sulfide or dimethyl sulfoxide. The single-layer film according to any one of claims 1 to 8, wherein at least a part of ethylene in the raw materials is derived from biomass. The single-layer film according to any one of claims 1 to 9, wherein at least a part of the vinyl ester among the raw materials is derived from biomass. The single-layer film according to any one of claims 1 to 10, which is a stretched film. The single-layer film according to any one of claims 1 to 11.
A vapor-deposited film comprising at least one inorganic vapor-deposited layer laminated on at least one surface side of the single-layer film. A multilayer film comprising the single-layer film according to any one of claims 1 to 11 or the vapor-deposited film according to claim 12. A film for heat sealing comprising the single-layer film according to any one of claims 1 to 11, the vapor-deposited film according to claim 12, or the multilayer film according to claim 13. The heat-sealing film according to claim 14, wherein the single-layer film is provided on the outermost surface layer as a heat-sealing layer.

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