JP4744834B2 - Resin composition and multilayer structure and container using the same - Google Patents

Description

  The present invention relates to a resin composition comprising a novel ethylene-vinyl alcohol copolymer (A) and a water-swellable layered inorganic substance (B), and a multilayer structure using the same, and more specifically, gas barrier properties. The present invention relates to a resin composition and a multilayer structure that are excellent in low-temperature deep drawability at low temperatures.

In general, an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) is excellent in transparency, gas barrier properties, aroma retention, solvent resistance, oil resistance, and the like. It is used for various packaging materials such as materials, pharmaceutical packaging materials, industrial chemical packaging materials, agricultural chemical packaging materials, and the like, and studies are being made to add water-swellable layered inorganic substances to EVOH for the purpose of further improving gas barrier properties. However, when a water-swellable layered inorganic substance is added to EVOH, the flexibility of EVOH is reduced, or a secondary structure in which a multilayer structure including one layer of EVOH containing a water-swellable layered inorganic substance is thermoformed into a cup or a tray. When molding is performed, streaks and whitening occur, and it is confirmed that appearance deteriorates, and in order to solve such a problem, it is proposed to add a water-soluble resin to a mixture of EVOH and a water-swellable layered inorganic substance. (For example, refer to Patent Document 1).
JP 2002-003609 A

  However, when the present inventors examined the above-mentioned method in detail, there is a concern that the barrier property is lowered under high humidity by adding a water-soluble resin, and the improvement of secondary moldability is also compared at 165 ° C. Although thermoforming at a high temperature shows an improvement effect, it has been confirmed that the film performance at a low drawing temperature of about 90 ° C. is caused by cracks in the EVOH layer, and the barrier performance is lowered. An excellent resin composition having excellent gas barrier properties even after being subjected to secondary molding at a low temperature and excellent secondary moldability at a low temperature and a multilayer structure using the same are desired.

Therefore, the present inventor has conducted extensive studies in view of the present situation, and as a result, the ethylene content is 20 to 60 mol%, and EVOH (A) containing the following structural unit (1) and a water-swellable layered structure are used. The present invention was completed by finding that the resin composition containing the inorganic compound (B) meets the above-mentioned purpose.
[Chemical 1]
- _[CH 2 -C (R1)] -
｜
HO-C-R2 (1)
｜
HO-C-R3
｜
R4
(Here, R1 to R4 are all hydrogen atoms .)

  In the present invention, the structural unit (1) is introduced into the main chain by copolymerization, and the content of the structural unit (1) is 0.1 to 30 mol in EVOH. It is preferable that EVOH having a water content of 20 to 70% by weight and a water-swellable layered inorganic material be melt-mixed and dried.

Since the resin composition of the present invention contains EVOH (A) and a water-swellable layered inorganic substance (B), and EVOH (A) has a specific structural unit, it has gas barrier properties at low temperatures. A resin composition excellent in secondary moldability and a multilayer structure and container using the same can be obtained.

Hereinafter, the present invention will be specifically described.
EVOH (A) used in the present invention is EVOH containing the above structural unit (1), that is, a structural unit having a 1,2-glycol bond, and its molecular chain, 1,2-glycol bond structure, for the coupling the binding chain (X), in that the gas barrier performance of the tree fat composition becomes good, 1, 2-glycol bond structure is directly is most preferred structure attached to the molecular chain. R1 to R4 are hydrogen atoms in that the gas barrier property of the resin composition is good.

The production method of EVOH (A) used in the present invention is not particularly limited, but when a structural unit in which a 1,2-glycol bond structure is directly bonded to the main chain, which is the most preferable structure, is taken as an example, 3,4-diol A method of saponifying a copolymer obtained by copolymerizing -1-butene, a vinyl ester monomer and ethylene, obtained by copolymerizing 3,4-diacyloxy-1-butene, a vinyl ester monomer and ethylene A method of saponifying the obtained copolymer, a method of saponifying the copolymer obtained by copolymerizing 3-acyloxy-4-ol-1-butene, a vinyl ester monomer and ethylene, 4-acyloxy- Method for saponifying a copolymer obtained by copolymerizing 3-ol-1-butene, a vinyl ester monomer and ethylene, 3,4-diacyloxy-2 Methyl-1-butene, saponifying the obtained copolymer by copolymerizing a vinyl ester monomer and ethylene are mentioned, also, 3, 4-diacyloxy-1-butene, a vinyl ester monomer and ethylene The method of saponifying the copolymer obtained by copolymerizing is preferable in terms of excellent copolymerization reactivity. Further, 3,4-diacetoxy-1-butene is used as 3,4-diasiloxy-1-butene. It is preferable to use it. A mixture of these monomers may also be used. Further, 3,4-diacetoxy-1-butane, 1,4-diacetoxy-1-butene, 1,4-diacetoxy-1-butane and the like may be contained as a small amount of impurities. Moreover, although such a copolymerization method is demonstrated below, it is not limited to this.

（ここで、Ｒはアルキル基であり、好ましくはメチル基である。）

（ここで、Ｒはアルキル基であり、好ましくはメチル基である。）

（ここで、Ｒはアルキル基であり、好ましくはメチル基である。）
なお、上記の（２）式で示される化合物は、イーストマンケミカル社から、上記（３）式で示される化合物はイーストマンケミカル社やアクロス社の製品を市場から入手することができる。 The 3,4-diol-1-butene is represented by the following formula (2), and the 3,4-diacyloxy-1-butene is represented by the following formula (3), 3-acyloxy-4-ol-1-butene. Represents the following formula (4), and 4-acyloxy-3-ol-1-butene is represented by the following formula (5).

(Here, R is an alkyl group, preferably a methyl group.)

(Here, R is an alkyl group, preferably a methyl group.)

(Here, R is an alkyl group, preferably a methyl group.)
The compound represented by the above formula (2) can be obtained from Eastman Chemical Co., and the compound represented by the above formula (3) can be obtained from Eastman Chemical and Acros.

  Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, Examples thereof include vinyl versatate, among which vinyl acetate is preferably used.

  There are no particular limitations on the copolymerization of 3,4-diacyloxy-1-butene, vinyl ester monomer, and ethylene, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, or emulsion polymerization may be used. Although it can be employed, solution polymerization is usually performed.

  The method for charging the monomer component at the time of copolymerization is not particularly limited, and any method such as batch charging, split charging, continuous charging, etc. may be employed.

Examples of the solvent used for such copolymerization include usually lower alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, and methanol is preferably used industrially.
The amount of the solvent used may be appropriately selected in consideration of the chain transfer constant of the solvent in accordance with the degree of polymerization of the target copolymer. For example, when the solvent is methanol, S (solvent) / M ( Monomer) = 0.01 to 10 (weight ratio), preferably 0.05 to 7 (weight ratio).

In the copolymerization, a polymerization catalyst is used. Examples of the polymerization catalyst include known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauryl peroxide, and t-butylperoxyneodeca Noate, t-butylperoxypivalate, α, α′bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3, -tetramethylbutylperoxyneodeca Peroxyesters such as noate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-hexylperoxypivalate, di-n-propylperoxydi Carbonate, di-iso-propyl peroxydicarbonate], di-sec- Til peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, dimethoxybutyl peroxydicarbonate, di Peroxydicarbonates such as (3-methyl-3-methoxybutylperoxy) dicarbonate, diacyl peroxides such as 3,3,5-trimethylhexanoyl peroxide, diisobutyryl peroxide, lauroyl peroxide, etc. Examples include low temperature active radical polymerization catalysts, and the amount of polymerization catalyst used varies depending on the type of catalyst and cannot be determined unconditionally, but is arbitrarily selected according to the polymerization rate. For example, when azobisisobutyronitrile or acetyl peroxide is used, 10 to 2000 ppm is preferable with respect to the vinyl ester monomer, and 50 to 1000 ppm is particularly preferable.
Moreover, it is preferable to select the reaction temperature of a copolymerization reaction from the range of 40 degreeC-boiling point with the solvent and pressure to be used.

  In the present invention, it is preferable to make the resin composition obtained by allowing the hydroxylactone compound or hydroxycarboxylic acid to coexist with the above catalyst to make the color tone good (close to colorless). The compound is not particularly limited as long as it has a lactone ring and a hydroxyl group, and examples thereof include L-ascorbic acid, erythorbic acid, glucono delta lactone, etc., preferably L-ascorbic acid and erythorbic acid are used. Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid, salicylic acid, and the like, and preferably citric acid is used.

  The amount of the hydroxylactone compound or hydroxycarboxylic acid used is 0.0001 to 0.1 parts by weight (more preferably 0.0005 to 100 parts by weight of vinyl ester monomer) in both batch and continuous systems. 0.05 part by weight, particularly 0.001 to 0.03 part by weight), and if the amount used is less than 0.0001 part by weight, the coexistence effect may not be sufficiently obtained. Exceeding parts by weight is not preferable because it results in inhibiting the polymerization of the vinyl ester monomer. In preparing such a compound in a polymerization system, there is no particular limitation, but usually an aliphatic ester (methyl acetate, ethyl acetate) containing a lower aliphatic alcohol (methanol, ethanol, propanol, tert-butanol, etc.) or a vinyl ester monomer. Etc.), a solvent such as water, or a mixed solvent thereof, and charged into the polymerization reaction system.

  In addition, what is necessary is just to determine the preparation amount of 3, 4- diacyloxy 1-butene etc. according to the introduction amount of said structural unit (1) desired.

  In the present invention, an ethylenically unsaturated monomer that can be copolymerized may be copolymerized as long as the effects of the present invention are not impaired during the above copolymerization. Examples of such monomers include propylene, 1 -Olefins such as butene and isobutene, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid and (anhydrous) itaconic acid, or salts thereof, or those having 1 to 18 carbon atoms Mono- or dialkyl esters, acrylamide, N-alkyl acrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salt, acrylamidopropyldimethylamine or its acid salt or its quaternary salt, etc. Acrylamides, methacrylamide, N-alkyl methacryl having 1 to 18 carbon atoms Methacrylamides such as amide, N, N-dimethylmethacrylamide, 2-methacrylamide propanesulfonic acid or salts thereof, methacrylamide propyldimethylamine or acid salts thereof or quaternary salts thereof, N-vinylpyrrolidone, N-vinylformamide N-vinylamides such as N-vinylacetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers, alkoxyalkyl vinyl ethers, vinyl chloride, vinylidene chloride , Vinyl halides such as vinyl fluoride, vinylidene fluoride, vinyl bromide, vinyl silanes, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3- Acrylamide-3-dimethylpropyl) - ammonium chloride, acrylamido-2-methylpropane sulfonic acid, vinyl ethylene carbonate, ethylene carbonate, and the like.

  Furthermore, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3- Cationic group-containing monomers such as methacryloyloxypropyltrimethylammonium chloride, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, 3-butenetrimethylammonium chloride, dimethyldiallylammonium chloride, diethyldiallylammonium chloride, acetoacetyl group-containing monomers And so on.

  Further, vinyl silanes include vinyl trimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylisobutyldimethoxysilane, vinylethyldimethoxysilane, vinylmethoxydioxysilane. Butoxysilane, vinyldimethoxybutoxysilane, vinyltributoxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyhexyloxysilane, vinyltrihexyloxysilane, vinylmethoxydioctyloxysilane, vinyldimethoxyoctyloxysilane, vinyltrioctyloxysilane , Vinylmethoxydilauryloxysilane, vinyldimethoxylauryloxysilane, vinylmethoxydioleoxysilane And vinyl dimethoxy I acetoxyphenyl silane.

  The obtained copolymer is then saponified. In such saponification, an alkali catalyst or an acid catalyst is used in a state where the copolymer obtained above is dissolved in alcohol or hydrous alcohol. Done. Examples of the alcohol include methanol, ethanol, propanol, tert-butanol and the like, and methanol is particularly preferably used. The concentration of the copolymer in the alcohol is appropriately selected depending on the viscosity of the system, but is usually selected from the range of 10 to 60% by weight. Catalysts used for saponification include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methylate, etc., sulfuric acid, Examples include acid catalysts such as hydrochloric acid, nitric acid, metasulfonic acid, zeolite, and cation exchange resin.

The amount of the saponification catalyst used is appropriately selected depending on the saponification method, the target degree of saponification, and the like. Usually, when an alkali catalyst is used, a vinyl ester monomer and 3,4-diacyloxy-1- 0.001-0.1 equivalent with respect to the total amount of monomers, such as butene, Preferably 0.005-0.05 equivalent is suitable. With regard to such a saponification method, batch saponification, continuous saponification on a belt, and continuous saponification of a tower type are possible depending on the target degree of saponification, etc. For reasons such as efficiency and ease of progress, tower saponification under constant pressure is preferably used. The pressure during saponification cannot be generally specified depending on the target ethylene content, but is selected from the range of ^{2 to} 7 kg / cm ² , and the temperature at this time is 80 to 150 ° C., preferably from 100 to 130 ° C. Selected.

Thus, an EVOH resin having the above structural unit (1) (a structural unit having a 1,2-glycol bond) is obtained. In the present invention, the ethylene content of the obtained EVOH is 20 to 60 mol. % and is (still preferably 20 to 50 mol%, particularly preferably 25 to 48 mol%), degree of saponification is not particularly limited, preferably the saponification degree 90 mol% or more (more preferably 95 mol% or more When the ethylene content is less than 10 mol%, the gas barrier property and appearance of the resulting molded product at high humidity tend to be reduced. Conversely, when the ethylene content exceeds 60 mol%, the gas barrier of the molded product tends to decrease. If the saponification degree is less than 90 mol%, the gas barrier property and moisture resistance of the molded product tend to be lowered, which is not preferable.

  Further, the melt flow rate (MFR) (210 ° C., load 2160 g) of the EVOH is not particularly limited, but is 0.1 to 100 g / 10 minutes (more preferably 0.5 to 50 g / 10 minutes, particularly 1 to 30 g / 10 min) is preferable, and when the melt flow rate is smaller than this range, the inside of the extruder tends to be in a high torque state at the time of molding, and the extrusion process tends to be difficult. However, the appearance and gas barrier properties at the time of heat-stretching molding tend to decrease, which is not preferable.

  Furthermore, the amount of the structural unit having a 1,2-glycol bond introduced into EVOH is not particularly limited, but is 0.1 to 50 mol% (more preferably 0.5 to 40 mol%, particularly 1 to 30 mol). If the amount introduced is less than 0.1 mol%, the effect of the present invention is not sufficiently exhibited. On the other hand, if it exceeds 50 mol%, the gas barrier property tends to decrease, which is not preferred. Further, in adjusting the amount of structural units having 1,2-glycol bonds, it is also possible to adjust by blending at least two types of EVOH having different introduction amounts of structural units having 1,2-glycol bonds. However, the difference in the ethylene content of EVOH at that time is preferably less than 2 mol%. Further, at least one of them may not have a structural unit having a 1,2-glycol bond.

The water-swellable layered inorganic compound (B) used in the present invention is not particularly limited, and examples thereof include clay minerals such as smectite and vermiculite, and synthetic mica. Specific examples of the former smectite include montmorillonite. , Beidellite, nontronite, saponite, hectorite, soconite, stevensite and the like. These may be natural or synthesized.
In the present invention, the degree of swelling of the water-swellable layered inorganic compound (B) (measured according to the standard test method volume method of the Japan Bentonite Industry Association) is preferably larger, and the degree of swelling is 85 ml / 2 g or more ( Further, it is preferably 90 ml / 2 g or more, particularly 95 ml / 2 g or more), and if the degree of swelling is less than 85 ml / 2 g, the gas barrier properties are insufficient, which is not preferred.

Considering the degree of swelling, montmorillonite is preferred as the water-swellable layered inorganic compound (B). Further, water-swellable fluoromica-based minerals such as Na-type fluorine tetrasilicon mica, Na-type teniolite, Li-type teniolite, Na-type hectorite are also preferably used.
Further, the aspect ratio of the water-swellable layered inorganic compound (B) is not particularly limited, but is preferably 500 or more.

  The resin composition of the present invention comprises the above EVOH (A) and the water-swellable layered inorganic substance (B), and the EVOH (A) of the resin composition and the water-swellable layered inorganic substance (B). The content ratio is not particularly limited, but the water-swellable layered inorganic material (B) is 0.1 to 20 parts by weight (more preferably 0.5 to 15 parts by weight, particularly 1 to 10 parts per 100 parts by weight of EVOH (A). (Parts by weight) is preferably contained, and if the content is less than 0.1 parts by weight, the effect of improving the gas barrier properties is small. Conversely, if the content exceeds 20 parts by weight, the appearance of the multilayer structure tends to deteriorate, which is not preferable. .

  The method of blending EVOH (A) and the water-swellable layered inorganic material (B) for obtaining the resin composition of the present invention is not particularly limited, but a melt-mixing method is preferable in that uniform mixing is possible, Furthermore, EVOH (A) having a water content of 20 to 70% by weight and the water-swellable layered inorganic substance (B) are preferably melt-mixed from the viewpoint of improving the dispersibility of the water-swellable layered inorganic substance (B).

Although it does not restrict | limit especially as a method of containing EVOH (A) 20-70weight% of water, It is preferable to contain water uniformly in EVOH (A), As such a method, the solution of EVOH (A) is included. Is precipitated in water, washed thoroughly with water to remove the solvent and contain water, a method of treating EVOH (A) in pressurized hot water for about 1 to 3 hours, and ethylene-acetic acid during the production of EVOH (A). Examples thereof include a method in which a paste after saponification of a vinyl copolymer is precipitated in water to contain water.
Of these, the method of precipitating the paste after saponification of the ethylene-vinyl acetate copolymer in water during EVOH (A) production is particularly preferred.
In addition, since EVOH and water are not contained uniformly only by mixing EVOH and water, the effect of the present invention cannot be exhibited.

  As the method of melt mixing, for example, a known kneading apparatus such as a kneader rudder, an extruder, a mixing roll, a Banbury mixer, a plast mill, etc. can be used. Usually, a single or twin screw extruder is used. It is industrially preferable to use it, and it is also preferable to provide a vent suction device, a gear pump device, a screen device, etc. as needed. In particular, it is possible to obtain a resin composition having excellent gas barrier properties by providing one or more vent holes in an extruder to make it open or by sucking under reduced pressure to control the moisture content after melt mixing. It is preferable in that it can be performed.

  When the above EVOH (A) and the water-swellable layered inorganic substance (B) are melt-mixed, there is no particular limitation, and EVOH (A) having a water content of 20 to 70% by weight, a water-swellable layered inorganic compound of powder ( B) is charged all at once into the hopper of the extruder, or only EVOH (A) having a water content of 20 to 70% by weight is supplied to the hopper, and the powdered water-swellable layered inorganic compound (B) is added to the cylinder of the extruder. It may be added from the middle (for example, vent hole), or water may be added to the water-swellable layered inorganic substance (B) and supplied to the extruder as a slurry or solution using a pump or the like. .

The resin composition of the present invention thus obtained is dried as necessary before being formed into a multilayer structure.
As such a drying method, various drying methods can be employed. For example, fluid drying in which substantially pellet-like EVOH is stirred and dispersed mechanically or with hot air, or a substantially pellet-like resin composition is given dynamic effects such as stirring and dispersion. As a dryer for performing fluidized drying, a cylindrical / grooved stirred dryer, a circular tube dryer, a rotary dryer, a fluidized bed dryer, a vibrating fluidized bed dryer, Conical rotary dryers, etc., and as a dryer for performing stationary drying, as a material stationary type, a batch box dryer is used, and as a material transfer type, a band dryer, tunnel dryer, Examples thereof include, but are not limited to, a mold dryer. It is also possible to combine fluidized drying and stationary drying.

  Air or an inert gas (nitrogen gas, helium gas, argon gas, etc.) is used as the heating gas used in the drying treatment, and the temperature of the heating gas is 40 to 150 ° C., and productivity and resin composition It is preferable in terms of preventing thermal deterioration. The drying treatment time depends on the water content of the resin composition and its treatment amount, but is usually preferably about 15 minutes to 72 hours in terms of productivity and prevention of thermal deterioration of the resin composition.

  The resin composition is dried under the above conditions. The water content after the drying treatment is 0.001 to 5% by weight (further 0.01 to 2% by weight, particularly 0.1 to 1% by weight). If the water content is less than 0.001% by weight, long-run moldability tends to decrease. Conversely, if it exceeds 5% by weight, foaming occurs during extrusion molding. There is a fear that it is not preferable.

  The resin composition of the present invention thus obtained can be used for melt molding or the like as it is, but in the present invention, a saturated aliphatic amide (for example, as long as the object of the present invention is not hindered by the resin composition) Stearic acid amide), unsaturated fatty acid amide (such as oleic acid amide), bis fatty acid amide (such as ethylene bis stearic acid amide), fatty acid metal salt (such as calcium stearate, magnesium stearate), low molecular weight polyolefin (such as Lubricants such as low molecular weight polyethylene having a molecular weight of about 500 to 10,000, or low molecular weight polypropylene), inorganic salts (for example, hydrotalcite), plasticizers (for example, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, hexanediol) Etc.), oxygen absorbers (for example, inorganic oxygen absorbers and In addition, reduced iron powders, further added with water-absorbing substances and electrolytes, aluminum powder, potassium sulfite, photocatalytic titanium oxide, and the like are ascorbic acid, fatty acid esters and metals thereof as organic compound-based oxygen absorbers. Salts, etc., hydroquinone, gallic acid, polyhydric phenols such as hydroxyl group-containing phenol aldehyde resin, bis-salicylaldehyde-imine cobalt, tetraethylenepentamine cobalt, cobalt-Schiff base complex, porphyrins, macrocyclic polyamine complex, polyethyleneimine -Coordinated conjugates of nitrogen-containing compounds such as cobalt complexes with transition metals, terpene compounds, reactants of amino acids and reducing substances containing hydroxyl groups, triphenylmethyl compounds, etc. Coordination conjugate of containing resin and transition metal (eg MXD NA) Iron and cobalt), tertiary hydrogen-containing resin and transition metal blend (eg, polypropylene and cobalt), carbon-carbon unsaturated bond containing resin and transition metal (eg, polybutadiene and cobalt) ), Photo-oxidatively disintegrating resins (eg, polyketone), anthraquinone polymers (eg, polyvinyl anthraquinone), etc., and further, photoinitiators (such as benzophenone) and peroxide supplements (commercially available oxidation). ), Heat stabilizers, light stabilizers, antioxidants, UV absorbers, colorants, antistatic agents, surfactants, antibacterial agents, anti-anti-oxidants, etc.) You may mix | blend a blocking agent, a slip agent, a filler (for example, inorganic filler etc.), other resin (for example, polyamide, polyolefin etc.), etc.

  Furthermore, it is possible to add an acid such as acetic acid and phosphoric acid or a metal salt thereof such as an alkali metal, alkaline earth metal, or transition metal to the resin composition of the present invention as long as the object of the present invention is not impaired. It is preferable to add boric acid or a metal salt thereof as a boron compound from the viewpoint of improving the thermal stability of the resin.

The amount of acetic acid added is 0.001 to 1 part by weight (further 0.005 to 0.2 part by weight, particularly 0.010 to 0.1 part by weight) with respect to 100 parts by weight of EVOH in the resin composition. If the amount added is less than 0.001 part by weight, the inclusion effect may not be sufficiently obtained. Conversely, if the amount added exceeds 1 part by weight, the appearance of the resulting molded product tends to deteriorate. Absent.
In addition, borate metal salts include calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate / potassium borate, ammonium borate (ammonium metaborate, ammonium tetraborate, Ammonium pentaborate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, Potassium octaborate), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), sodium borate (sodium metaborate) , Sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, etc.), Lead oxalate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), barium borate (barium orthoborate, metaborate) Barium, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, etc.), boron In addition to manganese oxide (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.), borax, carnite, inyoite , Borate minerals such as olivine, kyanite, zyberite, etc. Sand, boric acid, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate acid, eight sodium borate, etc.). Moreover, as an addition amount of a boron compound, 0.001-1 weight part (further 0.002-0.2 weight part, especially 0.005-0 in conversion of boron with respect to 100 weight part of all EVOH in a composition). .1 part by weight), and if the amount added is less than 0.001 part by weight, the effect of the content may not be sufficiently obtained. It is not preferable because it tends to deteriorate.

  Such metal salts include sodium, potassium, calcium, magnesium, and other organic acids such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, and behenic acid, sulfuric acid, sulfurous acid, carbonic acid, and phosphoric acid. And metal salts of inorganic acids such as acetate, phosphate and hydrogen phosphate are preferred. Further, the addition amount of the metal salt is 0.0005 to 0.01 part by weight (more preferably 0.001 to 0.05 part by weight, particularly 0 part per 100 parts by weight of EVOH in the resin composition). 0.0002 to 0.03 parts by weight), and if the amount added is less than 0.0005 parts by weight, the content may not be sufficiently obtained. The appearance of the resulting molded product tends to deteriorate, which is not preferable. In addition, when adding 2 or more types of alkali metal and / or alkaline-earth metal salt to EVOH, it is preferable that the total is in the range of said addition amount.

  The method of adding acids or metal salts thereof to the resin composition is not particularly limited. A) A porous precipitate of EVOH having a water content of 20 to 80% by weight is brought into contact with an aqueous solution of acids or metal salts thereof. A method of containing acids and metal salts thereof; a) EVOH homogeneous solution (water / alcohol solution, etc.) is mixed with acids and metal salts thereof, and then extruded into a coagulating solution in the form of a strand; C) A method of cutting pellets into pellets, c) A method in which EVOH and acids and their metal salts are mixed together and then melt-kneaded in an extruder, etc., and d) A resin composition and acids and its metal salts in batches A method of melt-kneading with an extruder after mixing, e) During the production of EVOH, the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the saponification step is neutralized with acids such as acetic acid and remains Acid such as acetic acid Sodium acetate and by-product, may be mentioned a method in which or adjusted by washing with water the amount of the alkali metal salts such as potassium acetate. In order to obtain the effects of the present invention more remarkably, the methods (a), (i) and (v), which are excellent in dispersibility of acids and metal salts thereof, are preferred.

  It is a preferred method for the resin composition of the present invention that the EVOH composition obtained by the above method a), i) or o) and the water-swellable layered inorganic material (B) are melt-mixed.

  Further, in the above resin composition, some monomer residues (3,4-diol-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy 4-ol-1-butene, 4-acyloxy-3-ol-1-butene, 4,5-diol-1-pentene, 4,5-diacyloxy-1-pentene, 4,5-diol-3-methyl- 1-pentene, 4,5-diol-3-methyl-1-pentene, 5,6-diol-1-hexene, 5,6-diacyloxy-1-hexene, 4,5-diacyloxy-2-methyl-1- Butene etc.) and saponified monomers (3,4-diol-1-butene, 4,5-diol-1-pentene, 4,5-diol-3-methyl-1-pentene, 4,5-diol-3 -Methyl-1-pe Ten may include 5,6-diol-1-hexene, etc.).

Thus, although the resin composition of the present invention is obtained, such a resin composition is useful for a molded product, particularly useful for melt molding, and such melt molding will be described below.
Examples of the molded product include single-layered or multilayered (laminated) films, sheets, containers, tubes, and the like, and examples of the laminating method when laminating with other base materials include the film of the resin composition of the present invention. , A method of melt extrusion laminating another substrate on a sheet, a method of melt extrusion laminating the resin to another substrate, a method of coextruding the resin and another substrate, and the resin (layer) And other base materials (layers) may be dry-laminated using known adhesives such as organic titanium compounds, isocyanate compounds, polyester compounds, polyurethane compounds, etc., but multilayer structures (laminates) A co-extrusion method is preferred because it can be easily produced.

  As the co-extrusion method, specifically, a known method such as a multi-many hold die method, a feed block method, a multi-slot die method, or a die external bonding method can be employed. As the shape of the die, there are a T die and a round die, and the T die is preferable in that the stretchability can be further improved by quenching immediately after film formation. The film forming speed is preferably 10 to 200 m / min from the viewpoint of productivity and stability of film properties. The melt molding temperature during melt extrusion is preferably 150 to 300 ° C.

  As such other base materials, thermoplastic resins are useful. Specifically, linear low density polyethylene, low density polyethylene, ultra-low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer Polymer, ionomer, ethylene-propylene (block and random) copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) ) Polyolefin resins and polyesters in a broad sense, such as copolymers, polybutenes, polypentenes and other olefins or copolymers, or those olefins alone or copolymers grafted with unsaturated carboxylic acids or esters thereof Resin, polyamide resin (including copolyamide) ), Polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene, aromatic or aliphatic polyketone, and reduction of these Polyalcohols, and other EVOH, etc., but from the point of practicality such as physical properties (particularly strength) of the laminate, polypropylene, ethylene-propylene (block or random) copolymer, polyamide, polyethylene, An ethylene-vinyl acetate copolymer, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN) are preferably used.

  Furthermore, when a substrate such as a film, a sheet, or a stretched film of the resin composition of the present invention is extrusion coated with another substrate, or a film, a sheet, or the like of another substrate is laminated using an adhesive, this is required. As the base material, any base material (paper, metal foil, uniaxial or biaxially stretched plastic film or sheet and its inorganic deposit, woven fabric, non-woven fabric, metallic cotton, wood, etc.) can be used in addition to the thermoplastic resin. It can be used.

The layer structure of the laminate is such that the resin composition layer of the present invention is a (a ₁ , a ₂ ,...), And another substrate, for example, a thermoplastic resin layer is b (b ₁ , b ₂ ,. If it is a film, sheet or bottle shape, not only a / b two-layer structure but also b / a / b, a / b / a, a ₁ / a ₂ / b, a / b ₁ / b ₂ , b ₂ / b ₁ / a / b ₁ / b ₂ , b ₂ / b ₁ / a / b ₁ / a / b ₁ / b _2, etc., and any combination is possible, and at least When R is a regrind layer comprising a mixture of the EVOH composition and a thermoplastic resin, b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / A / b, b / R / a / R / a / R / b, etc. In the filament form, a and b are bimetal type, core (a) -sheath (b) type, core ( b)-sheath ( ) Type, or can be any combination, such as eccentric core-sheath type. In the above layer structure, an adhesive resin layer can be provided between the respective layers as required, and various types of such adhesive resins can be used. However, it is not possible to say unconditionally, but the carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to an olefin polymer (the above-mentioned polyolefin resin in the broad sense) by an addition reaction, a graft reaction, etc. Examples of the modified olefin-based polymer include maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymer, anhydrous Maleic acid graft modified ethylene-ethyl acrylate copolymer, maleic anhydride Shift modified ethylene - one or a mixture of two or more species selected from vinyl acetate copolymers and the like as preferred. At this time, the amount of the unsaturated carboxylic acid or anhydride thereof contained in the thermoplastic resin is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, particularly preferably 0.03. ~ 0.5 wt%. If the amount of modification in the modified product is small, the adhesiveness may be insufficient. On the other hand, if the amount is too large, a crosslinking reaction may occur and the moldability may be deteriorated. Further, these adhesive resins can be blended with the EVOH composition of the present invention, other EVOH, rubber / elastomer components such as polyisobutylene, ethylene-propylene rubber, and the resin of the b layer. In particular, blending a polyolefin resin different from the base polyolefin resin of the adhesive resin is useful because the adhesiveness may be improved.

  The thickness of each layer of the laminate cannot be generally stated depending on the layer configuration, the type of b, the use and container form, the required physical properties, etc., but usually the a layer is 2 to 500 μm (further 3 to 200 μm), b The layer is selected from the range of about 10 to 5000 μm (more preferably 30 to 1000 μm), and the adhesive resin layer is about 1 to 400 μm (more preferably 2 to 150 μm).

  The base resin layer may contain an antioxidant, an antistatic agent, a lubricant, a core material, an antiblocking agent, an ultraviolet absorber, a wax and the like as conventionally known.

  The effect of the present invention is manifested in the secondary molding of the laminate thus obtained. The molding method is a mold using a plug, if necessary, by vacuum, compressed air, or vacuum / pressure forming. Examples thereof include a method of forming into a shape (straight method, drape method, air slip method, snapback method, plug assist method, etc.). Various molding conditions such as the molding temperature, the degree of vacuum, the pressure of compressed air, or the molding speed are appropriately set depending on the plug shape, the mold shape, the properties of the raw material sheet, and the like. In particular, by using the resin composition of the present invention, a container having excellent gas barrier properties and good appearance and gas barrier properties even when molded at a low temperature of 90 ° C. can be obtained.

  Containers obtained as described above are not only general foods but also seasonings such as mayonnaise and dressings, fermented foods such as miso, fats and oils such as salad oil, beverages, cosmetics, pharmaceuticals, detergents, cosmetics and other various containers. Useful.

  Hereinafter, the method of the present invention will be specifically described with reference to examples. In the following, “%” means a weight basis unless otherwise specified.

Polymerization example 1
An EVOH composition (A1) was obtained by the following method.
A 1 m ³ polymerization can with a cooling coil is charged with 500 kg of vinyl acetate, 35 kg of methanol, 500 ppm of acetyl peroxide (vs. vinyl acetate), 20 ppm of citric acid, and 14 kg of 3,4-diacetoxy-1-butene, and the system is nitrogen After substituting once with gas, then substituting with ethylene, injecting until the ethylene pressure reaches 45 kg / cm ² , stirring, and then raising the temperature to 67 ° C., and 3,4-diacetoxy-1-butene Polymerization was carried out while adding a total amount of 4.5 kg at 15 g / min, and polymerization was carried out for 6 hours until the polymerization rate reached 50%. Thereafter, the polymerization reaction was stopped to obtain an ethylene-vinyl acetate copolymer having an ethylene content of 38 mol%.

A methanol solution of the ethylene-vinyl acetate copolymer was supplied at a rate of 10 kg / hour from the top of the plate tower (saponification tower), and at the same time 0.012% of the remaining acetic acid groups in the copolymer. A methanol solution containing an equivalent amount of sodium hydroxide was fed from the top of the tower. On the other hand, methanol was supplied at 15 kg / hour from the bottom of the tower. The tower temperature was 100 to 110 ° C., and the tower pressure was 3 kg / cm ² G. From 30 minutes after the start of charging, a methanol solution of EVOH having a structural unit having a 1,2-glycol bond (EVOH 30%, methanol 70%) was taken out. The saponification degree of the vinyl acetate component of EVOH was 99.5 mol%.

  Next, the obtained methanol solution of EVOH was supplied at 10 kg / hour from the top of the methanol / water solution adjusting tower, methanol vapor at 120 ° C. was supplied at 4 kg / hour, and water vapor was supplied from the bottom of the tower at a rate of 2.5 kg / hour. At the same time, methanol was distilled from the top of the column at 8 kg / hour, and at the same time, 6 equivalents of methyl acetate with respect to the amount of sodium hydroxide used in the saponification was charged from the middle of the column at 95-110 ° C. From this, a water / alcohol solution of EVOH (resin concentration: 35%) was obtained.

  The obtained EVOH water / alcohol solution was extruded in a strand form from a nozzle with a pore diameter of 4 mm into a coagulation liquid tank maintained at 5 ° C. consisting of 5% methanol and 95% water. Cutting with a cutter gave EVOH porous pellets having a diameter of 3.8 mm and a length of 4 mm and a moisture content of 45%.

  After washing with 100 parts of water with respect to 100 parts of the porous pellets, the mixture was put into a mixed solution containing 0.032% boric acid and 0.007% calcium dihydrogen phosphate, and at 30 ° C. for 5 hours. The mixture was stirred to obtain an EVOH composition (A1) having a water content of 45% by weight.

  When this EVOH composition (A1) was dried, the pellets contained 0.015 parts by weight (in terms of boron) and 0.005 parts by weight (phosphorus) of boric acid and calcium dihydrogen phosphate with respect to 100 parts by weight of EVOH. Acid radical equivalent), and MFR was 4.0 g / 10 min.

The amount of 1,2-glycol bond introduced was calculated by measuring the ethylene-vinyl acetate copolymer before saponification with ¹ H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO). However, it was 2.5 mol%. In addition, “AVANCE DPX400” manufactured by Nippon Bruker Co., Ltd. was used for NMR measurement.

[ ¹ H-NMR] (see FIG. 1)
1.0 to 1.8 ppm: methylene proton (integrated value a in FIG. 1)
1.87 to 2.06 ppm: methyl proton 3.95 to 4.3 ppm: proton on the methylene side of structure (I) + unreacted 3,4-diacetoxy-1-butene proton (integral value b in FIG. 1) )
4.6 to 5.1 ppm: methine proton + proton on the methine side of structure (I) (integral value c in FIG. 1)
5.2 to 5.9 ppm: unreacted 3,4-diacetoxy-1-butene proton (integral value d in FIG. 1)

[Calculation method]
Since there are four protons in 5.2 to 5.9 ppm, the integral value of one proton is d / 4, and the integral value b is an integral value including the protons of the diol and the monomer. The integral value (A) of the proton is A = (b−d / 2) / 2, and the integral value c is an integral value including the protons on the vinyl acetate side and the diol side. Since the integral value (B) is B = 1− (b−d / 2) / 2 and the integral value a is an integral value including ethylene and methylene, the integral value (C) of one proton of ethylene is , C = (a−2 × A−2 × B) / 4 = (a−2) / 4, and the introduction amount of the structural unit (1) is 100 × {A / (A + B + C)} = 100 × Calculated from (2 × b−d) / (a + 2).

Moreover, the result of having similarly performed ¹ H-NMR measurement also about EVOH after saponification is shown in FIG. Since the peak corresponding to 1.87 to 2.06 ppm of methyl proton is greatly reduced, the copolymerized 3,4-diacetoxy-1-butene is also saponified into a 1,2-glycol structure. It is clear that

Polymerization example 2
An EVOH composition (A2) was obtained by the following method.
In polymerization example 1, the amount of methanol charged was 20 kg, 3,4-diacetoxy-1-butene was polymerized at 26 g / min while adding 8 kg in total, and no boric acid was added, and the ethylene content was 38 mol%. The amount of 1,2-glycol-bonded structural units introduced is 3.0 mol%, and the water content is 40 wt%, and 0.005 parts by weight of calcium dihydrogen phosphate with respect to 100 parts by weight of EVOH (in terms of phosphate group). An EVOH composition having an MFR of 5.2 g / 10 min after containing and drying was obtained.

Polymerization example 3
An EVOH composition (A3) was obtained by the following method.
70 of 3,4-diacetoxy-1-butene, 3-acetoxy-4-ol-1-butene and 1,4-diacetoxy-1-butene instead of 3,4-diacetoxy-1-butene in polymerization example 1: The procedure is the same except that a 20:10 mixture is used. The introduction amount of the structural unit having a 1,2-glycol bond is 2.0 mol%, the ethylene content is 38 mol%, the water content is 45 wt%, and EVOH is 100 wt%. A boric acid content of 0.015 parts by weight (in terms of boron), calcium dihydrogen phosphate of 0.005 parts by weight (in terms of phosphate radicals), and an EVOH composition having an MFR of 3.7 g / 10 min after drying are obtained. It was.

  Separately, the ethylene content does not contain the structural unit (1) is 38 mol%, the saponification degree is 99.5 mol%, the moisture content is 45 wt%, the MFR after drying is 3.5 g / min (210 ° C, 2160 g), An EVOH composition (A4) containing 0.015 parts by weight of boric acid (in terms of boron) and 0.005 parts by weight of calcium dihydrogen phosphate (in terms of phosphate groups) with respect to 100 parts by weight of EVOH was prepared.

Example 1
3 parts by weight of EVOH composition (A1) having a water content of 45% and natural montmorillonite (cation exchange capacity 109 meq / 100 g, “Kunipia F” manufactured by Kunimine Industries Co., Ltd.) as 100 parts by weight of EVOH as the water-swellable layered inorganic substance (B) The blend was fed to a twin screw extruder with one 30 mmφ L / D = 42 vent and melt mixed. The temperature setting zone immediately below the hopper was set to 50 ° C., the temperature setting of the intermediate portion (vent portion) was set to 90 ° C., and the setting temperature of the extruder outlet portion was set to 90 ° C.

  Then, the resin composition was extruded in a strand form from a strand die provided at the outlet of the extruder and cut to obtain resin composition pellets (water content 35%; diameter 2.5 mm, length 3 mm cylindrical). . Next, the obtained pellets were dried under a nitrogen stream at 90 ° C. to obtain pellets (water content 0.3%) of the intended resin composition.

  Pellet (resin composition) (a) obtained above, nylon-6 ["NOVAMID 1022-1" manufactured by Mitsubishi Engineering Plastics]] (b), linear low density polyethylene ["UF240" manufactured by Nippon Polyethylene Co., Ltd. ] (C) and adhesive resin ["Modic-AP M525" manufactured by Mitsubishi Chemical Corporation, maleic anhydride linear low density polyethylene] (d), amorphous polyester resin (f), feed block type coextrusion multilayer film molding machine (F) / (d) / (b) / (a) / (d) / (c) = 20/10/20/20/10/40 (μm; thickness) A laminate (multilayer film) was formed.

About the obtained laminated body, gas barrier property and secondary moldability were evaluated as follows.
(Gas barrier properties)
The above-mentioned multilayer film was measured for oxygen permeability (cc / m ² · day · atm) using an oxygen permeability measuring device “OX-TRAN 2/20” manufactured by MOCON under the conditions of 23 ° C. and 80% RH. .

(Secondary formability; appearance and gas barrier properties of containers)
Using a deep drawing type molding machine manufactured by Omori Machine Industry Co., Ltd., pressure drawing with a length of 10 cm, a width of 15 cm and a depth of 3 cm was performed at 90 ° C. The appearance at that time was evaluated as follows, and the further squeezed container was bonded to an aluminum plate, and the oxygen permeability (cc / cup) as the container was measured at 23 ° C., 50% RH, in air.
○ ・ ・ ・ Overall high transparency and no unevenness △ ・ ・ ・ Local whitening and streaks are observed × ・ ・ ・ Overall whitening and streaks are observed

Example 2
In Example 1, a resin composition was prepared in the same manner except that the EVOH composition (A2) was used instead of the EVOH composition (A1), and evaluation was performed in the same manner.

Example 3
In Example 1, a resin composition was prepared in the same manner except that the EVOH composition (A3) was used instead of the EVOH composition (A1), and the same evaluation was performed.

Comparative Example 1
In Example 1, it evaluated similarly except having used only the dried product of EVOH composition (A4) instead of the resin composition.

Comparative Example 2
In Example 1, a resin composition was prepared in the same manner except that the EVOH composition (A4) was used instead of the EVOH composition (A1), and the same evaluation was performed.

The evaluation results of Examples and Comparative Examples are summarized in Table 1.

[Table 1]
Gas barrier properties Appearance properties Gas barrier properties of containers
Example 1 0.77 ○ 0.004
〃 2 0.83 ○ 0.005
３ 3 0.70 ○ 0.004
Comparative Example 1 1.97 Δ 0.025
〃 2 0.95 × − *
*: Cannot be measured beyond the upper limit of measurement

Multilayer structures and vessels resin composition and using the same of the present invention is excellent in gas barrier properties, excellent in secondary formability at low temperatures, food packaging, pharmaceutical packaging materials, industrial chemical packaging materials, agricultural chemicals packaging materials It is useful as various packaging materials.

2 is a ¹ H-NMR chart before saponification of EVOH obtained in Polymerization Example 1. FIG. 2 is a ¹ H-NMR chart of EVOH obtained in Polymerization Example 1. FIG.

Claims (10)

It has an ethylene content of 20 to 60 mol% and contains an ethylene-vinyl alcohol copolymer (A) containing the following structural unit (1) and a water-swellable layered inorganic substance (B). Resin composition.
[Chemical 1]
- _[CH 2 -C (R1)] -
｜
HO-C-R2 (1)
｜
HO-C-R3
｜
R4
(Here, R1 to R4 are all hydrogen atoms .) The resin composition according to claim 1, wherein the structural unit (1) is introduced into the molecular chain of the ethylene-vinyl alcohol copolymer (A) by copolymerization . 3. The resin composition according to claim 1, wherein 0.1 to 30 mol% of the structural unit (1) is contained in the molecular chain of the ethylene-vinyl alcohol copolymer (A). The ethylene-vinyl alcohol copolymer (A) is obtained by saponifying a copolymer of 3,4-diasiloxy-1-butene, a vinyl ester monomer and ethylene. 3. The resin composition according to any one of 3 . The ethylene-vinyl alcohol copolymer (A) is obtained by saponifying a copolymer of 3,4-diacetoxy-1-butene, a vinyl ester monomer and ethylene. 4. The resin composition according to any one of 4 . Ethylene - one of claims 1-5, characterized in that it contains 0.001 parts by weight of boron in terms of the vinyl alcohol copolymer 100 parts by weight - vinyl alcohol copolymer (A) is a boron compound ethylene A resin composition as described above. The resin according to any one of claims 1 to 6 , wherein the water-swellable layered inorganic substance (B) is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the ethylene-vinyl alcohol copolymer (A). Composition. Ethylene moisture content of 20 to 70 wt% - vinyl alcohol copolymer (A) and after the water-swellable layered inorganic material (B) was melt-mixed, claim, characterized in that obtained by drying 1-7 Any resin composition. Multilayer structure, characterized in that it comprises at least one layer containing the resin composition according to any one of claims 1-8. A container obtained by secondarily molding the multilayer structure according to claim 9 .

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