JP2001192011A - Container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a container which is excellent in aroma retention and free from dyeing. SOLUTION: The container comprises a layer made of an ethylene-vinyl acetate copolymer saponified substance having a storage elastic modulus in water at 20 deg.C of 2×109 Pa or more, wherein the layer is provided as an innermost layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a container having a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as "EVOH") as an innermost layer. Related to an excellent container.

[0002]

2. Description of the Related Art In general, EVOH is excellent in transparency, gas barrier property, fragrance retention, solvent resistance, oil resistance and the like.
It is used after being molded into films and sheets of industrial chemical packaging materials, agricultural chemical packaging materials, etc., or containers such as bottles. Such gas barrier properties are not only barrier properties against oxygen and helium, but also odor components and medicinal properties. Because of its excellent barrier property and non-adsorption property to components, it is also useful as packaging containers (hollow containers such as bottles and tubes) for foods, beverages, pharmaceuticals, cosmetics, fragrances, toiletry products, etc. containing these components. , Especially considering the point of fragrance retention,
A container using EVOH for the innermost layer has been proposed.

For example, Japanese Patent Application Laid-Open No. Hei 1-218823 discloses a paper container using EVOH for the back (innermost) layer and a polyolefin resin for the surface layer.
No. 54 and Japanese Patent Application Laid-Open No. 3-112655 each disclose a gas-barrier multilayer container using two types of EVOHs as innermost layers that satisfy specific conditions.

[0004]

However, as a result of a detailed study of the container described in each of the above-mentioned publications, the present inventor has found that, in the case of a liquid such as orange juice which is an aroma component of the content, the liquid has a fragrance retaining property. Although the phenomenon of decrease with time was suppressed to some extent, it was not always sufficient.

[0005]

Accordingly, the present inventors have conducted intensive studies in view of the present situation, and as a result, have found that a layer made of EVOH having a storage elastic modulus in water at 20 ° C. of 2 × 10 ⁹ Pa or more is most suitable. The present inventors have found that the container disposed in the inner layer meets the above-mentioned object, and have completed the present invention.

The storage elastic modulus is a value measured when a vibration of 10 Hz is given in water, and is a value obtained by DMA (Dynamic MD).
It can be measured by an mechanical analyzer, for example, "DVA-225" manufactured by IT Measurement Control Co., Ltd.). In the present invention, for example, a film-shaped (length 25 mm, distance between chucks 15 mm) EVOH is 10 to 80. Up to ℃ 3
The storage modulus was continuously measured by the DMA while increasing the temperature at a rate of ° C / min.
Storage elastic modulus. The present invention relates to a container. To measure the storage elastic modulus of an EVOH layer disposed on the innermost layer of such a container, the EVOH layer is simply peeled off from another laminated layer. The measurement may be performed after the layer is formed into a film, and the method of peeling is not particularly limited, and the layer may be peeled using a solvent such as ethyl acetate or acetone. However, at the time of peeling, the peeling is performed so that the EVOH layer does not cause plastic deformation, and the measurement is performed after the solvent in the EVOH layer is sufficiently removed.

In the present invention, it is not clear that the effect of the present invention can be obtained by using EVOH having such a specific storage elastic modulus in the innermost layer. The packing state of the molecules is densely improved, and swelling by water is suppressed, and as a result,
It is presumed that the adsorption of the fragrance component is reduced.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The container of the present invention has a storage elastic modulus in water of 20 ° C. as described above of 2 × 10 ⁹ Pa or more (further 2 × 10 ⁹ Pa).
10 ^{9 to} 2 × 10 ¹¹ Pa, particularly 2 × 10 ⁹ to 2 × 10 ¹⁰ Pa
Pa), a layer made of EVOH (hereinafter referred to as R-EVOH) is disposed in the innermost layer, and the storage elastic modulus is 2 × 10
^If it is less than ⁹ Pa, the fragrance component of the content is adsorbed to the innermost layer, and the fragrance retention property is reduced, so that the object of the present invention cannot be achieved.

The R-EVOH is not particularly limited as long as it satisfies the above storage elastic modulus, but has an ethylene content of 20 to 60 mol% (furthermore, 25 to 60 mol%).
55 mol%), and the degree of saponification is 90 mol% or more (furthermore, 95 mol%).
If the ethylene content is less than 20 mol%, the hydrophilicity becomes too high, and the container may swell. Not enough, and the degree of saponification is 90 mol%
If it is less than 1, the water resistance decreases and the fragrance retention becomes insufficient, which is not preferable.

The melt flow rate (MFR) of R-EVOH (210 ° C., load 2160 g) is 0.1 to
100 g / 10 min (more preferably 1 to 50 g / 10 min) is preferred. If the melt flow rate is smaller than the above range, the inside of the extruder will be in a high torque state at the time of molding and extrusion processing will be difficult. If the thickness is larger than the range, the thickness of the R-EVOH layer of the obtained container may become non-uniform, which is not preferable.

The EVOH is obtained by saponifying an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer can be produced by any known polymerization method, for example, solution polymerization,
It is produced by suspension polymerization, emulsion polymerization, or the like, and saponification of an ethylene-vinyl acetate copolymer can also be performed by a known method.

In the present invention, a copolymerizable ethylenically unsaturated monomer may be copolymerized as long as the effects of the present invention are not impaired. Examples of such a monomer include propylene and 1-butene. , Olefins such as isobutene, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid,
Unsaturated acids such as (anhydride) maleic acid and (anhydride) itaconic acid or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, 1 to 1 carbon atoms
8, acrylamides such as N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, methacrylamide, having 1 to 18 carbon atoms Methacrylamides such as N-alkyl methacrylamide, N, N-dimethyl methacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, N-vinylpyrrolidone N-vinylamides such as, N-vinylformamide and 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 and alkoxyalkyl vinyl ethers; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide And vinylsilanes such as trimethoxyvinylsilane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl)-
Examples thereof include ammonium chloride and acrylamide-2-methylpropanesulfonic acid.

R- having a specific storage modulus as described above
The method for obtaining EVOH is not particularly limited, and examples thereof include a method of adding a particulate inorganic compound, performing a heat treatment, and adding a reinforcing fiber such as a glass fiber or a carbon fiber. Is used, and such a method will be described.

The particulate inorganic compound is not particularly restricted but includes, for example, silicon oxide, aluminum oxide, zirconium oxide, magnesium oxide, cerium oxide, tungsten oxide, molybdenum oxide and composites thereof. At least one or more can be selected from the following. These inorganic compounds are in the form of fine particles, and the particle diameter is preferably 0.01 to 7 μm, more preferably 0.01 to 6 μm, and particularly preferably 0.0 to 6 μm.
When the particle diameter is less than 0.01 μm, it is difficult to uniformly disperse the finely divided inorganic compound, and when the particle diameter exceeds 7 μm, the transparency of the container is undesirably reduced. Among the above inorganic compounds, silicon oxide (silicic acid) or silicon oxide-magnesium oxide (magnesium silicate) may be used.
Is preferred in terms of compatibility with

The content of the inorganic compound is EV
10 to 10000 ppm relative to OH (further 20 to 8 ppm
If the content is less than 10 ppm, the effect of the present invention may not be sufficiently obtained. Conversely, if the content exceeds 10,000 ppm, not only the transparency of the container is lowered but also the It is not preferable because a sufficient effect corresponding to the amount cannot be obtained.

There is no particular limitation on the inclusion of such an inorganic compound in EVOH. A) Water / alcohol of EVOH (methanol, ethanol, propanol, etc.)
The inorganic compound is directly added to a mixed solution of water or phenol or the like, or an aqueous dispersion (about 0.1 to 10% by weight) is added thereto and mixed, and then the EVOH containing the inorganic compound is added to a coagulation bath (water, water). / Alcohol mixed solvents, aromatic hydrocarbons such as benzene, ketones such as acetone and methyl ethyl ketone, ethers such as dipropyl ether, methyl acetate,
A method of precipitating in an organic acid ester such as ethyl acetate or methyl propionate, etc.) and then drying; b) EV
A method of precipitating a solution of OH in a coagulation bath, adding the inorganic compound to the obtained precipitate, and melt-kneading with an extruder or the like,
C) a method in which EVOH and the inorganic compound are mixed at once and then melt-kneading with an extruder or the like; and d) a method in which the inorganic compound is added during polymerization. In order to obtain the effects of the present invention more remarkably, the methods a) and 2) are preferable.

Thus, R which satisfies the storage elastic modulus of the present invention
-EVOH is obtained, and the EVOH contains a plasticizer and a plasticizer as long as the object of the present invention is not impaired.
Additives such as lubricants, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, coloring agents, antistatic agents, surfactants, antibacterial agents, desiccants, and polyolefins, polyamides, etc. It is also possible to blend other resins.
In particular, a hydrotalcite-based compound, a hindered phenol-based, a hindered amine-based heat stabilizer, and a metal salt of a higher aliphatic carboxylic acid can also be added as a gel generation inhibitor.

As the R-EVOH, two or more different R-EVOHs may be used, or a blend of R-EVOH and another EVOH (provided that the blend satisfies the storage modulus of the present invention). In this case, the ethylene content differs by 5 mol% or more, and / or
Alternatively, by using a blend of EVOH having a degree of saponification of 1 mol% or more, while maintaining gas barrier properties,
Furthermore, it is useful because the stretchability during high stretching and the secondary workability such as vacuum pressure forming and deep drawing are improved.

It is also preferable that R-EVOH contains an acid or a metal salt thereof in terms of improving the appearance, long-run moldability, interlayer adhesion and the like of the obtained multilayer hollow container. Is more preferably one of acetic acid, boric acid, and phosphoric acid, and the salt thereof is at least one or more of these alkali metal salts or alkaline earth metal salts.

Specific examples of the acid include acetic acid, propionic acid, boric acid, phosphoric acid, adipic acid, benzoic acid, citric acid, and the like. Preferably, acetic acid, boric acid, and phosphoric acid are used. Examples of the salts thereof include alkali metal salts and alkaline earth metal salts of the above acids.Specifically, examples of the acetate include sodium acetate, potassium acetate, calcium acetate, magnesium acetate, manganese acetate, and the like. Copper acetate, cobalt acetate, zinc acetate and the like,
Preferably, sodium acetate, potassium acetate, calcium acetate, and magnesium acetate are used. As the borate, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate. Potassium, 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, etc.), 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 borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.) ), Barium borate (barium orthoborate, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, tetraborate) Trimagnesium, pentamagnesium tetraborate, etc.), manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.) ), Borax, carnite, inyoite, dwarf stone,
Boron minerals such as Syanite and Zeyberite are exemplified, and preferably borax, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate,
Sodium pentaborate, sodium hexaborate, sodium octaborate, etc.), and the phosphates include sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate , Tripotassium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, tricalcium phosphate, magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, etc., preferably sodium dihydrogen phosphate , Potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate are used.

The content of such an acid or a metal salt thereof cannot be specified unconditionally depending on the kind thereof.
At the time of 10 to 500 ppm (further 20 to 300 pp
m) (in terms of metal, in the case of a metal salt), preferably about 10 to 10000 ppm (more preferably 20 to 1 ppm) in the case of boric acid (salt).
000 ppm) (in terms of boron), and
5 to 500 ppm for phosphoric acid (salt) (further 20 to 3 ppm)
00 ppm) (in terms of phosphoric acid radical). When the content is too small, the long run property at the time of melt molding may be inferior. On the other hand, when the content is too large, the thermal stability of the obtained R-EVOH deteriorates. Or the appearance of the resulting molded article may be unfavorably deteriorated.

The container of the present invention comprises a layer of R-EVOH having a specific storage modulus as described above as an innermost layer,
Such a container will be described below.

In the container of the present invention, other layers are not particularly limited as long as the R-EVOH layer is provided in the innermost layer, but the R-EVOH layer / thermoplastic resin layer, R-EVO
H layer / thermoplastic resin layer / thermoplastic resin layer, R-EVOH
Layer / thermoplastic layer / EVOH, R-EVOH layer / thermoplastic layer / EVOH / thermoplastic layer, R-EVOH
Layer / EVOH / thermoplastic resin layer, etc., and considering the aesthetics (glossiness) of the container, R-
The layer structure of EVOH layer / thermoplastic resin layer / EVOH is preferred. In the above-described laminated structure used for the container of the present invention, it is practical to use an adhesive resin between the respective layers.

Examples of such thermoplastic resins include polyolefin resins, polyester resins, polyamide resins,
Copolyamide, polystyrene resin, polycarbonate resin, polyvinyl chloride resin, polyvinylidene chloride, acrylic resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene, aromatic and aliphatic Polyketone, aliphatic polyalcohol and the like,
Preferably polyolefin resin, polyester resin,
(Copolymerization) A polyamide resin is used.

Specific examples of the polyolefin resin include linear low density polyethylene (LLDPE),
Low density polyethylene (LDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE),
High density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA) or partially saponified product thereof, ionomer, ethylene-propylene (block or random)
Copolymer, ethylene-acrylic acid copolymer, ethylene-
Methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer,
Polypropylene (PP), propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, homo- or copolymer of olefin such as polybutene, polypentene, polymethylpentene, or homo- or copolymer of these olefins Examples include polyolefin-based resins in a broad sense, such as a polymer obtained by graft-modifying an unsaturated carboxylic acid or an ester thereof and a blend thereof, and among them, linear low-density polyethylene (LLDPE), low-density polyethylene ( LDPE), ultra low density polyethylene (V
LDPE), ethylene-vinyl acetate copolymer (EV
A), an ionomer, an ethylene-propylene (block or random) copolymer, and polypropylene (PP) are preferably used.

Specific examples of the polyester resin include polyethylene terephthalate (PET), polyethylene terephthalate (PEN), and other copolymer components thereof (acid components: isophthalic acid, diphenyl-
Aromatic dicarboxylic acids such as 4,4′-dicarboxylic acid, diphenoxyethane dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and ester-forming derivatives thereof, adipic acid, sebacic acid,
Aliphatic dicarboxylic acids such as azelaic acid and succinic acid and their ester-forming derivatives, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and hexahydroterephthalic acid and their ester-forming derivatives, p-oxybenzoic acid, oxycaproline In addition to oxyacids such as acids and their ester-forming derivatives, trimellitic acid, pyromellitic acid, etc., glycol components: diethylene glycol,
Trimethylene glycol, tetramethylene glycol,
Aliphatic glycols such as neopentyl glycol, 1,4
Alicyclic glycols such as cyclohexane dimethanol,
Bisphenol A, aromatic glycols such as alkylene oxide adducts of bisphenol A, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycerin, 1,3-propanediol, pentaerythritol, etc.) And blends of PET and PEN,
Blends of other thermoplastic resins (MXD-6 nylon, polycarbonate, polyarylate, liquid crystal polymer, etc.) can be mentioned.

Specific examples of such (copolymerized) polyamide resins include polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecane Amide (nylon 11), polylauryl lactam (nylon 1
2), polyethylene diamine adipamide (nylon 2
6), polytetramethylene adipamide (nylon 4
6), polyhexamethylene adipamide (nylon 6
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2), polyoctamethylene adipamide (nylon 8
6), polydecamethylene adipamide (nylon 10
8), caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / ω-aminononanoic acid copolymer (nylon 6/9), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66), Lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/6
6), ethylenediamine adipamide / hexamethylenediammonium adipate copolymer (nylon 26/6
6), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 66/610), ethylene ammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 6 / 66/610), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexamethylene isophthalamide / terephthalamide copolymer or a polyamide resin modified with an aromatic amine such as methylenebenzylamine or metaxylenediamine And metaxylylenediammonium adipate. One or more of these blends are used, and among these, the melting point is 240 ° C. or less, and Melting point is preferably 160 to 230 ° C. of polyamide resin, specifically polycapramide (nylon 6), polylauryllactam (nylon 12), caprolactam / lauryllactam copolymer (nylon 6
/ 12), caprolactam / hexamethylenediammonium adipate copolymer (nylon 6/66) and the like.

The adhesive resin used for the adhesive resin layer is not particularly limited, and various ones can be used. Generally, unsaturated carboxylic acids or anhydrides thereof are converted to olefins. And a modified olefin polymer containing a carboxyl group obtained by chemically bonding to a polymer (polyolefin resin in a broad sense described above) by an addition reaction, a graft reaction, or the like. Examples of the anhydride include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride and the like, and among them, maleic anhydride is preferably used. Specifically, maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft-modified ethylene One or a mixture of two or more selected from vinyl acetate copolymers and the like is mentioned as a preferable example. At this time, the amount of the unsaturated carboxylic acid or its anhydride contained in the olefin polymer is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, and particularly preferably 0.1 to 1% by weight. 03 to 0.5% by weight. If the amount of modification in the modified product is small, the effect of improving interlayer adhesion is poor, and if it is too large, a crosslinking reaction occurs, and moldability may deteriorate, which is not preferable.

The adhesive properties of these adhesive resins are improved by blending a rubber / elastomer component such as polyisobutylene or ethylene-propylene rubber, or a polyolefin resin different from the base polyolefin resin of the adhesive resin. It is useful because it can improve.

In producing the container of the present invention, a known method can be employed. For example, 1) R-EV
A method of forming a multilayer structure (sheet, film, etc.) in which an adhesive resin or a polyolefin resin is laminated on the surface of a layer made of OH and then molding it into a container; 2) R-EVOH and an adhesive resin or a polyolefin resin And the like, in which a multi-layer container is molded directly by using a co-injection molding machine or the like.

In the method 1), first, R-EVOH
A multilayer structure is produced by laminating an adhesive resin or a polyolefin-based resin on the surface of a layer composed of, for example, an adhesive resin or a polyolefin-based resin on a film or sheet made of R-EVOH. Melt-extruding, etc., and conversely, R-EV
A method of melt-extruding OH or an adhesive resin, a method of co-extruding R-EVOH with an adhesive resin or a polyolefin resin, a method of co-injecting these resins,
And a method of dry laminating a film or sheet made of -EVOH and a film or sheet made of polyolefin resin using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound.

Next, the obtained multilayer structure is molded into a container. In this molding, a multilayer hollow container can be suitably obtained by applying a heat stretching treatment.

Here, the heat-stretch molding means that the multilayer structure is uniformly heated by various heaters,
It refers to the operation of uniformly forming into various shapes by vacuum force, pneumatic force, blow, etc.

The heat stretching may be any of uniaxial stretching and biaxial stretching. Examples of the heating stretching method include a roll stretching method, a tenter stretching method, a tubular stretching method, a stretch blow method, a deep drawing method, Vacuum forming method, pressure forming method, vacuum pressure forming method and the like can be adopted. In the case of biaxial stretching, any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be adopted. The temperature of the multilayer structure during the heat stretching is 80 to 17
The temperature is selected from the range of 0 ° C, preferably about 100 to 160 ° C.

In the present invention, it is particularly preferable to obtain hollow containers such as bottles, tanks and tubes by blow molding, and the production method is not particularly limited, either. Direct blow molding, injection blow molding,
A biaxial stretch blow molding method and the like can be mentioned. Further, the biaxial stretch blow molding method includes a cold parison method and a hot parison method. Further, it is preferable to further heat-treat the hollow container obtained by blow molding, since the impact delamination property and the gas barrier property are improved. The heat treatment temperature is 100 to 240 ° C., and the heat treatment time is 1 second or more.

In the method 2), a multilayer container such as a cup or a tray can be directly obtained by using a co-injection molding machine or the like without heating and stretching. It is also preferable to further heat-treat the multilayer container obtained in the same manner as in 1).

It is also possible to provide a regride (recycled scrap) layer as a layer structure, and the provision of such a regrind layer means that a large amount of scrap [EVOH and thermoplastic resin (particularly polyolefin-based resin) generated during the molding of the container. Consisting of [inside] R-EVOH layer / polyolefin resin layer / liglide layer / polyolefin resin layer [outside], [inside] R-EVOH Layer / polyolefin resin layer / liglide layer / polyolefin resin layer / EVOH layer [outside], [inside] R-EVOH layer / liglide layer / polyolefin resin layer / EVOH layer [outside], [inside] R-EVOH layer / Polyolefin resin layer / liglide layer / EVOH layer [outside], [inside]
EVOH layer / EVOH layer / liglide layer / polyolefin resin layer [outside]. In addition, it is preferable to use the above-mentioned adhesive resin between these layers as needed.

In the present invention, it is also possible to blend the components of the adjacent layers with the mating layer, and to blend a resin which improves the adhesion between the two layers.

Further, in obtaining a pouch (bag-shaped container), a known method can be adopted.
A method of forming a multilayer structure (film) in which an adhesive resin, a polyolefin-based resin, or the like is laminated on the surface of a layer made of EVOH, and then molding the film into a container can be used.

In the above method, first, R-EVOH
A multilayer structure is produced by laminating an adhesive resin or a polyolefin-based resin on the surface of a layer composed of, for example, an adhesive resin or a polyolefin-based resin on a film or sheet made of R-EVOH. Melt-extruding, etc., and conversely, R-EV
A method of melt-extruding OH or an adhesive resin, a method of co-extruding R-EVOH with an adhesive resin or a polyolefin resin, a method of co-injecting these resins,
And a method of dry laminating a film or sheet made of -EVOH and a film or sheet made of polyolefin resin using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound.

In the case of a pouch, it is also possible to blend the components of the adjacent layers with the mating layer or blend a resin which improves the adhesion between the two layers.

The (multi-layer hollow) container of the present invention thus obtained is useful for containers of general foods and medicines, but the container of the present invention has a scent-retaining property (a barrier property against aroma components and medicinal components). ), It is particularly useful as a packaging container (hollow container such as bottle, tube, etc.) for foods, beverages, pharmaceuticals, cosmetics, fragrances, toiletry products, etc. containing these components, Containers for wine, orange juice, etc., containers for lemon juice, etc., containers for seasonings and spices, containers for lotion, containers for bath salts (including medicinal use), containers for fragrances and deodorants, toothpastes and gels It is useful for containers for toothpastes, containers for liquid soaps, shampoos and rinses, containers for painkillers and anti-inflammatory agents, and the like.

[0044]

The present invention will be specifically described below with reference to examples.

In the examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1 EVOH [Ethylene content 34 mol%, saponification degree 99.
7 mol%, MFR 3.3 g / 10 min (210 ° C., load 2
(160 g)] (“Sylysia 310” manufactured by Fuji Silysia Chemical Ltd.), silicon dioxide main component, average particle diameter of 1.
4 μm) is melt-mixed with a twin-screw extruder (barrel temperature 230 ° C.) to 500 ppm, and the R-EV for the innermost layer is mixed.
OH was obtained.

Next, using a T-die having a die width of 450 mm, the above-obtained R-EVOH was formed into a single-layer film at a roll temperature of 30 ° C., and then 3.5 times in the machine direction with a tenter stretching machine.
Biaxially stretched film stretched 3.5 times in the transverse direction (thickness approx.
5 μm). The obtained film and a separately prepared multilayer film [LDPE (low density polyethylene, density;
928, “Novatech LF660H” manufactured by Mitsubishi Chemical Corporation)
/ Adhesive resin (“Admer LF50” manufactured by Mitsui Chemicals, Inc.
0 ") / EVOH (ethylene content 44 mol%, saponification degree 99.8 mol%, MFR 3.1 g / 10 min (210
° C, load 2160 g) = 30/10/30 μm thickness] and an anchor coating agent (polyurethane, “Adcoat AD-335A (main agent) / CAT-1 manufactured by Toyo Morton Co., Ltd.).
0 (curing agent) ”), and R-EVO
H / LDPE / adhesive resin / EVOH = 15/30/1
A multilayer film having a thickness of 0/30 μm was prepared.

A pouch (container) was prepared such that the R-EVOH layer of the multilayer film was the innermost layer.

The storage elastic modulus of the R-EVOH was 5.0 × 10 ⁹ Pa as measured by the method described in the text.
Met.

A commercially available 100% orange juice was sealed in the obtained container, left at 20 ° C. for 20 days, and the amount (L ₂₀ ) of d-limonene in the orange juice was measured. The ratio (L ₂₀ / L ₀ ) to the d-limonene amount (L ₀ ) was determined, and the fragrance retention was evaluated as follows.

○ ... 0.85 to 1.00 × ... less than 0.85 The R-EVOH obtained above was visually observed for the presence or absence of coloring, and the coloring property was evaluated as follows. did.

: No coloring was observed at all X: Coloring was remarkable Example 2 In Example 1, the ethylene content was 4 for R-EVOH.
4 mol%, saponification degree 99.8 mol%, MFR 3.3 g /
A container was obtained in the same manner except that EVOH for 10 minutes (210 ° C., load 2160 g) was used to obtain a container, which was similarly evaluated.

Incidentally, the storage elastic modulus of R-EVOH was 3.0 × 10 ⁹ Pa as measured by the method described in the text.

Example 3 In Example 1, the content of the amorphous silica was changed to 7000 p.
A container was obtained in the same manner except that the pressure was changed to pm, and the same evaluation was performed.

Incidentally, the storage elastic modulus of R-EVOH was 5.2 × 10 ⁹ Pa as measured by the method described in the text.

Example 4 In Example 1, the content of the amorphous silica was changed to 100 pp.
A container was obtained in the same manner except that the value was changed to m, and the same evaluation was performed.

The storage elastic modulus of R-EVOH was 4.5 × 10 ⁹ Pa as measured by the method described in the text.

Example 5 A container was obtained in the same manner as in Example 1 except that the stretching ratio of the biaxially stretched film was 2.0 times in the longitudinal direction and 2.0 times in the transverse direction. Was.

Incidentally, the storage elastic modulus of R-EVOH was 5.0 × 10 ⁹ Pa as measured by the method described in the text.

Example 6 R-EVOH was obtained in Example 1 by using a layered silicate (natural montmorillonite) instead of amorphous silica.

Next, using a multilayer extruder, EVOH
[Ethylene content 44 mol%, degree of saponification 99.8 mol%, MFR 3.1 g / 10 min (210 ° C., load 2160
g)] / adhesive resin (“Admer QF5” manufactured by Mitsubishi Chemical Corporation)
00 ”) / PP (polypropylene,“ Novatech EA9 ”manufactured by Mitsubishi Chemical Corporation) / adhesive resin (same as left) / R-EVO
A multilayer film having a thickness of H = 10/5/50/5/20 μm was formed. After the multilayer film was subjected to a heat treatment at 150 ° C. for 30 seconds, a pouch was produced so that the R-EVOH layer was the innermost layer, and evaluation was performed in the same manner as in Example 1.

The storage elastic modulus of R-EVOH was 2.5 × 10 ⁹ Pa as measured by the method described in the text.

Example 7 The same R-EVOH composition as in Example 1 was blow-molded into LDPE (low density polyethylene, density;
925, "Novatech LF660H" manufactured by Mitsubishi Chemical Corporation)
/ Adhesive resin (“Admer LF50” manufactured by Mitsui Chemicals, Inc.
0 ") / EVOH [ethylene content 34 mol%, degree of saponification 99.8 mol%, MFR 3.1 g / 10 min (210
° C, load 2160g)] / adhesive resin (left) / RE
VOH = 100/10/10/10/10 μm thick bottles were formed.

Incidentally, the storage elastic modulus of R-EVOH was 5.2 × 10 ⁹ Pa as measured by the method described in the text.

Example 8 In Example 7, the content of the amorphous silica was changed to 1000 p.
A container was obtained in the same manner except that the pressure was changed to pm, and the same evaluation was performed.

The storage elastic modulus of R-EVOH was 6.1 × 10 ⁹ Pa as measured by the method described in the text.

Example 9 Example 7 was the same as Example 7 except that PP (Mitsubishi Chemical's “Novatec EA9”) was used instead of LDPE, and “Admer QF500” manufactured by Mitsui Chemicals was used as the adhesive resin. An evaluation was performed.

Incidentally, the storage elastic modulus of R-EVOH was 6.1 × 10 ⁹ Pa as measured by the method described in the text.

Example 10 In Example 1, a layered silicate (natural montmorillonite) was used in an amount of 1000 ppm instead of the amorphous silica.
A container was obtained in the same manner except that R-EVOH was obtained, and the container was evaluated in the same manner.

The storage elastic modulus of R-EVOH was 5.3 × 10 ⁹ Pa as measured by the method described in the text.

Comparative Example 1 A container was obtained in the same manner as in Example 1 except that EVOH containing no amorphous silica was used instead of R-EVOH, and a container was obtained and evaluated in the same manner.

The storage elastic modulus of the EVOH was 1.5 × 10 ⁹ Pa as measured by the method described in the text.

Comparative Example 2 In Example 1, R-EVOH / LDPE / EVOH
= R-EV of a multilayer film having a thickness of 15/30/30 µm
Anchor coating agent (polyurethane, Toyo Morton “Adcoat AD-335A (main agent) /
A container was obtained in the same manner as above except that an LDPE layer (15 μm) was further provided via a “CAT-10 (curing agent)”) layer, and the container was evaluated in the same manner.

Table 1 summarizes the evaluation results of the examples and comparative examples.

[0075]

[0076]

As described above, the container of the present invention has a specific EVOH layer as the innermost layer, so that it has excellent fragrance preservation properties and also has such an EV.
OH layer without coloring, especially food containing fragrance components, etc.
Also useful as packaging containers (hollow containers such as bottles, pouches, tubes, etc.) for beverages, pharmaceuticals, cosmetics, fragrances, toiletry products, etc., containers for perfumes and fragrances, containers for wine and orange juice, containers for lemon juice, etc. Containers for seasonings and spices, containers for lotions, containers for bath salts (including medicinal products), containers for fragrances and deodorants, containers for toothpastes and gel-like toothpastes, containers for liquid soap, shampoo and rinse, It is useful for containers of analgesics and antiphlogistics.

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Claims (3)

[Claims] 1. The storage elastic modulus in water at 20 ° C. is 2 ×
A container comprising a layer composed of a saponified ethylene-vinyl acetate copolymer (Α) having a pressure of 10 ⁹ Pa or more disposed in the innermost layer. 2. The container according to claim 1, wherein the saponified ethylene-vinyl acetate copolymer (Α) contains 10 to 10000 ppm of a particulate inorganic compound. 3. A layer formed of a saponified ethylene-vinyl acetate copolymer (A), a hydrophobic thermoplastic resin layer laminated on the outside, and a saponified ethylene-vinyl acetate copolymer (共) layer further outside the layer. The container according to claim 1 or 2, wherein an adhesive resin layer is provided between each layer as needed.