JPH0911416A - Aromaproof multilayered container - Google Patents

Abstract

PURPOSE: To equip a layer produced by adding an amorphous or low scrystalline copolymer of an olefin and a cyclic olefin as an intermediate layer and provide a multilayered container excellent in aromaproofness, water retention and contents resistance and further laminar bondability, especially a crushable multilayered container. CONSTITUTION: This multilayered container is equipped with an inner and outer layers 11 and 13, which contain an olefin-based resin, and an intermediate layer 12, which contains an amorphous or low crystalline copolymer of an olefin and cyclic olefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layered fragrance container, and more particularly to a layer containing an amorphous or low crystalline copolymer of an olefin and a cyclic olefin as an intermediate layer. The present invention relates to a multilayer container excellent in aroma retention, water retention and content resistance, and a crushable multilayer container.

[0002]

2. Description of the Related Art Plastic crushable extrusion containers are widely used as packaging containers for storing various contents such as toothpaste, cosmetics, toiletry products, various chemicals, glues and adhesives, high-viscosity seasonings and foods. It is used.

[0003] In this crushable container, an ethylene-based polymer such as low-density polyethylene or ethylene-vinyl acetate copolymer is used because flexibility for squeezing the contents is required.

It has long been known to use oxygen-barrier resins to prevent the permeation of oxygen through the walls of containers, for example, the inner and outer layers of low density polyethylene and saponified ethylene-vinyl acetate copolymer. A multilayer extruded tube container comprising an intermediate layer of (ethylene vinyl alcohol copolymer) is also already known (for example, Japanese Patent Publication No. Sho 57-3).
No. 3223).

[0005]

A multilayer container using an oxygen-barrier resin such as an ethylene vinyl alcohol copolymer has a small permeation of oxygen gas through the vessel wall and is also excellent in aroma retention to some extent. However, there is a problem that the barrier property of the aroma component is still insufficient. Further, a gas barrier resin such as an ethylene vinyl alcohol copolymer has a drawback that its permeability to water vapor is considerably large and that the gas barrier property itself is deteriorated by moisture absorption of water vapor.

The inventors of the present invention did not adversely affect the content resistance and sealing property when an amorphous or low crystalline copolymer of olefin and cyclic olefin was used as an intermediate layer of a multi-layer container. Furthermore, they have found that the aroma and water retaining properties of this container can be significantly improved.

That is, an object of the present invention is to provide a layer containing an amorphous or low crystalline copolymer of an olefin and a cyclic olefin as an intermediate layer, and to provide aroma retention, water retention and content resistance, Furthermore, it is to provide a multilayer container having excellent interlaminar adhesiveness, particularly a crushable multilayer container.

[0008]

According to the present invention, an inner and outer layer containing an olefin resin and an intermediate layer containing an amorphous or low crystalline copolymer of olefin and cyclic olefin. An aromatizing multi-layer container is provided, which comprises:

According to the present invention, an inner and outer layer containing an olefin resin, and a first intermediate layer containing an amorphous or low crystalline copolymer of olefin and cyclic olefin, And a second intermediate layer containing a thermoplastic resin having an oxygen barrier property.

Amorphous to low crystalline copolymers of olefins and cyclic olefins are derived from 10 to 50 mol%, especially 20 to 48 mol% of cyclic olefins and the balance ethylene and 5 to 200 ° C. , Especially 40 to 1
Copolymers having a glass transition point of 90 ° C. are particularly suitable.

As the olefin resin, polyethylene or ethylene copolymer is suitable from the viewpoint of flexibility, but conversely, polypropylene or propylene copolymer can be used when a certain degree of hardness is allowed. .

The container of the present invention is 100 to 1 as a whole.
It is preferable that the inner wall has a thickness of 000 μm and the thickness ratio of inner layer: middle layer: outer layer is in the range of 2 to 96: 2 to 30: 2 to 96. In addition, when the second intermediate layer is provided, it has a container wall with a thickness of 100 to 1000 μm as a whole, and the thickness ratio of inner layer: first intermediate layer: second intermediate layer: outer layer is 2 to 94: 2. It is preferably in the range of 30: 2 to 30: 2 to 94.

The container of the present invention comprises inner and outer layers containing an olefin resin, an intermediate layer containing an amorphous or low crystalline copolymer of olefin and cyclic olefin, or an oxygen barrier. Formed by melt blow molding of a multi-layer parison with a second intermediate layer comprising a hydrophobic thermoplastic resin. The collapsible container can also be manufactured by bonding a pipe body, for example, an extruded pipe cut into a predetermined length, and a separately molded mouth, for example, a mouth formed by injection molding. .

[0014]

In a collapsible container, in order to impart extrudability or squeeze property of the contents to the vessel wall, it is desirable to reduce the wall thickness of the ordinary rigid or semi-rigid container from the viewpoint of light weight and resource saving. However, if the wall is thin,
Aroma components and water in the contents tend to escape to the outside through the vessel wall.

In the container of the present invention, an intermediate layer containing an amorphous to low crystalline copolymer (COC) of an olefin and a cyclic olefin is provided between the inner and outer layers containing the olefin resin. This is characterized in that the permeation of the aroma component and the permeation of water vapor through the vessel wall can be remarkably suppressed, and the storability of the contents can be remarkably improved.

See the example below. In these examples, phenylethyl alcohol (PEA) and phenylacetic acid methyl ester (PAM) are used as an index substance of an aromatic component.
A solution obtained by dissolving E) in ethyl alcohol was filled in various tube containers and then sealed, and this package was placed in a closed atmosphere, and the concentrations of PEA and PAME leaked into the atmosphere through the vessel wall of the tube container were measured. The results are shown (see the example described later for details of measurement conditions).

According to these results, in the case of the ethylene-vinyl acetate copolymer (EVA) single-layer tube container, the PEA concentration leaking into the atmosphere reaches 91.26 ng / ml (Comparative Example 2). In a tube container in which an amorphous or low crystalline copolymer of olefin and cyclic olefin is provided as an intermediate layer between the inner and outer layers of EVA, the PEA concentration leaked into the atmosphere is 1.6 ng / ml, that is, It is suppressed to about 1/100 (Example 1-2).
This tendency is exactly the same for other olefin resins. In a single-layer tube container of polyolefin elastomer (POPs) obtained by using a metallocene catalyst, the PEA concentration leaked to the atmosphere is 95.35 ng / ml.
(Comparative Example 1), the polyolefin-based elastomer (POP) obtained by using the metallocene-based catalyst
_In a tube container in which an amorphous or low crystalline copolymer of olefin and cyclic olefin is provided as an intermediate layer between the inner and outer layers of _S ), the PEA concentration leaked into the atmosphere is 1.90n.
g / ml, that is, suppressed to about 1/100 (Example 1)
-1). From the above facts, it is understood that the amorphous to low crystalline copolymer of olefin and cyclic olefin is completely different from other olefin resins and exhibits a particularly excellent barrier property against an aromatic component. To be done.

Similar excellent results are observed in water vapor permeability. That is, by providing an amorphous or low crystalline copolymer of an olefin and a cyclic olefin as an intermediate layer, the amount of water vapor permeation is on the order of one half or less of the value when the copolymer is not present. Therefore, it is possible to prevent problems such as defective extrusion due to deterioration of the contents and increase in the viscosity of the contents.

In the present invention, an amorphous to low crystalline copolymer (COC) of an olefin and a cyclic olefin is
It is also important to provide it as an intermediate layer between the olefin resin inner and outer layers. The above-mentioned COC has poor resistance to oily contents contained in paste or semi-solid, etc., and tends to cause crazes and cracks, and the contents resistance of the container, chemical resistance, extraction resistance, hygienic properties Insufficient in terms of the above, and also inferior in heat sealability at the time of heat-sealing the tube bottom, by using an olefin resin excellent in these various properties as the inner and outer layers, the above problems can be solved. .

The collapsible multi-layer container of the present invention has an excellent barrier property against scent components (aroma and flavor) and water vapor, and therefore has an advantage that the thickness of the vessel wall can be reduced. On the other hand, in a collapsible container, even if the thickness of the container wall is thinned, there is no problem in terms of extrudability of the content, but the shape retention of the container is reduced, and the filling workability of the content and the packaging are reduced. There is a problem that the appearance of the body becomes poor.

The amorphous or low crystalline copolymer of olefin and cyclic olefin used in the present invention has a flexural modulus of low density polyethylene of 1000 to 2000 kg / cm ^2.
And the flexural modulus is 23000 to 330.
It is as large as 00 kg / cm ^2, and it is useful for giving shape retention to the container.

Further, the amorphous or low crystalline copolymer of olefin and cyclic olefin has good thermal adhesiveness to olefin resin, and this copolymer (COC) and olefin resin are coextruded. By doing so, a laminate having excellent delamination resistance can be obtained.

In the collapsible container of the present invention, an amorphous or low crystalline copolymer of olefin and cyclic olefin is combined as a first intermediate layer and an oxygen barrier thermoplastic resin is combined as a second intermediate layer. You can do this,
It is possible to manufacture a collapsible container which has a barrier property against virtually all gases and is excellent in the retention of many aromas and flavors.

The amorphous or low crystalline copolymer of olefin and cyclic olefin is a copolymer derived from 10 to 50 mol% of cyclic olefin and residual ethylene and having a glass transition point of 5 to 200 ° C. Polymers are preferred.

When the content of the cyclic olefin is below the above range, the glass transition point is below the above range, and the barrier property of the aroma component is lowered. On the other hand, when the content of the cyclic olefin exceeds the above range, the glass transition point exceeds the above range, and the melt moldability of the copolymer and the adhesiveness with the olefin resin are deteriorated.

As the crushable container, when flexibility of the vessel wall is particularly desired, it is desirable to use polyethylene or an ethylene copolymer as the olefin resin for the inner and outer layers, while the vessel wall has a certain degree. When the rigid of is desired, as the olefin resin for the inner and outer layers,
It is preferable to use polypropylene or a propylene-based copolymer. Further, as a method of increasing the rigidity, the thickness of the amorphous or low crystalline copolymer layer of olefin and cyclic olefin can be increased. Rigidness to some extent enhances the springback property after extruding the contents, and enhances the shape retention of the container.

As the olefin resin for the inner and outer layers, when an ethylene polymer polymerized by using a metallocene catalyst, particularly a copolymer of ethylene and α-olefin is used, the fragrance component on the vessel wall and steam Since the barrier property is improved, it is convenient for the purpose of the present invention.

In the collapsible container of the present invention, the total thickness of the container is preferably in the range of 100 to 1000 μm. When it is thinner than the above range, the shape retention and strength of the container are lowered, while the thickness of the container is less than the above range. As the thickness increases, the weight of the container increases,
In addition, the extrudability decreases. From the combination of various characteristics, the thickness ratio of inner layer: middle layer: outer layer is 2 to 96: 2 to 30: 2.
It is preferably in the range of 96. In addition, when the second intermediate layer is provided, it has a container wall with a thickness of 100 to 1000 μm as a whole, and the thickness ratio of inner layer: first intermediate layer: second intermediate layer: outer layer is 2 to 94: 2. 30: 2 to 30: 2
It is preferably within the range of -94.

The collapsible container of the present invention comprises an inner and outer layer containing an olefin resin, and an intermediate layer containing an amorphous or low crystalline copolymer of olefin and cyclic olefin.
Alternatively, since it is formed by melt blow molding of a multi-layer parison provided with a second intermediate layer containing a thermoplastic resin having an oxygen barrier property, the production thereof is very easy.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION In FIG. 1 showing an example of the collapsible container of the present invention, this collapsible container is composed of a tubular container 1 and a lid 2. The tubular container 1 is formed by parison hollow molding. It has a screw-shaped extrusion port 3 formed integrally, a conical shoulder portion 4 connected to this, and a thin tubular body portion 5. The tubular body 5 has a cut edge 6, and after filling the contents from the edge, the opposing inner surfaces of the body are fused to form a sealed bottom.

In FIG. 2 showing another example of the collapsible container of the present invention, this collapsible container comprises a bottle-shaped container 10 having a small diameter and a lid 2. The bottle-shaped container 10 is a hollow parison. It has a screw-in extrusion port 3 integrally formed by molding, a conical shoulder 4 continuing from this, a thin cylindrical body 5, and a closed bottom 7 formed by a parison pinch-off. In this container, the contents are filled through the extrusion port 3, and after filling, the lid 2 is fastened and sealed.

In FIG. 3, which is an enlarged view of an example of the cross-sectional structure of the body portion 5, this container wall has an inner layer 11 mainly composed of an olefin resin and an amorphous or low-crystalline co-weight of olefin and cyclic olefin. It is formed of an intermediate layer 12 containing a coalesce and an outer layer 13 containing an olefin resin. It should be understood that the intermediate layer 12 and the inner and outer layers 11, 13 are firmly heat-bonded.

In FIG. 4, which is an enlarged view of another example of the cross-sectional structure of the body portion 5, this container wall has inner and outer layers 11 and 13 containing an olefin resin, and an amorphous or cyclic olefin and an olefin. It is similar to FIG. 3 in that it has an intermediate layer (first intermediate layer) 12 containing a low crystalline copolymer (COC), but contains a gas barrier thermoplastic resin in addition to the above layers. The second intermediate layer 14 is
Is provided via In the specific example shown in FIG. 4, CO
The C-containing first intermediate layer 12 is provided on the inner surface side of the vessel wall, and the gas barrier resin-containing second intermediate layer 14 is provided on the outer surface side of the vessel wall. On the contrary, the COC-containing first intermediate layer 12 is provided. It should be understood that the gas barrier resin-containing second intermediate layer 14 may be provided on the outer surface side of the vessel wall on the inner surface side of the vessel wall. It goes without saying that the adhesive layer 15 can be omitted when the gas barrier resin has thermal adhesiveness to COC or olefin resin.

In FIG. 5, which shows another example of the sectional structure of the body portion 5 in an enlarged manner, the vessel wall has the same layer type as in FIG. 4, but the olefin and the cyclic olefin are amorphous. The intermediate layer (first intermediate layer) 12 containing the low crystalline copolymer (COC) is provided on both sides of the second intermediate layer 14 containing the gas barrier thermoplastic resin. This configuration is particularly suitable for maintaining high gas barrier properties of the vessel wall in retort sterilization or the like, that is, for suppressing a decrease in gas barrier properties due to moisture. The crushable container is a pipe-shaped body (for example, a cut extruded pipe).
It is also manufactured by adhering a separately formed mouth portion (for example, injection molding).

Ethylene is preferred as the olefin from which an amorphous to low crystalline copolymer (COC) of olefin and cyclic olefin is derived, but propylene,
Carbon number 3 such as 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl 1-pentene, 1-decene
.About.20 alpha-olefins are used alone or in combination with ethylene.

The cyclic olefin is basically an alicyclic hydrocarbon compound having an ethylenically unsaturated bond and a bicyclo ring, particularly bicyclo [2,2,1] hept-2-.
It is a hydrocarbon compound having an ene skeleton, and specific examples thereof include the following, but of course the present invention is not limited thereto.

Bicyclo [2.2.1] hept-2-ene derivative; for example, the following formula (1)

Embedded image In the formula, R is a hydrogen atom, an alkyl group, a cycloalkyl group,
Alternatively, it is an alkylidene group, n is a number of 1 to 4 (the same applies hereinafter), and bicyclo [2.2.
1] Hept-2-ene derivative. In particular, bicyclo [2.
2.1] Hept-2-ene 6-methylbicyclo [2.2.1] hept-2-ene 5,6-dimethylbicyclo [2.2.1] hept-2-
En 1-Methylbicyclo [2.2.1] hept-2-ene 6-Ethylbicyclo [2.2.1] hept-2-ene 6-n-Butylbicyclo [2.2.1] hept-2-ene Ene 6-isobutylbicyclo [2.2.1] hept-2-ene 7-methylbicyclo [2.2.1] hept-2-ene.

Tricyclo [4.3.0.1 ^2.5 ] -3-
Decene derivative; for example, the following formula (2)

Embedded image In tricyclo [4.3.0.1 ^2.5] -3- decene derivative represented. In particular, tricyclo [4.3.0.1 ^2.5]
-3-decene 2-methyl-tricyclo [4.3.0.1 ^2.5] -3-decene 5-methyl-tricyclo [4.3.0.1 ^2.5] -3-decene.

Tricyclo [4.4.0.1 ^2.5 ] -3-
Undecene derivative; for example, the following formula (3)

Embedded image In tricyclo [4.4.0.1 ^2.5] -3- undecene derivative represented. In particular, tricyclo [4.3.0.1
^2.5] -3-undecene 10-methyl-tricyclo [4.4.0.1 ^2.5] -3
Undecen.

Tetracyclo [4.4.0.1 ^2.5 . 1
^7.10 ] -3-Dodecene derivative, for example, the following formula (4)

Embedded imageTetracyclo [4.4.0.1]^2.5 .
1^7.10] -3-Dodecene derivative. In particular, tetracyclo
[4.4.0.1^2.5 . 1^7.10] -3-dodecene 8-methyltetracyclo [4.4.0.1^2.5 .
1^7.10] -3-Dodecene 8-ethyltetracyclo [4.4.0.1^2.5 .
1^7.10] -3-Dodecene 8-propyltetracyclo [4.4.0.1^2.5 . 1
^7.10] -3-Dodecene 8-butyltetracyclo [4.4.0.1]^2.5 .
1^7.10] -3-Dodecene 8-isobutyltetracyclo [4.4.0.1]^2.5 . 1
^7.10] -3-Dodecene 8-hexyltetracyclo [4.4.0.1^2.5 . 1
^7.10] -3-Dodecene 8-cyclohexyltetracyclo [4.4.0.1]
^2.5 . 1^7.10] -3-Dodecene 8-stearyltetracyclo [4.4.0.1]^2.5 . 1
^7.10] -3-Dodecene 5,10-dimethyltetracyclo
[4.4.0.1^2.5 . 1^7.10] -3-Dodecene 2,10-dimethyltetracyclo [4.4.0.1]
^2.5 . 1^7.10] -3-Dodecene 8,9-dimethyltetracyclo [4.4.0.1]^2.5 .
1^7.10] -3-Dodecene 8-ethyl-9-methyltetracyclo [4.4.0.1
^2.5 . 1^7.10] -3-Dodecene 11,12-dimethyltetracyclo [4.4.0.1
^2.5 . 1^7.10] -3-Dodecene 2,7,9-trimethyltetracyclo [4.4.0.1
^2.5 . 1^7.10] -3-Dodecene 2,7-dimethyl-9-ethyltetracyclo [4.4.
0.1^2.5 . 1^7.10] -3-Dodecene 9-isobutyl-2,7-dimethyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 9,11,12-trimethyltetracyclo [4.4.
0.1^2.5 . 1^7.10] -3-Dodecene 9-ethyl-11,12-dimethyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 9-isobutyl-11,12-dimethyltetracyclo
[4.4.0.1^2.5 . 1 ^7.10] -3-Dodecene 5,8,9,10-tetramethyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-ethylidene tetracyclo [4.4.0.1^2.5 . 1
^7.10] -3-Dodecene 8-ethylidene-9-methyltetracyclo [4.4.
0.1^2.5 . 1^7.10] -3-Dodecene 8-ethylidene-9-ethyltetracyclo [4.4.
0.1^2.5 . 1^7.10] -3-Dodecene 8-ethylidene-9-isopropyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-ethylidene-9-butyltetracyclo [4.4.
0.1^2.5 . 1^7.10] -3-Dodecene 8-n-propylidene tetracyclo [4.4.0.1]
^2.5 . 1^7.10] -3-Dodecene 8-n-propylidene-9-methyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-n-propylidene-9-ethyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-n-propylidene-9-isopropyltetracyclo
[4.4.0.1^2.5 . 1^7.10] -3-Dodecene 8-n-propylidene-9-butyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-isopropylidenetetracyclo [4.4.0.1]
^2.5 . 1^7.10] -3-Dodecene 8-isopropylidene-9-methyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-isopropylidene-9-ethyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene 8-isopropylidene-9-isopropyltetracyclo
[4.4.0.1^2.5 . 1^7.10] -3-Dodecene 8-isopropylidene-9-butyltetracyclo [4.
4.0.1.^2.5 . 1^7.10] -3-Dodecene.

Pentacyclo [6.5.1.1 ^3.6 . 0
^2.7 . ^0.913 ] -4-Pentadecene derivative; for example, the following formula (5)

Embedded image Pentacyclo [6.5.1.1 ^3.6 .
0 ^2.7 . ^0.913 ] -4-Pentadecene derivative. In particular, pentacyclo [6.5.1.1 ^3.6 . 0 ^2.7 . 0 ^9.13 ] −
4-pentadecene 1,3-dimethylpentacyclo [6.5.1.1 ^3.6 .
0 ^2.7 . 0 ^9.13] -4-pentadecene 1,6-dimethyl-pent cyclo [6.5.1.1 ^3.6.
0 ^2.7 . 0 ^9.13 ] -4-Pentadecene 14,15-dimethylpentacyclo [6.5.1.1]
^3.6 . 0 ^2.7 . 0 ^9.13 ] -4-Pentadecene.

Pentacyclo [7.4.0.1 ^2.5 . 1
^9.12 . 0 ^8.13 ] -3-Pentadecene derivative, for example, the following formula (6)

[Chemical 6] Pentacyclo [7.4.0.1 ^2.5 .
^19.12 . 0 ^8.13 ] -3-Pentadecene derivative. In particular, pentacyclo [7.4.0.1 ^2.5 . ^19.12 . 0 ^8.13 ] −
3-Pentadecene methyl-substituted pentacyclo [7.4.0.1 ^2.5 .
^19.12 . 0 ^8.13 ] -3-Pentadecene.

Pentacyclo [6.5.1.1 ^3.6 . 0
^2.7 . 0 ^9.13 ] -4,10-Pentadecadiene derivative,
For example, the following formula (7)

Embedded image Pentacyclo [6.5.1.1 ^3.6 .
0 ^2.7 . 0 ^9.13 ] -4,10-Pentadecadiene derivative. In particular, pentacyclo [6.5.1.1 ^3.6 .
0 ^2.7 . 0 ^9.13 ] -4,10-pentadecadiene.

Pentacyclo [8.4.0.1 ^2.5 . 1
^9.12 . 0 ^8.13 ] -3-Hexadecene derivative, for example, the following formula (8)

Embedded image Pentacyclo [8.4.0.1 ^2.5 .
^19.12 . 0 ^8.13 ] -3-Hexadecene derivative. In particular, pentacyclo [8.4.0.1 ^{2.5. 19.12} . 0 ^8.13 ] −
3-hexadecene 11-methyl-- pentacyclo [8.4.0.1 ^2.5. 1
^9.12 . 0 ^8.13 ] -3-Hexadecene 11-ethyl-pentacyclo [8.4.0.1 ^2.5 . 1
^9.12 . 0 ^8.13 ] -3-Hexadecene 10,11-dimethyl-pentacyclo [8.4.0.1
^2.5 . ^19.12 . 0 ^8.13 ] -3-Hexadecene.

Pentacyclo [6.6.1.1 ^3.6 . 0
^2.7 . ^0.94 ] -4-hexadecene derivative, for example, the following formula (9)

Embedded image Pentacyclo [6.6.1.1 ^3.6 .
0 ^2.7 . 0 ^9.14 ] -4-Hexadecene derivative. In particular, pentacyclo [6.6.1.1 ^3.6 . 0 ^2.7 . 0 ^9.14 ]-
4-hexadecene 1,3-dimethylpentacyclo [6.6.1.1 ^3.6 .
0 ^2.7 . 0 ^9.14] -4-hexadecene 1,6-dimethyl-pent cyclo [6.6.1.1 ^3.6.
0 ^2.7 . 0 ^9.14 ] -4-Hexadecene 15,16-dimethylpentacyclo [6.6.1.1]
^3.6 . 0 ^2.7 . 0 ^9.14 ] -4-Hexadecene.

Hexacyclo [6.6.1.1 ^3.6 . 1
^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene derivative,
For example, the following formula (10)

Embedded image Hexacyclo [6.6.1.1 ^3.6 . 1
^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene derivative.
In particular, hexacyclo [6.6.1.1 ^3.6 . 1 ^10.13 .
0 ^2.7 . 0 ^9.14] -4-heptadecene 12-methyl hexa cyclo [6.6.1.1 ^3.6. 1
^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene 12-ethylhexanoate cyclo [6.6.1.1 ^3.6. 1
^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene 12-isobutyl hexamethylene cyclo [6.6.1.1 ^3.6.
1 ^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene 1,6,10- trimethyl-12-isobutyl hexamethylene cyclo [6.6.1.1 ^{3. 6.} 1 ^10.13 . 0 ^2.7 .
0 ^9.14 ] -4-Heptadecene.

Heptacyclo [8.7.0.1 ^2.9 . 1
^4.7 . 1 ^11.17 . 0 ^3.8 . 0 ^12.16 ] -5-Eicosene derivative, for example, the following formula (11)

Embedded imageHeptacyclo [8.7.0.1]^2.9.
1^4.7. 1^11.17. 0^3.8. 0 ^12.16] -5-Eikose
Derivatives. In particular, heptacyclo [8.7.0.1^2.9.
1^4.7. 1^11.17. 0^3.8. 0^12.16] -5-Eikose
N.

Heptacyclo [8.7.0.1 ^3.6 . 1
^10.17 . 1 ^12.15 . 0 ^2.7 . 0 ^11.16 ] -4-Eicosene derivative, for example, the following formula (12)

Embedded image Heptacyclo [8.7.0.1 ^3.6 . 1
^10.17 . 1 ^12.15 . 0 ^2.7 . 0 ^11.16 ] -4-Eicosene derivative. In particular, heptacyclo [8.7.0.1 ^3.6 .
1 ^10.17 . 1 ^12.15 . 0 ^2.7 . 0 ^11.16 ] -4-eicosene dimethyl-substituted heptacyclo [8.7.0.1 ^3.6 . 1
^10.17 . 1 ^12.15 . 0 ^2.7 . 0 ^11.16 ] -4-Eikosen.

Heptacyclo [8.8.0.1 ^2.9 . 1
^4.7 . 1 ^11.18 . 0 ^3.8 . ^12.17 ] -5-heneicosene derivative, for example, the following formula (13)

Embedded imageHeptacyclo [8.8.0.1]^2.9.
1^4.7. 1^11.18. 0^3.8. 0 ^12.17] -5-Henei
Cosene derivative. In particular, heptacyclo [8.8.0.1
^2.9. 1^4.7. 1^11.18. 0^3.8. 0^12.17] -5-f
Eikosen.

Heptacyclo [8.8.0.1 ^4.7 . 1
^11.18 . 1 ^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-heneicosene derivative, for example, the following formula (14)

Embedded image Heptacyclo [8.8.0.1 ^4.7 . 1
^11.18 . 1 ^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-heneicosene derivative. In particular, heptacyclo [8.8.0.1
^4.7 . 1 ^11.18 . 1 ^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-
Hene eicosene 15-methyl-heptacyclo [8.8.0.1 ^4.7 . 1
^11.18 . 1 ^13.16 . 0 ^3.8. 0 ^12.17 ] -5-heneicosene trimethyl-substituted heptacyclo [8.8.0.1 ^4.7 . 1
^11.18 . 1 ^13.16 . 0 ^3.8. 0 ^12.17 ] -5-Hen Eikosen.

Octacyclo [8.8.0.1 ^2.9 . 1
^4.7 . 1 ^11.18 . 1 ^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-
Docosene derivative, for example, the following formula (15)

Embedded imageOctacyclo [8.8.0.1^2.9.
1^4.7. 1^11.18. 1^13.16. 0^3.8. 0^12.17] -5
-Dococene derivatives. In particular, octacyclo [8.8.0.
1^2.9. 1^4.7. 1^11.18. 1^13.16. 0^3.8. 0
^12.17] -5-Dococene 15-methyloctacyclo [8.8.0.1^2.9. 1
^4.7. 1^11.18. 1^13.16. 0^3.8. 0^12.17] -5
Docosene 15-ethyloctacyclo [8.8.0.1^2.9. 1
^4.7. 1^11.18. 0^13.16. 0^3.8. 0^12.17] -5
Docosen.

Nonacyclo [10.9.1.1 ^4.7 . 1
^13.20 . 1 ^15.18 . 0 ^2.10 . 0 ^3.8 . 0 ^12.21 . 0
^14.19 ] -5-Pentacocene derivative, for example, the following formula (1
6)

Embedded image Nonacyclo [10.9.1.1 ^4.7 . 1
^13.20 . 1 ^15.18 . 0 ^2.10 . 0 ^3.8 . 0 ^12.21 . 0
^14.19 ] -5-Pentacocene derivative. In particular, nonacyclo [10.9.1.1 ^4.7 . 1 ^13.20 . 1 ^15.18 . 0
^2.10 . 0 ^3.8 . 0 ^12.21 . 0 ^14.19 ] -5-Pentacosendrimethyl-substituted nonacyclo [10.9.1.1 ^4.7 . 1
^13.20 . 1 ^15.18 . 0 ^{2. 10} . 0 ^3.8 . 0 ^12.21 . 0
^14.19 ] -5-Pentacocene.

Nonacyclo [10.10.1.1]^5.8. 1
^14.21. 1^16.19. 0^2.11. 0^4.9 . 0^13.22. 0
^15.20] -6-hexacocene derivative, for example, the following formula
(17)

Embedded imageNonacyclo [10.10.1.1 represented by^5.8. 1
^14.21. 1^16.19. 0^2.11 . 0^4.9. 0^13.22. 0
^15.20] -6-hexacocene derivative. In particular, nonacyclo
[10.10.1.1^5.8. 1^14.21. 1^16.19. 0
^2.11 . 0^4.9. 0^13.22. 0^15.20] -6-Hexacose
N.

Other examples of cyclic olefins include the following. 5-phenyl-bicyclo [2.2.1] hept-2-ene 5-methyl-5-phenyl [2.2.1] hept-2-
Ene 5-benzyl-bicyclo [2.2.1] hept-2-ene 5-tolyl-bicyclo [2.2.1] hept-2-ene 5- (ethylphenyl) -bicyclo [2.2.1] Hept-2-ene 5- (isopropylphenyl) -bicyclo [2.2.
1] hept-2-ene 5- (biphenyl) -bicyclo [2.2.1] hept-
2-ene 5- (β-naphthyl) -bicyclo [2.2.1] hept-2-ene 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-ene 5- (anthracenyl) -Bicyclo [2.2.1] hept-2-ene 5,6-diphenyl-bicyclo [2.2.1] hept-
2-ene cyclopentadiene-acenaphthylene adduct 1,4-methano-1,4,4a, 9a-tetrahydrofluorene 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene 8-phenyl- Tetracyclo [4.4.0.1 ^2.5 . 1
^7.10 ] -3-Dodecene 8-methyl-8-phenyl-tetracyclo [4.4.
0.1 ^2.5 . 1 ^7.10 ] -3-Dodecene 8-benzyl-tetracyclo [4.4.0.1 ^2.5 . 1
^7.10 ] -3-Dodecene 8-tolyl-tetracyclo [4.4.0.1 ^2.5 . 1
^7.10 ] -3-Dodecene 8- (ethylphenyl) -tetracyclo [4.4.0.
^12.5 . ^17.10 ] -3-Dodecene 8- (isopropylphenyl) -tetracyclo [4.
4.0.1 ^2.5 . 1 ^7.10 ] -3-Dodecene 8,9-diphenyl-tetracyclo [4.4.0.1
^2.5 . 1 ^7.10 ] -3-Dodecene 8- (biphenyl) tetracyclo [4.4.0.
^12.5 . 1 ^7.10 ] -3-Dodecene 8- (β-naphthyl) tetracyclo [4.4.0.1
^2.5 . 1 ^7.10 ] -3-Dodecene 8- (α-naphthyl) -tetracyclo [4.4.0.1
^2.5 . ^17.10 ] -3-Dodecene 8- (anthracenyl) -tetracyclo [4.4.0.
^12.5 . 1 ^7.10 ] -3-Dodecene (cyclopentadiene-acenaphthylene adduct) further added with cyclopentadiene 11,12-benzo-pentacyclo [6.5.1.1]
^3.6 . 0 ^2.7 . 0 ^9.13 ] -4-Pentadecene 11,12-benzo-pentacyclo [6.6.1.1]
^3.6 . 0 ^2.7 . 0 ^9.14] -4-hexadecene 11-phenyl - hexacyclo [6.6.1.1 ^3.6.
1 ^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene 14,15 benzo - heptacyclo [8.7.0.1
^2.9 . 1 ^4.7 . 1 ^11.17 . 0 ^3.8 . 0 ^12.16 -5-eikosen]

This copolymer (COC) has a content of 10 to 50.
It should be derived from mol%, in particular 20 to 48 mol%, of cyclic olefins and the balance ethylene and should have a glass transition point of from 5 to 200 ° C, in particular from 40 to 190 ° C.

The molecular weight of this copolymer is not particularly limited, but it is 0.1 to 5 dl when measured in decalin at 135 ° C.
/ G of intrinsic viscosity [η], and its crystallinity is generally 10% or less, as measured by X-ray diffraction.
In particular, it is 5% or less.

The above copolymer (COC) can be obtained by randomly polymerizing an olefin and a cyclic olefin in the presence of a known vanadium catalyst or metallocene catalyst.

A suitable copolymer (COC) is available from Mitsui Petrochemical Co., Ltd. under the trade name APEL.

As the olefin resin, olefin homopolymers and copolymers used in the production of containers and other resin molded products are preferably used. For example, low-density, medium-density or high-density polyethylene, linear low-density polyethylene, polypropylene, polybutene-1, polypentene-1, poly-4-methylpentene-1, propylene-ethylene copolymer, ionomer, ethylene-acryl copolymer Examples thereof include polymers and ethylene-vinyl acetate copolymers. Of course, these olefin resins can be used alone or in combination of two or more kinds.

These olefin-based resins generally have a viscosity of 0.
1 to 50g / 10min, especially 0.2 to 30g / 1
It preferably has an MFR (melt flow rate) of 0 min, and an extrusion grade or an injection grade can be appropriately selected and used according to the molding method.

Various olefin resins can be used in the container of the present invention depending on the purpose. For applications requiring light extrudability, ethylene-vinyl acetate copolymer (EVA) as an olefin resin, particularly one having a vinyl acetate content of 0.5 to 20% by weight, low-density polyethylene, wire Low density polyethylene is suitable.

When an ethylene polymer polymerized by using a metallocene catalyst, particularly a copolymer of ethylene and an α-olefin having 6 to 20 carbon atoms, is used as the olefin resin, an aromatic component and water vapor can be obtained. A collapsible multi-layer container having an excellent barrier property against is obtained. Suitable olefinic resins include α-olefins such as 1-octene
To 25 wt% ethylene-based copolymer, which is the Dow Chemical Company.
Available under the trade name AFFINITY.

Compounding agents known per se, such as pigments, fillers, antioxidants, lubricants, stabilizers, ultraviolet absorbers, etc., may be compounded in the above-mentioned olefin resin according to a formulation known per se.

The container of the present invention is 100 to 1 as a whole.
000 μm, in particular 150 to 650 μm in thickness, and a thickness ratio of inner layer: middle layer: outer layer of 2 to 96: 2.
~ 30: 2-96, especially 20-70: 3-20: 20-
It is preferably in the range of 70.

In the present invention, the oxygen permeability coefficient (PO ₂ ) is 5.5 × 10 ^{−12 from} the viewpoint of the storability and aroma retention of the contents.
cc · cm / cm ² · sec · cmHg (37 ° C, 0% RH) or less, especially 4.5 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less, thermoplastic resin alone or resin It is desirable to use the blend of 1) as the oxygen barrier resin.

The most preferable example of such a resin is
Examples thereof include ethylene-vinyl alcohol copolymers, particularly those having a vinyl alcohol unit content of 40 to 85 mol%, particularly 50 to 80 mol%. Such an ethylene-vinyl alcohol copolymer is obtained by copolymerizing ethylene or a combination of most of ethylene with a small amount of another olefin such as propylene, and a vinyl ester of a lower fatty acid such as vinyl formate, vinyl acetate or vinyl propionate. It is obtained by saponifying a polymer, particularly an ethylene-vinyl acetate copolymer, so that the degree of saponification becomes 96% or more, particularly 99% or more.

Other examples of the oxygen barrier resin include nylon resins, particularly nylon 6, nylon 8 and nylon 1.
1, nylon 12, nylon 6,6, nylon 6,1
0, nylon 10,6, nylon 6 / 6,6 copolymer,
Partially aromatic polyamide and the like can be mentioned.

As the partially aromatic polyamide, a substantially amorphous copolyamide having a dibasic acid component in combination with a terephthalic acid component and an isophthalic acid component in an amount larger than that of the terephthalic acid component is preferably used. .

As the diamine component in this partially aromatic copolymerized polyamide, an aliphatic diamine component, particularly a carbon number of 4 is used.
-25, preferably 6-18 linear branched alkylenediamine component units are used, and specific examples of the alkylenediamine component units include, for example, 1,4-diamino-1,1-dimethylbutane, 1, 4-diamino-1,1-ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1 ,Four-
Diamino-2,3-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,6-diamino-2,5- Dimethylhexane, 1,6-diamino-2,4-dimethylhexane,
1,6-diamino-3,3-dimethylhexane, 1,6-diamino-
2,2-Dimethylhexane, 1,9-diaminononane, 1,6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,
4,4-trimethylhexane, 1,7-diamino-2,3-dimethylheptane, 1,7-diamino-2,4-dimethylheptane, 1,
7-diamino-2,5-dimethylheptane, 1,7-diamino-2,2
-Dimethylheptane, 1,10-diaminodecane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane,
1,8-diamino-3,4-dimethyloctane, 1,8-diamino-
4,5-Dimethyloctane, 1,8-Diamino-2,2-dimethyloctane, 1,8-Diamino-3,3-dimethyloctane, 1,8-
Diamino-4,4-dimethyloctane, 1,6-diamino-2,4-
Diethylhexane, 1,9-diamino-5-methylnonane,
Examples of such components include 1,11-diaminoundecane and 1,12-diaminododecane. Among these, especially 1,6-diaminohexane, 1,8-diaminooctane, 1,
Ingredients such as 10-diaminodecane and 1,12-diaminododecane, or a mixture thereof are preferable.

In this copolyamide, the isophthalic acid component and the terephthalic acid component are 99: 1 to 65:
The aromatic dicarboxylic acid component other than the isophthalic acid and terephthalic acid components, such as phthalic acid, should be present in a molar ratio of 35, and generally in an amount of 15 mol% or less based on the above two components, as long as the essence thereof is not impaired. It may contain components such as 2-methylterephthalic acid and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acid components such as adipic acid, sebacic acid, or polyvalent carboxylic acid components such as trimellitic acid and pyromellitic acid. Further, in addition to the aliphatic diamine component, a small amount of an alicyclic diamine component, an araliphatic diamine, or the like may be contained as long as the essence is not impaired.

The copolyamide should have a molecular weight sufficient to form a film, and the intrinsic viscosity [η] measured in concentrated sulfuric acid at a temperature of 30 ° C. is preferably 0.5 dl / g or more. .

Further, high nitrile resin, vinylidene chloride resin, vinyl chloride resin and the like can be used for the purpose of the present invention.

The oxygen barrier resin can be used in the form of a so-called blend, for example, a blend of an ethylene-vinyl alcohol copolymer and a nylon resin can be used. Polymers and other resins such as polyethylene and ethylene-
Vinyl acetate copolymers or blends with ionomers can also be used for the purposes of the present invention, provided that the oxygen transmission coefficient is within the above range.

When there is no interlayer adhesion between the oxygen barrier resin and the moisture resistant resin, an adhesive layer is interposed between both resin layers.

As the adhesive resin, any of the above-mentioned resins having adhesiveness to both the oxygen barrier thermoplastic resin and the olefin resin or the cyclic olefin copolymer is used. Such adhesive resins generally include free carboxylic acids, carboxylic acid salts, carboxylic acid esters, carboxylic acid amides, carboxylic acid anhydrides, and carbonates. Thermoplastic polymers or blends of these polymers with other thermoplastic polymers are used. The carbonyl group concentration in these thermoplastic polymers may vary, but generally the carbonyl group concentration is 10 to 1400 mmol / 100 g.
Polymers, especially those containing in a concentration of 30 to 1200 mmol / 100 g polymer are preferred.

Suitable adhesives are polyolefins modified with at least one ethylenically unsaturated monomer of unsaturated carboxylic acids, acid anhydrides, esters, amides, etc., especially maleic acid, acrylic acid, methacrylic acid. , Crotonic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, ethyl acrylate,
Methyl methacrylate, ethyl maleate, acrylic acid 2
-Ethylhexyl, acrylic acid amide, methacrylic acid amide, coconut oil fatty acid amide, maleimide-modified polypropylene, high-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, etc., and ethylene-acrylate copolymer They are a combination, an ionomer (Surrin A manufactured by DuPont), a polyalkylene oxide / polyester block copolymer, a carboxymethyl cellulose derivative or a blend of these with a polyolefin. It should be noted that any of these resins having a low carbonyl group content can be used as a moisture resistant resin itself.

In the container using the oxygen barrier resin intermediate layer, the total thickness and the thickness ratio of each layer should be within the above-mentioned range.
To 200 .mu.m, in particular 10 to 150 .mu.m, while the adhesive resin is preferably used in a thickness of 3 to 50 .mu.m, especially 5 to 30 .mu.m.

Each of these resins is melt-kneaded in a number of extruders corresponding to the type of the resin, and they are merged in a multilayer multiple die so as to have the above-mentioned multilayer structure, and then coextruded through a die orifice to form a multilayer. A parison having the constitution is obtained, and then blow molding is carried out in a split mold, and the bottom is pinched off to obtain a bottomed extrusion bottle. The bottom of the bottle is cut, the contents are filled, and the open end is heat-sealed to obtain a tube container. Alternatively, a multi-layered pipe may be extruded and cut into a container body, and the mouth may be separately manufactured by injection molding, compression molding, or the like, and joined by melt bonding or the like to form a tube container.

[0079]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following examples.

Resin: As a resin for a multi-layer tube, an innermost and outermost layer is an ethylene-vinyl acetate copolymer Lexulon manufactured by Nippon Petrochemical Co., Ltd. and an olefin resin polymerized by using a metallocene catalyst as an olefin resin AFFINI.
TY was used. An olefin and cyclic olefin copolymer resin Apel manufactured by Mitsui Petrochemical Co., Ltd. was used for the intermediate layer. Also, as a second intermediate layer component manufactured by Kuraray Co., Ltd.
An ethylene-vinyl alcohol copolymer resin was used. Particularly, only when the ethylene vinyl alcohol copolymer is used as the second intermediate layer component, the ethylene vinyl alcohol copolymer, the olefin resin and the cyclic olefin copolymer, and the ethylene vinyl alcohol copolymer and the olefin are used. Adhesive resin admers were used to obtain adhesiveness between resin systems.

Molding: Using four extruders and a multilayer die, a laminated parison was prepared in a temperature range of 250 to 270 ° C., a mold temperature was 20 ° C., a cooling time was 12 seconds, and a blow pressure was 2 k.
² g with an outer diameter of 30 mm and a length of 20 cm under the condition of g / cm 2.
Multi-layer tube of 3 layers of species and 6 layers of species 4 (content capacity 200c
c, surface area 105 cm ² ) was subjected to direct blow molding.

Evaluation: 1) Fragrance retention test A multi-layer tube of two types and three layers (layer structure is the same as in FIG. 3) and a tube having only a single layer of olefin resin were examined. As the fragrance component, two types of aromatic compounds, 2-phenylethanol (2-Phenylethanol) and phenylacetic acid methyl ester (PhenylaceticAcid Methyl Ester) manufactured by Tokyo Chemical Industry Co., Ltd. were used. This fragrance ingredient in special grade ethanol 1
60 ml in each tube after dissolution to a concentration of 0000 ppm
Accurately injected. After the injection, the injection port was heat-sealed and sealed. A set of 4 tubes, total volume of 1350 ml
It was stored in a sealed flask with a septum. The storage temperature was 55 ° C. Seven days after the start of storage, 1 ml of gas was collected from the headspace portion outside the tube and inside the glass flask with a gas tight syringe and used for gas chromatography analysis. Gas chromatography (GC) was carried out using Shimadzu Corporation GC-9A with a PEG, 20M, 25m column, split ratio 1: 2, temperature range from 120 ° C to 250 ° C, sound speed 10 ° C / min. Was analyzed under the following conditions. Ph
enylacetic Acid Methyl Ester and 2-Phenylethanol
Have retention times of 2.7 min and 3.3, respectively.
min.

2) Water Vapor Permeability Test The prepared two-kind three-layer multi-layer tube and the olefin resin single-layer tube were used. The tube body was unsealed to obtain a rectangular test piece, and MOCON Permatran-W3 /
30 degree steam permeation tester, 40 ℃ constant temperature, 90% RH
Below, the value at the time when the amount of water vapor permeation was saturated was determined.

3) Oxygen Gas Permeability Test Similar to the water vapor permeability test, the tube was opened to obtain a rectangular test piece, which was kept at a constant temperature of 30 ° C. in an OX-TRAN2 / 20 type oxygen gas permeation tester manufactured by MOCON. 80% RH
Below, the value at the point where the oxygen gas permeation amount was saturated was determined.

Example 1 A polyolefin AFFINITY polymerized with a metallocene catalyst was used for the inner and outer layers, and the layer ratio of olefin and cyclic olefin copolymer resin in the middle layer was 5: 1: 5 and the wall thickness was 250 μm. A seed three-layer multi-layer tube was produced (Example 1-1) (layer structure is FIG. 3).

Similarly, an ethylene vinyl acetate copolymer resin was used for the inner and outer layers, and an olefin and cyclic olefin copolymer was used for the intermediate layer, and the layer ratio was 5: 1: 5. A multilayer tube was produced (Example 1-2) (layer structure is FIG. 3).

For comparison, a polyolefin AFFINITY single-layer tube polymerized by using a metallocene catalyst (Comparative Example 1), an ethylene vinyl acetate copolymer resin single-layer tube (Comparative Example 2), and an olefin and a ring in the innermost layer. A two-kind two-layer multi-layer tube having an olefin copolymer resin (Apel) and an olefin AFFINITY polymerized using a metallocene catalyst in the outer layer and having a layer ratio of 1:30 and a wall thickness of 300 μm was prepared (Comparative Example 3). .

Squeezeability was confirmed in all the molded tubes, and the result was that the flexibility was good.

To each of these tubes, 60 ml of the test solution in which the fragrance component was dissolved was poured, and after heat sealing, four tubes were set as one set and stored in a sealed glass flask container with a septum and a volume of 1350 ml. Seven days after the start of storage, a gas tight syringe was used to collect 1 ml of gas from the space outside the tube and inside the glass container, and GC
Analysis was carried out.

Further, the heat seal suitability for conducting this test was also examined. In tube molding, the bottom of a cylindrical blow product is flattened and heat sealed. Here, it was judged whether or not craze and whitening occurred in the deformed portion during crushing in this step. The gas analysis results and sealing suitability are shown in Table-1.

Polymerization was carried out using a multi-layer tube (Example 1-2) having an ethylene-vinyl acetate copolymer resin in the inner and outer layers and an olefin-cyclic olefin copolymer in the middle layer, and a metallocene catalyst in the inner and outer layers. Olefin AFFIN
In the fragrance test for multi-layer tubes having TY and olefin-cyclic olefin copolymer in the middle layer (Example 1-1) and respective inner and outer layer resin single layer tubes (Comparative Examples 1 and 2), From the obtained gas chromatogram, a remarkable difference in the aroma component barrier due to the intermediate layer resin was confirmed. The obtained chromatogram is shown in FIG.

Comparative Example 1 and Comparative Example 2 In the single layer tube,
The peak of 2-phenylethanol (3.3) is particularly large and the peak of phenylacetic acid methyl ester (2.7) is also large, whereas Examples 1-1 and 1 are used.
In the -2 multilayer tube, these peaks were significantly reduced. Further, while the gas component judged to be derived from the olefin-cyclic olefin copolymer was observed in Example 1-2, it was scarcely observed in Example 1-1, and the olefin-cyclic olefin copolymer was hardly observed. It was found that it is more preferable to use the resin for the inner and outer layers as in Example 1-1 when a multilayer tube having the intermediate layer as the intermediate layer is molded.

Also, 60 ml of olive oil was injected into each tube, heat sealed and stored at room temperature for 1 month.
The appearance was observed. The results are shown in Table 1. In this case, the presence or absence of oil resistance was judged by the occurrence of crazes and cracks due to the oil and fat component.

From Table 1, it is seen that the aroma retaining property is better in the two-kind three-layer multilayer tube (Examples 1-1 and 1-2) having an olefin and a cyclic olefin copolymer in the intermediate layer than in the single-layer tube. Met. On the other hand, the type 2 two-layer multi-layer tube (Comparative Example 3) having a copolymer of olefin and cyclic olefin in the inner layer thereof generated craze in the crushing step during heat sealing, and was not suitable for sealing. Not included in the fragrance test. From this result, it was determined that the resin-made multilayer tube of Comparative Example 3 was not suitable for tube molding.
Also, from the result of appearance observation after filling with olive oil, the multi-layer tube of Comparative Example 3 had whitening and craze on the entire surface including the seal portion, and oil resistance was not obtained.

Next, olefin AFFINITY polymerized using a metallocene catalyst was used for the inner and outer layers, and a copolymer resin of olefin and cyclic olefin was used for the intermediate layer.
Three-kind three-layer multi-layer tube (Example 1-1), two-kind three-layer multi-layer tube (Example 1-2) using ethylene-vinyl acetate copolymer resin for inner and outer layers, and polyolefin AFFINITY polymerized using a metallocene catalyst. Table 2 shows the results of the water vapor permeability test using cut-out pieces of the single-layer tube (Comparative Example 1) and the ethylene-vinyl acetate copolymer resin single-layer tube (Comparative Example 2). From Table-2, in any of the configurations, the two-layer, three-layer multilayer tube showed high water vapor barrier property.

From the above results, when molding a tube having an aroma retaining property, an oil resistance and a high water vapor barrier property, a copolymer resin of an olefin and a cyclic olefin is used as an intermediate layer, and other inner and outer layers are used. It was judged that a multilayer structure sandwiched with an olefin resin is suitable.

Example 2 In addition to Example 1, ethylene-
Using a vinyl alcohol copolymer resin, the layer structure from the content side to the outer layer side is olefin resin / olefin-
Cyclic olefin copolymer resin / adhesive layer / ethylene-vinyl alcohol copolymer resin / adhesive layer / olefin resin, the layer ratio of which is 40/10 / 2.5 / 5 / 2.5 /
40 multi-walled tubes of 4 types and 6 layers having a thickness of about 600 μm (Example 2-1) (layer structure is FIG. 4) and the layer structure is olefin / adhesive layer / ethylene-vinyl alcohol copolymer resin / adhesive layer / Olefin-Cyclic Olefin Copolymer Resin /
With olefins, this layer ratio is 40 / 2.5 / 5 / 2.5 /
A four-kind six-layer multilayer tube (Example 2-2) having a wall thickness of about 60 μm and a thickness of 10/40 (the layer structure is the reverse of that of FIG. 3) was produced.

Each of the obtained tubes had a squeeze property and showed flexibility. Further, when an oxygen gas permeability test under 80% RH was conducted, Examples 2-1 and 2-
2 both showed an oxygen permeation amount of 1.5 cc / m ² · day · atm or less, and confirmed the oxygen barrier property. Further, suitability for heat sealing was confirmed as in Example 1. Therefore, it was judged to be useful as a tube for contents which requires oxygen gas barrier properties in addition to aroma retaining properties and water vapor barrier properties.

[0099]

[Table 1] A: Phenylacetic Acid Methy Ester B: 2-Phenylethanol ○: Good △: Poor ×: Not suitable

[0100]

[Table 2]

Example 3 Polypropylene (Mitsui Petrochemical Co., Ltd., Hypol B-278) was used for the inner and outer layers, and the layer ratio of olefin and cyclic olefin copolymer resin for the intermediate layer was used in the same manner as in Example 1. Was 5: 1: 5 and the wall thickness was 510 μm, and a two-kind three-layer bottle (content volume 200 cc, surface area 95 cm ² ) was prepared (Example 3). However, the die is 230-250 ℃
Temperature range. For comparison, a bottle of polypropylene alone (wall thickness 490 μm) was also manufactured (Comparative Example 4).
The results are shown in Table-3.

[0102]

[Table 3] Polypropylene multi-layer bottles are also excellent in aroma retention and oil resistance.

[0103]

INDUSTRIAL APPLICABILITY According to the present invention, by using an amorphous or low crystalline copolymer of olefin and cyclic olefin as an intermediate layer for the inner and outer layers of the olefin resin, the content resistance and heat sealability are improved. It was possible to remarkably improve the fragrance-retaining property and the water-retaining property of this container while maintaining the excellent level of the above.

[Brief description of the drawings]

FIG. 1 is a side view showing an example of the container of the present invention.

FIG. 2 is a side view showing another example of the container of the present invention.

FIG. 3 is an enlarged sectional view showing an example of a sectional structure of a body portion.

FIG. 4 is a cross-sectional view showing, in an enlarged manner, another example of the cross-sectional structure of the body.

FIG. 5 is an enlarged sectional view showing still another example of the sectional structure of the body portion.

FIG. 6 is a gas chromatogram of gas that has permeated from the containers of Examples and Comparative Examples.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Tubular container 2 Lid 3 Extrusion port with screw 4 Conical shoulder 5 Body 6 Cut edge 7 Closed bottom 10 Bottle-shaped container 11 Inner layer 12 Intermediate layer (first intermediate layer) 13 Outer layer 14 Gas barrier property Second intermediate layer containing thermoplastic resin 15 Adhesive layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 23/00 LBZ C08L 23/00 LBZ 45/00 LKB 45/00 LKB

Claims (9)

[Claims] 1. An inner and outer layer containing an olefin resin, and an intermediate layer containing an amorphous or low crystalline copolymer of an olefin and a cyclic olefin. Fragrant multi-layer container. 2. An inner and outer layer containing an olefin resin, a first intermediate layer containing an amorphous or low crystalline copolymer of an olefin and a cyclic olefin, and an oxygen barrier thermoplastic resin. An aroma retaining multilayer container comprising a second intermediate layer containing a resin. 3. The amorphous or low crystalline copolymer of olefin and cyclic olefin is derived from 10 to 50 mol% of cyclic olefin and the balance of ethylene and has a glass transition point of 5 to 200 ° C. The aroma retaining multilayer container according to claim 1 or 2, which is a copolymer. 4. The fragrance-retaining multilayer container according to claim 1, wherein the olefin resin is polyethylene or an ethylene copolymer. 5. The aromatizing multilayer container according to claim 1, wherein the olefin resin is an ethylene polymer polymerized by using a metallocene catalyst. 6. The aromatizing multilayer container according to claim 1, wherein the olefin resin is polypropylene or a propylene copolymer. 7. The container is generally 100 to 100
The aroma retaining multilayer container according to claim 1, which has a container wall having a thickness of 0 μm and has a thickness ratio of inner layer: middle layer: outer layer within a range of 2 to 96: 2 to 30: 2 to 96. 8. The container is generally 100 to 100
It has a wall thickness of 0 μm, and the thickness ratio of inner layer: first intermediate layer: second intermediate layer: outer layer is 2 to 94: 2 to 30: 2 to 3.
The aroma retaining multilayer container according to claim 2, which is in the range of 0: 2 to 94. 9. The container comprises an inner and outer layer containing an olefin resin, an intermediate layer containing an amorphous or low crystalline copolymer of an olefin and a cyclic olefin, or an oxygen barrier. The multi-layer fragrance container according to claim 1 or 2, which is formed by melt blow molding of a multi-layer parison having a second intermediate layer containing a water-soluble thermoplastic resin.