JPH1059345A - Scent-retentive multilayer plastic container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a scent-retentive multilayer plastic container that is formed of a laminate of middle layers made of a cyclic olefin copolymer and inner and outer layers made of a linear olefin resin with adhesives in between and whose degradation in adhesion with a lapse of time after filing of scent component is effective dissolved. SOLUTION: A multilayer plastic container has inner and outer layers made of a linear olefin copolymer and middle layers made of a cyclic olefin co-polymer and they are laminated with adhesive resin layers in between. The adhesive resin is made of an ultra-low density linear polyethylene or its acid-modified compound with a density of 0.910-0.800g/cm<3> , that is obtained by copolymerizing ethylene and an α-olefin of 4-20% mol per resin.

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-retaining plastic container, and more particularly to an intermediate layer comprising a cyclic olefin copolymer and an inner / outer layer comprising a linear olefin resin and having an aroma component. The present invention relates to a scent-retaining plastic multilayer container in which deterioration of interlayer adhesiveness is prevented when contents are filled.

[0002]

2. Description of the Related Art Plastic multilayer containers are used for toothpaste,
Cosmetics, toiletry products, various chemicals, glue or adhesive,
It is widely used as a packaging container for storing various contents such as highly viscous seasonings and foods.

In this multilayer container, various plastic materials are used in combination in order to satisfy moldability, manufacturing cost, and various characteristics required for preserving the contents. In many cases, a linear olefin resin such as polyethylene or polypropylene is used from the viewpoints of moldability, hygienic properties, and cost.

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).

It is already known to produce a multilayer container by utilizing the fact that a cyclic olefin-based copolymer has excellent moisture permeability. For example, Japanese Patent Application Laid-Open No. 4-276
No. 253 describes a container for medical or food packaging, wherein the container has a wall having a multilayer structure including two layers of different materials, at least one of which is made of a thermoplastic norbornene-based polymer. Have been. It is also described that a polypropylene modified with chlorinated or maleic anhydride is used for bonding these layers.

JP-A-7-52340 discloses that in a multilayer plastic container having a structure in which at least two or more resin layers are laminated, an outer layer is a non-crystalline resin obtained by copolymerizing a cyclic olefin and ethylene, and an inner layer is formed. Is a polyolefin resin. It also describes that an acid-modified ethylene-α-olefin copolymer is used for adhesion between layers.

JP-A-7-266517 discloses that a cyclic olefin component of 5 to 60
A moisture-proof multi-layer extruded structure having excellent impact resistance and comprising at least three resin layers, wherein a polyolefin resin layer containing mol% is interposed is described. This known example also describes the use of an acid-modified olefin resin for interlayer adhesion.

[0008]

SUMMARY OF THE INVENTION The present inventors have previously described
When a cyclic olefin-based copolymer is used as an intermediate layer of a thermoplastic resin such as a normal olefin-based resin, it is possible to improve the fragrance retention and the like of a container without adversely affecting content resistance and sealing properties. (Patent pending).

[0009] However, when a content containing an aroma component is filled in a multilayer container having a cyclic olefin-based copolymer as an intermediate layer and a linear olefin-based resin as an inner and outer layer, and this is aged, the interlayer adhesion is reduced. It turned out that it deteriorated remarkably. That is, the cyclic olefin-based copolymer and the linear olefin-based resin have poor adhesiveness, and an adhesive resin is interposed between the two resin layers, as described in the above-mentioned prior art. Even if the adhesive resin used has a high adhesive strength before filling with the fragrant content, if the aging is performed after filling, the adhesive strength is significantly reduced and delamination occurs.

[0010] Despite the small amount of odorous components contained in the contents, the occurrence of delamination of the laminate gives a very strange feeling, which is present as an intermediate layer. The cyclic olefin-based copolymer has a large barrier property to the odorous component, and the fragrance component permeating the inner layer of the linear olefin-based resin acts on the interface between the cyclic olefin-based copolymer and the adhesive resin to form an adhesive. It is considered to cause deterioration.

When the present inventors select a specific ethylene-α-olefin copolymer as an adhesive resin between a cyclic olefin-based copolymer and a linear olefin-based resin, the adhesion deterioration due to the odorous component is reduced. It was found that it was effectively resolved.

That is, an object of the present invention is to provide a multilayer plastic container in which an intermediate layer made of a cyclic olefin-based copolymer and an inner and outer layer of a linear olefin-based resin are joined via an adhesive, and an odorous component is eliminated. It is an object of the present invention to provide a multi-layered fragrance-retaining plastic container in which the deterioration of adhesion when filled and aged is effectively eliminated.

[0013]

According to the present invention, a linear
Inner / outer layer made of olefin resin and cyclic olefin resin
An intermediate layer made of a copolymer is provided via an adhesive resin layer.
In a plastic multilayer container made of
4 to 20 mol% of α-olefin per ethylene and resin
And the density obtained by copolymerizing the compound is 0.910 to 0.1.
800 g / cm ^ThreeLinear ultra low density polyethylene or
A fragrance-retaining plastic, comprising an acid-modified product of
A multi-layer container is provided.

In the scent-retaining multilayer plastic container of the present invention: 1. The α-olefin constituting the linear ultra-low density polyethylene is an α-olefin having 4 to 8 carbon atoms; 2. The acid-modified product of the linear ultra-low density polyethylene is obtained by grafting 0.1 to 0.4 mol% of maleic anhydride per linear low-density polyethylene. 3. The linear ultra low density polyethylene or its acid-modified product has a melt flow rate of 0.4 to 30 g / 10 min. 2. The multilayer plastic container according to claim 1, wherein the linear olefin resin is polyethylene, polypropylene or a crystalline ethylene / propylene copolymer. 5. 10 to 50% by weight of cyclic olefin copolymer
5. a copolymer containing a cyclic olefin unit of 6. the cyclic olefin-based copolymer is a cyclic olefin-based copolymer having a glass transition point (Tg) of 60 ° C. or higher; The total thickness of the container is 100 to 1000 μm, the ratio of the total thickness of the inner and outer layers to the thickness of the intermediate layer of the cyclic olefin copolymer is 99: 1 to 70:30, and the thickness of the adhesive layer is 7. 3 to 40 μm; It is preferably a co-extrusion blow molded container.

In the present invention, among the ethylene-α-olefin copolymers, the density obtained by copolymerizing 6 to 20% by mole, particularly 10 to 20% by mole of α-olefin is 0.910 to 0%. .800 g / cm ³ , especially 0.
By selecting a linear ultra-low density polyethylene of 900 to 0.840 g / cm ³ or an acid-modified product thereof and using this for adhesion between the cyclic olefin copolymer and the linear olefin resin, the fragrance component is obtained. To prevent adhesive deterioration due to
The adhesive strength after aging can be kept at a high level.

The linear ultra-low density polyethylene (VLDPE) used in the present invention comprises a copolymer of ethylene and an α-olefin, like the generally known linear low-density polyethylene (LLDPE). Having a branched chain based on
It is intended to provide the above density range lower than LDPE. That is, generally, as the number of branched chains increases, the density decreases accordingly, and, for the same number of branched chains, as the length of the branched chains decreases, the density decreases. By using as an adhesive, it acts to effectively prevent deterioration by an odorous component at the bonding interface with the cyclic olefin-based copolymer.

See the example below. The content of α-olefin is lower than 6 mol% and the density is 0.910 g /
When an ethylene-α-olefin copolymer higher than ³ cm ³ is used as an adhesive (Comparative Examples 1 and 2), the initial peel strength is 2.0 kg / cm, which is satisfactory, but toothpaste filling is not sufficient. And the peel strength after aging decreases to almost zero. The same applies to the above-mentioned copolymer obtained by acid modification (Comparative Examples 3 and 4). In contrast, according to the present invention, when the content of α-olefin is 6 mol% or more,
When an ethylene-α-olefin copolymer having a density of 0.910 g / cm ³ or less was used as the adhesive (Examples 2 and 3), the peel strength after toothpaste filling and aging was still 1
kg / cm or more, especially when the content of α-olefin is 10 to 20 mol% and the density is 0.900 to 0.8
When 40 g / cm ³ of the ethylene-α-olefin copolymer was used as the adhesive (Examples 1, 4 and 5),
Peeling strength after toothpaste filling and aging is 2.0kg / cm
Is maintained above. The same is true for the above copolymer obtained by acid modification (Example 6).

In the case of a tube container for extruding the contents, a compressive deformation stress for extruding the contents is repeatedly applied at a time interval to the body of the container. The copolymer intermediate layer suppresses the permeation of the fragrance component and suppresses the delamination by the fragrance component, so that, together with light extrusion performance, excellent preservability of the contents can be obtained at the same time. .

[0019]

FIG. 1 shows an example of the multilayer container of the present invention.
The multilayer container comprises a tubular container 1 and a lid 2. The tubular container 1 has a threaded extrusion opening 3 integrally formed by parison hollow molding, and a conical shoulder portion 4 connected thereto. , And a thin cylindrical body 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 multilayer container of the present invention, this multilayer container comprises a bottle-shaped container 10 and a lid 2, and the bottle-shaped container 10 is integrally formed by hollow molding of a parison. It has a molded threaded mouth 3, a conical shoulder 4 connected thereto, a cylindrical body 5 and a closed bottom 7 formed by pinching off a parison. In this container, the contents are filled from the mouth part 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 5, this vessel wall is composed of an inner layer 11 made of a linear olefin resin, and an intermediate layer 12 containing a cyclic olefin copolymer. Outer layer 1 made of a linear olefin resin
3 is formed. Intermediate layer 12 and inner and outer layers 11, 1
3, adhesive layers 14 and 15 made of linear ultra-low density polyethylene are provided.

[Cyclic Olefin Copolymer] An amorphous to low crystalline copolymer of olefin and cyclic olefin (C
As the olefin from which OC) is derived, ethylene is preferable, and in addition, olefins having 3 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl1-pentene, and 1-decene are preferable. From 20 to 20 α-olefins are used alone or in combination with ethylene.

As the cyclic olefin, 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, but are not limited to, the following.

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, and 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-
Ene 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 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 derivatives; 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.

[0026] 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 [4.4.0.1
^2.5] -3-undecene 10-methyl-tricyclo [4.4.0.1 ^2.5] -3
Undesen.

[0027] tetracyclo [4.4.0.1 ^2.5. 1
^7.10 ] -3-Dodecene derivatives, for example, the following formula (4)

Embedded imageTetracyclo [4.4.0.1 represented by^2.5 .
1^7.10] -3-dodecene derivatives. In particular, tetracyclo [4.4.0.1^2.5 . 1^7.10] -3-do
Decene 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. Ten}] -3-dodecene 8-ethylidenetetracyclo [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-propylidenetetracyclo [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. Five} . 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. Five} . 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 ^9.13 ] -4-pentadecene derivative; for example, the following formula (5)

Embedded image Pentacyclo [6.5.1.1 ^3.6 .
0 ^2.7 . 0 ^9.13 ] -4-Pentadecene derivatives. 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-dimethylpentacyclo [6.5.1.1 ^3.6 .
0 ^2.7 . ^09.13 ] -4-pentadecene 14,15-dimethylpentacyclo [6.5.1.1
^3.6 . 0 ^2.7 . 0 ^9.13 ] -4-pentadecene.

[0029] pentacyclo [7.4.0.1 ^2.5. 1
^9.12 . 0 ^8.13 ] -3-pentadecene derivative, for example, the following formula (6)

Embedded image 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 equation (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.

[0031] 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 . ^09.14 ] -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-dimethylpentacyclo [6.6.1.1 ^3.6 .
0 ^2.7 . 0 ^9.14] -4-hexadecene 15,16-dimethyl-penta cyclo [6.6.1.1
^3.6 . 0 ^2.7 . ^09.14 ] -4-Hexadecene.

Hexacyclo [6.6.1.1 ^3.6 . 1
^10.13 . 0 ^2.7 . 0 ^9.14] -4-heptadecene derivatives,
For example, the following equation (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-isobutylhexacyclo [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 represented by^2.9.
1^4.7. 1^11.17. 0^3.8. 0 ^12.16] -5-eicose
Derivatives. In particular, heptacyclo [8.7.0.1^2.9. 1^4.7.
1^11.17. 0^3.8. 0^12.16] -5-eicosene.

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

Embedded imageHeptacyclo [8.7.0.1 represented by^3.6. 1
^10.17. 1^12.15. 0^2.7. 0^11.16] -4-Eicose
Derivatives. In particular, heptacyclo [8.7.0.1^3.6. 1^10.17. 1
^12.15. 0^2.7. 0^{11.1 6}] -4-Eicosene dimethyl-substituted heptacyclo [8.7.0.1^3.6. 1
^10.17. 1^12.15. 0 ^2.7. 0^11.16] -4-Eicose
N.

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

Embedded imageHeptacyclo [8.8.0.1 represented by^2.9.
1^4.7. 1^11.18. 0^3.8. 0 ^12.17] -5-Henei
Cocene derivatives. In particular, heptacyclo [8.8.0.1^2.9. 1^4.7.
1^11.18. 0^3.8. 0^12.17] -5-Hen eicosene.

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-Hyneeicosene derivative. In particular, heptacyclo [8.8.0.1 ^4.7 . 1 ^11.18 . 1
^13.16 . 0 ^3.8 . 0 ^{12.1 7]} -5-heneicosene 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-heneicosene.

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

Embedded image Octacyclo [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-docosene 15-methyloctacyclo [8.8.0.1 ^2.9 . 1
^4.7 . 1 ^11.18 . 1 ^13.16. 0 ^3.8 . 0 ^12.17 ] -5
Dococene 15-ethyloctacyclo [8.8.0.1 ^2.9 . 1
^4.7 . 1 ^11.18 . 0 ^{13 .16} . 0 ^3.8 . 0 ^12.17 ] -5
Dokosen.

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-Pentakocene derivative, for example, of the following formula (1
6)

Embedded imageNonacyclo [10.9.1.1] represented by^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
Pentacocene trimethyl-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
^15.206-hexacocene derivatives, for example,
(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^{Four .9}. 0^13.22. 0^15.20-6
-Hexacocene.

Other examples of cyclic olefins include
Can also be mentioned. 5-phenyl-bicyclo [2.2.1] hept-2-e
5-methyl-5-phenylbicyclo [2.2.1] hep
To-2-ene 5-benzyl-bicyclo [2.2.1] hept-2-e
5-tolyl-bicyclo [2.2.1] hept-2-ene 5- (ethylphenyl) -bicyclo [2.2.1] hep
To-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] hep
To-2-ene 5,6-diphenyl-bicyclo [2.2.1] hept-
2-ene cyclopentadiene-acenaphthylene adduct 1,4-methano-1,4,4a, 9a-tetrahydroph
Luorene 1,4-methano-1,4,4a, 5,10,10a-f
Xahydroanthracene 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.
1^2.5. 1^7.10] -3-Dodecene 8- (isopropylphenyl) -tetracyclo [4.
4.0.1.^2.5. 1^{7. Ten}] -3-dodecene 8,9-diphenyl-tetracyclo [4.4.0.1
^2.5. 1^7.10] -3-dodecene 8- (biphenyl) tetracyclo [4.4.0.
1^2.5. 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. 1^7.10] -3-Dodecene 8- (anthracenyl) -tetracyclo [4.4.0.
1^2.5. 1^7.10] -3-dodecene (cyclopentadiene-acenaphthylene adduct)
Compound to which lopentadiene is further added 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^{11.1 7}. 0^3.8. 0^12.16-5-A
Kosen]

This copolymer (COC) is 50 to 22
Mol%, in particular from 40 to 22 mol%, of cyclic olefins and the balance of ethylene and up to 200 ° C., in particular 1
It preferably has a glass transition point (Tg) of 50 to 60 ° C.

The molecular weight of the copolymer is not particularly limited, but is 0.1 to 5 dl 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-mentioned copolymer (COC) can be obtained by random polymerization of an olefin and a cyclic olefin in the presence of a vanadium catalyst or a metallocene catalyst known per se.

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

[Linear Olefin Resin] Examples of the olefin resin include low-, medium- or high-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, linear low-density polyethylene, and ethylene-propylene copolymer. Coalescence, polybutene-1,
Ethylene-butene-1 copolymer, propylene-butene-
1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ion-crosslinked olefin copolymer (ionomer), ethylene-acrylate copolymer, and the like. Among them, polyethylene and polypropylene are preferable, and as the polypropylene, a propylene homopolymer, a propylene-ethylene random copolymer, or a block copolymer is used.

The linear olefin resin is generally of an extrusion grade, for example, polyethylene is a melt index (ASTM D1238, 190 ° C.)
Is 0.001 to 2 g / 10 minutes, and the polypropylene has a melt index (ASTM D12).
38, 230 ° C.) of 0.05 to 5 g / 10 min.

The linear olefin-based resin may be blended with a compounding agent known per se, for example, a pigment, a filler, an antioxidant, a lubricant, a stabilizer, and an ultraviolet absorber according to a formulation known per se.

The olefin resin of the inner layer and the olefin resin of the outer layer are usually the same, but depending on the use of the container, the olefin resin of the inner layer and the olefin resin of the outer layer are different types. For example, as the outer layer resin, a resin having excellent gloss or a matting property can be used, and as the inner layer resin, a resin having excellent moldability can be used.

[Adhesive Layer] In the present invention, the density obtained by copolymerizing ethylene with 6 to 20 mol%, especially 10 to 20 mol% of α-olefin as an adhesive resin is 0.910 to 0. .800 g / cm ³ , especially 0.900
A linear ultra-low density polyethylene of 0.840 g / cm ³ or an acid-modified product thereof is used.

As the α-olefin, C 4 to C 8
Α-olefins such as butene-1, pentene-1, hexene-1, octene-1, 4-methylpentene-1 and the like are preferably used. As specific examples of the copolymer,
Ethylene-butene-1 copolymer, ethylene-pentene-
1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 copolymer, ethylene-4-methylpentene-1 copolymer, and the like, alone or as a blend of two or more. But also used.

Under the condition that the copolymerization ratio and the density of the α-olefin as a whole fall within the above ranges, the linear ultra-low-density polyethylene may be replaced with the ordinary linear low-density polyethylene (L
It should be understood that LDPE) can be used in blends.

The linear ultra-low-density polyethylene used as an adhesive has a melt index (ASTM D123).
8, 190 ° C.) is in the range of 0.4 to 30 g / 10 min, particularly 1 to 20 g / 10 min.

In the present invention, it is preferable to use linear ultra-low density polyethylene itself as an adhesive, but a graft copolymer obtained by grafting an unsaturated carboxylic acid or an anhydride thereof to linear ultra-low density polyethylene is used. You can also.

Examples of unsaturated carboxylic acids or anhydrides thereof include monocarboxylic acids such as acrylic acid and methacrylic acid, polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid, maleic anhydride, itaconic anhydride and the like. There are polycarboxylic anhydrides such as norbornene-2,3-dicarboxylic anhydride and monoesters of polycarboxylic acids such as monomethyl maleate, monoethyl maleate and monoisobutyl maleate. Of these, maleic anhydride is preferred.

The amount of the unsaturated carboxylic acid or its anhydride grafted is preferably in the range of 0.1 to 0.6 mol%, particularly 0.1 to 0.4 mol%, based on the linear ultra low density polyethylene. . Above the above range, the adhesive strength becomes saturated and constant.

[Layer Structure] The container of the present invention has a total thickness of 100 to 1000 μm, particularly 200 to 900 μm.
And the thickness of the intermediate layer of the cyclic olefin copolymer is preferably in the range of 5 to 30%, especially 10 to 25% of the total thickness in view of the properties of the container.

An inner layer made of a linear olefin resin,
The outer layer can be provided with the same thickness as each other,
From the viewpoint of the fragrance retention of the contents, it is preferable to provide the intermediate layer made of the cyclic olefin copolymer on the inner surface side, and in this case, the thickness ratio of the outer layer / inner layer is 50 to 99, especially 6
It is preferably in the range of 0 to 95.

The cyclic olefin-based copolymer layer has at least 25 μm, preferably 30 to 300 μm, from the viewpoint of fragrance retention.
It is preferable to have a thickness of m.

The adhesive layer preferably has a thickness of 3 to 40 μm, particularly 5 to 30 μm.

[Multilayer Plastic Container and Manufacturing Method] The plastic multilayer container of the present invention comprises a cyclic olefin copolymer serving as an intermediate layer, a linear olefin resin serving as an inner layer, an olefin resin serving as an outer layer, and an adhesive. The linear ultra-low-density polyethylene to be a layer is melted by a corresponding extruder, and merged in a die head so as to have a layer structure of an inner layer / adhesive layer / intermediate layer / adhesive layer / outer layer. It can be manufactured by co-extrusion. The laminate is extruded through a ring die into a molten parison, which is blow molded to produce bottles and tube containers. Further, by extruding through a T-die or the like, the sheet is formed into a sheet once, and the sheet is heated and melted, and then vacuum-formed, air-pressure formed, or plug-assist-molded to manufacture a cup container. Manufactured.

As the die head, a multilayer multi-die is used. The temperature of the die head varies depending on the type of the cyclic olefin copolymer used, but generally is 22.
A temperature of 0 to 250 ° C is suitable for suppressing the drawdown tendency while preventing gelation of the cyclic olefin-based copolymer.

The multilayer plastic container of the present invention is particularly useful as a packaging container for contents containing a fragrance component such as ethanol, phenylethyl alcohol, benzyl acetate, menthol, pinene, acetic acid, limonene and the like. Specifically, cosmetic perfumes such as perfume and cologne; creams such as cleansing cream, cold cream, hand cream, vanishing cream, foundation cream; Hair styling or hair cosmetics such as tics, hair creams, hair lotions, and hair tonics; watering, creaming, baby powders for infants, etc .;
Cosmetics such as: various liquid soaps, bath agents, bath salts, bubble baths, bath oils, detergents, shampoos, rinses, room fragrances, deodorant fragrances, toothpastes, leather creams, and other toiletries. Further, the container of the present invention includes various soft drinks such as carbonated drinks and drinks containing fruit juice; sweet products such as ice cream, pudding, jelly, chocolate, candy, biscuits, etc .; milk, butter, cheese, ham, sausage, beef, chicken. Livestock products such as meat and processed foods; Fish products such as kamaboko, fish, shellfish, laver;
It can also be used for packaging foods such as green tea, oolong tea, tea, cocoa, coffee, etc .; alcoholic beverages such as Western liquor, herbal liquor, liqueurs, etc .;

[0064]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, tests and evaluations were performed as follows.

Peel strength measurement: The bottle was filled with toothpaste, placed in a sealed glass container, and stored in a thermostat at 50 ° C. for 4 days. Next, the bottle was taken out, washed with water, air-dried, cut out into 15 mm × 50 mm sections, and one end was immersed in toluene. By the toluene treatment, the ethylene cyclic olefin resin layer serving as the intermediate layer was dissolved, and the clamp portion (LDPE layer) for peel strength measurement was exposed. Thereafter, using a tensile tester manufactured by Orientec, the tensile speed was 3
A T-shaped tensile test was performed at 00 mm / min, and the peel strength was measured.

Evaluation method of fragrance retention: Toothpaste 1
Then, after heat-sealing the mouth with an aluminum foil laminated film, three pieces were sealed and stored in a sealed glass container with a septum. The storage temperature is 37 ° C. After saving in January,
1 ml of gas in the gas phase of a sealed glass container with a septum was sampled and analyzed by gas chromatography (GC). GC analysis was performed using a Shimadzu GC-9A G column (60 m),
Column temperature 160 ° C, injection port temperature 22
Analysis was carried out at 0 ° C. with a carrier gas He.

Example 1 (Resin) For the innermost and outermost layers, low-density polyethylene and a melt index (MI) of 0.8 (ASTMD-1238 method) were used. Further, as the intermediate layer, the cyclic olefin content 2
An ethylene cyclic olefin copolymer having 2 mol%: Mw = 130,000 was used. In addition, in order to bond the innermost and outermost low-density polyethylene resin layer and the intermediate layer of ethylene cyclic olefin copolymer resin layer, ethylene and 11.5 mol% of 1-butene were used as an adhesive resin. A linear ultra-low density polyethylene (MI = 4 g / 10 min) made of a polymer and having a density of 0.885 g / cm ³ was used. (Molding) Using a multilayer extruder having three screw extruders, a low-density polyethylene resin as an outermost layer, an ethylene α-olefin copolymer resin as an adhesive layer, an ethylene cyclic olefin copolymer resin as an intermediate layer, and an innermost layer Was subjected to direct blow molding of a three-layer, five-layer structure made of a low-density polyethylene resin. The cylinder temperature during molding was different from the three types of cylinders. In particular, the temperature of the ethylene cyclic olefin copolymer resin was set at 250 ° C. in a part of the cylinder section. A column-shaped bottle having an inner volume of 180 ml and a total wall thickness of 600 μm and a layer ratio of 38%: 2%: 20%: 2%: 38% was prepared. The obtained results are shown in Tables 1 and 2.

Example 2 Except that a linear ultra-low-density polyethylene (MI = 4) consisting of a copolymer of ethylene and 7 mol% of 1-butene and having a density of 0.908 g / cm ³ was used as the resin for the adhesive layer. Produced a bottle in the same manner as in Example 1. Table 1 shows the obtained results.

Example 3 As an adhesive layer resin, ethylene and 6 mol% of 4-methyl-
The density consisting of a copolymer with 1-pentene is 0.902 g
A bottle was manufactured in the same manner as in Example 1 except that a linear ultra-low density polyethylene (MI = 4) of / cm ³ was used.
Table 1 shows the obtained results.

Example 4 Except for using a linear ultra-low-density polyethylene (MI = 4) made of a copolymer of ethylene and 20 mol% of 1-butene and having a density of 0.842 g / cm ³ , as the resin for the adhesive layer. Produced a bottle in the same manner as in Example 1. Table 1 shows the obtained results.

Example 5 A linear ultra-low density polyethylene (MI = 4) consisting of a copolymer of ethylene and 10 mol% of 1-octene and having a density of 0.860 g / cm ³ was used as the resin for the adhesive layer. Produced a bottle in the same manner as in Example 1. Table 1 shows the obtained results.

Example 6 As a resin for the adhesive layer, a density of 0.884 g / cm ³ consisting of a copolymer of ethylene and 11.5 mol% of 1-butene was used.
A bottle was produced in the same manner as in Example 1 except that the maleic anhydride graft polymer of linear ultra-low density polyethylene (modified amount = 0.2 mol%, MI = 4) was used. Table 1 shows the obtained results.

Comparative Example 1 A low-density linear polyethylene (MI = 4) consisting of a copolymer of ethylene and 5 mol% of 1-butene and having a density of 0.920 g / cm ³ was used as the resin for the adhesive layer. A bottle was manufactured in the same manner as in Example 1. Table 1 shows the obtained results.

Comparative Example 2 As an adhesive layer resin, ethylene and 5 mol% of 4-methyl-
The density consisting of a copolymer with 1-pentene is 0.910 g
A bottle was manufactured in the same manner as in Example 1 except that a linear low-density polyethylene (MI = 4) of / cm ³ was used. Table 1 shows the obtained results.

Comparative Example 3 As a resin for the adhesive layer, a maleic anhydride graft polymer of a linear low-density polyethylene having a density of 0.920 g / cm ³ consisting of a copolymer of ethylene and 5 mol% of 1-butene (modified) A bottle was manufactured in the same manner as in Example 1 except that the amount = 0.1 mol% and MI = 4) were used. Table 1 shows the obtained results.

Comparative Example 4 As a resin for the adhesive layer, a maleic anhydride graft polymer of a linear low-density polyethylene having a density of 0.918 g / cm ³ consisting of a copolymer of ethylene and 5 mol% of 1-butene (modified) A bottle was manufactured in the same manner as in Example 1 except that the amount was 0.4 mol% and MI was 4). Table 1 shows the obtained results.

Comparative Example 5 An ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%, saponification degree: 99%) was used as an intermediate layer, and ethylene and 5 mol% of 1-butene were used as an adhesive layer resin. The same procedure as in Example 1 was carried out except that a maleic anhydride graft polymer of a linear low-density polyethylene having a density of 0.918 g / cm ³ consisting of a polymer (modified amount = 0.2 mol%, MI = 4) was used. Manufactured a bottle. The obtained results are shown in Tables 1 and 2.

Comparative Example 6 Poly-1-butene (density 0.905) was used as the resin for the adhesive layer.
g / cm ³ , MI = 4), and a bottle was produced in the same manner as in Example 1. Table 1 shows the obtained results.

[0079]

[Table 1]

[0080]

[Table 2]

From the above results, the following becomes clear. From Table 1, the initial adhesive strength reaches practical strength without depending on the copolymerization ratio and density of α-olefin in the ethylene-α-olefin copolymer, but the toothpaste is filled with
It can be seen that when stored at 50 ° C., the copolymerization ratio and density of the α-olefin are closely related to the adhesive strength. That is, when the copolymerization ratio of the α-olefin was 5 mol% or less, the adhesive strength was rapidly lowered with the elapse of time after filling, and the result showed that the practical strength was not satisfied. In Comparative Example 6 in which poly-1-butene (crystalline polymer) was used as an adhesive, no initial adhesive strength was obtained, and short-chain branching was observed in interlayer adhesion between olefin and ethylene cyclic olefin copolymer. It turns out that it is impossible to conclude just by being. That is, ethylene-α
It has been found that it is important to keep the α-olefin copolymerization ratio of the olefin copolymer within a certain range and to keep the density within a certain range.

In Comparative Examples 3 and 4 using a resin obtained by acid-modifying an ethylene-α-olefin copolymer,
Compared with Comparative Examples 1 and 2 in which the acid modification was not performed, the adhesive strength after storage was so low that delamination occurred. From this, it is understood that the acid modification of the ethylene-α-olefin copolymer cannot be a decisive factor for adhesion. As shown in Example 6, it was found that even if it was acid-modified, if the copolymerization ratio of the α-olefin was 6 mol% or more, it was practical as an adhesive.

From Table 2, it can be seen that the permeation amount of 1-menthol when toothpaste is actually filled is much smaller in the bottle of Example 1 than in a container having a conventional ethylene vinyl alcohol copolymer as an intermediate layer. It turned out that the container of Example 1 had high fragrance retention.

[0084]

According to the present invention, among the ethylene-α-olefin copolymers, the density obtained by copolymerizing 6 to 20 mol%, particularly 10 to 20 mol% of α-olefin is 0.910%. From 0.800 g / cm ³ , particularly from 0.900 to 0.840 g / cm ^{3, and} a linear ultra-low density polyethylene or an acid-modified product thereof. By using it for bonding with odorant, it is possible to not only have excellent fragrance retention properties for the contents, but also prevent adhesion deterioration due to odorous components and maintain a high level of adhesive strength after aging.

[Brief description of the drawings]

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

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

FIG. 3 is an enlarged cross-sectional view illustrating an example of a cross-sectional structure of a body of a container.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Tubular container 2 Lid 3 Threaded extrusion opening 4 Conical shoulder 5 Cylindrical trunk 6 Edge 7 Sealed bottom 10 Bottle-shaped container 11 Inner layer made of linear olefin resin 12 Cyclic olefin copolymer 13 An outer layer composed of a linear olefin resin 14, 15 An adhesive layer composed of a linear ultra-low density polyethylene

Claims (9)

[Claims] 1. An inner / outer layer made of a linear olefin resin.
And an intermediate layer made of a cyclic olefin copolymer
Plastic multi-layer container provided with an adhesive resin layer
The adhesive resin is ethylene and 4 to 20 per resin
Density obtained by copolymerization with mol% of α-olefin
Is 0.910 to 0.800 g / cm ^ThreeLinear ultra-low density
Characterized by being made of polyethylene or its acid-modified product
Scented plastic multilayer container. 2. α constituting linear ultra-low density polyethylene
2. The multilayer plastic container according to claim 1, wherein the olefin is an α-olefin having 4 to 8 carbon atoms. 3. An acid-modified product of the linear ultra low density polyethylene is 0.1 to 0.4 mol% per linear low density polyethylene.
2. The maleic anhydride of claim 1 is grafted.
The multilayer plastic container according to any of the preceding claims. 4. The multilayer container according to claim 1, wherein the linear ultra-low-density polyethylene or its acid-modified product has a melt flow rate of 0.4 to 30 g / 10 min. 5. The multilayer plastic container according to claim 1, wherein the linear olefin resin is polyethylene, polypropylene or a crystalline ethylene / propylene copolymer. 6. The cyclic olefin-based copolymer has a content of 10 to 5
The fragrance-retaining plastic multilayer container according to claim 1, which is a copolymer containing 0% by weight of a cyclic olefin unit. 7. The multilayer plastic container according to claim 1, wherein the cyclic olefin-based copolymer is a cyclic olefin-based copolymer having a glass transition point (Tg) of 60 ° C. or higher. 8. The container has a total thickness of 100 to 1000.
The thickness of the adhesive layer is 3 to 40 μm, and the ratio of the total thickness of the inner and outer layers to the thickness of the cyclic olefin-based copolymer intermediate layer is 99: 1 to 70:30. Scented plastic multi-layer container. 9. The multilayer plastic container according to claim 1, which is a co-extrusion blow-molded container.