JP2000246838A - Heat resistant container or packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve an interlayer releasing strength, moistureproofness, transparency, flexibility, hand tearableness or the like, by laminating a layer of an ethylene-cyclic olefin random copolymer represented by a specific formula and a layer made of specific low crystalline or amorphous soft copolymer and a polyolefin composition. SOLUTION: A polyolefin multilayer laminate obtained by laminating a first layer of an ethyene-cyclic olefin random copolymer represented by the formula and a second layer of a composition containing 20 to 100 pts.wt. of low crystalline or non-crystalline soft copolymer having a crystallinity of 40% or below and a glass transition temperature of 0 deg.C or below and 0 to 80 pts.wt. of a polyolefin is formed, and treated at 50 deg.C or above (wherein n is 0 or 1, m is 0 or positive integer, q is 0 or 1, R1 to R18 and Ra, Rb are each H, a halogen or a hydrocarbon group, R15 to R18 may each form a ring of a double bond, R15 and R16 or R17 and R18 may each form an alkylidene group, and in the case of q of 0, a 5-member ring is formed).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate comprising a cyclic olefin resin layer and a low crystalline or amorphous soft copolymer (composition) layer, which is treated at a temperature of 50 ° C. or more. It relates to a heat-resistant container or packaging material.

[0002]

2. Description of the Related Art Cyclic olefin resins are excellent in transparency and moisture resistance, but may have problems such as oil resistance and difficulty in heat sealing. In order to solve these problems, the present applicant has disclosed a method of laminating a polyolefin-based resin layer having excellent oil resistance and heat sealability on a cyclic olefin-based resin layer. (JP-A-8-72210)
issue). However, although such a laminate has excellent initial interlayer adhesion, after the molded body is exposed to a high temperature by boiling sterilization, retort, steam sterilization, etc., the interlayer may be easily peeled off. Was desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to prevent the delamination strength from being reduced by sterilization treatment at high temperature, heat retention, etc., moisture proofness, transparency, flexibility, hand-cutting property, heat sealing property, and deadness. An object of the present invention is to provide a heat-resistant container or packaging material having excellent holding properties and the like.

[0004]

The heat-resistant container or packaging material according to the present invention comprises: (A): (A1); (a-1) a cyclic olefin represented by the following formula [1] or [2]: Ethylene / cyclic olefin random copolymer comprising a copolymer of ethylene and ethylene, (a-2) a ring-opened (co) polymer of a cyclic olefin represented by the following formula [1] or [2] or hydrogenation thereof: And (a-3) a graft modified product of the ethylene / cyclic olefin random copolymer (a-1) or a ring-opened (co) polymer of a cyclic olefin or a hydrogenated product thereof (a-2). A layer formed from at least one type of cyclic olefin-based resin selected from
2); selected from the group consisting of (a-1) an ethylene / cyclic olefin random copolymer, (a-2) a ring-opened (co) polymer or a hydrogenated product thereof, and (a-3) a graft-modified product. A first layer selected from the group consisting of a layer formed from a cyclic olefin resin composition comprising at least one cyclic olefin resin and (b) a polyolefin; and (B) a glass having a crystallinity of 40% or less. The transition temperature is formed from a polyolefin-based multilayer laminate in which at least two layers of a low crystalline or amorphous soft copolymer having a temperature of 0 ° C. or lower and a second layer formed from a polyolefin composition are laminated, It is characterized by being processed at a temperature of 50 ° C. or higher.

[0005]

Embedded image [In the formula [1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. You may. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. ]

Embedded image [In the formula [2], m is 0 or a positive integer, and h
Is 0 or a positive integer; j and k are 0, 1 or 2; R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ each independently represent a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group; Represents an atom or a group selected from R ^{19 to} R ²⁷
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group. ]

First, the resin used as the material of the heat-resistant container or packaging material of the present invention will be described. (A) Cyclic olefin-based resin and cyclic olefin-based resin composition First, the material of the film of one layer of the multilayer laminate forming the heat-resistant container or packaging material of the present invention (A1)
The cyclic olefin-based resin and the (A2) cyclic olefin-based resin composition containing the cyclic olefin-based resin will be described.

The (A1) cyclic olefin resin used in the present invention includes (a-1) ethylene and the above-mentioned formula [1]
Or a random copolymer with a cyclic olefin represented by [2], (a-2) a ring-opened (co) polymer of a cyclic olefin represented by formula [1] or [2] or a hydride thereof;
Alternatively, (a-3) a graft-modified product of the above (a-1) or (a-2) can be mentioned.

The (A1) cyclic olefin resin used in the present invention usually has a softening temperature (TMA) of at least 60 ° C. measured by a thermal mechanical analyzer,
Preferably it is 70-210 ° C, more preferably 80-1.
80 ° C. The softening temperature (TMA) was measured by placing a quartz needle having a diameter of 1.0 mm on the sheet and applying a load of 49 g.
When the temperature was raised at a rate of 5 ° C./min, the needles
635 mm penetration temperature.

(A1) The cyclic olefin-based resin comprises:
The intrinsic viscosity [η] measured in decalin at 35 ° C. is usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g.
-2.0 dl / g, more preferably 0.4-1.2 d
1 / g. Further, the (A1) cyclic olefin-based resin has a glass transition point (Tg) of usually 50 ° C. or more, preferably 60 to 200 ° C., and a crystallinity measured by an X-ray diffraction method of usually 0 to 20%. , Preferably 0-2%
It is.

First, the cyclic olefin used for producing the (A1) cyclic olefin resin as described above will be described. As the cyclic olefin, a compound represented by the formula [1] or [2] is used. In the formula [1], n is 0 or 1, and m is 0 or a positive integer. Further, R ^{1 to} R ¹⁸ and R ^a , R ^b
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.
Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Further, as the hydrocarbon group, an alkyl group having 1 to 20 carbon atoms,
Examples thereof include a halogenated alkyl group having 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the group include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the cycloalkyl group include a cyclohexyl group,
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

Further, in the above formula [1], R ¹⁵ and R ¹⁶
And R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are respectively bonded (jointly And a single or multiple ring may be formed, and the single or multiple ring thus formed may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here include the following.

[0012]

Embedded image In the above examples, the carbon atoms numbered 1 or 2 represent the carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) are bonded in formula [1]. Also, R
¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

Preferred examples of the cyclic olefin in the above formula [1] include a cyclic olefin represented by the following formula [1-1].

Embedded image In the above formula [1-1], n, m and R ^{1 to} R ¹⁸ represent the same as in the formula [1].

Further, as the cyclic olefin, a compound represented by the above formula [2] can also be used. In the above formula [2], m is 0 or a positive integer, h is 0 or a positive integer, and j and k are 0, 1 or 2
It is. Further, R ⁷ to R ¹⁵ and R ¹⁷ to R ^{1 8} is the formula [1]
Represents the same as Further, R ^{19 to} R ²⁷ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the formula [1]. Further, R ^19-
As the hydrocarbon group for R ²⁷ , an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms,
Examples thereof include a cycloalkyl group having 3 to 15 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. More specifically, as the alkyl group, a methyl group,
Ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and the like.Examples of the halogenated alkyl group include forming the above-described alkyl group. At least some of the hydrogen atoms are fluorine, chlorine,
Examples thereof include a group substituted with a bromine atom or an iodine atom.

Examples of the cycloalkyl group include a cyclohexyl group and the like, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Group, benzyl group and phenylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

Here, the carbon atom to which R ¹⁷ and R ¹⁸ are bonded and the carbon atom to which R ²¹ is bonded or the carbon atom to which R ¹⁹ is bonded are directly or a carbon atom having 1 to 3 carbon atoms.
May be bonded via an alkylene group of That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ¹⁷ and R ²¹ or the groups represented by R ¹⁸ and R ¹⁹ cooperate with each other. And a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH)
₂ -) or trimethylene group (-CH ₂ CH ₂ CH ₂ -) to form one alkylene group of the.

When j = k = 0, R ²³ and R ²⁰ or R ²³ and R ²⁷ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include R ²³ and R ²³ when j = k = 0.
^The following groups, in which ²⁰ further forms an aromatic ring, can be mentioned.

Embedded image In the above formula, h represents the same as h in Formula [2].

As the cyclic olefin represented by the above formula [1] or [2], specifically, bicyclo
[2.2.1] hept-2-ene derivative, tetracyclo [4.4.0.1
^2,5 .1 ^7,10 ] -3-dodecene derivative, hexacyclo [6.6.1.1
^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, 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, pentacyclo [6.6.1.1 ^3,6 .
0 ^2,7 .0 ^9,14] -4-hexadecene derivative, heptacyclo-5
Eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.3.0.1 ^2,5] -3- decene derivatives, tricyclo [4.4.0.1 ^2,5] -3- undecene derivatives, pentacyclo [6.5.1.1 ^{3, 6} .0 ^2,7 .0 ^9,13] -4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [7.
4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] -3-pentadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11, ^16] -4-eicosene derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1
^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} - 3-hexadecene derivative, heptacyclo [8.8.0.1 ^4,7 .1 ^11,18 .1
^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, Nonashikuro ^{[10.10.1.1 5,8 .1 14,21 .1 16,19 .0} 2,11 .0 4,9 .0 ^13,22 .
0 ^15,20] -5-hexacosenoic derivatives, 1,4-methano -1,4,4a, 9a
-Tetrahydrofluorene derivative, 1,4-methano-1,4,4a,
5,10,10a-Hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct and the like can be mentioned.

The following formula [1] or [2]
A more specific example of the cyclic olefin represented by is shown below.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The cyclic olefin represented by the above formula [1] or [2] can be produced by a Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure. These cyclic olefins can be used alone or in combination of two or more.

(A-1) to (a-) used in the present invention
The cyclic olefin-based resin of 3) has the above-mentioned formula [1]
Or using the cyclic olefin represented by [2], for example, in JP-A-60-168708 and JP-A-61-12.
0816, JP-A-61-115912, JP-A-61-115916, and JP-A-61-2713.
08, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407
JP, JP-A-64-106, JP-A-1-156
It can be manufactured by appropriately selecting conditions according to the method proposed by the present applicant in Japanese Patent Publication No. 308 and Japanese Patent Application Laid-Open No. 1-197511.

(A-1) Ethylene / cyclic olefin random copolymer The (a-1) ethylene / cyclic olefin random copolymer used as the (A1) cyclic olefin resin in the present invention is usually derived from ethylene. 30 to 30 structural units
It contains 90 mol%, preferably 40 to 80 mol%, of structural units derived from cyclic olefins in an amount of 10 to 70 mol%, preferably 20 to 60 mol%.
The ethylene composition and the cyclic olefin composition were ¹³ C-
Measured by NMR.

In this (a-1) ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from the cyclic olefin are randomly arranged and bonded, It has a substantially linear structure. The copolymer is substantially linear,
The fact that the copolymer has substantially no gel-like crosslinked structure can be confirmed by the fact that the copolymer is dissolved in an organic solvent and contains no insoluble matter. For example, when the intrinsic viscosity [η] is measured as described later, the copolymer is 135
C., can be confirmed by complete dissolution in decalin.

(A-1) Ethylene used in the present invention
In the cyclic olefin random copolymer, at least a part of the structural unit derived from the cyclic olefin represented by the formula [1] or [2] has the following structural formula [1-a] or [2-a], respectively. It is considered that it has the structure shown by. Further, at least a part of the cyclic olefin represented by the formula [1-1] has the following structural formula [1-1-
a].

[0047]

Embedded image In the above formulas [1-a] and [1-1-a], n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same as those in the formula [1]. In the formula [2-a], m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ represent the same as in formula [2].

The (a-1) random copolymer of ethylene and cyclic olefin used in the present invention is a structural unit derived from another copolymerizable monomer as necessary within a range not to impair the object of the present invention. May be contained. Examples of such other monomers include olefins other than the above-described ethylene or cyclic olefin, norbornenes, non-conjugated dienes, and the like.Specifically, propylene, 1-butene, 1-pentene , 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl -1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
Α-olefins having 3 to 20 carbon atoms such as 1-hexadecene, 1-octadecene, 1-eicosene, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl)
Cycloolefins such as 1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, 2-norbornene, 5-methyl-2-norbornene, 5-
Ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n-butyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-
Norbornene, norbornenes such as 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, Non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

These other monomers can be used alone or in combination of two or more. (A-1) In the ethylene / cyclic olefin random copolymer, the constitutional unit derived from the above other monomer is usually 20 mol% or less, preferably 10 mol%.
It may be contained in the following amounts.

(A-1) Ethylene used in the present invention
The cyclic olefin random copolymer can be produced by using the ethylene and the cyclic olefin represented by the formula [1] or [2] according to the production method disclosed in the above publication. Among these, the copolymerization is carried out in a hydrocarbon solvent, and a vanadium-based catalyst formed from a vanadium compound and an organic aluminum compound soluble in the hydrocarbon solvent as a catalyst, a titanium compound formed from a titanium compound and an organic aluminum compound are used as a catalyst. Using a zirconium complex formed from an aluminoxane and a zirconium complex having a polydentate compound in which at least two conjugated cycloalkadienyl groups are bonded via a lower alkylene group as a ligand (A-1) It is preferable to produce an ethylene / cyclic olefin random copolymer.

(A-2) Ring-opening (co) polymer of cyclic olefin The ring-opening (co) polymer of (a-2) cyclic olefin used in the present invention is represented by the above formula [1] or [2]. It comprises a structural unit derived from the cyclic olefin represented, and at least a part of this structural unit is considered to have a structure represented by the following formula [1-b] or [2-b].
Further, it is considered that at least a part of the cyclic olefin represented by the formula [1-1] has a structure represented by the following formula [1-1-b].

[0052]

Embedded image In the above formulas [1-b] and [1-1-b], n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same as those in the formula [1]. In the formula [2-b], m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ represent the same as in formula [2].

The cyclic olefin ring-opened (co) polymer (a-
2) contains the above-mentioned cyclic olefin as an essential component, but may contain another copolymerizable unsaturated monomer component if necessary, as long as the object of the present invention is not impaired. . Examples of the optionally copolymerized unsaturated monomer include a cyclic olefin represented by the following formula [3].

[0054]

Embedded image In the above formula [3], R ²⁸ and R ²⁹ are a hydrogen atom, a hydrocarbon group or a halogen atom, and may be the same or different. Also, t is an integer of 2 or more,
When R ²⁸ and R ²⁹ are repeated a plurality of times, they may be the same or different.

Examples of the monomer component represented by the above formula [3] include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, methylcyclopentene, methylcyclohexene, methylcycloheptene, methylcyclooctene, methylcyclononene. , Methylcyclodecene, ethylcyclopentene, ethylcyclobutene, ethylcyclooctene, dimethylcyclopentene, dimethylcyclohexene, dimethylcycloheptene, dimethylcyclooctene, trimethylcyclodecene, 2- (2-methylbutyl)
1-cyclohexene and the like can be mentioned.

As the unsaturated monomer which may be optionally copolymerized in addition to the above formula [3], specifically, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, Examples include cyclic olefins such as 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene. Such unsaturated monomers which may be optionally copolymerized may be used alone or in combination. Usually, 100 mol% of the cyclic olefin-based ring-opening (co) polymer (a-2) is used. It is used in an amount of less than 50 mol%.

Such a ring-opened (co) polymer can be produced by the production method disclosed in the above publication. Specifically, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the formula [1] or [2] in the presence of a ring-opening polymerization catalyst. As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, iridium or platinum, a nitrate or an acetylacetone compound, and a reducing agent, or titanium,
A catalyst comprising a halide or acetylacetone compound of a metal selected from palladium, zirconium or molybdenum and an organoaluminum compound can be used.

(A-2) Ring opening (co) used in the present invention
The hydride of the polymer is obtained as described above (a-
2) It is obtained by hydrogenating a ring-opened (co) polymer in the presence of a conventionally known hydrogenation catalyst. This (a-2) ring opening (co)
In the polymer hydride, among the structural units derived from the cyclic olefin represented by the formula [1] or [2],
It is considered that at least a part has a structure represented by the following formula [1-c] or [2-c]. Also, the equation [1]
-1] at least a portion of the cyclic olefin represented by
It is considered to have a structure represented by the following formula [1-1-c].

[0059]

Embedded image In the above formulas [1-c] and [1-1-c], n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same as those in the formula [1]. In the formula [2-c], m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ represent the same as in formula [2].

(A-3) Graft-modified product The graft-modified product (a-3) used in the present invention may be any of the above-mentioned (a-1) ethylene / cyclic olefin random copolymer or (a-2) A) a ring-opening (co) polymer of a cyclic olefin or a part of a hydride thereof is obtained by graft modification with a modifying agent;

Examples of the modifying agent include unsaturated carboxylic acids such as maleic anhydride, derivatives thereof such as acid anhydrides or alkyl esters of unsaturated carboxylic acids. In the graft modified product (a-3) used in the present invention, the content of the structural unit derived from the modifying agent is as follows:
Usually, it is 10 mol% or less.

The graft-modified product (a-3) is as follows:
A modifier is blended with (a-1) a random copolymer of ethylene / cyclic olefin or (a-2) a ring-opened (co) polymer of cyclic olefin or its hydride so as to obtain a desired modification ratio. It can be produced by graft polymerization, or can be produced by preparing a modified product having a high modification rate in advance, and then mixing the modified product with an unmodified cyclic olefin resin.

The (A1) cyclic olefin-based resin used in the present invention is selected from the group consisting of (a-1), (a-2) and (a-3) as described above. It may be a combination. In the present invention, (A
1) Among these, as the cyclic olefin resin,
(A-1) An ethylene / cyclic olefin random copolymer is preferably used.

The heat-resistant container or packaging material of the present invention comprises a first layer formed from the above-mentioned cyclic olefin-based resin (A1) and a low-crystalline to non-crystalline soft copolymer described later or The first layer formed from the cyclic olefin resin (A1) is formed from a laminate with the second layer formed from the composition (B) containing It may be formed from A2).

That is, (A2) the first layer composed of the cyclic olefin-based resin composition comprises (a-1) the above-mentioned ethylene / cyclic olefin random copolymer, and (a-2) the ring-opened (co)
It is formed from a cyclic olefin resin composition comprising at least one cyclic olefin resin selected from the group consisting of a polymer or a hydrogenated product thereof and (a-3) a graft modified product, and (b) a polyolefin.

As the polyolefin (b), a (co) polymer of an α-olefin having 2 to 20 carbon atoms is usually used. Specifically, examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1-butene.
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

The polyolefin (b) used in the present invention may be a homopolymer of the above-mentioned α-olefin or a copolymer of two or more α-olefins. . Further, (b) the polyolefin, within a range that does not impair the properties of the polyolefin,
In addition to the above α-olefin, norbornenes,
Other monomers such as non-conjugated dienes may be copolymerized. Examples of such other monomers include cyclobutene,
Cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene and 3a, 5,6,
Cycloolefins such as 7a-tetrahydro-4,7-methano-1H-indene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n- Butyl-2-norbornene, 5-isobutyl-
Norbornenes such as 2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene and 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-
Octadiene, dicyclopentadiene, 5-ethylidene-2
Non-conjugated dienes such as -norbornene and 5-vinyl-2-norbornene.

These other monomers can be used alone or in combination of two or more. Particularly, in the present invention, it is preferable that the polyolefin (b) is polyethylene and / or polypropylene. When the polyolefin (b) is polyethylene, the polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another α-olefin.

When the polyolefin (b) is, for example, polyethylene, a homopolymer of ethylene or a copolymer of ethylene having an ethylene content of 60 mol% or more, preferably 70 mol% or more, and another α-olefin. A polymer having a density of 0.830 g / cm ³ or more, preferably 0.87 to 0.94 g / cm ³ , and a melt flow rate at 190 ° C. of 0.01 to 100 g / 10 min, preferably 0.03 ~ 50g / 10min, Vicat softening point is 50 ~ 1
It is desirable to use one in the range of 40C, preferably 80-130C.

Other α-olefins copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-
Those having 3 to 14, preferably 3 to 10 carbon atoms such as pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene are exemplified. be able to.

When the polyolefin (b) is, for example, polypropylene, the polypropylene may be a homopolymer of propylene or a copolymer of propylene and another α-olefin. Is also good.
When the (b) polyolefin is polypropylene, it is a homopolymer of propylene or a copolymer of polypropylene having a propylene content of 70 mol% or more, preferably 80 mol% or more, and another α-olefin,
The density is 0.85 g / cm ³ or more, preferably 0.89 to 0.8.
91 g / cm ³ , 230 ° C. melt flow rate is 0.0
1 to 100 g / 10 min, preferably 0.05 to 50 g /
It is desirable to use one having a Vicat softening point in the range of 100 to 170C, preferably 110 to 160C for 10 minutes.

Other α-olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-
Penten, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc., having 2 to 14 carbon atoms (excluding propylene), preferably 2 to 2 carbon atoms 10 (excluding propylene).

The polyolefin (b) may be a graft-modified product. Examples of the modifier used here include unsaturated carboxylic acids such as maleic anhydride, derivatives thereof such as acid anhydrides or alkyl esters of unsaturated carboxylic acids, and the like. When the polyolefin (b) is a graft-modified product, the content of the structural unit derived from the modifier in the polyolefin (b) is usually 10 mol% or less.

Such a graft-modified product can be produced by blending a polyolefin with a modifier so as to obtain a desired modification ratio and graft-polymerizing the same. Alternatively, a modified product having a high modification ratio is prepared in advance, and then this modified product is prepared. It can also be produced by mixing a modified product and an unmodified polyolefin.

The proportion of the cyclic olefin resin (A1) in the cyclic olefin resin composition (A2) is usually 5%.
0% by weight or more, preferably 60 to 99% by weight, and the proportion of polyolefin (b) is usually less than 50% by weight, preferably 1 to 40% by weight.

The (A) cyclic olefin-based resin or cyclic olefin-based resin composition used in the present invention includes the above-mentioned (a-1) to (a-) as long as the object of the present invention is not impaired.
As a component other than 3) and (b), a rubber component for improving impact strength may be blended, or other resin components,
Heat stabilizers, weather stabilizers, light stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, dyes that absorb only light of a specific wavelength, pigments, natural oils,
Synthetic oils, waxes or translucent fillers can be added. The compounding amount of these other components is the proportion of the total amount of the cyclic olefin resin (A1) and the other components, or the total amount of the cyclic olefin resin (A1), the polyolefin (b) and the other components. Usually 5
It is desirably less than 0% by weight.

For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3 (3,5- Di-t-butyl-4-hydroxyphenyl)
Propionate]; fatty acid metal salts such as fatty acid calcium such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; and fatty acid esters of polyhydric alcohols.

These may be used alone. For example, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is mixed with zinc stearate and glycerin monostearate. They can be used in combination like a combination. In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol. As such a fatty acid ester of the polyhydric alcohol, one of the alcoholic hydroxyl groups of the trihydric or higher polyhydric alcohol may be used. Examples thereof include polyhydric alcohol fatty acid esters whose parts are esterified.

Examples of such fatty acid esters of polyhydric alcohols include glycerin monostearate,
Glycerin fatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, and glycerin dilaurate; pentaerythritol monostearate (pe
and fatty acid esters of pentaerythritol such as pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol distearate, and pentaerythritol tristearate. These may be used alone or in combination with each other.

The phenolic antioxidant is used in an amount of less than 10 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the essential components.
It is desirable to use less than 2 parts by weight, more preferably less than 2 parts by weight. The fatty acid ester of the polyhydric alcohol is desirably used in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the total of essential components.

The cyclic olefin resin composition (A) is prepared from the cyclic olefin resin (A1) and the polyolefin (b).
For the production of 2), a known mixing method can be adopted, for example, a method of mixing with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc. After melt-kneading, a method of granulating or pulverizing can be exemplified.

(B) Composition comprising low-crystalline or non-crystalline soft copolymer (c) and polyolefin (b) Next, a soft copolymer which is a material for forming the second layer of the heat-resistant molded article of the present invention. The composition comprising the polymer (c) and the polyolefin (b) will be described.

The low-crystalline or non-crystalline soft copolymer (c) used in the present invention is a soft thermoplastic resin having a JISA hardness of 100 or less, for example, EPR (ethylene / propylene rubber), EBR (Ethylene butene rubber)
Ethylene-α-olefin copolymer such as EP
Ethylene / α-olefin / diene terpolymer such as DM (ethylene / propylene / diene), EBDM (ethylene / butene / diene), SEBS (styrene / ethylene / butene / styrene block copolymer), SBS (styrene・ Butadiene / styrene block copolymer) SE
PS (styrene / ethylene / propylene block copolymer), SIS (styrene / isoprene / styrene block copolymer), polyisoprene, polyisobutylene,
Examples thereof include polybutadiene and styrene / butadiene rubber. Among them, the olefin elastomer E
PR, EBR, EPDM and the like are particularly preferably used.

ASTM D of Olefinic Elastomer
Melt flow rate (MF
R) is generally in the range of 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min. The density is usually 0.850 to 0.910 g / cm ³ , preferably 0.8.
In the range of 55 to 0.900 g / cm ³ and an ethylene content of 30 to 95 mol%, preferably 40 to 92 mol%
And the degree of crystallinity measured by X-ray diffraction is usually 40% or less, preferably 30% or less.

The α-olefin constituting the ethylene / α-olefin copolymer usually has 3 carbon atoms.
〜20 α-olefins are used. Examples of such α-olefins are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1
-Tetradecene and 1-octadecene can be mentioned. The α-olefin can be copolymerized alone or in combination.

The ethylene / α-olefin copolymer is a low-crystalline to amorphous polyolefin as described above, and the copolymer is described in ASTM D 3418.
Is usually 100 ° C. or lower. In the present invention, a composition may be prepared by blending a tackifier with the low crystalline to amorphous soft copolymer as described above.

Examples of the above tackifiers include alicyclic hydrocarbon resins obtained by hydrogenating an aliphatic hydrocarbon resin and / or an aromatic hydrocarbon resin. Among them, the hydrogenation rate is 80% or more, preferably 8%.
It is desirable to use 5% or more of an alicyclic hydrocarbon resin. The mixing ratio of the two is such that the ethylene / α-olefin copolymer is 60 to 98% by weight, preferably 70 to 98% by weight.
95% by weight, 2 to 40% by weight of aliphatic hydrocarbon resin and / or alicyclic hydrocarbon resin, preferably 5 to 3%
0% by weight. By using such a tackifier, the delamination strength can be increased.

Further, the low crystalline to amorphous soft polymer may be wholly or partially modified with an unsaturated carboxylic acid or a derivative thereof, or the low crystalline to amorphous soft copolymer. Modified polyethylene can be blended with the union. This modified polyethylene has a graft amount of the unsaturated carboxylic acid or its derivative of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, and a density of 0.920 to 0.98.
g / cm ³ , preferably 0.905 to 0.970 g / cm ³
And a crystallinity measured by an X-ray diffraction method of 45% or more, preferably 50 to 80%. In order to produce this modified polyethylene, a melt flow rate (MFR: ASTM D
1238, E) is in the range of 0.001 to 100 g / 10 min, the density is in the range of 0.905 to 0.980 g / cm ³ , and X
A homopolymer of ethylene having a crystallinity of 45% or more as measured by a line diffraction method may be used, or a copolymer in combination with an α-olefin may be used. Here, examples of the α-olefin that can be copolymerized with ethylene include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene.

Examples of the unsaturated carboxylic acids or derivatives thereof grafted on the polyethylene include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^TM (endocis-bicyclo acid). [2,2,1] hept-5-ene-2,3-dicarboxylic acid) and unsaturated carboxylic acids and derivatives thereof, for example, acid halides, amides, imides, acid anhydrides, esters and the like. Specific examples include maleenyl hydrochloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof are particularly preferable. Modification of polyethylene using a grafting agent as described above can be performed according to a conventionally employed method.

The polyolefin (b) constituting the composition comprising (B) the soft copolymer (c) and the polyolefin (b) used in the present invention is the polyolefin blended with the cyclic olefin in the above (A2). The same thing as (b) can be used. Both can be kneaded in advance with an extruder, a Banbury mixer, a roll, or the like, and then be used for molding, or can be molded as they are after performing a life rent of both. The composition ratio of the soft copolymer (c) and the polyolefin (b) is 20 to 10 for the soft copolymer (c).
0 parts by weight, preferably 30 to 90 parts by weight, 80 to 0 parts by weight of polyolefin (b), and preferably 70 to 10 parts by weight.

The heat-resistant container or packaging material of the present invention comprises (A) a layer made of a cyclic olefin-based resin (composition), and (B) a soft copolymer (c) and a polyolefin (b). It is formed from a laminate comprising a composition layer.

The lamination of the layer (A) of the cyclic olefin-based resin (composition), the layer (B) of the soft copolymer and the composition of the polyolefin, and (A) / (B), (B) / (A) ) /
Any combination such as (B), (A) / (B) / (A) can be adopted. Further, the above-mentioned laminate is further provided with a polyolefin such as polyethylene or polypropylene, an ethylene / vinyl alcohol copolymer, a polyamide such as nylon 6, nylon 6.6, a polyester such as PET or PBT, a polystyrene, a polycarbonate, an ethylene / vinyl acetate. Copolymers, resins such as polyvinyl chloride, polyvinylidene chloride, and cellophane, silica-deposited films, metal-deposited films such as aluminum, and metal foils such as aluminum foil may be laminated directly or via an adhesive layer.

In the heat-resistant container or packaging material of the present invention, (A) a cyclic olefin resin (composition)
The thickness of the layer and the composition layer composed of (B) the soft copolymer (c) and the polyolefin (b) can be appropriately set in consideration of the use of the heat-resistant container or the packaging material of the present invention. However, in the normal case, the thickness of the (A) cyclic olefin-based resin (composition) layer is in the range of 1 μm to 10 mm,
(B) The thickness of the composition layer comprising the soft copolymer (c) and the polyolefin (b) is in the range of 1 μm to 10 mm. The total thickness of the polyolefin multilayer laminate of the present invention varies depending on the use of the laminate, the number of layers to be laminated, and the like, but is usually in the range of 2 µm to 20 mm.

The above-mentioned cyclic olefin resin (composition) (A) layer and the composition (B) layer composed of the soft copolymer (c) and the polyolefin (b) are formed by, for example, a multilayer T-die method. Laminates by adopting a common multilayer laminate molding method such as a co-extrusion molding method such as a multilayer inflation method, an extrusion lamination method, a multilayer blow method, a two-color molding method, a sandwich molding method, a stamping molding method, and a pressing method. be able to. Further, uniaxial or biaxial stretching by a method such as a tenter method or a tubular method is also possible.

Since the molded article of the present invention has excellent initial adhesive strength, it can be used for various containers and packaging applications such as foods and pharmaceuticals. In particular, in the case of a temporary treatment at a temperature of 50 ° C or higher, or an application where the temperature is maintained at a temperature of 50 ° C or higher,
It is preferably used because the decrease in peel strength between layers is small.
Specific applications include food and pharmaceutical containers used for hot water sterilization, retort, hot fill, steam sterilization, etc.
Packaging and the like. Further, the molded article of the present invention is excellent in moisture resistance, hardly adsorbs ingredients of foods and medicines, is excellent in fragrance retention, and has little leaching from the molded article. Further, the sheet or film-shaped molded article is excellent in hand-cutting property, heat sealing property and dead-hold property, and is also excellent in vacuum or compressed air moldability.

[0096] Specific applications include containers and packaging for drugs, foods and the like. For example, infusion bags, medical containers and packaging such as reagent tubes, retort packs that require heat sterilization, jelly, pudding containers and lids used for these containers, food containers and packaging such as hot-fill containers,
Suitable for applications requiring processing at high temperatures.

[0097]

As described above, according to the present invention, a first layer comprising a specific cyclic olefin resin or a cyclic olefin resin composition and a first layer comprising a soft copolymer and a composition comprising a polyolefin are used. The two layers can be adhered and laminated well, and the adhesion strength between the layers is good even when treated at a temperature of 50 ° C. or more. Therefore, medical treatment, food containers, and packaging requiring heat sterilization and hot fill are required. And the like.

[0098]

EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to these examples.

Examples 1 to 9 and Comparative Examples 1 to 3 Films were prepared on the following conditions using three types of three-layer T-die cast molding machines using the raw materials described below. Table 1 shows the configuration of each layer. In the example in which two types of resins are used for one layer, the two types of resins were dry-blended in advance and kneaded with a molding machine at the time of molding. ● Outer layer 1: 30mmΦ single screw extruder Set temperature 250 ℃,
Screw rotation 30rpm ● Intermediate layer: 30mmΦ twin screw extruder Set temperature 250 ° C,
Screw rotation 100rpm ● Outer layer 2: 30mmΦ single screw extruder Set temperature 250 ° C,
Screw rotation 30rpm ● Die temperature: 250 ℃ ● Cooling roll temperature: 40 ℃

(Layer thickness) Outer layer 1 / Intermediate layer / Outer layer 2 = 30 μm / 30 μm / 30 μ
m (Measurement method) The initial peel strength of the film prepared by the above method and the peel strength after heating the film at 110 ° C. for 4 hours in a hot-air circulation oven were measured. The measurement was performed by cutting the film in a width of 15 mm in the extrusion direction (MD) of the film, and using a tensile tester, the peeling speed between the cyclic olefin-based resin layer and the resin layer in contact with the resin layer was 300 m by the T-peel method.
The peeling was performed under the condition of m / min. The temperature at the time of measurement was 23 ° C., and the relative humidity was 50%. Table 1 shows the measurement results.

[0102] (Materials used) cycloolefin resin (a) · ^ETCD:. Ethylene and tetracyclo [4.4.0.1 ^{2, 5} 1
^7,10 ] -3-dodecene random copolymer (ethylene content 6
5 mol%, TMA = 135 ° C., Tg = 125 ° C.
[Η] = 0.60 dl / g, MFR = 15 g / 10 min (260 ° C., 2.16 kg) Polyolefin (b) · PE-1: LLDPE, density 0.920 g / cm ³ , MFR
= 2.1 g / 10 minutes (190 ° C, 2.16 kg) PE-2: HDPE, density 0.968 g / cm ³ , MFR
= 5.2 g / 10 min (190 ° C., 2.16 kg) PP-1: Homo PP, density 0.910 g / cm ³ , MF
R = 6.5 g / 10 min (230 ° C., 2.16 Kg) Low crystalline to non-crystalline soft copolymer (c) · ELA-1: Ethylene / butene-1 copolymer (ethylene content 90 mol%, density 0.890 g / cm ³ , MF
R = 18 g / 10 min, crystallinity 20%, JISA hardness 8
6) ELA-2: ethylene-octene-1 copolymer (ethylene content 93 mol%, density 0.895 g / cm ³ , M
FR = 4 g / 10 min, crystallinity 30%, JISA hardness 9
3) ELA-3: ethylene-propylene copolymer (ethylene content 80 mol%, density 0.870 g / cm ³ , MF
R = 2.9 g / 10 min, crystallinity 9%, JISA hardness 6
0) Others PR-1: hydrogenated petroleum resin, Alcon P-125 (softening point temperature 125 ° C, bromination 2, Arakawa Chemical)

[0102]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/04 C08F 232/08 4J100 232/08 236/20 236/20 255/02 255/02 277/00 277/00 279/00 279/00 C08L 21/00 C08L 21/00 23/00 23/00 23/08 23/08 45/00 45/00 47/00 47/00 51/06 51/06 53/00 53/00 53/02 53/02 65/00 65/00 B65D 1/00 A F term (reference) 3E033 BA09 BA14 BA15 BA16 BA17 BA18 BA19 BA21 BA22 BA26 BB08 CA07 CA09 CA18 CA20 GA03 3E086 AD01 AD06 BA04 BA15 BB02 BB12 BB41 BB51 BB90 CA03 CA27 CA28 4F100 AK01B AK03A AK03B AK03K AK04A AK05 AK62 AK63 AK64 AK65 AL01B AL03A AL04A AL05A AL05B BA02 BA15 GB16 JA05B JA11B JA12B JD04 JJ03 JK06 JK13B JK17 JL12 JN01 4J002 AC06Y AC08Y AE035 BB03X BB05X BB10W BB12X BB14X BB15X BB15Y BB17X BB18Y BB20W BB20Y BB21W BB21X BB21Y BB28Y BK00W BL01Y BN03Y BN 05W BN05X BP01Y CE00W FD010 FD040 FD060 FD090 FD100 FD170 FD200 FD340 GF00 GG01 GG02 4J026 AA12 AA13 AA14 AA64 AA66 AC01 AC02 AC29 AC34 AC36 BA25 BA27 BA32 BA34 BA35 BA36 BA38 BA44 BB01 GA01 4J100 AA02P AA02Q AA03P AA03Q AA04Q AA08Q AA15Q AA16Q AA17Q AA18Q AA19Q AA21Q AR09P AR09Q AR11P AR11Q AR21P AR21Q AS01R AS15P AS15Q BA16H BA20H BB01P BB03P BB07P BC23P BC43P BC44P BC48P BC49P CA01 CA04 CA05 CA31 DA01 DA13 DA14 DA15 DA25 DA41 DA43 HA03 HC28 HC29 HC30 HC34 HC39 HC50 HC63 JA58

Claims (1)

[Claims] (A): (A1); (a-1) an ethylene / cyclic olefin random copolymer comprising a copolymer of ethylene and a cyclic olefin represented by the following formula [1] or [2]: (A-2) a ring-opening (co) polymer of a cyclic olefin represented by the following formula [1] or [2] or a hydrogenated product thereof:
And (a-3) selected from the group consisting of the ethylene / cyclic olefin random copolymer (a-1) or the ring-opened (co) polymer of cyclic olefin or the graft modified product of its hydrogenated product (a-2). A layer formed from at least one kind of cyclic olefin-based resin, or (A)
2); selected from the group consisting of (a-1) an ethylene / cyclic olefin random copolymer, (a-2) a ring-opened (co) polymer or a hydrogenated product thereof, and (a-3) a graft-modified product. A first layer selected from the group consisting of a layer formed from a cyclic olefin-based resin composition comprising at least one cyclic olefin-based resin and (b) polyolefin; and (B) a glass having a crystallinity of 40% or less. Low crystalline to amorphous soft copolymer (c) having a transition temperature of 0 ° C. or less
A polyolefin-based multilayer laminate obtained by laminating at least two layers of 0 parts by weight and a second layer formed from the composition of 0 to 80 parts by weight of the polyolefin (b), at a temperature of 50 ° C. or higher. Treated heat-resistant container or packaging. Embedded image [In the formula [1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. You may. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. ] [In the formula [2], m is 0 or a positive integer, and h
Is 0 or a positive integer; j and k are 0, 1 or 2; R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ each independently represent a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group; Represents an atom or a group selected from R ^{19 to} R ²⁷
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group. ]