JP2001038848A - Cyclic olefin resin composition and its molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate excellent in moisture-proofing properties and handling properties by forming a layer of a cyclic polyolefin resin or a composition containing the resin and a layer of a composition of a low crystalline or amorphous flexible polymer, a crystalline polyolefin resin, and a specified low crystalline or amorphous polymer. SOLUTION: A cyclic olefin resin A such as an α-olefin-cyclic olefin random copolymer of a copolymer of a cyclic olefin expressed by formula I or formula II and a 2-20C α-olefin and a layer B formed from a composition of 90-55 wt.% of a low crystalline or amorphous flexible polymer 0 deg.C or below in glass transition temperature and a crystalline polyolefin resin and 1-50 wt.% of a low crystalline or amorphous polymer of at least 50 deg.C glass transition temperature are formed to obtain a laminate suitable for a heat resistant container, etc. In the formula I, R1-R18, Ra, Rb are hydrogen atom, etc., and in the formula II, R7-R15, R17-R27 are hydrogenatom, halogenatom, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclic olefin resin laminate suitable for containers and packaging materials.
The present invention relates to a laminate suitable for a retort processed at a high temperature or an application requiring high-temperature sterilization.

[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 cyclic olefin-based resin laminate excellent in holdability and the like, particularly a laminate suitable for use in heat-resistant containers or packaging materials.

[0004]

Means for Solving the Problems The cyclic olefin resin composition according to the present invention comprises:

(A) (a-1) α-olefin / cyclic compound comprising a copolymer of a cyclic olefin represented by the following formula (1) or (2) and an α-olefin having 2 to 20 carbon atoms: An olefin random copolymer, (a-2) a ring-opened (co) polymer of a cyclic olefin represented by the following formula (1) or (2) or a hydrogenated product thereof, and (a-3) the α-olefin:・
At least one cyclic olefin-based resin selected from the group consisting of a cyclic olefin random copolymer (a-1) or a ring-opened (co) polymer of a cyclic olefin or a graft modified product of a hydrogenated product thereof (a-2) (A1) or a resin composition (A2) comprising the cyclic olefin-based resin (A1) and (b) polyolefin; and (B): a low crystalline to amorphous soft weight having a glass transition temperature of 0 ° C. or lower. At least one resin selected from the group consisting of a coalesced (c) and a crystalline polyolefin resin (b ').
Wt% and a glass transition temperature of 50 with a crystallinity of 40% or less.
It is a laminate in which at least two layers including a second layer formed from a composition of 1 to 50% by weight of a low-crystalline to non-crystalline polymer (d) having a temperature of not less than ° C are laminated.

[0006]

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. )

[0007]

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. )

Further, in the present invention, (B)
It is preferable that the low-crystalline or non-crystalline resin (d) having a crystallinity of 40% or less and a glass transition temperature of 50 ° C. or more constituting the layer is a cyclic olefin-based resin (A1).

Further, according to the present invention, there is provided a cyclic olefin-based resin laminate which can be used for applications treated at a temperature of 50 ° C. or higher. Furthermore, the present invention provides a laminate that can be used as a container or a packaging material, and the container or the packaging material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the cyclic olefin resin laminate according to the present invention and its use will be specifically described. The cyclic olefin-based resin laminate according to the present invention comprises (A) a cyclic olefin-based resin or a composition layer comprising the same, and (B) a low crystalline to amorphous soft polymer (c).
And 99 to 50% by weight of at least one resin selected from crystalline polyolefin resins (b ′) and a crystallinity of 4
At least two layers including a second layer formed from a composition of 1 to 50% by weight of a low crystalline or amorphous polymer (d) having a glass transition temperature of 50 ° C. or higher at 0% or less are laminated.

(A) a cyclic olefin resin (A1),
And cyclic olefin resin (A1) and polyolefin
Resin composition (A2) First, the cyclic olefin resin (A1) and the resin composition (A2) comprising the cyclic olefin resin and a polyolefin will be described.

The cyclic olefin resin (A1) used in the present invention includes (a-1) an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the above formula (1) or (2). (A-2) a ring-opened (co) polymer of a cyclic olefin represented by the formula (1) or (2) or a hydride thereof, or (a-3)
At least one selected from the graft-modified products of the above (a-1) or (a-2) can be mentioned.

The cyclic olefin resin (A1) preferably used in the present invention has a softening temperature (TMA) measured by a thermal mechanical analyzer of usually 60 ° C. or higher, preferably 70 to 210 ° C., and more preferably 70 to 210 ° C. Is 80 to 180 ° C. The softening temperature (TMA) is
Place a quartz needle with a diameter of 1.0 mm on the sheet and load 49 g.
When the temperature is raised at a rate of 5 ° C./min, the needle penetrates the sheet by 0.635 mm.

The intrinsic viscosity [η] of the cyclic olefin resin (A1) of the present invention measured in decalin at 135 ° C. is usually 0.01 to 10 dl / g, preferably 0.0 to 10 dl / g.
5 to 2.0 dl / g, more preferably 0.4 to 1.2
dl / g. Cyclic olefin resin (A1)
Has a glass transition temperature (Tg) of usually 50 ° C. or higher, preferably 60 to 200 ° C., and the degree of crystallinity measured by X-ray diffraction is usually 0 to 20%, preferably 0 to 2%.
It is.

Here, α-alkyl having 2 to 20 carbon atoms.
The olefin will be described. The α-olefin may be linear or branched, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
Linear α-olefin having 2 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; 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, etc. having 4 to 2 carbon atoms
And 0 branched α-olefins. Among these, a linear α-olefin having 2 to 8 carbon atoms is preferable, and a linear α-olefin having 2 to 4 carbon atoms is more preferable. Of these, ethylene is particularly preferred.

Next, the above-mentioned cyclic olefin will be described. The cyclic olefin of the present invention is a compound represented by the formula (1) or (2).

In the above formula (1), n is 0 or 1, and m is 0 or a positive integer. Also, 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. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group includes 1 to 20 carbon atoms.
An alkyl group having 1 to 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 halogenated alkyl 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, and a cycloalkyl group Examples thereof include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

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.

[0021]

Embedded image

In the above examples, the carbon atoms numbered 1 or 2 represent R in formula (1)
Represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded. Further, 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 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 meaning as in formula (1).

In the above formula (2), m is 0 or a positive integer, h is 0 or a positive integer, and j and k
Is 0, 1 or 2. Also, R ^{7 to} R ¹⁵ and R ¹⁷
To R ^{1 8} represents the same as equation (1). Furthermore, R ^{19 to} R
²⁷ 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.

Here, the halogen atom is the same as the halogen atom in the formula (1). In addition, R ¹⁹ to
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, 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 halogenated alkyl group include groups in which at least a part of the hydrogen atoms forming the above-described 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 and the like, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specifically, 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 combine with 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 has the same meaning 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 are more specific examples of the cyclic olefin represented by the above formula (1) or (2).

[0032]

Embedded image Bicyclo [2.2.1] hept-2-ene derivatives such as;

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives such as;

[0038]

Embedded image Hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] , such as -
4-heptadecene derivatives;

[0039]

Embedded image Octacyclo such as ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0
^3,8 .0 ^12,17] -5-docosene derivatives;

[0040]

Embedded image Pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivatives such as;

[0041]

Embedded image Heptacyclo-5-eicosene derivatives or heptacyclo-5-heneicosene derivatives such as;

[0042]

Embedded image Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives;

[0043]

Embedded image Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as;

[0044]

Embedded image Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene derivatives such as;

[0045] pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -
4-pentadecadiene

Embedded image Diene derivatives such as;

[0046]

Embedded image Pentacyclo such ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene derivatives;

[0047]

Embedded image Heptacyclo such as ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0
^11,16 ] -4-eicosene derivatives;

[0048]

Embedded image Nonashikuro such as ^{[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;

[0049]

Embedded image Pentacyclo such ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene derivatives;

[0050]

Embedded image Heptacyclo such as [8.8.0.14,7.1 ^{11 and 18} .1 ^13,16 .0 ^3,8 .0
^12,17 ] -5- ^heneicosene derivatives;

[0051] 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]} -6-hexacosenoic

Embedded image Nonashikuro such as ^{[10.10.1.1 5,8 .1 14,21 .1 16,19 .0} 2,11.
0 ^4,9 .0 ^{13, 22} .0 ^15,20] -6-hexacosenoic derivatives;

And furthermore,

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

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.

The (a-1) to (a-) used in the present invention
The cyclic olefin resin of 3) is represented by the above 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 methods described in JP-A-308-308 and JP-A-1-197511.

(A-1) α-Olefin ethylene / cyclic
Olefin Random Copolymer The (a-1) α-olefin / cyclic olefin random copolymer of the present invention usually contains 30 to 90 mol%, preferably 40 to 80 mol% of structural units derived from α-olefin.
It contains from 10 to 70 mol%, preferably from 20 to 60 mol%, of structural units derived from cyclic olefins in an amount of mol%. The α-olefin composition and the cyclic olefin composition are measured by ¹³ C-NMR.

In the present invention, (a-1) α-olefin / cyclic olefin random copolymer is particularly preferably used as a structural unit derived from ethylene,
An ethylene / cyclic olefin random copolymer comprising a structural unit derived from the aforementioned cyclic olefin.

(A-1) In the α-olefin / cyclic olefin random copolymer, the constitutional unit derived from the α-olefin having 2 to 20 carbon atoms and the constitution derived from the cyclic olefin as described above. It is preferable that the unit and the unit are randomly arranged and combined to have 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 below, this copolymer is 135
C., can be confirmed by complete dissolution in decalin.

In the (a-1) α-olefin / cyclic olefin random copolymer used in the present invention, at least a part of the structural unit derived from the cyclic olefin represented by the above formula (1) or (2). Is considered to have a structure represented by the following structural formula (1-a) or (2-a), respectively. Further, at least a part of the cyclic olefin represented by the formula (1-1) has the following structural formula (1-1-
It is considered to have the structure represented by a).

[0063]

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 have the same meaning as in formula (2).

The (a-1) α-olefin / cyclic olefin random copolymer used in the present invention is derived from another copolymerizable monomer, if necessary, as long as the object of the present invention is not impaired. It may contain a structural unit. Examples of such other monomers include olefins other than the above α-olefin or cyclic olefin having 2 to 20 carbon atoms, norbornenes, non-conjugated dienes, and the like.

Specifically, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene,
Methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro
Cycloolefins such as -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,
Norbornenes such as 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene and 5-fluoro-2-norbornene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5
Non-conjugated dienes such as -methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 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 α-olefin / cyclic olefin random copolymer having 2 to 20 carbon atoms, the constitutional unit derived from the above other monomer is usually 20 mol% or less, preferably 10 mol% or less. % Or less.

The (a-1) α-olefin ethylene / cyclic olefin random copolymer used in the present invention comprises α-olefin having 2 to 20 carbon atoms and formula (1) or
It can be produced by using the cyclic olefin represented by (2) and the production method disclosed in the above publication. Among these, this copolymerization is performed in a hydrocarbon solvent,
As a catalyst, a vanadium-based catalyst formed from a vanadium compound and an organoaluminum compound soluble in this hydrocarbon solvent, a titanium-based catalyst formed from a titanium compound and an organoaluminum compound, or at least two conjugated cycloalkadienyl groups are lower. (A-1) α-olefin / cyclic olefin random copolymer using a zirconium-based catalyst formed from a zirconium complex having a polydentate compound linked via an alkylene group as a ligand and an aluminoxane It is preferred to produce

(A-2) Ring Opening (Co) Weight of Cyclic Olefin
Coalescing or ring-opening (co) polymer of a cyclic olefin in is (a-2) for use in the hydrogenation product thereof present invention, the formula (1) or (2) a structural unit derived from cyclic olefin represented And at least a part of this structural unit is represented by the following formula (1-
It is considered to have the structure represented by 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).

[0069]

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 above-mentioned cyclic olefin-based ring-opening (co) polymer contains the above-mentioned cyclic olefin as an essential component. However, other copolymerizable copolymers may be used as necessary within a range not to impair the object of the present invention. It may contain a saturated monomer component. Examples of the optionally copolymerized unsaturated monomer include, for example, a cyclic olefin represented by the following formula (3).

[0071]

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.

The monomer component represented by the above formula (3) includes, for example, 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.

The unsaturated monomers which may optionally be copolymerized in addition to the above formula (3) include, 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 a 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.

The hydride of the ring-opened (co) polymer in (a-2) used in the present invention is obtained by converting the (a-2) ring-opened (co) polymer obtained as described above into a conventionally known one. It is obtained by hydrogenation in the presence of a hydrogenation catalyst. In the hydride of this ring-opened (co) polymer, at least a part of the structural units derived from the cyclic olefin represented by the formula (1) or (2) is represented by the following formula (1-c) or (2) It is considered to have the structure represented by -c). In addition, the expression (1-
It is considered that at least a part of the cyclic olefin represented by 1) has a structure represented by the following formula (1-1-c).

[0076]

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) The above (a-1) or (a-
2) Graft-modified product The graft-modified product (a-3) used in the present invention is the (a-1) α-olefin / cyclic olefin random copolymer or (a-2) cyclic olefin described above. Is obtained by graft-modifying a part of the ring-opening (co) polymer or a hydride thereof with a modifying agent.

Examples of the modifying agent include unsaturated carboxylic acids such as maleic anhydride, and derivatives thereof such as acid anhydrides and 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) an α-olefin / cyclic olefin random copolymer or (a-2) a ring-opening (co) polymer of a cyclic olefin or a hydride thereof so as to obtain a desired modification ratio. Alternatively, it 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 cyclic olefin resin (A1) 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, among these, as the cyclic olefin resin (A1), (a)
-1) α-olefin / cyclic olefin random copolymer is preferably used.

Next, the cyclic olefin resin composition (A2) comprising the cyclic olefin resin (A1) and the polyolefin (b) used in the present invention will be described. The cyclic olefin resin (A1) constituting the cyclic olefin resin composition (A2) is as described above.

[0082] As (b) used in the polyolefin present invention (b) a polyolefin, typically a (co) polymer of α- olefin having 2 to 20 carbon atoms are 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 an α-olefin homopolymer as described above 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 Cycloolefins such as 2,6,7a-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- Norbornenes such as 2-norbornene and 5-fluoro-2-norbornene; 1,4-hexadiene, 4-
Non-conjugated dienes such as methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene; And the like. These other monomers can be used alone or in combination of two or more.

In the present invention, the polyolefin (b) is preferably polyethylene and / or polypropylene. (B) When the polyolefin is polyethylene, the polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another α-olefin.

With respect to the degree of crystallinity, the above-mentioned polyolefins have high crystallinity, low crystallinity,
Furthermore, since it can be obtained widely even to amorphous ones,
Necessary crystalline materials can be selected according to the purpose of use.

(B) When the polyolefin 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. And have a density of 0.830 g / cm ³ or more, preferably 0.8
The melt flow rate at 7 to 0.94 g / cm ³ and 190 ° C. is 0.01 to 100 g / 10 min, preferably 0.03 to
It is desirable to use one having a Vicat softening point of 50 to 140 ° C, preferably 80 to 130 ° C, at 50 g / 10 min.

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.

Further, (b) the polyolefin is, for example,
In the case of polypropylene, the polypropylene may be a homopolymer of propylene or a copolymer of propylene and another α-olefin.
(B) When the polyolefin is polypropylene, a propylene homopolymer or a propylene content of 70
A copolymer of at least 80 mol%, preferably at least 80 mol%, of polypropylene and another α-olefin, having a density of at least 0.85 g / cm ³ , preferably 0.89 to 0.91 g / cm ^3.
cm ³ , 230 ° C. melt flow rate 0.01 to 100
g / 10 min, preferably 0.05 to 50 g / 10 min, and a Vicat softening point of 100 to 170 ° C, preferably 110 to 110 ° C.
It is desirable to use one in the range of 160 ° C.

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. (B) When the polyolefin 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, or a modified product having a high modification ratio is prepared in advance, and then It can also be produced by mixing a modified product and an unmodified polyolefin.

The proportion of the cyclic olefin resin (A1) in the resin composition (A2) is usually at least 50% by weight, preferably 60 to 99% by weight, and the proportion of the polyolefin (b) is usually less than 50% by weight. , Preferably 1 to 40% by weight
It is desirable that

The (A) cyclic olefin-based resin or cyclic olefin-based resin composition used in the present invention contains 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-diphenyl -t-butyl-4-hydroxyphenyl)
Phenolic antioxidants such as 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. Polyhydric alcohol fatty acid esters in which some of the hydroxyl groups have been esterified can be mentioned.

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 less than 10% by weight, preferably 5% by weight, based on 100% by weight of the total of essential components.
It is desirable to use it in a proportion of less than 2% by weight, more preferably less than 2% by weight. The fatty acid ester of polyhydric alcohol is 10% by weight based on 100% by weight of the total of essential components.
It is desirable to use less than 5% by weight, preferably less than 5% by weight.

For producing the resin composition (A2) from the cyclic olefin-based resin (A1) and the polyolefin (b), a known mixing method can be employed. For example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender Etc., after mixing, further single screw extruder,
After melt-kneading with a twin-screw extruder, a kneader, or the like, a method of granulating or pulverizing can be exemplified.

(B) Low crystal having a glass transition temperature of 0 ° C. or less
Crystalline or amorphous soft polymer (c) and crystalline polyolefin
At least one resin selected from the group consisting of
Low crystalline or non-crystalline polymer having a lath transition temperature of 50 ° C or higher
(D) Next, a low-crystalline to amorphous soft polymer (c) having a glass transition temperature of 0 ° C. or lower, which is a material for forming the second layer of the laminate of the present invention, and a crystalline polyolefin ( A composition comprising at least one resin selected from b ′) and a low-crystalline to non-crystalline polymer (d) having a glass transition temperature of 50 ° C. or higher will be described.

At least one resin selected from the group consisting of a low-crystalline to amorphous soft polymer (c) having a glass transition temperature of 0 ° C. or lower and a crystalline polyolefin (b ′) refers to a low-crystalline to amorphous soft resin. Although the polymer (c) and the polyolefin (b ') may be used alone, both the low crystalline to amorphous soft polymer (c) and the polyolefin (b') may be used. Which means that a low-crystalline to amorphous soft polymer (c) and / or a polyolefin (b ') is used. Therefore, the proportion of the low-crystalline to amorphous soft polymer (c) and the polyolefin (b ') used is 0 to 100 parts by weight of the low-crystalline to amorphous soft polymer (c) and the polyolefin (b'). ) Is 100 to 0 parts by weight.

(C) Low crystal having a glass transition temperature of 0 ° C. or less
Soft or Amorphous Soft Polymer As the low crystalline or amorphous soft polymer (c) having a glass transition temperature of 0 ° C. or less used in the present invention, a soft thermoplastic resin having a JIS A hardness of 100 or less is used. preferable. Specific examples include olefin-based elastomers, styrene-based copolymers, and other soft polymers. The crystallinity of the low crystalline to amorphous soft polymer of the present invention is preferably 40% or less.

Examples of the olefin elastomer include ethylene / α-olefin copolymers such as ethylene / propylene rubber (EPR) and ethylene / butene rubber (EBR);
Alternatively, a propylene / α-olefin copolymer such as propylene / butene rubber (PBR), ethylene / propylene / diene (EPDM), ethylene / butene / diene (E
(BDM) and the like, and a terpolymer of ethylene, propylene and a polyene such as triene. Styrene-based copolymers (styrene, ethylene, butene,
Styrene block copolymer (SEBS), styrene / butadiene / styrene block copolymer (SBS), styrene / ethylene / propylene block copolymer (SEP)
S) and styrene / isoprene / styrene block copolymer (SIS).

Other soft polymers include polyisoprene, polyisobutylene, polybutadiene, styrene.
Butadiene rubber and the like. Among them, olefin elastomers such as EPR, EBR, and EPDM are particularly preferably used.

In addition, the low-crystalline to non-crystalline soft polymer having a glass transition temperature of 0 ° C. or lower, which is the polymer described in the above polyolefin (b), may be used as the component (c). it can.

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 0.850-0.910 g / cm ³ , preferably 0.855
０0.990 g / cm ³ , the ethylene content is in the range of 30-95 mol%, preferably 40-92 mol%, and the crystallinity measured by X-ray diffraction is usually It is 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 non-crystalline 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 or amorphous soft polymer as described above.

Examples of the above tackifier include an alicyclic hydrocarbon resin 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 non-crystalline soft polymer may be wholly or partially modified with an unsaturated carboxylic acid or a derivative thereof, or the low-crystalline to non-crystalline soft polymer may be modified. May be blended with a modified polyolefin. Examples of the polyolefin before modification of the modified polyolefin include the above-mentioned (b) polyolefin. The modified polyolefin 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 0.905 to 0.980 g.
/ Cm ³ , preferably 0.920 to 0.970 g / cm ³ , and a crystallinity of 4 measured by an X-ray diffraction method.
The modified polyolefin is at least 5%, preferably in the range of 50-80%.

Of these, modified polyethylene is preferred. In order to produce the modified polyethylene, the melt flow rate (MFR: ASTM D1238, E) is set to 0.0.
01-100 g / 10 min, density 0.905-0.980
g / cm ³ , and a homopolymer of ethylene having a crystallinity of 45% or more as measured by an X-ray diffraction method can be used, or used as a copolymer in combination with an α-olefin. It is also possible. 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 polyolefin 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-
Unsaturated carboxylic acids such as ene-2,3-dicarboxylic acid) or derivatives thereof, for example, acid halides, amides, imides, acid anhydrides, esters and the like. Specific examples include maleenyl hydrochloride, maleimide, and maleic anhydride. Acid, citraconic anhydride, monomethyl maleate, dimethyl maleate,
Glycidyl maleate and the like can be mentioned. 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 the polyolefin using the above-described grafting agent can be performed according to a conventionally employed method.

Examples of the crystalline polyolefin (b ′) polyolefin include the polymers exemplified for the above-mentioned polyolefin (b).
Polymers having a crystallinity of more than 40% are used as polyolefin (b ').

(D) Low crystal having a glass transition temperature of 50 ° C. or higher
A crystalline or non-crystalline polymer having a glass transition temperature of 50 ° C. or more constituting the second layer (B) used in the present invention (d)
Are, for example, the above-mentioned cyclic olefin-based resin or its composition (A), polystyrene, polycarbonate, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, styrene / maleic anhydride copolymer, polyvinyl chloride, Polymethyl methacrylate,
Examples include polyphenylene oxide and epoxy resin. These resins may be in a state of a linear polymer or may be crosslinked.

X of the low-crystalline or amorphous polymer (d)
Crystallinity measured by the line diffraction method is usually 40% or less,
It is preferably at most 30%, and has a glass transition temperature of 50 ° C.
Or more, preferably 60 ° C. or more.

The low-crystalline to amorphous soft polymer (c) and / or polyolefin (b ′) forming the second layer (B) and the low-crystalline to amorphous polymer (d) are: After kneading with an extruder, a Banbury mixer, a roll, or the like in advance, it can be subjected to molding, or can be molded as it is after all components have been subjected to trifrent.

The composition of the soft polymer (c) and / or the polyolefin (b ') forming the second layer (B) and the low crystalline or non-crystalline polymer (d) comprises the soft polymer (c) ) 0 to 100 parts by weight and polyolefin (b ') 10
0 to 0 parts by weight in total 99 to 50% by weight, preferably 9
0 to 60% by weight of the low-crystalline to non-crystalline polymer (d) is 1
To 50% by weight, preferably 10 to 40% by weight.

The cyclic olefin resin (composition) (A) layer and the (B) layer composed of the soft polymer (c) and / or the polyolefin (b ') and the low crystalline or amorphous polymer (d) The form of lamination is (A) / (B),
Any combination such as (B) / (A) / (B) and (A) / (B) / (A) can be adopted. Further, in addition to the above laminate, polyethylene, polyolefins such as polypropylene, ethylene-vinyl alcohol copolymer,
Polyamide such as nylon 6, nylon 6.6, PE
Polyesters such as T and PBT, polystyrene, polycarbonate, ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, cellophane and other resins;
Silica-deposited film, metal-deposited film such as aluminum,
A metal foil such as an aluminum foil may be laminated directly or via an adhesive layer.

In such a laminate of the present invention,
(A) a cyclic olefin-based resin (composition) layer, and (B) a soft polymer (c) and / or a polyolefin (b ')
The thickness of the composition layer composed of the low-crystalline or amorphous polymer (d) can be appropriately set in consideration of the use of the laminate of the present invention. Layer thickness 1μ
m to 10 mm, and the thickness of the layer (B) is 1 μm.
It is in the range of 〜１０10 mm. And the thickness of the entire cyclic olefin-based resin laminate of the present invention, the use of this laminate,
Although it depends on the number of layers to be laminated, it is usually 2 μm
〜20 mm.

A composition comprising the above-mentioned cyclic olefin resin (composition) (A) layer, a soft polymer (c) and / or a polyolefin (b ') and a low crystalline or amorphous polymer (d). The product (B) layer includes, for example, a co-extrusion molding method such as a multilayer T-die method, a multilayer inflation method, an extrusion lamination method, a multilayer (injection) blow method, a two-color molding method, a sandwich molding method, a stamping molding method, and a press. Lamination can be performed by employing a general method of forming a multilayer laminate such as a method. Further, uniaxial or biaxial stretching by a method such as a tenter method or a tubular method is also possible.

The laminate of the present invention has an excellent initial adhesive strength and can be used for various containers and packaging applications for foods, pharmaceuticals and the like. In particular, in applications where the film is temporarily treated at a temperature of 50 ° C. or higher, or is kept or heated at a temperature of 50 ° C. or higher, it is preferably used because the peel strength between layers is less reduced. Specific applications include hot water sterilization, retort,
Containers and packaging for foods and pharmaceuticals used for hot fill, steam sterilization, and the like. Further, the laminate of the present invention is excellent in moisture-proof properties, hardly adsorbs components of foods and medicines, is excellent in fragrance retention, and has little leaching from the laminate. Further, the sheet or film-shaped laminate has excellent hand-cutting properties, heat-sealing properties, and dead-hold properties, and also has excellent vacuum or pressure forming properties.

As specific applications, containers and packaging for drugs, foods and the like can be mentioned. 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.

[0124]

As described above, according to the present invention, the first layer made of a specific cyclic olefin resin or a cyclic olefin resin composition, a soft polymer and / or a polyolefin, and low crystallinity or non-crystallinity. The second layer made of the crystalline polymer composition can be adhered and laminated well, and the adhesive strength between the layers is good even at a temperature of 50 ° C. or more. It can be suitably used for medical treatment, food containers, packaging and the like that require hot fill.

[0125]

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

Measurement method of each physical property TMA (softening temperature): A quartz needle having a diameter of 1.0 mm was placed on a sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5 ° C./min. Tg (glass transition temperature): Measured at a heating rate of 10 ° C./min using DSC. MFR (Melt Flow Rate): ASTM D1238
It measured based on. Crystallinity: measured by the X-ray diffraction method.

Examples 1 to 4 and Comparative Examples 1 to 4 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 an example in which a plurality of resins are used in one layer, a predetermined resin was dry-blended in advance, and the molding was performed while kneading with a molding machine.・ A layer: 30 mmΦ single screw extruder set temperature 250 ° C., screw rotation 30 rpm ・ B layer: 30 mmΦ twin screw extruder set temperature 250 ° C., screw rotation 100 rpm ・ C layer: 30 mmΦ single screw extruder set temperature 250 ° C., screw rotation 30rpm ・ Die temperature: 250 ℃ ・ Cooling roll temperature: 40 ℃

(Layer thickness) A layer / B layer / C layer = 30 μm / 30 μm / 30 μm (Measurement method) The initial adhesive strength of the film prepared by the above method and the film were heated at 110 ° C. for 4 hours in a hot-air circulation oven. The adhesive strength after heating was measured. The measurement was carried out by cutting the film in a width of 15 mm in the extrusion direction (MD) of the film and peeling the layer A and the layer B using a tensile tester at a peeling rate of 300 mm / min by the T-peel method. . The temperature at the time of measurement was 23 ° C., and the relative humidity was 50%.
Met. Table 1 shows the measurement results.

[0129] (Materials used) <raw material used in the A layer> cycloolefin resin (a) ETCD: ethylene and tetracyclo ^[. 4.4.0.1 ^2,5 1 ^7,10]
-3-dodecene random copolymer (ethylene content 65 mol%, TMA = 135 ° C., Tg = 125 ° C., crystallinity =
0%, [η] = 0.60 dl / g, MFR = 15 g / 1
0 min (260 ° C., 2.16 kg) polyolefin (b) EB: ethylene / butene-1 copolymer (ethylene content 9
0 mol%, density 0.890 g / cm ³ , MFR = 18 g
/ 10 min (190 ° C., 2.16 Kg), Tg = −40
° C, crystallinity 20%, JIS A hardness 86)

<Raw Materials Used for Layer B> Crystalline polyolefin resin (b ') PE: linear low density polyethylene (LLDPE), density 0.9
20 g / cm ³ , MFR = 2.1 g / 10 min (190
° C, 2.16 Kg), low crystalline to non-crystalline soft weight with a crystallinity of 50% and glass transition temperature of 0 ° C or less
Combined (c) EP: ethylene-propylene copolymer (ethylene content 8
0 mol%, density 0.870 g / cm ³ , MFR = 2.9
g / 10 minutes (190 ° C., 2.16 Kg), Tg = −40
° C, crystallinity 9%, JIS A hardness 60) Low crystalline to amorphous soft with glass transition temperature 50 ° C or higher
Polymer (d) Other PR using the above-mentioned cyclic olefin resin (ETCD) PR: hydrogenated petroleum resin, Alcon P-125 (softening point temperature 125 ° C, bromine number 2, Arakawa Chemical) <Resin used for layer C > The same PE as that used for layer B was used.

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) C08L 45/00 C08L 51/00 51/00 B65D 1/00 BF term (reference) 3E033 BA14 BB08 3E086 AA23 AD01 BA04 BA15 BB22 BB41 BB51 CA03 CA27 4F100 AK02A AK02B AK03A AK03B AK04A AL03A AL04A AL05A AL05B BA02 BA15 GB15 GB16 JA05B JA11B JA12B JC00 JD04 EJ03 JK06 JK13 JL12 JN01 BB00 BB00 BB00 BB00 BB00 BB00 BB03

Claims (6)

[Claims] (A) (a-1) an α-olefin comprising a copolymer of a cyclic olefin represented by the following formula (1) or (2) and an α-olefin having 2 to 20 carbon atoms: A cyclic olefin random copolymer, (a-2) a ring-opened (co) polymer of a cyclic olefin represented by the following formula (1) or (2) or a hydrogenated product thereof, and (a-3) the α: -Olefin ・
At least one cyclic olefin-based resin selected from the group consisting of a cyclic olefin random copolymer (a-1) or a ring-opened (co) polymer of a cyclic olefin or a graft modified product of a hydrogenated product thereof (a-2) (A1) or a layer formed from a resin composition (A2) comprising the cyclic olefin resin (A1) and (b) a polyolefin; and (B): low crystallinity having a glass transition temperature of 0 ° C. or lower. Or at least one resin 99 to 50 selected from an amorphous soft polymer (c) and a crystalline polyolefin resin (b ′)
Wt% and a glass transition temperature of 50 with a crystallinity of 40% or less.
A laminate comprising at least two layers of a low crystalline or amorphous polymer (d) having a temperature of not less than 1 ° C. and a second layer formed from a composition of 1 to 50% by weight. 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. ) 2. The method according to claim 1, wherein (a-1) has 2 to 2 carbon atoms.
The laminate according to claim 1, wherein the 20 α-olefin is ethylene. 3. The low-crystalline to non-crystalline polymer (d) comprises:
3. The laminate according to claim 1, wherein the laminate is the cyclic olefin-based resin (A1). 4. 4. The laminate according to claim 1, which can be used for a treatment at a temperature of 50 ° C. or higher. 5. The laminate according to claim 4, wherein the laminate can be used as a container or a packaging material. 6. A container or packaging material comprising the laminate according to any one of claims 1 to 5.