JP3285666B2 - Food or pharmaceutical ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-laminated elastic body which is safe and sanitary for use in various containers, particularly containers for foods and medicines, carriers, instruments, packaging materials and the like.

[0002]

2. Description of the Related Art The Food Sanitation Law is a law concerning packaging and utensil materials for food containers, and is described as non-toxic, tasteless, and odorless. This hygiene includes heat resistance and hot water resistance. Pharmaceutical containers are required to have a high degree of hygiene and safety because they have a great effect on the human body. As a rubber product for food, a laminated product for heat-sterilized food packaging obtained by blending EPDM with tocopherol (Japanese Unexamined Patent Publication No.
Various techniques have been developed, for example, US Pat.

[0003] Further, as a rubber product for medical supplies and medical devices having a resin film laminated on the surface, a technique of laminating a polypropylene (abbreviated as PP) film on vulcanized rubber (Japanese Utility Model Publication Nos. 44-5751 and 44-27753). No. 4), a plug coated entirely with fluororesin having excellent chemical resistance (Japanese Utility Model Publication No. 45-17831), and a rubber plug whose chemical surface is wrapped with ethylene trifluoride resin (Japanese Utility Model Application No. 49-21346).
And a method of manufacturing a stopper in which the surface of a rubber stopper, in particular, a chemical solution is laminated with a fluororesin film (Japanese Patent Publication Nos. 52-1355, 5
4-9119, 57-53184, JP-A-61-27
2134, JP-A-2-23961), a rubber stopper in which a fluoro rubber is laminated on IIR (JP-B-63-4310).
4, Japanese Utility Model Application Laid-Open No. 55-47850).

[0004] In the above-mentioned known techniques, no matter what kind of rubber compounding agent is used, eluate or exfoliated matter is generated from the rubber compounding agent and rubber, thereby contaminating external chemicals and the like. Therefore, by wrapping in a fluororesin, PE or PP resin film, it has been a means for preventing external (chemical solution) contamination. However, films made of sanitary fluororesins, PE, PP, etc., have a weak adhesive force surrounding the rubber surface and easily peel off. In addition, although there is a technique for strongly bonding the film surface by corona discharge treatment or the like, it is an advanced technique and has a problem in economics.

[0005]

A technique of laminating a resin containing a cyclic olefin compound as a main component on a rubber surface (Japanese Patent Application Laid-Open No. 5-38785) is known. The olefin resin has a softening temperature of 9
Since the resin is a hard resin at 0 ° C. or higher, elasticity and flexibility are not sufficient, and there has been a problem that when a molded product such as a rubber stopper is deformed, the laminated film is peeled or cracked. Furthermore, the transition metal (aluminum, titanium, vanadium, etc.) used as a catalyst component remains in a large amount in the cyclic olefin-based resin used here, and has a problem that it is eluted into a chemical solution. The present invention has been made in view of the above-described problems, and has excellent adhesiveness with an elastic body, and has excellent elasticity and flexibility, and a resin for lamination containing a pharmaceutically and chemically inert resin. It is an object of the present invention to provide a resin laminated elastic body using the same.

[0006]

According to the present invention, there is provided a group consisting of a random addition copolymer of an α-olefin and a cyclic olefin (a-1) and a hydrogenated product (a-2) of (a-1). And its glass transition temperature (Tg)
Is characterized by using a resin-laminated elastic body obtained by laminating a laminating resin containing at least one cyclic olefin-based resin (a) having an elastic recovery rate of 50% or less and 20% or more on an elastic body surface .
Food or pharmaceutical packaging material is provided. In addition,
The laminating resin is a cyclic olefin resin (a), and other
A composition containing a thermoplastic resin (b).
A packaging material for food or medicine is provided.

Also, α-olefins and cyclic olefins
Of random addition copolymers (a-1) and (a-1)
Selected from the group consisting of hydrogenated products (a-2), and
The glass has a glass transition temperature (Tg) of 50 ° C or less and an elastic recovery rate of
At least one or more cyclic olefin-based resins (a)
Lamination elasticity obtained by laminating lamination resin containing
Food or pharmaceutical utensils characterized by the use of
Provided.

Also, α-olefins and cyclic olefins
Of random addition copolymers (a-1) and (a-1)
Selected from the group consisting of hydrogenated products (a-2);
The transition temperature is 50 ° C or less and the elastic recovery rate is 20% or more.
At least one or more cyclic olefin resin (a)
Is a graph in which is graft-modified with a graft monomer.
Laminating resin containing modified c-olefin resin (c)
The use of a resin laminated elastic body laminated on the elastic body surface
A packaging material for food or medicine is provided.

The laminating resin is a cyclic olefin.
Resin (a) and graft-modified cyclic olefin resin
A food or a composition characterized by being a composition containing (c)
Is provided with pharmaceutical packaging materials. In addition, the tree for lamination
Fat is a graft-modified cyclic olefin-based resin (c), and
That the composition contains another thermoplastic resin (b)
A packaging material for food or medicine is provided. Sa
Further, the laminating resin is a cyclic olefin resin
(A), another thermoplastic resin (b), and a graft-modified ring
A composition containing a fibrous olefin resin (c)
A packaging material for food or medicine is provided.

Also, α-olefins and cyclic olefins
Of random addition copolymers (a-1) and (a-1)
Selected from the group consisting of hydrogenated products (a-2);
The transition temperature is 50 ° C or less and the elastic recovery rate is 20% or more.
At least one or more cyclic olefin resin (a)
Is a graph in which is graft-modified with a graft monomer.
Laminating resin containing modified c-olefin resin (c)
The use of a resin laminated elastic body laminated on the elastic body surface
A food or pharmaceutical device is provided.

The cyclic olefin-based resin (a) has a content of 0.1% .
Intrinsic viscosity [η] (1) within the range of 0.05 to 10 dl / g.
(Measured in decalin at 30 ° C.). Previous
The cyclic olefin resin (a) has the following formula [X], and
It may have a repeating unit represented by [Y].
You.

Embedded image

[0012]

Embedded image

[0013]

[0014]

Hereinafter, the present invention will be described specifically. As described above, the resin laminate elastic body of the present invention has a glass transition temperature (Tg ) selected from the group consisting of the random addition copolymer (a-1) and the hydrogenated product (a-2) of (a-1). ) Is 50
It is characterized in that a laminating resin containing a cyclic olefin-based resin (a) or a graft-modified cyclic olefin-based resin (c) having an elastic recovery of 20% or more at a temperature of not more than ° C is laminated on the surface of the elastic body. .

1. Cyclic olefin resin (a) Random addition copolymer of α-olefin and cyclic olefin (a-1) The α-olefin used in the present invention is not particularly limited. Formula [X]

Embedded image (In the formula [X], Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.).

In the repeating unit represented by the general formula [X], ^Ra represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, n-butyl group, n-hexyl group, n-octyl And n-octadecyl group. In addition, the general formula [X]
Specific examples of the α-olefin that gives a repeating unit represented by the following are, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, Examples thereof include 1-decene and 1-eicosene.

The cyclic olefin used in the present invention includes a cyclic olefin and a cyclic diene. Cyclic Olefin The cyclic olefin used in the present invention is not particularly limited, and examples thereof include those which give a repeating unit represented by the general formula [Y].

In the repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom or a carbon atom
To 20 hydrocarbon groups, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom. Here, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
C1-C20 alkyl groups such as n-butyl group, isobutyl group, t-butyl group, hexyl group and the like, C6-C20 aryl groups such as phenyl group, tolyl group, benzyl group, alkylaryl group and aryl C1-C20 such as alkyl group, methylidene group, ethylidene group and propylidene group
Having 2 to 2 carbon atoms such as an alkylidene group, a vinyl group and an allyl group
And 20 alkenyl groups. Where R
^b , R ^c , R ^f and R ^g exclude an alkylidene group. In addition,
When any of R ^d , R ^e , and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen substituents having 1 to 20 carbon atoms such as a halogen group such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specifically as a substituent containing a nitrogen atom,
Examples thereof include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the cyclic olefin giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, -Methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5
-Phenylnorbornene, 5-benzylnorbornene,
5-ethylidene norbornene, 5-vinyl norbornene, 1,4,5,8-dimetano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2,3-
Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Hexyl-1,4,5,8-dimetano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Ethylidene-1,4,5,8-dimethano-1,2,2
3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2,3-dichloro-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5 , 5,6
-Trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene and the like.

Further, a repeating unit represented by the following formula [Z] may be given.

[0023]

Embedded image (Wherein, l is an integer of 0 or 1, m and n are
R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁵ (or R ⁶ )
And R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. )

Specific examples of the cyclic olefin that provides the repeating unit represented by the formula [Z] include 5-methyl-
5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene
Ene, 5- (ethylphenyl) -bicyclo [2.2.
1] Hept-2-ene, 5- (isopropylphenyl)
-Bicyclo [2.2.1] hept-2-ene, 1,4-
Methano-1,1a, 4,4a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Hexahydroanthracene, cyclopentadiene-acenaphthylene adduct, 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-ene, 5- (anthracenyl) -bicyclo [2.2.1] hept- 2-ene can be mentioned.

Cyclic Diene The cyclic diene used in the present invention is not particularly restricted but includes, for example, 1,3-cyclopentadiene and 1,3-cyclopentadiene.
Cyclohexadiene, 1,4-cyclohexadiene, 5
-Ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,3
-Cyclooctadiene, 1,4-cyclooctadiene,
1,5-cyclooctadiene, 5-methylene-2-norbornene, dicyclopentadiene, dimethyldicyclopentadiene, and

Embedded image And the like. Among these, norbornene, norbornene derivatives, 5-ethylidene-2-norbornene, 5-vinylnorbornene and dicyclopentadiene are particularly preferred. The cyclic diene may have at least two double bonds, and includes, for example, a cyclic triene.

The composition ratio of the α-olefin and the cyclic olefin in the copolymer obtained by random addition polymerization of the α-olefin and the cyclic olefin used in the cyclic olefin resin (a) is represented by mol%, 80: 20-99.
9: 0.1 is preferred. When the amount of the α-olefin is less than 80 mol%, Tg and elastic modulus increase, and the elastic recovery and flexibility of the obtained resin decrease. On the other hand, if the content of the cyclic olefin is less than 0.1 mol%, the crystallinity of the copolymer becomes high, and the effect of introducing the cyclic olefin becomes insufficient in terms of elastic recovery. More preferably, the molar ratio is 8
2:18 to 99.5: 0.5, especially 8 in molar ratio.
5:15 to 98: 2 is most preferred.

When ethylene is used as the α-olefin, in addition to ethylene, the following general formula:

Embedded image (R ^p is a hydrocarbon group having 1 to 20 carbon atoms, preferably propylene, 1-butene, 4-methyl-1-butene, 1-
Octen. )), The composition ratio of ethylene to 5-99.
It is preferably 8 mol%, 75 to 0.1 mol% of the α-olefin of the general formula , and 20 to 0.1 mol% of cyclic olefins. More preferably, ethylene 32-
99 mol%, and 50 to 0.5 mol% of α-olefin ,
And 18 to 0.5 mol% of cyclic olefins. Among them, it is most preferable that the content is 55 to 98 mol% of ethylene, 30 to 1 mol% of α-olefin , and 15 to 1 mol% of cyclic olefins. In this case, ethylene and the α-olefin are 80 to 99.
It is preferably 9 mol%.

In the method of random addition polymerization of an α-olefin and a cyclic olefin , for example,
An on-complex type or an aluminoxane type can be used. Among them, an ion complex catalyst having high polymerization activity is preferable. For example, a catalyst containing the following compounds (A) and (B) as main components or the following compounds (A), (B) and (C)
By copolymerizing an α-olefin and a cyclic olefin using an ion complex-based catalyst containing
A copolymer can be produced efficiently. (A) Group IVB tetravalent transition metal compound (B) Compound capable of forming an ionic complex from transition metal compound (A) or a derivative thereof (C) Organoaluminum compound

[0029]

[0030] As the transition metal compounds (A)
Is preferably a compound containing a transition metal selected from Group IVB of the periodic table , that is, titanium (Ti), zirconium (Zr) or hafnium (Hf). A cyclopentadienyl compound represented by (II) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr
Or Hf atom, Cp is a cyclopentadienyl group,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ are each σ
Ligands such as binding ligands, chelating ligands, and Lewis bases are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, C1-C20 alkoxy groups, C6-C6
Examples of the aryl group include an aryl group, an alkylaryl group or an arylalkyl group having 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples include an acetylacetonate group and a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d
Is an integer of 0 to 4, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
Examples thereof include a 4-trimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and a trimethylsilylcyclopentadienyl group. Further, specific examples of R ^{1 to} R ⁴ in the above formulas (I) to (IV) include:
For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom as a halogen atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms; 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; phenyl group, tolyl as C6-C20 aryl group, alkylaryl group or arylalkyl group Group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group, (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, tetrahydrofuran, etc. as Lewis bases Ethers, tetra Thioethers such as drothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2′-bipyridine, and phenanthroline , Triethylphosphine,
Phosphines such as triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene,
Isoprene, pentadiene, 1-hexene and derivatives thereof; examples of cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. . Examples of the crosslink by the covalent bond of A in the above formula (III) include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a 1,1′-cyclohexylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethylstannylene crosslink. And the like.

Examples of such compounds include the following and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of Formula (III) Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dichloro zirconium, dimethylsilylene bis (cyclo (Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Examples include zirconium compounds, hafnium compounds, and titanium compounds having one or more of an alkyl group, an alkoxy group, and a halogen atom such as a compound in which zirconium is replaced with hafnium or titanium. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetraphenoxy zirconium, tetrakis (2-ethylhexyloxy) zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy trichloro zirconium, dibutoxy dichloro zirconium Bis (2,6-di-t-butylphenoxy) dimethyl zirconium, bis (2,6-di-t-butylphenoxy) dichlorozirconium, zirconium tetrakis (acetylacetonate),

[0037]

[0038]

[0039]

[0040]

Further, as the transition metal compound, the following general formula:
[U] can be mentioned.

Embedded image Wherein, ^{R q} is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ^{Y a} is ^{-O -, - S -, -} NR s -, - PR s
-Or a neutral two-atom donor ligand selected from OR ^s , SR ^s , NR ^s ₂ , and PR ^s ₂ , and M ¹
An element is selected from periodic table Group IVB, Z ^a is, S
_{^{iR s 2, CR s 2,}} SiR s 2 -SiR s 2, CR s
_{^{2 -CR s 2, CR s =}} CR s or ^GeR _s 2, B,
R ^s and BR ^s ₂ . R ^s is a hydrogen atom, carbon number 1
20 hydrocarbon group, a halogen atom, or a selected portion combinations thereof with non-hydrogen atom substituent containing oxygen or nitrogen or silicon atoms and up to 20, or Y ^a, Z ^a or Y two or more R ^s groups from both the ^a and Z ^a form a condensed ring. ]

The compound (B) is not particularly limited, but any compound can be used as long as it can form a cationic species from the transition metal compound (A) or a derivative thereof. For example, an ionic compound (B-1) capable of forming an ionic complex from the transition metal compound (A) or a derivative thereof, specifically a compound comprising a cation and an anion having a plurality of groups bonded to an element, particularly A coordination complex compound comprising a cation and an anion having a plurality of groups bonded to an element can be suitably used. As the compound comprising such a cation and an anion having a plurality of groups bonded to an element, a compound represented by the following formula (V) or (VI) can be suitably used. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or R ¹¹ M ⁶⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group, V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, V
Group III, IA Group, IB, Group IIA, element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms group, an organometalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7, n is an integer of 2 to 8 and k is an integer of 1 to 7 of an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine, diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ include B, Al, Si,
P, As, Sb, etc., preferably B or P, Li Specific examples of ^{M 5, Na, Ag, Cu} , Br, I, I 3 , etc.,
Specific examples of M ⁶ include Mn, Fe, Co, Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; an aryl group having 6 to 20 carbon atoms,
A phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group as an alkylaryl group or an arylalkyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group; F, Cl, Br,
I: Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include the same as those described above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. Among the compounds of the formulas (V) and (VI), M
Those in which ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V): triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltributyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate
Tetrabutylammonium borate, tetrakis (pentafluorophenyl) borate (tetraethylammonium),
Tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl))
Ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), dimethyltetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

Pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N
-Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p
-Cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis ( Tetraphenylphosphonium pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, triethylammonium hexafluoroarsenate,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than those of the formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris (3,5-bis (trifluoromethyl) phenyl) boron and triphenylboron can also be used. is there. Further, as the compound (B), aluminoxanes (B-2) can also be used. As aluminoxanes, specifically,

[0051]

Embedded image (R ¹⁶ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a hydrogen atom, and a halogen atom. But they may be different.
s indicates the degree of polymerization and is usually 3 to 50, preferably 7 to 40.
It is. Aluminoxane represented by the formula:

[0052]

Embedded image (R ¹⁶ is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3 to 50, and preferably 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (VIII), preferred are methylaluminoxane, ethylaluminoxane and isobutylaluminoxane having a degree of polymerization of 7 or more. Further, the aluminoxane may be a modified aluminoxane which is obtained by modifying an aluminoxane with a compound having active hydrogen such as water and which is insoluble in a general solvent.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the method is not particularly limited.
The reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, crystal water contained in a metal salt or the like A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

Further, as the compound (B), a Lewis acid may be used. The Lewis acid (B-3) is not particularly limited, and may be an organic substance or a solid inorganic substance. As organic substances, boron compounds and aluminum compounds, and as inorganic substances, magnesium compounds and aluminum compounds are preferably used. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1′-bi-2-naphthoxy)
Aluminum methyl, magnesium compounds include magnesium chloride and diethoxymagnesium, aluminum compounds include aluminum oxide and aluminum chloride, and boron compounds include triphenylboron, tris (pentafluorophenyl) boron, and tris [3,5-bis (Trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri (n-butyl) boron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, Tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris (3,5-difluorophenyl) boron, bis (Pentafluorophenyl Fluoro boron, diphenyl fluoro boron, bis (pentafluorophenyl) chloro boron, dimethyl fluoro boron, diethyl fluoro boron,
Di (n-butyl) fluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) dichloroboron, methyldifluoroboron, ethyldifluoroboron,
(N-butyl) difluoroboron can be mentioned.

Here, the mixing ratio (molar ratio) of the compound (A) and the compound (B) is such that the compound (B) is a compound (B).
-1), 10: 1 to 1: 100, preferably 2: 1 to 1:10, and when compound (B-2) was used, 1: 1 to 1: 100,000, preferably 1 : 10
1: 10,000.

The mixing ratio (molar ratio) of the compound (A) to the compound (B-3) is from 1: 0.1 to 1: 2,000, preferably from 1: 0.2 to 1: 1,000, particularly Preferably 1:
0.5 to 1: 500. As the compound (B), (B-1), (B-2) and (B-3) can be used alone, but two or more of these can be used in combination.

Examples of the organoaluminum compound as the component (C) include those represented by the following general formula (IX). R ¹⁷ _r AlQ _3-r (IX) (R ¹⁷ is an alkyl group having 1 to 20, preferably 1 to 12 carbon atoms, Q is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or 6 carbon atoms. -20 to 20 aryl groups.
r is an integer of 0 to 3. Specific examples of the compound of the formula (IX) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, and diisobutyl Aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned.

The amount of component (C) used is generally 0 to 2,000 mol, preferably 5 to 2000 mol per mol of component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable.

There are no particular restrictions on the manner of use of the catalyst component. For example, the components (A) and (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. It may be used in contact. Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance.
The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system. The catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

The use ratio of the catalyst to the reaction raw material is such that the raw material monomer / the above component (A) (molar ratio) or the raw material monomer / the above component (B) (molar ratio) is 1 to 10 ⁹ , especially 1
It is preferable to be a 00-10 ^7.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. As the polymerization solvent, a non-aromatic solvent is used. For example, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and cyclooctane; aliphatic hydrocarbons such as hexane, octane, decane and dodecane; and halogenated hydrocarbons such as chloroform and dichloromethane are used. be able to. These solvents may be used alone or in a combination of two or more.
Further, a monomer such as an α-olefin may be used as the solvent.

Regarding the polymerization conditions, the polymerization temperature is 50-250.
C. is preferred, more preferably 70 to 220C, and most preferably 80 to 200C. The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg /
cm ² G, preferably normal pressure to 50 kg / cm ² G.
As a method for adjusting the molecular weight of the copolymer, it is possible to select the amount of each catalyst component used and the polymerization temperature, and furthermore, to carry out the polymerization reaction in the presence of hydrogen. The concentration of the obtained copolymer is preferably from 5 to 500 g / l, preferably from 10 to 40 g / l.
0 g / l is more preferred.

In the cyclic olefin resin used in the present invention, at least a part of the double bond present in the random addition copolymer (a-1) of the α-olefin and the cyclic olefin is hydrogenated. The hydrogenated product (a-2) thus obtained can also be used.

The method of hydrogenating (hydrogenating) this cyclic olefin copolymer is usually carried out in a solution of the polymer in an organic solvent. As this solvent, a hydrocarbon solvent such as cyclohexane, methylcyclohexane, benzene, toluene and xylene is used. The concentration of the cyclic olefin copolymer solution can be determined as appropriate, but hydrogenation is usually carried out at a concentration of 0.1 to 30% by weight, preferably 1 to 20% by weight. As the hydrogenation catalyst used in the method of the present invention, any catalyst generally used for hydrogenating an olefin compound can be used, and is not particularly limited. Examples thereof include the following. . As the heterogeneous catalyst, nickel, palladium, platinum or a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina and titanium oxide, for example, nickel / silica, nickel / diatomaceous earth,
Palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be mentioned. Examples of the nickel-based catalyst include a Raney nickel catalyst, and examples of the platinum-based catalyst include a platinum oxide catalyst and platinum black. Examples of the homogeneous catalyst include those based on a metal of Group VIII of the periodic table, for example, Ni, Co compounds such as cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, and nickel acetylacetonate / triethylaluminum. Examples thereof include those composed of an organometallic compound of a metal selected from Groups IA, IIA, and IIIB of the periodic table, and Rh compounds. Also, MS Saroane (MSS)
Aloan et al. discloses a Ziegler-based hydrogenation catalyst (J. Am. Chem. Soc., 85, 4014 (1)
983)) can also be used effectively. Examples of these catalysts include the following. _{Ti (O-iC 3 H 7} ) 4 - (iC 4 H 9) 3 Al, T
_{i (O-iC 3 H 7} ) 4 - (C 2 H 5) 3 Al, (C 2
_{H 5) 2 TiCl 2 - (} C 2 H 5) 3 Al, Cr (ac
ac) _3- (C ₂ H ₅ ) ₃ Al, Na (acac) _3-
(IC ₄ H ₉ ) ₃ Al, Mn (acac) ₃ — (C ₂ H
₅ ) ₃ Al, Fe (acac) _3- (C ₂ H ₅ ) ₃ A
1, Ca (acac) _2- (C ₂ H ₅ ) ₃ Al, (C _{2
H 5 COO) 3 Co- (C} 2 H 5) 3 Al, hydrogenated (hydrogenation) reaction, in homogeneous or heterogeneous depending on the type of catalyst, of 1 to 150 atm hydrogen pressurization, 0 to 180 ° C. And preferably at a reaction temperature of 20 to 120 ° C. The hydrogenation rate can be arbitrarily adjusted in the range of 0 to 100% by changing reaction conditions such as hydrogen pressure, reaction temperature, reaction time, and catalyst concentration. In order to exhibit excellent thermal stability, it is preferable that 30% or more of the unsaturated bonds in the copolymer be hydrogenated, more preferably 50% or more, and further preferably 8% or more.
The hydrogenation rate is 0% or more. After-treatment, after the hydrogenation reaction, removal of the catalyst by centrifugation, filtration, or in the case of Ziegler catalysts by deactivation of the acid, etc., followed by precipitation of the reaction product in a large amount of a polar solvent such as acetone or alcohol After that, the solvent is removed and dried to obtain a hydride of the olefin copolymer.

Examples of the soluble vanadium-based catalyst include a catalyst comprising a vanadium compound and an organoaluminum compound which are soluble in a hydrocarbon solvent used as a reaction solvent. Here, as the vanadium compound used as a catalyst, a compound represented by the formula VO (OR) _a V _b or the formula V (OR) _c X _d can be exemplified. However, in the above formula, R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦
3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 3 ≦ c + d ≦ 4.

Furthermore, the vanadium compound may be an electron donor adduct of the vanadium compound represented by the above formula. Examples of these vanadium compounds include VO
Cl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ )
₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , V
_{O (O-n-C 4} H 9) Cl 2, VO (OC 2 H
₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (O
-N-C ₄ H _{9) 3} and _{VCl 3 · 2 (OC 8 H} 17 O
H) and the like. These vanadium compounds can be used alone or in combination.

Examples of the electron donor which forms an adduct with the above-mentioned vanadium compound include alcohols having 1 to 18 carbon atoms and phenols having 6 to 20 carbon atoms (these phenols have a lower alkyl group. ), Carbon number 3-1
5 ketones, 2-15 carbon aldehydes, 2 carbons
Oxygen-containing electron donors such as esters of carboxylic acids, organic acids or inorganic acids having up to 30 carbon atoms, acid halides having 2 to 15 carbon atoms, ethers having 2 to 20 carbon atoms, acid amides, acid anhydrides and alkoxysilanes. And nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate. These electron donors can be used alone or in combination. As the organoaluminum compound used here, a compound having at least one Al-carbon bond in a molecule can be used.

[0068]

[0069]

[0070]

[0071]

2. Thermoplastic resin (b) The laminating resin used in the present invention may contain the cyclic olefin resin (a) alone as described above, or may contain the cyclic olefin resin (a) and other thermoplastic resins. The composition of (b) may be used. The thermoplastic resin (b) is not particularly limited, but specific examples thereof include high-density polyethylene, low-density polyethylene, polyethylene such as linear low-density polyethylene, ethylene / 1-butene copolymer, and ethylene. 4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer and its metal salt, polypropylene, ethylene / propylene copolymer, Propylene / 1-butene copolymer, poly 1-butene, 1-butene / 4-methyl-1 pentene copolymer,
Poly 4-methyl-1-pentene, poly 3-methyl-1-
Butene and the like can be mentioned. In addition, as the thermoplastic resin, besides, polystyrene, ABS resin, AS resin, polyvinyl alcohol, polymethyl methacrylate,
Polyvinyl chloride, polyvinylidene chloride, fluororesin (polytetrafluoroethylene, etc.), polycarbonate, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide,
Polyether sulfone, polyamide, polyimide, polyphenylene oxide, polyacetal, and the like can be used. Particularly preferred as a thermoplastic resin is H
DPE, LDPE, L-LDPE, polypropylene, ethylene / propylene copolymer, polystyrene, polyvinyl chloride and the like. In addition, two or more thermoplastic resins can be used in combination as needed. By using a composition containing such a thermoplastic resin, the heat resistance of the resin,
Adhesion can be improved. The orientation ratio of the thermoplastic resin is not particularly limited and depends on the physical properties of the other component, that is, the cyclic olefin-based resin.
The content is preferably 1 to 99.9% by weight, particularly preferably 0.5 to 90% by weight. In the present invention, other resins, elastomers, and the like can be added in addition to the thermoplastic resin, if necessary. For example, by adding a polar group-containing polymer, dyeing properties, antistatic properties, and hydrophilicity can be imparted, and various additives such as a filler or a stabilizer can be blended. Specific examples of the additive that can be blended include the following. Examples of the filler include an inorganic filler and an organic filler, and a known filler can be used without any particular limitation. Examples of usable fillers include silica, diatomaceous earth, alumina,
Titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, aluminum nitride, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium titanate,
Examples include barium sulfate, calcium sulfite, talc, clay, mica, calcium silicate, montmorillonite, bentonite, carbon black, graphite, aluminum powder, molybdenum sulfide, and the like. In addition, various additives include heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, foaming agents, dyes, pigments, natural oils, synthetic oils, waxes, etc. And the mixing ratio can be determined appropriately. 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 (3,3
Phenolic antioxidants such as 5-di-t-butyl-4-hydroxyphenyl) propionate), metal salts of fatty acids such as zinc stearate, calcium stearate and calcium 1,2-hydroxystearate, glycerin monostearate, glycerin mono Examples include polyhydric alcohol fatty acid esters such as laurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, for example, tetrakis (methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane and zinc stearate, A combination with glycerin monostearate and the like can be exemplified.

3. Graft-modified cyclic olefin-based resin (c) The graft-modified cyclic olefin-based resin (c) used in the present invention can be prepared by graft-modifying the above-mentioned cyclic olefin-based resin (a) with a graft monomer. .

As the graft monomer used for producing the graft-modified cyclic olefin resin (c) used in the present invention, an unsaturated carboxylic acid or a derivative thereof is preferable. Examples of such unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,
Examples thereof include isocrotonic acid and nadic acid TM (endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid). Further, examples of the derivative of the unsaturated carboxylic acid include unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic imides, and ester compounds of unsaturated carboxylic acids. . Specific examples of such derivatives include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate,
Mention may be made of dimethyl maleate, glycidyl maleate, glycidyl acrylate and glycidyl methacrylate.

These graft monomers can be used alone or in combination. Among the above graft monomers, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid TM or acid anhydrides thereof, glycidyl methacrylate and glycidyl acrylate are particularly preferable.

The graft-modified cyclic olefin resin (c) used in the present invention can be prepared by, for example, various methods known in the art using the above-mentioned graft monomer and the unmodified cyclic olefin resin (a). And can be produced by denaturation. For example, there is a method in which the cyclic olefin-based resin (a) is melted, and a graft monomer is added for graft polymerization, or a method in which the resin is dissolved in a solvent and the graft monomer is added for graft copolymerization.
Further, as a method for producing the graft-modified cyclic olefin-based resin (c), a method in which an unmodified cyclic olefin-based resin (a) is modified by blending a graft monomer so as to have a desired graft modification rate, A graft-modified cyclic olefin resin (c) having a graft modification rate is prepared, and the graft-modified cyclic olefin resin (c) having a high modification rate is prepared.
Is diluted with an unmodified cyclic olefin resin (a) to produce a graft-modified cyclic olefin resin (c) having a desired modification ratio. In the present invention, the graft-modified cyclic olefin resin (c) produced by any method
Can also be used. The modification rate of the graft-modified cyclic olefin resin (c) used in the present invention is usually 0.01 to 5% by weight, preferably 0.1 to 5% by weight.
４4% by weight.

As the graft-modified cyclic olefin resin (c) used in the present invention, the graft-modified cyclic olefin resin (c) obtained as described above may be used as it is, or the graft-modified cyclic olefin resin (c) may be further used. An unmodified cyclic olefin resin (a) may be blended with the olein resin (c). In this case, the graft modification rate in the mixture of the graft-modified cyclic olefin resin and the unmodified cyclic olefin resin is usually
It is prepared in the range of 0.01 to 5% by weight, preferably 0.1 to 4% by weight.

Such a reaction is preferably performed in the presence of a radical initiator. By using a radical initiator, the graft monomer can be efficiently graft-copolymerized. Grafting reaction is usually 60-350 ° C
At a temperature of The radical initiator is usually used in an amount of 0.1 to 100 parts by weight of the cyclic olefin resin (a) to be modified.
It is used in an amount ranging from 001 to 5 parts by weight.

If necessary, the graft-modified cyclic olefin resin (c) or the composition of the graft-modified cyclic olefin resin (c) and the cyclic olefin resin (a) may be added to the other thermoplastic resin (C). b) may be blended. The blending ratio of the thermoplastic resin (b) is the same as in the case described above.

4. Various physical properties of cyclic olefin-based resin (a) The cyclic olefin-based resin used in the present invention needs to have a glass transition temperature (Tg) of 50 ° C or less.
Use of such a resin has an effect that a laminated elastic body which is soft at a temperature equal to or higher than the glass transition temperature (Tg) and has excellent elastic recovery can be obtained. The preferred glass transition temperature (Tg) is -30 to 45C, and most preferably -30 to 40C. The glass transition temperature (Tg) depends on the intended use and the required physical properties, depending on the type of polymer or copolymer monomer used for the resin,
By changing the composition, it can be arbitrarily changed.

The cyclic olefin resin used in the present invention preferably has an intrinsic viscosity [η] of 0.05 to 10 dl / g measured in decalin at 135 ° C. If the intrinsic viscosity [η] is less than 0.05 dl / g, the strength of the laminated elastic body may decrease, and if it exceeds 10 dl / g, the moldability into the laminated elastic body may be deteriorated. More preferred intrinsic viscosity [η] is 0.1 to 8 dl / g.

The cyclic olefin resin used in the present invention has a melt index (MI) [190 ° C., 2.16
kg] is preferably 0.001 to 10,000 g / 10 minutes. If it is less than 0.001 g / 10 minutes, the moldability may be significantly deteriorated, and if it exceeds 10,000 g / 10 minutes, the strength of the laminated elastic body may decrease. It is more preferably 0.01 to 5,000 g / 10 min, and most preferably 0.1 to 100 g / 10 min.

The elastic recovery of the cyclic olefin resin used in the present invention is 20% or more , and more preferably 30% or more. If it is less than 20%, for example, when the rubber stopper is deformed, peeling may occur between the elastic body and the laminating resin.

The molecular weight of the cyclic olefin resin is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 5,000,000, particularly 5 2,000 to 1,000,000, number average molecular weight Mn is 500 to 1,000,000, especially 2,000 to 80
000, and a molecular weight distribution (Mw / Mn) of 1.3.
To 4, particularly preferably 1.4 to 3. When the molecular weight distribution (Mw / Mn) is more than 4, the content of the low molecular weight substance increases, which may cause stickiness when formed into a laminated elastic body.

Further, the cyclic olefin resin preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. If the crystallinity exceeds 40%, the elastic recovery and transparency of the laminated material may be reduced. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

Further, the cyclic olefin resin may be a DSC
Is preferably below 90 ° C. 90 sharp melting peaks by DSC
A resin having a temperature of not less than ° C. may have insufficient randomness of the arrangement of the polymerization components, and may have insufficient elasticity when molded into a laminated material. In addition, the broad melting peak by DSC is more preferably in the range of 10 to 85 ° C. In the DSC measurement, the melting point (melting) peak of the cyclic olefin-based resin used in the present invention is not sharply observed. Is not.

The cyclic olefin-based resin used in the present invention may be a resin consisting of only those having physical properties in the above-mentioned range, or a resin partially containing a resin having physical properties out of the above-mentioned range. There may be. In the former case, a mixture of resins having different Tg whose glass transition temperature (Tg) is 50 ° C. or lower may be used. In the latter case, it is sufficient that the entire physical property value is included in the above range.

5. Elastic body The elastic body used in the present invention is not particularly limited,
Specific examples include thermoplastic polyurethane, styrene / butadiene block copolymer, and styrene / isoprene block copolymer. Specific examples of the rubbers include natural rubber, styrene / butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, ethylene / propylene rubber (EP
M), EPDM, chlorinated polystyrene rubber, urethane rubber and the like. Further, a resin foam or the like may be used.

6. Laminating Method In the present invention, there is no particular limitation on a method of laminating a laminating resin containing a cyclic olefin resin (a) or a graft-modified cyclic olefin resin (c) on the surface of the elastic body. ) Or (c) is soluble in general-purpose solvents, so that n-hexane, cyclohexane, heptane, toluene, xylene, tetralin, decalin,
A method of mixing about 1 to 10% by weight of an aliphatic or aromatic solvent such as 1,2,4-trichlorobenzene or a mixed solvent thereof, applying or spraying it on the surface of the elastic body, and then drying.
Alternatively, a method in which the film is formed into a film by a known technique (molding such as T-die casting and inflation) and laminated on the surface of the elastic body can be used. The lamination on the surface of the elastic body does not necessarily have to be the entire surface, and the form of lamination can be appropriately determined depending on the purpose of use.

[0090]

EXAMPLES The present invention will be described more specifically with reference to the following examples. The measurement of physical properties was as follows. Molecular weight distribution (Mw / Mn) Waters ALC / GPC-150C [column:
Tosoh TSK HM + GMH-6 × 2], solvent:
1,2,4-Trichlorobenzene, temperature: 135 ° C., measured in terms of polyethylene. Using an elastic recovery rate autograph, a tensile speed of 62 mm / min and a width of 6 m
m, a 50 mm (L ₀ ) measuring piece between the clamps was stretched by 150% and pulled, kept as it was for 5 minutes, then suddenly shrunk without being bounced, and after one minute, the sheet length between the clamps (L ₁ ) was measured and determined by the following equation. Elastic recovery (%) = [1- {L ₁ −L ₀ } / L ₀ ] × 100 melt index (MI) The measurement was performed according to JIS-K7210 at 190 ° C. and 2.16 kg. Reference Example 1 (Copolymerization of ethylene and 2-norbornene) At room temperature under a nitrogen atmosphere, 15 liters of toluene, 23 mmol of triisobutylaluminum (TIBA), 38 micromol of tetrabutoxyzirconium, and tetrakis (pentafluoro) in a 30 liter autoclave at room temperature. 60 micromoles of anilinium phenyl) borate were added in this order, followed by 2.9 liters of a toluene solution containing 70% by weight of 2-nobornene (19 mols as 2-norbornene). After the temperature was raised to 80 ° C., the reaction was carried out for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7.5 kg / cm ² . After the completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate the polymer. This polymer was collected by filtration and dried to obtain a cyclic olefin copolymer (A1). The yield of the cyclic olefin copolymer (A1) was 3.21 kg.
Met. The polymerization activity was 928 kg / gZr.

The obtained cyclic olefin copolymer (A)
Physical properties of 1) were as described below. 30 of ¹³ C-NMR
The sum of a peak based on ethylene and a peak based on methylene at the 5th and 6th positions of norbornene, which appears around ppm, and 3
The norbornene content determined from the ratio to the peak based on a methylene group at the 7-position of norbornene appearing at around 2.5 ppm was 10.1 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.03 dl / g, and the crystallinity determined by X-ray diffraction was 2.0%. Bipron 11-EA manufactured by Toyo Bolding Co., Ltd. as a measuring device
Using a mold, a test piece having a width of 4 mm, a length of 40 mm, and a thickness of 0.1 mm was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz. When the transition temperature (Tg) was determined, the Tg was 4 ° C.
When the weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were determined, Mw was 62,300,
Mn was 33,900 and Mw / Mn = 1.84.
10 by Perkin Elmer 7 series DSC
When the melting point (Tm) was measured at a rate of temperature rise of -50 ° C to 150 ° C at a rate of ° C / min, Tm was 78 ° C (broad peak).

Reference Example 2 (copolymerization of ethylene and 2-norbornene) In Reference Example 1, the amount of tetrabutoxyzirconium used was 75 μmol, and the amount of anilinium tetrakis (pentafluorophenyl) borate was 150 μmol. -A cyclic olefin copolymer (A2) was prepared in the same manner as in Reference Example 1 except that the amount of norbornene used was 7.5 mol, the ethylene partial pressure was 6 kg / cm ² , and the polymerization temperature was 90 ° C. Obtained. The yield of the cyclic olefin copolymer (A2) was 2.66 kg. Polymerization activity is 3
It was 89 kg / gZr. The norbornene content obtained in the same manner as in Reference Example 1 was 5.2 mol%, the intrinsic viscosity [η] was 1.17 dl / g, the crystallinity was 4.7%, and Tg was obtained.
Is 0 ° C., Mw is 73,600, Mn is 36,400, M
w / Mn was 2.02 and Tm was 92 ° C. (broad peak).

[0093]

Reference Example 3 (Copolymerization of ethylene and dicyclopentadiene) A stirrer was placed at the center of a dried 5000 ml three-necked flask.
A dropping funnel was attached. Under a nitrogen atmosphere, 2,500 ml of dehydrated toluene and 150 g of dehydrated DCP were put, and 31 g of ethylene aluminum sesquichloride was used as a catalyst.
4.2 g of dichloroethoxyoxovanadium was added, and a mixed gas (1/2) of a dry ethylene gas and a nitrogen gas was passed for 7 minutes, and the mixture was further polymerized at 20 ° C. for 60 minutes through the mixed gas for 30 minutes. The copolymerization was stopped by adding 30 ml of methanol to precipitate a resin body, washed with acetone, and dried at about 60 ° C. to obtain 88 g of a copolymer. DCP in this copolymer was 68 mol%.

An autoclave with a stirrer having a capacity of 1000 ml, 500 g of a cyclohexane solution containing 10% by weight of the copolymer resin obtained above and 5 g of palladium carbon were charged, and the inside of the reactor was replaced with hydrogen. . Next, the hydrogen pressure was raised to 70 atm at the same temperature, and hydrogenation was performed for 8 hours while replenishing hydrogen to the same pressure. Next, the catalyst in the reaction product was removed by centrifugation and filtration, precipitated in a large amount of a mixed solvent of acetone-isopropyl alcohol (1: 1), filtered and dried to obtain 48 g of a resin (B).
[Η] of this resin (B) was 1.53 and Tg was 130 ° C.

[0096]Examples 1-2  More thanReference Examples 1-2The resin of the present invention obtained in(A1)-
(A2)Was used to perform lamination coating on the rubber stopper substrate. Substrate
The BR rubber compound was prepared as follows. BR (Nipol BR1242S, manufactured by Zeon Corporation, cis content 37.2%, ML_{1 + 4} 100 ° C 53) 100 parts by weight Powdered polyethylene (manufactured by Seikagaku Corporation) 3 parts by weight Titanium oxide (manufactured by Ishihara Sangyo) 15 parts by weight Calcined clay (manufactured by Burgess Pigment) 20 parts by weight 2,5-dimethyl -2,5-di (t-butylperoxy) hexane 1 part by weight Vinyl tris (β-methoxy) silane 1 part by weight BR rubber compounding operation and vulcanizing operation are performed by SRIS
Meeting standard) 3603. Vulcanization conditions are temperature 1
Mold at 60 ° C. for 12 minutes. Fig. 1 shows the molded rubber product.
Of the rubber substrate 1 according to the present invention.
Resin(A1)-(A2)Immersed twice in toluene solution of
Immersed to a thickness of about 0.1 mm, at a temperature of about 70 ° C
Dry completely and form a film on the rubber surface as shown in Fig. 1.
Done. Using only the samples obtained above and the rubber substrate
For those without resin lamination (Comparative Example 1), a hygiene test was performed.
In accordance with JP11 “43. Test method for rubber stopper for infusion”
Table 1 shows the results of the tests. Also these
Stopper into a glass container filled with a chemical solution,
A special sanitary test is performed on the
Table 2 shows the results.

The details of the special hygiene test are as follows. Number of fine particles (test for the number of particles generated from rubber stoppers): Put 10 rubber stoppers in a hard glass bottle, and add 300 ml of dust-free water
In addition, the container opening is wrapped with a film and vibrated by hand at about 2 revolutions / second for 20 seconds. Then, after standing still for one hour, the number of fine particles in water is measured with a light shielding type automatic fine particle measuring device (manufactured by HIAC). The presence of fine particles of 5 μm or more in the injection solution is a most important item because it causes problems such as blockage of blood vessels.

Separation of rubber fragments (Fragmentati)
on); 5 ml of water is placed in a 100 ml bottle, a rubber stopper is stoppered, and then an aluminum cap is tightened. Test needle 2
2 ml of water is poured into a syringe equipped with 2G (0.70 × 32 mm), and this is passed through the needle holder of the rubber stopper 20 times. After the water in the syringe is poured into the bottle at the time of the 20th penetration, the syringe needle is pulled out. After the inside of the bottle is vibrated, the rubber stopper is removed, the content liquid is filtered, and the number of rubber pieces on the filter paper is counted. This test method is an improvement of the BS method, and the BS standard is three rubber pieces or less, but the industry currently requires less than two rubber pieces.

Test of gas component in head space: 8 ml of a 2% by weight saline solution was put into the glass bottle, a rubber stopper was stoppered, and an aluminum cap was further tightened. This glass bottle is heated in a pressure vessel at a temperature of 80 ± 1 ° C. for 60 minutes and then left for about 10 hours. Next, 5 ml of the gas in the head space in the bottle is sampled with a gas syringe, and this is measured by gas chromatography. Column: 10% OV-
101 (180-200 mesh WHP), carrier gas He 50 ml / min, column temperature 100-200 ° C.
(4 ° C./min temperature rise), peak presence / absence, and magnitude. This test is a test for examining the generation of trace amounts of gas by rubber and compounding agents, which has recently become a problem.

Alkali-resistant solution test: 10 rubber stoppers were placed in an alkali-resistant container, and a 0.5% by weight solution of sodium carbonate, which was 10 times the weight of the rubber stopper, was added. And tighten. Next, at a temperature of 80 in a pressure vessel.
Heat at 30 ° C. for 30 minutes. After leaving to cool to room temperature, the rubber stopper was removed after cooling, and the test solution was applied to a quartz cell at a wavelength of 430 nm.
The transmittance of the visible part at 50 nm is measured. Pass 95% or more. This test is a basic test for examining the relationship between rubber and a chemical solution, and rubber products with low transmittance are unsuitable.

Water absorption test: vulcanized rubber product was treated at a temperature of 8
Dry at 0 ° C. and normal pressure for 3 hours. Next, after being left in a desiccator containing a desiccant for about 1 hour, the weight (D) is precisely weighed. Next, the rubber stopper is immersed in 10 times the volume of purified water and heated as it is in a pressure vessel at a temperature of 80 ± 1 ° C. for 30 minutes. After cooling, only the rubber stopper was left in a desiccator for 30 minutes to remove water on the surface, and the weight (E) at that time was precisely weighed, and ((E)
-(D) / (D) × 100) (%) is determined, and a weight increase of 2% by weight or less is regarded as acceptable.

Slip test: A rubber stopper is placed on a fluororesin plate, one end of the plate is fixed, and the rubber stopper moves when the other end is raised at a constant speed. The angle at which this movement starts is measured.

[0103]

[Table 1]

[0104]

[Table 2]

[0105] except for using Example 3-4 and the rubber plug obtained in Comparative Example 2 Examples 1-2, and Reference Example 3 obtained in the cyclic olefin resin (B) Example
Using rubber stoppers (Comparative Example 2) prepared in the same manner as in Examples 1 and 2, these rubber stoppers were compressed and deformed by 30% in the thickness direction.
After holding in that state for 1 hour, the operation of returning to the original state was performed ( Examples 3 and 4 and Comparative Example 2), and changes such as peeling and tearing of the laminated film were examined. Table 3 shows the results. As shown in this table, the rubber stopper obtained by laminating the cyclic olefin-based resin obtained in the present invention passed the standard value of JP11. Also, there was no peeling, tearing, etc., even with deformation such as compression.

[0106]

[Table 3]

[0107]

As described above, the resin-laminated elastic body used in the present invention has excellent adhesion between the elastic body and a laminating resin containing a resin laminated on the surface thereof, and Since the laminating resin itself is excellent in elasticity and flexibility, the elastic body does not break or peel when deformed. Further, since the laminating resin is medically and chemically inert, the laminating resin does not elute even when immersed in a chemical solution or the like. Therefore, it is possible to ensure safety and maintain hygiene even when used for medical and food components without contaminating chemicals and the like, and without being deteriorated by the surrounding environment due to its high moisture resistance. .

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an embodiment of a rubber stopper according to the present invention.

[Explanation of symbols]

 1. Rubber base (elastic body) 2. Resin for lamination

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-45612 (JP, A) JP-A-4-185331 (JP, A) JP-A-4-276253 (JP, A) JP-A-1- 316262 (JP, A) JP-A-3-69356 (JP, A) JP-A-5-38785 (JP, A) JP-A-4-353518 (JP, A) JP-A-3-188145 (JP, A) JP-A-3-726 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (8)

(57) [Claims] 1. A glass selected from the group consisting of a random addition copolymer of an α-olefin and a cyclic olefin (a-1) and a hydrogenated product (a-2) of (a-1), and a glass thereof. A transition temperature (Tg) of 50 ° C. or less and an elastic recovery of 20
% Or more of a resin for lamination containing at least one cyclic olefin resin (a) on the surface of the elastic body.
A packaging material for food or medicine characterized by being used . 2. The food or medical device according to claim 1 , wherein the laminating resin is a composition containing a cyclic olefin resin (a) and another thermoplastic resin (b).
Packaging materials for chemicals . 3. A glass selected from the group consisting of a random addition copolymer of an α-olefin and a cyclic olefin (a-1) and a hydrogenated product (a-2) of (a-1), and a glass thereof. A transition temperature (Tg) of 50 ° C. or less and an elastic recovery of 20
% Or more of a resin for lamination containing at least one cyclic olefin resin (a) on the surface of the elastic body.
A food or pharmaceutical appliance characterized by being used . 4. A glass transition temperature selected from the group consisting of a random addition copolymer of an α-olefin and a cyclic olefin (a-1) and a hydrogenated product (a-2) of (a-1). Is 50 ° C. or less and the elastic recovery is 20% or more;
It is characterized by using a resin-laminated elastic body obtained by laminating a laminating resin containing a graft-modified cyclic olefin-based resin (c) obtained by graft-modifying at least one or more cyclic olefin-based resins (a) with a graft monomer. You
Food or pharmaceutical packaging material . Wherein said laminating resin, claims, characterized in that a composition containing the cyclic olefin resin (a), and graft modified cycloolefin resin (c)
4. The packaging material for food or medicine according to 4 . Wherein said laminating resin, according to claim 4, characterized in that it is a composition containing a graft modified cycloolefin resin (c), and other thermoplastic resin (b)
Food or pharmaceutical packaging material . 7. The composition according to claim 1, wherein the laminating resin is a composition containing a cyclic olefin resin (a), another thermoplastic resin (b), and a graft-modified cyclic olefin resin (c). Food or pharmaceutical packaging material according to claim 4.
Fees . 8. A glass transition temperature selected from the group consisting of a random addition copolymer of an α-olefin and a cyclic olefin (a-1) and a hydrogenated product (a-2) of (a-1). Is 50 ° C. or less and the elastic recovery is 20% or more;
It is characterized by using a resin-laminated elastic body obtained by laminating a laminating resin containing a graft-modified cyclic olefin-based resin (c) obtained by graft-modifying at least one or more cyclic olefin-based resins (a) with a graft monomer. You
Food or pharmaceutical equipment .