JP3274702B2 - Multilayer material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a layer containing a specific cyclic olefin copolymer, and is used for food packaging materials, medical materials, containers, containers, electronic materials, automobile members, building materials, civil engineering materials. The present invention relates to a multilayer material that can be effectively used as a material or the like (hereinafter, may be referred to as a multilayer member).

[0002]

2. Description of the Related Art
Polyolefin-based films are widely used as packaging materials for foods and the like. In this case, since the polyolefin-based film usually has no oxygen barrier property, it is often used in combination with a film made of nylon, saponified ethylene-vinyl acetate copolymer, or the like. However, the polyolefin-based film has a disadvantage that the adhesive strength to the adherend material is lower than that of EVA or the like. On the other hand, EVA
If EVA is used, the processability is poor, and if EVA is used for food, there is a problem that the contents smell.

[0003] On the other hand, Japanese Patent Application Laid-Open No. 2-196832 discloses a biaxially stretched film comprising a copolymer of ethylene and a specific cyclic olefin. It has been suggested that it may be used. However, the publication does not only show the specific properties and manufacturing method of such a laminated film, but also has a high glass transition temperature of 50 to 230 ° C. and a high tensile strength. However, it has a low elongation and a high elastic modulus, and thus has different physical properties from those of a film which is usually used frequently. Further, the film made of the above-mentioned copolymer has insufficient heat-sealing properties with other films and poor adhesion. This is disclosed in Japanese Unexamined Patent Publication No. Sho 62-27.
This is also apparent from the fact that the copolymer is modified with α, β-unsaturated carboxylic acid in No. 412 to improve the adhesiveness.

On the other hand, Japanese Patent Application Laid-Open No. 2-269752 discloses the following soft polymer (A) and cyclic olefin polymer (B) in order to provide a molded article having a high surface hardness and excellent scratch resistance. Together with the soft polymer (A) /
The weight ratio of the cyclic olefin polymer (B) is 98/2 to 3
A 0/70 thermoplastic elastomer composition is disclosed. Soft polymer (A): a cyclic olefin-based copolymer comprising an ethylene component, another ethylene component, and a cyclic olefin component and having a glass transition temperature of 0 ° C. or lower. Cyclic olefin-based polymer (B): ethylene and , An addition polymer with a cyclic olefin,
However, a cyclic olefin polymer having an intrinsic viscosity of 0.5 to 10 dl / g and a glass transition temperature of 60 ° C. or higher, however, the soft polymer (A) contained in such a thermoplastic elastomer composition may be used alone. It is not intended to be used, but is added to impart rubber-like properties to the cyclic olefin-based polymer (B), and has adhesiveness, heat sealability, transparency, and the like as intended by the present invention. This was far from the purpose of providing a multilayer material having a layer excellent in elastic recovery properties. Also, Japanese Patent Application Laid-Open
No. 27412 discloses a modified cyclic olefin polymer grafted with an unsaturated carboxylic acid, an unsaturated epoxy monomer or the like. However, such a modified cyclic olefin-based polymer may have a glass transition temperature of more than 200 ° C. and form a layer excellent in adhesiveness, heat sealability, transparency, and elastic recovery as intended by the present invention. It has been difficult to provide a multilayer material having such a material. That is, in order to bond such a modified cyclic olefin-based polymer, for example, high-temperature pressing conditions of 200 ° C. or more were required. Further, JP-A-52-72780 discloses a ring-opened polymer of a norbornene derivative having a cyano group or the like,
A laminate in which a polycarbonate resin or the like is laminated using an ultraviolet curable adhesive is disclosed. However,
The ring-opening polymer used in such a laminate also has a high glass transition temperature, and a multilayer material having a layer excellent in adhesiveness, heat sealability, transparency and elastic recovery as intended by the present invention. It was difficult to provide. The present invention has been made in view of the above circumstances, and has as its object to provide a multilayer material having a layer excellent in adhesiveness, heat sealability, transparency, and elastic recovery.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a cyclic olefin copolymer having a specific structure having a specific glass transition temperature (Tg) has an adhesive property, a heat seal property and a transparent property. The present inventors have found that the above-mentioned object is effectively achieved when such a copolymer is used for a multilayer material, and the present invention has been accomplished.

That is, the present invention has a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin, has a glass transition temperature (Tg) of 30 ° C. or lower, and has an elastic recovery defined by the following formula: Provided is a multilayer material having at least one layer containing a cyclic olefin-based copolymer having a ratio of 20% or more. Elastic recovery rate (%) = [1-{(L ₁ −L ₀ ) / L ₀ }] × 100 [L ₀ is the length between the clamps of the autograph (50 m
m) and L ₁ is a width of 6 m at a tensile speed of 62 mm / min.
m, stretch the test piece between the clamps by 150% and pull
This is the length (mm) of the sheet between the clamps after one minute, after contracting after keeping the same state for one minute. ]

Hereinafter, the present invention will be described in more detail.
The multilayer material of the present invention has one or more layers containing a cyclic olefin copolymer having an ethylene unit and a cyclic olefin unit.

[0008]

The cyclic olefin is not particularly limited, but may be, for example, a compound represented by the following general formula [Y]:

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ¹ or R ^m may form a ring with each other, and R ^{b to} R ^m may be the same or different from each other.) Is mentioned.

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 substituents containing a halogen atom, an oxygen atom or a nitrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Alkyl groups having 1 to 20 carbon atoms such as -butyl group, isobutyl group, t-butyl group, hexyl group, etc .; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, benzyl group, alkylaryl group or arylalkyl. , A methylidene group, an ethylidene group, a propylidene group, etc.
Carbon number 2 such as alkylidene group, vinyl group, allyl group of 0
And -20 alkenyl groups. However,
R ^b , R ^c , R ^f and R ^g exclude an alkylidene group. Note that R
^{When any of d} , R ^e , and R ^{h to} R ^m is an alkylidene group,
The carbon atom to which it is attached has no other substituents.

Specific examples of the substituent containing a halogen atom include halogen substituents such as fluorine, chlorine, bromine and iodine, and halogen substituents having 1 to 20 carbon atoms such as chloromethyl, bromomethyl and chloroethyl. 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-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
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-dimetano-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-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned. Among these, norbornene or a derivative thereof is particularly preferred.

The cyclic olefin copolymer used in the present invention is basically obtained by copolymerizing ethylene and a cyclic olefin as described above, but within a range not to impair the object of the present invention. In addition to these two essential components, another copolymerizable unsaturated monomer component may be used as necessary. Specific examples of such an optionally copolymerizable unsaturated monomer include propylene and 1-butene.
Α-olefins other than ethylene , among the above-mentioned cyclic olefin components, those not previously used, cyclic dienes such as dicyclopentadiene and norbornadiene, and chain dienes such as butadiene, isoprene and 1,5-hexadiene. And monocyclic olefins such as cyclopentene and cycloheptene. Among them, cyclic dienes such as 5-ethylidene-2-norbornene, 5-vinylnorbornene and dicyclopentadiene are preferred.

The cyclic olefin copolymer used in the present invention has a content of ethylene units [ ethylene ] and a content of cyclic olefin units [y] of 80 to 9 [ ethylene ].
[Y] is 20 to 0.1 mol% with respect to 9.9 mol%, particularly [ ethylene ] is 82 to 99.5 mol%, and [y] is 1 to 10 mol%.
It is preferable that [y] is 15 to 2 mol% with respect to 85 to 98 mol% of [ ethylene ]. When the content of ethylene units [ ethylene ] is less than 80 mol%, the glass transition temperature (Tg) and the tensile modulus of the copolymer are increased, and the adhesion of the cyclic olefin-based copolymer-containing layer in the obtained multilayer material is increased. Properties and heat sealing properties may be insufficient. On the other hand, when the content of the cyclic olefin unit [y] is less than 0.1 mol%, the crystallinity of the copolymer becomes high, and the effect of introducing the cyclic olefin component such as adhesiveness becomes insufficient.

The cyclic olefin copolymer used in the present invention is a substantially linear copolymer in which ethylene units and cyclic olefin units are linearly arranged and does not have a gel-like crosslinked structure. Preferably, there is. The absence of a gel-like crosslinked structure can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C. In addition, as long as it can be melt-molded, it may contain a gel.

The cyclic olefin copolymer used in the present invention preferably has an intrinsic viscosity [η] of 0.01 to 20 dl / g measured in decalin at 135 ° C. If the intrinsic viscosity [η] is less than 0.01 dl / g, the strength may be significantly reduced, and if it exceeds 20 dl / g, the moldability may be significantly deteriorated. More preferred intrinsic viscosity [η] is 0.05 to 10 dl / g.

Although the molecular weight of the cyclic olefin copolymer used in the present invention is not particularly limited, the weight average molecular weight Mw measured by gel permeation chromatography (GPC) (in terms of polyethylene) is 1,0.
00 to 2,000,000, especially 5,000 to 1,000
000, the number average molecular weight Mn is 500 to 1,000,
000, especially 2,000 to 800,000, 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 compound increases, which may cause stickiness when the layer containing the cyclic olefin copolymer is used as the surface layer.

The cyclic olefin copolymer used in the present invention must have a glass transition temperature (Tg) of 30 ° C. or less. By using such a copolymer, a multilayer material that can be suitably used at a low temperature can be obtained. A more preferred glass transition temperature (Tg) is -30 to 20C, particularly -30 to 15C. In this case, the cyclic olefin-based copolymer used in the present invention can control the glass transition temperature (Tg) arbitrarily by changing the type and composition of the monomer, and is used for the intended application and use. The glass transition temperature (Tg) can be arbitrarily changed according to the temperature or the like.

The cyclic olefin copolymer used in the present invention has a crystallinity of 0 to 4 as measured by an X-ray diffraction method.
It is preferably 0%. If the crystallinity exceeds 40%, the adhesiveness and the heat sealability may decrease. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer used in the present invention has an elastic recovery rate of 20% or more when used alone . If the elastic recovery is less than 20%, for example, when the article is packaged as one constituent layer of a multilayer material, the article may be sagged or the holding power may be reduced. A more preferable elastic recovery rate is 30% or more, particularly 40% or more.

The elastic recovery was measured using an autograph at a pulling speed of 62 mm / min, a width of 6 mm, and a distance between clamps of 5 mm.
A ₀ mm (L ₀ ) test piece is stretched by 150% and pulled.
After maintaining the same state for 1 minute, the sheet is suddenly contracted without being rebounded, and after 1 minute, the sheet length between the clamps (L
₁ ) is a value determined by the following equation. Elastic recovery rate (%) = [1 − {(L ₁ −L ₀ ) / L ₀ }] ×
100

The cyclic olefin copolymer used in the present invention preferably has a broad melting peak of less than 90 ° C. by DSC (measurement of temperature rise). DSC (heating measurement)
Copolymer having a sharp melting peak at 90 ° C or higher due to a wide distribution of the composition of the copolymer of cyclic olefin and ethylene , resulting in insufficient adhesion of the cyclic olefin copolymer-containing layer. There is. In addition, it is more preferable that the broad melting peak by DSC (temperature rise measurement) is in the range of 10 to 85 ° C. In DSC (measurement of temperature rise), the melting point (melting peak) of the olefin-based copolymer is not seen sharply, and especially in the case of those having a low crystallinity, almost no peak is observed at the level of ordinary polyethylene measurement conditions. Does not appear. Further, the cyclic olefin copolymer used in the present invention preferably has one or more relatively small sub-peaks on the high temperature side of the main peak in the crystallization peak by DSC (temperature drop measurement). Due to the characteristics of the thermal properties described above, the physical properties of the cyclic olefin-based copolymer-containing layer can be obtained, and a multilayer material can be formed stably, for example, a molding temperature range is widened.

The cyclic olefin copolymer used in the present invention may be a copolymer consisting of only those having physical properties in the above-mentioned range, and some copolymers having physical properties out of the above-mentioned range are included. May be used. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The method for producing the cyclic olefin copolymer used in the present invention is not limited as long as it satisfies the requirements of the claims. However, the catalyst containing the following compounds (A) and (B) as a main component or the following compound: Efficient production can be achieved by copolymerizing ethylene and a cyclic olefin using a catalyst containing (A), (B) and (C) as main components. (A) IVB group transition metal compound containing a tetravalent transition metal (B) wherein by reacting with the transition metal compound to form an ionic complex compound (C) an organic aluminum compound

[0025]

Such a transition metal compound (A) is prepared from titanium
(Ti), zirconium (Zr) or hafnium
(Hf) , in particular, of the following general formula (I), (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 each represent a σ-binding ligand, a chelating ligand, a ligand such as a Lewis base, etc. Represents a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
Aryl group, alkylaryl group or arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, etc., and the chelating ligand is acetyl. Examples thereof include an acetonate group and a substituted acetylacetonate group.
A represents a covalent crosslink. a, b, c, and d each represent an integer of 0 to 4, and e represents an integer of 0 to 6. R ¹ ,
Two or more of 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
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof. Examples of the crosslink by a covalent bond of A in the above formula (III) include, for example, a methylene bridge, a dimethylmethylene bridge, an ethylene bridge, 1,1′-
Examples include a cyclohexylene cross-link, a dimethylsilylene cross-link, a dimethylgermylene cross-link, and a dimethylstannylene cross-link.

Examples of such compounds include the following compounds 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 the formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) (Pentadienyl) dimethyl zirconium, 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, tetrachloro zirconium, tetrabromo zirconium,
Butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate),

[0033]

[0034]

[0035]

[0036]

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([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 groups VB, VIB and V of the periodic table, respectively.
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 and diphenylphosphine;
Dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, diethyl thioether, thioethers such as tetrahydrothiophene, ethyl
Esters such as rubenzoate . Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, S
b, etc., preferably B or P, as completely as examples of ^{M 5} L
i, Na, Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6 Mn, Fe, Co,} Ni, Zn and the like.

[0040] Specific examples of ^Z 1 to Z ⁿ may, for example, dimethylamino group as a dialkylamino group, a diethylamino group; methoxy group as an alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group; to 6 carbon atoms A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 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, p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl 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. Can be here,
The alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected from an integer of 1 to 5.
Among the compounds of the formulas (V) and (VI), those in which M 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, tetrakis
[3,5-bis (trifluoromethyl) phenyl] dimethylanilinium borate, triethylammonium hexafluoroarsenate,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (ferromanganese tetraphenylporphyrin), 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 formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris
[3,5-bis (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following general formulas (VII), (VIII) and (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents an alkoxy group or a halogen atom having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0047]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0048]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the number of repeating units is preferably from 3 to 50, and preferably from 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (IX), preferred are an alkyl group having 3 or more carbon atoms, especially an alkyl group-containing aluminum compound having at least one or more branched alkyl group or an aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a polymerization degree of 7 or more, or a mixture thereof, high activity can be obtained. Further, a modified aluminoxane obtained by modifying the aluminoxane represented by the formulas (VII) to (IX) with a compound having active hydrogen such as water is also preferably used.

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, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The catalyst used in the production of the olefin-based copolymer of the present invention comprises the above-mentioned components (A) and (B) or (A)
(B) and (C) are the main components. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1:
It is preferably from 0.01 to 1: 100, particularly preferably from 1: 0.5 to 1:10, especially preferably from 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The component (C) is used in an amount of usually 0 to 2,000 mol, preferably 5 to 5 mol per mol of the 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 is no limitation on the mode 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 usage ratio of the catalyst to the reaction raw material is such that the raw material monomer / the component (A) (molar ratio) or the raw material monomer / the 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. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane;
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in 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 -100 to 2
The temperature is preferably set to 50 ° C., particularly −50 to 200 ° C.
The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 10 hours.
0 kg / cm ² G, preferably normal pressure to 50 kg / cm ² G
It is. 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 multilayer material of the present invention has at least one layer containing the above-mentioned cyclic olefin-based copolymer, and is usually composed of one or more layers containing the above-mentioned cyclic olefin-based copolymer and another material. It is obtained by laminating or joining the above layers or molded bodies.

The other material is not particularly limited, but is preferably a material selected from synthetic polymers, natural polymers, metals, metal oxides, and mixtures thereof.
Here, the synthetic polymer may be either a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include a polyolefin resin, a polystyrene resin, a condensation polymer, and an addition polymerization polymer. Specific examples of the polyolefin resin include high-density polyethylene, low-density polyethylene, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, and butene as a comonomer component.
Linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer obtained using 1, hexene-1, octene-1, 4-methylpentene-1, 3-methylbutene-1, etc. Saponified product, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene ionomer, polyvinyl chloride,
Examples include polyvinylidene chloride and polypropylene. Specific examples of the polystyrene resin include general-purpose polystyrene, isotactic polystyrene, syndiotactic polystyrene, and high-impact polystyrene (modified with rubber). Specific examples of the condensation polymer include polyacetal resin, polycarbonate resin, polyamide resin such as nylon 6, nylon 6.6, polyethylene terephthalate, polyester resin such as polybutylene terephthalate, polyphenylene oxide resin,
Polyimide resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin and the like can be mentioned. Specific examples of the addition-polymerized polymer include a polymer composed of a polar vinyl monomer, a polymer composed of a diene, and the like.Polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer And hydrogenated diene chains. Further, it may be a thermoplastic elastomer. One or more of these thermoplastic resins can be used. Specific examples of the thermosetting resin include a phenol resin, an epoxy resin, an unsaturated polyester resin, and a fiber reinforced product of these resins.

The natural polymers include paper, fiber, cloth,
Organic substances such as wood, metals are aluminum, copper, iron, nickel, tin, chromium, silver, stainless steel, duralumin, brass, metal oxides are ceramics, glass,
Alumina, silica and the like can be mentioned. The other materials described above can be appropriately determined by one or a combination of a plurality of materials depending on the purpose of use of the multilayer material.

The shape and state of each layer or portion constituting the multilayer material of the present invention are not limited, but include, for example, a film, a sheet, a fiber (a woven cloth, a non-woven cloth), various molded articles, and a sintered body. Examples include a compact, a single crystal, a foam, and a porous body. Therefore, it may be a multilayer case such as a surface coating layer of a granular material. In addition, the method of forming each material into a multilayer is not particularly limited, and a known method can be employed. Specifically, for example, when the other material is a thermoplastic resin, a co-extrusion method, Lamination method,
There is a pressing method. When the other material is metal, particularly when the metal to be laminated is relatively thin, there are a lamination method, a metal vapor deposition method, an electrostatic coating method, and the like. Further, in the case of laminating on a molded article or a thick material, there is a method of coating the surface by heat fusion, impregnation, application or the like of a film or sheet. Furthermore, after casting or applying an organic solvent solution in which the cyclic olefin copolymer is dissolved,
It can also be obtained by evaporating this solvent.

[0060] In the multilayer material of the present invention, at least one layer is a layer containing at least a part of the above-mentioned cyclic olefin copolymer. That is, this layer may be composed of only a cyclic olefin-based copolymer,
Cyclic olefin copolymers and other materials (thermoplastics,
Filler or the like). Here, when a resin composition comprising a cyclic olefin copolymer and a thermoplastic resin is used for a multilayer material, the mixing ratio of the cyclic olefin copolymer and the thermoplastic resin is as follows:
Although it depends on the situation and cannot be unambiguously determined, it is usually 0.5 to 99.5% by weight of the cyclic olefin copolymer.
And 99.5 to 0.5% by weight of a thermoplastic resin.

Further, the cyclic olefin copolymer includes:
Various additives and fillers can be added. Examples of the additive include a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a foaming agent, a dye, a pigment, a natural oil, a synthetic oil, and a wax. The compounding amount may be an appropriate amount. 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
Alkyl 5-di-t-butyl-4-hydroxyphenyl) propionate; phenolic compounds such as 2,2'-oxamidobis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate Antioxidants, zinc stearate; calcium stearate;
Fatty acid metal salts such as calcium 12-hydroxystearate, glycerin monostearate; glycerin monolaurate; glycerin distearate; pentaerythritol monostearate; pentaerythritol distearate; polyhydric alcohol fatty acid esters such as pentaerythritol tristearate And the like. These may be blended alone or in combination. For example, tetrakis [methylene-3 (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate] methane and a combination of zinc stearate and glycerin monostearate.

The fillers include inorganic fillers and organic fillers, and these are not particularly limited, and known fillers may be used. The fillers may have various shapes such as granular, powdery, liquid, whisker, and fibrous. is there. Specifically, aluminum, copper, iron, nickel, tin, chromium, silver, stainless steel, duralumin, brass, silica, diatomaceous earth, alumina, titanium oxide, aluminum oxide, zinc oxide, tin oxide, silicon oxide, oxide Zirconium, barium titanate, cadmium sulfide, silicon nitride, magnesium oxide,
Pumice powder, pumice balloon, aluminum hydroxide, aluminum nitride, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate,
Barium titanate, barium sulfate, calcium sulfite,
Talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, carbon black, diamond, graphite, aluminum powder, ferrite, molybdenum sulfide, silicon carbide, titanium carbide, carbon fiber, boron Examples include fiber, silicon carbide fiber, ultrahigh molecular weight polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, Kevlar fiber, metal fiber, and the like. When the cyclic olefin-based copolymer and the inorganic filler or the organic filler are blended, the content is usually 20 to 95% by weight, preferably 40 to 90% by weight of the cyclic olefin-based copolymer, The filler is 80 to 5% by weight, preferably 60 to 10% by weight.

Although the shape and mode of the multilayer material of the present invention are various, for example, the surface of a film, sheet, fiber, cloth, molded body, sintered body, single crystal, foam, porous body or the like is formed in a ring shape. Examples thereof include those coated, laminated, impregnated or coated with an olefin-based copolymer-containing layer, and composites thereof. When a cyclic olefin-based copolymer having a specific glass transition temperature as described above is used as one layer of a multilayer material, when it is used as an adhesive layer, it can be bonded with a high strength between adherend material layers. When used as a base material, high heat seal strength can be obtained at a low heat seal temperature.When used as a main constituent layer of a multilayer material, it has excellent elastic recovery and transparency, and also has the function of the adherend material. This has the advantage that a multi-layered material can be obtained. The multilayer material of the present invention is widely used in various fields, such as films, sheets (especially, a stampable sheet), containers, packaging materials, automobile parts, electric / electronic parts, building materials, and civil engineering materials.

[0064]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. First, prior to the production of a multilayer material,
A cyclic olefin copolymer of No. 2 was produced.

Reference Example 1 (Copolymerization of ethylene and 2-norbornene) In a nitrogen atmosphere at room temperature, 15 liters of toluene, 15 mmol of triisobutylaluminum (TIBA), 0.75 mmol of zirconium tetrachloride were placed in a 30 liter autoclave at room temperature. 0.75 mmol of anilinium tetrakis (pentafluorophenyl) borate are added in this order, followed by 1.5 liters of a toluene solution containing 70% by weight of 2-norbornene (9.2-norbornene.
9 mol) was added. After the temperature was raised to 50 ° C., the reaction was carried out for 60 minutes while continuously introducing ethylene so that the ethylene partial pressure became 5 kg / cm ² . After the completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate the polymer. The polymer was collected by filtration and dried to obtain a cyclic olefin copolymer (a1). The yield of the cyclic olefin copolymer (a1) was 3.58 Kg.
The polymerization activity was 52 Kg / gZr.

The obtained cyclic olefin copolymer (a)
Physical properties of 1) were as described below. 30 of ¹³ C-NMR
The sum of the peak based on ethylene and the peak based on methylene at the 5- and 6-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 7.3 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.69 dl / g, and the crystallinity determined by X-ray diffraction was 1.0%. Using a Vibron 11-EA type manufactured by Toyo Boulding Co., Ltd. as a measuring device, a measuring 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. The glass transition temperature (Tg) was determined from the peak of the loss modulus of elasticity (E ") of the sample, and the Tg was 2 ° C. When the weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were determined at 135 ° C. in terms of polyethylene,
Mw is 99,200, Mn is 52,200, Mw / Mn
Was 1.90. Using a Perkin-Elmer 7 series DSC at a rate of 10 ° C./min, -50 ° C.
When the melting point (Tm) was measured in the range of 150 ° C., the Tm
Was 81 ° C (broad peak) ° C.

REFERENCE EXAMPLE 2 (Copolymerization of ethylene and 2-norbornene) In a nitrogen atmosphere at room temperature, 15 l of toluene, 23 mmol of triisobutylaluminum (TIBA), 38 μmol of zirconium tetrachloride, tetrakis were placed in a 30 l autoclave at room temperature. 60 micromoles of anilinium (pentafluorophenyl) borate are added in this order, followed by 2.9 liters of a toluene solution containing 70% by weight of 2-norbornene (19 liters as 2-norbornene).
Mol) was added. 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 8 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 (a2). The yield of the cyclic olefin copolymer (a2) was 3.32 kg. The polymerization activity was 959 Kg / gZr.

The physical properties of the cyclic olefin copolymer (a2) measured in the same manner as described above were as follows. The norbornene content is 10.3 mol% and the intrinsic viscosity [η] is 0.1.
99 dl / g, crystallinity 1.0%, glass transition temperature (Tg) 3 ° C., Mw 56,900, Mn 29,3
00, Mw / Mn 1.94, melting point (Tm) 73 ° C
(Broad peak) ° C.

Next, Examples and Comparative Examples using the cyclic olefin-based copolymer obtained in the above Reference Example and other resins will be described. Examples 1-2 and Comparative Examples 1-2 The cyclic olefin-based copolymers a1 and a2 were hot-pressed at 190 ° C to obtain a film having a thickness of 100 µm. From this, a test piece having a length of 50 mm and a width of 15 mm was cut out. A multi-layered material was formed by superimposing various adherends of the same shape made of the materials shown in Table 1 on the test piece and a test piece made of another resin, and pressing them at the temperature and pressure shown in Table 1 for 10 minutes. . The crimping surface was 25 mm in length and 15 mm in width. The obtained multilayer material was subjected to a T-peel test at a tensile speed of 10 m.
The peel strength was measured at a load of 1 cm per minute. Table 1 shows the results.

[0070]

[Table 1]

[0071]

As described above, in the multilayer material of the present invention, the cyclic olefin copolymer-containing layer is excellent in adhesiveness, heat sealability, transparency and elastic recovery.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-156308 (JP, A) JP-A-2-269752 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 27/00 C08F 210/02 C08L 23/08

Claims (2)

(57) [Claims] 1. It has a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin, has a glass transition temperature (Tg) of 30 ° C. or lower, and has an elastic recovery rate defined by the following formula of 20%. A multilayer material having at least one layer containing a cyclic olefin copolymer having the above value. Elastic recovery (%) = [1-{(L ₁ −L ₀ ) / L ₀ }] × 100 [L ₀ is the length between the clamps of the autograph (50 m
m), and L ₁ is 6 m in width at a tensile speed of 62 mm / min.
m, stretch the test piece between the clamps by 150% and pull
This is the length (mm) of the sheet between the clamps after one minute, after contracting after keeping the same state for one minute. ] 2. A layer comprising the cyclic olefin-based copolymer and a layer or a molded article comprising at least one material selected from a synthetic polymer, a natural polymer, a metal, a metal oxide and a mixture thereof. The multilayer material according to claim 1, wherein: