JP3255692B2 - Shape recoverable molded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shape-recoverable molded article that can be effectively used as an industrial molded article, toy, seal / covering article, etc. More specifically, it can be deformed at room temperature. In addition, the present invention relates to a shape-recoverable molded article that can be recovered to an original shape by heating to a certain temperature or more.

[0002]

2. Description of the Related Art
Known shape memory resins include those based on norbornene rubber, trans polyisoprene, and cross-linked polyethylene. However, these shape memory resins are used in general thermoplastic resins because they are ultra-high molecular weight polymers to increase the entanglement of molecular chains or cross-links are generated by electron beam irradiation or the like. It is impossible or very difficult to process with the hot melt molding method used. In addition, since it contains unsaturated bonds, it has poor weather resistance and also has a problem in transparency.

On the other hand, as a resin which exhibits shape memory and eliminates the above-mentioned problems, it is a random copolymer of a specific cyclic olefin and ethylene and has a glass transition temperature (Tg) of 20 to 80 ° C. Is disclosed (Japanese Patent Application Laid-Open No. 61-211315). However, Japanese Patent Laid-Open No.
Since the molded article made of the copolymer disclosed in Japanese Patent Application Laid-Open Publication No. H10-27163 has a Tg of room temperature or higher, first, as shown in FIG. 2, the resin molded article is deformed in a temperature range of Tg or higher and lower than the molding temperature, and then cooled to a temperature below Tg. In this case, the deformation is fixed, and when used, the material is heated again to a temperature of Tg or more to recover the original shape. For this reason, there has been a problem that a specific temperature-controlled facility is required in order to deform the molded product. Further, the copolymer described in JP-A-61-211315 does not show shape memory when Tg is lower than room temperature, and when Tg is higher than room temperature, the rigidity is increased at room temperature, The molded article does not show elasticity. For this reason, the field of use was greatly restricted.

Further, a shape memory resin having a Tg of 10 ° C. or higher (Japanese Patent Laid-Open No. 59-535528) and a shape memory resin having a Tg of -10 ° C. or lower (Japanese Patent Laid-Open No. 62-86025) have been proposed. . However, the former resin still employs a shape memory process as shown in FIG. 2, and the latter resin is disadvantageous in that it cannot be remolded because it is crystallized and has insufficient transparency and is a rubber vulcanizate. It had.

The present invention has been made in view of the above circumstances, and exhibits elasticity at room temperature, can be deformed at room temperature, and has moldability, weather resistance, transparency, and the like.
An object of the present invention is to provide a shape-recoverable molded article having excellent remoldability.

[0006]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that when a cyclic olefin copolymer having a specific structure having a specific glass transition temperature (Tg) is used as a molding material, The inventors have found that the object is effectively achieved, and have accomplished the present invention. That is, the present invention is a copolymer obtained by copolymerizing ethylene with a cyclic olefin giving a repeating unit represented by the following general formula [Y], and having a glass transition temperature (Tg) of 10 ° C. or lower. Provided is a shape-recoverable molded article comprising a certain cyclic olefin-based copolymer.

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

Since the cyclic olefin copolymer used in the present invention has a Tg of 10 ° C. or less, it exhibits excellent elastic recovery properties in a normal temperature range (room temperature), like a rubber, against a small strain. Further, even when a large distortion is applied to the molded article at room temperature and the molded article is forcibly deformed, when the molded article is heated to a temperature range from room temperature to lower than the molding temperature, the original shape can be easily recovered. Therefore, as shown in FIG. 1, the molded article of the present invention can be arbitrarily deformed in a room temperature region and can be restored to its original shape by heating. Such a resin molded body exhibiting shape recovery similar to that of the shape memory alloy has not been known in the past.

Further, the cyclic olefin copolymer used in the present invention is not of a usual high molecular weight type, so that it is easy to mold, and it does not contain unsaturated bonds, so that it has excellent weather resistance and good transparency. Things.

Hereinafter, the present invention will be described in more detail.
The shape-recoverable molded article of the present invention comprises a cyclic olefin-based copolymer obtained by copolymerizing ethylene with a cyclic olefin giving a repeating unit represented by the following general formula [Y].

[0010]

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

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, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and the like. An alkyl group having 1 to 20 carbon atoms such as a hexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, a propylidene group; Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as an alkylidene group having 1 to 20 carbon atoms, a vinyl group and an allyl group. ^{However, R b, R c, R} f, R g excluding an alkylidene group. When any one 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 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 as described above with a cyclic olefin giving a repeating unit represented by the general formula [Y]. However, as long as the object of the present invention is not impaired, other copolymerizable unsaturated monomer components may be used, if necessary, in addition to these two essential components. Specific examples of the unsaturated monomer which may be optionally copolymerized include α-olefins other than ethylene such as propylene and 1-butene, and the above-mentioned cyclic olefin components among the above-mentioned cyclic olefin components. None, cyclic dienes such as dicyclopentadiene and norbornadiene,
Examples include chain dienes such as butadiene, isoprene, and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin copolymer needs to have a glass transition temperature (Tg) of 10 ° C. or less. By using such a copolymer, it is possible to obtain a molded article which exhibits elasticity at room temperature and can be deformed at room temperature. A more preferred glass transition temperature (Tg) is -30 to 10C, particularly -30 to 5C. 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.

Further, the cyclic olefin-based copolymer is D
It is preferable that the melting point by SC is 90 ° C. or lower, particularly 10 to 85 ° C., particularly 20 to 80 ° C., or that no clear melting point is exhibited. In this case, the cyclic olefin-based copolymer preferably has a broad melting peak of less than 90 ° C. by DSC. Copolymers whose DSC has a sharp melting peak at 90 ° C. or higher have insufficient uniformity of copolymerization of cyclic olefin and ethylene, and have sufficient shape recovery when formed into a shape recovery molded product. May not be obtained. In the DSC measurement, the melting point (melting peak) of the cyclic olefin-based copolymer used in the present invention is not sharply observed. No peak.

In the cyclic olefin copolymer used in the present invention, the ratio of the content of repeating units derived from ethylene [ethylene] to the content of repeating units derived from cyclic olefin [y] ([ethylene]: [y ]) Is usually 70 to 99.8 mol%: 30 to 0.2 mol%, preferably 80 to 99 mol%: 20 to 1 mol%. When the content of the cyclic olefin repeating unit [y] exceeds 30 mol%, Tg may be higher than room temperature,
If the amount is less than mol%, shape recovery and transparency may decrease.

The cyclic olefin copolymer is a substantially linear copolymer in which repeating units derived from ethylene and repeating units derived from a cyclic olefin are randomly arranged, and has a gel-like crosslinked structure. It is preferable not to do so. 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.

The cyclic olefin copolymer has an intrinsic viscosity [η] of 0.005 to 2 as measured in decalin at 135 ° C.
It is preferably 0 dl / g. If the intrinsic viscosity [η] is less than 0.005 dl / g, the strength of the shape-recoverable molded article may decrease, and if it exceeds 20 dl / g, the moldability into the shape-recoverable molded article may be deteriorated. . More preferred intrinsic viscosity [η] is 0.05 to 10 dl / g.

The molecular weight of the cyclic olefin copolymer is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 2,000,000, Especially 5,000 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 compound increases, which may cause the surface to become sticky when molded into a shape-recoverable molded article.

Further, the cyclic olefin copolymer preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. When the crystallinity exceeds 40%, the transparency is lowered, and the shape recovery may be lowered. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer used in the present invention preferably has a tensile modulus of not more than 3,000 kg / cm ² . Tensile modulus is 3,000Kg / c
Beyond m ^2, the the flexibility becomes insufficient when used for shape recovery moldings. More preferred tensile modulus is 50 to 2,000 Kg / cm ² , especially 100 to 1,
It is 500 kg / cm ² .

The cyclic olefin copolymer used in the present invention may be a copolymer consisting of only those having the above-mentioned physical properties. In this case, the copolymer has a glass transition temperature (Tg) of 10 ° C. or lower. It may be a mixture of copolymers having certain different Tg. Further, the copolymer may partially contain a copolymer having physical properties outside the above range. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The cyclic olefin copolymer used in the present invention can be produced by using a compound (A) represented by the following general formulas (I) to (IV) as a catalyst.

[0026] ^{_{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 represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindene. A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a phenyl 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. Hydrogen atom, oxygen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 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. ]

Further, the cyclic olefin copolymer used in the present invention comprises a catalyst containing the following compounds (A) and (B) as main components or a compound containing the following compounds (A), (B) and (C) as main components. The catalyst can be efficiently produced by using a catalyst. (A) a transition metal compound (B) a compound which reacts with a transition metal compound to form an ionic complex (C) an organoaluminum compound

The substituted cyclopentadienyl groups in the above formulas (I) to (III) include, 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 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) 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, tetrachloro zirconium, tetrabromo zirconium, butoxytrichloro zirconium, dibutoxy dichloro zirconium, bis (2,5-di-t-butylphenoxy) Dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate),

The transition metal compound containing a VB-VIII group transition metal is not particularly limited. Specific examples of the chromium compound include, for example, tetramethylchromium, tetra (t
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridetricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) Chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like can be mentioned.

Specific examples of the manganese compound include, for example, tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like.

Specific examples of the nickel compound include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogenbis (bis (tricyclohexylphosphine) nickel), chlorohydridobis (tricyclohexyl) Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allylnickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel _{chloride, (C 6 H 5) Ni} {OC (C 6 H 5) CH = P (C 6 H 5) 2} {P (C 6 H 5) 3}, ( _{C 6 H 5) Ni {OC} (C 6 H 5) C (SO 3 Na) = P (C 6 H 5) 2} {P (C 6 H 5) 3} and the like.

Specific examples of the palladium compound include, for example, dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanate) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
(1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate and the like can be mentioned.

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, and M ³ and M ⁴ are VB group, VIB group and 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, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; 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 are B, Al, Si, P, As, Sb and the like, preferably B or P, and specific examples of M ⁵ are Li, Na, A
g, Cu, Br, I, I 3 , etc., specific examples of M ⁶ M
n, 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 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 ones as mentioned above can be mentioned. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group 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. (V), (V
Among the compounds of the formula (I), 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)
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-bis (trifluoromethylphenyl)] borate, triethylammonium hexafluoroarsenate,

Compound of formula (VI) : Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate, 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.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following formulas (VII), (VIII) or (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.

[0048]

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

[0049]

Embedded image (R ¹² 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 (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.

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. 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 cyclic olefin-based copolymer has the above components (A) and (B) or the above components (A), (B) and (C) as main components. is there. 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: 0.01 to 1: 100, particularly 1: 1: 0.
5 to 1:10, preferably 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 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. The use form of the catalyst is not limited. 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. May be used.
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. Further, the catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

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. Regarding the polymerization conditions,
Polymerization temperature is -100 to 250C, especially -50 to 200C
It is preferable that The ratio of the catalyst used to the reaction raw material is expressed by: raw material monomer / component (A) (molar ratio)
Alternatively, the raw material monomer / the component (B) (molar ratio) is 1
It is preferably from 10 to 10 ⁹ , particularly preferably from 100 to 10 ⁷ . Further, 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.
cm ² G. As a method of adjusting the molecular weight of the polymer,
The amount of each catalyst component, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can 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, pentane, hexane,
Aliphatic hydrocarbons such as 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.

The method for producing the shape-recoverable molded article of the present invention is not limited, and it can be produced by a conventional method using the above-mentioned cyclic olefin copolymer. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixed extruder, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder Extrusion molding, injection molding, compression molding, blow molding, rotational molding or thermoforming from a sheet is performed using a screwless extruder or the like. Among these, extrusion molding and injection molding can be particularly preferably employed.

The cyclic olefin-based copolymer may contain other elastomers, if necessary, and various additives such as stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc. Agents, anti-blocking agents, lubricants, slip agents, anti-fog agents, foaming agents, flame retardants, inorganic fillers, organic fillers, dyes, pigments and the like can be added.

The shape-recoverable molded article of the present invention can be formed into an arbitrary shape depending on the purpose and application, for example, a sheet shape, a pipe shape, a block shape and the like. The shape-recoverable molded article of the present invention thus formed can be used in various applications that can utilize the shape-recovery property described above, for example, industrial molded products, toys,
Automobiles such as seal supplies, coating supplies, joining materials for pipes of different diameters, internal or external laminates of pipes and rods, medical materials such as dental materials, casts, tableware, stationery, decorations, bumpers, etc. Used for members for

[0058]

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 the shape-recoverable molded product, the cyclic olefin-based copolymers of Reference Examples 1 to 4 below were produced.

[0059]Reference Example 1  (1) Tetrakis (pentafluorophenyl) borate
Preparation of Rosenium Ferrocene (Cp_TwoFe) 20 mmol and concentrated sulfuric acid 40
And the reaction at room temperature for 1 hour.
Obtained. This solution was poured into 1 liter of water and stirred to obtain
Aqueous solution of deep blue
Nyl) lithium borate 20 mmol aqueous solution 500 ml
Added to the turtle. The precipitated pale blue solid was collected by filtration and washed with water.
After washing 5 times using 500 ml, the dried under reduced pressure
The desired product tetrakis (pentafluorophene)
Nil) ferrocenium borate ([Cp_TwoFe] [B (C₆F
_Five)_Four]) 17 mmol were obtained.

(2) Copolymerization of ethylene and 2-norbornene At room temperature under nitrogen atmosphere, 15 liters of toluene, 23 mmoles of triisobutylaluminum (TIBA) and 0.11 mmoles of biscyclopentadienyl zirconium dichloride were placed in a 30 liter autoclave at room temperature. 0.15 mmol of ferrocenium tetrakis (pentafluorophenyl) borate prepared in the above (1) was added in this order, followed by 2.25 liter of a toluene solution containing 70% by weight of 2-norbornene (15. (0 mol), and the mixture was heated to 90 ° C. and reacted for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7 kg / cm ² . After the reaction,
The polymer solution was poured into 15 liters of methanol to precipitate a polymer, and the polymer was collected by filtration and dried.
A cyclic olefin copolymer (a1) was obtained. The yield of the cyclic olefin copolymer (a1) was 3.48 kg. The polymerization activity was 347 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 9.2 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.99 dl / g, and the crystallinity determined by X-ray diffraction was 1.0%. Using a piperon 11-EA type manufactured by Toyo Boulding Co., Ltd., 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 3 ° C. ALC / OPC150C manufactured by Waters, Inc. was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. 135 ° C
The weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene.
Mw is 54,200, Mn is 28,500, Mw / Mn
= 1.91. 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 73 ° C (broad peak) ° C.

Reference Example 2 Reference Example 1 was repeated except that the amount of biscyclopentadienyl zirconium dichloride was changed to 0.075 mmol and the amount of 2-norbornene was changed to 7.5 mol in (2) of Reference Example 1. In the same manner as in the above, a cyclic olefin-based copolymer (a2) was obtained. The yield of the cyclic olefin copolymer (a2) was 2.93 kg, and the polymerization activity was 428 kg / gZr. The norbornene content obtained in the same manner as in Reference Example 1 was 4.9 mol%, and the intrinsic viscosity [η] was 1.22 dl.
/ G, glass transition temperature (Tg) is -7 ° C, Mw is 72,
400, Mn is 36,400, Mw / Mn is 1.99,
Melting point (Tm) was 84 ° C. (broad peak).

[0063]Reference Example 3  In (2) of Reference Example 1, biscyclopentadienyl
0.064 mM zirconium dichloride
Ferrotetrakis (pentafluorophenyl) borate
The amount of senium used was 0.11 mmol, 2-norbornene
7.5 mol, polymerization temperature 70 ° C, ethylene
9Kg / cm partial pressure^TwoExcept that
As a result, a cyclic olefin-based copolymer (a3) was obtained. Ring
The yield of the olefin copolymer (a3) was 2.36 kg,
The total activity was 460 Kg / gZr. Reference Example 1
The norbornene content determined in the same manner as described above was 4.5 mol%,
Intrinsic viscosity [η] is 3.07 dl / g, glass transition temperature
(Tg) is −8 ° C., Mw is 213,000, and Mn is 11
4,000, Mw / Mn 1.87, melting point (Tm) 8
1 ° C (broad peak).

[0064]Reference example 4  In (2) of Reference Example 1, triisobutylaluminum
30% ethyl aluminum sesquichloride
0 mmol, biscyclopentadienyl zirconium di
VO (OC_TwoH_Five) Cl_Two30 mi
Remol and tetrakis (pentafluorophenyl)
F) Ferrocenium borate is not used and 2-norvol
7.5 moles of Nene, 40 ° C polymerization temperature, ethylene
3Kg / cm^TwoAnd the polymerization time was 180 minutes.
Except for the above, the cyclic olefin copolymer was prepared in the same manner as in Reference Example 1.
A body (a4) was obtained. Cyclic olefin copolymer (a4)
Was 420 g. Also, as in Reference Example 1,
Is 18 mol%, intrinsic viscosity
[Η] is 1.09 dl / g, and melting point (Tm) is 105 ° C.
(Sharp peak), glass transition temperature (Tg) 25
° C and Mw / Mn were 2.95.

Next, Examples and Comparative Examples using the cyclic olefin copolymers a1 to a4 obtained in Reference Examples 1 to 4 and a commercially available thermoplastic resin will be described. Example 1 The copolymer a1 obtained in Reference Example 1 was press-molded (press temperature: 190 ° C.) to form a sheet having a thickness of 0.1 mm, and a rectangular test piece having a width of 20 mm and a length of 100 mm was cut out. Was. This was set on an autograph (80 mm between the chucks), pulled at room temperature until the distance between the chucks became 320 mm, and left for 2 minutes. When the test piece was removed from the autograph and immersed in water at a temperature of 60 ° C., the shape recovered to a length of 103 mm within one second. The residual strain according to the following equation was 3%. Residual strain (%) = {(length of test piece after recovery / initial length of test piece) -1} × 100

Examples 2 to 4 and Comparative Examples 1 to 2 Molding and testing were carried out in the same manner as in Example 1 except that the copolymers shown in Table 1 were used and that the water temperature during shape recovery was changed. Was. The time required for recovery and the residual strain were as shown in Table 1.

[0067]

[Table 1]

[0068]

As described above, the shape-recoverable molded article of the present invention has excellent shape-recovery properties, exhibits elasticity at room temperature, is capable of molding and deforming molded articles at room temperature, and has a weather-resistant property. It has properties such as excellent transparency and transparency.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a deformation behavior of a shape-recoverable molded article of the present invention.

FIG. 2 is an explanatory diagram showing a deformation behavior of a conventional shape memory resin.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-234716 (JP, A) JP-A-2-167318 (JP, A) JP-A-4-7307 (JP, A) JP-A-61- 211315 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 210/00-210/18 C08F 232/08

Claims (3)

(57) [Claims] 1. A copolymer obtained by copolymerizing ethylene with a cyclic olefin giving a repeating unit represented by the following general formula [Y], and having a glass transition temperature (Tg) of 1
A shape-recoverable molded article formed of a cyclic olefin copolymer having a temperature of 0 ° C. or lower. Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1;
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or 1. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) 2. The shape-recoverable molded article according to claim 1, wherein the cyclic olefin is norbornene or a norbornene derivative. 3. The cyclic olefin-based copolymer has a melting point of 90.
The shape-recoverable molded product according to claim 1 or 2, which is at most 0C.