JP3165503B2 - Foamable resin composition and foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to flexibility, elasticity, elongation,
A foam having excellent low-temperature properties and good adhesiveness, which can be suitably used as a building material, a packaging material, a cushioning material, a heat insulating material, an automobile part, a vibration damping material, and a foaming property for obtaining the foam. It relates to a resin composition.

[0002]

2. Description of the Related Art Hitherto, polyolefin polymers such as polyethylene and polypropylene and foams such as polystyrene have been widely known, and low foams have been used for building materials as synthetic wood, for example. The highly foamed material is used for, for example, a heat insulating material.
On the other hand, elastomer foams made of natural rubber or synthetic rubber are known, but these have the drawback that the production process becomes complicated because a vulcanizing device is required for their production. Therefore,
Soft polyolefin resin to omit the vulcanization step,
For example, foams made of ethylene / vinyl acetate copolymer or low-density polyethylene are also used, but these have inferior elasticity and tensile properties as elastomers as compared with rubber.

On the other hand, JP-A-2-289632 discloses a foamable polymer composition comprising a copolymer of ethylene and a specific cyclic olefin and a foaming agent, and a foam obtained by foaming this composition. Is disclosed. However, the copolymer shown here has a glass transition temperature of 5
The temperature is as high as 0 to 230 ° C., and although it has excellent heat resistance, it does not have elastomeric elasticity, flexibility and tensile properties. This is also evident from the fact that the tensile elongation at break of the foam is at most 6%. Further, a polyurethane foam is known as a flexible foam, but it has poor water resistance, and its use is limited.

The present invention has been made in view of the above circumstances, and provides a resin foam having excellent flexibility, elasticity, elongation, water resistance, and low temperature characteristics, and a resin composition for obtaining the foam. With the goal.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a blowing agent is blended with a cyclic olefin copolymer having a specific structure having a specific glass transition temperature (Tg) and foamed. In such a case, the present inventors have found that a foam satisfying the above requirements can be obtained, and have accomplished the present invention.

That is, the present invention relates to a cyclic olefin copolymer having a repeating unit derived from an α-olefin and a repeating unit derived from a cyclic olefin and having a glass transition temperature (Tg) of 30 ° C. or lower; And a foamable resin composition comprising the agent. Further, the present invention provides a foam obtained by foaming the foamable resin composition.

Hereinafter, the present invention will be described in more detail.
First, the cyclic olefin copolymer used in the foamable resin composition of the present invention will be described in detail. As the cyclic olefin copolymer, those having a repeating unit derived from an α-olefin and a repeating unit derived from a cyclic olefin and having a glass transition temperature (Tg) of 30 ° C. or lower are used. Here, the α-olefin is not necessarily limited, but for example, the following general formula [X]

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

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

The cyclic olefin 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 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 more. 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, 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-dimetano-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 an α-olefin and a cyclic olefin as described above. In addition to these two essential components,
If necessary, another copolymerizable unsaturated monomer component may be used. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above-mentioned α-olefin components, those not previously used, among the above-mentioned cyclic olefin components, Examples thereof include those not used, cyclic dienes such as dicyclopentadiene and norbornadiene, chain dienes such as butadiene, isoprene, and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin copolymer used in the present invention has a content of [alpha] -olefin unit [x] and a content of cyclic olefin unit [y] of [x] of 80 to 99.9 mol%. [Y] is 20 to 0.1 mol%, particularly [x] is 82 to 99.5 mol%, and [y] is 18 to 0.5 mol%, especially [x] is 85 to 98 mol%. [Y] is 1
Preferably it is 5 to 2 mol%. When the content [x] of the α-olefin unit is less than 80 mol%, the glass transition temperature (Tg) and the tensile modulus of the copolymer are increased, and the obtained foam has elastic recovery, impact resistance, The elasticity 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 elastic recovery may become insufficient. is there.

The cyclic olefin copolymer used in the present invention is a substantially linear copolymer in which α-olefin units and cyclic olefin units are linearly arranged, and does not have a gel-like crosslinked structure. Preferably, it 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.

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 substance increases, which may cause stickiness of the foam.

The cyclic olefin copolymer used in the present invention must have a glass transition temperature (Tg) of less than 30 ° C. By using such a copolymer, a foam that can be suitably used at a low temperature can be obtained. A more preferred glass transition temperature (Tg) is -30 to 20C, particularly-
30-15 ° C. 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%. When the crystallinity exceeds 40%, impact resistance, elasticity and the like may be reduced. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer used in the present invention desirably has a tensile modulus of less than 3,000 kg / cm ² . When the tensile modulus is 3,000 Kg / cm ² or more, the impact resistance of the foam may be insufficient. More preferred tensile modulus is 50 to 2,000 kg /
cm ² .

The cyclic olefin copolymer used in the present invention preferably has an elastic recovery of 20% or more. If the elastic recovery is less than 20%, the flexibility and elasticity when used as a foam may be insufficient. A more preferable elastic recovery rate is 30% or more, particularly 40% or more. The elastic recovery rate was measured using an autograph at a pulling speed of 62 mm / min, a width of 6 mm, and a distance between clamps of 50 mm (L
The test piece of ₀ ) was stretched by 150%, pulled and kept as it was for 5 minutes, then rapidly shrunk without rebound, and after 1 minute, the sheet length (L ₁ ) between the clamps was measured. This is a value obtained by an 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)
A copolymer having a sharp melting peak at 90 ° C or higher due to a wide distribution of the copolymer composition of a cyclic olefin and an α-olefin, resulting in insufficient impact resistance and elasticity of the foam. 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. In addition, the cyclic olefin copolymer used in the present invention has a crystallization peak by DSC (temperature drop measurement),
It is preferable to have one or more relatively small sub-peaks on the high temperature side of the main peak. Due to the characteristics of the thermal properties described above, the physical properties of the foam can be obtained, and the foam can be molded stably, for example, the 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, but a catalyst containing the following compounds (A) and (B) as main components or the following compound (A):
By efficiently copolymerizing an α-olefin and a cyclic olefin using a catalyst containing (B) and (C) as main components, it is possible to efficiently produce the copolymer. (A) a transition metal compound (B) a compound which reacts with a transition metal compound to form an ionic complex (C) an organoaluminum compound

In this case, the transition metal compound (A) may be selected from the groups IVB, VB, VIB, VIIB, VIB of the periodic table.
Transition metal compounds containing transition metals belonging to Group II can be used. As the transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum and the like are preferable, and among them, zirconium, hafnium, titanium, nickel and palladium are preferable.

Examples of the transition metal compound (A) include various compounds. In particular, compounds containing a transition metal of Group IVB and Group VIII, particularly a transition metal selected from Group IVB of the periodic table, ie, Compounds containing titanium (Ti), zirconium (Zr) or hafnium (Hf) can be suitably used. Particularly, compounds represented by the following general formula (I),
A cyclopentadienyl compound represented by (II) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV)

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

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
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, 2,2 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 a methylene bridge, a dimethylmethylene bridge, an ethylene bridge,
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, 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 transition metal is not particularly limited, and 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 }.

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, 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-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, 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 include B, Al, Si, P, As, Sb
Preferred examples of B or P, M ⁵ are Li,
Na, Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6 Mn, Fe, Co,} Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 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-di (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) borate
Tetrabutylammonium borate, tetrakis (pentafluorophenyl) borate (tetraethylammonium),
Tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl))
Ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), dimethyltetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

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

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (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, tri (pentafluorophenyl) boron, tri (3,3)
5-Di (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 indicates 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 which is insoluble in a usual solvent obtained by modifying an aluminoxane represented by the formulas (VIII) 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 foamable resin composition of the present invention comprises the above-mentioned cyclic olefin copolymer and a foaming agent. Various methods can be adopted as a method of blending the cyclic olefin-based copolymer and the blowing agent, as described later.
In the present invention, the type of the foaming agent is not particularly limited, and may be selected from one or more of an evaporative foaming agent and a decomposable foaming agent as appropriate. As the evaporative foaming agent, any liquid can be used as long as it does not dissolve or swell the cyclic olefin-based copolymer at normal temperature and normal pressure and has a boiling point not higher than the heat molding temperature of the base material used. For example, examples of the evaporative foaming agent that is liquid at normal temperature include hydrocarbons, alcohols, esters, ethers, ketones, and halogenated carbons, and preferably saturated hydrocarbons having 5 to 14 carbon atoms. Specific examples include hexane, heptane, octane, decane and the like. Examples of the volatile blowing agent which is a gas at normal temperature include propane, methyl chloride, and Freon gas (such as Freon 12). Of these, hexane and chlorofluorocarbon are preferred.

Various types of decomposable foaming agents can be used as long as they are stable at room temperature, have a decomposition temperature not higher than the heat molding temperature of the base material used, and generate a gas such as nitrogen gas when decomposed. Are available. This decomposition type blowing agent can be classified into an inorganic blowing agent and an organic blowing agent,
Sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, azide compounds (CaN ₃ , B
aN ₃ ), ammonium nitrite and the like. As the organic foaming agent, hydrazine-benzyl condensate, organic carbonyl azide, azobisalkylphosphonate, tetrahydrodioxazine and the like can be used. Specifically, azodicarbonamide (ADCA), azobisformamide (ABFA), azobis Isobutyronitrile (AZD
N), diazoaminobenzene (DAB), N, N'-dinitrosopentamethylenetetramine (DPT), N,
N'-dimethyl-N, N'-dinitroterephthalamide (DMDNTA), benzenesulfonyl hydrazide (B
SH), p-toluenesulfonyl hydrazide (TS
H), p ', p'-oxybisbenzenesulfonyl hydrazide (DBSH), p-toluenesulfonyl semicarbazide, oxalyl hydrazide, nitroguanidine, hydrazodicarbonamide, barium azodicarboxylate, trihydrazinotriazine and the like. . Of these, azodicarbonamide is preferred.

The amount of the foaming agent to be used can be appropriately determined according to the type of foam to be produced, the foaming ratio, etc., but is usually 0.05 to 100 parts by weight per 100 parts by weight of the cyclic olefin copolymer.
50 parts by weight, preferably 0.1 to 35 parts by weight.

The composition of the present invention may optionally contain a foaming aid such as a foaming accelerator, a foam retarder, and a foam nucleating agent. The type of the foaming aid is not limited, but the foaming aid exhibiting the foaming promoting action is citric acid when the foaming agent is sodium bicarbonate, or a combination of urea and fatty acid ammonium when the foaming agent is DPT or phthalic acid. Acid monoureide is effective, and borate is effective when the blowing agent is OBSH. The foaming aid acting as a foam nucleating agent is added for the purpose of making foaming of the foam fine and uniform, and a metal soap such as magnesium stearate or an inorganic substance such as silica or talc may be used. Examples of the foaming aid that performs the function of closing cells include polyvalent carboxylic acids, such as citric acid, succinic acid and salts, esters, and amides thereof, and a foaming aid that acts as a foam nucleating agent. Examples thereof include inorganic fine powders such as silica, calcium carbonate, and carbon black. Further, if necessary, other known foaming aids can be used.

In the present invention, a base material having an unsaturated bond can be used, and a crosslinking agent can be added to the composition to carry out foam crosslinking, whereby a foam having better quality can be obtained. Obtainable. In this case, as a method of containing an unsaturated bond in the base material, a method of using an α-olefin / cyclic olefin / diene copolymer obtained by copolymerizing a diene such as a cyclic diene as a cyclic olefin copolymer, or a method of using a base material Examples thereof include a method in which an α-olefin / cyclic olefin copolymer and a diene-containing soft resin are used in combination. Examples of the crosslinking agent include commonly used organic peroxides and diazo compounds. Specifically, benzoyl peroxide,
Dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, tert
-Butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile and the like. The amount of the crosslinking agent used is 0.01% by weight or more based on the copolymer,
Preferably it is 0.03-1% by weight.

The composition of the present invention may further contain various additives, if necessary, for example, stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, and heat stabilizers, antistatic agents, anti-blocking agents, and lubricants. , Slip agent, anti-fog agent, foaming agent, flame retardant,
Inorganic fillers, organic fillers, dyes, pigments and the like can be blended.

The foam of the present invention is obtained by foaming the foamable resin composition described above. In this case, the method for producing the foam of the present invention is not limited. For example, the foam can be efficiently produced by the following method. That is, a composition comprising the cyclic olefin-based copolymer or another thermoplastic resin and the like is heated to a softening temperature or higher in the presence of a foaming agent to foam and mold. In this case, the foaming agent may be mixed with the base material prior to heat foaming, or may be mixed at the time of heat foaming. As a method of mixing the blowing agent prior to the heat foaming, for example, a method of mixing the blowing agent when producing a cyclic olefin-based copolymer, a method of impregnating a copolymer powder as a base material, Examples include a method of impregnating polymer pellets, a method of dry blending with copolymer powder or copolymer pellets, and the like. Here, when using the method of impregnating a foaming agent, the impregnating property can be improved by blending with another resin. Particularly, in order to obtain a uniform foaming agent, it is effective to blend a compatible thermoplastic resin such as an ethylene-propylene copolymer and a good impregnating property into a fluid foaming agent such as a solvent.
As a method of mixing a foaming agent at the time of heating and foaming, besides a method of dry blending with a copolymer powder or a copolymer pellet, for example, from the middle of an extrusion screw of a molding machine, propylene, methyl chloride, freon gas or the like at room temperature. There is a method of blowing a gas blowing agent.

In the present invention, a foam may be obtained by the above-mentioned foaming by heating, and this may be further formed into a foamed molded article by various molding methods. May be. As a method of molding or heat foam molding, a known method may be appropriately employed, and for example, fusion molding, extrusion foam molding, injection foam molding, or the like can be employed. Further, in the heat foaming (bead foam type method) for foaming from beads or sheets, it is preferable to carry out molding at a temperature higher than the glass transition temperature and 20 ° C. higher than the softening point. When the molding temperature is lower than the glass transition temperature, the molecular motion is frozen and foaming is difficult. On the other hand, when the molding temperature exceeds a temperature higher by 20 ° C. than the softening point, the molding materials are mutually melted, and the characteristics of the bead foaming method cannot be utilized.

The foam of the present invention has an expansion ratio of 1.1 to 4
It is preferably 0.0 times, particularly preferably 1.2 to 20 times.
In this case, the low-magnification foam can be produced by, for example, injection molding, extrusion molding, or extrusion multilayer foaming using a foamed layer as an intermediate layer or an outer layer. Can be obtained well.
Further, a high-magnification foam can be produced by, for example, extrusion molding, mold foaming, or the like. In addition, the molding shape of the foam of the present invention is not particularly limited, and can be various shapes.
For example, it can be formed into beads, sheets, cups, trays, rods, and other three-dimensional shapes.
The foam thus obtained is excellent in flexibility, elasticity, elongation and low-temperature properties, and also has good adhesiveness.
It can be suitably used as a building material, a packaging material, a heat insulating material, an automobile part, an anti-vibration material and the like.

[0065]

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 foamable resin composition and the foam, the cyclic olefin-based copolymer of the following Reference Example was produced.

Reference Example 1 (1) Preparation of ferrocenium tetra (pentafluorophenyl) borate Ferrocene (Cp ₂ Fe) 20 mmol and concentrated sulfuric acid 40
The reaction with milliliters was carried out at room temperature for 1 hour to obtain a dark blue solution. This solution was poured into 1 liter of water and stirred, and the resulting deep blue aqueous solution was added to 500 ml of an aqueous solution of 20 mmol of lithium tetra (pentafluorophenyl) borate. The light blue solid that had precipitated was collected by filtration and washed with water 5
After washing five times with 00 ml, the product was dried under reduced pressure and the desired product ferrocenium tetra (pentafluorophenyl) borate ([Cp ₂ Fe] [B (C
₆ F ₅ ) ₄ ]), 17 mmol.

(2) Copolymerization of ethylene and 2-norbornene In a 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 under a nitrogen atmosphere. 0.15 mmol of ferrocenium tetra (pentafluorophenyl) borate prepared in (1) above was added in this order,
Subsequently, 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 completion of 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 to obtain a cyclic olefin-based copolymer (a1). 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 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 3 ° C. ALC / GPC150C manufactured by Waters Co., Ltd. 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).

Next, examples using the cyclic olefin-based copolymer obtained in the above reference example will be described. Example 1 To 100 parts by weight of the flakes of the cyclic olefin copolymer a1 obtained in Reference Example 1, 1 part by weight of azodicarbonamide as a foaming agent and 0.1 part by weight of dicumyl peroxide as a foaming aid were added. To obtain a foamable resin composition. This composition was placed in a compression mold and heated at 230 ° C.
Was heated and foamed. The obtained foamed molded article had an expansion ratio of 2.1. Example 2 The procedure of Example 1 was repeated, except that 100 parts by weight of the flakes of the cyclic olefin copolymer a2 obtained in Reference Example 2 were used instead of the cyclic olefin copolymer a1.
The obtained foamed molded article had an expansion ratio of 2.3.

[0071]

As described above, the foam obtained by foaming the foamable resin composition of the present invention has excellent flexibility, elasticity, elongation, water resistance, low-temperature properties, and good adhesiveness. Things.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-277638 (JP, A) JP-A-2-289632 (JP, A) JP-A-5-97933 (JP, A) JP-A-5-97933 132590 (JP, A) JP-A-5-262899 (JP, A) JP-A-5-271485 (JP, A) JP-A-5-271487 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C08J 9/00-9/42 C08L 23/00-23/36

Claims (2)

(57) [Claims] 1. A cyclic olefin copolymer having a repeating unit derived from an α-olefin and a repeating unit derived from a cyclic olefin and having a glass transition temperature (Tg) of 30 ° C. or lower, and a foaming agent. A foamable resin composition, comprising: 2. A foam obtained by foaming the foamable resin composition according to claim 1.